Applied Clay Science 87 (2014) 219227

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Applied Clay Science

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Research paper

Exfoliation of vermiculites with chemical treatment using hydrogen

peroxide and thermal treatment using microwaves
Celia Marcos , Irene Rodrguez
Dpto. Geologa e Instituto de Organometlica Enrique Moles, Universidad de Oviedo, C/ Jess Arias de Velasco s/n, 33005 Oviedo, Spain

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents the investigation about chemical and thermal exfoliation of vermiculites from Santa Olalla
Received 6 June 2013 (Huelva, Spain), Libby (Montana, USA) and Gois (Brasil). Four experiments were made: 1) Reaction of each sam-
Received in revised form 31 October 2013 ple from Santa Olalla, Libby and Gois with hydrogen peroxide solution of 30% and 50% respectively, at different
Accepted 9 November 2013
times for each sample. 2) Irradiation of Libby and Gois samples with microwaves for 20 s. 3) Reaction of Gois
Available online 2 December 2013
samples with hydrogen peroxide solutions of 30 and 50 mass%, respectively, into microwave oven for 20 s. 4)
Keywords:
Abrupt heating of Libby vermiculite at 1000 C for 1 min in an oven once stabilized (~2 h).
Vermiculite The original and treated vermiculite samples were characterized by X-ray diffraction (XRD) and
Exfoliation thermogravimetry; their chemical composition was obtained by electron microprobe and their morphology
Hydrogen peroxide was examined with the scanning electron optical and microscopy.
Microwave The results of this study, in relation to the treatments with hydrogen peroxide, showed that: 1) The purest sam-
ples like those from Santa Olalla suffered minor changes (slight structural disorder) and the exfoliation was
lower; while others like Libby, with higher content of iron and interlayer potassium, could suffer major changes
with the formation of a new phase through interstratied phases, and the exfoliation grade was higher. 2) The
exfoliation speed of the samples increased with the peroxide hydrogen concentration and might be attributed
to higher dissolution of dissolved and/or exchanged amounts of cations such as sodium, potassium, magnesium
and iron. In relation to the microwave irradiation: 1) No major structural changes in the investigated samples
were observed as no major changes were observed in the XRD patterns of the treated samples in relation to
the untreated ones. 2) Samples like those from Gois, which did not exfoliate when irradiated with microwaves,
exfoliate when treated with hydrogen peroxide and simultaneously irradiated with microwaves for a few
seconds.
2013 Elsevier B.V. All rights reserved.

1. Introduction It is well known that when vermiculite is strongly heated at high

Vermiculites are a signicant group of phyllosilicates 2:1 clay
minerals, with relatively large specic area (~100 m2/g). Water and
other inorganic or organic substances can be adsorbed in the expandable
interlayer space (Bergaya et al., 2006; Hindman, 1992; Jayabalakrishnan
and Mahimaraja, 2007; Strand and Stewart, 1983). They are very extend-
ed materials for different applications because of their availability and low
cost.
Vermiculites can be exfoliated by thermal treatment and chemical
methods (Mamina et al., 1990; Marcos and Rodrguez, 2010, 2011;
Marcos et al., 2009; Myers, 1963; Obut and Girgin, 2002; Suquet et al.,
1991; gl, 1997; gl and Girgin, 2002; Weiss et al., 2006). Water
content, type of interlayer cations and interstratications of the
vermiculite are factors that inuence highly in its exfoliation (Justo
et al., 1993; Mamina et al., 1990; Marcos et al., 2009).
Corresponding author.
E-mail address: cmarcos@uniovi.es (C. Marcos).
temperature ( 1000 C) during a short period of time, the water
situated between layers is quickly converted into steam, exerting a
disruptive effect upon the structure (Baumeister and Hahn, 1976;
Marcos and Rodrguez, 2010; Marcos et al., 2009; Obut and Girgin,
2002; Wada, 1973a,b; Walker, 1961). As a consequence, a highly porous
thermal-exfoliated material is formed. The thermal exfoliation occurs in
a direction approximately perpendicular to the layers. This property of
exfoliation is explained as due to the explosive release of interlamellar
water molecules by heating, and causes the vermiculite to expand to
twenty or thirty times their original size normal to the basal cleavage
and to change its structure. The silicate structure vanishes after dehy-
dration and the reappearing of a new structure depends on interlayer
cations and their content, particle size and time of treatment. During
the nal stage, individual water molecules tend to be trapped in the
interior of the interlayer by the convergence of the silicate layers near
the edges (Bergaya et al., 2006).
Vermiculite as raw or when exfoliated material nds use in
construction products, agriculture, horticulture, as acoustic and thermal
insulator, adsorbent and other applications (Wada, 1973b; Strand and

0169-1317/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2013.11.008
220 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227
Table 1
Water contents (mass%) derived from TG.
Water content (wt.%)
Conventional Microwave 1000 C for 1 min H2O2 reaction
30%
Santa Olalla 25.6a 24.9a 4.9a
Gois 12.1 12.2 5.6 12.1
12.7b
Libby 10.3 11.1 3.4 10.9
a
Taken from Marcos et al. (2009).
b The procedure for the rst and third experiments was the following:
Samples irradiated simultaneously with microwave.
Stewart, 1983; Hindman, 1992; Obut and Girgin, 2002; Williams-Daryn
and Thomas, 2002; da Silva et al., 2003; Xu et al., 2005; Sumathi et al.,
2005; Jimnez de Haro et al., 2005; Brigatti et al., 2005; Bergaya et al.,
2006; Jayabalakrishnan and Mahimaraja, 2007).
Chemical processes utilizing hydrogen peroxide have been used for
exfoliation or chemical activation of 2:1 clay minerals. Suquet et al.
(1991) described the preparation of porous materials by chemical acti-
vation of natural vermiculite. Muromtsev et al. (1990) studied reactions
of vermiculite with 30% H2O2 solution at 20 C and 80 C. Obut et al.
(2003) studied exfoliation on large akes (on the scale of cm) of phlog-
opite and vermiculite after treatment with different concentrations
(150%) of H2O2 for different periods of time (130 h). No change in
the XRD patterns of the vermiculites treated with H2O2 solutions was
found by some authors (Muromtsev et al., 1990; Obut and Girgin,
2002), although others as Weiss et al. (2006) reported changes.
The aim of this study was twofold: 1) Get more data on the exfolia-
tion of vermiculites treated with H2O2 to try to clarify whether or not
structural changes occur; and 2) to make sure that determined vermic-
ulites like that one from Gois (Brasil), which did not exfoliate with
microwave, exfoliate using a simultaneous treatment of microwave
irradiation and H2O2 reaction.
2. Experimental
The vermiculite samples came from Santa Olalla (Huelva, Spain),
Gois (Brasil) and Libby (Montana, USA).
Vermiculites were studied as received, in the case of the Gois
sample after elimination of other minerals by hand-picking.
Square shaped samples from Santa Olalla (yellowish-green in color)
and Libby (dark green in color) were prepared with an average size of
15 9 mm and a thickness of 0.200.34 mm; other samples from
Libby with average size of 6 6 mm and a thickness of 0.10.4 mm
were also used. The Gois samples (brownish in color) had an average
size of 1 1 mm and thickness of 0.080.5 mm.
Chemical analyses of the untreated sample of Libby were performed
by means of energy dispersive spectroscopic analysis using a CAMEBAX-
Fig. 1. Appearance of Santa Olalla akes after 20 h treatment with H2O2 solution at 30% (a) and 50% (b).
MBXSX-50 electron microprobe with an acceleration voltage of 15 kV
and a beam current of 15 mA.
Four experiments were made: 1) Reaction of each sample from
Santa Olalla, Libby and Gois with hydrogen peroxide solution of 30
and 50 mass% (henceforth 30% and 50%) respectively, at different
50%
times for each sample at room temperature. 2) Irradiation of Libby
and Gois samples with microwaves for 20 s. 3) Reaction of Gois sam-
12.1
ples with hydrogen peroxide solutions of 30% and 50%, respectively, into
12.9b
11.4
microwave oven for 20 s. 4) Abrupt heating of Libby vermiculite at
1000 C for 1 min in an oven once stabilized (~2 h).
1) Preparation of four sets of two 30 ml beakers. One of the two beakers
of each set containing 10 ml of H2O2 solution of 30% concentration and
the other 10 ml of H2O2 solution of 50% concentration. 2) Preparation of
two portions of each sample, four in the case of Gois sample. 3) pH
measuring of the starting H2O2 solutions of 30% and 50% concentrations.
4) Introduction of each sample portion in one beaker with H2O2 solu-
tion. All of the solutions were kept without stirring for different time pe-
riods. 5) Introduction of two beakers with the H2O2 solutions of 30% and
50% concentrations, respectively, and the Gois sample into microwave
oven for 20 s. 6) Separation of the solid of each beaker by ltration, after
the time established; washing with distilled water at room temperature
and drying of samples at 40 C for 4 h; and measuring of the pH of the
H2O2 solutions at 30% and 50%.
Finally, the study and analysis (thickness measurement, calculation
expansibility, optical and electron microscopy images, X-ray diffraction,
etc.) of the treated samples were made.
The experiments with microwave were carried out with a micro-
wave oven (SHARP R64sT) working at 2.45 GHz and 800 W. The tem-
perature seemed not to exceed 100 C (Obut et al., 2003; Walkiewicz
et al., 1988). In a microwave oven, heating depends on the power of
the oven and of the contents of the water, density and sample quantity.
Therefore, different containers and sample holders (glass Petri dishes
with and without glass lids, porcelain crucibles with and without porce-
lain lids, glass dishes for microwave heating with and without lids) and
different microwave exposure times (from 10 s to 600 s) were used.
The expansibility, k (k = density of the raw sample/density of the ex-
panded sample), was measured by the change of the apparent density. A
known volume of sample was weighed, and expanded by introducing the
sample in the microwave and then weighed again. The nal and initial
volumes for obtaining the apparent volume (nal volume minus initial
volume) were measured by tipping the loose fragments into a measuring
graduate glass cylinder in mm without compactation, before and after the
expansion in the microwave. The density of the raw and the expanded
sample was obtained from the weight and volume apparent.
The X-ray powder diffraction patterns were taken with a PHILIPS X'
PERT PRO diffractometer, at 40 mA and 45 kV (Cu-K radiation;
= 1.5418 ), 2 370, 2 step scans of 0.02 and a counting time of
1 s per step.
 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227 221

Fig. 2. Appearance of Libby akes after 2 h treatment with H2O2 solution at 30%, on one side (a) and the opposite (b).

Fig. 3. Appearance of Libby akes after 2 h treatment with H2O2 solution at 50%. The surface undulation in the outermost and intermediate exfoliation sheets (a and b) and corrugation in a
slightly innermost exfoliation sheet (c) can be seen.

The XRD patterns in the ake were taken with a Seifert XDR 3000T/T. 31.00 (0.08)% Cr2O3 and 9.68 (0.20)% K2O. The cations were obtained
The machine settings were 30 mA and 40 kV (Cu-K radiation; using the MINPET program (MINPET GEOLOGICAL SOFTWARE, 146 DV
= 1.5418 ), 2 range 210, 2 step scans of 0.02 and a counting Chateau Masson-Angers, Quebec, Canada). The calculations to obtain
time of 20 s per step. the cation contents were based on 24 anions (20 structural oxide ions
Morphology of the exfoliated vermiculites was examined with a LEICA and 4 OH ions). Because electron microprobe techniques do not allow
MZ16A binocular microscope and with a JEOL-6610LV scanning electron us to distinguish between Fe2 + and Fe3+, the Fe2+ content for Libby
microscope (SEM). For the SEM, the samples were coated with gold. was calculated by the semi-empirical formula proposed by Laird and
The thermogravimetric analyses were performed between 25 C Albee (1981). The distribution of cations among the different structural
and 1100 C using a Mettler Toledo Stare System thermobalance and
porcelain crucible with a heating rate of 10 C/min. The total mass loss
was determined gravimetrically by heating the samples in air at
1000 C in a mufe furnace and assumed due entirely as water. The
initial sample mass was of 18 mg.
The technique used to detect the ions released into the H2O2 solution
was ICP-mass with a 7500ce Agilent (Agilent Technologies) instrument
equipped with collision cell/reaction using helium as the collision gas to
avoid as far interferences.
The pH was measured with a Crison Compact Titrator.
All of the equipment belong to the Servicios Cientco-Tcnicos de la
Universidad de Oviedo.

3. Results and discussion

The result of the chemical analyses for the Libby sample in terms of
mass content of the oxides of the elements was the following: 38.66
(0.42)% SiO2, 13.02 (0.08)% Al2O3, 20.58(0.55)% MgO, 8.60 (0.29)% FeO
(total iron), 21.17 (0.12)% TiO2, 0.03 (0.04)% CaO, 0.20 (0.11)% Na2O, Fig. 4. Appearance of Libby akes after 20 h treatment with H2O2 solution at 50%.
222 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227

positions was carried out according to Foster (1963): (a) all the silicon
was allotted to the tetrahedral group, together with enough Al3+ to
bring the total to 4.00. When there was not enough Al3+ to complete
the tetrahedral group, Fe3+ was then allotted to the tetrahedral group
to complete it. (b) Any remaining Al3+ and Fe3+, with the Fe2+, Ti4+,
Cr3+, Mn2+, plus all the Mg2+ or enough Mg2+ to ll three positions
were assigned to the octahedral group. (c) Any remaining Mg2+, plus
the Ca2+, Na+, and K+, were nally assigned to interlayer positions.
The structural formulas for unit cell for the samples were:
3 2
Mg0:76 K0:01 Ca0:05 Na0:04 Mg4:92 Al0:59 Fe0:41 Fe0:02 Ti0:04 Mn0:02 Si5:66 Al2:34 O20 : OH4
According to the division of vermiculites proposed by Marcos et al.
(2009), Santa Olalla and Gois would belong to type-1 and Libby to
type-2.
The distribution of the cationic charge of the Libby sample, calculated
from the cation distribution, was of 12.31 in octahedral sheet and of
29.67 in tetrahedral sheet; these values agreed with the proposition of
Kster (1982) for vermiculite. The charge in the interlayer space (1.92),
generated by the charge imbalance in the structure, was larger than
that corresponding to Santa Olalla (1.65) and Gois (0.74) samples,
which also had lower content of potassium plus magnesium.

for Santa Olalla (Marcos and Rodrguez, 2010);

3 2
Mg0:25 K0:20 Ca0:01 Na0:04 Mg4:02 Al0:61 Fe1:23 Fe0:04 Ti0:09 Mn0:01 Si6:46 Al1:54 O20 : OH4

for Gois in accordance with Marcos and Rodrguez (2010); and

3 2
K1:84 Ca0:01 Na0:078 Mg4:57 Al0:78 Fe0:93 Fe0:14 Ti0:13 Cr0:12 Mn0:01 Si5:76 Al0:24 O20 : OH4

for Libby.
The water content considered as the total mass loss obtained from
the thermogravimetric analysis for the investigated samples is in
Table 1.

Fig. 5. SEM images of exfoliated Gois sample after 2 + 1/2 h H2O2 (50%) treatment: Fig. 6. SEM images of exfoliated Gois sample after 4 h H2O2 (30%) treatment: a) side
a) side view; b) and c) enlarged views. view; b) and c) enlarged views showing the undulations and corrugations.
 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227 223

Table 3
Cations released in increase order of concentration.

H2O2 % Time (h) Cations released in increase order of concentration

Santa Olalla 30 20 K, Br, Mg, Fe

50 Na, Mg, K, Fe, Al
Libby 30 20 K, Na, Ba, Mg, Fe
50 Na, K, Fe, Mg, Al, Cr, Ba
Gois 30 4 K, Na, Mg, Fe, Ti, Al
50 2.5 Na, K, Mg, Fe, Al, Ti, Ba

after treatment with H2O2, as well as the surface undulation and

corrugation that increased with the reaction time, are presented.
The changes in average thickness of the Santa Olalla and Libby sam-
ples (Table 2) were observed with respect to H2O2 concentration (30
and 50%) and reaction time (5 and 20 h); main parameters that directly
affect the chemical exfoliation characteristics (Obut and Girgin, 2002).
Experimental results showed that for Santa Olalla and Libby samples
in the ake the exfoliation was higher with H2O2 solution at 50% and re-
action time of 20 h. Furthermore, the exfoliation of Libby sample was
higher than that of Santa Olalla, as might be expected (Marcos and
Rodrguez, 2011; Marcos et al., 2009) due to its higher content of iron
and interlayer potassium.
The reaction of Gois sample with 30% H2O2 solution caused 100% of
exfoliation of the same and occurred after 4 h, while with 50% H2O2
solution it took place after 2.5 h, and the color of the samples changed
to gold. Exfoliation of Gois sample was considered in terms of expansi-
bility factor k because of the little size of the particles. The k factor for
2.5 h reaction with 30% H2O2 solution was slightly lower, 6.71, than
for 4 h reaction with 50% H2O2, 7.13.
In all the tests the exfoliation of the samples was higher when the re-
action was carried out with H2O2 solution at 50% than at 30%, which
agreed with that observed by Obut and Girgin (2002) for vermiculite.
The exfoliation speed (thickness or volume/ time) of the samples
Santa Olalla, Libby and Gois increased with the concentration of H2O2
(see Table 2). The fact that the exfoliation speed of the samples in-
creased with the hydrogen peroxide concentration might be attributed

Fig. 7. SEM images of exfoliated Gois sample after 20 h H2O2 (50%) treatment: a) side
view; b) and c) enlarged views showing the undulations and corrugations.

The appearance and texture of the samples changed with the H2O2
or H2O2 and microwave irradiation treatments. In the images taken
with the binocular microscope of treated Santa Olalla and Libby akes
(Figs. 14), corrugated and undulating surfaces and silver in color can
be observed. In Figs. 57, SEM images of exfoliated vermiculite akes
from Gois showing the appearance of aky pastry or accordion-like

Table 2
Changes in thickness of Santa Olalla and Libby samples and volume of Gois sample after
H2O2 treatment (30 and 50%) and exfoliation speed (thickness/time (mm/h) or volume/
time (ml/h)).

Reaction time (h) 0 4 2.5 5 20

H2O2 % 30 50 30 50 30 50 30 50
Average thickness Santa 0.21 0.32 1.23 4.37 1.39 4.74
(mm) Olalla
Thickness/time 0.2 0.9 0.1 0.2
(mm/h)
Average thickness (mm) Libby 0.21 0.25 4.0 5.5 6.0 13.5
Thickness/time 0.8 1.1 0.3 0.7
(mm/h)
Volume (ml) Gois 1 6 7.5
Fig. 8. SEM images of a Libby ake irradiated with microwaves for 20 s: a) top view;
Volume/time (ml/h) 1.3 2.6
b) enlarged side view.
224 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227

Fig. 9. Appearance of exfoliated Gois akes (image taken with binocular loupe).

to higher dissolution of dissolved and/or exchanged amounts of cations

like Na, K, Mg and Fe (see Table 3).
On the other hand, Libby vermiculite, as vermiculites of type-2, gave
contents of Fe2+ and K+ ions higher than vermiculites of type-1, as the
Santa Olalla one. Fe2 + ions would facilitate the xing of the K+ ions
(Marcos and Rodrguez, 2010), which was responsible of a larger
exfoliation after heating at elevated temperatures (Marcos et al., 2009).
Sample from Libby irradiated with microwaves was expanded by
100% practically in glass Petri dish for 20 s (Fig. 8). On the contrary,
sample from Gois did not expand at any time and in any container.
The Gois sample expanded by 100% when it was introduced into a
beaker with H2O2 solution (30% and 50%) and after placed into micro-
wave oven for 20 s. In Fig. 9, the appearance of an exfoliated Gois Fig. 10. SEM images of a Gois ake treated with H2O2 solution at 50% and irradiated simul-
taneously with microwaves for 20 s: a) side view; b) enlarged view from a); c) enlarged
ake as an example can be observed. SEM images of undulations and
view from b).
corrugations of a Gois ake treated with H2O2 solution at 50% and
irradiated simultaneously with microwaves for 20 s can be observed
in Fig. 10. of the solution became slightly more basic and the cations released are
The expansibility value (k) obtained under microwave treatment for presented in Table 4 in increasing order of concentration.
20 s for the vermiculite from Libby was 6.8, slightly lower than the value The ake XRD of the untreated and treated Santa Olalla samples in
of 7.3 obtained for a vermiculite from China (CHG) by Marcos and ake with H2O2 is presented in Fig. 16. Treatment of H2O2 at 50% for
Rodrguez (2011). Libby sample with higher content of K+ than Santa 20 h produced a more pronounced increase of (002) reection intensity
Olalla (Table 4) and other samples (Marcos and Rodrguez, 2011) gave than H2O2 treatment at 30% for 20 h, which was similar to the starting
higher exfoliation value after microwave heating, which demonstrated sample. The corresponding d value of this reection (14.46 ) was prac-
again that K+ was the responsible cation of its larger exfoliation tically the same in the untreated and treated samples. The intensity
(Marcos et al., 2009). The color of the exfoliated akes changed to silver increase of the major reection might be interpreted as due to the
color with greenish tint. In Fig. 11, the appearance of exfoliated Libby increase in structural ordering caused probably by the slightly water
akes can be seen. adsorption.
The expansibility values (k) obtained under microwave treatment
and H2O2 solutions at 30 and 50%, respectively, during 20 s for the
vermiculite from Gois were 8.14 and 7.13. The rst value was higher
and the second was equal to that obtained with H2O2 treatment only.
The color of the exfoliated akes changed to gold (Fig. 9) and the size Table 4
Cation content of the vermiculites.
was smaller for the sample treated with H2O2 solution at 50%.
The solution pH values were determined after removing the sample Santa Ollallaa Goisa Libby
when nishing the treatments and the results are given in Figs. 1215. Fe 2+
0.02 0.04 0.14
The slight increasing trends in the solution pH values for increasing Fe3+ 0.41 1.23 0.93
reaction times for the two H2O2 concentrations used can be seen. This Mg2+ 0.76 0.25 0.00
increase can be explained by the exchange of H+ ions with the dissolved K+ 0.01 0.20 1.84

cations in the samples (Obut and Girgin, 2002). In all treatments, the pH a
Marcos et al. (2009).
 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227
Fig. 11. Appearance of exfoliated Libby akes after being irradiated with microwaves for
20 s.
The powder XRD of Libby samples in the ake is presented in Fig. 17.
The XRD patterns of the starting Libby sample indicated the coexistence
of the (d = 14.32 ) 2-WLHS phase (WLHS = Water Layer Hydration
State) with the interstratied phases with d = 12.02 and
d = 10.03 , as the major reections. A similar XRD pattern was obtain-
ed for the irradiated sample with microwaves for 20 s, indicating no
structural change. It was previously reported that microwave heating
inhibited the dehydrationrehydration more strongly than dehydration
in vacuum (Marcos et al., 2003). The water content (Table 1) was almost
equal to that of the starting sample; the slight difference can be attribut-
ed to measurement conditions. On the contrary, the XRD of the sample
heated abruptly at 1000 C for 1 min showed that the major reection
with d = 10.03 increased its intensity. This reection could corre-
spond to anhydrous vermiculite or muscovite (Marcos et al., 2009;
Ruiz-Conde et al., 1996). In contrast, this reection has been interpreted
(Collins et al., 1992) as a second-order reection arising from and
ordered alternation of one-and zero-layer hydrates, but could also cor-
respond to a random interstratication of one- and zero-layer hydrates.
However, in this case and due to the experimental conditions and
according to Marcos et al. (2009) and Marcos and Rodrguez (2010), it
was assumed that the 10.03 reection would correspond to musco-
vite (JCPDS card no 7-0025) although there is no XRD pattern in the
Fig. 12. Change of pH with reaction time for Santa Olalla sample.
225
Fig. 13. Change of pH with reaction time for Libby sample.
2 range of 2030 where the more intense reection of muscovite
at 3.3 would occur. Water loss about 7% (Table 1) was interpreted
as due to the abrupt desorption of the interlayer water molecules
when the sample was heated up to 1000 C for a minute which pro-
voked the expansion of the vermiculite particles as revealed by SEM
(Fig. 8). The 25.16 phase present in the powder XRD patterns of the
Libby sample could be due to the existence of a superstructure, formed
by regular 1:1 interstratication, during and after the oneone/zero
layer collapse vermiculite (Marcos et al., 2003; 2009; Reichenbach and
Beyer, 1994; Ruiz-Conde et al., 1996). The ake XRD of the Libby sam-
ples in ake treated with H2O2 solutions is presented in Fig. 18. Principal
reection the one with d = 10.2 , probably muscovite (JCPDS card no
7-0025) as explained above can be observed. The typical reection of
vermiculite with d about 14.3 (seen enlarged in inset) with very low
intensity can also be observed. This might suggest a structural change
which might have been performed through the formation of an inter-
stratied phase like the present in the pattern with d = 29.2 , proba-
bly by hydration during the treatment with hydrogen peroxide, as it
occurs with other treatments (Collins et al., 1992; Marcos et al., 2003;
Reichenbach and Beyer, 1994; Ruiz-Conde et al., 1996; Warshaw et al.,
1960). Change would have been a slower process in powder than in
ake sample; while the H2O2 reaction was taking place, certain concen-
trations of some cations were released to the solution while others were
reorganized to congure probably the mica-like structure.
Fig. 14. Change of pH with reaction time for Gois sample.
226 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227

Fig. 18. Flake XRD of treated Libby sample in ake.

Fig. 15. Change of pH with reaction time into the microwave oven for 20 s for Gois
sample.

The powder XRD pattern of untreated sample from Gois (Fig. 19)
showed the coexistence of the 2-WLHS phase (d = 14.3 ) with the
interstratied phase with d = 12.2 . No signicant change was ob-
served in the treated samples except a slight increase of the reection
intensity of the sample treated with H2O2 and simultaneously irradiated
with microwaves, probably indicating structural order caused by the
increase of water content. The intensity would have changed more if
there had been structural reorganization (Marcos and Rodrguez,
2010; Marcos et al., 2009).

4. Conclusions

In the treatments of the vermiculite samples (Santa Olalla, Libby and

Fig. 16. Flake XRD of Santa Olalla.
Gois) with hydrogen peroxide, the purest samples like those from
Santa Olalla suffered minor changes (slight structural disorder) and
the exfoliation was lower; while others like those from Libby, with
higher content of iron and interlayer potassium, could suffer major
changes as formation of a new phase (d = 10.2 , probably muscovite)
through interstratied phases, and the exfoliation was higher. The
exfoliation speed of the samples increased with the peroxide hydrogen
concentration and might be attributed to higher dissolution of dissolved
and/or exchanged amounts of Na, K, Mg, and Fe cations.
Microwave irradiation caused no major structural changes in the
samples studied as no major changes were observed in the XRD
patterns of the treated samples in relation to untreated ones. Samples
as those from Gois which did not exfoliate when irradiated with
microwaves, did exfoliate when treated simultaneously with hydrogen
peroxide for a few seconds.

Fig. 17. Powder XRD of Libby samples in ake (~4 5 mm). Fig. 19. Powder XRD of Gois sample.
 C. Marcos, I. Rodrguez / Applied Clay Science 87 (2014) 219227
Acknowledgments
We appreciated very much the help of the editor F. Bergaya and the
two reviewers during the revision of the manuscript.
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