B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio

ISSN-0366-3175-BSCVB9, VOLUMEN 44 NUMERO 3 MAYO-JUNIO 2005

 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
ISSN-0366-3175-BSCVB9, VOLUMEN 44 NUMERO 3 MAYO/JUNIO 2005
Publicacin bimestral sobre ciencia y tecnologa de la cermica y el vidrio
PORTADA: SUMARIO
B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio BIOEUTECTICO pseudowollastonita (psW)

- - fosfato triclcico ( TCP), despus de
III Editorial
3 semanas de inmersin en SFA. La psW se
ha disuelto y el -TCP se ha transformado en ARTCULOS
hidroxiapatito.

Autores 135 Materiales biocermicos cristalinos.

P.N. De Aza, F. Guitin, S. De Aza.
P.N. de Aza, A. H. de Aza, S. de Aza
146 Un estudio comparativo de actuadores Piezoelctricos y Magnetoestrictivos para
estructuras inteligentes
J.L. Pons
155 De la Ingeniera Qumica a la Tecnologa Cermica: una revisin de la investigacin en
ISSN-0366-3175-BSCVB9, VOLUMEN 44 NUMERO 3 MAYO-JUNIO 2005
el Instituto de Tecnologa Cermica
A. Barba
Edita: 169 Mecanismos de inversin de la magnetizacin e interacciones en sistemas magnticos:
SOCIEDAD ESPAOLA DE CERAMICA Y VIDRIO
Despacho 176
campo coercitivo versus campo de conmutacin y desimanacin trmicamente asistida
Instituto de Cermica y Vidrio, CSIC F. Cebollada, J.M. Gonzlez, J. de Frutos and A.M. Gonzlez
C/ Kelsen 5, 28049 Madrid
Tlf: +34 - 91 735 58 60; Fax: +34 - 91 735 58 43 177 Fenmenos magnetoelctricos en sistemas monobsicos y composites
web: www.secv.es; e-mail: secv@icv.csic.es Liliana Mitoseriu
Presidente: Jorge Bakali
Secretara General: Miguel ngel Rodrguez 185 Clnqueres Prtland Belticos. Sntesis y Anlisis Mineralgico.
Tesorera: Marina Villegas ngeles G. de la Torre, Miguel A. G. Aranda, Antonio H. de Aza, Pilar Pena and Salvador
de Aza.
Redaccin y Administracin: C/ Kelsen 5,
28049 Madrid, Spain. Tel.: +34 - 91 735 58 60
Fax: +34 - 91 735 58 43
Secretaria de Redaccin: Ofelia Sanz, Pedro Cubero. CONTENTS
E-mail: secv@icv.csic.es - Pgina web: www.secv.es

Realizacin, Maquetacin y Fotolitos: AS & A Design, S.L. PAPERS

Pol. Ind. Ronda Sur, Nave 39. 12006 Castelln
Tel. 964 25 70 89. Fax: 964 24 10 10 - e-mail: info@asadesign.com
Edicin e Impresin: Faenza Editrice Ibrica, S.L. 135 Crystalline Bioceramic Materials
Pol. Ind. Ronda Sur, Nave 39. 12006 Castelln P.N. de Aza, A. H. de Aza, S. de Aza
Tel. 964 25 37 62. Fax: 964 24 10 10 - e-mail: info@faenza.es
Exclusiva Publicidad: Faenza Editrice Ibrica, S.L. 146 A comparative analysis of Piezoelectric and Magnetostrictive actuators in Smart
Depsito Legal: CS-385-1998
Structures
El Boletn de la SECV forma parte de los fondos documentales de distintas J.L. Pons
bases de datos bibliogrficas. S. C. I.; Indice Espaol de Ciencia y Tecnologa;
Chemical Abstracts; PASCAL; Georef; SDIM; Silica y WCA recogen de forma 155 From Chemical Engineering to Ceramic Technology: A Review of Research at the Instituto
sistemtica los trabajos originales publicados en la revista.
de Tecnologa Cermica
Todos los trabajos recibidos se someten antes de su publicacin a la revisin A. Barba
crtica de dos supervisores.
169 Reversal mechanisms and interactions in magnetic systems: coercivity versus switching
rgano de difusin de: ALAFAR, AICE, CEVISAMA y CEVIDER. eld and thermally assisted demagnetization
La SECV agradece al Instituto de Cermica y Vidrio, la colaboracin F. Cebollada, J.M. Gonzlez, J. de Frutos and A.M. Gonzlez
de su personal en la publicacin de la revista.
177 Magnetoelectric phenomena in single-phase and composite systems
Los autores de los trabajos asumen toda la responsabilidad que Liliana Mitoseriu
pudiera derivarse de los mismos.

Queda prohibida la reproduccin total o parcial, an citando su procedencia, 185 Belite Portland Clinkers. Synthesis and Mineralogical Analysis
sin permiso de la SECV. ngeles G. de la Torre, Miguel A. G. Aranda, Antonio H. de Aza, Pilar Pena and Salvador
Precio de la suscripcin anual: 150 C- de Aza.
Miembro Fundador ECERS (European Ceramic Society).
Miembro Internacional Commission on Glass (IGG)
Miembro Union Scientifique Continentale du Verre (USCV) V TESIS
Copyright: textos, grficos, fotografas - SECV.
IX IN MEMRIAM
XI NOTICIAS
XXI CALENDARIO

Marzo-Abril (2005) I
 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
EDITOR

Jos Francisco Fernndez

Instituto de Cermica y Vidrio, CSIC

Editores Asociados:

Arte y Diseo: Jaume Coll. Museo Nacional de Cermica Gonzlez Mart

Ciencia Bsica: Antonio Ramrez de Arellano Lpez. Universidad de Sevilla
Electrocermica: Amador Caballero. Instituto de Cermica y Vidrio, CSIC
Esmaltes y Pigmentos Cermicos: Juan Carda Castello. Universidad Jaume I.
Ladrillos y Tejas: Jorge Velasco. AITEMIN. Centro Tecnolgico de la Arcilla Cocida
Materias Primas: M Flora Barba. Instituto de Cermica y Vidrio, CSIC
Medio Ambiente: Jos Miguel Morte Poles. QUACER, SL
Pavimentos, Revestimientos Cermicos y Cermica Blanca: Antonio Barba. Instituto de Tecnologa Cermica
Refractarios: Antonio H. de Aza. Instituto de Cermica y Vidrio
Vidrios: Alicia Durn. Instituto de Cermica y Vidrio, CSIC

Comit Redaccin: E. Criado, P. J. Sanchez-Soto

Comit Editorial Internacional:

J. L. Batista (P); R. Brook (GB); S. de Aza (E); F. Cambier (B); P. Durn (E); A. Escardino (E); G. Fantozzi (I); J. M Fernndez-Navarro (E);
A. Garca-Verduch (E); C. Guillemet (F); P. F. James (GB); E. Mari (RA); N. Claussen (A); A. West (G.B.) F. Marques (P); J. S. Moya (E); F.
Nicoletti (I); T. Yamamoto (J); M. Yoshimura (J); C. Miratvilles (E); V. Orera (E);

TEMTICA SCOPE

Los autores deben seleccionar un mximo de 4 palabras clave de la lista
adjunta. De forma opcional se puede aadir 2 palabras claves designadas por el
autor que no se encuentre en la lista.
La lista de palabras clave debe aparecer en la pgina del ttulo de cada
trabajo enviado seguida del resumen. La direccin completa del autor debe
adjuntare incluyendo el correo electrnico de contacto.
Sntesis y procesamiento
Acabado. Conformado. Fusin. Laminados. Laminas gruesas/delgadas.
Materias primas. Mtodos de deposicin. Molienda. Prensado. Procesamiento.
Reactividad. Recubrimientos. Secado. Sinterizacin. Sol-gel. Suspensiones.
Sntesis.
Authors must select a maximum of 4 keywords from the attached
list. Authors can nominate 2 additional keywords not included in the list.
Keywords must be indicated in the title page of each paper submitted. Authors
complete address including email must be also included.
Synthesis and processing
Coatings. Deposition methods. Drying. Finishing. Melting. Milling.
Pressing. Processing. Raw materials. Reactivity. Shaping. Sintering. Sol-gel.
Suspensions. Synthesis. Thick/Thin Films.
Structure and microstructure

Estructura y microestructura Composites. Diffraction methods. Grain boundaries. Grain growth.

Impurities. Interphases. Microstructure. Microscopy. Nanocomposites.
Bordes de grano. Crecimiento de grano. Diagramas de fases. Espectroscopia. Nanoparticles. Non-destructive tests. Phase diagrams. Porosity. Spectroscopy.
Ensayos no destructivos. Impurezas. Internases. Materiales compuestos. Mtodos Surfaces.
de difraccin. Microscopa. Microestructura. Nanocomposites. Nanopartculas.
Porosidad. Supercies. Properties

Propiedades Chemical properties Colour Conductivity Corrosion Electric/Dielectric

Color. Conductividad. Corrosin. Desgaste. Dureza. Fatiga. Fractura.
Modelizacin. Piezoelectricidad. Plasticidad. Propiedades elctricas/
dielctricas. Propiedades ferroelctricas. Propiedades magnticas. Propiedades
Mecnicas. Propiedades pticas. Propiedades trmicas/termomecnicas.
Propiedades qumicas. Reologa.
Aplicaciones
Actuadores. Aisladores. Aplicaciones Estructurales. Aplicaciones
Magnticas. Arqueometra. Bateras. Biocermicas/biovidrios. Cermica
roja/blanca. Cermicas no oxdicas. Esmaltes. Fritas. Herramientas de corte.
Membranas. Pavimentos y revestimientos. Pilas de Combustible. Porcelana.
Recubrimientos funcionales. Refractarios. Sellos/Unin. Semiconductores.
II Sensores. Substratos. Superconductotes. Varistores. Vitrocermicas.
properties Fatigue Ferroelectric properties Fracture Hardness Magnetic
properties Mechanical properties Modelling Optical properties Piezoelectricity
Plasticity Rheology Thermal/ Thermomechanic properties Wear resistance.
Applications
Actuators. Archeometry. Batteries. Bioceramics/bioglasses. Cutting
Tools. Frits. Fuel cells. Functional coatings. Glass ceramics. Glazes/enamels.
Insulators. Magnetic applications. Membranes. Non-oxide ceramics. Porcelain.
Red/white ceramics. Refractories. Sealing/joining. Semiconductors. Sensors.
Structural applications. Substrates. Superconductors. Tiles. Varistors.
B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
E D I T O R I A L

ECERS 2005

Una nueva edicin del Congreso de la Sociedad Europea de Cermica es siempre una buena noticia para el sector
cermico. La celebracin de dicho evento en Eslovenia es por lo tanto un motivo de alegra para la comunidad cientca
e industrial.
En esta edicin el Congreso se ha organizado entorno a siete simposios que concentrarn la atencin de especialistas
en el mbito de la investigacin y el desarrollo. El alto nivel de los asistentes y su elevado nmero permite pensar en un
acontecimiento exitoso. Durante este congreso se abordan los principales avances en: Ciencia Bsica, Procesamiento,
Mtodos de Anlisis, Nanomateriales inorgnicos, Cermica estructural, Biocermica y Cermica Tradicional.
En el interior de estas pginas los miembros de la Sociedad y dems lectores de este Boletn pueden encontrar el
listado de las conferencias plenarias y conferencias invitadas. Esperemos que esta informacin sea de utilidad y les
anime a participar en este singular evento. Este nmero de Bol. Soc. Esp. Ceram. V. incluye trabajos invitados en ingles.
La revista forma parte desde 1998 del SCI y publica trabajos tanto en espaol como en ingles.
La Sociedad Espaola de Cermica y Vidrio como integrante de la sociedad Europea de Cermica saluda a todos los
asistentes a ECER05 y transmite las ms sinceras felicitaciones a los organizadores.

A new Conference of the European Ceramic Society is always a good new for the ceramic sector. The occurrence of
this event in Slovenia thus causes happiness to the scientic and industrial community.
In this opportunity ECERS organizes seven symposiums that will catch the attention of specialist in the research
and development of ceramic materials. The high level and the number of participants allow thinking in a successful
event. During this conference the advances in the following areas will be discussed: Basic Science, Processing, Analytical
Methods, Inorganic Nanomaterials, Materials in Electromagnetic elds, Bioceramics and Traditional Materials.
Inside this issue, both the Society members and the readers can nd the list of the Key Notes and Invited Conferences
of ECERS05. We hope that this information would be of interest and encourage the participation in this unique event.
This issue of Bol. Soc. Esp. Ceram. V. includes invited papers written in English. The journal entered in SCI since 1998
and regularly publishes scientic papers in both spanish and english languages.
The Spanish Society of Ceramic and Glass as part of the European Ceramic Society welcomes to the ECERS05
participant and want to express their congratulation to the organizers for their excellent effort.

Marzo-Abril (2005) III

 B O L E T I N D E L A S O C I E DA D E S PA O L A D E
Cermica y Vidrio
N O R M A S D E P U B L I CAC I N - INSTRUCTIONS FOR PAPERS
ENVIO DE ARTCULOS
El trabajo original y dos copias se entregarn en la Redaccin del Boletn de la
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1. TITULO. El ttulo deber ser conciso y reflejar con la mayor precisin el contenido
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4. PALABRAS CLAVE. A continuacin del resumen se indicarn las palabras clave que
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1. INTRODUCCIN
2. PARTE EXPERIMENTAL
2.1. Identificacin de las materias primas
2.1.1. Anlisis qumico
2.1.1.1. Granulometra
El empleo de smbolos, abreviaturas de magnitudes fsicas y unidades debern ajustarse
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8. PRUEBAS DE IMPRENTA. Los autores recibirn las correspondientes pruebas de
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SUBMISSION OF PAPERS
The original paper and two copies should be sent to the Conference Secretariat
or to the Redaccin del Boletn de la Sociedad Espaola de Cermica y Vidrio,
ICV- CSIC, C/ Kelsen 5. 28049 Madrid.
1. TITLE. It should be concise and reflect the contents of the publication.
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2. EXPERIMENTAL PROCEDURE
2.1. Identification of raw materials
2.1.1. Chemical analysis
2.1.1.1. Granulometry
The use of symbols, abbreviations or acronyms of physical magnitudes should
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 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
A R T I C U L O

Crystalline Bioceramic Materials

P. N. DE AZA, A. H. DE AZA*, S. DE AZA*
Instituto de Bioingeniera, Universidad Miguel Hernndez, Elche, Alicante, Spain.
*Instituto de Cermica y Vidrio, CSIC. Campus de Cantoblanco, Madrid, Spain

A strong interest in the use of ceramics for biomedical engineering applications developed in the late 1960s. Used initially
as alternatives to metallic materials in order to increase the biocompatibility of implants, bioceramics have become a
diverse class of biomaterials, presently including three basic types: relatively bioinert ceramics; bioactive or surface reactive
bioceramics and bioresorbable ceramics.
This review will only refer to bioceramics sensus stricto, it is to say, those ceramic materials constituted for nonmetallic
inorganic compounds, crystallines and consolidated by thermal treatments of powders to high temperatures. Leaving
bioglasses, glass-ceramics and biocements apart, since, although all of them are obtained by thermal treatments to high
temperatures, the first are amorphous, the second are obtained by desvitrification of a glass and in them vitreous phase
normally prevails on the crystalline phases and the third are consolidated by means of a hydraulic or chemical reaction to
room temperature.
A review of the composition, physiochemical properties and biological behaviour of the principal types of crystalline
bioceramics is given, based on the literature data and on the own experience of the authors.

Key words: alumina, zirconia, zirconia-toughened alumina, graphite, hydroxyapatite, bioactive silicates, bioeutectic, tricalcium
phosphate

Materiales biocermicos cristalinos

A finales de los aos sesenta se despert un gran inters por el uso de los materiales cermicos para aplicaciones biomdicas.
Inicialmente utilizados como una alternativa a los materiales metlicos, con el propsito de incrementar la biocompatibilidad
de los implantes, las biocermicas se han convertido en una clase diversa de biomateriales, incluyendo actualmente tres tipos:
cermicas cuasi inertes; cermicas bioactivas o reactivas superficialmente y cermicas reabsorbibles o biodegradables.
En la presente revisin se hace referencia a las biocermicas en sentido estricto, es decir, a aquellos materiales constitutitos
por compuestos inorgnicos no metlicos, cristalinos y consolidados mediante tratamientos trmicos a altas temperaturas.
Dejando aparte los biovidrios, los vitrocermicos y los biocementos, puesto que, si bien todos ellos son obtenidos por
tratamiento trmicos a altas temperaturas, los primeros son amorfos, los segundos son obtenidos por desvitrificacin de un
vidrio, prevaleciendo normalmente la fase vtrea sobre las fases cristalinas, y los terceros son consolidados mediante una
reaccin qumica o hidrulica a temperatura ambiente.
As pues, teniendo en cuenta la abundante bibliografa sobre el tema y la experiencia propia de los autores, se presenta una
revisin de la composicin, propiedades fisicoqumicas, aplicaciones y comportamiento biolgico de los principales tipos de
biocermicas cristalinas.

Palabras clave: almina, zircona, almina-circona, grafito, hidroxiapatito, silicatos bioactivos, bioeutecticos, fosfato triclcico.

1. INTRODUCTION

Bioceramics are those engineered materials that find their
applications in the field of medicine [1]. Traditionally, the
brittleness, the low mechanical fracture toughness and the
low resistance to the impact have limited the applications
of the ceramic materials. Nevertheless, a strong interest in
the use of ceramics for biomedical engineering applications
were developed at the end of the years sixty. New ceramics,
with very improved properties, contributed to increase the
possibilities of using ceramics in biomedicine and their use
has extended considerably since then [2,3].
The great chemical inertia of the ceramics, their high
compression strength and their aesthetic appearance, made
that these materials began to be used in dentistry, mainly
in dental crowns. Later their use extended to orthopaedic
applications [4-6].
Used initially as alternatives to metallic materials in order
to increase the biocompatibility of implants, bioceramics can
be classified from different points of views [7, 8]:
(a) According to the type of answer of the living host
(b) According to the application to which they are destined
[9]
(c) According to the characteristics of the material [10]
However, in this review, the classification, according to the
answer of the living host, is going to be followed, because it
is considered more in accordance with the application of the
bioceramic materials. Then, according with this, bioceramics
can be divided in Bioinert; Bioactive or Surface Reactive and
Biodegradable or Resorbable Materials.

Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005) 135

 P. N. DE AZA, A. H. DE AZA, S. DE AZA

2. BIOINERT CERAMICS prostheses. The first clinical use of total hip prosthesis with
an alumina head and alumina socket was in 1971. The long-
Relatively Bioinert ceramics undergo little or no chemical term coefficient of the pair alumina/alumina and the wearing
changes when they are exposed to physiological environments. down index decrease with time and approaches the value of a
They maintain their physical and mechanical properties while normal healthy joint [18].
in the host. The answer of the host to these bioceramics is The main problem with total hip system is the loosening
the formation of a very fine fibrous tissue capsule of varying of the acetabular component, which is caused by wear debris.
thickness, several micrometers or less, that surround implant For this reason alumina is used only in the head of femur since
materials. The fixation of implants in the body is made through numerous clinical studies indicates that alumina/ultrahigh
a strong mechanical interlocking, by tissue ingrowth into molecular weigh polyethylene (UHMWPE) pair reduces wear
undulating surfaces [11]. When high strength is required, the
bond is made by perforations in the implants using threads,
cements, etc. When so high strength are not required can be
used porous inert bioceramics, with sizes of pore between 100
and 150 m, which guarantee the growth of the tissue towards
within implants assuring its fixation [12-14].
Typical examples of these bioinert ceramics are: Alumina
(-Al2O3); Zirconia (ZrO2), Alumina-Zirconia and Pyrolytic
Carbon.

2.1. Alumina

Alumina of high density and purity (99.5 % in weight of

-Al2O3), with an average grain size < 4 m is probably, the
bioinert ceramic material of greater biological interest. This
material was developed, as alternative to used metallic alloys
in load-bearing hip prosthesis and in dental implants, to
display an excellent biocompatibility, good resistance to the
corrosion, to form a very fine fibrous capsule, to have a low
coefficient of friction and good mechanical properties as much Fig. 1.- Microstructure of an alumina for hip prosthesis obtained by
high strength as wear resistance [15-17]. HIP at 1500C.
According to the International Standards Organization
(ISO), the purity of the alumina that is used in biomedical debris by a factor of 10 or greater [19-21]. Figure 1 shows the
applications has to be over 99.5 %, being the rest of the typical microstructure of an alumina used in the femur head.
impurities (SiO2, Na2O, K2O, CaO, etc.) below 0.1 % in weight, Other clinical applications of alumina are the used for
in order to avoid a large grain increase during sintering. screws, tooth-root implants, orbital walls, implants for
An increase of average grain size to 7 m can decrease maxillofacial reconstructions, dental implants etc. Between
mechanical properties by about 20 %. It is normal the addition these last ones, the most well known application is the
of approximately 0.5 wt. % of MgO that acts as inhibitor of Tbingen implant [22-24] employee like substitute dental
immediately after the extraction or in edentulous regions. The
TABLE I. CHARACTERISTICS OF AL2O3 IMPLANTS
effectiveness of these implants is of 92.5 %. The cross-sectional
Properties Al2O3 Implants ISO 6474-81 fracture is the most frequent failure of these implants, due to
relatively low resistance to the flexion, being the main cause
Al2O3 (wt. %) > 99,8 99,50
of failure. Due to it, the use of alumina single crystals began
Density (g/cm ) 3
> 3,93 3,90 to used as dental implant [25, 26] with resistance to flexion 3
times over polycrystalline alumina. However, the use of single
Average grain size (m) 36 <7
crystals do no eliminate the basic disadvantage of alumina
Surface roughness (Ra)
0,02 bioceramics (low fracture toughness), which for alumina
(m)
single crystals is equal to 4-5 MPa m1/2. These alumina single
Hardness (Vickers) 2300 > 2000 crystals are obtained generally by grown and crystallization
Compressive strength
4500 from a melt or by the Verneuil method [27].
(MPa)
Bending strength (MPa)* 550 400 2.2. Zirconia
Young modulus (GPa) 380
It has become a popular alternative to alumina as structural
Toughness (KIc)(MPa m) 5-6 bioinert ceramics because, properly treated, it has a greater
resistance to the fracture (greater fracture toughness) of any
Threshold (KI0) (MPa m) ~ 2,5
monolithic ceramics. On the other hand, zirconia is also
exceptionally inert in the physiological environment and
the grain growth. Table I shows the characteristics of alumina presents very good static fatigue strength. In addition, the
implants, according to Ratner et al. [17], together with the ISO zirconia/UHMWPE pair displays lower coefficient of friction
6474-81 requirements. than the alumina/UHMWPE pair, with the consequent
The most common application of alumina bioceramics diminution of particles to the physiological environment [28
is in the area of orthopaedics as component in hip and knee - 30].

136 Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005)

CRYSTALLINE BIOCERAMIC MATERIALS

Zirconia presents three different crystalline forms: TABLE II. CHARACTERISTICS OF TWO TYPES OF ZIRCONIA MATERIALS

monoclinic, from room temperature to 1100 C, tetragonal,

from this temperature to 2372 C, and cubic, from this last Properties TZP Mg-PSZ
temperature to the melt at 2680 C. The monoclinic Purity 97 % 96.5
tetragonal transformation is of martensitic type, and therefore
reversible when warming up or to cool down through the % Y2O3 3 mol %
transition temperature (1100 C). This happens with an % MgO 3,4 mol %
increase of volume of the order of 3 to 5 %, which produces
the cracking or fracture of the pieces. In order to avoid this Density(g/cm3) 6.05 5.72
transformation, and even increase the toughness of the zirconia
Average grain size (m) 0.2 0.4 0.42
materials, the use of totally or partially stabilized tetragonal or
cubic zirconia by suitable additives is recommended. Zirconia Bending strength (MPa) 1000 800
of higher toughness is usually obtained by stabilizing its
Compressive strength (MPa) 2000 1850
tetragonal phase by doping it with yttria (3 mol %), followed
by a suitable heat treatment, considering the binary system Young Modulus (GPa) 150 208
ZrO2 - Y2O3 [31]. In this way the zirconia bioceramic is totally
Hardness(Vickers) 1200 1120
a tetragonal material with a microstructure formed by very
small grains of the order of 0.2 to 0.5 m. The additives most Fracture toughness (KIC) (MPam) 78 8
widely used in biomedical applications are the yttria (Y2O3)
and the magnesia (MgO). Threshold (KI0) (MPam )

~ 3,5 0,2
Between all the ceramic materials, zirconia are those where
their mechanical properties depend more of the sintering On the other hand, the potential radioactivity of the
process, because is necessary to have a balance between the zirconia prosthesis, although the detected activity has been
density and the average grain size of the bioceramic [32]. small, the long-term effects of the alpha radioactivity still must
Figure 2 shows a typical microstructure of a tetragonal be evaluated.
zirconia containing 3 mol % of yttria and Table II illustrates Nevertheless, very recently, French Government has
the characteristics of tetragonal zirconia stabilized with yttria prohibited the manufacture, distribution, export and use of
(TZP = tetragonal zirconia polycrystals) versus partially these prostheses in France by decision of the July 22, 2003,
stabilized zirconia with magnesia (Mg-PSZ = magnesia because of having detected frequent breakage of femoral
partially stabilized zirconia) [33]. heads made in zirconia [37].

2.3. Alumina-Zirconia

Recently, the orthopaedic community reports significant

in-vivo failures, due to the slow crack growth, of alumina and
zirconia prostheses. Consequently, researches have been made
with a new generation of alumina-zirconia nano-composites
having a high resistance to crack propagation, which may offer
the option to improve lifetime and reliability of ceramic joint
prostheses. De Aza et al. [38, 39] have put in evidence that,
tailoring the microstructure by refining powder processing
using a new colloidal processing synthesis route, is possible
to produce alumina-zirconia nano-composites at the top end

Fig. 2.- Typical microstructure of a tetragonal zirconia containing 3

mol % of yttria

Recently studies on new TZP materials, doped with yttria,

tested in simulated body fluids and in animals, have shown
slight decreases in fracture toughness and young modulus
[34-36]. The observed strength, after two years, is sill much
higher that the strength of alumina bioceramics tested under
similar conditions. Because the zirconia/zirconia pair displays
a wear rate 5000 times greater than the alumina/alumina pair, Fig. 3.- Microstructure of an alumina - 10 vol.% zirconia nanocompos-
those do not have to be used in articulated surfaces. ite. Dark phase = alumina; clear phase = zirconia

Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005) 137

 P. N. DE AZA, A. H. DE AZA, S. DE AZA

of they strength spectrum. Figure 3 shows a microstructure of

one of these composite alumina-zirconia materials. These new
composites can display not only a greater toughness (KIC) that
the monolithic materials previously mentioned, otherwise,
and what it is more important, a greater threshold for the
stress intensity factor (KI0), under which crack propagation
does not take place (Table III). This threshold represents an
intrinsic property for a given material that gives information
of its mechanical behaviour more realistic than the widely
used toughness, which means only fast crack growth [40-41].

TABLE III.

Fracture
Tougnhess Hardness H
Material threshold
KIc(MPam) (Vickers)
KI0(MPam)

Alumina (Al2O3) 2.5 0.2 4.2 0.2 160050

Zirconia
3.5 0.2 5.5 0.2 129050
(3Y-TZP)
Composite
4.0 0.2 5.9 0.2 153050
(Al2O3-10% ZrO2)
On the other hand, since hardness and chemical stability
are equally important in the orthopaedic field, these composite
materials, with relatively low contents of zirconia (10 % in
volume), present similar hardness values than alumina (Table
II) and are not susceptible to the hydrothermal instability
observed in some cases of stabilised zirconia bioceramics (low
temperature degradation). These nanomaterials may offer
the option to improve the lifetime and reliability of ceramic
femoral heads, so contributing to improve the quality of life
of a large number of patients. Further, surgical operations and
consequently the suffering of people as well as the high cost
of such operations will be avoided.
2.4. Carbon
Carbon presents a great variety of forms: amorphous
Fig. 4.- Pyrolitic graphite (PG) deposited on a graphite fiber (GF)[45]
Its great cellular biocompatibility with the blood and the
soft tissue as well as its excellent thromboresistance, does
carbon material to be used fundamentally in applications
of the circulatory apparatus, blood vessel and mechanical
cardiac-valve prosthetic devices, being this last the most
extended application. Nowadays, most of the modern heart
valves are made with a coating of LTI on a polycrystalline
graphite substrate or like a monolithic material [44].
In both cases is frequently added up to 10 wt.% of silicon,
often in the form of discrete sub-micron -SiC particles
randomly dispersed in a matrix of roughly spherical micron-
size subgrains of pyrolitic carbon. The doping with silicon
improves the mechanical properties of pyrolitic carbons, issue
of great importance in the heart valves, where the joint is
subject to degradation by cyclic fatigue or stress corrosion and
possible cavitations by erosion during the life of the patient.
Some structural and mechanical properties of graphite and
biomedical turbostratic carbons is shown in Table 4 [45].
TABLE IV. STRUCTURAL AND MECHANICAL PROPERTIES OF GRAPHITE AND
BIOMEDICAL TURBOSTRATIC.

carbon, graphite, diamond, vitreous carbon and pyrolitic

Silicon
carbon. Some of them display the most excellent properties of Polycrystalline
Alloyed LTI
ULTI Vapor
Properties Graphite Deposited
biocompatibility, chemical inertia and thromboresistance that Substrate
Pyrolitic
Carbon
any other bioceramics. Another advantage of these materials Carbon

is that their physical characteristics are close to those of the Density (kg. m-3) 1,500 1,800 1,700 2,200 1,500 2,200
bone [42]. Thus, their densities, according to the type carbon,
Crystalline Size (nm) 15 250 35 8 - 15
change between 1.5 - 2.2 g/cm3, and their elastic modules
between 4 - 35 GPa. In spite of all the mentioned varieties, Expansion Coefficient
0,5 5 56 ---
(10-6 K-1)
only three types of carbon are used for biomedical devices:
the pyrolitic carbon, in its two varieties of low temperature Hardness (DPH) 50 120 230 370 150 250

isotropic (LTI) and ultra-low temperature isotropic (ULTI), Youngs Modulus

4 12 27 31 14 21
(GPa)
and the vitreous carbon. The three types of carbon have
disordered lattice structures and are collectively referred to as Flexural Strength (MPa) 65 300 350 530 345 - 690
turbostratic carbons. While the microstructure of turbostratic Fracture Strain (%) 0.1 0.7 1.5 2.0 2.0 5.0
carbon might seem very complicated due to its disordered
Fracture Toughness
nature, it is in fact quite closely analogous to the structure of (MPa m)
1.5 0.9 1.1 ---
graphite, but with at random oriented layers [43].
Pyrolitic carbon is widely used for implant fabrication. It
is normally used as surface coating. Figure 4 shows a pyrolitic
Whereas the pyrolitic carbons coating have been applied
carbon deposited on a graphite fibre. Pyrolitic carbon devices
in zones in contact with the blood, due to their excellent
are typically made, from a hydrocarbon gas in a fluidized-bed,
thromboresistance, the vitreous carbons have been studied
via a chemical vapour-deposition method.
mainly to bond to soft and hard tissues, without inflammatory

138 Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005)

CRYSTALLINE BIOCERAMIC MATERIALS
answer in the adjacent tissues. Similar behaviour has been
registered for pyrolitic carbons LTI and ULTI.
Apart from of the mistral and aortic heart valves, there are
applications in dental field [46] and middle ear reconstruction
and in devices of LTI coating on titanium to make easy the
circulation of the blood. Recently, success was achieved in
coating ULTI onto the surfaces of blood vessel implants made
of polymers. The coating has excellent compatibility with
blood and is thin enough not to interfere with the flexibility
of the grafts [47].
3. BIOACTIVE CERAMICS
Generally, when an artificial material is implanted in
the body, it is encapsulated by uncalcified fibrous tissue
that isolates it from the surrounding. This is a normal
reaction intended to protect the body from foreign substances.
However, in the early 1970s, Hench et al. [48] found that a
glass, called Bioglass; of the complex system Na2O-CaO-
SiO2-P2O5, induced the formation of no fibrous tissue, but
rather came into direct contact with the surrounding bone and
formed a tight chemical bond with it.
Since then, other types of glasses and glass-ceramics have
also been found to bind to living bone [49-51], Hench et al.[52-
53], Gross et al. [54-55], Karlon et al. [56-57] and Kokubo et
al. [58-59]. These bone-binding materials are called bioactives
materials.
The appearance of this type of bioceramics born of the need
to eliminate the interfacial movement that takes place with the
implantation of bioinert ceramics. Consequently, L. L. Hench
Fig. 5.- (a) TEM image showing overall morphology of the HA crystals.
(b) High-resolution TEM image of HA crystals and (c) Selected-area
diffraction pattern of the region. HA acicular crystals change to rods to
equi-axed crystals with increasing carbonate content
Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005)
proposes in 1967 to the U.S.A. Army Medical Research and
Development Command, a research based on the modification
of the chemical composition of ceramics, and glasses so that
they have chemical reactivity with the physiological system
and form chemical bond between the surfaces of implant
materials and the adjacent tissue.
Upon implantation in the host, bioactive ceramics form a
strong bond with adjacent tissue. Except hydroxyapatite, which
bond directly to living bone, the rest of bioactive materials
bond to bone through a carbohydroxyapatite layer (CHA)
biologically active, which provides the interfacial union with
the host. This phase is chemical and structurally equivalent
to the mineral phase of the bone, and the responsible of the
interfacial union.
The interface of union between bioactive materials and
tissue is usually extremely strong. In many cases, the interfacial
strength of adhesion is equivalent to or greater than the
cohesive strength of the implant material or the tissue bonded
to the bioactive implant. Generally, the break takes place in
the implant or in the bone but almost never in the interface
[60-63].
However, not only certain types of glasses and glass-
ceramics are bioactives. Other ceramic materials sensus
stricto are also bioactives. The typical example is the
hydroxyapatite, which is the only one that bond directly
to bone and other examples are: certain silicates (diopside
and wollastonite) and a new group of ceramic materials
denominated Bioeutctics, as it will be exposed next.
3.1. Hydroxyapatite
Hydroxyapatite (HA) is the primary mineral content of
bone representing 43 wt.%. HA is a calcium phosphate whose
stoichiometric formula corresponds to a: Ca10(PO4)6(OH)2, with
a Ca/P molar ratio = 1.67. HA belong the mineral family of
Apatites whose name derived from Greek means
deception or deceit, due to the facility it was confused with
other mineral species like the beryl or the tourmaline [64].
HA displays ionic character, and its crystalline structure
can be describe like a compact hexagonal packing of oxygen
atom with metals occupying the tetrahedral and octahedral
holes of the periodic network. The basic apatite structure
is hexagonal with space group P63/m and approximate
lattice parameters a=9.4 and c=6.9 , being the fluorapatite
(Ca10(PO4)6F2) the representative example of this structure.
Nevertheless, HA presents a low symmetry, monoclinic,
due to the distortion of the ion OH with respect to the ideal
model that would represent the position of spherical ion F
in the fluorapatite. Nevertheless, in most of the works in the
field of biomaterials it assumed that HA has a fluorapatite
structure but with lattice parameter a=b=9,418 and c=6,884
. ==90 and =120, Z=2. The unit cell contains 10 Ca+2, 6
PO43- and 2 groups OH [65].
HA allows the substitution of many other ions in their
structure. These substitutions can take place in the positions
of the calcium ions (Ca2+) or in the phosphate groups (PO4)3 or
hydroxyls groups (OH). Consequences of these substitutions
are changes in its properties like lattice parameters,
morphology, solubility etc., without significant change in the
symmetry. Thus for example, the substitution of F by OH
involve a contraction in the a axis without change in the c
axis, associated to an increase in the crystallinity and imparts
greater stability to the structure. On the other hand, this imply
that the fluorapatite is less soluble than the HA and that all
139

F free apatites, including biological apatites. Many other
ions can enter in the HA network, affecting the properties,
crystallinity, thermal stability, rate of dissolution etc.
The mechanical properties of the HA are similar to those of
the most resistant components of the bone. HA has an elastic
modulus of 40-100 GPa; dental enamel: 74 GPa, the dentine:
21 GPa, and the compact bone: 18-12 GPa. Nevertheless,
dense bulk compacts of HA have mechanical resistances of
the order of 100 MPa versus the 300 MPa of the human bone,
diminishing drastically their resistances in the case of porous
bulk compacts..
HA differs from biological apatites (enamel, dentin, bone,
etc.) in physical and mechanical properties, stoichiometry,
composition, crystallinity and other properties. Biological
apatites are usually calcium-deficient and are always carbonate
substituted. It is therefore more appropriate that biological
apatites be referred as carbonate apatite (carbohydroxyapatites)
a not as hydroxyapatite or HA, where groups (CO3)2- replace
group (PO4)3- and where the Ca2+ is replaced by Na+ to balance
the charges [66, 67].
The methods of obtaining HA are very varied, including
hydrothermal systems, precipitation methods, hydrolysis,
solid-state reactions and hydrothermal reactions (6870).
However, when prepared from aqueous reactions either
by precipitation or hydrolysis methods, the HA obtained is
usually calcium deficient (Ca/P molar ratio lower than the
stoichiometric value of 1.69). When the precipitation reaction
is carried out under very basic conditions, the precipitate will
contain carbonate, which makes the Ca/P molar ratio higher
than the stoichiometry value. Figure 5 shows an electron
image of CO3-apatite crystals.
The interest as biomaterial of HA comes clearly by its
similarity with the mineral phase of the bone tissue. In
principle, HA would be the most suitable material as much for
the restoration as for the substitution of the bone. However,
the relatively low strength and toughness of HA arouses little
interest among researchers when the focus of attention is on
dense structural samples. Therefore, its use is restricted to all
those applications where mechanical efforts are not required,
finding its application mainly as coating on metallic substrata,
with the object to accelerate and to increase the fixation of
prostheses to the bone [71, 72].
Industrial and laboratory techniques, used for HA
coating onto metallic substrates, include plasma spraying,
laser ablation, electrophoretic deposition, sputtering and
hot isostatic pressing. Being the first one, the most used,
mainly in the coating of hip prostheses, being achieved,
in this way, what has been called biological fixation of the
prosthesis. [73, 74]. Among other applications are: a) coating
of dental and maxillofacial prosthesis; b) dental implants; c)
middle ear reconstruction; d) augmentation of alveolar ridge;
e) periodontal defects; f) spinal surgery; g) pulp-capping
materials [75].
3.2. Bioactive Silicates
It has been considered that to show bioactivity, glasses and
glass-ceramics must contain both CaO and P2O5, which are the
main components of the hydroxyapatite [76, 77]. Conversely,
Ohura et al. [78] have recently observed that CaO-SiO2 glasses,
free of P2O5 as well as those containing very small amounts of
P2O5, form the HA layer on their surfaces (bioactivity), when
they are soaked in simulate body fluid (SBF), whereas CaO-
P2O5 glasses free of SiO2 do not form HA layer in SBF. This
140
P. N. DE AZA, A. H. DE AZA, S. DE AZA
seems to indicate that bioactive materials can be obtained
with compositions based on the CaO-SiO2 system rather than
in the CaO-P2O5. Taking into account these observations,
Noami et al. [79, 80] and De Aza et al. [81-92] have shown
that two polycrystalline chain silicate materials: diopside and
wollastonite are also bioactives.
3.2.1. Wollastonite
Pseudowollastonita (CaSiO3), the high temperature form of
wollastonite, displays in its structure calcium ion chains easily
removals by protons, as Bailey and Reesman [93] showed it
in the study of the kinetic of dissolution of the wollastonite
in H2O-CO2 systems. This fact suggests the possibility of
extraction of calcium ions, from the wollastonite structure, by
protons from the SBF, facilitating therefore the precipitation
and formation of a HA layer on the surface of the material.
De Aza et al. have demonstrated the formation of a HA-
like layer on the surface of pseudowollastonite ceramic both
in vitro [81-83, 85, 90] and in vivo [86,87]. Experiments
in vitro involved immersion of the material in SBF with an
ion concentration, pH and temperature virtually identical to
human blood plasma, and in human parotid saliva (HPS).
Figure 6 shows the overall microstructure of a polished
cross-section of the pseudowollastonite sample after one-
month immersion in simulated body fluid and its relevant
X-ray maps for calcium, silicon and phosphorous elements.
This microcharacterisation of the interface showed that the
reaction zone was composed of two chemically dissimilar
layers formed on the pseudowollastonite surface. The outer
layer was composed of a CaO/P2O5-rich phase, identified as
HA-like phase by thin-film X-ray diffraction [83], while the
underlayer, in direct contact with the pseudowollastonite
substrate, was rich in amorphous silicon as was characterized
by TEM, selected-area diffraction pattern and EDS analysis
[83].
Fig. 6.- SEM image of a cross-section of pseudowollastonite after one
month immersion in SBF and X-ray elemental maps of Ca, Si and P
The mechanism involved in the HA layer formation was
described by De Aza et al.[94] as follows: at pH 7.25 of the
SBF, the reaction mechanism start through an ionic exchange
of H3O+, from the SBF, by labile calcium ions. This induces
Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005)
CRYSTALLINE BIOCERAMIC MATERIALS

the formation of an amorphous hydrogel silica layer and a 3.3. Wollastonite-Tricalcium Phosphate (Bioeutectic)
sudden increase in pH from 9.0 to 10.5 at the wollastonite/SBF
interface. This condition determines the partial dissolution Natural and synthetic materials have been used clinically
of amorphous silica and the subsequent precipitation of HA. for many years to reconfigure anatomic structures for aesthetic
According to De Aza et al., this mechanism is common for both and therapeutic reasons in several different surgical situations,
amorphous and crystalline silica-based bioactive material. however many outstanding problems remain unsolved.
The authors also have evaluated the cytotoxicity of the The most important is the process of total osteointegration
pseudowollastonita [89] and the suitability of the material of ceramic implants in the human body. When bioactive
as a substratum for cell attachment and the ability to affect materials are implanted in a living body, the interaction
osteoblast at a distance from the material surface [91, 92]. These between the bone tissue and these materials usually take place
experiments demonstrate that extracts of pseudowollastonite only on their surfaces, with the remaining bulk of the material
do not show any significant cytotoxic effects and confirm unchanged, often causing a harmful shear stress.
the biocompatibility of this material. On the other hand, To improve the ingrowth of new bone into implants
osteoblastic cells attached and proliferated on the surface (osteointegration), the use of materials with an appropriate
to the ceramic. In addition, osteoblastic cells, at a distance interconnected porous structure has been recommended [95-
form the material, exhibited a dramatic alteration on their 100]. The design of a porous ceramic implant material has the
appearance. This reinforces the suggestion that the release potential of controlling the bone ingrowths. However, porous
of soluble factors, silicon and calcium from the wollastonite, materials have very poor mechanical properties.
is responsible for much of the biological activity of this A new approach to overcoming this problem was proposed
material. by De Aza et al [101-106].This is based on designing dense
In vivo experiments were consisted of implanting bioactive ceramic materials with the ability to develop an in
small cylinders of pseudowollastonite into rat tibias [86, situ porous hydroxyapatite-like (HA) structure when they are
87]. Histological observations twelve weeks after implant implanted into a living body. The material was composed of
show that the bone in contact with the surface of the
pseudowollastonite appeared to be progressively replaced by
bone with laminar arrangement. The new bone was growing
in direct contact with the pseudowollastonite implants after
only 3 weeks. Figure 7 shows SEM micrograph of polished
cross-sections of pseudowollastonite implant after six weeks
of implantation. The individual X-ray maps of the silicon,
calcium and phosphorous distribution are also included. The
calcium phosphate phase corresponds to new bone tissue
as reported by histological examination. At twelve weeks of
implantation, new bone was still growing at the interface.
Overall, these results suggest that pseudowollastonite
is biocompatible and osteoconductive and it can be used
for substitution or repair of bone tissues in places where
mechanical solicitations are not high.

Fig. 8.- SEM image of the microstructure of the eutectic material

(Bioeutectic) and detail of a colony. White and black lamellae pseu-
Fig. 7.- SEM image of a cross-section of pseudowollastonite implant af- dowollastonite and -tricalcium phosphate respectively. Sample etch-
ter six weeks of implantation and X-ray elemental map of Si, Ca and P ing with dilute citric acid.

Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005) 141

 P. N. DE AZA, A. H. DE AZA, S. DE AZA

two phases, pseudowollastonite (CaSiO3 = psW) of bioactive

character and resorbable -tricalcium phosphate (-TCP).
Taking into account the bone structure, the microstructure
of the material was developed by slow solidification of the
eutectic composition of the system wollastonite-tricalcium
phosphate (60 wt% psW and 40 wt% -TCP)[107].
Figure 8 shows a SEM image of the microstructure of
the eutectic material (Bioeutectic), which consists of quasi-
spherical colonies formed by alternating lamellae of psW
and -TCP with a morphology which correspond to irregular
eutectic structure [108-110].
The material, exposed to simulated body fluid (SBF) for one
week, transforms partially dissolving the pseudowollastonite
lamellae and forming a porous structure of HA-like that
mimic porous bone by a pseudomorphic transformation of the
-TCP, according to the reaction:
3[Ca3(PO4)2] + Ca2+ + 2(OH)- Ca10(PO4)6(OH)2
Figure 9 shows clearly the partial dissolution and
transformation of the Bioeutectic after one week soaking in
SBF.

Fig. 10.- SEM images of a fresh fracture of the Bioeutectic after im-
mersion in a stream of SBF for three weeks. (A) General view of the
material completely transformed into a porous HA structure similar to
porous bone. (B) Detail of a colony after transformation.

Fig. 9.- SEM image of a cross-section of the Bioeutectic after one week
soaking in SBF and Si, P, and Ca X-ray maps.
Conversely, when the material is immersed in a slow
stream of SFB (50 cm3/h) instead of using a static solution,
them a complete transformation of the material takes place
given rise to a HA artificial porous bone as is shown in Figure
10.
Therefore, the Bioeutectic material is the only bioactive
material, at present, which is totally colonized in SBF.
Consequently, it is expected it behaves similarly in in vivo
experiments facilitating the osteointegration of the implant.
These studies are actually carried out.
4. BIODEGRADABLE OR RESORBABLE MATERIALS
The resorbable ceramics began to be used in 1969. These
types of bioceramics are dissolved with time and are gradually
replaced by natural tissues. A very thin or non-existent
interfacial thickness is the final results. They would be the
ideals implants, since only remain in the body while their
function is necessary and disappear as the tissue regenerates.
Their greater disadvantage is that their mechanical strength
diminishes during the reabsorption process.
Consequently, the function of these materials is to participate
in the dynamic process of formation and reabsorption that
takes place in bone tissues; so they are used like scaffolding
or filling spaces allowing to the tissues their infiltration and
substitution [111].
All the resorbable ceramics, except plaster (CaSO4H2O), are
based on calcium phosphates, varying their biodegradability
in the sense:
-TCP > TCP >>>> HA
The biodegradation rate is increased, as it is logical,
as: a) specific surface increases (powders are more quickly
biodegraded that porous solids and these more quickly
than dense solids); b) when crystallinity decreases; c) when
grain and crystal size decrease; d) when e.g. there are ionic
substitutions of CO32-, Mg2+ and Sr2+ in HA.
The factors that tend to decrease the rate of biodegradation
include e.g.: a) F substitution F in HA; b) Mg2+ substitution
in - TCP and c) lower - TCP/HA ratios in biphasic
compounds.

142 Bol. Soc. Esp. Ceram. V., 44 [3] 135-145 (2005)

CRYSTALLINE BIOCERAMIC MATERIALS
The biodegradation or reabsorption of calcium phosphates
is caused by three factors:
1) Physiochemical dissolution, which depends on
the solubility product of the material and local pH of its
environment. New phases may be formed, such as amorphous
calcium phosphates, dicalcium phosphate dihydrate,
octacalcium phosphate, and anionic substituted HA.
2) Preferential attack of the grain boundaries and physical
disintegration in small particles.
3) Biological factors, such as phagocytosis, which causes
a decrease in local pH concentration, the cellular activity and
the site of implantation.
One of the few bioceramics that satisfy partially these
requirements is the tricalcium phosphate (TCP).
4.1. Tricalcium phosphate
The tricalcium phosphate (TCP) is the biodegradable
phosphate par excellence. TCP has a stoichiometric formula
Ca3(PO4)2 with a Ca/P molar ratio = 1.15. The TCP is a neutral
compound in which the 6 positive charges of the Ca+2 ions
are compensated by 6 negative charges of the anions PO43.
It belongs to the family of the Whitlockites that respond to
general formulate (Ca,Mg)3 (PO4)2, so that the calcium can be
replaced partial or totally by magnesium.
The TCP is a material that displays polymorphism. Three
polymorphs are known: , and ` phases, from low to high
temperature of stability respectively [112,113].
The phase crystallizes in the hexagonal system, and
their lattice parameters are: a = 10.429 and c = 37.38. ==
90 and =120. The phase crystallizes in the orthorhombic
system with lattice parameters: a = 15,22 , b = 20,71 and c
= 9.109. == = 90 and finally the phase crystallize in the
monoclinic system, with lattice parameters: a = 12.887, b =
27.280 and c = 15.219== 90 and =126.2 [114].
The phase is stable from room temperature up to 1150
10 C C to which transforms into the phase. This is stable
from this temperature up to 1475 5 C to which transforms
into the phase which is stable up to the melting temperature.
The - transition is completely reversible in both senses.
Equally it happens with the transition, although if the
phase is abruptly quenched it can be mestastably preserved
at room temperature.
As the synthesis of HA, the synthesis of -TCP, in aqueous
solution, is affected by many physical and chemical parameters,
what presents great difficulty to obtain a product 100% pure
[115-116]. However, pure -TCP can be easily obtained by
solid state reaction of calcium and phosphorus compounds
with relationships Ca/P = 1,5.
Applications are temporary fillings and periodontal
defects.
ACKNOWLEDGMENTS
The authors thank to CICYT the financial support of the
Project MAT2003-08331-C02-01-02
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Recibido: 12.01.05
Aceptado: 28.03.05
145
 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
A R T I C U L O

A comparative analysis of Piezoelectric and Magnetostrictive

actuators in Smart Structures
J.L. PONS
Institute of Industrial Automation -- CSIC, Ctra. Campo Real, Km. 0.200, 28500 Arganda del Rey, Spain

This paper introduces a comparative analysis of Piezoelectric (PZ) and Magnetostrictive (MS) actuators as components
in smart structures. There is an increasing interest in functional structures which are able to adapt to external or internal
perturbations, i.e. changes in loading conditions or ageing. Actuator technologies must perform concomitantly as sensors
and actuators to be applicable in smart structures. In this paper we will comparatively analyze the possibility of using PZ
and MS actuators in smart structures and in so doing their capability to act concomitantly as sensors and of modifying their
material characteristics. We will also focus on the analysis of how them can be integrated in structures and on the analysis
of the most appropriate structures for each actuator. The operational performance of PZ (Stacks) and MS actuators will be
compared and eventually some conclusions will be drawn.
Keywords: Piezoelectric actuators, Magnetostrictive actuators, smart structures.

Un estudio comparativo de actuadores Piezoelctricos y Magnetoestrictivos para estructuras inteligentes

Este artculo presenta un estudio comparativo de actuadores Piezoelctricos (PZ) y Magnetoestrictivos (MS) como
elementos integrantes de estructuras inteligentes. Existe un inters creciente en estructuras activas que puedan adaptarse a
perturbaciones tanto internas como externas, por ejemplo, ante cambios en carga estructural o ante su envejecimiento. Para
que un actuador forme parte de una estructura inteligente, debe poder actuar tambin como sensor. Este artculo presenta
un estudio comparativo del uso de actuadores PZ y MS en estructuras inteligentes y, como consecuencia, de su habilidad
para actuar y medir simultneamente as cmo para modificar sus caractersticas mecnicas. Nos centraremos tambin en
el anlisis de como pueden integrase en estructuras y cuales son las ms indicadas para cada actuador. Se compararn las
caractersticas operacionales de los actuadors PZ multicapa y los MS.
Palabras clave: Actuadores Piezoelctricos, Actuadores Magnetoestrictivos, estructuras inteligentes

1. INTRODUCTION

There is a vast set of transducing materials on which
emerging actuator technologies (EATs) are being based.
Emerging actuators are characterized by exploiting new (or
at least newly developed) transducing phenomena. This is
the case of piezoelectricity, electrostriction, magnetostriction,
electro- and magneto-rheology as well as thermal or
magnetically triggered Shape Memory transformations, see
(1) for a comprehensive discussion.
Most of these transducing phenomena are reversible in that
they allow the conversion both from mechanical to electrical
energy and from electrical to mechanical energy. As such,
materials exhibiting such transducing phenomena can be
exploited both as sensors and as actuators. In other instances,
they can perform concomitantly in both directions.
Amongst the different EATs, the best established
technologies are Piezoelectric (PZ) actuators and
Magnetostrictive (MS) actuators. Both technologies allow two
directional transduction, and various studies have addressed
the concomitant implementation of MS and PZ technologies
as sensors and actuators, (2).
Electroceramics have been proposed as the basis for
developing acceleration sensors, (3), in the development of
solid state gyroscopes or for pressure sensors in the field of
biomechanics, (4). In all these instances, the direct piezoelectric
effect is exploited and the deformation of the electroceramic is
somehow related to the target physical variable to be sensed.
In a similar fashion, the Villari effect in magnetostrictive
actuators, that is the reverse magnetostrictive effect, has been
used to develop force sensors, see (5) for more details. In
addition, a particular instance of the reverse magnetostrictive
effect, the so-called Matteuci effect has been exploited in the
development of torque sensors.
However, during the last decades, the application of
both PZ and MS materials to emerging actuators is gaining
momentum. On the one hand, PZ materials have been
proposed as the basis of both resonant and non-resonant
actuators. Most likely, the Travelling Wave Ultrasonic Motor,
(6), can be regarded as the paradigmatic resonant PZ actuator.
Amongst the various different non-resonant drives, inchworm
actuators, multimorph benders and PZ stack actuators are the
most relevant implementations, (1). On the other hand, MS
materials have led to non-resonant actuators, and have been
chiefly applied in active control of vibrations, (7).
Both MS and PZ actuators have been successfully
proposed as constitutive components of smart structures.
The fundamental feature in this approach is the concomitant
sensing and actuation. In this context, simultaneous sensing
and actuation using piezoelectric materials has been extensively
studied, (8). In this instance, the intrinsic requirements for
setting up the magnetic and the electrical field in MS and PZ
actuators respectively lead to significant differences in the
type of smart structures they can be integrated in.

146 Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)

A COMPARATIVE ANALYSIS OF PIEZOELECTRIC AND MAGNETOSTRICTIVE ACTUATORS IN SMART STRUCTURES
The present paper has the main objective of establishing
a comparison between MS and PZ materials as the basis for
emerging actuators in smart structures. In so doing, a first
section will briefly set the basis of both piezoelectricity and
magnetostriction. Section 3 will be devoted to study the active
modulation of the stiffness both in MS and PZ materials as
a property commonly exploited in the integration of active
materials in smart structures. Section 4 will analyze the
properties of MS and PZ materials with regard to concomitant
sensing and actuation. This will lead to a discussion of various
different approaches in integrating MS and PZ actuators in
active structures in section 5. Eventually, their operational
characteristics will be discussed in section 6 and the paper will
end with a section devoted to highlighting some conclusions.
2. PIEZOELECTRICITY AND MAGNETOSTRICTION
2.1. Piezoelectricity and electrostriction
The piezoelectric effect can be described as modification
of the polarization of a dielectric arising from the mechanical
energy of the stress. Materials exhibiting such an effect are
said to be piezoelectric materials. The piezoelectric effect is
reversible in the sense that when an electric field is applied, a
mechanical strain will arise. This is the converse piezoelectric
effect.
The quasi-linear, low hysteresis piezoelectric effect can be
mathematically described by what are known as constitutive
equations. The reader is referred to (1) for a detailed derivation
of these equations. Here we will only introduce them as they
are relevant to the next sections:
The piezoelectric effect as described by equation [1]
is present in poled piezoelectric ceramics. However, some
materials exhibit a quadratic dependence of the strain on
the polarization known as an Electrostrictive effect. The
constitutive equation describing the quadratic relationship
between strain and polarization is:
Equation [2] can now be expanded in Taylor series around
a DC bias electric field, E0. For small variations of the electric
field around the DC bias, it follows:
and
The functional relationship between strain and applied
electric field is quadratic. Equation [3] indicates that the
electrostrictive behavior of small AC electric fields around
a DC bias electric field may be regarded as the same as the
piezoelectric behavior with a remanent polarization equivalent
to the bias electric field, i.e. P0=E0/(-0).
2.2 Piezomagnetism and Magnetostriction
Magnetostriction is the phenomenon whereby magnetic
domains in a ferromagnetic material are reoriented and
Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)
aligned in response to an applied external magnetic field.
As a consequence of the magneto-elastic coupling in these
materials, there is a macroscopic change in length in the
direction of imanation.
Magnetostriction can be described as being the
analog of piezoelectricity in the magnetic domain. In fact,
magnetostriction is a process of transduction between elastic
mechanical energy (strain) and magnetic energy. However,
there are evident significant differences between the two
phenomena. The equations governing the magnetostrictive
effect, magnetostriction constitutive equations, contain both
linear and quadratic terms in the magnetic field strength. In
tensor notation this is:
[4]
where Sij is the mechanical strain, Tkl is the mechanical stress,
cHijkl is the mechanical compliance under zero magnetic field
(H=0), Hm is the magnetic field strength, Tkm is the magnetic
permeability under constant mechanical stress, dmij are the
piezomagnetic displacement coefficients coupling linearly
magnetic and mechanical variables, mijkl is the magnetostrictive
coefficient coupling quadratically magnetic and mechanical
variables, and Bk is the magnetic flux density.
The equation coupling strain to magnetic filed strength
can be obtained from thermodynamic potential functions, and
according to equation [4] it has the following form:
[5]
[1] In equation [5], c1 defines the piezomagnetic effect. In
order for a material to exhibit piezomagnetism, the crystal
structure must me anisotropic. However, all ferromagnetic
materials exhibit magnetostriction, i.e. c2 0. Therefore,
the phenomenological description of piezomagnetism and
magnetostriction is equivalent to the phenomenological
description of piezoelectricity and electrostriction. The typical
strain versus applied magnetic field curve for magnetostrictive
materials is depicted in figure 1. It shows the quadratic
dependance of strain on magnetic field strength.
[2]
[3]
Fig. 1- Quadratic functional relation between strain and magnetic field
intensity in magnetostrictive materials.
147

Carrying on with the analogy between electrical and
magnetic domains, for a pure magnetostrictive material
(exhibiting crystal symmetry and thus no piezomagnetism),
the magneto-mechanical coupling will be described by:
[6]
which, for the direction of imanation, reduces to:
[7]
Notice that equation [6] represents a quadratic dependence
of strain on magnetic field strength. Once the magnetostrictive
coefficients are defined for a particular material, equation [6]
indicates that the magnetostrictive material will contract or
expand when either positive or negative magnetic fields are
applied.
Consequently, equation [7] describes a way of converting
unidirectional displacements in a magnetostrictive domain
into two-directional displacements by means of a bias magnetic
field strength, H0, a technique widely adopted in the design of
magnetostrictive actuators.
The process is schematically depicted in figure 2. Due
to the quadratic relationship between strain and magnetic
field, the driving frequency presents non-linearity and the
rate of the strain is twice the rate of the applied magnetic
field (black lines in figure 2). When a bias DC magnetic field,
H0, is applied, the strain becomes quasi-linear around the
bias magnetic field and the non-linearity in the frequency is
eliminated (grey, dashed lines in figure 2).
Fig. 2- Linearization and two-directional operation with magnetostric-
tive materials.
3. CONTROL OF STIFFNESS IN PZ AND MS ACTUATORS
In the application of emerging actuators in smart structures,
a common approach is to use the controllable change of
stiffness of embedded actuators as a means of stiffening
the structure and change its resonance characteristics. Both
PZ and MS materials can result in programmable stiffness
systems. This section describes the ability of PZ and MS
actuators in controlling the stiffness.
148
J.L. PONS
3.1 Programmable stiffness in PZ materials
In normal, passive materials the mechanical stiffness, K, is
defined as the ratio of applied force to deformation:
[8]
In the case of PZ actuators, because of the active nature of
the material, there is the possibility of programmable stiffness.
The force-deformation ratio for piezoelectric actuators is highly
dependent on the electrical boundary conditions applied to
the actuator electrodes.
In this context, there are three possible situations depending
on the electrical boundary conditions:
1. Short circuited or voltage controlled actuators. In this
situation, a ``low stiffness is achieved. Under deformation,
the charge generated by the piezoelectric effect is free to flow
and equilibrate.
2. Open circuit or charge/current controlled actuators.
In this situation, the charge is blocked at the electrodes of
the actuator when a force is applied. Blocking of the charge
(either because the circuit is open or because the control fixes
its value) results in an electric field that will oppose the force.
The outcome of this situation is greater stiffness (twice as
much as in case 1).
3. Impedance controlled actuators. In this case the control
loop applied to the piezoelectric actuator sets the reference
mechanical impedance for the piezoelectric actuator, i.e. the
reference charge/current is increased as a result of changes
in actuators strain. At the upper limit, when the reference
impedance is very high, the control strategy is equivalent to
a position control of the piezoelectric motor, and the apparent
stiffness of the actuator is virtually infinite.
3.2 The Y-effect in MS materials
The Youngs modulus, Y, in structural materials is a
parameter used to define the materials stiffness. It is calculated
as the ratio of change in stress to the corresponding change in
strain in a given material.
In transducing materials, and in particular in
magnetostrictive materials, there is a coupling between
the stiffness (Youngs modulus) and the imanation state of
the material. As a consequence, the Youngs modulus for
magnetostrictive materials is not constant but rather is a
function of the imanation state.
A change in the Youngs modulus of a magnetostrictive
material is commonly to be expected. Giant magnetostrictive
materials undergo strains of the order of 1500-2000 ppm in
response to changes in the imanation state. The strains that these
materials can exhibit when a pure mechanical load is applied
are much lower that those produced by magnetostriction.
Consequently, we may expect the effective elastic modulus,
as the ratio of stress to strain, to be considerably affected by
imanation.
The so-called Y-effect is defined as the relative change in
Youngs modulus upon application of an external magnetic
field, H, with respect to Youngs modulus at zero magnetic
field, H=0, (10):
[9]
Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)
A COMPARATIVE ANALYSIS OF PIEZOELECTRIC AND MAGNETOSTRICTIVE ACTUATORS IN SMART STRUCTURES

It is worth noting that Youngs modulus undergoes a
change even where the strength of the magnetic field is higher
than the saturation imanation. This indicates that the Y-effect
cannot be convincingly explained only on the basis of the
reorientation of magnetic domains due to external fields.
The maximum reported magnitude of the Y-effect (11)
is of the order of 1, that is Youngs modulus is doubled as
a consequence of the change in the imanation state of the
magnetostrictive material. Moreover, since the resonance
frequency of a magnetostrictive rod is:
[10]
A piezoelectric actuator establishes a flow of energy
from the electrical to the mechanical domain according to
the constitutive equations of the piezoelectric effect. When
no external load is applied to a piezoelectric stack actuator,
the displacement (strain) will be a non-linear, hysteretic
function, S1(V), of the voltage applied at the input port.
Wherever an external force is applied to the actuator, it will
act as a disturbance to the output displacement. The complete
relationship between strain, voltage and load will take the
form of equation [11] and is commonly called an operator-
based actuator model of the piezoelectric stack transducer
(12).

it follows that the change in Youngs modulus is related to

the change in the resonant frequency squared. It can be seen
that this property of magnetostrictive materials can be used in
tunable vibration absorbers based on this technology.
Table 1 shows the properties of three magnetostrictive and
electrostrictive materials. The table shows mechanical, thermal
and electrical as well as electrostrictive and magnetostrictive
properties.
[11]
where k is the piezoelectric stack stiffness.
Similarly, the charge developed in the piezoelectric stack,
Q(t), will be a direct function of the load applied to the
transducer, f(t). This time, the voltage-induced charge during
operation will act as a disturbance to the operator-based

TABLA I. MAGNETOSTRICTIVE AND ELECTROSTRICTIVE PROPERTIES OF SOME MATERIALS

Property Units Terfenol-D Hiperco PZT-2

Mechanical Properties

Density Kgm-3 9.25103 8.1103 7.5103

Youngs modulus, H=0 GPa 26.5 206 110

Youngs modulus, B=0 Gpa 55.0 - 60

Speed of sound ms -1
1690 4720 3100

Electrical properties

Resistivity 10-6 cm 60.0 0.23 0.01

Magnetoestrictive and Electrostrictive Properties

Permeability - 9.3 75 1300

Curie Temperature C 387 1115 300

Maximum strain ppm 1500-2000 40 400

Coupling factor - 0.72 0.17 0.68

d33 mA , mV
-1 -1
1.710 -9
- 30010-12

Energy density Jcm-3 14-2510-3 - 103

4. CONCOMITANT SENSING AND ACTUATION WITH PZ

AND MS ACTUATORS

When dealing with the application of actuators in smart
structures, the ability to perform both as a sensor and as
an actuator is of paramount importance. In this section,
we will introduce a discussion on how Piezoelectric and
Magnetostrictive actuators can be used concomitantly as
sensors and actuators.
Piezoelectric actuators are suitable to adopt various
different configurations, basically stacks and cantilevers for
direct actuation. On the other hand, MS actuators adopt always
the configuration in which a rod of magnetostrictive material
is subject to the magnetic field. Therefore, only Piezoelectric
stacks can be compared to Magnetostrictive actuators, since
stroke and stiffness are of the same order.
sensor model described by equation [12].
[12]
where d is the piezoelectric coefficient and Q1(V) is a non-
linear hysteretic function of the voltage.
Again, even though the PZ stack cannot be used to impose
a displacement (strain) and to concomitantly sense it, the
sensor model of equation [12] can be used to estimate the
load on the actuator: i.e. the piezoelectric stack is being used
concomitantly to impose a displacement and to sense the load.
The estimated load can then be used to compensate for its
disturbing effect on the displacement of equation [11] (12).

Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005) 149


Fig. 3- Bridge circuit for producing a signal proportional to the actua-
tors velocity in concomitant sensing and actuation: while the actuator
is driven by means of voltage V, the bridge unbalance, Vv, is propor-
tional to the actuators velocity U.
A model of the transduction process can be used to
implement both functions (sensing and actuation) at a time.
Before discussing this possibility in detail, let us introduce
here equation [13], which describes the relationship between
effort and flow variables in the electric-circuit analogy:
and [13]
The first equation describes the transducer as an actuator,
i.e. the application of a voltage, V, leads to a current drawn, I,
and to an output velocity, v. The Laplace transform of this first
equation is:
[14]
The overall electrical voltage includes a term dependant
on the current drawn, ZeI(j), and a term related to the output
velocity, TemU(j). This equation indicates that the output
velocity could be estimated by measuring the overall voltage,
V, and subtracting the voltage drop, VZe across the actuators
blocked impedance, VZe=Ze I(j).
The above result provides the basis for estimation of
the actuators motion from a Bridge Circuit configuration, as
shown in figure 3. This result is important in that it could lead
to: (i) modification of the actuators behavior (for instance
its damping characteristics) through the implementation of
feedback control loops based on the estimation of the velocity,
and (ii) collocated and concomitant sensing and actuation.
If a copy of the actuators blocked impedance is used in the
bridge circuit branch as depicted in figure 3, the voltage across
the bridge, Vv, is proportional to the actuators velocity.
The first approach, i.e. modification of the actuators
damping properties, has been studied in the context of voice
coil loudspeakers (13). In this case, the feedback from the
unbalanced bridge voltage is utilized to increase damping
around the resonance frequencies. The second approach has
150
J.L. PONS
been implemented in collocated and concomitant position and
velocity feedback in PZ actuators, see (14) and (8).
The main problem in this approach is measurement of the
actuators blocked impedance. It has been found that in most
implementations, the blocked impedance, rather than being
constant and independent of the actuators motion, is a non-
linear function of the current drawn.
Ideally, if output velocity could be estimated from the
voltage across the bridge, Vv, the sensing part of the electric-
circuit analogy (see equation [13]) could then be used to
produce an estimate of the mechanical conjugate variable (the
force).
In the context of concomitant sensing and actuation based
on magnetostrictive materials, let us recall here the linearized
version of the constitutive equations for the magnetostrictive
effect:
[15]
Equation 15 describes the coupling between magnetic
and mechanical variables in the direct and converse
magnetostrictive effect. The first equation describes the
transducer as an actuator, that is, the resulting displacement
is a function of the applied magnetic field strength. It further
includes the coupling between mechanical variables, i.e. the
displacement resulting from mechanical load.
The second part of the constitutive equation describes the
transducer in the role of sensor, relating the mechanical load to
the magnetic induction. Again, this part includes the coupling
between the magnetic field variables: i.e. the applied magnetic
field strength results in magnetic induction.
The two equations can be combined by solving the first
part for H and substituting it in the second part to yield:
[16]
Equation [16] describes the sensor model for the
magnetostrictive transducer. It formulates the relationship
between the resulting magnetic induction in the
magnetostrictive material, B, and the applied force, T, and
displacement, S. Faradays law can be used to determine the
magnetic induction in the material. This states that the voltage
induced in a coil wrapped around the magnetostrictive
material is:
[17]
where N is the number of turns in the coil and A is the cross
sectional area.
Equation [17] indicates that the voltage in such a sensor
configuration is proportional to the rate of change of force
(jerk) and to the rate of change of displacements (velocity)
in the magnetostrictive material. It can be demonstrated (5)
that the magnetostrictive process is fully reversible and
and that the term in equation [17] corresponding to
the velocity is one order of magnitude smaller than the terms
Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)
A COMPARATIVE ANALYSIS OF PIEZOELECTRIC AND MAGNETOSTRICTIVE ACTUATORS IN SMART STRUCTURES
relating to force. Therefore, for harmonic excitations, a model
for the force measured by the transducer would be:
[18]
The design of magnetostrictive transducers as sensors
is equivalent to their design as actuators. Moreover, as we
assumed that , this implies that if the transducer is
designed for efficient operation as an actuator, it will be a
high-sensitivity sensor. These are commonly used in sonar
transducers where a transducer designed as an efficient
emitter also yields the best results as a receiver.
For combined sensor and actuation operation of
Magnetostrictive actuators, the Bridge Circuit configuration
can be implemented. To do this, the linearized constitutive
equations for the Magnetostrictive effect, equation [15], must
be rewritten in line with the electric-circuit analogy.
We commence the process by multiplying the sensing
part of equation [15] by the actuators cross sectional area A.
Considering that , it follows that:
[19]
Now, if we take the time derivative of equation [19],
multiply the equation by N (the number of turns in the MS
actuator coil) and note that and ,
we obtain:
[20]
The Laplace transform of equation [20] can now be
developed. In addition, if we take into account low frequency
excitation of the transducer, we can assume that the materials
Fig. 4- Bridge circuit configuration for concomitantly using a MS ac-
tuator as a sensor.
Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)
deformation obeys Hookes law (T=Y ). Given these
assumptions, we can write:
[21]
where Y is the Youngs modulus, l is the length of the
Magnetostrictive actuator and L is the inductance of the MS
actuator coil.
A simple inspection of equations [21] and [14] will
show that Ze = jL, that is, the blocked impedance of the
Magnetostrictive actuator (which is required to complete the
second branch of the Bridge Circuit) is simply the inductance
of the solenoid (with the MS material as the core) used to drive
the MS actuator (see figure 4).
A similar approach can be used to derive the second part
of equation [13]. It can be shown, (2), that this produces:
[22]
If the solenoid inductance is used in the second branch
of the Bridge Circuit, the voltage across the bridge ought to
be proportional to the actuators velocity. However, this is
not the case, and the reason is that the blocked impedance is
non-linearly dependent on the current drawn. Consequently,
concomitant sensing and actuation with MS actuators is
difficult to achieve, although some authors, (2), have reported
positive results in narrow frequency bands around the
actuators mechanical resonance.
5. PZ AND MS ACTUATORS IN SMART STRUCTURES
5.1 PZ actuators in smart structures
As we discussed in the introduction, most of the emerging
actuator technologies can perform both as sensors and
as actuators. Amongst them, MS, PZ and Shape Memory
Actuators, SMA, are the most appropriate to be integrated in
active structures. Like SMA actuators, MS and PZ actuators
can perform also as sensors. Unlike SMA actuators, PZ
and MS actuators cannot be used to concomitantly impose
and sense the same output variable, but they can sense the
conjugate variable to the imposed one.
When discussing piezoelectric actuators, it can be pointed
out that current drawn, i, is in principle proportional to
the actuators velocity, vp. In this material, the following
approximate relationships hold:
[23]
[24]
[25]
where l is the actuator change in length, Q is the change in
charge and ap is the actuators acceleration.
According to the above equations, if control is achieved
by feeding the current drawn directly back in a negative
control loop, the result is equivalent to a direct velocity
feedback approach. Direct velocity feedback, in a collocated
sensor/actuator pair (the condition of collocated sensors
151
 J.L. PONS

and actuators indicates that the sensor directly measures the
action of the actuator, condition that will be always met in
actuators acting concomitantly as sensors), leads to stable
active damping control schemes, see (15). Therefore, since a
piezoelectric smart actuator is intrinsically collocated, this
approach greatly facilitates the implementation of active
vibration control in smart structures.
5.2 MS actuators in smart structures
Magnetostrictive actuators are best suited for active
vibration control of structures. Moreover, they are a typical
example of a smart actuator. However, they are not suitable
for integration in any type of structure.

Fig. 5- Piezoelectric actuator bonded to a structure and connected to a

RCL circuit for passive damping.

In the previous section, we discussed how the electrical

boundary conditions applied to a piezoelectric actuator can
result in programmable actuator stiffness. Programmable
stiffness can be applied for voluntary stiffening in response to
monitoring functions.
Two actuation approaches can be envisaged for piezoelectric
actuators:
1. As linear actuators. In this approach, they replace
conventional actuators in controlling structure parameters.
As noted earlier, this actuation approach is not suitable for
development of the smart structure concept as sensor and
actuator functions are lumped rather than distributed.
2. As surface bonded actuators. The piezoelectric material
is laminated and bonded in thin layers to the structure (see
figure 5). This can serve for the application of either axial or
bending loads.
Both actuation approaches are most commonly used to
enhance the damping characteristics of the structure to which
they are attached (first case) or embedded (second approach).
As regards surface bonded actuators, in controlling damping,
again there are two possible strategies:
1.Passive damping. In this approach, the actuator is bonded
to the structure and is electrically connected to a passive RLC
circuit. The actuator acts as a voltage source when driven by
the structural vibrations through the direct piezoelectric effect.
The electrical energy is dissipated at the resistor. This results
in an apparent increase of structural damping.
Some selectivity in the damping process can be achieved
by tuning the RLC characteristics of the passive circuit to the
target frequency (see figure 5).
2.Active damping. In this mode, the piezoelectric actuators
are integrated in a feedback control strategy, in an active
control strategy or in a feed-forward control strategy. In
any of these control algorithms, the piezoelectric actuator
can perform as a smart actuator, i.e. sensing and actuating
Fig. 6- 3D truss in which a linear MS actuator is integrated for active
concomitantly.
vibration isolation.

152 Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)

A COMPARATIVE ANALYSIS OF PIEZOELECTRIC AND MAGNETOSTRICTIVE ACTUATORS IN SMART STRUCTURES
In particular, planar configurations (similar to bonded
laminate piezoelectric actuators (see figure 5) are not ideal
for magnetostrictive actuators. This is due to the difficulty
of creating a uniform magnetic field for such a planar
configuration.
Magnetostrictive actuators are more suitable for integration
in discrete structures like three-dimensional trusses (see figure
6) and structures with structural cables (bridges or buildings).
There, they can take the place of passive structural elements
and thus offer the possibility of cancelling out structural
vibrations, see (7).
The issue of active control of truss structures has been
comprehensively studied by (15). We will not go into more
detail here; for more details the reader is referred to (1).
Magnetostrictive actuators can be used in the context of
vibration suppression in smart structures, in three different
modes:
1. Stiffeners.
2. Dampers.
3. Active elements.
Stiffeners make use of the Y-effect, which allows a two-
fold increase in the actuators stiffness. By changes induced
in the structural stiffness of the structure in which they are
integrated, the resonance frequency can be modified to prevent
resonance amplification following external excitation.
Magnetostrictive actuators can also be used as dampers in
active damping control approaches. The role of the actuator in
this control scheme is to enhance the structural damping by
means of direct velocity feedback or similar approaches.
Finally, they can be applied in active vibration cancellation
control schemes, both feed-forward and feedback. In this
approach the MS actuator will provide the necessary
secondary disturbance to cancel out vibrations. As in the case
of piezoelectric or Shape Memory actuators, both sensing and
driving functions can be implemented concomitantly. This is
discussed in more detail in the next section.
6 OPERATIONAL CHARACTERISTICS OF PZ AND MS
ACTUATORS
This section analyzes the performance characteristics of
Piezoelectric and Magnetostrictive actuators. The reader is
referred to (1) for a comprehensive comparative analysis of
all emerging actuator technologies, but here we pay particular
attention to a comparative analysis of MS and Piezoelectric
actuators since these have the closest figures of merit. In this
comparison we will mainly focus on PZ stack actuators since
they best resemble the operation of MS linear actuators. Other
Piezoelectric actuators, i.e. cantilever or multimorph actuators,
could be included but their operational characteristics differ
too much from MS actuators to be directly compared.
6.1 Static performance
Magnetostrictive and Piezoelectric stack actuators can be
classified together as high force devices. The absolute value of
force in these actuators is in the kilonewton range (F 1 kN).
Relative forces for MS actuators (for instance as compared
to cross sectional area or size) nevertheless become several
orders of magnitude lower than relative forces in Piezoelectric
actuators. This is mainly due to the accompanying components
required to set up bias magnetic fields or to prestress the
Magnetostrictive actuator. While Piezoelectric stack actuators
Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)
can be directly applied to drive the load, MS actuators require
coils to set up the magnetic field and in most implementations
permanent magnets to apply bias fields.
Stroke in MS actuators is of the order of 1500-2000 ppm
for static applications and close to 4000 ppm where resonance
amplification is used in dynamic applications. In absolute
value, the displacement is limited in practice to some tenths
of a mm. Stroke is higher in MS actuators than in Piezoelectric
stack actuators (which is of the order of 1000 ppm in static
conditions), but the performance of Piezoelectric stack and
MS actuators is very similar in terms of the relative stroke (for
instance with respect to the length of the actuator).
6.2 Dynamic performance
The energy density of Magnetostrictive actuators is in the
range of WV 10-3 J/cm3 and must therefore be considered
low. If only the magnetostrictive material were considered,
the energy density would be closer to that of Piezoelectric
actuators, but here again, the bulky accompanying elements
cause reduced work density.
The bandwidth of MS actuators is high, f 1 kHz. Together
with Piezoelectric stack actuators and some Piezoelectric
Multimorph drives, they have the highest frequency bandwidth
of all emerging actuator technologies. MS drives are driven at
lower frequencies than Piezoelectric stack actuators. There are
two main reasons for this:
1. Lower Youngs modulus. MS materials exhibit a lower
Youngs modulus than Piezoelectric materials (two to three
times lower). This results in lower resonance frequency of
MS materials, which in turn limits the maximum driving
frequency for actuators based on this technology.
2. Eddy currents. Changing magnetic fields induce electrical
currents (eddy currents) in the magnetostrictive materials,
and these lead to material heating and lost efficiency; the
higher the frequency of the magnetic field, the stronger are
the currents induced. This imposes a practical limit on the
maximum frequency attainable with MS actuators, otherwise
efficiency is highly reduced.
Power density in MS actuators is a result of the two
previous figures of merit. Since both energy density and
bandwidth are lower in MS actuators than in Piezoelectric
drives, absolute power density values are low, of the order of
1 W/cm3, which is up to three orders of magnitude lower than
in Piezoelectric stack actuators.
6.3 Other performance characteristics
The temperature range of operation for MS actuators is
limited in practice by the materials Curie temperature. The
Curie temperature for Terfenol-D is close to 380 C, which is
higher than the Curie temperature for PZT materials.
Driving voltages for MS actuators are lower than they
are for Piezoelectric stack actuators. Power supply for this
technology is readily available from several manufacturers.
Unfortunately, the MS material itself is much less readily
available. While PZT materials can be found in several grades,
the only available MS material grade is Terfenol-D.
7. CONCLUSIONS
This paper has introduced a comparative analysis of PZ
(stacks) and MS actuators with regard to their application as
153

smart actuators in active structures. As such, the concomitant
sensing and actuation, their ability to change material
parameters (stiffness) and their operational characteristics
have been studied and compared.
PZ and MS actuators have been pointed out as two of the
most relevant and well established emerging actuators. As
to their ability to perform both as sensors and actuators this
is based on the direct piezoelectric effect and on the Villari
and Matteuci effects. These phenomena allow the sensing
of the conjugate variable, i.e. if the actuator is establishing
a displacement, concurrent estimation of the force can be
accomplished. Furthermore, this paper has introduced the
estimation of both conjugate variables based on models of the
electrical circuit analogy for PZ and MS actuators.
Something similar can be said of their ability of modifying
the actuator stiffness. This is of importance when the actuator
is integrated in smart structures as a means of changing their
resonance characteristics.
PZ (stack) and MS actuators exhibit similar static operational
properties, in particular stroke and force. In what they differ
the most is in the dynamic operational characteristics. The
resonance frequency of MS actuators is lower than the one
of PZ actuators. This affects the maximum driving frequency
and is closely related to the lower Youngs modulus of MS
actuators and to the limits due to eddy currents.
Both actuators are suitable to be embedded in smart
structures, but PZ actuators can be easily bonded in thin
laminar structures while MS actuators are more suited to be
included in truss like structures. One of the most limiting
factors for MS actuators in comparison with PZ actuators is in
the low availability of materials and grades.
154
J.L. PONS
REFERENCES
1. J.L. Pons, Emerging Actuator Technologies: a Micromechatronic Approach,
John Wiley & Sons Ltd., Chichester, England, 2005.
2. J. Pratt, Design and analysis of a self-sensing Terfenol--D magnetostrictive
actuator, M. Sc. Thesis, Iowa State University, Ames, 1993.
3. P. Ochoa, M. Villegas, J.L. Pons, M.A. Bengochea, J.F. Fernndez,
Piezocomposites metal-cermica como elementos activos en acelermetros,
Bol. Soc. Esp. Cerm. V., 41, 1, pp. 126-130, 2002.
4. J.C. Moreno, J.F. Fernndez, P. Ochoa, R. Ceres, L. Caldern, E. Rocon,
J.L. Pons, Aplicacin de sensores electrocermicos a la caracterizacin
biomecnica, Bol. Soc. Esp. Cerm. V., 43 (3), pp. 670-675, 2004.
5. M.J. Dapino, R.C. Smith, F.T. Calkins, A. Flatau, A Coupled Magnetomechanical
Model for Magnetostrictive Transducers and its Application to Villari-effect
Sensors, Journal of Intelligent Material Systems and Structures, 13, 737-747,
2002.
6. D. Mesonero-Romanos, J.F. Fernndez, M. Villegas, R. Ceres, E. Rocon,
J.L. Pons, Comparacin entre excitacin resonante y forzada de motores
electrocermicos, Bol. Soc. Esp. Cerm. V., 43 (3), pp. 725-731, 2004.
7. P.A. Bartlett, S.J. Eaton, J. Gore, W.J. Matheringham and A.G. Jenner,
High-power, low frequency magnetostrictive actuation for anti-vibration
applications, Sensors and Actuators A, 91, 133-136, 2001.
8. N.W. Hagwood, E.H. Anderson, Simultaneous sensing and actuation using
piezoelectric materials, Active and Adaptive Optical Components, SPIE,
1543, 409-421, 1991.
9. C.Z. Rosen, B.V. Hiremath, R. Newnham eds., Piezoelectricity, American
Institute of Physics, New York, 1992.
10. A.B. Flatau, M.J. Dapino, F.T. Calkins, High bandwidth tunability in a
smart vibration absorber, SPIE Smart Structures and Materials Conf., San
Diego, CA, 463-473, 1998.
11. A.E. Clark, H.T. Savage, Giant magnetically induced changes in the elastic
moduli in Tb(0.3)Dy(0.7)Fe(2), IEEE Transactions on sonics and ultrasonics,
50-52, 1975.
12. K. Kuhnen, H. Janocha, Compensation of the Creep and Hysteresis Effects
of Piezoelectric Actuators with Inverse Systems, Actuator98, 309-312,
1998.
13. E. de Boer, Theory of motional feedback, IRE Transactions on Audio, 15-
21, 1961.
14 J.J. Dosch, D.J. Inman, E. Garca, A self-sensing piezoelectric actuator for
collocated control, Journal of Intelligent Material Systems and Structures,
3, 166-185, 1992.
15. A. Preumont, Vibration control of active structures, Kluwer Academic
Publishers, 1997.
Recibido: 10.02.05
Aceptado: 21.04.05
Bol. Soc. Esp. Ceram. V., 44 [3] 146-154 (2005)
 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
A R T I C U L O

From Chemical Engineering to Ceramic Technology: A Review of

Research at the Instituto de Tecnologa Cermica
A. BARBA
Instituto de Tecnologa Cermica. Universitat Jaume I. Castelln. Spain.
Department of Chemical Engineering. Universitat Jaume I. Castelln. Spain.

The present paper provides an overview of the research conducted at the Instituto de Tecnologa Cermica (ITC). ITC research
focuses on the application of Chemical Engineering principles to the study of raw materials, unit operations involved ceramic
materials manufacturing processes, chemical reactions occurring in the course of the manufacturing processes, finished
product properties, and other aspects of ceramic manufacturing processes related to the field of Chemical Engineering.

Keywords: Chemical Engineering, Ceramic Technology, raw materials, unit operations, chemical reaction engineering, finished products,
environment

De la Ingeniera Qumica a la Tecnologa Cermica: una revisin de la investigacin en el Instituto de Tecnologa

Cermica

En este artculo se recoge una revision de la investigacin realizada en el Instituto de Tecnologa Cermica (ITC). La
investigacin del ITC se basa en la aplicacin de los principios de la Ingeniera Qumica al estudio de: las materias primas,
las operaciones unitarias propias de los procesos de fabricacin de materials cermicos, las reacciones qumicas que tienen
lugar a lo largo de dichos procesos de fabricacin, las propiedades de los productos acabados, y otros apectos de los procesos
de fabricacin relacionados con el campo de la Ingeniera Qumica.
Palabras clave: Ingeniera Qumica, Tecnologa Cermica, materias primas, operaciones unitarias, ingeniera de la reaccin qumica,
producto acabado, medio ambiente.

1. INTRODUCCIN

The Instituto de Tecnologa Cermica (ITC) is a mixed
institute established by agreement between Universitat Jaume
I of Castelln (UJI) and the Asociacin de Investigacin de las
Industrias Cermicas (AICE), the Ceramic Industry Research
Association.
ITCs mission is to foster and develop whatever technical
activities contribute to enhancing the competitiveness of the
Spanish ceramic sector, essentially by:
1. Research and Development, and Technological
Consultancy in response to the needs of the ceramic sector.
2. Technology Transfer, applying, assimilating, adapting
(whenever required) and implementing technologies from
other industrial fields in the ceramic sector.
3. Training at different levels:
Level 1. Ongoing training of ITC research and technical
staff. Staff are kept abreast of the latest technical and scientific
advances by attending courses, congresses and technical
conferences.
Level 2. Disseminating the knowledge gained and generated
at ITC towards ceramic technicians in the companies, by
delivering monographic courses.
Level 3. Teaching the Chemical Engineering degree course
at UJI, which specialises in ceramic materials processing.
Level 4. Teaching the PhD programme, Chemical
Engineering: Ceramic Materials Processing, of the UJI Chemical
Engineering Department.
4. Technological services, designed to support and assist
companies by performing analyses and tests, studying
and testing finished products, and providing consulting in
quality management, as well as running an information and
documentation service for the sector.
Of the above lines of work, the present paper deals with
the R&D work performed at ITC over the last 35 years. For
further information on the other activities, please visit the
ITC Web site(1) or see the references(1-4). The focus of ITCs
R&D work has been largely determined by the following three
fundamental facts:
1. Over 270 companies in the Spanish ceramic sector
are associated in ITC. These include leading raw materials
suppliers, floor and wall tile manufacturers, frit, glaze and
pigment producers, and additive suppliers. The industries
making up the ceramic sector have witnessed spectacular
growth and development in the last 20 years. As an example,
Figure 1 shows the sales growth of the ceramic floor and wall
tile branch (Spain is currently the worlds third ceramic tile
producer), and of frits, glazes and colours (of which Spain is
at present, qualitatively and quantitatively, the worlds top
producer). This evolution has been driven by continuous
investment in research, product development and innovation
by these industries. R&D actions have played a key role in this
development, particularly in achieving a better understanding
of the manufacturing processes and improving finished
product quality. ITC is the most important Spanish expert
R&D Centre in this field, and has generated and disseminated

Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005) 155

 A. BARBA

3. The American Institute of Chemical Engineers (AIChE)(6)

and the Institution of Chemical Engineers (IChemE)(7) both
define Chemical Engineering as a branch of engineering
related to: processes in which materials undergo a change
in composition, energy content or physical state; means for
processing these; the resultant products and their application
for useful purposes. Chemical Engineering has its foundations
in mathematics, physics and chemistry; its operations unfold
on the basis of knowledge contributed by these sciences,
by other branches of engineering, by biology and by social
sciences. The practice of Chemical Engineering lies in the
conception, design, innovation and application of processes
and their products; Chemical Engineering also has do to with
economic development, the design, construction, operation,
control and management of chemical plants for these processes,
Fig. 1 - Growth of certain Spanish ceramic branches.
and research and teaching in these fields. Similarly, the
Organisation for Economic Co-operation and Development
much of the knowledge that has progressively been acquired,
(OECD) defines Technology as the whole systematic
while collaborating in the application of this knowledge on an
knowledge and information necessary for manufacturing a
industrial scale.
product, applying a process or giving a service(8). In turn,
2. ITC technical staff have degrees in Chemical Engineering
Professor Ring concludes that Ceramic Technology is the
or related fields (Chemistry or Industrial Chemistry). Twenty
application of scientific and engineering principles to ceramic
ITC staff members lecture in the UJI Chemical Engineering
manufacturing processes(9). In the same sense, Ceramic
Department (comprising 1 Emeritus Professor, 2 Professors, 10
Technology or Ceramic Engineering will consist of applying
Associate Professors and 7 Assistant Professors) and conduct
scientific principles to industrial ceramic processes in order
research at ITC. These lecturers teach different courses in
to save time, energy and raw materials and to make the best
the Chemical Engineering degree syllabus of 345 credits, 50
products with the greatest uniformity and reproducibility at
credits being in Ceramic Technology. They also participate
the lowest possible cost. In other words, Ceramic Technology
in the PhD programme, Chemical Engineering: Ceramic
consists of applying Chemical Engineering (Transport
Materials Processing, by teaching and supervising doctoral
Phenomena, Unit Operations, Chemical Reaction Engineering,
dissertations. For further information, please visit the UJI
Process Engineering, Industrial Plant and Equipment Design,
Chemical Engineering Department Web site(5). The remaining
Control, Economy and so on) to the industrial processes
ITC technical staff (30 university graduates and 14 technicians)
involved in making ceramic products.
are hired by AICE and their technical work is also conducted
In view of these three factors, it is readily understandable
at ITC. Figure 2 schematically illustrates the make-up of ITC
that ITCs R&D work essentially focuses on studying the
personnel.
process stages (unit operations) involved in the manufacture

Fig. 2 - ITC staff.

156 Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005)

FROM CHEMICAL ENGINEERING TO CERAMIC TECHNOLOGY: A REVIEW OF RESEARCH AT THE INSTITUTO DE TECNOLOGA CERMICA
of any type of ceramic material or product (primarily ceramic
tile, frits, glazes and colours, brick and roof tiles, but also
porcelain, majolica and earthenware, sanitary ware, refractories
and technical ceramics). Every manufacturing process is
considered to start with raw materials and end with a finished
product. In this sense, ITC R&D work basically encompasses
five fields (Figure 3):
1. Raw materials, estimating and determining their
physico-chemical characteristics.
2. Unit operations, studying each manufacturing process
stage. Although there are numerous manufacturing processes,
each can be broken down into a series of steps, known as
operations, which in turn appear in process after process.
These operations have common techniques and are based
on the same scientific principles. The processes involved
can comprise unit operations, such as: mixing, milling,
agglomerating (granulating or spray drying), storing, forming
(pressing, extruding, casting, etc.), drying, glazing and
decorating, sintering, finishing, etc. Control and automation
are also features considered in every unit operation.
Fig. 3 - Fields of ITC R&D activity.
3. Chemical reaction engineering, studying the chemical
transformations that occur throughout the manufacturing
process.
4. Finished products, determining and enhancing product
properties, seeking new applications and developing new
products.
5. General aspects of the whole process, such as energy
saving or efficiency, eco-related features or economy,
traditionally included in the chemical engineering field.
Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005)
Please note that the following sections only deal with
published ITC R&D results. ITC has obviously done much
more R&D work and obtained more results than those set out
in this paper, but these still remain confidential, either because
private companies have funded the research, or because they
are protected by patents (Table I details the ITC patents). The
impact of ITC research as a whole on the Spanish ceramic
sector has been dealt with elsewhere(2-4).
2. RAW MATERIALS
The research conducted in raw materials has focused
principally on the raw materials used in manufacturing
ceramic bodies(10) and in fabricating frits, glazes and pigments
or other similar products.
Raw materials for ceramic bodies have thus been
characterised from numerous viewpoints: geological(11-
13), physical (by dilatometric(14), thermogravimetric
and thermodifferential analysis(15-16), and particle size
distribution(17)), chemical (by X-ray fluorescence(18-20),
infrared spectroscopy(21) and potentiometric methods(22)),
mineralogical (by X-ray diffraction(23)) and technological(24)
(by measuring the properties that enable determining raw
materials behaviour in each manufacturing process stage
in which they are to be used, such as plasticity(25-27) or
carbonate content(28-30)). Sometimes, in order to perform
the characterisation, it has been necessary to adapt the
instrumental methods to the nature of the raw materials. In
157
 A. BARBA

TABLE I. ITC PATENTS

Publication number Title Date granted

Mtodo y aparato para la determinacin de la

ES 8507263 16-08-85
compactacin de productos cermicos

Secadero de microondas para moldes de escayola y

U 0288843 16-01-86
piezas cermicas
Aparato para la determinacin simultanea de
ES 2002792 la fluidez y de la densidad aparente de polvos 01-10-88
cermicos granulados
Procedimiento y equipo para determinar
ES 2019197 la densidad aparente de piezas cermicas, 01-06-91
conformadas por prensado
Equipo para determinacin de la consistencia de
ES 2019750 01-07-91
una barbotina de esmalte cermico

ES 2049146 Dispositivo para la determinacin de la plasticidad 20-09-95

Dispositivo de muestreo para materiales

ES 2049145 20-09-95
pulverulentos, ridos, filamentosos y otro

ES 2068743 Procedimiento de obtencin de zeolita A 26-09-95

Mquina de ensayo para determinar el

ES 2070663 comportamiento de materiales empleados en el 30-08-96
revestimiento de suelos ante un trfico peatonal
Perfeccionamientos en dispositivos para la
ES 2051232 determinacin de la densidad aparente de 01-02-97
materiales slidos
Dispositivo y mtodo para la determinacin de
ES 2077500 16-10-97
eflorescencia en ladrillos

Dispositivo para la aplicacin de suspensiones sobre

U 1036515 16-12-97
soportes cermicos

ES 2088821 Dispositivo para el control de pantallas serigrficas 07-01-98

Procedimiento y equipo para determinar la

distribucin de temperaturas en mquinas trmicas
ES 2102943 09-02-98
con sistemas de rodillos para transporte del
producto
Sistema de evaluacin del comportamiento
ES 2108603 05-06-98
mecnico de recubrimientos aplicados sobre soporte

ES 2114821 Dispositivo para la evaluacin de brillo no especular 18-12-98

Dispositivo y procedimiento de evaluacin de la

ES 2176090 13-07-00
resistencia al impacto de materiales frgiles
Vehculos y tintas endurecibles por una radiacin
ES 2147066 ultravioleta y procedimiento de utilizacin de los 01-04-01
mismos en la fabricacin de baldosas cermicas.
Dispositivo y mtodo de control automtico de
ES 2165760 15-05-03
aportacin de fluidos

Vehculos y tintas autoendurecibles para la

ES 2181527 16-06-04
decoracin de baldosas cermicas

ES 2182680 Vehculos y tintas serigrficas en base acuosa 01-07-04

Dispositivo para la fabricacin de baldosas

ES 2174695 01-09-04
cermicas con superficie variable

the last 30 years, the foregoing features of many Spanish clays
have been exhaustively studied, particularly of the clays in
the proximity of the Castelln manufacturing district(31-37).
Characterising raw materials for ceramic bodies has allowed:
establishing selection criteria(38) that match the characteristics
of the manufacturing process involved and of the targeted
end product(39-41); implementing systems for assuring
consistent raw materials quality, setting up industrial-scale
homogenisation systems(42-44) and quality controls(45); and
systemising the acquired knowledge(46).
The raw materials used in making frits, glazes and
pigments(47), such as zircon(48), carboxymethylcellulose(49-
50), sodium tripolyphosphates(51) and the screen printing
vehicles for preparing ceramic inks(52) have also been
characterised, while certain characterisation methods(53) have
been adapted to effect this characterisation. These studies
have enabled implementing appropriate raw materials quality
controls(54).
ITC has also conducted research into the use of clay raw
materials for making non-traditional ceramic materials, such

158 Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005)

FROM CHEMICAL ENGINEERING TO CERAMIC TECHNOLOGY: A REVIEW OF RESEARCH AT THE INSTITUTO DE TECNOLOGA CERMICA
as mullite(55-56), and into the valorisation of certain industrial
wastes by reusing these as raw material in manufacturing
traditional ceramic products. Thus, the sludges arising in
ceramic tile, brick and roofing tile manufacture have been
reused in the same production process(57-59). Fired tile
scrap(60), marble-working wastes(61-62) and leather-tanning
wastes(63) have similarly been reused in the foregoing
manufacturing processes, while sludges from ceramic tile
manufacture(64-66) and refinery fluid catalytic cracking (FCC)
residue(67) have been reused in raw materials mixtures for
ceramic glazes.
In addition, studies have been successfully undertaken on
the reuse of spent catalysts from refinery FCC units as a basic
raw material in zeolite synthesis(68-69).
The above research done in characterising and selecting
raw materials, together with research on process stages and
the properties of ceramic products (set out below), has enabled:
designing a methodology for formulating compositions with
a view to selecting the most appropriate formulation (raw
materials mixture) for the particular needs of each product
and process; designing suitable formulations for frits(70-
71), glazes(72-73), earthenware(74), ceramic flooring(75-80),
wall tile(81), and, in general, any type of ceramic tile(82-86);
regulating the formulations for optimising product properties
and behaviour in each process stage.
3. UNIT OPERATIONS
3.1 Mixing, milling, agglomerating and storing
These four unit operations serve to condition the raw
materials mixture for subsequent forming.
The first ITC studies into conditioning raw materials
mixtures for ceramic bodies focused on determining the
production costs and capital outlay involved in the two
possible ways of mixing, milling and agglomerating, namely
by the wet method or the dry method, in order to select the
most appropriate process from an economic standpoint(87-
88). This research has allowed implementing the wet powder
preparation process in ceramic tile manufacturing, a milestone
in the evolution of the ceramic tile sector. In addition, the
possibility has also been examined of conditioning the raw
materials mixture by the wet method in continuous(89) or
batch processes.
The choice of the wet processing approach for ceramic
body raw materials mixtures has led to extensive research into
the rheological behaviour of clay suspensions(90) in general,
and of concentrated clay suspensions(91) in particular. Thus,
the influence of solids content, the effect of quartz addition,
deflocculant content(92-94) and the influence of test conditions
on the suspension flow curve(95) have been studied. One
of the most important results of this research has been the
introduction of the metasilicate-tripolyphosphate mixture, as
a deflocculant for clay suspensions(96), which has enabled
significantly raising the suspension solids content, notably
improving productivity and reducing energy consumption.
The effect has also been studied of the presence of ions on clay
suspension rheology(97). The research conducted in the field
of clay suspension rheology has allowed establishing the clay
particle interaction mechanisms as a function of suspension
solids and deflocculant content(98).
Research into the spray-drying operation has concentrated
on determining the values of the process variables in order to
Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005)
produce a granulated powder with appropriate characteristics
(especially granule size distribution) for appropriate pressing,
die filling and packing for fabricating ceramic bodies(99-101).
One of the most practical results of these studies has been the
development of a system of on-line measurement of industrial
granulated spray-dried powders(102), which has enabled
controlling spray-dryer operation by automatic adjustment of
drying gas temperature and suspension flow rate as a function
of the resulting powder moisture content(103), achieving
significant energy savings in this unit operation(104).
Another ITC line of research has involved relating spray-
dried powder characteristics to powder behaviour. Thus,
studies have been undertaken on the influence of the nature,
size and moisture content of spray-dried powder on powder
flowability(105-106), as this last parameter significantly affects
the subsequent packing stage and hence the quality of the
resulting ceramic body. In this sense, two methods have also
been developed for measuring powder bulk density(107) and
hardness(108).
As spray-dried powder is usually stored in silos and
hoppers prior to discharge for use as press feed, ITC has also
studied the storing operation. The main research focus has
centred on designing storage facilities that suppress breaks in
the powder discharge flow caused by bridging and powder
segregation, owing to size differences. The Jenike theory
has thus been applied in studying the influence of discharge
opening diameter, discharge angle and silo surface area on the
type of flow(109).
ITC has similarly conducted research into the conditioning
of raw materials mixtures for ceramic glazes. Thus, the
influence of water hardness(110-111), pH(112), additives(112)
and frit solubility(113-118) on glaze suspension rheology has
also been studied. In addition, the feasibility of using different
suspending agents, such as sepiolite(119) and carboxymeth-
ylcellulose(120), has been tested, examining their effect on
glaze suspension rheology and on the consolidated glaze layer
coating the ceramic body.
Finally, ITC research has also addressed the dispersion
process of screen printing ink particles in a liquid(121). This
has enabled developing and fine-tuning different methods for
quantifying the level of dispersion.
3.2 Forming
Two unit operations are widely used in forming ceramic
bodies: extrusion of a plastic mass(122-123) and dry uniaxial
pressing, the latter being the most widespread in the ceramic
tile sector and, hence, the most extensively studied at ITC.
However, other forming methods have also been studied,
such as the use of gels(124). The main features studied in the
pressing operation follow.
One course of study has addressed the relation of granulated
powder characteristics (granule size distribution(125-126) and
moisture content(127)) and pressing variables (especially
pressing pressure(127)) to the properties of the resulting
green(128) and sintered(129-131) bodies.
A further research line has focused on optimising
the pressing cycle(132-137) and each step in the pressing
operation, especially die filling(138-139) and extraction of
the compact(140-141). Understanding this cycle enables
largely avoiding pressing-related defects, such as cracks or
deformations caused by stresses from friction between the
compact and the die walls.
Although the clay formulations used to obtain ceramic
159

bodies are plastic, ITC has also studied the pressing of non-
plastic materials, which require additives to form highly
compact products, free of defects. Consequently, studies have
been carried out into the influence of different plasticizers(142)
on spray-dried powder characteristics, the development of the
pressing cycle, the presence of defects in green bodies and the
properties of sintered bodies.
A fast and simple way of establishing the porosity of
the ceramic compact is by determining its bulk density. ITC
introduced the bulk density test in industrial ceramic tile
processing as a control parameter, and has investigated and
designed different methods for the industrial bulk density
determination(143-146). Research has followed into the
relationship between bulk density and mechanical strength,
air permeability and liquid sorptivity of green bodies. In this
field, the research results can be classified in two large groups.
First, it was established that the mechanical strength(147-148)
of green bodies needed to be sufficiently high to avoid product
deterioration or breakage during transport in the course of the
following unit operations or process stages; this meant strict
control of green tile compaction(149-153), ensuring there were
no bulk density or moisture gradients in the piece when it left
the press(154-155). Secondly, high air permeability(156-157)
was found to facilitate the subsequent drying operation, while
good liquid sorptivity(158-163) was indispensable for proper
glazing of the green bodies.
3.3 Drying
The drying of green ceramic bodies has been another ITC
field of research.
Drying process kinetics has been studied and
mathematically modelled(164-166). The drying rate has been
related to drying air characteristics(167-168) (temperature,
humidity, speed and direction relative to the body) and to
the characteristics of the green body(169) (thickness, moisture
content and microstructure, using parameters such as porosity,
permeability, tortuosity and pore size distribution).
ITC has also studied the industrial drying operation. An
assembly has been developed for measuring temperature
profiles inside industrial dryers(170). This has led to improved
industrial dryer design(171-172), while industrial drying has
been optimised by reducing running times and enhancing the
technical characteristics of the dried bodies(173). Finally, ITC
has also studied the feasibility of using tunnel dryers at the
entrance of ceramic roller kilns to reduce energy consumption
in sintering, and avoid crack formation in the bodies owing to
rapid drying inside the kiln(174-175).
3.4 Glazing and decorating
ITC research in glazing has focused on engobe and
glaze suspension rheology. The relation of suspension
rheology to applied layer properties(176) and to suspension
properties (composition, particle size distribution, stability,
temperature) has also been extensively studied, in order to
adapt glaze suspension rheology to different new glazing
techniques(177).
Research into the decoration of ceramic bodies has
addressed screen printing ink rheology and the characterisation
of printing screens, in order to suppress defects involving
small colour differences in the finished product, known as
shades(178-182).
160
A. BARBA
3.5 Sintering
As with other ITC research work, research in sintering has
focused primarily on ceramic tile. Research into the thermal
expansion of glasses and bodies, into body temperature
distribution during sintering(183) and into the simulation of
body deformations during sintering(184-186) have yielded
the knowledge required to co-sinter the glaze and ceramic
body, controlling the curvatures and stresses caused by
glass-ceramic body interactions(187-193) and enhancing
finished product quality. The influence of maximum
sintering temperature and dwell time on several sintered
body properties (microstructure(194-196), bulk density, linear
shrinkage, water absorption, dimension stability(197) and
thermal expansion(198)) have also been studied. A further
line of research has focused on determining the causes of
black core formation during sintering and on eliminating
black coring by oxidation. In this regard, oxidation process
kinetics has been modelled, relating the process rate to body
microstructure (porosity, tortuosity and pore size distribution),
organic matter content, thickness of the body, etc.(199-206).
The knowledge gained in tile sintering has enabled optimising
the operating conditions of the roller kiln, which appeared in
the 1980s. This optimisation has also required research into the
influence of several parameters(207-210) (pressure curve(211),
combustion air flow rate(212), measurement of transverse
temperature gradients(213-214), thermal energy transmission
mechanisms(215), etc.) on roller kiln performance. The resulting
optimisation has allowed reducing thermal and electric energy
consumption during sintering(216) and throughout the entire
process(217-220).
In addition to ceramic tile sintering(221-222), ITC has also
undertaken research into the sintering of technical ceramics,
such as ferrites(223).
Finally, studies have been conducted on the resistance
of kiln rollers to thermal shock(224) and to gas and liquid
contamination, which can alter roller composition and
microstructure(225).
3.6 Finishing
Finishing can involve various sintered body treatments:
cutting, grinding and polishing, etc.
Traditional ceramic bodies generally need no finishing
treatment: only a certain type of porcelain tile is polished(226-
227). Thus, ITC has examined the influence of certain polishing
variables (e.g. rotating speed and grit size) on porcelain tile
properties(228-231) (roughness, gloss, microhardness and
apparent porosity). For polishing operation control, ITC has
also developed a method using a pin-on-disk tribometer(232).
4. CHEMICAL REACTION ENGINEERING
Chemical reaction engineering is a classic chemical
engineering subject, which deals with chemical transformations.
ITC research in this area has essentially focused on three
main fields: reactions in glasses, inorganic ceramic pigment
synthesis and ceramic powder synthesis.
Various reactions occurring in glasses have been studied.
Thus, the devitrification mechanism and kinetics of crystalline
phase formation (e.g. diopside(233) and gahnite(234)) from
different oxide glasses have been determined(235). Further
lines of research in this field have addressed the optimum
temperature range for maturing different glasses(236), the
Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005)
FROM CHEMICAL ENGINEERING TO CERAMIC TECHNOLOGY: A REVIEW OF RESEARCH AT THE INSTITUTO DE TECNOLOGA CERMICA
influence of temperature on the formation of crystalline
phases from zirconium-containing glasses(237-241), phase
separation in glasses used in wall tile manufacturing(242-243),
and studies of several heterogeneous glasses(244-246). The
influence of certain glaze additives (e.g. kaolin(247)) on glass
ceramic body reactions(248) and on bubble development in
the glass during sintering(249-251) has also been investigated.
The knowledge gained from this work has enabled improving
the technical and aesthetic properties of glasses used in
ceramic tile manufacture.
Studies have been undertaken on the synthesis of different
inorganic pigments to determine synthesis kinetics (to
establish optimum synthesis conditions) and enhance their
pigmenting strength. A subject of particular attention has
been the synthesis of the black iron-chromium pigment(252-
256), determining the formation reaction mechanism and
the influence of the nature of the constituent raw materials,
oxide composition, raw materials particle size distribution,
temperature and dwell time on the kinetics, and on the Lab
coordinates of the resulting colour.
The formation kinetics of other types of ceramic powders,
such as ferrites, has also been studied(257).
5. FINISHED PRODUCTS
ITC research in ceramic finished products has focused on
three aspects: i/ determining the most important properties
of different products (ceramic tile, glazes, frits, pigments, etc.)
with a view to ensuring their suitability for intended use(258),
ii/ developing and/or adapting characterisation techniques
for determining the aforementioned properties, and iii/
studying defects stemming from the manufacturing process
(mixing defects, forming defects, drying defects, sintering
defects, planarity defects, efflorescence, laminations, etc.).
Furthermore, key properties have been determined of
ceramic tile(259-261), porcelain tile(262-266), engobes
(the influence of plastic materials has been studied(267)),
glazes(268), glasses (hardness(269-272), mechanical
properties(273-274), opacification(275-277), transparency(278),
gloss(279-281), abrasion resistance(282-286), porosity(287),
chemical resistance(288)), earthenware(289), pigments (their
stability in different ceramic frits has been tested(290-291)),
roofing tiles and bricks (quality(292) and frost resistance(293-
295)). Other research lines have dealt with the influence
of printing screen open area and thickness on ceramic tile
colour(296) and, in the case of ferrites, the influence of bulk
density and microstructure on magnetic permeability(297).
Several methods have been developed and fine-tuned for
determining the chemical composition of traditional(298-303)
and technical(304) ceramics, frit sealing temperature(305),
mechanical properties of bodies(306-307), fracture toughness
of glasses(308), ceramic tile scratch hardness(309-311), ceramic
tile wear processes(312) and efflorescence(313).
Finally, defects in finished products(314-317) have been
analysed and their origin identified, in order to try to suppress
such defects. Defects have been studied and classified in terms
of the manufacturing process stage involved (mixing(318-
319), forming(302-321), drying(322), glazing(323-324),
decorating(325) and sintering(326-329)), relation to impurities
in raw materials(330-331), and defects occurring concurrently
in different manufacturing process stages (curvatures(332-
333), laminations(334-336), planarity(337), fracture(338),
efflorescence(339-340) and shades(341)).
Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005)
6 . ENVIRONMENT AND ECONOMY
Two items usually included in the field of chemical
engineering are the economics of the manufacturing process,
and the latters relation to the environment.
In the last fifteen years, ITC has done extensive work on
the eco-relationship of the traditional ceramic industries(342-
345). An important line of research has dealt with waste
characterisation and measurement, with the development of
methodologies for this purpose(346-347), focusing on liquid
effluents(348), solid wastes(349-350) and gas emissions(351-
353). Other studies have addressed waste management(354-
356): this has led to the reuse of solid wastes and liquid effluents
in the traditional ceramic manufacturing process(357-359),
and cleaning of gas emissions(360-362). Particular attention
has been devoted to waste immobilisation(363-364) and the
behaviour of immobilised wastes, studying their leaching
kinetics(365-366). Regulatory and pollution prevention
requirements, as well as eco-management issues, have also
received due attention(367-371).
Finally, work by ITC has also addressed energy saving(372-
374) and cost effectiveness(375-376).
7. SOME FINAL REFLECTIONS
The research done in Ceramic Technology or Ceramic
Engineering has involved applying Chemical Engineering
principles to ceramic manufacturing processes, and has
encompassed the entire spectrum of the ceramic process: raw
materials, unit operations, chemical reaction engineering,
finished products, etc.
The understanding acquired in these fields and the
industrial implementation of this knowledge has brought the
technology currently being used in the manufacture of ceramics
and, particularly, of traditional ceramics, to a highly developed
stage. Further research will foreseeably lead to relatively minor
technological improvements; thus, evolutionary research will
solely give rise to incremental technological developments.
Only if the technology used in certain fields alters radically,
can the technology of traditional ceramic manufacturing
processes be expected to change substantially; this will require
so-called revolutionary research, which means undertaking
high-risk research with long-term results.
The following potential fields of revolutionary research in
traditional ceramic manufacturing processes are only briefly
outlined as examples:
1. Raw materials: development of new compositions.
2. Unit operations: development of new techniques
in sintering (microwaves), decorating (ink jet printing,
rotogravure, flexography, and laser) and finishing (glazed tile
polishing).
3. Chemical reaction engineering: development of new
glasses (oxynitrides) and colours (soluble colours).
4. Finished products: developing products with new
properties and functions, such as glass tiles, smart products,
self-cleaning products or safe products.
5. General aspects of the whole process: development of
a new process for manufacturing ceramic materials; process
optimisation (reducing costs and minimising wastes); energy
and eco-improvements (reducing environmental impacts by
implementing Best Available Techniques (BAT) for air, water
and waste treatment, reducing gaseous emissions, liquid
effluents and solid wastes, saving energy and water).
161

However, ITC staff training in Chemical Engineering
enables ITC to position its research work within a broader
frame than that of purely traditional or technical ceramic
manufacturing processes.
Indeed, every unit operation is governed by a few basic
laws in the field of transport phenomena, which include
momentum transfer, energy transfer (conduction, convection
and/or radiation) and mass transfer. Knowledge of transport
phenomena is one of the cornerstones of Chemical Engineering.
Consequently, ITCs prospective research in this field could
consist of improving the unit operations of current ceramic
manufacturing processes (for traditional as well as for technical
ceramics), or of investigating new unit operations that might
be incorporated into these processes or, even, of studying the
application of ceramic unit operations to other manufacturing
processes in which powders are processed: certain chemicals,
pharmaceuticals, metals, foods, etc.
Similar remarks are applicable to ITC research in
chemical reaction engineering, another keystone of Chemical
Engineering. Basic laws governing chemical reactions are
found in thermodynamics and kinetics. ITCs prospective
research could address not only solid-solid or devitrification
reactions (very common in traditional and technical ceramics),
but also any other kind of chemical reaction.
Other fields, such as process engineering, environmental
engineering or energy efficiency are typical branches of
Chemical Engineering.
Finally, ITC research has an essentially open outlook,
because Chemical Engineering is a powerful tool for studying
any chemical process from an engineering point of view
and, particularly, processes that handle solids (such as
ceramics and others). The specific future research lines that
might be envisaged will depend on the evolution of ceramic
manufacturing facilities and of the socioeconomic context in
which ITC and Universitat Jaume I of Castelln are located.
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Recibido: 10.01.05
Aceptado: 30.03.05
Bol. Soc. Esp. Ceram. V., 44 [3] 155-168 (2005)
 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
A R T I C U L O

Reversal mechanisms and interactions in magnetic systems:

coercivity versus switching field and thermally assisted
demagnetization
F. CEBOLLADA,A) J.M. GONZLEZ,B) J. DE FRUTOSC) AND A.M. GONZLEZA)
a)
Departamento de Fsica Aplicada a las Tecnologas de la Informacin, EUIT de Telecomunicacin, Universidad Politcnica de Madrid,
Cra. de Valencia, Km 7, 28031 Madrid, Spain.
b)
Instituto de Ciencia de Materiales de Madrid - CSIC, 28049 Cantoblanco, Madrid, Spain, and Instituto de Magnetismo Aplicado, RENFE-UCM,
Pinar de las Rozas, Madrid, Spain.
c)
Departamento de Fsica Aplicada a las Tecnologas de la Informacin, ETSI de Telecomunicacin, Universidad Politcnica de Madrid,
Ciudad Universitaria s/n, 28040 Madrid, Spain

In this paper we present a comparative analysis of the magnetic interactions and reversal mechanisms of two different
systems: NdFeB-type alloys with grain sizes in the single domain range and Fe-SiO2 nanocomposites with Fe concentrations
above and below the percolation threshold. We evidence that the use of the coercivity as the main parameter to analyse
them might be misleading due to the convolution of both reversible and irreversible magnetization variations. We show that
the switching field and thermally assisted demagnetization allow a better understanding of these mechanisms since they
involve just irreversible magnetization changes. Specifically, the experimental analysis of the coercivity adquisition process
for the NdFeB-type system suggests that the magnetization reversal is nucleated at the spin misalignments present due to
intergranular exchange interactions. On the other hand, the study of the magnetic viscosity and of the isothermal remanent
magnetization (IRM) and direct field demagnetization (DCD) remanence curves indicates that the dipolar interactions are
responsible for the propagation of the switching started at individual particles.

Keywords: magnetization reversal, coercivity, switching field distribution, magnetic interactions, magnetic viscosity.

Mecanismos de inversin de la magnetizacin e interacciones en sistemas magnticos: campo coercitivo versus campo
de conmutacin y desimanacin trmicamente asistida

En este artculo presentamos un anlisis comparativo de la influencia de la microestructura a travs de las interacciones
magnticas en los mecanismos de inversin de la magnetizacin en dos sistemas diferentes: aleaciones tipo NdFeB con tamaos
de grano en el rango de monodominio y nanocompuestos de Fe-SiO2 con concentraciones de Fe tanto por encima como por
debajo del umbral de percolacin. Ponemos de manifiesto que el uso del campo coercitivo como parmetro de anlisis puede
llevar a equvocos debido a la coexistencia de variaciones reversibles e irreversibles de la magnetizacin. Tambin mostramos
que el campo de conmutacin y la desimanacin trmicamente asistida permiten una mejor comprensin de dichos
mecanismos ya que reflejan exclusivamente cambios irreversibles de imanacin. Concretamente, el anlisis experimental del
proceso de adquisicin de coercitividad de los sistemas tipo NdFeB sugiere que la inversin de la magnetizacin se nuclea
en los desalineamientos de los espines debidos a las interacciones de canje intergranular en las fronteras de grano. Por otra
parte, el estudio de la viscosidad magntica y de las curvas de remanencia isoterma (IRM) y de remanencia de desimacin
DC (DCD) de los nanocompuestos de Fe-SiO2 indica que las interacciones dipolares son responsables en este sistema de la
propagacin de la conmutacin, que se genera en partculas individualmente consideradas.

Palabras clave: inversin de la magnetizacin, coercitividad, distribucin de campos de conmutacin, interacciones magnticas, viscosidad
magntica.

1. INTRODUCTION

The hysteresis (extrinsic) properties of magnetic materials
are strongly dependent on their particular microstructures.
The improvement and versatility of preparation techniques
in the last decades have allowed the production of many
types of high quality magnetic materials, ranging from
metallic systems to different oxides, usually with very well
controlled morphologycal and structural features, even down
to a nanoscopic scale. Among these techniques are ultrarrapid
quenching, sputtering, molecular beam epitaxy, pulsed laser
deposition, etc. New phenomenology has emerged from
these materials, due a combination of factors such as reduced
dimensionality (size and surface effects) and interphase
coupling: oscillatory exchange coupling in multilayers, spin-
dependent scattering effects in multilayers and granular
systems, colossal magnetoresistance, exchange bias across
ferro-antiferromagnetic interfaces, enhanced soft behaviour
of nanocrystalline alloys and hard behaviour of the so-called
spring magnets, giant coercivity of nanoparticulated systems
and configurational anisotropy in nanoelements (1). From
a technological point of view, new devices are springing
associated to this phenomenology, related to magnetic
recording, spintronica (the control of electron current through
spin), magneto electromechanical systems... (2)
One of the main problems for the control of the extrinsic
properties of these new materials lies in the preponderant
role of the magnetic interactions either in their relaxation
behaviour and/or in their hysteresis processes. Exchange
(short ranged) and dipolar (longe range) interactions compete

Bol. Soc. Esp. Ceram. V., 44 [3] 169-176 (2005) 169


in a multiscale problem involving structural features in a
broad range of lengths. The analysis of magnetic interactions
is still a challenging problem due to several factors: (i) the lack
of measurement techniques or probes to analize the values of
the relevant magnetic energies -mainly exchange, anisotropy
and magnetoelastic- in local environments that can be very
different from those of bulk phases (e.g. surfaces, grain
boundaries or interfaces), and that are responsible in many
ocassions for the start of the magnetization reversal; (ii) the
absence of simple predictive theories or models to take into
account the influence of interactions on the magnetization
and relaxation processes; (iii) there are no easy-to-interpret
experimental procedures that can yield direct values of the
strength of the interactions.
In a general scheme, the effect of the interactions on
the behaviour of magnetic systems can be assesed through
their field-dependent magnetization processes (hysteresis)
and through their thermally assisted magnetization-
demagnetization processes (3, 4). In the case of the hysteresis
processes, the interactions may just modify the field sensed
by the regions that trigger the switching of the magnetization
without affecting the reversal mode in itself, although in many
cases they also modify the magnetization switching mode,
leading to mechanisms that require an enterely new approach
for their analysis. In most cases the interactions cannot be
treated in the basis of a mean field approach, this being
specially true when the reversal starts from highly localized
regions of the samples or when the reversal mode is modified
by the interactions. The thermally-assisted magnetization-
demagnetization, as a general idea, yields the range of energies
(involved in the reversal of the regions where the switching
starts) that are accessible to thermal fluctuations along a given
time window (5). The lapse of this time window may vary from
thousands of seconds -for conventional DC magnetization
measurements- to even picoseconds for some spectroscopic
techniques. However, and according to the assertions of the
previous paragraph, the lack of general experimental routines
to directly measure interactions compels us to design the
specific measurement strategy in order to evaluate them,
depending on the particular features of the samples under
study or the experimental techniques available.
In this paper we present a comparison of the analysis
of the magnetic interactions in two systems with different
characteristic structural lengths and reversal mechanisms,
by using techniques related to their hysteresis mechanisms
(remanence curves and similar) and thermally-assisted
demagnetization. We will show first the analysis of a series of
samples consisting of Fe nanoparticles embedded in silica, with
concentrations above and below the percolation threshold.
Then we will present results on the coercivity acquisition of a
set of NdFeB-type alloys with grain sizes in the single domain
range.
2. Fe-SiO2 SYSTEM
The magnetism of nanoparticles is extremely complex
due to a combination of factors. First, the breaking of the
local symmetry at the surface, which represents a significant
percentage of the total particle mass, may give rise to
phenomena such as spin canting or modified local anisotropy
(6). Second, size effects may also become important, specially
for particle sizes of the order of the exchange or magnetostatic
correlation lengths, leading to highly inhomogeneous
170
F. CEBOLLADA,A) J.M. GONZLEZ,B) J. DE FRUTOSC) AND A.M. GONZLEZA)
magnetization distributions inside the particles or to modified
spin-wave spectra. Third, magnetic interactions dependent
on the specific particle shape and size distribution, as well as
on the degree of dispersion of the particles- greatly influence
the hysteresis processes of particulate systems (7).
In the case of Fex(SiO2)1-x nanocomposites, x being the
volume concentration, most authors have reported high
coercivities, well above the maximum theoretical values
associated to switching through coherent rotation (about 180
Oe for an isotropic distribution of particles), even up to about
1.5 kOe at room temperature. The maximum coercivity for
most batches of samples takes place at concentrations about
x=0.3-0.4, sharply decreasing for higher concentrations, and
it cannot usually be correlated with parameters such as the
variation of particle size or shape with concentration (8-10).
This suggests that (dipolar) interactions play a fundamental
role in the magnetization process of this type of composites.
2.1 Experimental
We present some results on the effects of the interactions
in a series of Fex(SiO2)1-x nanocomposites, prepared by ball
milling with concentrations in the range x=0.2-0.6. The average
grain size of the particles, as evaluated through XRD, is 18 nm
almost independent of the concentration and milling time.
Transmission electron microscopy (TEM) studies revealed
the existence of a broad particle size distribution, ranging
from a few nanometers to about 40 nm, in all samples. They
also showed that particle clusters are more frequent in those
samples with concentrations x=0.5 and 0.6, as expected. The
magnetic studies, carried out in an EG&G vibrating sample
magnetometer (VSM) under maximum applied fields of 1T,
showed a maximum in the coercivity and in the remanence-to-
saturation ratio for x=0.3 (Figure 1). The maximum coercivity,
380 Oe, is well above the coherent rotation value (11), in
agreement with most reports in the literature.
Fig. 1.- Concentration dependence of the coercivity for the 60 h milled
(squares) and 48 h milled (triangles) samples, and of the reduced re-
manence (stars) for the 60 h milled sample.
The fact that the coercivity of this set of samples cannot be
correlated with parameters such as grain size or shape lead
us to analyse the role of magnetic (dipolar) interactions in
their switching mechanisms. This we did by comparing the
magnetic viscosity and irreversible processes corresponding
either to the virgin (first) magnetization curve and to the
demagnetization curve. In order to separate the reversible
Bol. Soc. Esp. Ceram. V., 44 [3] 169-176 (2005)
REVERSAL MECHANISMS AND INTERACTIONS IN MAGENETIC SYSTEMS: COERCIVITY VERSUS SWITCHING FIELD AND THERMALLY ASSISTED DEMAGNETIZATION
processes from the irreversible, remanence curves were used
due to the fact that upon application and subsequent removal
of a given field only irreversible changes in the magnetization
are measured. More specifically, the well known Isothermal
Remanent Magnetization (IRM) and DC Demagnetization
remanence (DCD) curves were employed to measure the sign
and intensity of the interactions (12). The IRM plots result from
the measurement of the remanence Mr(H) upon application
and removal of a field H in a previously demagnetized sample
and goes from 0 to Mrmax; Hm is the field required to reach the
maximum remanence while H1/2 is the magnetization process
mean swithing field, i.e. the field required to achieve half
the maximum remanence. The DCD curves also result from
remanence measurements but by starting from a previously
saturated state and applying negative fields, Mr thus varying
from +Mrmax to -Mrmax; in this process H1/2 (absolute value) is
the mean switching field, i.e. the field required to get null
remanence (switching 50% of the sample). It is important to
note that the mean switching field is the equivalent to the
coercivity when just irreversible processes are considered, in
contrast to the conventional coercivity, which includes both
reversible and irreversible magnetization processes. From
these curves, the irreversible susceptibility irr and switching
field distribution SFD can be calculated as
irr= dMr(H)/dH,
SFD= d[Mr/Mr max]/dH (magnetization)
Fig. 2.- Switching field distributions for the magnetization (a) and de-
magnetization (b) processes.
Bol. Soc. Esp. Ceram. V., 44 [3] 169-176 (2005)
and
SFD= d[Mr/2Mr max]/dH (demagnetization), (2b)
and the M plots can be obtained from the equation
M(H)= mDCD(H) - [1-2mIRM(H)] (3)
where mIRM (mDCD) is the IRM (DCD) remanent magnetization
for a given field H, normalised to Mrmax. Positive (negative)
M values indicate that the magnetization process from
an initially demagnetized state is softer (harder) than the
demagnetization from saturation, which is usually associated
with magnetizing (demagnetizing) interactions.
The SFDs corresponding to the magnetization process
from the demagnetized state, shown in Figure 2(a), evidence
broad distributions with a long tail up to almost 3 kOe. An
important feature is that very large fields are required to
switch most of the particles: the peaks of the distributions
vary between 610 and 820 Oe and mean switching fields H1/2
about 1 kOe were obtained. The width of the distributions
and H1/2 increase with decreasing concentration (Figure 3), in
(1)
(2a)
Fig. 3.- Mean switching fields for the magnetization (H1/2) and demag-
netization (H1/2) processes, as a function of concentration; peak widths,
also as a function of concentration, for the magnetization (HIRM) and
demagnetization (HDCD) processes, respectively.
Fig. 4.- M curves for the different samples.
171

contrast to the maximum coercivity being obtained at x=0.3.
The SFDs corresponding to the demagnetization process, as it
can be seen in Figure 2(b), exhibit basically the same features
but shifted to lower fields, as evidenced by the lower values of
the mean switching fields H1/2. The only noticeably difference
is that the demagnetization starts practically from null fields,
which suggest the presence of strong local demagnetizing
fields at remanence. As a general idea, no qualitative changes
with concentration x are observable in both SFD types, which
suggests that there is no change in the switching mechanism
for concentrations near the percolation threshold (xp~0.5).
The M curves, obtained from the remanence curves, are
presented in Figure 4 and evidence negative (demagnetizing)
interactions whose intensity increase with concentration, as
expected. Again, no qualitative differences are observed for
concentrations, respectively, below and above the percolation
threshold.
In order to gain insight into the switching mechanism, the
magnetic viscosity S of the samples was analysed along both
the magnetization and demagnetization processes. Magnetic
viscosity can be obtained from the evolution of magnetization
with time at constant applied field as:
S=-dM/d[Lnt]. (4)
Fig. 5.- Viscosity as a function of the applied eld for the samples with
x=0.3 and x=0.6, for the magnetization (a) and demagnetization (b)
processes, respectively.
172
F. CEBOLLADA,A) J.M. GONZLEZ,B) J. DE FRUTOSC) AND A.M. GONZLEZA)
The activation volume va corresponds to the volume of the
regions of the sample that are susceptible of being reversed by
means of thermal fluctuations, in the time window defined in
the experiment (in this case, the measuring lapse of time, about
2000 s). In other terms, it is a measure of the energy barriers
involved in the reversal mechanism, by considering that this
energy is somewhat proportional to the activation volume
times the effective anisotropy in that region. The activation
volume can be calculated from the following expression
Va=kBTirr/oSmaxMs (5)
where Smax is the maximum viscosity of a given sample (5).
Figure 5 shows the field dependence of the viscosity for
the x=0.3 and x=0.6 samples, for the magnetization (a) and
demagnetization processes (b). From the figure it is evident
that the maximum viscosity occurs at fields very close to their
respective mean switching fields, H1/2 and H1/2. The activation
volumes calculated from these curves yield particle diameters
that are in the range from 15 to 18 nm, which are very close to
the grain size obtained from the XRD data.
2.2 Discussion
In this work we have studied the switching mechanisms of a
set of Fe-SiO2 nanocomposites. Although the coercivity exhibits
a maximum at x=0.3, it cannot be correlated with any observed
variation of particle size or shape or any other parameter in
our samples; in fact many authors have observed a maximum
at similar concentrations in sets of particles characterized
by narrow size distributions of equiaxed particles (8-10). We
must point out that the coercivity, taken as the field (absolute
value) required to attain null magnetization in a previously
saturated sample, is not a suitable parameter to analyse
in detail the (irreversible) switching mechanisms because
it involves both reversible and irreversible magnetization
variations. We believe that the analysis of the irreversibilities
is a more significant approach, from the point of view of the
switching mechanisms. In particular, the real coercivity of
our samples -evaluated through the mean switching fields
H1/2 and H1/2- evidences a monotonic increase with decreasing
concentration, which shows that the maximum coercivity at
x=0.3 is an artefact that is not relevant for the analysis of their
reversal mecanisms. In addition to this, the narrower SFDs
for high Fe concentrations indicate that a higher percentage
of the particles reverse their magnetization in a coupled way
for these concentrations. From these data it is apparent that
the reversal mechanism is specifically ruled by the magnetic
(dipolar) interactions. The analysis of the SFDs and M curves
have evidenced that it is harder to magnetize a demagnetized
sample that a previously magnetized sample. This can be due
to the tendency of the particles to form closed flux structures;
this structures, present in the demagnetized state, are dificult
to break and lead to high switching fields (note that the
magnetization SFDs are almost null for H=0). On the other
hand, when coming back to zero field from a saturated state,
the spontaneous tendency to form closed structures even at
zero or very low negative fields makes the demagnetization of
the samples very easy and explains why the demagnetization
SFDs present maxima close to H=0. To complete this picture,
the size of the regions involved in the triggering of the reversal
process calculated from viscosity measurements- is very
close to the mean particle size. This suggests that although the
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REVERSAL MECHANISMS AND INTERACTIONS IN MAGENETIC SYSTEMS: COERCIVITY VERSUS SWITCHING FIELD AND THERMALLY ASSISTED DEMAGNETIZATION

dipolar interactions may propagate the reversal of groups of

coupled particles, it is started for individual particles.

3. NdFeB-TYPE ALLOYS

3.1 Coercivity acquisition process

NeFeB-type alloys are hard magnets based on the R2Fe14B

phases (R= Nd, Pr, Dy, etc.) with anisotropy fields of the
order of 10 T. Suitable microstructures in these magnets yield
coercivities well above 1 T, leading to the most successful family
Fig. 7.- Sketch of the coercivity acquisition process in an inhomogene-
of hard magnets in the last two decades (13). Many of these
ous environment.
alloys, with grain sizes in the range from tens of nanometers
to a few microns, present magnetization curves from the
is the field required to -starting from the demagnetized state-
reach a remanence Mr1/2=Mr max/2, that is to make coercive
50% of the grains involved in the first step. This coercivity
acquisiton process takes place in a more or less homogeneous
environment, with the average magnetization pointing in the
positive direction, except for those grains that were already
coercive (those involved in the second magnetization step,
whose average magnetization is still null).

(ii) inhomogenous environment

Starting fom Mr1/2, i.e. with 50% of the initially soft grains
already coercive, we apply negative fields, as shown in Fig. 7.
After applying a field -H1/2 and removing the field a remanence
equal to Mr1/2/2 is obtained, which indicates that we have
reversed 50% of the yet soft grains (i.e. 25% of the initially soft
Fig. 6.- Sketch of the virgin magnetization curve of a NdFeB-type mag- grains). If the applied field, starting again from Mr1/2, is Hm the
net, showing two high susceptibility steps. remanence after removing the field is now null. Hm is the field
required to make coercive all the remaining soft grains (50% of
demagnetized state (virgin curves) that are characterized by the initially soft grains). The difference is that in this process
two high susceptibility steps, the first one occurring at low we have been dealing with low magnetization, about zero, this
fields, and the second one at high fields, close to the (absolute) reflecting an inhomogeneous environment, with many grains
value of the critical field (the field at which the maximum of pointing in either positive and negative direction.
the susceptibility takes place in the demagnetization curve)
(14). Fig. 6 shows a sketch of a typical magnetization curve;
TABLE I. SAMPLES COMPOSITION AND PREPARATION PARAMETERS
for fields above Hm all the soft grains involved in the first
reversal step are now coercive and, if the field is reversed back
from Hm, values close to the critical field are required to switch
their magnetization (dotted curve in Fig. 6). Sample Composition Preparation Anneal
Mechanical
A Nd13.6Dy2.4Fe76B8 700oC, 30 min
Alloying
(i) homogeneous environment
B Nd12Dy3Fe76B9 Melt spinning 700oC, 30 min
The remanence Mr max measured after taking the field to Hm
in the virgin curve represents that of the initially soft grains, C Nd9Pr6Fe76B9 Melt spinning -
i.e. those involved in the first magnetization step. The field H1/2 D Nd6Pr9Fe76B9 Melt spinning 580oC, 15 min

TABLE II. COMPARISON OF THE FIELDS REQUIRED TO REVERSE 50% OF THE GRAINS IN A HOMOGENOUS (H1/2) AND INHOMOGENEOUS (H1/2) ENVIRONMENT IN ISOTROPIC
AND ORIENTED SAMPLES (14), BOTH IN T AND REDUCED TO THEIR RESPECTIVE SATURATION MAGNETIZATION VALUES.

Sample Composition M (T) H (T) H (T) H /M H /M

0 S 0 1/2 0 1/2 1/2 S 1/2 S

A (iso) Nd Dy Fe B 1.47 0.34 0.76 0.23 0.52

13.6 2.4 76 8

B (iso) Nd Dy Fe B 1.24 0.3 0.83 0.25 0.69

12 3 76 9

C (iso) Nd Pr Fe B 1.55 0.4 0.95 0.26 0.61

9 6 76 9

D (iso) Nd Pr Fe B 1.5 0.4 0.8 0.27 0.53

6 9 76 9

OR1* Pr Fe B 1.29 0.61 1.93 0.47 1.5

17 75 8

OR2* Pr Fe B 0.45 0.8 1.8 1.77 4

17 75 8

OR3* NdFeB 1.29 0.87 1.89 0.67 1.47

OR4* NdFeBV 1.29 0.75 2.05 0.58 1.59

Bol. Soc. Esp. Ceram. V., 44 [3] 169-176 (2005) 173


3.2 Experimental results and discussion
Our samples were prepared by out-of-equilibrium
techniques (mechanical alloying and melt spinning) and
submitted to thermal annealing to crystallize them (except
sample C, that was already crystalline in the as-quenched
state). Table 1 shows the compositions and preparation
parameters of all of them. The microstructure of all samples
was characterized by an homogeneous isotropic distribution
of grains of the hard 2:14:1 phase with sizes of about 150-200
nm, well below the single domain size for these alloys (15),
as evidenced through XRD and SEM studies. In all cases the
percentage of grains with sizes above about 400 nm is less tan
5%.
Fig. 8.- Initial magnetization curves and demagnetization curves of NdFeB type samples.
174
F. CEBOLLADA,A) J.M. GONZLEZ,B) J. DE FRUTOSC) AND A.M. GONZLEZA)
The virgin and demagnetization curves were measured
in an induction device based on a 12 T superconducting
coil and, as it can be seen in Fig. 8, exhibit the low field,
high susceptibility region. By following the measurement
procedures to analyse the acquisition of coercivity already
described for either a homogeneous or inhomogeneous
environment, the fields H1/2 and H1/2 were obtained. Table 2
shows values of the saturation magnetization, of H1/2 and H1/2,
and of H1/2 and H1/2 normalized to Ms, for our samples and for
a set of oriented samples from other authors (14), prepared by
sintering and with grain sizes of the order of 1 m. As it can be
seen, quite homogeneous values are obtained for H1/2 and H1/2
for the isotropic samples and also for the oriented ones.
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REVERSAL MECHANISMS AND INTERACTIONS IN MAGENETIC SYSTEMS: COERCIVITY VERSUS SWITCHING FIELD AND THERMALLY ASSISTED DEMAGNETIZATION

The field required to achive coercivity in 50% of the grains

is about 2 to 3 times larger for an inhomogeneous environment
than for a homogeneous one, independent of the samples
being isotropic or oriented. However, when comparing
isotropic and oriented samples, values systematically twice
larger, approximately, are observed for the oriented ones.
An important issue is that sample OR2, whose saturation
magnetization is really different from the rest of the samples,
still presents quite similar values of H1/2 and H1/2.
The fact that the acquisition of coercivity is more difficult
to achive in inhomogeneus environments could be explained
if we consider that dipolar fields rule this process. In an
inhomogeneous environment a large amout of poles and high
stray fields are expected, associated with many discontinuities
in the magnetization across the grain boundaries. However,
in this case we should expect that the values obtained for the
isotropic environment are larger than those of the oriented
ones, which is not the case. In addition to it, it is obvious that
sample OR2 shows that the field required to achive coercivity
can not be correlated with the saturation magnetization; Fig. 9.- Reduced switching field as a function of the exchange-to-ani-
this sample, with an excess B content, has a saturation sotropy ratio for an intergranular exchange coupling equal to 80% the
magnetization that is roughly one third that of the rest of bulk value.
the samples, but it still has similar H1/2 and H1/2 values. This
leads us to believe that the dipolar fields, although they must
be present and contribute to the internal field sensed by the
grains during the coercivity acquisition process, do not rule
the coercivity acquisition process, i.e. a different mechanism
must be responsible for the reversal of the grains.
The role of exchange coupling across the grain boundaries
in the magnetization-demagnetization process of NdFeB and
similar alloys has been the object of a lot of works, many
of them devoted to simulation, and it is considered to lie
in the origin of the fact that the field required to switch
their magnetization is one order of magnitude below the
initially expected value, i.e. the anisotropy field HK (16-18). In
particular, intergranular exchange couplig becomes extremely
important in nanocrystalline (spring) magnets, for which the
exchange length (basically the length of a domain wall, which
for these magnets is a few nanometers) is of the order of the
grain size; this yields a more homogeneous magnetization
distribution and, consequently, enhances their remanence,
but, as a countereffect, it decreases their coercivity (19).
Regarding intergranular exchange coupling, it is expected
to be smaller than the intragranular (bulk) exchange, due to
the lattice distortion across the boundary. However, different
simulation jobs have evidenced that the wall-like structure
appearing at it acts as a nucleation site for the magnetization
reversal, yielding coercivity values in the correct order of
magnitude if the boundary exchange is a few tens percent of Fig. 10.- Model of magnetization and demagnetization processes
the bulk value (16-18). As en example, Figure 9 presents the of NdFeB type alloys, based on avalanches due to intergranular ex-
switching field HS required to reverse the magnetization of a change coupling.
grain with a neighbouring grain with (initially) antiparallel
magnetization, for an intergranular coupling of 80% the bulk for the main features of the magnetization and demagnetization
value and for different values of the exchange-to-anisotropy process: in an initially demagnetized sample there are always
ratio. Reasonable values of this ratio are in the order of unity grains with antiparallel neighbours that can be reversed at
(it is close to 2 for the Nd2Fe14B phase). Switching field values low fields, leading to an avalanche process. If the reversal is
are in the order of 0.05 to 0.2HK. It is important to note that not complete, the process is more or less reversible; however,
if both grains present parallel magnetization, the switching if the reversal is fully achieved (e.g. in the demagnetiation
field (to reverse both) rises again to values about HK. This of a previously saturated sample) no antiparallel grains are
intergranular exchange based mecanism (see Fig. 10) accounts available for triggering a low field reversal.

Bol. Soc. Esp. Ceram. V., 44 [3] 169-176 (2005) 175


4. CONCLUSSIONS
We have analysed in this paper the role of interactions
on the switching mecanisms of two types of magnets
ruled, respectively, by dipolar and integranular-exchange
interactions. In both cases a strategy was used based on
the comparison of the evolution of the magnetization and
demagnetization processes with a variable parameter, Fe
concentration and MS for the Fe-SiO2 composites and the
NdFeB-type magnets, respectively. We have also shown that,
from the point of view of the switching mechanisms the SFDs,
obtained from remanence measurements, are clearly more
significant than coercivity.
In the particular case of the Fe-SiO2 composites, our
results clearly suggest that closed flux structures present in
the demagnetized state are responsible for the high switching
fields required to magnetize the samples. The reversal in these
samples is triggered by individual particles and propagated
by dipolar interactions, irrespectively of the Fe concentration
being either above or below the percolation threshold. In
the case of the NdFeB-tpe magnets, we have shown that
intergranular exchange accounts for most of the features
observed in the high susceptibility regions of demagnetized
samples as well as for the higher fields required to reverse
previously saturated samples.
REFERENCES
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Hadjipanayis and G.A. Prinz (eds.), Plenum Press, New York, 1991.
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Co/Ni multilayers, J. Magn. Magn. Mater. 242-245, 518-520 (2002).
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and M. P. Morales, Magnetic behaviour and percolation in mechanically
alloyed Fe-SiO2 granular solids, J. Magn. Magn. Matter. 221, 207-214
(2000).
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Mater, Thermally activaed demagnetization in Fe-SiO2 granular solids,
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Papaefthyomiou, Effect of preparation conditions on the hysteresis
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Recibido: 10.01.05
Aceptado: 07.04.05
Bol. Soc. Esp. Ceram. V., 44 [3] 169-176 (2005)
 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
A R T I C U L O

Magnetoelectric phenomena in single-phase

and composite systems

LILIANA MITOSERIU1,2
1
Dept. of Solid State and Theoretical Physics, Al. I. Cuza Univ., Bv. Carol 11, Iasi 700506, Romania, e-mail: lmtsr@uaic.ro
2
Dept. of Chem. & Process Eng., Univ. of Genoa, P.le Kennedy, I-16129 Genoa, Italy

In the present review, the main phenomenology and problematic related some of the most interesting magnetoelectric
systems (materials having in the same phase magnetic and ferroelectric order and interaction between them, giving rise to
the magnetoelectric effect) is presented. Some single-phase systems as manganites, BiFeO3 and relaxor magnetoelectrics
mainly interesting from a fundamental point of view, as well as diphasic composites with a high potentiality in applications
are discussed. The coupling between ferroelectric and magnetic activity in magnetoelectric multiferroics opens the possibility
of controlling magnetic properties through electric fields and vice versa, giving to these materials a large potentiality for
applications in spintronics, multiple state memory elements or novel memory devices which might use electric and/or
magnetic fields for read/write operations.

Key Words: Magnetoelectric, Multiferroic, Manganites, BiFeO3, Relaxor, Composite.

Fenmenos magnetoelctricos en sistemas monobsicos y composites

Resumen: En esta revisin, se presentan la fenomenologa y principales problemas relacionados con los sistemas
magnetoelctricos ms interesantes. En el efecto magnetoelctrico el orden magntico y ferroelctrico se dan en una misma
fase con interaccin entre ellos. Se abordan sistemas monobsicos como manganitas, BiFeO3 y magnetoelctricos relaxores y
composites difsicos que poseen tanto un inters desde el punto de vista fundamental como un alto potencial de aplicaciones.
El acoplamiento entre la actividad ferroelctrica y magntica en multiferricos magnetoelctricos abre la posibilidad de
controlar las propiedades magnticas a travs de campos elctricos y viceversa, dotando a estos materiales de numerosas
aplicaciones en espintrnica, elementos de memoria de estados mltiples o novedosas aplicaciones de memoria que pueden
emplear campos elctricos y/o magnticos en operaciones de lectura/escritura.

Palabras clave: magnetoelectrico, multiferrico, manganitas, BiFeO3, relaxor, composite

1. INTRODUCTION

Multifunctional or smart materials combining several accompanied by hysteresis). Ferroelectrics, ferromagnetics

properties in the same structure in order to produce new or
enhanced phenomena have stimulated much scientific and
technological interest within the scientific community in the last
years. One of the most interesting categories of multifunctional
systems is the magnetoelectrics, i.e. materials showing
magnetoelectric effects. Having simultaneous magnetic
and ferroelectric activity, possible attractive functionalities
caused by the interactions between electric polarization and
spontaneous magnetization can be envisaged. The primary
magnetoelectric (ME) effect is defined by the appearance
of an electric polarization under a magnetic field P(H): ME
output or a magnetization at the application of an electric
field M(E): EM output. The ME of second order (or secondary
ME) consists on variation of the permittivity under magnetic
field (H) or the magnetic permeability at the application of an
electric field (E). Materials exhibiting ME properties can be
single-phase and composites (di- or poliphasic systems).
A ferroic system has an order parameter switchable by
an adequate driving force or field (phenomena normally
and ferroelastics are typical examples of ferroics. The electric
polarization, magnetic moment and strain can be switched
from one ordered state to the opposite one by means of an
electric, magnetic or stress field, respectively. If the same
system possess two or more ferroic properties in the same
phase, is named multiferroic (1.-). Thus, the magnetodielectrics
are multiferroic materials.
The history of the ME effect dates back to early 1894,
when Pierre Curie stated that it would be possible for
an asymmetric crystalline body to polarize directionally
under the influence of a magnetic field (2.-). Based on
crystal symmetry considerations, Landau and Lifshitz (3.-)
demonstrated that a linear ME can occur in magnetically
ordered crystals, while Dzyaloshinskii (4.-) predicted the
existence of the ME effect in antiferromagnetic Cr2O3. This was
the first system proved as showing ME coupling, measuring
the electric field induced magnetization (5.-) or detection of
the magnetic field-induced polarization (6.-). One of the first
prepared ferromagnetic ferroelectric material was the weakly

Bol. Soc. Esp. Ceram. V., 44 [3] 177-184 (2005) 177


ferromagnetic nickel iodine boracite, Ni3B7O13I (7.-). Following
many more multiferroic boracite compounds with the general
formula M3B7O13X, where M is a bivalent cation of Mg2+, Cr2+,
Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, etc. and X a monovalent anion
like OH, F, Cl, Br, I or NO3, all of them having complex ferrielectricity and ferro/antiferro/ferri-magnetism), the ME
structures with many atoms per formula unit and more than
one formula per unit cell were synthesized. The large number
of inter-ionic interactions in the boracites prevented isolation
of the essential factors causing multiferroicity and of the nature
of the coupling between the magnetic, electric polarization
and structural order parameters. The simultaneous presence
of ferroelectricity and ferromagnetism in coexistence with
ferroelasticity in nickel boracite Ni3B7O13I activates coupling
between the spontaneous polarization, spontaneous
magnetization and spontaneous deformation. It has been
found that a field-induced 180 reversal of the spontaneous
polarization causes a symmetry-conditioned 90 reorientation
of the spontaneous magnetization (and reciprocally: a
magnetic field-induced 90 reorientation of the spontaneous
magnetization causes a 180 reversal of the spontaneous
polarization) (8,9.-). Another class of early discovered ME
materials are the antiferromagnetic-ferroelectrics perovskite
ceramics Pb(Fe1/2Nb1/2)O3 (PFN) (10.-) and Pb(Fe1/2W1/3)O3,
PFW (11.-). Later single-crystals of PFN were grown and the
presence of a weak spontaneous moment in the ferroelectric
phase below 9 K was confirmed (12.-). The ME effect has
been found in numerous compounds in the last few decades
(13,14.-), in materials with the perovskite structure, rear-earth
manganites, yttrium iron garnets, pseudo-ilmenites, BaMeF4
(Me = Mn, Fe, Co, Ni), Cr2BeO4 and inverted spinels (14,15).-.
The discovery of a linear ME effect in the antiferromagnetic-
ferroelectric BiFeO3 (16.-) and in its solid solutions with
Bismuth or Barium titanate led to a new class of ME in which
the ferroelectric and magnetic phases coexist up to high
temperatures (17-21.-). Among the single-phase ME materials,
particularly strong ME effects, as initially envisioned, have not
so far been measured, so that they have not yet found large
scale applications in technology. In order to increase the ME
response, a large number of di- or polyphasic composites in
various forms have been investigated, as summarized by Ryu
et al. (14.-).
The primary requirement for the observance of ME effect is
the coexistence of magnetic and electric dipoles. Single-phase
materials exhibiting ME effect have an ordered structure
and require the presence of a ferroelectric/ferrielectric/
antiferroelectric state. They are described by both a dipolar
(electric) and a magnetic order parameter. These materials
should show two types of phase transitions: one from
ferroelectric to paraelectric state and the other one from
a magnetic ordered state (ferromagnetic/ferrimagnetic/
antiferromagnetic) to a non-ordered paramagnetic state. The
ME effect arises due to the local interaction between the
ordered magnetic and ferroelectric sublattices. The conditions
for the occurrence of ferroelectricity and magnetic order
in the same material requires: (i) the presence of adequate
structural building blocks permitting ferroelectric-type ionic
movements, i.e. off-centre displacement associated to the
spontaneous polarization in ferroelectrics, (ii) magnetic-
interaction pathways for the magnetic order, usually of the
superexchange type, and (iii) to satisfy symmetry conditions
(14.-).
To be technologically viable, ME materials must exhibit
high ME coefficients, so that an intense activity was dedicated
to look for new materials or structures in order to enhance the
178
LILIANA MITOSERIU
ME effect. The possible applications include magnetic-electric
sensors in radioelectronics, optoelectronics and microwave
electronics and transducers in instrumentation. Apart
from the properties of the parent phases (ferro/antiferro/
effect adds a supplementary freedom degree in designing
materials for new applications. The coupling between the
ferroelectric and magnetic activity in multiferroics opens the
possibility to manipulate the magnetic properties through
electric fields and vice versa, giving to these materials large
potentiality for applications in spintronics, multiple state
memory elements or novel memory devices which might use
electric and/or magnetic fields for read/write operations.
Although highly exciting for potential applications the single-
phase magnetodielectric multiferroism is quite rare, being
restricted to only few systems. Although a young topic, the
ME multiferroism already put to the scientific community very
interesting problems from the point of view of fundamental
physics, due to the apparent opposite requirements concerning
to the d-orbital occupancy for ferroelectric and magnetic order
(N.A. Hill and A. Filippetti, Why are there any magnetic
ferroelectrics?(9.-). Recently a few different mechanisms have
been proposed to explain these contradiction and to find the
possible compatibility of the two types of orders (22-24.-).
2. SINGLE-PHASE SYSTEMS
2.1. Manganites: RMnO3 and RMn2O5.
The interest in investigating the manganites appeared
after the discovery of the colossal magnetoresistance in
(La,Ca)MnO3 (26,27.-). The majority of the recent research has
focused on manganites in which the large, A-site, cation is a
rare earth, R, from the left hand side of the lanthanide series.
The manganites of these large rare earth ions (La- to Dy-
manganites) all crystallize in the cubic perovskite structure,
with the same low temperature orthorhombic distortion.
Another type of manganite structure is hexagonal. Both types
show A-type antiferromagnetic ordering of the Mn3+ ions. In
addition to the magnetic ordering, the hexagonal manganites
also undergo a phase transition to a non-centrosymmetric low
temperature state which has ferroelectric ordering. The family
of ME materials with formula RMn2O5: R3+Mn3+Mn4+O52- (in
which R is a rare-earth ion from Pr to Lu, but also can be Y
and Bi) are hexagonal manganites showing both magnetic
and ferroelectric long-range order at temperatures lower
than 3040 K. At room temperature RMn2O5 crystals are
characterized by an orthorhombic crystal structure with
space group Pbam (28.-), in which Mn4+ is at centre of oxygen
octahedron and Mn3+ is at the centre of the base of a square
pyramid. The octahedra share their edges forming a ribbon
similar as in rutile structure, a MnO5 bipyramid forms a bridge
connecting these ribbons and a larger R3+ ion is surrounded by
eight oxygen atoms. The spontaneous polarization lies along
the b crystallographic direction. The systems belonging to
this family have two low-temperature phase transitions with
simultaneous changes in the magnetic and structural states at
T1~1520 K and T2~3540 K. The nature of the first transition
is not clear in detail, while the second one is a simultaneous
magnetic and ferroelectric phase transition, T2 = TN,C (29.-).
Magnetic, dielectric and magnetoelectric (ME) properties of
several crystals with different R ions were studied in the last
years (25,30,31.-).
Bol. Soc. Esp. Ceram. V., 44 [3] 177-184 (2005)
MAGNETOELECTRIC PHENOMENA IN SINGLE-PHASE AND COMPOSITE SYSTEMS
A very beautiful work proving that a multiferroic system
from the family RMn2O5 exhibits a profound interplay between
electrical polarization and the applied magnetic field was
recently published by Hur et al. for TbMn2O5 (25.-). The
authors demonstrated that a highly reversible switching of the
electrical polarization can be obtained with moderate magnetic
fields of (02) T. By the combined application of electric and
magnetic fields, a permanent imprint to the polarization
is also obtained (Fig. 1). These results point to new device
applications of the multiferroics such as magnetically recorded
ferroelectric memory.
The other types of manganite compounds with formula
RMnO3: R3+Mn3+O32- can also crystallize in two structural
phases: hexagonal for R=Ho, Er, Tm, Yb, Lu, or Y, which have
small ionic radii, and orthorhombic phase for R=La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, or Dy, which possesses a greater ionic
radius. In these compounds, the angle Mn-O-Mn is close to
180, facilitating magnetic ordering via an indirect exchange
interaction between the Mn ions through the O ions. While
magnetic ordering occurs in both hexagonal and orthorhombic
manganites, ferroelectric ordering occurs only in the hexagonal
ones, which belong to the non-centrosymmetric P63cm space
group. From this family, mostly YMnO3 was investigated (32-
35.-). Among the most recent and interesting studies dedicated
to YMnO3, is worth to mention the spatial mapping of coupled
antiferromagnetic and ferroelectric domains, obtained by
imaging with optical second harmonic generation (34.-). The
coupling was explained as originating from an interaction
between magnetic and electric domain walls, which leads to
a configuration that is dominated by the ferroelectromagnetic
product of the order parameters.
Fig.1.- Dielectric constant and total polarization vs. magnetic field in
TbMn2O5 at 3 and 28 K. The picture shows the orientation of the net
polarization at H=0 and high fields (34.-).
Many efforts have been dedicated to understand the
mechanisms of ferroelectricity (and the possible ME effect)
in perovskite manganites by comparison with the classical
ferroelectric perovskites (8,9,22-24.-). The mechanism driving
the ferroelectricity in perovskite ferroelectrics such as BaTiO3
and isomorphs is incompatible with the existence of a
spontaneous magnetic moment. The central Ti ion in BaTiO3
is shifted from its position in the ideal perovskite structure
(the centre of its surrounding oxygen octahedron) along one
Bol. Soc. Esp. Ceram. V., 44 [3] 177-184 (2005)
crystallographic axis , creating an electric polarization in the
ferroelectric state. This off-centring is stabilized by energy-
lowering covalent bond formation, in which charge transfers
from the filled oxygen 2p orbitals into the d states of the
transition metal ion. For this mechanism, the d orbitals must
be empty. On the other hand, in order to have magnetic order
in transition metal ions, a partly filled d shell is necessary. It
results that the classical mechanisms driving the ferroelectricity
in perovskites are incompatible with a non-zero magnetic
moment and other alternative mechanisms for the off-centre
displacement causing ferroelectricity are required in magnetic
ferroelectrics (9.-).
A possible way to avoid this incompatibility is proposed
by Efremov et al. (22.-) based on the concept of charge
ordering in doped perovskite-structure manganites. When
LaMnO3 (or related compounds in which the charge on the
Mn ions is formally 3+) and CaMnO3 (in which the Mn charge
is formally 4+) are alloyed, the resulting arrangement of Mn3+
and Mn4+ ions can be ordered; this is called charge ordering.
In charge-ordered and orbitally ordered perovskites it is
possible to make use of the coupling between magnetic and
charge ordering to obtain ferroelectric magnets. In particular,
in doped manganites with formula R1-xCaxMnO3 where R=La,
Pr, etc. and x0.5 there is a type of charge ordering that is
intermediate between site-centred and bond centred. Such
a state breaks the inversion symmetry and is predicted to
be magnetic and ferroelectric (22,23.-). Aken et al. (35.-)
proposed another mechanism for the nature of the ferroelectric
phase transition in hexagonal YMnO3 using a combination
of structural analysis and first-principles density-functional
calculations. It was demonstrated that ferroelectricity in YMnO3
arises from a buckling of the MnO5 polyhedral combined with
the unusual Y coordination and the triangular and layered
MnO5 network. The calculations showed that the mechanism
originating ferroelectricity is entirely driven by electrostatic
and size effects, rather than the usual changes in chemical
bonding associated with the ferroelectric phase transitions in
other perovskite oxides. In contrast to the chemically stabilized
ferroelectrics, this mechanism for ferroelectricity permits the
coexistence of magnetism and ferroelectricity (35.-).
2.2 BiFeO3 system
In the eighties, Ismailzade et al. (16,36.-) reported the
presence of a linear ME effect in BiFeO3, a compound of
antiferromagnetic-ferroelectric nature. Its combination with
bismuth titanate and barium titanate forms a family with
the general formula Bi4Bim3Ti3Fem3O3m+3 (m = 4, 5 and 8) or
BaxBi1-xTixFe1-xO3 in which the coexistence of ferroelectric and
magnetic properties exists up to high temperatures (17,28.-
). In its bulk state, BiFeO3 has a rhombohedral-distorted
perovskite structure R3c (a=b=c=5.63 , ===59.4) at room
temperature. It has long been considered an antiferroelectric
because of its superstructure and low values of dielectric
constant; it was ultimately classified as ferroelectric with a
TC around 1103 K. BiFeO3 is an antiferromagnet with a Nel
temperature TN=310 C (37,38.-), also showing a weak ferro/
ferri magnetic characteristic in some temperature ranges (39.-
). Having such a high Curie temperature, it was expected to
present a high spontaneous polarization in its ferroelectric
state (for example, PbTiO3 with TC=763 K, has a spontaneous
polarization of ~80-100 C/cm2). Practically, only low
values of the polarization and of the dielectric constant were
determined experimentally at room temperature, mainly due
179

to the semiconducting properties of BiFeO3, which does not
allow proper electrical poling and leads to high dielectric
losses. In ferroelectric ceramics the resolution of dielectric
anomaly becomes difficult in such cases. Low resistivity of
the sample at room temperature makes the observation of the
ferroelectric loop very difficult as well, this seriously limits the
applications of this material. In order to enhance the resistivity
and to observe a P(E) hysteresis loop, measurements were
performed on a high purity single-crystal at 80 K (40.-). This
experiment allowed to find a spontaneous polarization of
3.5 C/cm2 along the (001), indicating a value of 6.1 C/cm
along the (111) direction. Therefore, the saturation of the
loop was not observed even at fields as high as 55 kV/cm.
Saturated ferroelectric hysteresis loops were observed recently
at room temperature in the single-phase BiFeO3 ceramics
obtained by rapid liquid phase sintering (41.-), with values
of the spontaneous polarization, remanent polarization and
coercive field of 8.9 C/cm2, 4.0 C/cm2, and 39 kV/cm,
respectively, under an applied field of 100 kV/cm (41.-
). The high conductivity and leakage found especially at
higher temperatures were considered firstly caused by the
high difficulty to produce single phase of BiFeO3 (so that
even very small impurities segregated at boundaries could
have a doping effect and transform the dielectric into a
semiconductor). On the other hand, even in very pure BiFeO3,
due to the spontaneous change of the oxidation state of Fe
(3+/2+), oxygen vacancies are formed as a result of electrical
neutrality requirement, giving rise to thermal activated hoping
conductivity.
In order to diminish the mentioned problems, it was
adopted the method of forming binary solid solutions with
other perovskites with good dielectric properties as BaTiO3
(42-44.-), PbTiO3 (45.-) or systems as BiFeO3RFeO3BaTiO3
in which R=La, Dy, Pr (46.-). In the last compounds, remnant
polarization Pr=3-7 C/cm2 and remnant magnetization
Mr=0.06-0.2 emu/g were reported (45.-). For the solid
solutions of xBiFeO3-(1-x)BaTiO3, which was mostly studied,
the structure was found as rhombohedral up to x=0.67 mole%,
tetragonal at concentrations x<6 mole % and cubic in between
(42.-). In the BiFeO3-rich region, these ceramics show a weak
ME coupling effect (43.-). Therefore, even in solid solution
state, the problems of losses were only partially solved.
Although in single-crystal, ceramics and in solid solutions
the properties are strongly affected by high loss and leakage due
to nonstoichiometry defects and space charge characteristics,
good properties were found in the last years in BiFeO3 films
obtained by Pulsed Laser Deposition (PLD), that seems to allow
a better control of the composition and oxygen-stoichiometry
within the entire volume of the sample (19,47-50.-). Wang et
al. (19.-) growth pure heteroepitaxial films of BiFeO3 thin films
with thickness in the range of 50 to 500 nm onto (100) single
crystal of SrTiO3 substrates. These films had not rhombohedral
crystalline state as the bulk material, but tetragonal-like
structure with a small monoclinic distortion of about 0.5.
This resulted in a compressive stress imposed by the SrTiO3
substrate electrode, which has an in-plane lattice parameter
smaller than of BiFeO3. These films presented both saturate
P(E) hysteresis loops with a remnant polarization Pr=55 C/
cm2 and magnetic m(H) loops with a saturation of 150 emu/
cm3 and coercivity around 200 Oe. The authors considered the
high values of polarization as resulting from the stabilization
of the monoclinic phase by the in-plane compressive stress
imposed by the epitaxial bottom electrode. The in-plane stress
is smaller when the thickness of film is increasing, as proved
180
LILIANA MITOSERIU
by the data of thicker films. The values computed for the total
energy and polarization by first-principle calculations using
local-spin density approximation of Ps=63.2 C/cm2 for the
tetragonal distorted state, by comparison with Ps=6.6 C/cm2
characteristic to the rhombohedral phase were also in favour
of this interpretation (19.-).
On the contrary, Eerenstein et al. recently reported much
lower values for magnetization and polarization for similar
films. (47.-). They concluded that ferroelectric polarization
is not enhanced by strain in epitaxial BiFeO3 thin films.
In addition, the authors explained the large value of
magnetization reported in (19.-) as coming from the possible
large percentage of Fe2+ in the film volume. But a high density
of Fe2+ causing a high number of oxygen vacancies required
for the neutrality condition would result in low electrical
resistivity, unlike reported by Wang et al. (19.-), and thus
strongly limiting the ME applications of such films. The
authors concluded that an increased thickness-dependent
magnetization found in (19.-) is not an intrinsic property of
fully oxygenated and coherently strained epitaxial BiFeO3 thin
films characterised by a high electrical resistivity. Rather, high
magnetizations are possible achieved only in de-oxygenated
films, but loosing the ferroelectric performance due to a
consequent increasing conductivity (47.-). Although few other
explanations were proposed, the mechanism responsible for
very different polarization and magnetization characteristics
found in different epitaxial BiFeO3 films is still unclear, being a
hot topic under debate between various groups (19,47-49.-).
Fig.2.- Ferroelectric hysteresis loop of BiFeO3 polycrystalline lm
showing giant polarization 49.- (courtesy of Yun et al.)
Moreover, even higher polarization were found in
polycrystalline films of BiFeO3 of 300 nm thickness deposited
by PLD onto Pt/TiO2/SiO2/Si substrates by Yun et al. (49,50.-).
The remnant polarization at room temperature was determined
as 100 C/cm2, considerably higher than any value previously
reported in this system. By decreasing the temperature down
to 90 K, a giant switchable polarization with the largest values
ever measured for a ferroelectric material, was found (remnant
and saturation polarizations Pr=146 C/cm2 and Ps=158 C/
cm2 for a 20 V maximum applied voltage, as presented in Fig.
Bol. Soc. Esp. Ceram. V., 44 [3] 177-184 (2005)
MAGNETOELECTRIC PHENOMENA IN SINGLE-PHASE AND COMPOSITE SYSTEMS
2) (49.-). This extraordinary result suggests that heteroepitaxial
growth is not absolutely required for obtaining superior
polarization in BiFeO3. The phase symmetry seems to play
again a determinant role on the ferroelectric properties (in this
case: tetragonal symmetry with the space group P4mm and
high tetragonal distortion c/a=1.018).
According to the overall mentioned results, there are
few possible causes for the high values of polarization in
BiFeO3 films, by comparison with bulk: a) Extrinsic effects,
as the constrained structures in epitaxial ultrathin films
(19.-); in this case, is not explained the origin of the giant
polarization in polycrystalline film reported in ref. (49.-); b)
An intrinsic origin characteristic to the pure and defect-free
BiFeO3 (the nominal Bi/Fe ratio and oxygen stoichiometry
that are controlled during the PLD deposition reduces the
leakage in the films by comparison with the bulk samples), as
possibly obtained in the polycrystalline BiFeO3 films and not
in bulk ceramics (49,50.-); c) The strong ferroelectric response
might be associated with the tetragonal phase. In this case,
the origin of the tetragonal phase (obtained in constrained
and in stress-free epitaxies and in polycrystalline films)
instead of the rhombohedral one typical for bulk BiFeO3
system is unclear, as well as its role (maybe determinant)
on the high ferroelectric polarization; d) Other new possible
switching mechanism activated in thin films and not allowed
in bulk structures. This last possibility is supported by large
ferroelectric polarizations of 90100 C/cm2 resulted from
calculations within density functional theory with local spin-
density approximation, consistent with possible large atomic
displacements in the ferroelectric phase (51.-). According to
these calculations, all the range of experimental polarizations
reported in literature, including the recent exceptional high
values, might be correct and not artefacts related to high
losses or leakage effects. They can instead correspond to very
distinct switching paths and mechanisms in the structural
space allowing a simultaneous magnetic and ferroelectric
activity and a coupling between them. Anyway, further
measurements on well-characterized bulk and film samples
are required to confirm this interpretation and to clarify the
controversial properties of BiFeO3 system.
a)
Fig.3.- Ferroelectric-paraelectric (a) and succession of magnetic transitions (b) with composition-dependent characteristic temperatures in (1-
x)PFW-xPT (57,58.-).
Bol. Soc. Esp. Ceram. V., 44 [3] 177-184 (2005)
2.3 Magnetoelectric relaxors
In the complex perovskite relaxor compounds with formula
A(B1B2)O3 the angles in the chain B1-O-B2 are close to 180.
Therefore, when transition element ions lie in the octahedral B
positions, they may become ordered via an indirect exchange
interaction through the oxygen ions. Since the ferroelectric
ordering in the perovskite lattice arises mainly from the
displacements of A and B ions, if magnetic ions are introduced
into the octahedral B position, simultaneous ferroelectric and
magnetic activity and possible ME coupling might appear.
This is another route for obtaining ME materials.
Russian researchers started to obtain this type of materials
in the period of 1950-1960, based on the idea of replacing some
of the d0 B cations in ferroelectric perovskite oxides by magnetic
dn cations (10,11.-). Using this approach, they produced the
first synthetic ferromagnetic-ferroelectric material:
(1x)Pb(Fe2/3W1/3)O3xPb(Mg1/2W1/2)O3, in the early 1960s. In
this system, the Mg2+ and W6+ ions are diamagnetic and their
off-centre displacement is responsible for the ferroelectricity,
while the formally d5 Fe3+ ion is responsible for the magnetic
ordering. Other examples include B-site ordered Pb2(CoW)O6
(52.-) which is ferroelectric and ferromagnetic, B-site disordered
Pb2(FeTa)O6 (52.-) which is ferroelectric and antiferromagnetic,
with weak ferromagnetism below 10 K. As a result of dilution
of the magnetic ions, these materials all have rather low
Curie or Nel temperatures. However a number of simple
perovskite materials are known to have ferroelectric and
magnetic (mostly of the antiferromagnetic type) ordering. The
interaction of the ordered subsystems can result in ME effect,
where the dielectric properties may be altered by the onset of
the magnetic transition or by the application of a magnetic
field, and vice versa. Due to their complex chemical structure,
many of these systems are ferroelectric relaxors, which are
very interesting because of high dielectric, piezoelectric and
pyroelectric constants, particularly at the Morphotropic Phase
Boundary, MPB, composition, when forming solid solutions
with ferroelectrics like PbTiO3, PT, or others.
Among them, a renewal of interest in the last years was
particularly oriented to investigate the Pb-based magnetic
b)
181

relaxors: Pb(Fe2/3W1/3)O3, PFW, (53-57.-), PbNi1/3Nb2/3O3, PNN,
(57.-) or PbFe1/2Nb1/2O3, PFN, (58.-), Pb(Co1/2W1/2)O3 (59.-) and
their solid solutions. Particularly, in the case of (1-x)PFW-
xPT solid solutions, which were systematically investigated
previously by us, both ferroelectric (relaxor)-paraelectric (Fig.
3 a) (55.-) and magnetic phase transitions (Fig. 3 b) were found
(56.-).
A succession of magnetic transitions from weak
ferromagnetic-antiferromagnetic, TN1, and antiferromagnetic-
paramagnetic, TN2, state with increasing temperature take
place, with characteristic temperatures TN1, TN2 dependent on
the composition x. For the pure relaxor composition, PFW,
non-linear m(H) was found at low temperatures (Fig. 4).
An interesting fact is the change of m(H) towards a triple
hysteresis loop with a central loop at 7 kOe and two lateral
loops at (7, 45) kOe, in the Curie region for the transition
relaxor-ferroelectric at around Tc=175 K. Since the relaxor-to-
paraelectric phase transition is not accompanied by structural
changes that might influence the magnetic properties via
magnetostructural interaction, this fact was interpreted
as a demonstration of a magnetoelectric coupling in this
ceramic (56.-). The magnetoelectric coupling was explained
trough microstructural characteristics of PFW and PFW-
PT ceramics, which contain both disordered and partially
ordered nanopolar clusters between the off-valence cations
on the B-site (59.-). The magnetic interactions giving rise to
the observed behaviour might be ascribed as follows: a) in the
Fe/W ordered nanopolar domains, a weak superexchange of
Fe3+ O W O Fe3+ type of interaction responsible for the the piezoelectric phase, iv) no leak of the accumulated charges
magnetic anomaly at low temperature TN1 and b) in the Fe/W
disordered regions, a stronger superexchange of Fe3+ O
Fe3+ pathway interaction is responsible for the magnetic
ordering at higher temperatures TN2. The paramagnetic
behaviour indicates the presence of magnetically isolated Fe3+
ions: in a perfect ordered system on the B-site of the perovskite
cell, all of the magnetic Fe3+ ions are isolated. It results a
direct relationship between the ferroelectric order degree
and the magnetic behaviour (54,56.-). This picture explains
Fig.4.- The magnetic hysteresis loops m(H) for PFW ceramic at a few
temperatures. Note the triple hysteresis loop at TC=175 K (58.-).
182
LILIANA MITOSERIU
the magnetic properties of PFW and of some other complex
perovskites, as the ordered Pb(Co1/2W1/2)O3 which shows a
single magnetic ordering at the temperature TN1=8 K (61.-) and
also was applied to obtain information about the degree of
order in the relaxor PNN, in connection with the concentration
of magnetic ions Ni2+ (57.-).
3. MAGNETOELECTRIC COMPOSITES
A second class of magnetoelectric materials consists of
two-phase composites. The search for such systems was
promoted by practical needs, due to very low values of the
magnetoelectric voltage coefficient found in single-phase
materials (of the order of 120 mV/cmOe, far insufficient for
practical applications) and by the low temperature range for
the ME effect, mostly at cryogenic temperatures. As presented
by Ryu et al. (14.-), the ME effect is realized on the basis of
the concept of product properties (60.-). According to this
principle, a suitable combination of two phases such as a
combination of piezomagnetic and piezoelectric phases or a
combination of magnetostrictive and piezoelectric phases, can
yield a desirable ME property. The conceptual conditions for
the ME effect in composites were pointed out by Boomgaard
(61.-), as following: i) the individual phases should be in
chemical equilibrium, ii) no mismatch between grains, iii) high
values for the magnetostriction coefficient of piezomagnetic or
magnetostrictive phase and of the piezoelectric coefficient of
through the piezomagnetic or magnetostrictive phase and v)
deterministic strategy for poling of the composites. Following
this principle, various ME composites have been reported,
such as Ni(Co,Mn)Fe2O4-BaTiO3, CoFe2O4-BaTiO3, NiFe2O4-
BaTiO3, LiFe5O8-BaTiO3, CuFeCrO4-BaPbTiO3, CoFe2O4-
Bi4Ti3O12, NiFe2O4-Pb(ZrTi)O3 , (Ni,Zn)Fe2O4-Pb(ZrTi)O3, etc.
(14,60-66.-). Particularly, giant values of the ME coefficients
dE/dH of tens to hundreds of V/cmOe were obtained
in bilayer and multilayer laminate composites of good
piezoelectrics (as Pb(ZrTi)O3 or PbMg1/3Nb2/3-PbTiO3) with
high magnetostrictive materials, as terfenol-D (66-68.-).
It is worth to mention also the recent nanostructured
composite of BaTiO3-CoFe2O4 deposited onto single-crystal
SrTiO3 (001) substrates reported by Zheng et al. (69.-), in
which a 3D-heteroepitaxy (in-plane and out-of-plane) with
self-assembled hexagonal arrays of CoFe2O4 nanopillars of 20-
30 nm embedded in a BaTiO3 matrix was grown. This system
showed a strong coupling of the order parameters through
the heteroepitaxy of the two lattices. Temperature dependent
magnetic measurements illustrated the coupling between the
two order parameters, which is manifested as a change in
magnetization at the ferroelectric Curie temperature. Quasi-
static ferroelectric measurements demonstrate well-defined
ferroelectric hysteresis loop with a spontaneous polarization
Ps=23 C/cm2 and piezoelectric measurements revealed a clear
hysteresis loop with a maximum value of d33 around 50 pm/V.
The magnetic data show a saturation magnetization of 350
emu/cm3 with a strong anisotropy between the out-of-plane
(001) and in-plane (100) directions. The coupling between the
electric and magnetic order parameters in the self-assembled
nanostructures was proved by an anomaly (drop) of the
magnetization of 16 emu/cm3 around the ferroelectric Curie
temperature of TC=390 K (69).-.
Bol. Soc. Esp. Ceram. V., 44 [3] 177-184 (2005)
MAGNETOELECTRIC PHENOMENA IN SINGLE-PHASE AND COMPOSITE SYSTEMS
4. CONCLUSIONS
The field of ME materials is a very active topic, particularly
in the last 5 years, when extensive research has been conducted
on various types of structures. The dielectric polarization of a
material under a magnetic field or an induced-magnetization
under an electric field (ME effect) requires the simultaneous
presence of long-range ordering of magnetic moments and
electric dipoles. The ME effect is particularly low in bulk
single-phase materials, thus limiting their applicability in
practical devices. This is probably due to the impossibility
of controlling in the whole bulk volume the composition,
stoichiometry and defect structure. A better control of these
characteristics seems to be obtained in PLD films, particularly
in the case of BiFeO3 system, in which high values of
the spontaneous polarization by comparison with the bulk
materials have been reported. The origin of the very scattered
(sometimes author-dependent) values of the ferroelectric
characteristics in bulk and epitaxial or polycrystalline films
produced by various prestigious groups in the last years is still
unclear, although few different (and some of them new and
innovative) mechanisms, supported by results of first principle
calculations, were proposed. From the fundamental point of
view, the single-phase materials, particularly the controversial
BiFeO3 system are still very interesting for further studies and
far to be understood. On the practical point of view, it seems
that a good alternative are the ME composites exploiting the
product property of the materials and giving rise to giant
values of the ME coefficient.
ACKNOWLEDGEMENTS
The author is grateful to prof. Robert Freer, Univ. of
Manchester, UK and to the members of the MC of the COST
525 Action for their interest in multifunctional magnetoelectric
materials.
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Recibido: 29.03.05
Aceptado: 21.04.05
Bol. Soc. Esp. Ceram. V., 44 [3] 177-184 (2005)
 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
A R T I C U L O

Belite Portland Clinkers.

Synthesis and Mineralogical Analysis
A. G. DE LA TORRE,1* M. A. G. ARANDA,1 A. H. DE AZA,2 P. PENA2 and S. DE AZA2
Departamento de Qumica Inorgnica, Universidad de Mlaga, Teatinos s/n, 29071 Mlaga, Spain
1

2
Instituto de Cermica y Vidrio, CSIC, c/ Kelsen n 5, Campus de Cantoblanco, 28049 Madrid, Spain. *mgd@uma.es

The quaternary system CaO-SiO2-Al2O3-Fe2O3 has been taken into account to design five compositions of belite Portland
clinkers with belite (Ca2SiO4) contents ranging from 60 to 65 wt%, located in its primary phase field of crystallization. The
synthesis of these belite clinkers has been studied by high temperature microscopy, dilatometry, differential thermal analysis
and thermogravimetric analysis. As a result, the optimum clinkerization temperature has been established at 1360 5C. The
quantitative phase analyses of the clinkers were carried out by X-ray powder diffraction with the Rietveld methodology. The
mineralogical composition depends on the initial dosages, on the highest temperature achieved and on the time of residence
at this temperature. The reaction was completed at 1365C during 15 min (free CaO <0.5 wt%), in those conditions the -belite
form is stabilized and the harmful transformation is avoided.

Keywords: Belite Portland clinkers, Phase Equilibrium Diagrams, Rietveld Method

Clnqueres Prtland Belticos. Sntesis y Anlisis Mineralgico.

Teniendo en cuenta el sistema cuaternario CaO-SiO2-Al2O3-Fe2O3, se han diseado cinco composiciones de clnqueres
Prtland belticos, con contenidos del 60 y del 65% en peso de belita (Ca2SiO4), situadas en su campo primario de cristalizacin.
La sntesis de estos clnqueres belticos se ha estudiado in situ por microscopa de alta temperatura, dilatometra y anlisis
trmico diferencial y termogravimtrico. La temperatura ptima de clinquerizacin, determinada con estas tcnicas, ha sido
de 1360 5C. Los anlisis cuantitativos de los clnqueres se llevaron a cabo por difraccin de rayos-X con la metodologa
Rietveld. Los porcentajes de las diferentes fases dependen de las dosificaciones iniciales, de la temperatura alcanzada y del
tiempo de residencia a dicha temperatura. Se ha conseguido una reaccin total (%CaO libre < 0.5% en peso) tratando a 1365C
durante 15 min, en cuyas condiciones se estabiliza la forma de la belita y se evita la transformacin perjudicial .

Palabras clave: Clnqueres Prtland belticos, diagramas de equilibrio, mtodo de Rietveld.

1. INTRODUCTION

The production of one ton of standard Portland cement
releases into the atmosphere 0.54 ton of CO2 resulting from
the decomposition of calcite. In addition, the process uses vast
amounts of energy, particularly for clinkering and milling.
Thus, to obtain a ton of cement requires to use 60130 kg
of fuel and an average 110 Kwh of power, which result in
the release of CO2 resulting from oxidation of the fuel in the
furnace and from the use of fossil fuels to obtain electrical
power. The production of Portland cement using coal as fuel
releases ~ 0.97 ton of CO2 per ton of clinker. The overall CO2
emissions of the cement industry are ~ 6% of all anthropogenic
carbon dioxide and account for 4% of the global warming
of the planet (1). Finding effective ways of reducing such
emissions should therefore be a strong research priority. The
production of belite Portland cements is one of such solution
as it releases decreased amounts of CO2.
Standard Portland clinker contains four major crystalline
components, namely: alite (Ca3SiO5), belite (Ca2SiO4), ferrite
(Ca4Al2Fe2O10) and tricalcium aluminate (Ca3Al2O6), in
approximate proportions of 60, 15, 10 and 10 wt%, respectively
(2). In cement nomenclature, these components are designated
C3S, C2S, C4AF and C3A, respectively, with C = CaO, S =
SiO2, A = Al2O3 and F = Fe2O3. The formation of the principal
component, alite, requires the use of a clinkering temperature
of about 1450 C in the furnace in the absence of additional
melting agents. Conversely, belite Portland clinkers contain
more than 50 wt% of belite as the main crystal phase, in
addition to alite, ferrite and tricalcium aluminate (3). These
clinkers therefore contain less calcium than do standard
Portland cements; as a result, their production releases less
CO2 from the decomposition of calcite into the atmosphere
(0.50 ton CO2 per ton of clinker). In addition, the optimum
clinkerization temperature for these clinkers is roughly 100 C
lower than that for standard Portland clinker, which helps to
reduce CO2 emissions from fuel burning.

Bol. Soc. Esp. Ceram. V., 44 [3] 185-191 (2005) 185

 . G. DE LA TORRE, M. A. G. ARANDA, A. H. DE AZA, P. PENA and S. DE AZA

containing sulphur (8); others have developed alternative

production methods involving temperatures below 1350 C
(e.g. hydrothermal synthesis followed by calcination at a
moderate temperature) (9).
On the other hand, a combination of Rietveld methodology
(10) and X-ray powder diffraction (XRPD) is the most efficient
tool for the quantitative phase analysis (QPA) of mixtures of
crystalline substances (11, 12). This approach uses no standard,
but requires the prior knowledge of the crystal structures of
all the phases present as it involves comparing a theoretical
XRD pattern obtained from the crystal structures and the
experimental one, provided by the diffractometer.
In this work, belite Portland clinkers with five different
compositions were prepared based on previously reported

Fig. 1.- Polymorphic transformations of Ca2SiO4 with heating (2).

Belite Portland cements provide more durable concretes

than does standard Portland cement; however, belite cement
is more difficult to mill and reacts more slowly with water.
This entails making the belite reactive, whether by stabilizing
its high-temperature polymorphs, by decreasing its crystal
size or both (5). Stoichiometric C2S occurs as five different
polymorphs (Fig. 1) being the form which prevails in
standard Portland cement; contributing its hydration products
to concrete strengthening, particularly after 28 days of curing
(2). Belite forms are more reactive than all others, so they
require to be stabilized at room temperature. This can be
accomplished by alkalis, sulphur or barium additions or
by quenching from 1300 to 900 C (6,7). These treatments
are intended to offset the low reactivity of -belite relative
to C3S and hence to obtain a high strength at early curing
stages. Some authors have obtained reactive belite phases

Fig. 3.- Projections of the eutectic surfaces bounding the primary

Fig. 2.- Projection of the eutectic surface bounding the primary phase
field of crystallization of C2S for a plane of 65 wt% C2S onto the op-
posite side CaOC12A7C4AF of the tetrahedron. The secondary crys-
tallization area for each component and the primary crystallization
fields for C3S and CaO are also shown.
phase eld of crystallization of C2S onto the opposite side C3SC3A
C4AF of the tetrahedron for the planes: (a) 60 wt% C2S (the symbols
, and , denote the compositions of B60_1, B60_2 and B60_p,
respectively) and (b) 65 wt% C2S (the symbols ", and , de-
note the compositions of B65_1, B65_2 and B65_3, respectively). The
secondary crystallization area for each component and the primary
crystallization elds for C3S and CaO are also shown.

186 Bol. Soc. Esp. Ceram. V., 44 [3] 185-191 (2005)

BELITE PORTLAND CLINKERS. SYNTHESIS AND MINERALOGICAL ANALYSIS

Tabla I. Dosages, as oxide percent weights, used to obtain the different belite clinkers. Values of different parameters and the
theoretical mineralogical compositions of the clinkers.

Clinker CaO/% SiO2/% Al2O3/% Fe2O3/% K2O/% Na2O/% LSF AR SR C2S/% C3S/% C4AF/% C3A/%
B60_1 63.16 25.12 6.37 5.25 0.08 0.02 78 1.21 2.16 60 16 16 8
B60_2 63.80 25.11 7.04 3.94 0.09 0.02 78 1.79 2.29 60 16 12 12
B65_1 62.70 25.52 6.39 5.28 0.08 0.02 76 1.21 2.19 65 11 16 8
B65_2 63.41 25.59 6.98 3.91 0.09 0.02 77 1.79 2.35 65 11 12 12
B65_3 64.27 26.52 6.13 2.99 0.08 0.02 77 2.05 2.91 65 15 9 11
B60_p 60.31 23.00 7.38 9.19 0.09 0.03 76 0.8 1.39 60 8 28 4

Tabla II. Chemical composition of the calcite and kaolin used
to obtain the belite clinker raw mixtures.
Calcite
CaO 56.01
SiO2
Al2O3
Fe2O3
K2O
Na2O
MgO 0.016
TiO2
SrO 0.005
SO3 0.011
LOI (1000 C) 43.96
data for the quaternary system CaOSiO2Al2O3Fe2O3 (1315),
within the subsystem, C2SC3SC3AC4AF is comprised. This
quaternary phase equilibrium diagram was developed using the
projection method (16, 17). The clinkering process was studied
in situ by using high-temperature microscopy, dilatometry,
differential thermal analysis and thermogravimetry. All phases
detected were quantified by using the Rietveld method.
2. EXPERIMENTAL
2.1. Formulation of belite clinkers. Representation and
projection methods
Based on the solid state compatibilities of C2S within the
CaOSiO2Al2O3Fe2O3 system, and assuming that C2S would
form no solid solution to an appreciable extent, a tentative
projection, in the C2SC12A7C4AFCaO sub-system, of the
binary eutectic surface defining the primary crystallization
volume of C2S on the opposite side C12A7C4AFCaO of the
tetrahedron was made, for a plane of 65 wt% of C2S. The
projection is shown in Fig. 2. In all the figure, C2S is the primary
crystallization phase except in the regions designated a-c-e-f
and f-e-CaO, where the primary phases are C3S and CaO,
respectively in fact, their primary crystallization volumes
intersect the plane of 65 wt% of C2S. The bold dashed lines are
the projections of the ternary eutectic lines (monovariant lines)
defining the secondary crystallization fields of the different
phases. The figure also shows the projections of the invariant
points for the sub-systems C2SC12A7C3AC4AF (eutectic,
1280 C) and C2SC3SC3AC4AF (peritectic, 1338 C). The
solid straight lines ab and C4AFC3A are the intersections of
the compatibility triangles C3SC3AC4AF and C2SC3AC4AF
Kaolin respectively with the plane of 65 wt% C2S. These lines define
0.31 the compatibility areas where, in the solid state, the following
48.59 phases coexist: CaOC4AFC3SC3A (zone CaO-a-b), C2SC3S
37.13 C4AFC3A (zone a-b-C3AC4AF) and C2SC3AC4AFC12A7
0.25 (zone C3A-C4AFC12A7).
0.13 Based on the previous projection, the composition zone
0.46 for obtaining belite clinkers, containing C3S as a secondary
0.05 phase, is restricted to the area bounded by a-c-C3A-g-1348.
0.01 The auxiliary dotted line connecting the CaO vertex with the
peritectic point at 1338 C splits such a zone in two areas. In
the upper portion, the phase sequence during crystallization
will be: C2S + L C2S + C3S + L C2S + C3S + C4AF + L C2S
13.07
+ C3S + C4AF + C3A + L C2S + C3S + C4AF + C3A and in the
lower portion it will be: C2S + L C2S + C3S + L C2S + C3S
+ C3A + L C2S + C3S + C3A + C4AF + L C2S + C3S + C3A +
C4AF (L denotes liquid phase).
In order to formulate and represent the composition of the
clinkers, as a function of the phases constituting belite clinkers
(viz. C2S, C3S, C4AF and C3A), two additional projections, in
the C2SC3SC4AFC3A sub-system, of the binary eutectic
surface defining the primary crystallization volume for C2S
on the opposite side C3SC4AFC3A of the tetrahedron were
obtained, for the planes corresponding to 60 and 65 wt% C2S.
The projections are shown in Fig. 3. In the figure, the lines
and the areas they bound have the same meaning as those
in Fig. 2. As can be seen, invariant points fall outside both
projections, and so do virtually all eutectic lines. Figure 3a
depicts two of the compositions [viz. B60_1 () and B60_2
] and Fig. 3b the other three [viz. B65_1 , B65_2 and
B65_3 ()]. All formulations have been theoretically designed
with C3S proportions greater than 10 wt%, as this phase is
very important in ensuring adequate strength at early curing
stages.
2.2. Synthesis of belite clinkers
Table I shows the dosages, as oxides, used to prepare
each belite clinker. It also shows the theoretical mineralogical
composition, lime saturation factor (LSF), alumina ratio (AR)
and silica ratio (SR) of each. These parameters are defined as
follows:
LSF = 100CaO/(2.8SiO2 + 1.2Al2O3 + 0.65Fe2O3);
AR = Al2O3/Fe2O3;
SR = SiO2/(Al2O3 + Fe2O3)

Bol. Soc. Esp. Ceram. V., 44 [3] 185-191 (2005) 187

 . G. DE LA TORRE, M. A. G. ARANDA, A. H. DE AZA, P. PENA and S. DE AZA

Belite clinker has a low LSF value relative to standard

Portland cement (7580 vs 9499) (7).
Raw mixtures were prepared by weighing appropriate
amounts of the four raw materials: calcite, kaolin, quartz and
iron oxide. Calcium was supplied as Merck reagent-grade
CaCO3. The source of aluminium, which also contained
silicon, was a kaolin from Caobar (Spain), the mineralogical
composition of which, as determined by X-ray powder
diffraction, was kaolinite [Al2Si2O5(OH)4] plus small amounts of
-quartz (-SiO2) and trace of muscovite [KAl2(AlSi3O10)(OH)2].
The kaolin dosage used was based on the total Al2O3 and SiO2
contents (Table II). The silicon deficiency was corrected by
adding -quartz (99.59% ABCR). Finally, the iron source was
Fe2O3 (99.95% AlfaAesar). Mixtures were blended by hand in
an agate mortar with the aid of ethyl alcohol and dried in a
stove at 60 C. This treatment was performed by triplicate.
All raw mixtures were pressed at about 150 MPa into Fig. 4.- (a) Variation of the area as a function of temperature for sam-
pellets of ~ 1.8 g with ~ 16 mm of diameter. The pellets were ple B65_1. (b) Dilatometric curve for the same sample as a function
placed on Pt/Au crucibles and heated at 5 C/min to 900C, of temperature.
which was held for 30 min. Then, the temperature was raised
at 5 C/min up to 1365 C and held for 15 min. Finally, the
samples were quenched in air at a rate of approximately 2000
C/min between 1365 and 800 C.
A second set of pellets, with the same composition, was 2.4. Analysis of XRPD patterns
subjected to a slightly different thermal treatment. Thus, the
temperature was raised at the same rates, but the holding X-ray powder diffraction patterns were analysed by using
time at 1365 C was 2 h rather than 15 min. The quenching the Rietveld method as implemented in the GSAS software
conditions were the same as before. We shall henceforth use _ package (18). Peak shapes were determined by using the
b to designate the raw mixtures treated at 1365 C for 2 h (e.g. pseudo-Voigt function (19) with its associated axial divergence
the B60_1 composition thus processed is named B60_1_b). correction (20). The Gaussian part of all the phases was
fixed, whereas the Lorentzian part of those phases at high
2.3. Analytical techniques proportions was freely refined.

The analytical composition of the calcite used (Table II)

was determined by X-ray fluorescence spectroscopy on a 3. RESULTS AND DISCUSSION
Phillips PW-1404 spectrophotometer and that of the kaolin
(Table II) by inductively coupled plasma atomic emission The clinkering and melting processes of the raw mixtures
spectroscopy (ICP-AES) on an IRIS Advantage instrument were examined by high-temperature microscopy. Samples
from Thermo Jarrel Ash. were pressed into cylindrical pellets 3 mm high 2 mm in
The thermal behaviour of the raw mixtures was examined by diameter. This size ensured that surface tension forces during
high-temperature microscopy (HTM), using Leica equipment
(Wetzlar, Germany) and an alumina support. Samples were
heated up to 1525 C at a rate of 5 C/min. The instrument
was equipped with an automatic image analysis system (EMI
v. 1.5). The dilatometric profile for each raw mixture was
recorded on a Setsys 16/18 dilatometer from Setaram, using a
heating rate of 5 C/min up to 1320 C. Finally, the differential
thermal and thermogravimetric analysis (DTATG) of the
raw mixtures were performed in platinum crucibles, using
a Netzsch STA 409 instrument equipped with a TASC 414/2
controller; samples were heated up to 1450 C at a rate of 5
C/min in an air stream.
X-ray powder diffraction data were obtained at room
temperature on a Siemens D5000 diffractometer with /2
geometry (reflection), CuK1,2 (1.542 ) radiation and a curved
secondary graphite monochromator. Samples were vertically
loaded into the methacrylate holder and rotated at 15 rpm
during the measuring period. The diffractometer optics
comprised three slits of 2 (divergence), 2 (anti-divergence)
and 0.2 mm (reception). The X-ray tube was operated at 40 kV
at 30 mA. Scans were done with a step size of 0.03 over the
2 range from 10 to 70. The step time was 18 s (10 h/ pattern)
for the clinkers obtained in 15 min and 5 s (2.8 h/ patterns) for Fig. 5.- (a) Thermogravimetric (TG) and (b) differential thermal anal-
those obtained in 2 h. ysis (DTA) curves for sample B60_1.

188 Bol. Soc. Esp. Ceram. V., 44 [3] 185-191 (2005)

BELITE PORTLAND CLINKERS. SYNTHESIS AND MINERALOGICAL ANALYSIS

the melting process would be much greater than hydrostatic

pressure. The images obtained were used to determine the
onset of sintering, its maximum, the softening point and
the melting point (half-sphere). As an example, Fig. 4 shows
the variation of the area as a function of temperature for
sample B65_1 [curve a] as obtained by HTM. The figure also
includes selected images illustrating the changes observed.
Curve b is the dilatometric profile [i.e. the sintering curve
(l/l 100)] for the same raw mixture. As can be seen,
above ~ 800 C the raw mixture started to shrink through
decarbonation. This process was subsequently offset by the
strong expansion observed between about 1000 and 1180 C
in the dilatometric profile (Fig. 4, curve b), which resulted in a
slope change between about 980 (point 1) and 1250 C (point 2)
in curve a. This suggests the occurrence of expansive chemical
reactions over this temperature range. The combined analysis
of the dilatometric and area change data reveals that chemical
reactions (e.g. belite formation) prevail over sintering in such a
range. At point 2 (~ 1250 C in Fig.4, curve a), sintering regains
its prevalence by effect of the formation of a liquid phase; as
the proportion in such a phase rises, the contraction rate of
the raw mixtures substantially increases between points 2
(1250 C) and 3 (1358 C). The above-described behaviour was
virtually identical for the five mixtures studied.
Fig. 5 shows the DTA and TG curves for mixture B60_1,
as a representative example for all the compositions. Curve a
shows mass changes as a function of temperature (TG). Curve
b is the differential thermal analysis (DTA) profile. A small
endothermic peak, corresponding to a weight loss resulting
from the dehydroxylation of kaolin, is observed at ~ 500 C
(point 1). The endothermic peak at ~ 880 C (point 2), with a
substantial weight loss associated, is due to the decomposition
of CaCO3. The sharp exothermic peak at ~ 980 C (point 3)
corresponds to the coordination change of aluminium in meta- Fig. 6.- Selected range of the Rietveld plots for clinker B65_1 (top) and
kaolin (amorphous) during its transformation into a spinel-like B65_1_b (bottom). The major peaks for each phase are labelled.
transient phase prior to the formation of mullite (21, 22). An
additional, very small endothermic peak is observed at ~ 1190 was established to be at 1360 5 C. The raw mixtures were
C (point 4), which coincides with the invariant point for the therefore thermally treated at 1365 C for 15 min, as previously
mullitesilicafeldspar sub-system (23) and can be assigned to described, in order to obtain the corresponding clinkers.
the formation of a transient liquid due to impurities present in The QPA for the clinkers were determined by using the
the kaolin. Finally, the curve includes two endothermic peaks Rietveld method; the results are shown in Table III together
at high temperatures. One, at ~ 1350 C (point 5) for the five with the agreement factors (weight profile R-factor) for each
raw mixtures, corresponds to the formation of a permanent refinement. The table also gives the references to the structural
liquid phase. The other, at ~ 1380 C (point 6), corresponds to descriptions used to obtain the theoretical XRPD patterns
the H transformation in belite upon heating (24). for each phase. The Rietveld results are normalized to 100%
From the area changes, dilatometry, DTA and TG data, the crystallinity (i.e. the presence of amorphous, non-diffracting
optimum clinkerization temperature for all the compositions phases was excluded). All samples were found to contain

Tabla III. Results of Rietveld QPA of belite clinkers obtained by heating at 1365 C/15 min. The data are normalized to 100%
crystallinity. The aggrement factor (RWP) for each fit is also shown.

Clinker -C2S % -C2S % total C2S /% C3S % C4AF % C3A % RWP %

B60_1 54.8(2) 2.6(3) 57.4 20.1(3) 13.3(2) 9.2(2) 9.4
B60_2 52.1(3) 3.4(4) 55.5 21.6(3) 8.1(2) 14.8(2) 10.5
B65_1 63.0(2) 4.3(5) 67.3 11.8(3) 12.4(2) 8.5(2) 9.7
B65_2 60.6(2) 2.0(3) 62.6 14.6(3) 8.0(2) 14.8(2) 9.9
B65_3 61.3(2) - 61.3 18.0(3) 5.3(2) 15.4(2) 9.7
Reference/
(25) (25) (26) (27) (28)
Structure

Bol. Soc. Esp. Ceram. V., 44 [3] 185-191 (2005) 189


Tabla IV. Results of Rietveld QPA of belite clinkers obtained by heating at 1365 C/2 h. The data are normalized to 100%
crystallinity.
Clinker -C2S/% -C2S/% Total C2S /%
B60_1_b 46(1) 6(1)
B60_2_b 46(1) 5(1)
B65_1_b 45(1) 15(1)
B65_2_b 49(1) 9(1)
B65_3_b 51(1) 8(1)
-C2S, C3S, C4AF and C3A. Free CaO was never present in
amounts greater than 0.3 wt%; consequently, the degree of
clinkerization under these conditions was quite adequate.
Four clinkers contained a small amount of H-C2S (see Table
III). Heating for only 15 min at 1365 C, followed by quenching
in air, ensured the absence of the -C2S -C2S transformation
in all cases. This polymorphic transformation during cooling
must be avoided since form is hydraulically inactive.
As an example, Fig. 6 shows a selected portion of the
Rietveld plots for the clinkers B65_1 and B65_1_b. The peaks
mainly due to a given phase are labelled. The lower curve, in
each pattern, represents the difference between the theoretical
and experimental data; the flatter it is, the higher is the quality
of the analysis.
The mineralogical composition obtained (Table III) is
very similar to the theoretical composition calculated from
the solid state compatibilities (Table I). The proportion of C3S
always exceeded 10 wt%, which is highly desirable for the
above-described reasons. However, it also highly desirable
to stabilize an increased amount of the -C2S in order to
activate the cements and to obtain a higher strength at early
stages during the curing process. Studies on these subjects are
currently under way.
Additionally, an interesting result which brings information
about the location of the invariant point of the C2SC3SC3A
C4AF system has to be pointed out. Thus, the proportion of the
ferrite phase, C4AF, was always below its theoretical value and
its diffraction peaks were very broad. To clarify this, the full
width at the half maximum (FWHM) of the 2 ~ 12 peak for
C4AF in clinker B60_1 was measured, being 0.24. This value
suggests that the C4AF phase crystallizes during cooling,
consequently the auxiliary line connecting the CaO vertex
with the invariant point (Figs 2 and 3) should lie above all the
selected compositions rather than as tentatively shown in Figs
2 and 3. In order to fork the location of the invariant point,
a new composition in the 60 wt% C2S plane was prepared,
namely B60_p, +, (see Fig. 3a and Table I). This raw mixture
was subjected to the thermal treatment for the b series and the
FWHM for the same C4AF diffraction peak was measured and
found to be 0.09. This lower value indicates that the C4AF
diffraction domains in this clinker are larger than in clinker
B60_1 (i.e. that it had enough time to crystallize and grow). In
addition, in clinker B60_p it was the C3A phase that showed
the broadest peaks. Consequently, the auxiliary dotted line
should lie in between those for B60_1 and B60_p.
The influence of the clinkering time on the growth of belite
crystals was examined by heating the previous compositions
at the same temperature but a longer time (2 h). Obviously,
the belite crystals in the new clinkers should be larger. This
is being currently studied by electron microscopy. However,
the results so far confirm that quenching in air fails to
completely prevent the -C2S -C2S transformation in this
190
. G. DE LA TORRE, M. A. G. ARANDA, A. H. DE AZA, P. PENA and S. DE AZA
C3S/% C4AF/% C3A/%
52 33(1) 7(1) 8(1)
51 30(1) 6(1) 13(1)
60 25(1) 9(1) 6(1)
58 25(1) 6(1) 11(1)
59 25(1) 4(1) 12(1)
samples (see Fig. 6, bottom). The QPA for these clinkers are
shown in Table IV. As can be seen, there was no trace of the
most reactive phase of belite (H-C2S), however, there was
an appreciable amount of the non-hydraulic form (-C2S). On
the other hand, a longer period of heating at 1365 C yields to
higher proportions of alite in these compositions (Table IV).
Consequently, belite Portland clinkers should be clinkered for
a short time at 1365 C in order to avoid substantial growth of
belite crystals which prevent the harmful transformation of
during cooling.
4. CONCLUSIONS
The projection of the eutectic surface bounding the primary
field of crystallization of C2S in the C2SC3SC3AC4AF system
allowed locating within such a volume two series of belite
clinkers with 60 and 65 wt% C2S, respectively, and variable
proportions of C3S, C3A and C4AF.
HTM, DTA, TG and dilatometric studies allowed
establishing 1365 5 C as the optimum clinkerization
temperature. Thermal treatment of the raw mixtures at such
temperature for 15 min allowed to obtain clinkers with -C2S
containing a small amount of form and to avoid the
harmful transformation . However, such transformation
could not be avoided with increasing time of treatment.
The Rietveld method to obtain QPA was extended to belite
Portland clinkers.
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Stepheson, M. Aylmore, N. Agron-Olshina, Outcomes of the International
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Recibido: 14.02.05
Aceptado: 30.03.05
191
 TESIS DOCTORAL
Proceso de colado en cinta para decoracin de materiales
cermicos

TESIS DOCTORAL
TESIS DOCTORAL

ELENA SOLERA CARLAVILLA

Departamento de Electrocermica. Instituto de Cermica y Vidrio, CSIC,
C/Kensel 5, 28049 Madrid. Espaa

Las baldosas para pavimentos y como base para el proceso de cola-

revestimientos constituyen uno de
los principales productos en el sector
de la cermica y vidrio espaol. El
volumen de mercado en la actuali-
dad de dichos materiales es cercano
al 44% del total si se engloban junto
a la fabricacin de fritas y esmaltes.
El creciente desarrollo de estos mate-
riales viene precedido de un esfuerzo
importante en I+D+i, fruto del cual
se introducen procesos y productos
innovadores, tales como: la monococ-
cin, el gres porcelnico, decoracin
en seco, esmaltes funcionales... Las
nuevas tendencias en decoracin y
la adaptacin de procesos de fabri-
cacin desarrollados en otras reas tecnolgicas nutren
de ideas al sector de pavimentos y revestimientos,
siendo un origen constante de nuevas posibilidades
y permitiendo as el incremento de la competitividad
empresarial.
Uno de los procesos tecnolgicos que han desper-
tado un inters creciente durante los ltimos aos es
el de colado en cinta de materiales cermicos. Este
inters tiene su origen, por un lado en la dimensin
laminar de los esmaltes, mientras que por otro lado
puede representar un mtodo alternativo de obtencin
de pavimentos y revestimientos. Los procesos de cola-
do en cinta se emplean en la produccin de materiales
electrocermicos, en particular para la obtencin de
distintos componentes como condensadores, ferritas,
varistores, termistores, aisladores etc. y para la obten-
cin de dispositivos multicapa interconectados. Este
tipo de procesos est por tanto desarrollado y existen
soluciones tecnolgicas para la produccin reproduci-
ble y masiva de materiales cermicos. Sin embargo su
traslacin requiere, junto al estudio de los parmetros
de proceso, la adaptacin del mismo a las caractersticas
fsico-qumicas de los esmaltes.
La presente tesis doctoral se ha centrado en el
empleo del proceso de colado en cinta para el desarrollo
de procesos flexibles de decoracin aplicables en pavi-
mentos y revestimientos cermicos empleando esmalte
cristalino.
En primer lugar, se ha estudiado el comportamiento
reolgico y las propiedades de las barbotinas cermi-
cas de composicin industrial que se van a emplear
do. Se han establecido las condiciones
de estabilidad idneas para que, con
la incorporacin de los aditivos de
colado (aglomerante y plastificantes),
se obtenga una barbotina defloculada
con un comportamiento pseudoplsti-
co adecuado. Se ha establecido el efec-
to de la concentracin de los aditivos
sobre las propiedades de la barbotina
y cmo stos afectan a la lmina resul-
tante. Se han estudiado las variables
de colado, determinando la concen-
tracin y densidad de la barbotina, la
velocidad y apertura de las cuchillas
de colado, el proceso de secado, y la
densidad y flexibilidad de las lmi-
nas resultantes. En general, se ha observado que una
adecuada dispersin y homogeneidad en la barbotina
conducen a lminas con un mejor empaquetamiento y
ausencia de defectos.
Se ha estudiado la evolucin trmica de las lminas
de esmalte cristalino en comparacin con un esmalte de
lnea. Ambos materiales sinterizan por un mecanismo
de flujo viscoso pero presentan ligeras diferencias atri-
buibles a un empaquetamiento caracterstico para cada
material. Estas diferencias se han establecido mediante
la determinacin de la curva de viscosidad con la tem-
peratura, en la que se observa una aumento del valor
de viscosidad, que se corresponde con la presencia de
desvitrificaciones. Si la eliminacin de los compuestos
orgnicos es muy rpida en las lminas de colado en
cinta se produce la aparicin de poros en la lmina en
verde. Se ha constatado que la presencia de partculas
cristalinas refractarias en el esmalte estabiliza estos
poros dando lugar a defectos en esmalte final si su
tamao excede un tamao crtico. La eliminacin de
dichos poros se favorece con la disminucin de la vis-
cosidad con la temperatura, siendo ms efectiva dicha
eliminacin para las temperaturas en las que las fases
cristalinas funden en el seno de la fase vtrea. Se ha rea-
lizado una caracterizacin detallada de la evolucin de
la porosidad con la temperatura empleando de forma
comparativa las tcnicas de Microscopa Electrnica
de Barrido, perfilometra y Microscopa de Fuerzas
Atmicas.
Por otra parte se ha establecido que la utilizacin
de procesos de Turbinas de Alta Velocidad de Cizalla

V Mayo-Junio (2005)
 mejora la dispersin de las barbotinas cermicas. En
TESIS DOCTORAL
los ensayos realizados con tintas de serigrafa se ha
comprobado que la mejora en la dispersin se traduce
en un aumento del rendimiento de color de la tinta, de
tal manera que se ha trabajado con barbotinas pseudo-
plsticas de baja viscosidad con un contenido en slidos
mayor y una reduccin del porcentaje en pigmentos, y
as se han obtenido tintas serigrficas que producen un
color similar al de referencia.
Se ha estudiado la aplicacin de las lminas de
colado en cinta como motivos de decoracin. Se han
determinado la variacin dimensional en coccin de
los motivos de decoracin con el espesor y longitud de
los mismos, delimitndose las zonas en las que se pue-
den obtener motivos isodimensionales con la pieza en
verde. Se ha determinado el mecanismo de integracin
de dichos motivos sobre un esmalte base y el rendi-
miento de color de dichos motivos. La incorporacin
de pigmentos a la matriz vtrea permite la disminucin
de la viscosidad a la temperatura de consolidacin del
esmalte y as la unin con el esmalte base es completa.
Mayo-Junio (2005)
Se ha comprobado que la variacin lineal del color con la
TESIS DOCTORAL
proporcin de pigmentos en los motivos de decoracin
permite, para concentraciones elevadas, un mayor ren-
dimiento de color cuando estos pigmentos se incorporan
en la lmina externa.
Este trabajo de tesis doctoral ha sido protegido en
la patente Proceso flexible de decoracin de produc-
tos cermicos (fecha de publicacin: 16-07-2003), por
parte del CSIC y ha dado lugar a una marca registrada,
Decortape.
La Tesis Doctoral se defendi en el saln de Actos
del Instituto de Cermica y Vidrio (CSIC), el pasado
2 de febrero de 2005. La calificacin concedida fue de
Sobresaliente Cum Laude por unanimidad del tribu-
nal que estuvo compuesto por: D. Vicente Fernndez
(Presidente), Dra. Marina Villegas Gracia (Secretaria),
Jos M Pastor Baraja, Antonio Barba Juan y Dr. Jos
de Frutos Vaquerizo. El trabajo de tesis doctoral se ha
llevado a cabo en el Instituto de Cermica y Vidrio bajo
la direccin del Dr. D. Jos Francisco Fernndez Lozano
con la financiacin de la empresa Keraben S. A.
VI
 TESIS DOCTORAL
Control de la Microestructura Funcional en Varistores Cermicos de
Alto Voltaje basados en ZnO-Bi2O3-Sb2O3
TESIS DOCTORAL
MARCO PEITEADO LPEZ
Departamento de Electrocermica. Instituto de Cermica y Vidrio (C.S.I.C.)
c/ Kelsen 5. 28049 Madrid (Espaa).
Los materiales cermicos basa-
dos en el sistema ternario ZnO-Bi2O3-
Sb2O3 presentan comportamiento
varistor (voltage dependent resistor).
Este comportamiento viene defini-
do por una transicin abrupta desde
un estado aislante elctrico a otro
conductor, para un cierto valor del
campo elctrico aplicado. Debido a
esta propiedad, estos materiales se
emplean para la fabricacin de dis-
positivos protectores frente a sobre-
tensiones, fundamentalmente en apli-
caciones de alto voltaje. En particular,
los varistores basados en ZnO son
los ms utilizados para la fabricacin
de pararrayos, aunque su campo de
aplicacin se va extendiendo gradualmente. A pesar de
la importancia tecnolgica de estos materiales, existen
numerosos aspectos relacionados con su diseo que an
no son bien conocidos debido a la complejidad qumica
y fsica del sistema, hasta el punto de que la mayor
parte de su desarrollo se ha llevado a cabo de manera
emprica, movido por la demanda tecnolgica.
El comportamiento varistor se origina en una
microestructura funcional con unas caractersticas bien
definidas. Para alcanzar esta microestructura, la com-
posicin qumica del material involucra de cinco a siete
xidos diferentes, lo que a su vez aumenta notablemen-
te la dificultad del procesamiento del material cermico.
Sin embargo, ni siquiera una herramienta tan esencial
para el diseo del material como es el diagrama de
fases en equilibrio del sistema base ZnO-Bi2O3-Sb2O3, es
conocida. Dentro de este contexto el trabajo descrito en
esta memoria de Tesis Doctoral centra su investigacin
en dos objetivos fundamentales. Por un lado, resulta
necesario adquirir un conocimiento bsico acerca de la
evolucin trmica del sistema base ZnO-Bi2O3-Sb2O3,
para de este modo establecer los criterios que permitan
disear el procesamiento del material. Por otro lado,
este conocimiento debe permitir abordar el problema
del control de dicha evolucin microestructural y por
tanto de la repuesta elctrica final del varistor.
Los mecanismos que gobiernan la evolucin
microestructural del material varistor dependen fuerte-
mente de las reacciones que tienen lugar en el sistema
ZnO-Bi2O3-Sb2O3 durante el ciclo trmico de sinteri-
zacin, que, de este modo, constituyen el eje central
sobre el cual se configura la microestructura funcional
VII
TESIS DOCTORAL
del varistor. La presente memoria de
tesis pone de manifiesto que en dicho
sistema ternario y manteniendo una
relacin Sb2O3/Bi2O3 superior a la uni-
dad caracterstica de la composicin
de varistores, existen dos caminos de
reaccin simultneos. Ambos caminos
se inician con la formacin del com-
puesto intermedio Sb2O4 y conducen
a la formacin de una fase espinela
Zn7Sb2O12 directamente relacionada
con el proceso de control del creci-
miento de los granos de ZnO. Sobre la
base de ello se ha identificado el efecto
que ejerce sobre el comportamiento
del varistor el hecho de favorecer y/o
eliminar alguna de estas reacciones
mediante el uso de diferentes estrategias de procesa-
miento: la mezcla de los xidos constituyentes, la incor-
poracin de la fase espinela previamente sintetizada o
la introduccin de una etapa de calcinacin previa al
conformado y a la sinterizacin, se traducen en respues-
tas elctricas diferentes que son debidas a una diferente
evolucin de la microestructura durante el tratamiento
trmico. El anlisis cintico del proceso de crecimiento
de los granos de ZnO en los diferentes sistemas ensaya-
dos revela adems la existencia de un intervalo de tem-
peraturas y tiempos de sinterizacin en el cual resulta
posible obtener una variacin sistemtica del voltaje
de conmutacin del varistor. Este hecho ha permitido
obtener por primera vez y de una forma cuantitativa
una expresin emprica que establece la dependencia
existente entre la variacin de la respuesta elctrica del
varistor y los parmetros del ciclo trmico.
Don Marco Peiteado Lpez es Doctor en Ciencias
Qumicas por la Universidad Autnoma de Madrid.
Defendi la Tesis Doctoral en el Departamento de
Qumica Inorgnica de la Facultad de Ciencias de
la Universidad Autnoma de Madrid, el da 3 de
Diciembre de 2004, con la obtencin por unanimidad
de Sobresaliente Cum Laude como calificacin. El
tribunal estuvo formado por el Dr. Vicente Fernndez
Herrero, como presidente, la Dra. Rosa Mara Medina
como secretaria, y los doctores Dra. Marina Villegas,
Dr. Emilio Morn y Dr. Jos de Frutos, como vocales.
La mencionada Tesis Doctoral fue llevada a cabo en el
Departamento de Electrocermica bajo la direccin del
Dr. Amador Caballero Cuesta.
Mayo-Junio (2005)
 SOCIEDAD ESPAOLA DE CERAMICA Y VIDRIO

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 IN MEMRIAM
Profesor Francisco Gonzlez Garca,
Investigador y docente
IN MEMRIAM
FRANCISCO GONZLEZ GARCA
El Profesor Francisco Gonzlez Garca falleci el da 28 de octubre de 2.004 en Sevilla, a la edad de 88 aos.
Catedrtico de Qumica
Inorgnica de la Universidad de
Sevilla, ex Rector de la Universidad
de Sevilla, Gran Cruz y Encomienda
de la Orden Civil de Alfonso X El
Sabio al mrito docente.
La Universidad de Sevilla celebr,
el pasado da 18 de Febrero un Acto
de Homenaje en memoria del Excmo.
Sr. D. Francisco Gonzlez Garca,
No es fcil hacer un recuerdo del
paso por esta vida de una persona
como el Profesor Dr. D. Francisco
Gonzlez Garca, pero intentaremos
realizar en esta nota una semblanza
de su vida y de su obra. Lo hacemos
desde el recuerdo, algunos de los ms
jvenes que conocimos de cerca su persona y su figura
como cientfico.
Don Francisco estuvo muy relacionado con la inves-
tigacin universitaria, sobre materias primas, silica-
tos y materiales cermicos, con el Consejo Superior
de Investigaciones Cientficas (CSIC) y con la propia
Sociedad Espaola de Cermica y Vidrio (SECV) desde
sus comienzos.
Para hacer una semblanza en recuerdo del Profesor
Gonzlez Garca, debemos mencionar, en primer
lugar, las palabras del actual Rector Magnfico de
la Universidad de Sevilla en el Acto de Homenaje a
ttulo pstumo en su memoria, en las que resalt que
la institucin universitaria Sevillana vivi una de sus
etapas ms fructferas durante el rectorado del Profesor
Gonzlez Garca, quien sin duda puso entonces los
cimientos de la modernizacin de la Universidad de
Sevilla.
Francisco Gonzlez Garca naci el ao 1916, en nueva Facultad de Qumica del Campus Universitario
la pequea localidad granadina de Cacn, municipio
de unos cuatrocientos habitantes, en la frontera con la
provincia de Mlaga. Uno de sus primeros maestros
de escuela supo ver el talento especial de Francisco a la
edad de cuatro aos y anim a su familia a potenciarlo.
Curs los estudios de Magisterio y los superiores de
Ciencias, Seccin de Qumicas, en la Universidad de
Granada con el resultado de un brillante expediente
acadmico, adems de hacer una carrera militar, por
circunstancias de la poca que le toc vivir. Realiz
el Doctorado bajo la direccin del eminente Profesor
Gutirrez Ros, colaborando tambin con el Profesor
Martn Vivaldi. Su tesis doctoral titulada Estudio de
los silicatos de la serie isomorfa montmorillonita-beide-
IX
IN MEMRIAM
llita, en la que se identificaron nuevos
miembros de esta serie, se public en
la revista Anales de la Real Sociedad
Espaola de Fsica y Qumica en 1948.
En el ao 1952 consigui ganar,
tras unas duras oposiciones, una
ctedra de Qumica Inorgnica en la
Universidad de Sevilla. Y a la ciudad
de Sevilla vino destinado para desa-
rrollar su carrera. Su gran colaborador
en tareas docentes y de investigacin,
Dr. D. Guillermo Garca Ramos, quien
adems lo conoci durante ms de
35 aos, nos lo dice con las siguien-
tes palabras en su discurso con oca-
sin del Homenaje tributado por la
Sociedad Espaola de Arcillas y nom-
bramiento como Socio de Honor el 8 de Septiembre de
1987, tambin en Sevilla:
Una fra noche de febrero de 1952, a principios de
mes, el Profesor Gonzlez Garca llegaba a Sevilla por la
estacin de San Bernardo, procedente de Granada, pues
acababa de ganar la ctedra de Qumica Inorgnica de
esta Universidad, tras unas brillantes oposiciones.El
investigador que les habla lo esperaba en la estacin,
dado que nos habamos conocido en Granada, nuestra
tierra natal, en cuya Universidad habamos estudiado
la misma carrera.
As pues, el Profesor Gonzlez Garca se incorpor a
la Universidad de Sevilla en el Curso 1952-1953 e inici
as sus actividades docentes e investigadoras, primero
en la vieja sede de la Universidad en la calle Laraa.
Posteriormente, desde los aos 60, en la seccin de
Ciencias en el edificio de la Fbrica de Tabacos, hasta
que se retir por imperativo legal a los 70 aos ya en la
de Reina Mercedes. Los que suscribimos, junto a tan-
tos y tantos discpulos, asistimos a su ltima clase
magistral en la que record sus principios y carrera
en la docencia y en la investigacin. En 1986 fue nom-
brado Profesor Emrito en la misma Universidad. La
Universidad de Sevilla rindi homenaje por su labor
docente y a su legado cientfico el mes de Febrero pasa-
do, pero tambin record su compromiso acadmico
en la gestin universitaria, destacndolo como una
figura clave. Primero como Director del Departamento
de Qumica Inorgnica de la Universidad de Sevilla,
despus como Decano de la Facultad de Ciencias (1962-
1968) y, entre 1977 y 1981, como Rector Magnfico de
la Universidad de Sevilla. El propio Departamento de
Mayo-Junio (2005)
 Qumica Inorgnica tom la decisin, refrendada por las
IN MEMORIAM
autoridades competentes, de hacerle un homenaje conti-
nuado en vida dndole su nombre al mismo, quedando
como Departamento de Qumica Inorgnica Francisco
Gonzlez Garca.
Un importante descubrimiento en sus primeras
investigaciones fue observar la prdida de la capaci-
dad de rehidratacin de las montmorillonitas cuando
se han saturado previamente con pequeos cationes,
como son Li, Mg Zn, publicando este descubrimiento
en una revista espaola. Este hecho fue tambin objeto
de investigacin por Greene-Kelly, ignorando la previa
publicacin en espaol, como ha sucedido muchas veces.
El resultado es que se le viene a denominar como efecto
Green-Kelly. Sin embargo, esta aportacin espaola fue
recogida por el Profesor Douglas M.C. MacEwan en su
captulo sobre montmorillonitas publicado en el clsico
libro de Brown y Brindley en 1961. Esta serie de estu-
dios y los siguientes realizados con montmorillonitas
fueron objeto de otras Tesis Doctorales dirigidas por el
Profesor Gonzlez Garca, en las que se descubri, como
resultado de gran inters, que la expansin de los sili-
catos laminares por etilenglicol no es la misma cuando
se acta sobre muestras saturadas con cationes de gran
tamao relativo y pequea carga, como K. Esto ha servi-
do para diferenciar despus los silicatos laminares di- y
trioctadricos.
Desde su incorporacin en 1952 a la ctedra de
Qumica Inorgnica en Sevilla, el Profesor Gonzlez
Garca continu las investigaciones que haba comen-
zado en la Universidad de Granada, dentro del campo
de los Silicatos y de la Edafologa. En el ao 1953 funda
el Centro de Edafologa y Biologa Aplicada del Cuarto
(CEBAC), centro del Consejo Superior de Investigaciones
Cientficas (CSIC), primero como Seccin del Instituto
de Edafologa de Madrid, hoy denominado Instituto de
Recursos Naturales y Agrobiologa de Sevilla (IRNAS) y
llega a ser su Director hasta 1976. En palabras del Profesor
M. Lora-Tamayo se cre el Instituto de Edafologa de
Madrid y, como seccin de l, la correspondiente en
Sevilla, bajo la direccin del profesor Gonzlez Garca,
que ha dado a sta el nivel de Instituto y elevado su
categora funcional notablemente.
Entre sus ms destacadas responsabilidades, fue
Director del Instituto Nacional de Edafologa Jos M
Albareda desde 1966 hasta 1979, ao en el que des-
aparece en una nueva reestructuracin. Presidente del
Patronato Alonso de Herrera en 1970 durante cuatro aos
y Presidente de la Divisin de Ciencias durante dos aos,
Vocal de la Comisin Asesora de Investigacin Cientfica
y Tcnica desde 1960 y miembro del Comit Cientfico
de la misma. Director del Departamento de Qumica
Inorgnica de la Universidad de Sevilla, Decano de la
Facultad de Ciencias (1962-1968) y Rector Magnfico de
la Universidad entre 1977 y 1981. Presidente de la Real
Academia Sevillana de Ciencias desde su constitucin,
continuada despus por el Profesor D. Rafael Mrquez.
Dentro de su labor investigadora dirigi ms de 50
tesis doctorales, siendo la ltima la dirigida a uno de los
autores de esta nota (Manuela Raign). Ms de 10 tesis
tratan sobre la gnesis, propiedades y aplicaciones de
arcillas, estudiando entre otras la gnesis y transforma-
ciones de las vermiculitas, siendo el mineral procedente
de Santa Olalla (Huelva) objeto de la tesis doctoral del
Investigador del CSIC Guillermo Garca Ramos, trabajo
que fue presentado en 1960 al VII Congreso Internacional
de Ciencia del Suelo (Madison, Wisconsin). En otros
Mayo-Junio (2005)
trabajos de tesis que dirigi se estudiaron la gnesis de
IN MEMORIAM
caolines de Sierra Morena, las arcillas decolorantes de
Lebrija (fundamentalmente paligorsquticas), as como
la de otros minerales relacionados, tales como diatomi-
tas y tremolita. Tambin dirigi tesis doctorales sobre la
geoqumica del Fe, Co y Mn, as como un amplio estudio
de los suelos del valle del Guadalquivir. En el CEBAC
(CSIC) de Sevilla, en colaboracin con el Departamento
de Qumica Inorgnica, se estudiaron los distintos sue-
los de Andaluca, dando lugar a los mapas edafo-agro-
biolgicos de Espaa, destacando los de Huelva, Cdiz,
Crdoba, etc.
Junto a sus colaboradores, public 14 trabajos
sobre Arcillas Cermicas de Andaluca, la mayora
en el Boletn de la Sociedad Espaola de Cermica y
Vidrio, desde 1964 hasta 1980. Y adems, elabor junto
a varios colaboradores el Mapa de arcillas cermicas de
Andaluca. Con posterioridad, tambin en sus ltimos
trabajos figuran otros sobre aplicaciones industriales de
arcillas en el campo de la Cermica y Refractarios, as
como en el de Arqueometra en cuanto a estudio, compo-
sicin, tecnologa y procedencia de los materiales arqueo-
lgicos. En relacin con las Tesis que dirigi, public ms
de 200 trabajos, siendo unos 50 de ellos, sobre arcillas, lo
que le vali el reconocimiento de la comunidad cientfi-
ca, nacional e internacional, en el campo de la Qumica
Inorgnica, incluyendo los silicatos y compuestos orga-
nometlicos. Entre los profesores e investigadores que se
formaron en su Departamento y en el CSIC en Sevilla, se
pueden contabilizar ms de una docena de Catedrticos
de Universidad, incluyendo a su hijo Francisco (catedrti-
co en la Universidad de Sevilla) y su hijo poltico Ernesto
Carmona (catedrtico en la Universidad de Sevilla y
un referente internacional en el campo de la Qumica
Organometlica), as como un nmero superior a 20
investigadores del CSIC; algunos de ellos continan, en
parte, la lnea de investigacin sobre silicatos que comen-
z a desarrollar en Sevilla desde 1952.
Entre los reconocimientos que tuvo, destaca el
Premio Nacional de Investigacin Francisco Franco,
uno de los ms prestigiosos en su poca, adems de la
Gran Cruz y la Encomienda de la Orden de Alfonso X El
Sabio, concedida al mrito docente.
Los que escribimos esta semblanza y le recordamos,
adems de ser alumnos de Don Francisco en su asigna-
tura de Qumica Inorgnica, en Segundo Curso de la
Licenciatura en Ciencias Qumicas, trabajamos duran-
te algunos aos, junto con el Dr. Garca Ramos, en el
departamento que dirigi, donde inici nuestros prime-
ros pasos en el campo tan apasionante de la investiga-
cin cientfica, en particular la de Silicatos y Tecnologa
Cermica, de lo que le estaremos siempre agradecidos.
Fue nuestro Catedrtico-Padrino en las respectivas Tesis
de Licenciatura (1985 y 1992). La direccin de su ltima
tesis doctoral sobre materiales cermicos de cordierita
tiene fecha de 1998.
Es innegable el esfuerzo realizado y la dedicacin al
estudio y al trabajo de Don Francisco durante toda su
vida, su rigor expositivo que brillaba en la docencia que
imparta, su carcter estricto y exigente en el rendimien-
to y el celo investigador que posea, como cientfico, en
su afn de descubrir y formar a sus discpulos. l mismo
mencionaba que uno de sus mayores orgullos era haber
sido superado por ellos. Nos queda su obra cientfica y
su recuerdo. Descanse en paz, despus de una larga y
fructfera vida.
M. Raign Pichardo y P. J. Snchez-Soto
X
 NOTICIAS

NOTICIAS
NOTICIAS

IX Conference & Exhibition Invited Lectures:

Jiping Cheng, The Pennsylvania State University,
of the European Ceramic University Park, USA, Microwave sintering of ceramics
and composites
Society, 19 - 23 June, 2005, Brian Derby, University of Manchester, School
Portoro, Slovenia of Materials, Manchester, UK, Highly concentrated
ceramic suspensions for ink jet printing
Paul Bowen, Institut des Matriaux, EPFL, Lausanne,
Switzerland, Colloidal processing of nanosized ceramic
Highlights from programme
powders - from self-assembled layers to sintered
nanoceramics
Plenary Lectures:
Chartier Thierry, Ceramic Processing Group, SPCTS
Stephen Wood, University of Sheffield, Institute of
UMR CNRS, ENSCI, Limoges, France, Freeform
Work Psyhology, UK Whos Affraid of Nanotechnology
fabrication for shaping 3D ceramic parts with a high
The Social Debate
dimensional resolution: Ink-jet printing
Norbert Kroo, Hungarian Academy of Science,
Sridhar Komarneni, The Pennsylvania State
Hungary, ERA, FP7, ERC and Central Europe
University, University Park, USA, Novel synthesis of
Tanja Pak, University of Ljubljana, Academy of Fine
nanorods and nanowires
Arts, Slovenia, Searching for the Infinite in the Finite
Slavko Bernik, Institut Joef Stefan, Slovenija, The
Artists Approach to Design with Glass
mechanism of grain growth in Al2O3-doped ZnO
Zhijian Shen, Stockholm University, Sweden, SPS
Symposium A: Basic Science
processing of ceramics with tailored microstructures
Koji Watari, National Institute of Advanced
Key Note Lectures:
Industrial Science and Technology, Nagoya, Japan,
Suk-Joong L. Kang, KAIST, Taejona, Korea, Use of
Novel pressure sintering technology for thick film and
Defects for Microstructure Control in Ceramics
laminate-centrifugal sintering
Yuri Gogotsi, Drexler University, USA, to be
announced later
Sunggi Baik, Pohang University, Korea, Structure
Symposium C: Analytical Methods
and Dynamics of Ferroelectric Domains in Epitaxial PZT
Key Note Lecture:
Thin Films-Synchrotron Radiation Study
Robert Sinclair, Materials Science and Engineering,
Invited Lectures:
Stanford University, USA, In situ studies of
Gary L. Messing, The Pennsylvania State University,
crystallization and anisotropic properties of a high K
University Park, USA, Co-sintering of Integrated
dielectric oxide
Ceramics
Invited Lectures:
Dragan Uskokovic, Institute of Technical Sciences,
Frederic ThibulStarzyk, Universite de Caen-
Belgrade, SiC, Designing of fine particles for
Basse Normandie, CAEN CEDEX, France, Infrared
contemporary technology
spectroscopy of ceramics and oxides: from lattice defects
J. P. Gluha, University of Missouri-Rolla, USA,
to surface properties
Reaction chemistry in the synthesis of complex Bi-Zn-
Velimir Radmilovic, University of California,
niobates of interest for electronic applications
Berkeley, USA, (111) fiber texure formation in 3C - SiC
films on Si(100) substrates
Symposium B: Processing
Jian-Min Zuo, University of Illinois, Urbana-
Champaign, USA, Structure and growth of carbon and
Key Note Lectures:
boron nitride nanotubes
Fritz Aldinger, Max-Planck-Institut fr
Wilfried Sigle, Max-Planck-Institut fr
Metallforschung, Stuttgart, Germany Progress in
Metallforschung, Stuttgart, Germany, Analytical
bioinspired synthesis of ceramic materials
transmission electron microscopy-present and future
Lennart Bergstrm, Arrhenius Lab., Stockholm
Alojz Kodre, University of Ljubljana and Institut
University, Sweden, Interfacial engineering of inorganic
Joef Stefan, Slovenija, X-ray absorption spectroscopy
materials: Tailoring organic additives for direct casting
in analysis of chemical structure
and optimised processing of ceramic, hard metal and
Cerny Radovan, Universite de Geneve, Switzerland
cementitious materials
Diffraction methods for materials characterization
Ralf Riedel, Technische Universitt Darmstadt,
Horst Boehm, J. Gutenberg Universitt, Mainz,
Germany, Polymer derived ceramics

XI Mayo-Junio (2005)
 Germany, Mechanisms as Structural Phase transitions
NOTICIAS
Peter Petrov, London South Bank University, UK,
Advanced Methods for Thin Films Characterisation
Symposium D: Inorganic Nanomaterials
Invited Lectures:
Suzuki Yoshikazu, Institute of Advanced Energy,
Kyoto, Japan, Microstructure and properties of long
titanate nanofibers prepared from natural rutile
Akinc Mufit, Iowa State University, USA, Fructose
as dispersant for nanosize alumina suspensions
Nadine Millot, University of Burgundy, Ames,
France, Nanostructured oxides:influence of preparation
route on the relevant properties
Alain Peigney, Universit Paul-Sabatier, Toulouse
Cedex, France, Carbon nanotubes: CCVD synthesis
methods and application to ceramic matrix composites
Sevchenko Ya.Vladimir, Grebenshchikov Institute
of Silicate Chemistry RAS, Saint Petersburg, Russia,
Structural chemistry of the nanoworld
Stephen Freiman, NIST, Geithersburg, USA, Fracture
at the nanoscale or How we will ensure reliability
Polona Umek, Instiute Jozef Stefan, Slovenia,
Cu(OH)2 nanoribbons: synthesis and magnetic
properties
Kuzmany Hans, Universitaet Wien, Austria, Tube-
tube interaction and high curvature effects in double-
wall carbon.
Specially Invited on Nanowire Session:
Vincenc Nemanic, Institute Jozef Stefan, Slovenia,
Inorganic nanotubes a new perspective for field
emission devices
Maja Remskar, Institute Jozef Stefan, Slovenia,
Synthesis, electron microscopy and applications of
inorganic nanotubes
Madoka Tokumoto, National Institute of Advanced
Industrial Science and Technology, Japan, Nonlinear
optical property of carbon nanotubes and its application
as saturable absorbing device for optical fiber
communication
Chris Ewels, Laboratoire de Physique des Solides,
France, Modelling and spectroscopy of titania based
nanostructures
Daniel Vrbanic, Faculty of Chemistry and Chemical
Technology, Slovenia, Structure of Mo6S3I6 nanowires
Igor Vilfan, Institute Jozef Stefan, Slovenia, Density-
functional theory of various Mo-S-I nanowires:stability
and elastic properties
Valeria Nicolosi, University of Dublin -Trinity College,
Ireland, Mo6S4. I4.5 nanowires: characterization of a novel
material purification, solubilization and structure studies
Abdou Hassanien, Nanotechnology Research
Institute AIST, Japan, The atomic structure, mechanical
and electronic properties of carbon and dichalcodenide
nanotubes
Robert Dominko, National Institute of Chemistry,
Slovenia, Nano-structured materials as candidates for
high density Li-ion batteries
Fabrice Dassenoy, LTDS, Ecole Centrale de Lyon,
France, Tribological performances of Mo-S-I nanowires
Hiromichi Kataura, Nanotechnology Research
Institute AIST, Japan, Single-wall carbon nanotubes
grown in ceramics
Mayo-Junio (2005)
Denis Arcon, Instiute Jozef Stefan, Slovenia,
NOTICIAS
Synthesis, Structural determination and adsorption
properties of titania based nanotubes
Symposium E: Materials in Electromagnetic
Fields
Key Note Lectures:
Joachim Maier, Max Planck Institute for Solid State
Research, Stutgart, Germany, Size effects in ceramic
nano-materials: transport, reactivity and storage
Jean-Luc Adam, Universit de Rennes, Rennes Cedex,
France, Non-oxide glassy materials for photonics
Yukio Sakabe, Murata Manufacturing Co.,Ltd.,
Japan, Application of nano-sized BaTiO3 powder for
advanced electroceramics
Invited Lectures:
Taras Kolodiazhnyi, National Institute for Materials
Science, Tsukuba, Japan, Bipolaron ground state in
chemically doped BaTiO3
Anne - Lise Adenot, CEA Le Ripault, Monts, France,
Fundamental limitations of bulk microwave magnetic
materials and new opportunities as building blocks of
metamaterials
Masayuki Nogami, Nagoya Institute of Technology,
Japan, Fast proton-conducting sol-gel glasses for fuel
cell electrolyte
Evelyne Fargin, Inst. de Chimie de la Matire
Condense de Bordeaux, Univ. de Bordeaux 1, France,
Transparent ceramics for high power laser applications:
influence of the Yttria powder morphology on the
densification ability
Norbert Klein, Forschungszentrum Jlich GmbH,
Institut fr Schichten und Grenzflchen, Jlich, Germany,
Electromagnetic bandgap structures for milimetre wave
applications
Jan Van Herle, cole Polytechnique Fdrale de
Lausanne, Lausanne, Switzerland, Local current
measurement in a solid oxide fuel cell repeat element
Peter Supancic, University of Leoben, Austria,
Mechanical reliability and fracture of electroceramics
John TS Irvine, School of Chemistry, University of St.
Andrews, St. Andrews, UK, A new approach to short
range order in zirconia electrolytes
Philippe Tailhades, CIRIMAT UMR-CNRS, Universit
Paul-Sabatier, Toulouse Cedex, France, Elaboration
and physico-chemical properties of delafossite films
and metalic copper/spinel ferrite films, deposited on
conventional glass substrates
Symposium F: Structural Ceramics
Key Note Lectures:
Michael J. Hoffmann, Institute for Ceramics in
Mechanical Engineering, Karlsruhe, Germany, Silicon
nitride ceramics-materials engineering at the atomic
level
Koichi Niihara, ISIR, Osaka University, Osaka, Japan,
New nanocomposite ceramic materials with multi
functionality
Invited Lectures:
Alida Bellosi, Institute for Science and Technology,
Faenza, Italy, UHTC-Ultra High Temperature Ceramics:
State of Art and Future Directions
XII
 Tanja Lube, Montana Universitt Leoben, Leoben,
NOTICIAS
Austria, A silicon nitride reference material A testing
program of ESIS TC6
Pavol Sajgalik, Institute of Inorganic Chemistry, SAS,
Bratislava, Slovakia, Preparation of SiC-(Nb,Ti)(ss) -
(Ti, Nb)C(ss) cermets by in-situ reaction
William J. Clegg, University of Cambridge,
Cambridge, UK, Hardness and the resistance of the
crystal lattice to dislocation motion
Torrecillas Ramon, INCAR-CSIC, Oviedo, Spain,
Alumina nanocomposites for structural applications
Tatsuki Ohji, Advanced Manufacturing Research
Institute, Nagoya, Japan, Ceramics with hyper-
organized structure and their applications
Hua-Tay Lin, Oak Ridge National Laboratory, Oak
Ridge, USA, Development of silicon nitride ceramic
components for advanced turbine and microturbine
systems
Mrityunjay Singh, NASA Glenn Research Center,
Cleveland, USA, Robust joining and integration of
advanced ceramics and composites: challenges,
opportunities and realities
Hasan Mandal, Anadolu University, Eskisehir,
Turkey, Novel SiAlON ceramics for cutting tool
applications
Symposium G: Bio-Ceramics
Key Note Lectures:
Wolfram Hland, Ivoclar Vivadent AG, Schaan,
Liechtenstein, Principles and phenomena of
bioengineering with glass-ceramics
Tadashi Kokubo, Chubu University, Aichi, Japan,
Titania-based bioactive materials
Invited Lectures:
Chikara Ohtsuki, Nara Institute of Science and
Technology, Nara, Japan, Design of novel bioactive
materials through organic modification of calcium
silicate
Anna Tampieri, Institute for Science and Technology,
Faenza, Italy, Biomimetic apatites as precursors of new
bio-hybrid composites
Hyoun-Ee Kim, Seoul National University,
Seoul, Korea, Hydroxyapatite-based composites for
biomedical applications
Mike Swain, Faculty of Dentistry, University of
Sydney, Sydney, Australia, Advanced dental ceramics:
are they appropriate?
Antoni P. Tomsia, Lawrence Berkeley National
Laboratory, Berkeley, USA, Complex nanocomposites
for bone regeneration
I-Wei Chen, Department of Materials Science and
Engineering, University of Pennsylvania, Philadelphia,
USA, Multifunctional nanoparticles and their
hierarchies for biomedical applications
Roger Morrell, National Physical Laboratory,
Teddington, UK, S Hughes (Morgan Advanced
Ceramics), Factors influencing the reliability of ceramic
femoral components
Symposium H: Traditional Materials
Key Note Lectures:
Jos M.F. Ferreira, Universidade de Aveiro, Aveiro,
XIII
Portugal, Recycling of industrial residues in traditional
NOTICIAS
ceramic formulations the stride for a clean and
friendly environment
Tiziano Manfredini, Universit di Modena e Reggio
Emilia, Modena, Italy, Thermal spraying to coat
traditional ceramic substrates: case studies
Arnaldo Moreno Berto, Instituto de Technologia
Cermica, Castelln, Spain, Ceramic tiles: above and
beyond traditional applications
Invited Lectures:
Fernanda Andreola, Universit di Modena e Reggio
Emilia, Modena, Italy, CRT glass as secondary raw
material for ceramic glaze
Dilshat Tulyaganov, University of Aveiro, Aveiro,
Portugal, Influence of lithium oxide as auxiliary flux
on the properties of triaxial porcelain bodies
Emilio Criado Herrero, Instituto de Cermica y
Vidrio, Madrid, Spain, Perspectives for the refractories
industry: complexity and challenges
Jeff Smith, University of Missouri-Rolla, Rolla, USA,
Interaction of alumina with lime-based refractory ceramic
nozzles during casting of aluminum-killed steel
Leonardo Esposito, Centro Ceramico Bologna, Italy,
Polishing of porcelain stoneware tiles and induced
damage
Giuliano Tari, CERAM Research, Stoke-on-Trent,
UK, A non destructive method to assess delamination
of ceramic tiles
Electroceramics X
Toledo (Spain)
18-22 June, 2006
Aim & Scope:
Electroceramics have been consolidated in the last
decade as one of the most attractive areas in material
science because of the combination of basic science and
technological impact. Ceramics having mainly electric,
magnetic and optical functions are entering very fast in
the nanoworld, which means an unique opportunity.
The series of Electroceramics meetings have become
an important forum to discuss recent advances and near
future key points for the development of this area. As
the main conference in this topic, Electroceramics X will
serve the community as a meeting point for researchers
and engineers and will contribute to the dissemina-
tion of new ideas. At this time, Electroceramics X will
be hold in the three cultures town of Toledo, which
offers an unforgettable place to stay and enjoy, with the
best of the Spanish heritage and hospitality.
Conference Topics:
CERAMIC PROCESSING
Powder Synthesis
Thick and Thin Film Technologies. Multilayer
Structures
Nanotechnologies
Sintering and Microstructure Development
Grain Boundary Engineering
Mayo-Junio (2005)
 CHARACTERIZATION Treasurer: F. Capel (ICV-CSIC, SECV)
NOTICIAS

NOTICIAS
A.C. Caballero (ICV-CSIC)
Powders and Ceramics N. Casa (ICMAB-CSIC)
Electric and Magnetic Ceramics. J. Cascn (UCLM)
Space Charges J. de Frutos (ETSIT-UPM)
Ageing and breakdown X. de la Fuente (ICMA-CSIC)
Ionic, Electronic and Mixed Conduction J.M. Iraizoz (UCLM)
Transport phenomena, diffusion J.L. Pons (IAI-CSIC)
Defects in Electroceramics J.M. Riveiro (UCLM)
Microscopy, diffraction, spectroscopy, J. Velasco (SECV)
J. de la Villa (SECV)
APPLICATIONS
Abstract Submission:
Dielectrics, Ferroelectrics, Piezoelectrics, Pyroelectrics
Microwave Dielectrics Abstracts are to be submitted on line by the Presenting
Optical ceramics Author and prepared according to the on-line Abstract
Magnetic and Superconducting Ceramics, GMI, GMR Instructions available at the Conference website.
Spintronics The Scientific Committee will refer all abstracts and,
Electronic Packaging if accepted, will decide the presentation form (oral or
Sensors, Actuators, Transducers poster) according to authors suggestion and program
Varistors, PTCR, NTCR requirements.
Fuel Cells, Batteries, Membranes Multiple papers from the same Presenting Author
would be discouraged in order to open opportunities for
International Advisory Board: the broadest possible participation.
The accepted papers should be presented at
Chairman: Jos F. Fernndez (Spain) Electroceramics X by at least one of the authors.
Abstract submission ends on November 15, 2005.
Honorary Chairman: P.H. Duvigneaud (Belgium) Acceptance notification will be provided by February
1, 2006.
R. Brook (UK) R. Buchanan (USA)
M.L. Calzada (Spain) R. Freer (UK) Publication:
S. Gevorgian (Sweden) J.M. Haussonne (France)
S.I. Hirano (Japan) H.G. Kim (Korea) Authors are invited to submit papers for its publi-
S.B. Krupanidhi (India) M. Kosec (Slovenia) cation in a special issue of the Journal of the European
V. Lantto (Finland) M. Lejeune (France) Ceramic Society. Acceptance of papers is subject to
L. Li (China) F. Marques (Portugal) peer review.
L. Mitoseriu (Romania) M. Miyayama (Japan)
P. Nanni (Italy) D. Payne (USA) Keydates:
J. Petzelt (Czech Republic) G. Rosenman (Israel)
J. Schoonman (The Netherlands) N. Setter (Switzerland) Submission off Abstracts November 15, 2005
D. Suvorov (Slovenia) E. Traversa (Italy) Notification of Abstract Acceptance February 1, 2006
H. Tuller (USA) J.A. Varela (Brazil) Preliminary Program February 28, 2006
R. Waser (Germany) W. Wolny (Denmark) Hotel Accommodation March 15, 2006
W.G. Zhu (Singapore). Registration at Reduced Rate April 15, 2006
Deadline for Registration May 22, 2006
National Scientific Committee: Paper submission June 22, 2006
J.L. Acosta (ICTP-CSIC) M.A. Alario (UCM),
A. Albareda (UPC) C. Arag (UAM), Venue:
F. Briones (IMM-CNM-CSIC) J.B. Carda (UJI)
F. Cebollada (UPM) R. Ceres (IAI-CSIC) Electroceramics X will take place at Beatriz Hotel in
A. Domnguez (US) C. Gmez (UPN) Toledo (Spain).
A. Hernando (UCM) C. Miravitlles (ICMAB-CSIC) Toledo is situated near to Madrid (75 km), the capital
F.R. Montero de Espinosa (IA-CSIC) C. Moure (ICV-CSIC) of Spain, and is full of many charming narrow, winding
R. Navarro (UZA) P. Nuez (ULL) streets, which are almost like a labyrinth. The diverse archi-
V.M. Orera (ICMA-CSIC) L. Pardo (ICMM-CSIC) tectural styles that traverse the centuries from Gothic to
J. Pascual (UMA) J. M. Prez (UPV) Baroque have benefited from the citys ties to the Christians,
A. Rodrguez (ICMSE-CSIC) M.A. Sears (UDC) Moors and Jews. Toledo is very accessible on foot. June is a
R. Sirera (UNAV) J.D. Solier (UNEX) sunny month with very warm temperatures.
A. Vrez (UCIII)
Accommodations:
Organizing Committee:
Rooms at Beatriz Hotel will be available at spe-
Chairman: J. F. Fernndez (ICV-CSIC) cial fares (Deadline for Beatriz Hotel Accommodation:
Secretary: M. Villegas (ICV-CSIC) March 15, 2006).

Mayo-Junio (2005) XIV

 Hotel Beatriz los atractivos futuros mercados vemos oportunidades
NOTICIAS

NOTICIAS
beatriztoledo@beatrizhoteles.com de crecimiento enormes para el sector. El objetivo de
Fax: +34 925 21 58 65 nuestra estrategia de marketing es un aumento adicional
de nuestros participantes feriales de todo el mundo
As one of Europes most visited tourist sites, Toledo coment Detlev R. Gantenberg, gerente de Messe
has a number of hotels and other types of accommoda- Mnchen GmbH.
tions. El recinto ferial de Mnich convence por su central
posicin geogrfica, as como el ultramoderno aeropuerto
Further information: internacional y con conexiones excelentes. CERAMITEC
se celebra en una de las ciudades ms bonita y agradable
http://electro-x.etsit.upm.es de Europa.
Ya en la ltima edicin del 2003 asistieron
Address: Sociedad Espaola de Cermica y Vidrio aproximadamente 25.000 visitantes profesionales
Instituto de Cermica y Vidrio procedentes de 106 pases a Mnich, en la que 765
Kelsen 5 expositores de 41 pases presentaron su oferta. La
28049 Cantoblanco. Madrid. Spain mayora de los visitantes se trataban de profesionales
Phone: +34 91 735 58 40 de alta categora con competencia decisoria, entre ellos
Fax: +34 91 735 58 43 muchos propietarios de empresas, gerentes y directores
e-mail: electroceramics-x@icv.csic.es de departamento.
En el ao 2006 CERAMITEC se posiciona
internacionalmente como saln lder con su nica oferta
Organize: completa para la industria cermica y la industria de
pulvimetalurgia.

Ms informaciones: www.ceramitec.de

Fabricado con biogs,

Cermica Piera se avanza
a las estrategias del sector
para cumplir con el proto-
colo de Kioto

Cermica
Nueva fecha ferial: Piera present
por primera vez
CERAMITEC del 16 al 19 de en Construmat el
EcoManual, un
mayo de 2006 en Mnich nuevo ladrillo
manual de alta
calidad lanzado
En la reunin del 24 de febrero de 2005, el consejo al mercado hace
de expositores de CERAMITEC se reforz con nuevos unos meses que
miembros internacionales. De comn acuerdo se ha supone un salto
fijado como nueva fecha del 16 al 19 de mayo de cualitativo con
2006. De esta manera, Messe Mnchen satisface las respecto a los ladrillos manuales fabricados hasta la
expectaciones y los deseos de los expositores y visitantes fecha, puesto que se han logrado mantener inalterables
y presenta una solucin a la constelacin problemtica las propiedades estticas exclusivas de este material
de las ferias en el ao 2006. La reduccin a cuatro das (no hay dos unidades que sean iguales) garantizando,
facilita el intercambio concentrado de informaciones a su vez, un comportamiento fsico y tcnico propio de
entre expositores y visitantes profesionales. los ladrillos fabricados en serie. Se trata de un produc-
CERAMITEC 2006 presenta una extensa oferta de to nico con unas prestaciones superiores a cualquier
maquinara, equipos, instalaciones, procesos y materias ladrillo manual realizado hasta la fecha. Y este logro se
primas para cermica y pulvimetalurgia. Ningn saln ha conseguido adems utilizando una fuente de energa
internacional especializado internacional del ramo alternativa: el biogs, lo que constituye una experiencia
presenta una oferta de productos tan amplia. pionera dentro del sector de la construccin en Espaa y
Con el 65 por ciento de expositores y visitantes que asegura que no slo el material (totalmente natural),
profesionales procedentes del extranjero CERAMITEC sino buena parte del proceso de produccin es ecolgico
destaca por su orientacin internacional nica. El objetivo y respetuoso con el medio ambiente.
es extender an ms esa internacionalizacin. En

XV Mayo-Junio (2005)
 Cabe resaltar que la utilizacin del Biogs como
NOTICIAS

NOTICIAS
fuente de energa alternativa en la produccin ha evi-
tado el consumo de casi 5.000.000 de litros de combus-
tibles fsiles. Asimismo, Cermica Piera deja de emitir
9.000 toneladas de CO2 a la atmsfera al ao.
Por lo tanto, esta iniciativa constituye un referente
fundamental para las empresas del sector en un contex-
to como el actual, marcado por la puesta en marcha del
protocolo de Kioto, la aplicacin del cual debe contribuir
a una industria ms limpia pero no por ello menos com-
petitiva, para no comprometer el progreso econmico y
social del pas.
Entre las prestaciones tcnicas, EcoManual Piera
destaca por ser un ladrillo hidrofugado (repele el agua
de lluvia), sin eflorescencias y no heladizo, con una
casa, construida exclusivamente con vidrio, incluyendo
absorcin media del 8% y unos ndices de resistencia a
el suelo, las paredes, las fachadas, las cubiertas y todo el
la compresin de 495 Kg/cm2 y de succin de 0,05 g/cm2
mobiliario. Incluso la zona exterior, que ocupa 312m2,
x min. Como consecuencia de todas estas cualidades,
cont con espacios urbanos realizados en su totalidad
EcoManual Piera dispone del certificado AENOR,
con dicho material. Es la primera vez que se realiza una
por haber superado satisfactoriamente la norma UNE
estructura de este tipo completamente de vidrio.
67.109.
Vitro Cristalglass fue el encargado de proveer los
Adems, el EcoManual Piera sobresale por su tole-
500m2 de vidrio necesarios para su construccin. Para
rancia dimensional y sus cuatro caras vistas, lo cual le
el proyecto se utilizaron varios tipos de vidrio, como el
convierte en un ladrillo de fcil colocacin, debido a que
Isolar Multipact, vidrio de seguridad para la proteccin
el operario no tiene que preocuparse de la cara que que-
de personas y bienes, combinado con butirales de
dar en el exterior. De esta forma, el tiempo de ejecucin
varios colores. Adems, la casa dispuso de dobles
se reduce considerablemente.
acristalamientos con persianas interiores (Isolar Sun-
El EcoManual Piera ofrece numerosas aplicaciones
Flex), vidrios mateados, serigrafiados, etc. Tambin se
decorativas tanto en cerramientos exteriores como inte-
pudo apreciar el Superdual-T, la ltima novedad de
riores, permitiendo distintas posibilidades estticas gra-
Vitro Cristalglass, que se caracteriza por tener un doble
cias a la variedad de formatos: se encuentra disponible
efecto visual: desde el exterior, la fachada se aprecia
en dos medidas (28 x 13,5 x 4,5 cm. y 24 x 11,5 x 4,5 cm.)
totalmente blanca, gracias a la multitud de pequeos
y en tres colores (rojo, claro y levante).
puntos blancos aplicados al vidrio; sin embargo, en el
Cermica Piera fue creada hace casi 40 aos. Est
interior, debido a un efecto ptico, apenas se perciben
integrada dentro de un grupo empresarial que incluye
esos puntos, permitiendo la total visin a travs del
tambin a Cermicas Pierola, Almar y DCPAL, cons-
cristal.El xito de Vitrohouse.com ha permitido a los
tituyendo uno de los principales grupos del sector en
organizadores del proyecto mostrar cmo el vidrio
Catalua.
puede ser un material completamente eficaz en la
Es una empresa especializada en la fabricacin de
construccin de cualquier vivienda. Dicho material,
ladrillos cermicos a partir de arcillas de singular cali-
adems, responde a los criterios de la arquitectura
dad procedentes de la zona de Piera, en la provincia
sostenible, puesto que es completamente reciclable y su
de Barcelona, que comercializa sus productos por toda
vida til es ilimitada.
Espaa.
Es la nica empresa del sector del ladrillo manual en
Catalua que dispone de una certificacin de calidad de
la fbrica y del producto. Indice internacional de revis-
tas de idioma castellano
Vitro Cristalglass El Instituto Iberoamericano de Informacin en
acristala la vivienda Ciencia y Tecnologa, es una sociedad profesional
creada con el propsito de canalizar informacin cien-
virtual de Construmat tfico-tecnolgica entre investigadores, acadmicos y
profesionales de todos los pases Iberoamericanos. El
Vitro Cristalglass, una de las principales empresas principal objetivo de la organizacin es la promocin
de la industria de la transformacin del vidrio del del conocimiento, desarrollo y aplicacin de todas las
pas, ha colaborado con ANAVIF (Asociacin Nacional actividades que impliquen el uso y difusin de informa-
para la Vivienda del Futuro) en el acristalamiento del cin cientfica y tecnolgica, con fines de investigacin,
ambicioso prototipo Vitrohouse.com. Se trata de una docencia y desarrollo de nuestros pases, en todos sus
vivienda virtual y sostenible, diseada por Luis de aspectos, ya sean prcticos o tericos.
Garrido, especialista en arquitectura sostenible. El ndice Internacional de Revistas Cientficas y
El proyecto, que se pudo visitar a lo largo de la pasada Tecnologa Actualidad Iberoamericana constituye
feria Construmat, cont con un gran xito de asistencia. el medio de materializa la comunicacin frecuente
Ms de 70.000 visitantes accedieron a los 126m2 de la y peridica con los asociados y con todas las perso-

Mayo-Junio (2005) XVI

 nas e instituciones interesadas. Adems, Actualidad
NOTICIAS
Iberoamericana publica informacin sobre congresos
futuros y pasados, y sobre investigacin que se realiza
en distintas universidades e instituciones iberoameri-
canas.
El Indice Actualidad Iberoamericana es publicado
junto con el Centro de Informacin Tecnolgica (CIT), y
su revista internacional, arbitrada y ampliamente indi-
zada, Informacin Tecnolgica, publicada en forma
ininterrumpida desde 1990.
Como Ud. sabe su revista esta siendo incluida desde
hace algn tiempo en nuestro ndice Internacional
Actualidad Iberoamericana. El ndice es incluido en
forma peridica y gratuita en nuestra pgina en Internet
(www.citchile.cl; www.ditchile.cl/b2.htm).
Adems del ndice, el Centro de Informacin
Tecnolgica edita desde el ao 1990 la revista
Informacin Tecnolgica (ISSN 0716-8756) en formato
impreso en papel. Desde comienzos del ao 2004, la
revista est tambin incorporada a la biblioteca elect-
nica Scielo (www.scielo.org). La incorporacin a Scielo
(ISSN 0718-0764) le ha dado a nuestra la ms amplia
cobertura y est llegando a miles de investigadores de
toda ibero Amrica, con ms de 25 mil artculos descar-
gados durante el ao 2004. Hemos querido aprovechar
esta amplia cobertura y alcance para informar sobre
Actualidad Iberoamericana a travs de Scielo y promo-
ver as las revistas que indicamos, entre las que est la
suya.
A partir del primer numero del ao 2005, hemos
incluido un resumen de Actualidad Iberoamericana
en nuestra revista Informacin Tecnolgica, tanto en la
versin impresa como en la versin electrnica. Bajo el
Titulo En Sntesis, la revista resume lo publicado en
el ltimo nmero de nuestro ndice Internacional, del
que su revista forma y seguir formando parte. Por lo
tanto, a partir de ao 2005, Actualidad Iberoamericana
seguir siendo publicada en forma completa en nuestra
pgina WEB (www.citchile.cl/b2.htm) e incluiremos un
resumen de cada nmero en nuestra revista impresa y
en Scielo (www.scielo.cl)
Curso de Fundamentos de
Reologa
Los prximos das 4 y 5 de Julio de 2005 en el
Instituto de Cermica y Vidrio del CSIC se impartir el
curso del FUNDAMENTOS DE REOLOGA. Este curso
va dirigido a aquellos tcnicos (qumicos, farmacuticos,
fsicos, ingenieros, etc...) y profesionales de la Industria
y de Organismos de Investigacin y Universidades que
precisan la reologa para desempear su trabajo.
El curso est apoyado por las empresas IFI y Thermo
Electron Corporation, que presta sus equipos ms
modernos para la realizacin de las prcticas. Se impar-
tirn clases tericas, en las que se expondrn los funda-
mentos de las medidas reolgicas, y clases prcticas, en
las que se llevarn a cabo las medidas experimentales.
El precio del curso es de 250 con cuota especial de
150 para becarios de Universidades y OPIs. En ambos
XVII
casos, la cuota de inscripcin incluye los derechos de
NOTICIAS
asistencia al curso, las comidas y la documentacin.
Contacto:
A.Javier Snchez.
Instituto de Cermica y Vidrio, CSIC
C/ Kelsen 5, 28049 Madrid.
Tel. 917355840, Fax: 917355843.
email(ajsanchez@icv.csic.es
http://www.icv.csic.es/cursos/reologia.
Mediciones de resistencia, de
I-V pulsada y de conductancia
diferencial.
El modelo 2182A cuenta con un poderoso conjunto
de nuevas capacidades para que los investigadores las
utilicen con las nuevas fuentes de corriente CC modelo
6220 y de corriente CA/CC modelo 6221. Ahora los
usuarios podrn realizar mediciones de resistencia, de
I-V pulsada y de conductancia diferencial de manera
ms rpida y exacta que antes, en muchos casos sin
necesidad de un amplificador lock-in o un puente de
resistencia CA. Esta combinacin tambin es til en
muchas aplicaciones nanotecnolgicas por su capacidad
para medir resistencia mientras disipa una cantidad
muy pequea de potencia en el dispositivo bajo test
(DUT).
Caractersticas y ventajas principales. El modelo 2182A
puede disminuir la desviacin DC y el ruido propios
de mediciones de bajo voltaje con altas velocidades,
mayores a las que se poda lograr con nanovoltmetros
anteriores o DMMs de alta sensibilidad. El instrumento
es capaz de realizar mediciones p-p de 15nV a tiempos
de respuesta de 1 segundo, y mediciones p-p de 40-50nV
a tiempos de 60 milisegundos.
La unidad incluye un modo delta incorporado
para coordinar mediciones con una fuente de corriente
inversa (operacin con un solo botn cuando se utiliza
con modelos 6220/6221 de Keithley) de hasta 24Hz
con ruido de 3nVrms/raz-Hz, lo cual crea un sistema
optimizado para mediciones de precisin de materiales
o dispositivos de baja resistencia. La nueva operacin
de modo delta alterna prcticamente tres veces ms
rpido que su modelo anterior, reduciendo el ruido de
medicin en casi un factor de dos. Adems, el nuevo
modo delta incorpora un nuevo mtodo de cancelacin
que disminuye los efectos provocados por voltajes
termoelctricos cambiantes, por un factor de diez en
comparacin con su antecesor.
Cuando se sincroniza con la frecuencia de lnea, el
modelo 2182A proporciona rechazo al ruido de 110dB en
la frecuencia y disminuye el efecto de corrientes AC en
modo comn. La unidad ofrece dos canales para medir
voltaje o temperatura; o el segundo canal se puede
utilizar para leer la razn de una resistencia desconocida
directamente a un resistor de referencia. Incluye clculos
de termocupla para tipos J, K, N, T, E, R, S y B.
Mayo-Junio (2005)
 Se combina con los nuevos modelos 6220/6221 de
Jornada sobre refractarios en
NOTICIAS

NOTICIAS
fuentes de corriente de Keithley. Cuando se integra el
modelo 2182A con cualquiera de las nuevas fuentes siderurgia
de corriente, modelos 6220 6221, se crea un poderoso
sistema de test capaz de actuar como un solo instrumento.
Cuando se enlaza con el modelo 6221 habilitado por MADRID.
Ethernet, el sistema combinado funciona de manera Mircoles, 15 de Junio
efectiva como un sistema nanovoltmetro controlado de 2005.
por Internet, permitiendo a los clientes controlar tanto
Instituto de Cermica y
la generacin como la medicin a travs de una sola
Vidrio.
direccin IP para Internet.
C/ Kelsen n 5
Algunas de las capacidades ms importantes del Campus de
modelo 2182A, cuando se combina con los modelos 6220 Cantoblanco
6221, incluyen: 28049 Madrid.

Amplio rango de medicin, desde 10 nano-ohms Organiza:

(ruido ms bajo) a 1 Gohms.
Los modelos 622X y 2182A pueden llevar a cabo medi-
ciones de conductancia diferencial, cada vez ms comu-
nes para caracterizar materiales de semiconductores y
nanotecnologa, a una velocidad diez veces mayor y con
un ruido menor a las soluciones existentes, incluyendo
amplificadores lock-in y puentes de resistencia AC.
Cuando se combina con el modelo 6221, el modelo
puede soportar mediciones de resistencia e I-V pulsadas
con pulsos tan cortos como 50 microsegundos, incluso
a bajas corrientes. Pulsos cortos se traducen en menor
potencia en el DUT, lo cual es de especial importancia
en dispositivos muy pequeos en los que una cantidad
muy pequea de potencia sera suficiente para destruir-
los o para producir una lectura no vlida. Para eliminar
offsets DC y ruido en la frecuencia de lnea en estas
mediciones de pulsos de alta sensibilidad, el modo pul-
sado de los modelos 6221/2182A utiliza tanto la lnea de
sincronizacin como las tcnicas de modo delta.
Con ms de 50 aos de experiencia en medicio-
nes, Keithley Instruments (www.keithley.com) se ha
convertido en lder mundial en avanzados sistemas e
instrumentos de tests elctricos de DC a RF (radiofre-
cuencia), adaptados a las necesidades especializadas
de fabricantes electrnicos para tests de produccin de
alto rendimiento, monitoreo de procesos, desarrollo de
productos e investigacin. En base a sus fortalezas en
soluciones de medicin elctrica para investigacin,
Keithley se ha convertido en lder en tecnologa de tests
de produccin para industrias inalmbricas, optoelec-
trnicas, de semiconductores y otros segmentos electr-
nicos de precisin a nivel mundial. El valor que damos
a nuestros clientes es una combinacin de tecnologa en
mediciones de precisin y una valiosa comprensin de
sus aplicaciones para mejorar la calidad y rendimiento
de sus productos.
Instrumentos De Medida S.L.
Pedroeras, 37
28043 Madrid
www.idm-instrumentos.es
Seccin de Refractarios.
Sociedad Espaola de
Cermica y Vidrio.
S.E.C.V.
Colaboran:
Asociacin Nacional de
Fabricantes de Refractarios A.N.F.R.E. e Instituto de
Cermica y Vidrio.
I.C.V.
Consejo Superior de Investigaciones Cientficas C.S.I.C.
El objetivo de la reunin es darle continuidad a las
sesiones que, con cierta regularidad, se venan organi-
zando desde la Seccin de Refractarios de la SECV para
analizar la coyuntura y las innovaciones tecnolgicas
ms significativas que se van produciendo en el campo
de las aplicaciones industriales de los refractarios. En
dichas jornadas han venido participando con asidui-
dad tcnicos de compaas siderrgicas, productores
e instaladores de refractarios as como investigadores
de distintas instituciones. En esta ocasin se pretende
examinar los rpidos cambios que se estn experimen-
tando en la situacin del refractario en el campo de la
siderurgia.
PROGRAMA
Mircoles, 15 de Junio de 2005.
9:00 Bienvenida y Presentacin de la Jornada.
D. Jorge Bakali. Presidente de la S.E.C.V.
D. Fernando Franco, Presidente de la Seccin
de Refractarios de la S.E.C.V., D. Emilio
Criado, Vicepresidente, y D. Antonio H. De
Aza, Secretario
Presentacin del I.C.V.
D. ngel Caballero
Director del I.C.V.
09:30 Criterios de Seleccin de Materiales
Refractarios para Siderurgia Integral.
D. J. Manuel Garca Paz.
Jefe de Laboratorios
ARCELOR

Mayo-Junio (2005) XVIII

10:00 Experiencias en el Empleo de Refractarios en la
Siderurgia No Integral.
XLV Congreso
D. Juan Laraudogoitia SECV
Jefe del Dpto. Acera Centro de Investigacin.
SIDENOR
Sociedad Espaola de Cermica y Vidrio
10:30 Refractarios en la Produccin de Acero Inoxidable.
D. Javier Ferrer.
Jefe de Seccin Fusin y Refractarios. SEVILLA
D. Rafael Rodrguez. 2-5 noviembre 2005
Jefe de A.O.D.
ACERINOX
En este ao 2005, la Sociedad Espaola de Cermica y
11:00 Caf Vidrio (SECV) celebrar su XLV Congreso Anual en la ciudad
11:30 Situacin de la Investigacin sobre Refractarios y de Sevilla, durante los das, 2, 3, 4 y 5 de Noviembre. Para ello,
su Aplicacin en la Siderurgia en Brasil. contar con la colaboracin de la Universidad de Sevilla, el
D. Elson Longo Instituto de Ciencias de Materiales de Sevilla (Centr o mixto
Dtor. Dpto. de Materiales. Universidad Federal San CSIC-US) y el Instituto de Cermica y Vidrio (CSIC-Madrid)
Carlos. Sao Paulo. La SECV viene celebrando desde su fundacin en 1960 un
Presidente de la Sociedad Brasilea de Pesquisa de Congreso anual en que se analiza la situacin tecnolgica del
Materiales. Brasil. sector cermico y las innovaciones que se aportan desde la
investigacin que se realiza en Universidades y otros organis-
12:00 El Papel Clave del Grafito en los Refractarios
Mixtos mos pblicos de investigacin.
Da. Carmen Baudn. A lo largo de estos aos, los congresos de la SECV han
Dpto. de Cermica. I.C.V. recorrido las principales regiones en que las industrias cermi-
ca y vidriera tienen una presencia significativa. As en los lti-
12:30 Investigaciones Recientes sobre Refractarios en el mos aos los Congresos han recalado regiones como Galicia,
I.C.V. Valencia, Aragn, Andaluca, Pas Vasco y Madrid.
D. Antonio H. De Aza.
Dpto. de Cermica. I.C.V. Secretario de Seccin de
Refractarios de la S.E.C.V.
13:00 Conclusiones y Coloquio.
Homenaje a D. Carlos Ribera Azcarate.
D. Fernando Franco, D. Emilio Criado y
D. Antonio H. De Aza.
Junta Directiva de la Seccin de Refractarios de la
S.E.C.V.
13:30 Comida de trabajo
Comida Buffet.
Patio central del I.C.V.
15:00 16:30 Mesa Redonda: Problemticas del Sector
del Refractario. Costes y Competencia
Asociacin Nacional de Fabricantes de Refractarios
A.N.F.R.E.
16:30 17:00 Caf
17:00 18:00 Visita a las instalaciones del I.C.V.
18:00 Fin de la Jornada
Para cualquier aclaracin o consulta contactar con el
Secretario de la Seccin de Refractarios, Antonio H. De Aza, en
la direccin de correo electrnico siguiente: aaza@icv.csic.es

XIX Mayo-Junio (2005)

 Sevilla, capital de Andaluca, es una de las ciudades que Lugar de celebracin:
ms veces ha acogido la organizacin de estos congresos. La
primera vez fue en el ao 1967 y posteriormente en 1978 y Universidad de Sevilla
1995 la SECV volvi a celebrar su Congreso Anual. Se cum- Vicerrectorado de Postgrado y Doctorado
plen, pues, diez aos desde la ltima organizacin de dicho Edificio Pabelln de Mxico
evento en esta ciudad. P de las Delicias, Esq. Avda. Eritaa. 41013 Sevilla
Sevilla ha mantenido desde la antigedad una gran
tradicin en la fabricacin de la cermica y el vidrio.
Desgraciadamente, son pocas las industrias que an sobre- Informacion y Secretara:
viven en este sector, sin embargo, la investigacin cientfica
alcanza un nivel comparable al de otras regiones espaolas, SECV
en particular, en lo que se refiere a la caracterizacin de mate- Csic-Campus de Cantoblanco
riales y materias primas, gracias a la disponibilidad de centros Cno. Valdelatas s/n. Cantoblanco
especializados, como son: CITIUS (Centro de Investigacin, 28049 Madrid
Tecnologa e Innovacin (Universidad de Sevilla), ICMSE
(Instituto de Ciencias Materiales de Sevilla (Centro mixto secv@icv.csic.es
CSIC-US) y el CNA (Centro Nacional de Aceleracin) que www.secv.es
disponen de una completa dotacin de recursos materiales y Tel. 91 735 58 60/40
humanos. Fax. 91 735 58 43
Este congreso contar, adems de las entidades acadmicas
y de investigacin citadas con anterioridad, con las entidades
polticas andaluzas y las empresas pblicas y privadas, tanto
andaluzas como el resto de Espaa.

Mayo-Junio (2005) XX
 CA L E N DA R I O
Fecha Lugar Evento Direccin

15-19 mayo 2005 Estambul 20 th International Enamellers Congres www.enamellers2005

(Turqua)

18-19 mayo 2005 Toledo Curso de Tecnologa Cermica Aplicada nieves.villar@aitemin.es

(Espaa)

29-31 mayo 2005 Scandinavian Nordiska glastekniska Freningen. The Scandinavian birgitta.h.ohlsson@glafo.es
(Sweden) Society of Glass Technology 55th Annual Meeting Tel.: +46 470 767 050

15 junio 2005 Madrid Jornada sobre Refractarios en Siderurgia aaza@icv.csic.es

(Espaa)

19-23 junio 2005 Portoroz IX Conference and eshibition ECERS www.ecers2005portoroz.com

(Slovenia)

30 junio 1 julio 2005 Teruel VII Reunin Nacional de Electromecnica http://www.unsa.edu.pe

(Espaa) copemat@unsa.edu.pe

4-5 julio 2005 Madrid Curso de Fundamentos de Reologa ajsanchez@icv.csic.es

(Espaa)

10 - 15 julio 2005 Hawai Novel and Emerging Ceramic Composites http://www.unsa.edu.pe

( EE.UU)

17-19 agost 2005 Isla del Padre de Tx XXIV Convencin Mexicana de Cermica 2005 soceram@prodigy.net.mx
(USA) www.sociedadceramicanorte.com.mx

26-28 septiembre 2005 Salamanca SEA 05 www.usual.es/sea05

(Espaa)

2-5 noviembre 2005 Sevilla XLV Congreso SECV secv@icv.csic.es

(Espaa)

12-15 febrero 2006 Castelln IX Congreso Mundial de la Calidad del Azulejo y del www.qualicer.org
(Espaa) Pavimento Cermico qualicer@camaracs.es
Tel.: +34 964 35 65 00
Fax: +34 964 35 65 10

18-22 junio 2006 Toledo Electroceramics X electroceramics-x@icv.csic.es

(Espaa)

Ferias y Exposiciones
Fecha Lugar Evento Direccin

24-25 mayo 2005 Praga Glassman Europe 05 Tel.: +44 (0) 1737 855 116
(Repblica Checa) Fax: +44 (0) 1737 855 463
www.glassmediaonline.com

27-29 mayo 2005 Getxo XXXII Feria de Artesana de Getxo Tel.: 94 491 40 80
(Espaa) info@getxokultura.com

1-4 septiembre 2005 LAlcora 25 Concurso Internacional de Cermica www.alcora.org/museu

(Espaa) museu@alcora.org
Tel.: +34 964 362 368
Fax: +34 964 386 455

27-30 septiembre 2005 Bilbao Feria Internacional de la Subcontratacin Tel.: 944 285 416
(Espaa)

26-30 octubre 2005 Lea de Palmeira EXPONOR - Feria Internacional do Porto info@exponor.pt
(Portugal) Tel.: +351 808 30 14 00
Fax: +351 299 981 482

XXI Mayo-Junio (2005)

 B O L E T I N D E L A S O C I E DA D E S PA O L A D E

Cermica y Vidrio
DIRECTORIO DE EMPRESAS

Direccin Descripcin Empresa

Fritas, esmaltes, colores cermicos, gra- Avda. de Onda, s/n

villas de vidrio, etc. 12210 Ribesalbes (Castelln)
C.C. BONET Tel. +34 964 625 000
Fax +34 964 625 134
e-mail: mail.es@ccbonet.com

Fritas, esmaltes, etc. Ctra. Castelln, km. 22

12110 Alcora (Castelln)
Tel. + 34 964 36 03 25
ESMALTES, S.A.
Fax: + 34 964 36 17 87
e-mail: info@esmaltes.com
www.esmaltes.com

Fritas, esmaltes CV 20, Km. 8 .

y colores cermicos. 12200 ONDA (Castelln). Espaa.
Telf. +34 964 777600
FRITTA, S.L. Fax. +34 964 530709
E-mail: fritta@fritta.com
www.fritta.com

Arenas feldespticas. P. Castellana, 77, 14

Arenas silceas. 28046 Madrid
INDUSTRIAS Feldespatos potsicos Tel. 91 397 20 84
DEL CUARZO, S.A. Fax 91 397 23 65
www.incusa.es

Feldespatos Sodicos Muelle de la Cermica, s/n.

Cuarzo Puerto de Castelln
KALTUN IBERICA, 12100 Grao de Castelln
Tel. 964 73 70 50
S.L. Fax 964 28 62 65
mangel@kaltun.com
www.kaltun.com.tr

Zirconios, Rutilo, Colemanitas, Ulexita, P Alameda,17

Borax Penta, cido Brico, Cuarzo, 46010 Valencia
Feldespatos, Caoln, Carbonato de Bario,
MARIO PILATO Bix. de Manga-neso, Cromita, Almina Tel. 96 339 32 70
BLAT, S.A. calcinada, espodumeno, wollastonita, bolas Fax. 96 369 08 50
de almina, x. de cinc, xs. metlicos,
magnesita, engobe inferior.

Hornos para: cermica, vidrio, Manel Ferrs, 101, E-08190,

laboratorio, fundicin y tratamiento Sant Cugat del Valls (Barcelona)
termicos. Tel. 93 674 83 39
NABERTHERM
Fax: 93 675 62 76
IBRICA S.L.
info@nabertherm.es
www.nabertherm.es

Direccin
San Roque 15
12004 Castelln (Castelln)
Tel. 964 34 26 26
Fax 964 21 36 97
Ctra. Luchancha-Asua, 24
48950 ASUA (Vizcaya)
Tel. 94 453 15 63
Fax 94 471 04 45
reyma@reyma.com
C/Forcall, 4 - Grupo S. Andrs
12006 Castelln (Espaa)
Tel. 964 25 59 46
Fax. 964 25 40 00
www.serviquimia.com
castellon@serviquimia.com
Ptda. Foyes Ferraes, s/n
12110 Alcora (Castelln)
Tel. +34 964 36 78 00
Fax. +34 964 38 61 92
info@tierraatomizada.com
Trinquete, 27 - 46940
Manises (Valencia)
Tel. + 34 96 154 51 00
Fax: +34 96 154 75 00
BOLETN DE LA SOCIEDAD ESPAOLA DE CERMICA Y VIDRIO DIRECTORIO DE EMPRESAS
Descripcin Empresa
Nefteline syenite, xidos de tierras raras,
xidos metlicos, talcos, alminas, corin-
dones, carbonatos, nitrato, dolomitas, QUOX
tripolifosfato sdico, silicatos, caolines, QUIMIALMEL S.A.
cuarzo, poliglicoles metvanadatos, sul-
fatos, etc
Hornos de colada continua para
esmaltes cermicos, hornos de fritas
(ingeniera y revestimiento) llave en REYMA MATERIALES
mano, material refractario para fritas,
REFRACTARIOS, S.A.
aislamientos especiales WDS.
Reactivos y materiales laboratorio.
Especialistas en montajes de
laboratorios cermicos.
SERVIQUIMIA, S.L.
Tierra atomizada para pavimento y
revestimiento.
TIERRA ATOMIZADA
Pastas y materias
primas cermicas
VICAR, S.A.