Research Article

Received: 5 October 2009 Revised: 4 March 2010 Accepted: 22 March 2010 Published online in Wiley Interscience: 7 May 2010

(www.interscience.com) DOI 10.1002/xrs.1258

Chemical characterisation by WD-XRF

and XRD of silicon carbide-based grinding tools
M. F. Gazulla,∗ M. P. Gómez, M. Orduña and M. Rodrigo
This paper addresses the chemical characterisation of silicon carbide-based grinding tools. These are among the most widely
used grinding tools in the ceramic sector, and instruments are required that enable the grinding tool quality to be controlled,
despite the considerable complexity involved in determining grinding tool chemical composition. They contain components
of quite different nature, ranging from the silicon carbide abrasive to the resin binder. To develop the analysis method,
grinding tools containing silicon carbide with different grain sizes were selected from different tile polishing stages. To develop
the grinding tool characterisation method, the different measurement process steps were studied, from sample preparation,
in which different milling methods (each appropriate for the relevant type of test) were used, to the optimisation of the
determination of grinding tool components by spectroscopic and elemental analyses. For each technique, different particle
sizes were used according to their needs. For elemental analysis, a sample below 150 µm was used, while for the rest of the
determinations a sample below 60 µm was used. After milling, the crystalline phases were characterised by X-ray powder
diffraction and quantified using the Rietvel method. The different forms of carbon (organic carbon from the resin, inorganic
carbon from the carbonates and carbon from the silicon carbide) were analysed using a series of elemental analyses. The other
elements (Si, Al, Fe, Ca, Mg, Na, K, Ti, Mn, P and Cl) were determined by wavelength-dispersive X-ray fluorescence spectrometry,
preparing the sample in the form of pressed pellets and fused beads. The chemical characterisation method developed was
validated with mixtures of reference materials, as there are no reference materials of grinding tools available. This method can
be used for quality control of silicon carbide-based grinding tools. Copyright
c 2010 John Wiley & Sons, Ltd.

Introduction control method is required that ensures constant quality, despite

Polishing is a very important process stage in porcelain tile
manufacture, owing to the cost involved and the aesthetic and
technical qualities it provides.[1] Porcelain tile polishing is per-
formed with grinding tools that contain abrasives. The abrasives
used in the tile industry may be divided into two groups: natural
abrasives, notably corundum, quartz, diamond, emery (consisting
of alumina, silicon and iron oxide) and garnet (a mixture of alkaline-
earth silicates); and artificial abrasives, the most widely used being
silicon carbide, corundum, boron carbide and artificial diamond.[2]
One of the most common ways of using abrasives in the tile in-
dustry is as conglomerates of abrasives or grinding tools, i.e. form-
ing a compact body of abrasive grains held together by a binder.[2]
The type of abrasive used depends basically on the type of material
to be machined. Thus, silicon carbide (SiC) is used when working
with materials such as brass, aluminium, hard metal, glass, marble
or ceramics.[3] In general, SiC is used as abrasive in applications in-
volving materials of high hardness for fine grinding and honing.[2]
In the ceramic tile sector, grinding tools are used in the tile pol-
ishing stage, a stage that developed from the pursuit of aesthetic
qualities, seeking to imitate natural products like marble or granite,
in addition to enhancing certain properties such as mechanical
strength, resistance to chemical attack or stain resistance.[4]
Grinding tool properties and shape depend on the abrasive
composition and grain size, binder and porosity. Conventional
grinding tools usually contain aluminium oxide or SiC as abrasive,
and a vitreous binder or resin.[5] Magnesium oxychloride is the
most widely used binder owing to its low cost and simple
manufacturing process.[4]
The present paper focuses on the chemical characterisation
of SiC-based grinding tools because these are among the most
the complexity involved in determining grinding tool chemical
composition.
These materials pose considerable problems for analysis
because they contain components of very different nature, from
the SiC abrasive itself to the resin (organic constituent).
The methods described in the literature on SiC analysis deal
with the analysis of refractory materials[6,7] or the determination
of the different forms of carbon present in SiC.[8 – 10] Other studies
on powdered SiC highlight the problem of not having standard
materials and the method of verifying the accuracy of the results
by comparing the methods,[11] as well as impurity analysis with
electrothermal atomic absorption spectrophotometry and induc-
tively coupled plasma optical emission spectrometry, particularly
stressing how the sample is prepared.[12,13] There are also a series
of standard methods of SiC analysis in various materials, such as
when SiC is bonded with nitride, by total-carbon and free-carbon
analysis.[14] There are methods specified in Deutscher Institut
für Normung (DIN) standards for SiC phase calculation from the
determination of total carbon and free carbon.[15] Various meth-
ods, involving coulometry, gravimetry and conductimetry, are
described for determining free carbon[16] and total carbon.[17]
There are also different International Organization for Standardis-
ation (ISO) test methods for the determination of total carbon and
free carbon by coulometry, gravimetry, conductimetry, infrared (IR)
absorption, and thermoconductivity, and for the determination of
∗ Correspondence to: M. F. Gazulla, Instituto de Tecnología Cerámica,
Asociación de Investigación de las Industrias Cerámicas, Universitat Jaume I,
Castellón 12006, Spain. E-mail: marife.gazulla@itc.uji.es
Instituto de Tecnología Cerámica, Asociación de Investigación de las Industrias
267

widely used grinding tools in the ceramic sector and a quality Cerámicas, Universitat Jaume I, Castellón 12006, Spain

X-Ray Spectrom. 2010, 39, 267–278 Copyright

c 2010 John Wiley & Sons, Ltd.

Table 1. Selected grinding tools and abrasive grain size
Grinding tool Average grain size (µm)[16]
Grinding tool 36 525
Grinding tool 150 82
Grinding tool 280 36.5
Grinding tool 600 9.3
Grinding tool 1500 2.0
SiC by direct methods or indirect (calculation) methods in SiCs and
SiC-based refractories.[18,19]
However, no studies are reported in which all SiC-based
grinding tool components are analysed, not even the SiC content.
This study was therefore undertaken, primarily, to establish a
systematic procedure for the characterisation of grinding tools
that contain SiC, using elemental analysis, wavelength-dispersive
X-ray fluorescence spectrometry (WD-XRF), and X-ray diffraction
(XRD) in order to have a rapid, simple and reliable method of
determining grinding tool composition and quality.
Experimental
Selection of the grinding tools
SiC-based grinding tools were selected from the different
tile polishing phases, thus involving grinding tools containing
different silicon carbide grain sizes. The selected grinding tools,
as well as the average silicon carbide grain sizes, are detailed in
Table 1.
The grinding tool number refers to the average abrasive
grain size according to the Federation of European Producers
of Abrasives Products (FEPA) classification.[20] The FEPA standards
rate grinding tools in terms of average grain size as macrogrits and
microgrits. Thus, grinding tool 36 and grinding tool 150, with a
larger average grain size, belong to the macrogrit group, while the
280, 600 and 1500 grinding tools belong to the microgrit group.
Grain size is determined by dry sieving in the case of grinding tools
268
Figure 1. Schematic illustration of the initial grinding tool analysis approach.
www.interscience.com/journal/xrs Copyright

c 2010 John Wiley & Sons, Ltd.
M. F. Gazulla et al.
in the macrogrit group, while it is determined by sedimentation in
the microgrit group.[21]
Experimental
Different steps may be distinguished in the chemical characterisa-
tion of SiC-based grinding tools, ranging from sample preparation
to the determination of each grinding tool component by various
techniques. Phase composition was analysed by XRD, while the
chemical composition was determined by WD-XRF. The differ-
ent forms of carbon as well as total carbon was determined by
elemental analysis with a combustion furnace and IR detection.
A method of characterising SiC-based refractory bricks was
reported in a previous paper.[6] The same scheme was used in this
study to design a new method for analysing grinding tools that
contain SiC as the principal abrasive. The initial approach to this
grinding tool analysis method is schematically illustrated in Fig. 1.
The different steps used in SiC-based grinding tool analysis are
described below.
Sample preparation
Sample preparation is critical for the determination of chemical
composition by WD-XRF for various reasons: on one hand, the
reduction of the particle size allows the homogenisation of the
sample to be analysed; on the other, a small particle size is
necessary to favour mixing with the flux and avoid the presence
of unmelted materials during bead preparation, and it is also
necessary for pellet preparation to minimise the particle size effect
in the measurement by WD-FRX. Therefore, a milling prior to the
analysis to obtain the appropriate particle size is necessary.
Grinding tools are very difficult materials to mill because of their
low brittleness and high hardness, making sample preparation
a key analysis step. The sample preparation was as follows: first,
portions of the grinding tools were cut with a diamond disc; each
portion was then crushed in a jaw crusher, and subsequently
milled. The crushing step is needed to entail the minimum
comminution required to enable the crushed fraction to be appro-
priately used in the milling process, since in crushing the sample
may be contaminated by the jaw material, principally iron.[19]
X-Ray Spectrom. 2010, 39, 267–278
Chemical characterisation of grinding tools by WD-XRF and XRD

The sample was milled in a tungsten carbide ring mill for the
minimum time required to obtain an optimum sample particle
size for the various determinations, since excessive milling could
oxidise SiC to SiO2 . It is recommended that milling be performed
for the shortest time needed to obtain a particle size below
150 µm.[15] As bead preparation needs small particle size, two
millings of the sample were necessary: first, the sample was milled
to obtain a particle size below 150 µm and, subsequently, a second
milling was carried out to obtain a particle size below 60 µm. For
the determination of both particle sizes, the residues below 2% at
150 and 60 µm were calculated by sieving the samples through
150 and 60 meshes, respectively. The sample milled below 150 µm
was used for the determination of organic, inorganic and total
carbon as well as sulfur, while the sample milled below 60 µm
was used for the determination of the crystalline phases and the
chemical analysis. There was a specific milling of a fraction of the
sample below 150 µm in an agate ring mill to obtain a fraction
below 60 µm, at which the analysis of tungsten was carried out.
In addition to the oxidation problem that might occur in SiC
milling, milling in a tungsten carbide mill poses a possible sample
contamination problem: if the typical hardness values of the
material to be analysed are compared with those of the tungsten
carbide mill, SiC has a Knoop hardness of 2400 HK, while that
of tungsten carbide is 1900 HK.[3] As a result, ring wear occurs
and the sample is contaminated with tungsten carbide, thereby
making it necessary to correct the total carbon determination for
the amount of contamination.[19,22] This is done by analysing the
tungsten concentration, there being no tungsten in the grinding
tools. The resulting value is then used to determine the carbon
resulting from the milling contamination, which will subsequently
need to be subtracted from the total carbon value.
All the samples were measured in powder form. For this purpose,
a sample milled below 60 µm was used.[24] The milled sample was
back-filled into an appropriate specimen holder for the instrument
used. The amount of specimen was just enough to underfill the
holder when slightly pressed.
A quantitative phase analysis was also performed.[25,26] Data
were processed in a Rietveld refinement.[27,28] The Rietveld analysis
program DIFFRACplus TOPAS version 4.2 was used in this study,
assuming a pseudo-Voigt function to describe the peak shapes.
The refinement protocol included the background, the scale
factors as well as the global-instrument, lattice, profile and texture
parameters. The basic approach was to get the best diffraction
data, using, in this case, fluorite as an internal standard, identify
all the crystalline phases present in the sample and input basic
structural data for all phases. Then, the computer modelled the
data until the best fit to the experimental pattern was obtained.
WD-XRF analysis
First, pressed pellets were prepared for semi-quantitative WD-XRF
analysis of the elements present in the grinding tools, using a semi-
quantitative analysis program based on fundamental parameters.
On the basis of the semi-quantitative and XRD analysis, samples
were then prepared as pellets and beads, depending on the
element to be analysed. By bead preparation, elements not
susceptible of volatilising during the process were analysed: Si, Al,
Fe, Ca, Mg, K, Ti, Mn, P and W. Na and Cl are elements that, in
these materials, form phases that volatilise during the calcination
process because of the high temperatures involved, and therefore
sample preparation was in the form of pellets.

Phase analysis Instrumental. Beads were prepared in a PANalytical model

PERL X’3 fusion bead preparation machine. The measurements
The crystalline phases in each studied grinding tool were identified,
were made with a PANalytical model AXIOS X-ray fluorescence
prior to WD-XRF analysis, by XRD in order to establish whether
wavelength-dispersive spectrometer with a Rh tube, 4 kW power
and how much SiC was present and which admixtures might have
and three detectors: flow gas proportional, scintillation and sealed
been added to the grinding tools,[23] a particularly important issue
gas. The WD-XRF measurement conditions used are given in
for chemical analysis.
Table 2.
The XRD data were obtained using a BRUKER Theta–Theta
model D8 Advance diffractometer with Cu Kα radiation (λ =
1.54183 Å` ). The generator settings were 45 kV and 30 mA. The Fused bead preparation. Whenever possible, sample preparation
XRD data were collected in a 2θ of 5–90◦ with a step width of was in the bead form as sample dilution with flux minimises the
0.015◦ and a counting time of 1.2 s per step. A V Å` NTEC-1 detector matrix effect, while the formation of a uniform glass suppresses
was used. the influence of the mineralogical structure and the particle size.

Table 2. Measurement conditions for chemical analysis by WD-XRF

Collimator Voltage Intensity Angle Time
Element Line Crystal (µm) Detector (kV) (mA) (2θ) (s)

Si Kα InSb 111-C 550 Flow 30 100 144 799 40

Al Kα PE 002 550 Flow 30 100 144 943 40
Fe Kα LiF 200 150 Flow + sealed 60 50 57 515 20
Ca Kα LiF 200 550 Flow 30 100 113 152 16
Mg Kα PX 1 550 Flow 30 100 22 703 30
K Kα LiF 200 550 Flow 30 100 136 739 12
Ti Kα LiF 200 150 Flow + sealed 40 75 86 167 18
Mn Kα LiF 200 150 Flow + sealed 60 50 62 971 16
P Kα Ge 111 550 Flow 30 100 141 042 16
Na Kα PX 1 550 Flow 30 100 27 435 40
Cl Kα Ge 111 550 Flow 30 100 92 767 60
269

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 M. F. Gazulla et al.

Table 3. Chemical composition and uncertainty of the kaolin used Table 4. Composition of the CSs for WD-FRX measurement, samples
for the dilutions of the samples for the analysis of Na and Cl in pellets being prepared as beads

Kaolin used for dilution Composition (wt%)

Element Composition (wt%) Reference material CS 1 CS 2 CS 3 CS 4 CS 5

SiO2 49.8 ± 0.2 SRM 1886a Portland Cement 4.9 1.0 15.0 10.0 3.0
Al2 O3 36.10 ± 0.15 BCS-CRM No 267 silica Brick 10.5 19.0 10.0 13.0 30.0
Fe2 O3 0.46 ± 0.02 BCS-CRM No 319 Magnesite 40.0 49.0 58.0 44.7 43.8
CaO 0.10 ± 0.02 BCS-CRM No 348 Ball Clay 43.5 30.0 – – –
MgO 0.08 ± 0.01 SRM 70a potassium Feldspar 0.5 – – – –
Na2 O <0.01 ± 0.01 CERAM AN41 China Clay – – 15.0 32.0 22.0
K2 O 0.45 ± 0.02 WO3 Merck 0.6 1.0 2.0 0.30 1.2
TiO2 0.14 ± 0.02
MnO <0.01 ± 0.01
P2 O 5 0.06 ± 0.01
Cl <0.01 ± 0.01 Table 5. Composition of the CSs for WD-FRX measurement, samples
Loss on ignition (1025 ◦ C) 12.7 ± 0.1 being prepared as pellets

Composition (wt%)
Certified reference material CS 6 CS 7 CS 8 CS 9 CS 10
In a previous study,[6] it had been verified that samples with
a high SiC content could not be prepared as beads. In the GBW03102 Kaolin 99.0 97.0 94.0 90.0 85.0
present study, it was verified that beads could be prepared when NaCl from Fluka 1.0 3.0 6.0 10.0 15.0
the SiC concentration was smaller than 10% and the particle
size was below 60 µm. Therefore, for bead preparation, the SiC
concentration and particle size needed to be below 10% and the types of samples being studied are commercially unavailable,
60 µm, respectively. reference materials were appropriately mixed in order to obtain
As a result, the sample obtained in the first milling step was compositions similar to those of the samples to be analysed.
milled again to obtain a residue below 2% at 60 µm by sieving it The WD-XRF measurements were calibrated and validated with
through a 60-µm mesh, as was explained in sample preparation the following reference materials and chemical standards:
section. This sample with a particle size below 60 µm was used not
only for bead preparation but also for pellet preparation. For bead 1. Reference materials for calibration using WD-XRF: SRM 98b
preparation, the samples were weighed into a platinum crucible Plastic Clay, BCS-CRM No 348 Ball Clay, SRM 70a Potassium
and the flux (a 50 : 50 mixture of lithium metaborate and lithium Feldspar, CAS 5 Ball Clay, CERAM AN41 China Clay, CERAM
tetraborate) was added in a 1 : 10 sample/flux ratio. A 250 g l−1 so- 2CAS1 Ball Clay, BCS-CRM No 267 Silica Brick, GBW03102 Kaolin,
lution of LiI from Merck was used as a bead-releasing agent, added BCS-CRM No 319 Magnesite, SRM 1886a Portland Cement, NaCl
at a concentration of 2% of the total weight of the sample and flux. from Fluka and WO3 from Fluka.
The samples were calcined at a temperature of 1025 ◦ C to 2. Reference materials for validation using WD-XRF: BCS-CRM
eliminate volatile components, and partially oxidise the carbide, No. 389 High-purity Magnesite, BCS No. 394 Calcined Bauxite,
before being prepared as beads. The resulting beads then allowed EURONORM-ZRM No. 777-1 Silikastein, EURONORM-CRM No.
Si, Al, Fe, Ca, Mg, K, Ti, Mn, P and W to be analysed. Loss on ignition 782/1 Dolomite, GBW03123 Wollastonite, GBW03122 Kaolin,
was determined at a temperature of 1025 ◦ C using a LECO model IPT-72 Sodium Feldspar, NaCl from Merck, MgCl2 from Merck
TGA-701 thermogravimetric analyser. and WO3 from Merck.
Table 4 shows the composition of each calibration standard (CS)
Pellet preparation. Na and Cl were characterised using an for the analysis of Si, Al, Fe, Ca, Mg, K, Ti, Mn, P and W, the samples
uncalcined sample milled at a particle size below 60 µm, prepared being prepared as beads.
as pressed pellets, weighing out 9.0000 g sample, adding 2.5 ml Table 5 shows the composition of each CS for the analysis of Na
of a 13.7% solution of n-butyl methacrylate in acetone as a binder, and Cl, the samples being prepared as pellets. The mixing of both
mixing them in an agate mortar and forming at a pressure of materials was done in a tungsten carbide ring mill.
100 kN in a hydraulic press.[29] Different dilutions of the samples Table 6 details the element concentration ranges, together with
were made by mixing the sample in a tungsten carbide ring mill the root mean square (RMS) values for the corresponding calibra-
with high-purity kaolin with controlled composition, free of the tion curves. The RMS value is obtained from the following equation:
elements to be analysed, in order to obtain a matrix similar to


that of the calibration and validation standards used in the WD- 
 (C ∗ − C)2
XRF measurement and to minimise any possible errors due to 
matrix effects. The chemical composition of the kaolin used for the RMS = (1)
n−p
dilutions, along with the uncertainty, is presented in Table 3.
where C ∗ is the theoretical concentration, C is the calculated
WD-XRF measurement calibration and validation. Quantitative concentration, n is the number of CS and p is the number of
WD-XRF chemical analysis requires the availability of reference parameters calculated from the regression (slope, ordinate at the
270

materials. However, since reference materials corresponding to origin and inter-element coefficients)

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c 2010 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 267–278
Chemical characterisation of grinding tools by WD-XRF and XRD

In order to determine the quantities of the different components

Table 6. Element concentration ranges and RMS values for the
calibration curves in the sample, it is necessary to identify the different forms of
carbon. Thus, at temperatures around 500 ◦ C, it may be assumed
Element Concentration that all the carbon from the organic matter has decomposed, which
(wt%) RMS range
in the present case would correspond to carbon from the resin.
SiO2 0.3 21.0–40.7 Carbonates decompose at higher temperatures: CaCO3 between
Al2 O3 0.3 6.7–14.5 850 and 930 ◦ C, MgCO3 between 650 and 730 ◦ C and dolomite
Fe2 O3 0.04 2.40–2.88 between 650 and 930 ◦ C. As a result, at 950 ◦ C all the carbon
CaO 0.10 2.18–11.70 present in the sample has been analysed, except the carbon from
MgO 0.4 36.5–52.9 the SiC since, with the technique used, without the addition of a
K2 O 0.04 0.28–1.06 catalyst, SiC does not decompose at temperatures below 1100 ◦ C,
TiO2 0.017 0.054–0.504 which was determined by differential thermal analysis.
MnO 0.006 0.072–0.107 In order to determine the different forms of carbon, an
P2 O 5 0.008 0.001–0.032 instrument is therefore required that allows the test temperature
W 0.02 0.24–1.59 to be modulated. Organic carbon (Corg ) and carbon at 950 ◦ C
Na2 O 0.10 0.93–8.28 (Corg + Cinorg ) were determined with a LECO model RC-412 carbon
Cl 0.13 0.6–9.1 elemental analyser, subjecting the sample to a heating process at
500 and 950 ◦ C, respectively, in a tube furnace with a circulating
oxygen stream in which combustion took place. CO2 was released
in the reaction, which was led to an IR cell.
Table 7. LOQ of the elements analysed in the grinding tools The reference materials used to validate the determination of
total carbon, carbon at 950 ◦ C, organic carbon and sulfur are
Element LOQ (wt%) detailed below.
SiO2 0.1 1. Reference material with certified free carbon concentrations:
Al2 O3 0.05 SRM 112b Silicon Carbide.
Fe2 O3 0.01 2. Reference materials with certified total carbon concentrations:
CaO 0.01 BCS-CRM 359 Nitrogen Bearing Silicon Carbide, 112b Silicon
MgO 0.1 Carbide, GBW07402 Soil, and GBW07404 Soil.
K2 O 0.01 3. Reference materials with certified organic carbon concentra-
TiO2 0.01 tions: GBW07402 Soil, GBW07403 Soil, and GBW07404 Soil.
MnO 0.01 4. Reference materials with certified sulfur concentrations:
P2 O 5 0.01 GBW07402 Soil, GBW07404 Soil, and SRM 1886a Portland
W 0.01 Cement.
Na2 O 0.02
Cl 0.01 Table 8 shows the LOQ of total carbon and sulfur for CS-200
analyser and the LOQ of carbon at 950 ◦ C and organic carbon for
RC-412 analyser, calculated from Eqn (2).

The limit of quantification (LOQ) was determined from the

measurement of a sample which has 0.5 times the concentration
of the lowest calibration sample for each analyte. That sample
was measured seven times under reproducibility conditions. In
compliance with the International Union of Pure and Applied
Chemistry rules, the LOQ, which expresses the ability to quantify
an analyte, is calculated from the expression:[30]
LC = 10 × s
Table 7 shows the LOQ for each element calculated from
Eqn (2).
Elemental analysis of organic carbon, carbon at 950 ◦ C, total carbon
and sulfur
Total carbon and total sulfur were determined with a LECO model
CS-200 carbon and sulfur elemental analyser, consisting of an
induction furnace that reaches temperatures of 2000 ◦ C operating
in oxygen atmosphere, and CO2 and SO2 detection system with
respective IR cells.
This test simultaneously analysed all forms of carbon present
in the samples: carbon from the resin, from the SiC and from the
Determination of silicon carbide
The traditional gravimetric method of determining silicon carbide
is a very long and tedious procedure, involving extensive handling
of the sample.[31] In this method, each sample component is made
to react with different acids until SiC is obtained just by itself.
Such sample treatment can lead to errors by default or excess,
depending on particle size and the other phases in the sample.[6]
(2) SiC content in the studied grinding tools was therefore
determined by analysis of total carbon and carbon at 950 ◦ C,
as set out in the consulted test standards,[14,15,18,19] in which silicon
carbide content is indirectly calculated from the result obtained
on subtracting the carbon analysed at 950 ◦ C from total carbon.
Table 8. LOQ of S, Ctotal , Corg and C950 ◦ C
LOQ
Element (mg·kg−1 )
S 50
Ctotal 100
Corg 100
C950 ◦ C 100
271

carbonates.

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 M. F. Gazulla et al.

Table 11[32] ; cknown was calculated from the values of the standards
Table 9. Crystalline phases identified in the studied grinding tools
used, while cexp was obtained from the measurements.
Crystalline phases The uncertainty was calculated from the expression:
Name Formula
s
u=t× √ (3)
Silicon carbide SiC n
Halite NaCl
Magnesium hydroxychloride hydrate (Mg3 (OH)5 Cl)· 4H2 O where u is measurement uncertainty with a 95% level of
Bassanite CaSO4 (0.5·H2 O) confidence, t is statistical value of Student’s-t for 95% probability
Dolomite CaMg(CO3 )2 and (n − 1) degrees of freedom and n is the number of
Calcite CaCO3 measurements of the sample.
Magnesite MgCO3 At least three measurements were made under reproducibility
Periclase MgO conditions.
Talc Mg3 (OH)2 Si4 O10 In order to compare the results obtained with the known
Brucite Mg(OH)2 values of the validation standards, the difference between both
Quartz SiO2 was compared with the related uncertainty, i.e. the combined
Corundum α-Al2 O3 uncertainty of the known and measured values, as set out in the
Sodalite Na4 Cl(Al3 Si3 O12 ) literature.[33]
The absolute value of the difference between the average
measurement value and the known value is calculated as follows:
Table 10. Composition of the validation standards for WD-XRF
measurement, samples being prepared as beads m = |cexp − cknown | (4)

Composition (wt%)
where m is the absolute value of the difference between the
Reference material A B C D G H measurement and the known value, cexp is the measured value
and cknown is the known value.
BCS No. 389 49.9 49.9 53.7 53.2 52.0 50.1
The uncertainty of m is calculated from the uncertainty of
BCS No. 394 18.7 13.5 15.5 12.1 15.6 14.2
the known value and the uncertainty of the measurement result
EURONORM-ZRM Nr. 777-1 21.5 11.8 11.3 16.8 11.1 12.3
according to the following formula:
GBW03123 2.5 19.8 7.9 5.9 7.9 8.9
IPT-72 7.4 5.0 11.6 12.0 11.6 12.0 
WO3 MERCK – – – – 1.8 2.5 um = u2exp + u2known (5)

where um is the combined uncertainty of the result and of the

Results
Crystalline phase analysis
The qualitative crystalline phase determination of the studied
grinding tools is presented in Table 9.
The mineralogical analysis shows that, among other phases,
these grinding tools contain magnesium oxychloride, which, as
reported in the literature, is one of the most extensively used
binders in grinding tool manufacture,[4] and silicon carbide (the
most widely used abrasive in the polishing process in the ceramic
sector). Other phases also appear, such as corundum, which
are added as an admixture to optimise the polishing process
(enhancing grinding tool hardness and contact with the surface to
be polished), and sulfates, which increase grinding tool resistance
to water when the tools work in an aqueous medium,[23] as well as
smaller quantities of calcium and magnesium carbonates, halite,
talc, quartz and sodalite.
Chemical analysis
Results of the validation standards
In order to validate the WD-XRF measurements, compositions
were prepared by mixing certified reference materials. The
composition of each validation standard is presented in Table 10,
the samples being prepared as beads.
The results obtained in the WD-XRF measurement of the
272
known value, uexp is the uncertainty of the measurement result
and uknown is the uncertainty of the known value.
The expanded uncertainty Um is obtained by multiplying um
by a coverage factor (k), which is usually equal to 2 and corresponds
approximately to a 95% level of confidence. Therefore,
Um = 2 × um (6)
The fitness of the method was verified by comparing m
with Um , so that if m ≤ Um , there is no significant difference
between the measurement result and the known value. The results
of this comparison are detailed in Table 12.
The results obtained show that m ≤ Um is obeyed, so that
there are no significant differences, which validates the developed
measurement method for both the major and the minor elements.
In order to validate the WD-XRF measurement of Cl and
Na, in which the sample was prepared as pellets, validation
standards were prepared by mixing different quantities of NaCl
with controlled kaolin that contained none of the elements to
be analysed. To ensure mixture homogenisation, the composition
was mixed in a tungsten carbide ring mill, after which pellets
were prepared under the same conditions as those used for the
samples. The compositions of the prepared validation standards
are detailed in Table 13 and the results obtained in the WD-XRF
measurement of Cl and Na are given in Table 14. The comparison
of the measurement results of the validation standards with the

validation standards, along with their uncertainty, are listed in known value in the Cl and Na measurement are given in Table 15.

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c 2010 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 267–278
 X-Ray Spectrom. 2010, 39, 267–278
Table 11. Results obtained in the WD-XRF measurement of the validation standards

Validation A B C D G H
standard
components (wt%) cknown cexp cknown cexp cknown cexp cknown cexp cknown cexp cknown cexp

Copyright

SiO2 28.0 ± 0.2 27.9 ± 0.2 25.7 ± 0.2 25.9 ± 0.2 23.6 ± 0.2 23.7 ± 0.2 27.9 ± 0.2 28.0 ± 0.2 23.5 ± 0.2 23.4 ± 0.2 25.3 ± 0.2 25.1 ± 0.2
Al2 O3 18.40 ± 0.06 18.5 ± 0.1 13.30 ± 0.06 13.2 ± 0.1 16.40 ± 0.06 16.4 ± 0.1 13.40 ± 0.06 13.3 ± 0.1 16.44 ± 0.06 16.4 ± 0.1 15.29 ± 0.06 15.4 ± 0.1
Chemical characterisation of grinding tools by WD-XRF and XRD

Fe2 O3 0.59 ± 0.02 0.57 ± 0.03 0.53 ± 0.02 0.54 ± 0.03 0.53 ± 0.02 0.53 ± 0.03 0.47 ± 0.02 0.49 ± 0.03 0.53 ± 0.02 0.51 ± 0.03 0.50 ± 0.02 0.49 ± 0.03
CaO 2.48 ± 0.04 2.51 ± 0.05 9.20 ± 0.05 9.24 ± 0.10 4.44 ± 0.04 4.42 ± 0.05 3.78 ± 0.04 3.79 ± 0.05 4.40 ± 0.04 4.43 ± 0.05 4.81 ± 0.04 4.84 ± 0.05
MgO 48.3 ± 0.2 48.5 ± 0.2 48.4 ± 0.2 48.2 ± 0.2 52.1 ± 0.2 52.2 ± 0.2 51.6 ± 0.2 51.7 ± 0.2 50.4 ± 0.2 50.5 ± 0.2 48.6 ± 0.2 48.8 ± 0.2
K2 O 0.15 ± 0.01 0.17 ± 0.01 0.13 ± 0.01 0.13 ± 0.01 0.21 ± 0.01 0.21 ± 0.01 0.22 ± 0.01 0.23 ± 0.01 0.21 ± 0.01 0.22 ± 0.01 0.22 ± 0.01 0.23 ± 0.01
TiO2 0.68 ± 0.01 0.66 ± 0.04 0.48 ± 0.01 0.47 ± 0.04 0.54 ± 0.01 0.55 ± 0.04 0.46 ± 0.01 0.48 ± 0.04 0.54 ± 0.01 0.52 ± 0.04 0.51 ± 0.01 0.50 ± 0.04
MnO 0.01 ± 0.01 0.01 ± 0.01 0.02 ± 0.01 0.02 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01
P2 O 5 0.12 ± 0.01 0.12 ± 0.01 0.09 ± 0.01 0.09 ± 0.01 0.16 ± 0.01 0.16 ± 0.01 0.15 ± 0.01 0.14 ± 0.01 0.16 ± 0.01 0.15 ± 0.01 0.16 ± 0.01 0.15 ± 0.01

c 2010 John Wiley & Sons, Ltd.

W – – – – – – – – 1.43 ± 0.01 1.45 ± 0.02 1.98 ± 0.01 1.97 ± 0.02

Number of replicates: at least n = 3 in reproducibility conditions.

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273
 M. F. Gazulla et al.

Table 12. Comparison of the measurement result of the validation standards with the known value, where m is the difference between the
measured and the known value, and Um is the expanded uncertainty

Validation A B C D G H
standard
components (wt%) m Um m Um m Um m Um m Um m Um

SiO2 0.1 0.57 0.2 0.57 0.1 0.57 0.1 0.57 0.1 0.57 0.2 0.40
Al2 O3 0.1 0.23 0.1 0.23 0 0.23 0.1 0.23 0.04 0.23 0.11 0.23
Fe2 O3 0.02 0.07 0.01 0.07 0 0.07 0.02 0.07 0.02 0.07 0.01 0.07
CaO 0.03 0.13 0.04 0.22 0.02 0.22 0.01 0.13 0.03 0.13 0.03 0.13
MgO 0.2 0.57 0.2 0.57 0.1 0.57 0.1 0.57 0.1 0.57 0.2 0.57
K2 O 0.02 0.03 0 0.03 0 0.03 0.01 0.028 0.01 0.03 0.01 0.03
TiO2 0.02 0.08 0.01 0.08 0.01 0.08 0.02 0.08 0.02 0.08 0.01 0.08
MnO 0 0.03 0.01 0.03 0 0.03 0 0.03 0 0.03 0 0.03
P2 O 5 0 0.03 0.01 0.03 0 0.03 0.01 0.03 0.01 0.03 0.01 0.03
W – – – – – – – – 0.02 0.04 0.01 0.04

developed measurement method for the determination of organic

Table 13. Composition of the validation standards for the WD-XRF
carbon, carbon at 950 ◦ C, total carbon and sulfur.
measurement of Cl and Na

Composition (wt%)
Results of the analysis of grinding tool samples
Chemical standards E F
Analysis of W. In order to determine the carbon from the silicon
Kaolin 97 93
carbide phase, the WC concentration in the sample (resulting from
NaCl 3 7
sample contamination caused by milling in the tungsten carbide
ring mill) needs to be determined. This was done by analysing the
W concentration by WD-FRX, using this value to calculate the WC
Table 14. Results of the validation standards for the WD-XRF concentration and, from this, calculating the C concentration. The
measurement of Cl and Na results obtained for W, WC and C from the sample contamination
in milling are presented in Table 18.
E F
Element cknown cexp cknown cexp
Analysis of Si, Al, Fe, Ca, Mg, Na, K, Ti, Mn, P, S, Cl, Corg, Ctotal and C950 ◦ C .
Cl (wt%) 1.82 ± 0.05 1.84 ± 0.05 4.24 ± 0.05 4.31 ± 0.05 Corg , Ctotal , C950 ◦ C , Na, Cl and S were analysed in the uncalcined
Na2 O (wt%) 1.59 ± 0.05 1.64 ± 0.05 3.71 ± 0.05 3.75 ± 0.05 sample, while Si, Al, Fe, Ca, Mg, K, Ti, Mn and P were analysed in
the calcined sample.
Number of replicates: at least n = 3 in reproducibility conditions.
The results obtained for organic carbon, carbon at 950 ◦ C, total
carbon and carbon from the silicon carbide phase are listed in
Table 19. Carbon from SiC was calculated by subtracting the value
Table 15. Comparison of the measurement results of the validation of carbon at 950 ◦ C and the value of carbon from the WC phase,
standards with the known value in the Cl and Na measurement, where caused by milling contamination, from total carbon.
m is the difference between the measured and the known value and The complete analysis of each sample, the value of SiO2 , which
Um is the expanded uncertainty includes all the silicon present in the sample (expressed as an
E F oxide), comprising the silicon forming SiC and the silicon forming
SiO2 , is presented in Table 20.
Element m U m U

Cl (wt%) 0.02 0.14 0.07 0.14

Na2 O (wt%) 0.05 0.14 0.04
The outcomes show that m ≤ Um is always obeyed, so that
there are no significant differences, which validates the developed
method for the measurement of both Cl and Na.
The results obtained in the validation of the measurement of
organic carbon, carbon at 950 ◦ C, total carbon and sulfur are given
in Table 16, where the uncertainty was calculated from Eqn (3).
The outcomes of the comparison of both results, calculating the
absolute value of the difference between the measurement and
the known value (m ) and the expanded uncertainty (Um ), are
detailed in Table 17. The results show that m ≤ Um is obeyed,
274
Quantification of crystalline phases. The quantitative analysis of
0.14
crystalline phases was performed using the Rietveld method.
However, it was not possible to obtain resolved structures
of magnesium oxychloride and sodalite phases for refinement
using the Rietveld approach. To solve this problem, all samples
were mixed with a known concentration of fluorite, used as
an internal standard. This allowed determining the percentage
corresponding to the sum of these crystalline phases. With the
help of the chemical analysis, the concentration of these crystalline
phases was determined separately.
The validation of the quantification of the other compounds
was carried out by preparing mixtures of known concentration of
silicon carbide, halite, talc, quartz and corundum and processing
them as had been done for the samples.

so that there are no significant differences, which validates the Good adjustment factors were obtained in all cases.

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c 2010 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 267–278
 X-Ray Spectrom. 2010, 39, 267–278
Table 16. Results obtained in the determination of organic carbon, carbon at 950 ◦ C, total carbon and sulfur of the analysed reference materials

SRM 112b GBW07404 BCS-CRM No. 359 GBW07402 SRM1886a

Copyright

Concentration (wt%) Concentration (wt%) Concentration (wt%) Concentration (wt%) Concentration (wt%)
Chemical characterisation of grinding tools by WD-XRF and XRD

Element Certified Experimental Certified Experimental Certified Experimental Certified Experimental Certified Experimental

C950 ◦ C 0.26 ± 0.03 0.24 ± 0.03 0.65 ± 0.10 0.64 ± 0.04 – – 0.75 ± 0.10 0.75 ± 0.04 – –
Ctotal 29.43 ± 0.08 29.48 ± 0.15 0.65 ± 0.10 0.66 ± 0.05 23.46 ± 0.13 23.50 ± 0.15 0.75 ± 0.10 0.77 ± 0.05 – –
S – – 180 ± 36 (ppm) 190 ± 50 (ppm) – – 210 ± 43 (ppm) 230 ± 50 (ppm) 0.834 ± 0.032 0.846 ± 0.05
Corg – – 0.62 ± 0.08 0.63 ± 0.04 – – 0.49 ± 0.08 0.50 ± 0.03 – –

Number of replicates: at least n = 3 in reproducibility conditions.

c 2010 John Wiley & Sons, Ltd.

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275
 M. F. Gazulla et al.

Table 17. Comparison of the measurement result of the validation standards with the known value for organic carbon, carbon at 950 ◦ C, total
carbon and sulfur, where m is the difference between the measured and the known value and Um is the expanded uncertainty

SRM 112b GBW07404 BCS-CRM No 359 GBW07402 SRM1886a

Element m Um m Um m Um m Um m Um

C950 ◦ C (wt%) 0.02 0.08 0.01 0.21 – – 0 0.22 – –

Ctotal (wt%) 0.05 0.34 0.02 0.22 0.04 0.40 0.02 0.22 – –
S (wt%) – – 10 ppm 123 ppm – – 20 ppm 132 ppm 0.01 0.12
Corg (wt%) – – 0.01 0.18 – – 0.01 0.17 – –

Table 18. Results of the determination of carbon from the WC phase

Grinding tool 36 Grinding tool 150 Grinding tool 280 Grinding tool 600 Grinding tool 1500

W (wt%) 0.90 ± 0.01 0.82 ± 0.01 0.85 ± 0.01 0.90 ± 0.02 0.96 ± 0.01
WC (wt%) 0.96 ± 0.01 0.87 ± 0.01 0.90 ± 0.01 0.96 ± 0.02 1.02 ± 0.01
CWC (wt%) 0.06 ± 0.01 0.05 ± 0.01 0.06 ± 0.01 0.06 ± 0.01 0.06 ± 0.01

Number of replicates: at least n = 3 in reproducibility conditions.

Table 19. Results of total carbon, carbon at 950 ◦ C and carbon from the silicon carbide phase

C content (wt%) Grinding tool 36 Grinding tool 150 Grinding tool 280 Grinding tool 600 Grinding tool 1500

Ctotal 6.39 ± 0.06 4.58 ± 0.05 6.29 ± 0.06 4.83 ± 0.05 5.44 ± 0.06
Corg 3.19 ± 0.04 3.10 ± 0.04 3.21 ± 0.04 3.09 ± 0.04 3.12 ± 0.04
C950 ◦ C 3.65 ± 0.04 3.63 ± 0.04 4.41 ± 0.04 3.57 ± 0.04 3.88 ± 0.04
CSiC 2.70 ± 0.10 0.90 ± 0.09 1.80 ± 0.10 1.20 ± 0.09 1.50 ± 0.10

Number of replicates: at least n = 3 in reproducibility conditions.

Table 20. Complete chemical analysis of the studied grinding tools

Grinding tool
components (wt%) Grinding tool 36 Grinding tool 150 Grinding tool 280 Grinding tool 600 Grinding tool 1500

SiO2 total 24.0 ± 0.2 15.8 ± 0.1 14.1 ± 0.1 9.9 ± 0.1 13.4 ± 0.1
Al2 O3 9.8 ± 0.1 13.6 ± 0.1 7.66 ± 0.05 10.1 ± 0.1 7.2 ± 0.1
Fe2 O3 0.41 ± 0.01 0.13 ± 0.01 0.69 ± 0.02 0.61 ± 0.01 0.69 ± 0.01
CaO 1.41 ± 0.04 0.70 ± 0.02 4.62 ± 0.04 1.83 ± 0.03 1.47 ± 0.03
MgO 31.4 ± 0.3 31.2 ± 0.3 29.3 ± 0.3 28.4 ± 0.3 29.5 ± 0.3
Na2 O 5.88 ± 0.04 8.08 ± 0.04 8.68 ± 0.04 12.6 ± 0.05 12.8 ± 0.06
K2 O 0.04 ± 0.01 0.06 ± 0.01 0.02 ± 0.01 0.03 ± 0.01 0.04 ± 0.01
TiO2 0.27 ± 0.01 0.37 ± 0.01 0.27 ± 0.01 0.25 ± 0.01 <0.01 ± 0.01
MnO 0.03 ± 0.01 <0.01 ± 0.01 0.03 ± 0.01 0.03 ± 0.01 0.04 ± 0.01
P2 O 5 <0.01 ± 0.01 <0.01 ± 0.01 0.02 ± 0.01 0.02 ± 0.01 0.01 ± 0.01
SiC 9.0 ± 0.3 3.0 ± 0.3 6.0 ± 0.3 4.0 ± 0.3 5.0 ± 0.3
LOI (1025 ◦ C) 36.1 38.5 44.9 49.4 47.6
S 0.65 ± 0.04 0.56 ± 0.04 0.35 ± 0.03 0.31 ± 0.03 0.38 ± 0.03
Cl 14.0 ± 0.1 15.8 ± 0.1 15.8 ± 0.1 18.2 ± 0.1 23.2 ± 0.1

Number of replicates: at least n = 3 in reproducibility conditions.

Characterization of the grinding tools. The complete analysis of
the SiC-based grinding tools, taking into account the phase analysis
obtained, is presented in Table 21.
The chemical and mineralogical analysis data show that the
studied grinding tools are basically made up of SiC and corundum
as abrasives and magnesium oxychloride as binder, in addition
276
calcite, periclase, talc, brucite and quartz, in variable quantities,
depending on the grinding tool.
When the analysis results for the silicon carbide phase in the
grinding tools obtained by XRD and elemental analysis of the
different forms of carbon are compared, no significant differences
are observed. Either method can therefore be used, depending on

to other minor constituents such as halite, bassanite, dolomite, the available equipment.

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c 2010 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 267–278
Chemical characterisation of grinding tools by WD-XRF and XRD

Table 21. Composition, expressed as a percentage by weight, of the components present in the studied grinding tools

Crystalline phases (wt%) Grinding tool 36 Grinding tool 150 Grinding tool 280 Grinding tool 600 Grinding tool 1500

Silicon carbide (SiC) 9.0 ± 0.5 3.0 ± 0.3 6.0 ± 0.5 4.0 ± 0.5 5.0 ± 0.5
Halite (NaCl) 11.0 ± 0.5 13.0 ± 0.5 13.0 ± 0.5 16.0 ± 0.8 21 ± 1
Magnesium hydroxychloride 53 ± 2 56 ± 2 58 ± 2 60 ± 3 53 ± 2
hydrate ((Mg3 (OH)5 Cl)·
4H2 O) + other organic
binders)
Bassanite (2CaSO4 (H2 O)) <1 1.0 ± 0.3 <1 1.0 ± 0.3 <1
Dolomite (CaMg(CO3 )2 ) <1 <1 5.0 ± 0.5 2.0 ± 0.3 2.0 ± 0.3
Calcite (CaCO3 ) <1 <1 5.0 ± 0.5 2.0 ± 0.3 1.0 ± 0.3
Magnesite (MgCO3 ) <1 <1 <1 <1 <1
Periclase (MgO) 1.0 ± 0.3 1.0 ± 0.3 <1 <1 1 ± 0.3
Talc (Mg3 (OH)2 Si4 O10 ) 9.0 ± 0.5 <1 5.0 ± 0.5 4.0 ± 0.5 4.0 ± 0.5
Brucite (Mg(OH)2 ) 3.0 ± 0.3 3.0 ± 0.3 <1 3.0 ± 0.3 3.0 ± 0.3
Quartz (SiO2 ) 5.0 ± 0.5 10.0 ± 0.5 1.0 ± 0.3 <1 4.0 ± 0.5
Alumina and corundum 10.0 ± 0.5 13.0 ± 0.5 6.0 ± 0.5 9.0 ± 0.5 6.0 ± 0.5
(α-Al2 O3 )
Sodalite (Na4 Cl(Al3 Si3 O12 )) <1 <1 2.0 ± 0.3 <1 <1

Number of replicates: at least n = 3 in reproducibility conditions.

Figure 2. Synoptic scheme of the steps used in the full characterisation of silicon carbide-based grinding tools.

The method proposed in this paper for the complete
characterisation of SiC-based grinding tools is schematically il-
lustrated in Fig. 2.
Conclusions
1. A method is presented for the complete chemical charac-
terisation of SiC-based grinding tools, using elemental and
spectroscopic analysis techniques to determine all grinding
tool components. The method can be used for grinding tool
quality control.
2. The phases making up the grinding tools were analysed and
quantified by XRD. This provided the information needed to
address the chemical analysis, since grinding tools, in addition
quantities of other admixtures, such as sulfates, to provide
individual grinding tools with different properties.
3. Milling is an important step in grinding tool chemical analysis.
Milling can be performed in a WC mill provided milling
conditions are suitably controlled to obtain an appropriate
particle size distribution; the contamination that the material
undergoes during milling is also duly corrected by tungsten
analysis.
4. WD-XRF was used in analysing the elements in the grinding
tools. Samples were prepared as beads and pellets, depending
on the element to be analysed. The absence of certified
reference materials with a composition similar to that of the
analysed samples made it necessary to prepare compositions
by mixing the available reference materials in order to validate
277

to containing abrasives and binders, also contain different the measurements.

X-Ray Spectrom. 2010, 39, 267–278 Copyright

c 2010 John Wiley & Sons, Ltd. www.interscience.com/journal/xrs

5. Carbon elemental analysers with variable operating temper-
ature were used to determine the different forms of carbon:
organic carbon, carbon at 950 ◦ C (corresponding to organic
carbon and carbon from the carbonates) and total carbon com-
prising all forms of carbon: organic carbon, inorganic carbon
and carbon from the silicon carbide phase. This information
enabled the SiC concentration to be calculated, since SiC can-
not be separated by the gravimetric method without oxidising
in the course of the process or other sample components
being retained together with the SiC.
6. The SiC in these SiC-based grinding tools can be determined by
the two developed methods, namely by XRD or by elemental
analysis, since both methods yield good results.
Acknowledgements
This study was funded by the Valencia Institute of Small
and Medium-sized Enterprise (IMPIVA) in frame of the Re-
search, Development and Innovation programme, through the
IMIDIC/2007/103 and IMIDIC/2008/15 projects, corresponding to
the Plan for company services centres and REDIT Technology In-
stitutes, as well as by the European Union through the European
Regional Development Fund.
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