J Therm Anal Calorim
DOI 10.1007/s10973-017-6705-6
A study of thermal decomposition of antigorite from dunite
and lizardite from peridotite
Nshan Zulumyan1,2 • Anna Isahakyan1 • Hayk Beglaryan1,3 • Stella Melikyan1,2
Received: 22 February 2017 / Accepted: 10 September 2017
Ó Akadémiai Kiadó, Budapest, Hungary 2017
Abstract Two varieties of serpentines, antigorite and
lizardite originated from dunite and peridotite, respec-
tively, were previously undergone heat treatment in the
range from 396 to 1128 °C and then leached via an original
approach to the acid processing of dehydrated serpentines.
Because of unsaturated (weak) Si–O(Si) bonds existing in
the serpentines structure, ortho- [SiO4]4-, di- [Si2O7]6-
and other silicate units are easily leached from dehydrated
serpentines in the form of soluble silicic acids along with
magnesium compounds via this approach, whereas the
more complex fragments largely comprised of metasilicate
[(SiO3)2-]n chains remain in the unreacted mass The yields
of silicic acids produced from heated serpentines are
variable. The influence of thermal treatment on both the
serpentinite samples was investigated by thermal, X-ray
diffraction and chemical analyses. The data derived from
the experimental studies allowed to reveal the distribution
of primary ortho- [SiO4]4- and meta- [(SiO3)2-]n silicate
units in the silicate layers inherent in these serpentine
minerals and to understand its influence on the mechanism
of their decomposition including the high-temperature
phase transformations into forsterite Mg2SiO4 and enstatite
Mg2Si2O6.
& Nshan Zulumyan
zulumnshan@rambler.ru
1
The Institute of General and Inorganic Chemistry of the
National Academy of Sciences of the Republic of Armenia
(IGIC NAS RA), Argutyan str. 10, lane 2, 0051 Yerevan,
Armenia
2
Armenian State Pedagogical University after Kh. Abovyan,
Tigran Mets Avenue 17, 0010 Yerevan, Armenia
3
Yerevan State University, 1 Alex Manoogian, 0025 Yerevan,
Armenia
Keywords Serpentine polymorph  Dehydroxylation 
Silicic acids  Low-temperature forsterite  Silicate units
Introduction
Serpentine minerals (Mg, Fe)3Si2O5(OH)4 belong to phyl-
losilicate group (layer-type silicates or sheet silicates) and
are the main constituents of serpentinites. They are the
products of hydrothermal alteration of magnesium-rich
silicate minerals (e.g., olivine (Mg, Fe)2SiO4) and appear in
mafic and ultramafic rocks1 [1, 2]. They have layer struc-
tures built of 1:1 alternately stacked tetrahedral and octa-
hedral sheets. The tetrahedral sheets (silicate layers),
representing the complex silicate anions, can be regarded
as resulting from the two-dimensional polymerization of
Si-centered tetrahedra sharing three oxygen atoms with
neighboring tetrahedra. The unshared oxygen atoms are
bonded to Mg atoms that jointly with OH groups form the
octahedral sheets.
There are three widespread natural polymorphs of ser-
pentine: lizardite, antigorite and chrysotile, whose impor-
tant natural deposits occur in Armenia, Italy, Russia, USA,
Canada, Paraguay, New Zealand and so on. Their silicate
layers were mainly formed by polycondensation of
hydrated orthosilicic H4SiO4 and metasilicic (H2SiO3)n
acids under hydrothermal conditions below 500 °C [1]. In
turn, these acids had been synthesized from ortho-
[SiO4]4-and meta- [(SiO3)2-]n silicate anions involved in
1
Mafic rocks have around 50% or less (55–45%) silica and a lot of
magnesium and iron, and ultramafic ones contain silica less than 45%,
generally more than 18% MgO.
123

the process of serpentinization from parent ultramafic rocks
that could be dunites,2 peridotites3 and pyroxenites4 [2].
Heat treatment of different serpentine polymorphs gen-
erally leads to their dehydration up to 200 °C and dehy-
droxylation, i.e., hydroxyl water formation from OH
groups and its removal, in the range of 600–800 °C that is
accompanied by their crystalline structure decomposition
and transformation into amorphous state. Subsequent
heating above 800 °C results in their amorphous mass
crystallization into forsterite Mg2SiO4 and enstatite Mg2-
Si2O6. [3–10]. But in some serpentine samples forsterite
crystallization begins in the zone of dehydroxylation before
the complete destruction of the mineral crystalline structure
[11, 12]. Despite the detailed investigations of dehydrox-
ylation and high-temperature crystallization into forsterite
and enstatite for serpentine polymorphs [13–16], the
meaningful structural study of serpentines requires alter-
native, unconventional methods.
For this reason, thermal decompositions of Armenian
and American serpentine minerals belonging to the same
polymorph modifications, particularly, antigorite and
lizardite, and originated from different parent rocks
(dunites, peridotites and peroxynites) were studied with
using a new approach to the acid processing of dehydrated
serpentines [17–20]. This technique has allowed producing
different amount of silicic acids from serpentines and
thereby revealing the presence of unsaturated (weak) Si–
O(Si) bonds in the siloxane Si–O–Si bridges of serpentines
silicate layers [18–20]. These findings are correlated with
the formation of Si–O–Si bridges from ortho- and
metasilicate anions under hydrothermal conditions below
500 °C. Naturally, the very Si–O(Si) bonds arising between
ortho- and metasilicate anions under such conditions are
splittable with comparative ease upon different influences
[18, 20], whereas another Si–O(Si) bonds intrinsic in pri-
mary metasilicate chains [(SiO3)2-]n that had been previ-
ously formed in magma under high pressure at temperature
over 1000 °C prior serpentinization and then involved in
the serpentine formation from parent pyroxene minerals in
the form of metasilicic acid (H2SiO3)n remain intact when
being exposed to any effects [21, 22]. Because of the weak
Si–O(Si) bonds in serpentines structure, dehydroxylation
indispensably stimulates partition of the mineral silicate
layers into silicate anions of different complexities: ortho-
[SiO4]4-, di-[Si2O7]6-, [Si3O10]8-, [Si4O13]10-, etc., up to
2
Dunite is an ultramafic plutonic igneous rock. The mineral
assemblage is greater than 90% olivine (Mg,Fe)2SiO4 with minor
amounts of pyroxene(Mg,Fe)2Si2O6 and other minerals (chromite and
pyrope).
3 ring in ultramafic rocks, thereby predicting the amount of
Peridotite is an ultramafic plutonic igneous rock consisting mostly
of olivine (40–90%) and pyroxene.
4
Pyroxenite is an ultramafic plutonic igneous rock that consists of
dark minerals in the pyroxene group plus a little olivine (10%).
123
N. Zulumyan et al.
meta- [(SiO3)2-]n. The number of splitting Si–O(Si) bonds
in the siloxane bridges directly depends upon the amount of
hydroxyl water releasing on heating [20]. Ortho-, di- and
the other silicate anions made up of relatively short single
chains with the repeating unit of SiO2-3 can be easily lea-
ched from the silicate layers in the form of silicic acids,
whereas the more complex fragments largely comprised of
metasilicate chains remain in the unreacted mass.
The whole point is that serpentine polymorph, whether it
be chrysotile, lizardite or antigorite, manifests different
number of cutting Si–O(Si) bonds when being exposed to
thermal or mechanical effects, resulting in the formation of
considerable, but different amount of soluble silicic acids
in the solution produced via this method [17–20]. It has
been established that, regardless of polymorph, the mech-
anism of temperature-induced decomposition of serpenti-
nes structure, including dehydroxylation, forsterite and
enstatite formation, is dependent on two factors: the dif-
ferent allocation and the proportion of hydrated ortho- and
metasilicate anions originally involved in the process of
serpentine formation [20]. Moreover, primary ortho-
[SiO4]4- and meta- [(SiO3)2-]n silicate units can either be
more or less evenly distributed in the silicate layers of the
same serpentine polymorph [20]. Nevertheless, the mech-
anism of serpentines thermal decomposition, topotactic
relationships between the distribution of silicate units in
their silicate layers and phases of forsterite and enstatite
formed on heating still require further investigations and
special knowledge.
In the present work, we wished to go on examining and
comparing specific properties of the silicate layers inherent
in serpentines. Serpentinites belonging to different poly-
morphs, antigorite and lizardite, and originated from dif-
ferent parent rocks, dunite and peridotite, from deposits of
Armenia and Italy have undergone the similar investiga-
tions, involving the differential thermal analysis (DTA),
X-ray diffraction study and chemical analyses. These
studies will help us to widen our knowledge about possible
variants of these silicate unit distributions in serpentines
structure, and their influence on the trend of thermal
decomposition and phase transformations in these
minerals.
Serpentine minerals are considered to be promising raw
materials for the high-yield production of magnesium-
containing compounds and silica [17, 23–29] representing
interest for the pure and applied material sciences [30–32].
The systematic fundamental knowledge gained in such a
way leads to a deeper insight into a fascinating
microstructural world and hydrothermal processes occur-
synthesized soluble silicic acids, magnesium- and iron-re-
lated compounds and creating all the prerequisites for the
A study of thermal decomposition of antigorite from dunite and lizardite from peridotite
development of cost-effective methods of serpentinites
processing.
Experimental
The main subjects of our study were the samples of ser-
pentinites located in the occurrences of Shorja (Armenia)
(the sample of Sh-1) and Monti Livornesi (Italy) (the
sample of CHR-23).
Both the samples were finely powdered. One gram of
the powder was taken from each of the samples for the
chemical analysis [33]. It was decomposed by fusing with a
total of 6 g of Na2CO3 and K2CO3 at the temperature of
900 °C in an electric furnace. The produced melt was
treated by hydrochloric acid HCl and filtered. Silica
remained on the filter. The determination of SiO2 content
was performed by the gravimetric method. A certain
amount of the filtrate was selected for the determination of
the rest of elements. They were reported as their oxides.
FeO and Fe2O3 were determined by colorimetric method.
R2O3 group was precipitated in the filtrate by ammonium
hydroxide NH4OH (pH = 8). The gravimetric method was
applied for the determination of Al2O3 in the R2O3 group.
The contents of MgO and CaO were measured in the
solution without R2O3 group by complexometric method.
Loss in mass of the samples at 950 °C was reported as
volatile matter. The chemical composition of these samples
is given in Table 1.
Dehydroxylation and recrystallization of these samples
were studied in air by DTA from room temperature up to
1000 °C and by X-ray diffractometry. The mass of the test
samples subjected to DTA and X-ray diffraction study was
220 mg.
DTA and thermogravimetry (TG) measurements were
performed by using Derivatograph Q–1500D equipment
produced by the MOM company (Hungary) in air at a
heating rate of 10 °C min-1 with TG sensitivity 200 mg.
Samples of equal mass were investigated in platinum
crucibles.
X-ray powder diffraction (XRPD) data were obtained
using Dron-3 diffractometer (Russia) equipped with nickel
filter, under the following conditions: CuJa-radiation;
power supply 25 kV/10 mA; angular range 2h = 8°–80°
step width 1°; counting time 30 s per step at the room
Table 1 The chemical composition of the Sh-1 and CHR-23 samples
Samples Components/mass%
SiO2 Al2O3 Fe2O3
Sh-1 43.24 0.08 5.94
CHR-23 37.43 3.01 5.28
temperature in air. All the reflections were identified and
interpreted using the ICDD-JCPDS database of crystallo-
graphic 2004. The average crystallite size (L) of forsterite
formed in the samples on heating has been estimated by the
Scherrer formula: L ¼ 0:94 k=b cosh where k is the X-ray
wavelength in Å and b is the peak width of the diffraction
peak profile at half maximum height resulting from small
crystallite size in radians [34]. The instrumental line
broadening was subtracted by using the Gaussian func-
tions, and all the values were automatically calculated by
the OriginPro 2016 software.
In addition, both the samples preliminarily crushed by
hand were ground with a vibratory ball mill for 1 h. Part of
the powders was sieved through the sieve 250 holes sm-2
to achieve size’s distribution of about 100–200 lm, with a
maximum grain size of about 250 lm, and then annealed at
the temperatures of 396, 441, 496, 553, 594, 647, 702, 748,
801, 852, 893, 952, 1000 and 1128 °C for 1 h using Wise
Therm F digital muffle furnace (China). After heat treat-
ment at a certain temperature, each of the samples was
subjected to X-ray diffraction analysis. Each of the heated
samples was leached by diluted hydrochloric acid (6–10%)
for 10 min, and the sludge formed was decanted and fil-
tered [17]; 30 mL of the filtrate was separated for chemical
analysis, and unreacted residues that remained after the
acid processing of the serpentinite samples were annealed
at different temperatures and also subjected to X-ray
diffraction analysis.
The chemical analysis was carried out by above-men-
tioned gravimetric, complexometric and colorimetric
methods [33].
Results and discussions
The XRPD patterns of the samples point to the predomi-
nance of antigorite in the sample of Sh-1 (Card No
07–0417) and lizardite in the CHR-23 sample (Card No
84–1391), whereas the Sh-1 sample contains a tangible
amount of lizardite (Fig. 1).
The extraction ratios of main components that moved
into the solution during the acid processing of the Sh-1 and
CHR-23 samples heated at different temperatures were
calculated, and their graphic presentations are represented
in terms of their oxides (Fig. 2). Since our interest was
FeO MgO CaO Volatiles SUM
3.48 34.80 – 11.88 100.42
1.99 38.78 0.91 12.38 98.87
123

Intensity/counts per second
An
An An
Liz
Liz
10 20 30 40 50
2θ/°
Fig. 1 The XRPD patterns of the Sh-1 and CHR-23 serpentinites
samples. Legend: Liz—lizardite; An—antigotite
focused on the amount of MgO, SiO2 and volatile content
of the rocks, the chemical analysis of the samples did not
attempt to differentiate the other individual metal oxides,
and their total amount (R2O3) is just shown (Fig. 2).
Water loss values on heating were estimated from the
mass loss measured by weighting the specimens annealed
at different temperatures, and their graphic presentation is
shown in Fig. 3. It should be noted that the maximum
percentage of water in these serpentines is 13.4%.
After the acid processing of the Sh-1 and CHR-23
samples previously heated up to the temperature of 553 °C,
a negligible amount of silicic acids (less than 4%) is dis-
covered in the solution (Fig. 2). On heating up to this
temperature, the yields of magnesium compounds pro-
duced from the Sh-1 sample do not exceed 18%, whereas
magnesium amount leached from the CHR-23 sample
reaches 28% (Fig. 2). This difference in magnesium com-
pounds yields can be explained by the presence of another
Mg-containing impurities in the CHR-23 sample. Besides,
the slow and smooth trend of curve corresponding to water
removal is traceable on the TG curves of these samples up
to the temperature of 594 °C (Fig. 4). For the Sh-1 sample,
this event is conditioned by the process of hydroxyl water
formation. In comparison with the Sh-1 sample, the amount
of water released from the CHR-23 sample on heating up to
594 °C is comparably greater (2.3%) (Fig. 3), despite the
low yields of silicic acids (Fig. 2). As stated above, the
yield of silicic acids leached from dehydrated serpentines
directly depends upon the amount of hydroxyl water
formed in the minerals on heating [20]. Consequently, in
the case of the CHR-23 sample, this process is not con-
nected to the dehydroxylation and therefore decomposition
of this serpentine, but it can be referred to the releasing of
hygroscopic water conditioned by impurities. At the same
123
N. Zulumyan et al.
time, there are no phase changes in the XRPD patterns of
both the samples heated within the temperature range
396–553 °C (Figs. 5, 6). These data are indicative of the
fact that despite the beginning of the mineral transforma-
tion into amorphous state, the processes of ‘‘brucite’’ layer
(Mg(OH)2) dehydroxylation and breakage of relatively
unsaturated Si–O(Si) bonds in the siloxane bridges do not
occur in the serpentines crystalline structure up to this
An An Sh-1 temperature.
The incomplete minerals destruction and the slow pro-
cess of hydroxyl water formation are observed up to the
Liz
Liz CHR-23 temperature of 553 °C (Figs. 3, 4). Above this temperature,
the yields of soluble silicic acids and magnesium com-
60 70 pounds begin increasing and reach their maxima: SiO2
(37.18 and 40.02%) at 801 and 748 °C, MgO (90.52 and
77.36%) at 702 and 647 °C for the Sh-1 and CHR-23
samples, respectively (Fig. 2). At the same time, on the TG
curves of both the samples the abrupt increase in water
released on heating begins from the temperature of 600 °C
(Fig. 4). As can be seen from the experimental data, water
formation at the temperature of about 600 °C leads to the
increase in the compounds concentration in the solution. As
stated above, serpentines dexydroxylation causes the cut-
ting of the unsaturated Si–O(Si) bonds resulting in the
releasing of isolated orthosilicate units. In turn, these
released units immediately participate in the process of
silicic acids formation during the acid processing. Hence,
this temperature can be considered a starting point for the
process of these minerals dehydroxylation, and therefore,
their silicate layers partition. It should be noted that on the
DTA curve of the Sh-1 sample the endothermic effect with
minimum at 690 °C must be originated by the decompo-
sition of lizardite because antigorite is not decomposable at
such a low temperature (Fig. 4) [9]. Another endothermic
event, the shoulder at 636 °C hardly traceable, can be
referred to the destruction of clinochrysotile (Fig. 4) [9]
that cannot be identified by the X-ray diffraction study
because of a negligible amount.
The appearance of crystalline forsterite reflections (Card
No 85–1362) in the XRPD patterns of the CHR-23 and Sh-1
samples treated at the temperature of 594 and 647 °C,
respectively, indicates that orthosilicate units regenerated
during the silicate layers partition immediately initiate the
formation of forsterite crystals at these temperatures
(Figs. 5, 6). The forsterite formed at such relatively low
temperatures can be conventionally called the low-temper-
ature forsterite, and at higher temperatures (810–830 °C)—
the high-temperature forsterite. As stated above, the
destruction of crystalline antigorite takes place at higher
temperatures (*700 °C). Consequently, the low-tempera-
ture forsterite formed in the Sh-1 sample at 647 °C is arisen
from orthosilicate units released by the decomposition of
clinochrysotile and lizardite.
A study of thermal decomposition of antigorite from dunite and lizardite from peridotite

100 100 Sh-1

Sh-1
CHR-23
CHR-23
80 80

60 60
SiO2, %

MgO, %
40 40

20 20

0 0
300 400 500 600 700 800 900 1000 300 400 500 600 700 800 900 1000

Temperature/°C Temperature/°C

100 Sh-1
CHR-23

80

60
R2O3, %

40

20

0
300 400 500 600 700 800 900 1000
Temperature/°C

Fig. 2 The plots of the extraction ration of main components: MgO, SiO2, R2O3 for the Sh-1 and CHR-23 samples versus temperature

The data of the chemical and the X-ray diffraction
analyses allow concluding that at the temperature of
600 °C the crystalline structure decomposition of both the
serpentines is accompanied by the simultaneous synthesis
of the low-temperature forsterite crystals. The fact of for-
sterite formation at such low temperatures abundantly
evidences that certain parts in the serpentines silicate layers
are largely comprised of the primary hydrated orthosilicate
units locally accumulated and bonded with each other by
unsaturated Si–O(Si) bonds. This is the case, when in
siloxane bridges the breaking of Si–O(Si) bonds initiated
by hydroxyl water formation promotes the release of such
amount of orthosilicate units that is enough for the progress
of their spontaneous local arrangement along with Mg2?
cations resulting in the formation of the isolated crystals of
forsterite at relatively low temperatures.
This phenomenon can be given the following interpre-
tation. The silicate layers of these serpentines samples were
largely formed via the polycondensation of orthosilicic
acids that had been synthesized by the hydration of
orthosilicate anions of primary rocks. This is the reason
why the partition of some sections in the silicate layers is
accompanied by the regeneration of a considered amount
of orthosilicate units that immediately stimulate the local
formation of forsterite crystals.
The intensive diffraction peaks of forsterite are readily
discovered in the XRPD patterns of the Sh-1 and CHR-23
samples heated at the temperature of 647 °C (Figs. 5, 6).
For the Sh-1 sample, they are traceable along with the
reflections of undecomposed antigorite (Fig. 5) At the
same time, there are no diffraction peaks of forsterite in the
XRPD pattern of the residue remained after the acid

123
 N. Zulumyan et al.

12 Sh-1
CHR-23
10

8 1128 °C
H2O, Mass/%

6
1000 °C

Intensity/counts per second

952 °C
2

0 893 °C

100 200 300 400 500 600 700 800 900 852 °C
Temperature/°C
748 °C
Fig. 3 The plot of H2O loss value for the Sh-1 and CHR-23 samples
versus temperature 702 °C

100
Sh-1 822 647 °C
40
98

20 96 594 °C
594
DTA /a.u.

mass/%
Endo 1 Exo

94 10 20 30 40 50 60
DTA
0 636 2θ/°
92
690
-20 90
Fig. 5 The XRPD patterns of the Sh-1 sample heated at the
TG
mentioned temperatures. Legend: white circle—serpentine; black
88 circle—forsterite; black up-pointing triangle—clinoenstatite; black
-40 square—protoenstatite; black down-pointing triangle—enstatite;
770
86 black star—hematite; black diamond—impurities
150 300 450 600 750 900
Temperature/°C processing: 21.76 and 35.69% SiO2, 75.43 and 77.36%
40 100 MgO for the Sh-1 and CHR-23 samples, respectively
CHR-23 (Fig. 2). The forsterite reflections of low intensities
98
812
become hardly noticeable only in the XRPD patterns of the
20
96 residues for the Sh-1 and CHR-23 samples annealed at 852
Endo 1 Exo

and 748 °C, respectively (Figs. 7, 8). The higher yields of

DTA /a.u.

mass/%

DTA
0 94 SiO2 and MgO are also maintained up to 801 and 748 °C,
92 respectively (Fig. 2).
-20 The evaluation of crystallite size of the forsterite formed
90 in the range of 647–952 °C is shown in Table 2. Relatively
TG
88
gradual increase in crystallite size of forsterite is observed
-40
712
with the increase in temperature (Table 2).
86 Everything points to the fact that the crystals of the low-
150 300 450 600 750 900
Temperature/°C temperature forsterite arisen in these samples by heat
treatment within the temperature range of 647–748 °C are
Fig. 4 Differential thermal curves for the Sh-1 and CHR-23 samples. nanosized and have smaller dimensions and are therefore
TG thermo gravimetric or mass loss curve, DTA differential thermal easily and rapidly decomposable by the acid processing.
analysis curve. The vertical axis label applies to the DTA curve
The dissolution of the low-temperature forsterite in diluted
acids can be demonstrated by the following reaction:
processing of the same samples (Figs. 7, 8). On the other
hand, a sufficient amount of SiO2 and MgO is discovered in Mg2 SiO4 þ 4Hþ ! H4 SiO4 þ 2Mg2þ
the solutions produced from these samples via the acid

123
A study of thermal decomposition of antigorite from dunite and lizardite from peridotite

1128 °C

1000 °C
1128 °C

952 °C
1000 °C
892 °C

Intensity/counts per second

952 °C
Intensity/counts per second

893 °C
852 °C
852 °C
748 °C 748 °C
702 °C

702 °C

647 °C
647 °C
594 °C

553 °C 594 °C

10 20 30 40 50 60
2θ/°
Fig. 6 The XRPD patterns of the CHR-23 sample heated at the
mentioned temperatures. Legend: white circle—serpentine; black
circle—forsterite; black up-pointing triangle—clinoenstatite; black
square—protoenstatite; black down-pointing triangle—enstatite;
black star—hematite; black diamond—impurities
The noticeable differences in the yields of soluble silicic
acids and magnesium compounds are traced for the Sh-1
samples annealed within the interval of 647–893 °C,
whereas this event is less tangible for the CHR-23 samples:
the yields of SiO2 and MgO vary between 35.75–40.02%
and 64.47–74.78%, respectively (Fig. 2). In the XRPD
patterns of both the samples heated within the same tem-
perature range, the intensive diffraction peaks of forsterite
solely appear (Figs. 5, 6).
Although at the temperature of 647 °C some part of
hydroxyl water (8.11%) is still present in the decomposed
mass of the CHR-23 sample (Fig. 3), the high and virtually
invariable yields of SiO2 and MgO are discovered in the
solution within the temperature range of 647–893 °C
(Fig. 2). At the same time, the forsterite diffraction peaks
of similar intensities are registered for the samples heated
within the same interval (Fig. 6). All these indicate that
majority of the serpentinous rock is already decomposed at
this temperature.
10 20 30 40 50 60
396 °C
2θ/°
70
Fig. 7 The XRPD patterns of the residue remained after the acid
processing of the Sh-1 sample heat-treated at the mentioned
temperatures. Legend: white circle—serpentine; black circle—
forsterite; black up-pointing triangle—clinoenstatite; black square—
protoenstatite; black down-pointing triangle—enstatite; black star—
hematite; black diamond—impurities
The absence of antigorite reflections in the XRPD pat-
terns of the Sh-1 sample annealed at the temperature of
702 °C (Fig. 5) and the highest yields of MgO (90.52%)
leached from the same sample (Fig. 2) evidence the com-
plete decomposition of this serpentine crystalline structure
at this temperature. Nevertheless, the DTA curve of this
sample displays the endotherm with minimum of 770 °C
pointing to the antigorite decomposition at the temperature
higher than 702 °C (Fig. 4). This discrepancy in the tem-
perature of the sample decomposition can only be
accounted for the influence of heat duration on the phase
transformations occurring in the mineral (Fig. 5). At the
temperature of 702 °C and above, some water is still
observed in the amorphous mass of the destructured sample
(Fig. 3). The process of hydroxyl water removal was
obviously impeded because of the more compact and dense
crystalline structure of lizardite constituting the sample.
After analyzing the yields of SiO2 jointly with the X-ray
diffraction patterns, it can be stated that up to 800°C the
serpentines decomposition caused by the Si–O(Si) bonds
cutting is accompanied by the simultaneous formation of

123
 N. Zulumyan et al.

exothermic effect of the low-temperature forsterite for-

mation (Fig. 4).
In spite of the fact that for the Sh-1 sample on heating up
to 750 °C the yields of silicic acids remain invariable
1128 °C (29.65–30.04%), the amount of magnesium compounds
abruptly decreases from 90.52 to 75.43% (Fig. 2). This
event might be referred to the compaction of serpentine
1000 °C packs caused by the water removal that is preceded by the
process of dehydroxylation (Figs. 3, 4).
952 °C
As stated above, the low-temperature forsterite crystals
formed at 647 °C and easily decomposable by the acid
Intensity/counts per second

10 20 30 40 50
2θ/°
Fig. 8 The XRPD patterns of the residue remained after the acid
processing of the CHR-23 sample heat-treated at the mentioned
temperatures. Legend: white circle—serpentine; black circle—
forsterite; black up-pointing triangle—clinoenstatite; black square—
protoenstatite; black down-pointing triangle—enstatite; black star—
hematite; black diamond—impurities
the low-temperature forsterite crystals. Consequently, in
the DTA curves the endothermic effects with minimum of
770 and 712 °C for the samples Sh-1 and CHR-23,
respectively, originate from the overlap of two endothermic
effects produced by the processes of (1) serpentinite
decomposition and (2) hydroxyl water removal, with the
892 °C
processing exist in the samples Sh-1 and CHR-23 on
852 °C heating up to 748 and 801 °C, respectively. On the
diffraction patterns of the residue for both the samples, the
801 °C
unreacted forsterite reflections of lower intensity are barely
registered within the temperature range of 748–852 °C
(Figs. 7, 8). The gradual increase in forsterite diffraction
peaks is observable on subsequent heating up to 1000 °C
(Figs. 7, 8). It is quite logical to suggest that the high-
748 °C
temperature forsterite crystals, which must not be easily
702 °C
decomposable by acid processing, begin forming within the
interval of 800 and 850 °C. Therefore, the intensive
exothermic peak with maximum of 822 °C and less intense
exothermic one with maximum of 812 °C in the DTA
in. curves of the Sh-1 and CHR-23 samples, respectively, must
be produced by the process of the high-temperature for-
60 70
sterite formation (Fig. 4).
The high yields of SiO2 and MgO in combination with a
slight increase in the forsterite reflections intensities on the
diffraction patterns of the residue for the Sh-1 and CHR-23
samples heated within the temperature range of 800–893 °C
demonstrate that the forsterite crystals formed on heating up
to 893 °C are also less resistant to the acid influence
(Figs. 2, 7 and 8). The reducing of the silicic acids con-
centration in the solution (from 28.91 and 39.62% up to
22.92 and 23.16% and lower for the Sh-1 and CHR-23
samples, respectively) (Fig. 2), jointly with the increasing in
forsterite diffraction peaks intensities for the samples resi-
due annealed at the temperature of 952 °C and higher

Table 2 Forsterite crystal sizes calculated by the Scherrer formula for h = 18.3 (d = 2.46 Å, hkl (112)) and h = 26 (d = 1.748 Å, hkl (222))
Temperature/°C Sample Sh-1 Sample CHR-23
h = 18.3, h = 26, h = 18.3, h = 26,
cos h = 0.9494, cos h = 8987, cos h = 0.9494 cos h = 8987
hkl (112) hkl (222) hkl (112) hkl (222)
b L/nm b L/nm b L/nm b L/nm

647 3.0 9 10-3 50.8 4.0 9 10-3 40.27 3.0 9 10-3 50.8 3.5 9 10-3 46.0
-3 -3 -3
702 2.8 9 10 54.4 3.5 9 10 46.00 2.8 9 10 54.4 3.5 9 10-3 46.0
748 3.0 9 10-3 50.8 3.8 9 10-3 42.40 2.5 9 10-3 60.9 3.0 9 10-3 53.7
893 2.1 9 10-3 72.6 2.6 9 10-3 62.20 2.0 9 10-3 76.2 2.5 9 10-3 64.4
952 2.0 9 10-3 76.2 2.5 9 10-3 64.70 1.8 9 10-3 84.7 2.2 9 10-3 73.2

123
A study of thermal decomposition of antigorite from dunite and lizardite from peridotite
(Figs. 7, 8) reveals that the forsterite crystals become more
acid resistant at the temperatures higher than 900 °C. The
Scherrer equation shows that the growth of nanocrystallite
size of forsterite is also highly provided when the temper-
ature increases up to 952 °C (Table 2). These experimental
data suggest that only subsequent heating above 900 °C
results in the forsterite crystals enlargement usually pre-
ceded by their recrystallization into the units structurally
more ordered and therefore more inert to acids.
The concentration of silicic acids and magnesium
compounds is decreased by 4% in the solution leached
from the Sh-1 samples heated within the temperature range
of 801–852 °C (Fig. 2). These data and the appearance of
clinoenstatite reflections in the XRPD patterns of the Sh-1
sample heated at the temperature of 852 °C evidence that
the mineral silicate layers partition accompanied by for-
sterite formation is followed by the separation of
orthosilicate units from metasilicate chains that are
involved in the process of clinoenstatite formation (Fig. 5).
The existence of clinoenstatite reflections in the XRPD
pattern of the residue, which remain after the acid pro-
cessing of this sample, indicates that clinoenstatite does not
undergo acid processing (Fig. 7).
Heat treatment above 850 °C does not promote the
increase in the compounds in the solutions. The solutions
demonstrate that the concentrations of all the extracted
components begin reducing above 850 °C (Fig. 2). In the
XRPD patterns of the residue produced from these sam-
ples, and forsterite reflections appear (Fig. 7). These data
are indicative of the fact that the above-mentioned abrupt
decline of the leached components concentrations is caused
by the formation of enlarged forsterite crystals with
ordered structure which are not decomposable by diluted
acids during the ten-minute processing. In addition, the
compaction of the decomposed silicate layers, which fol-
lows the hydroxyl water removal, can also cause this event.
To our belief, hydroxyl water cannot immediately go out of
the interspaces and penetrate through the amorphous mass,
so it takes some time for its removal. As a result, this
process is still in progress at higher temperatures.
As a distinct from the Sh-1 sample, in the solutions lea-
ched from the CHR-23 sample, the yields of SiO2 and MgO
are high and relatively constant from 650 up to 892 °C
included (Fig. 2). As for clinoenstatite reflections, they are
firstly registered in the diffraction patterns of both the CHR-
23 sample and its residue annealed at 952 °C, and their
intensities gradually increase on heating above this temper-
ature (Figs. 6, 8). The less intense exothermic peak with
maximum of 812 °C on the DTA curve of the CHR-23
sample (Fig. 4) and the weak reflections of forsterite fixed on
the diffraction patterns of the residue for the same sample
annealed above 893 °C (Fig. 8) abundantly evidence a small
portion of the high-temperature forsterite formed.
The recrystallization and enlargement of the forsterite
crystals cause the noticeable increasing in the forsterite
diffraction peaks intensities in the XRPD patterns of the
residue produced above 893 °C (Fig. 8).
It is quite logical to suggest that the relatively low
intensity of the exotherm on the DTA curve of the CHR-23
sample indirectly points to a small portion of orthosilicate
units that remained unbound after the formation of the low-
temperature forsterite and participated in the high-tem-
perature forsterite crystals formation via diffusion, whereas
the exothermic peak of more intensity on the DTA of the
Sh-1 indicates more number of orthosilicate units involved
in the process of the high-temperature forsterite synthesis.
Moreover, the heat released by the forsterite formation in
the Sh-1 sample immediately initiates the process of cli-
noenstatite formation whose reflections are discovered in
the X-ray patterns of this sample annealed at 850 °C. In the
CHR-23 sample, clinoenstatite crystals are formed at
950 °C after the forsterite formation.
The serpentines decomposition on heating up to 950 °C
can be represented by the following simplified reaction:
nMg6 ðSi4 O10 ÞðOHÞ8 ! 2nMg2 SiO4
þ Mg2n ðSi2 O6 Þn þ4nH2 O
Besides clinoenstatite reflections, enstatite ones are
fixed in the diffraction patterns of both the serpentines
samples (Figs. 5, 6) and their residue annealed at 1000 °C
(Figs. 7, 8). Subsequent heating of both the systems up to
1128 °C results in the transformation of clinoenstatite into
protoenstatite (Card No 85–2494) that does not react with
diluted acids. This fact is proved by protoenstatite reflec-
tions of similar intensities traced in the XRPD patterns of
both the samples and their residues. The decreasing in the
forsterite diffraction peaks intensity for these samples can
be explained by the participation of forsterite in the process
of protoenstatite formation.
The simplified versions of the thermal decomposition
for these serpentines samples are represented in Fig. 9.
All these results can be summarized in a few sentences.
The partition of silicate layers for these serpentines sam-
ples really begins from the temperature of 600 °C and is
accompanied by the releasing of a great number of
orthosilicate units that are immediately involved in the
process of the low-temperature forsterite formation. So the
source of the narrowed endothermic peak observable
within the temperature range of 700–800 °C is the overlap
of two endothermic events caused by the serpentinites
decomposition: (1) dehydroxylation, including hydroxyl
water removal, and (2) Si–O–(Si) bonds cutting, with the
exothermic process of the low-temperature forsterite for-
mation. As for the exothermic peak with maximum within
the temperature range of 800–820 °C, it is mainly referred
to the process of the high-temperature forsterite formation
123
 N. Zulumyan et al.

CHR-23 (lizardite sample ) Sh-1 (antigorite sample )

600 ÷800 °C
–H 2O (dehydroxylation ) 600 ÷ 800 °C
–H 2O (dehydroxylation )
low- fragments
temperature low- fragments
forsterite k ∙ Mg2+
l ∙ SiO32– temperature
(Mg2 SiO4 ) forsterite k ∙ Mg2+
m ∙ SiO4– l ∙ SiO32–
4
( Mg2 SiO4)
m ∙ SiO4–4
800 ÷950 °C

800 ÷950 °C
low-temperature high-
forsterite temperature high -temperature clinoenstatite,
(Mg2 SiO4 ) forsterite forsterite enstatite
( Mg2 SiO4) ( Mg2 SiO4) (Mg2 Si2O6)
950 ÷1000 °C
crystallization,
recrystallization
950 ÷1000 °C
crystallization, recrystallization

high-temperature clinoenstatite , high -temperature

forsterite enstatite forsterite
(Mg2 SiO4 ) (Mg2 Si2O6) (Mg2 SiO4)

1000 °C >
1000 °C >

high -temperature protoenstatite

high-temperature protoenstatite forsterite (Mg2 Si2O6)
forsterite (Mg2 Si2O6 ) (Mg2 SiO4 )
(Mg2 SiO4 )

Fig. 9 Schematic representation of the proposed thermal decomposition sequence for the Sh-1 antigorite and CHR-23 lizardite samples

whose intensity depends upon the number of orthosilicate
units taking part in the high-temperature forsterite crystals
formation via diffusion. The complete destruction of these
serpentines structure takes place up to 750 °C.
All told, in the structure of the Sh-1 sample the content of
orthosilicate anions involved in the process of silicate layers
formation was higher than in the CHR-23 one. Naturally, its
silicate layers had been arisen from dunite in which olivine
(Mg, Fe)2SiO4 constitutes over 90%. As for peridotite, that
was the parent rock for the CHR-23 sample, the portion of
(Mg, Fe)2SiO4 can be variable from 40 up to 90%.
Conclusions
The studies of these two serpentine polymorphs upon
heating have revealed that the process of serpentine silicate
layers decomposition beginning from the temperature of
600 °C and completing up to 750 °C can be accompanied
by the formation of low-temperature forsterite crystals
nanosized and easily dissolved in diluted acids. The fact of
the serpentine crystalline structure destruction along with
the simultaneous formation of forsterite crystals points to
the presence of certain parts in the serpentines silicate
layers largely made up of orthosilicate units bonded and
situated side by side. In this case, on the DTA curves the
endothermic event corresponding to the serpentine
decomposition distinguishes a more sharpened and nar-
rowed form. The greater amount of forsterite is produced,
the more sharpened and narrowed shape the endothermic
peak has.
Subsequent heat treatment leads to the formation of the
high-temperature forsterite that appears as an exothermic
event at higher temperatures (800–820 °C). The intensity
of this exotherm depends upon the number of orthosilicate
units remaining unbound after the process of the low-
temperature forsterite formation. The intensive exothermic
peak points not only to a great amount of the high-tem-
perature forsterite synthesized but also to a considerable
portion of orthosilicate units inherent in serpentine

123
A study of thermal decomposition of antigorite from dunite and lizardite from peridotite
structure. If the high-temperature forsterite is synthesized
in sufficient quantities, the energy released by its formation
can be enough for the progress of clinoenstatite formation
from metasilicate chains.
Evidently, this trend of serpentine decomposition is
intrinsic to the silicate layers which are not distinguished
by the even distribution of ortho- and metasilicate units,
but are built of a considerable number of orthosilicate ones.
Acknowledgements This work was supported by the RA MES State
Committee of Science, in the frames of the research project no 16YR-
1D025. Authors are very grateful to Dr. M. Mellini for providing the
CHR-23 sample and information about its occurrence.
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