Minerals Engineering 15 (2002) 271275

www.elsevier.com/locate/mine

A study of synthetic forsterite refractory materials using

waste serpentine cutting
T.W. Cheng *, Y.C. Ding, J.P. Chiu
Department of Materials and Mineral Resources Engineering, National Taipei University of Technology, Taipei, Taiwan, ROC
Received 5 November 2001; accepted 31 January 2002

Abstract
There are more than 40 serpentine mines in Taiwan, and most of them are located in Hualien (Eastern Taiwan). Almost all the
serpentine dimension stones produced from these mines are exported. Crushed serpentine is used as a ux material for iron-making.
There are more than 0.54 million tons of serpentine waste produced per year during mining operation. This serpentine waste, at the
moment, has no commercial value. The purpose of this research is to develop a process to manufacture synthetic forsterite refractory
using serpentine waste with the addition of magnesium-based compounds by sintering technology. The test results show that,
compared with MgO, the addition of MgOH2 or MgCO3 can react with serpentine completely to produce better forsterite at lower
temperature. The process is feasible and provides a potential usage of serpentine waste in the future. 2002 Elsevier Science Ltd.
All rights reserved.
Keywords: Industrial minerals; Environmental; Recycling; Wasteprocessing

1. Introduction
The serpentine in Taiwan was formed from gabbro
and olivine during metamorphism process. The major
mineral is serpentine, and it also contains pyrite, magnetite, ilmenite, olivine and other traces of minerals. It
has dark green appearance with hardness of 35. The
utilization of serpentine is divided into two categories:
dimension stone and crushed rock. There were
24; 266 m3 of dimension stone produced (approximate
value US$4,050,000) in year 2000, and most of them
were exported for building decoration. For crushed
serpentine rock, the production was 328,840 tons (approximate value of US$4,900,000) in the same year, and
the crushed serpentine was mainly supplied to China
Steel as a ux material for iron-making (Chen, 2001).
On top of this, there are 0.54 million tons of serpentine
waste produced each year (Ministry of Economic Affairs, 1996). This is due to the well-developed joints in
the serpentine orebody as well as the stringent requirements of the particle size (680 mm) and chemical
composition of serpentine by iron-making company.
*
Corresponding author. Tel.: +886-2-2771-2171; fax: +886-2-27317185.
E-mail address: twcheng@ntut.edu.tw (T.W. Cheng).

The waste also creates considerable environmental

problems.
There have been several investigations on the use of
serpentine waste in various elds (Ministry of Economic
Aairs, 1996; Kanari et al., 1998; Carniglia, 1992; Tsai
et al., 1988; Song, 1978; Levin et al., 1964). For example,
fertilizer production (Ministry of Economic Aairs,
1996), soil amelioration (Ministry of Economic Aairs,
1996), extraction of amorphous silicate (Ministry of
Economic Aairs, 1996), and extraction of pure magnesium compounds (Kanari et al., 1998; Tsai et al.,
1988) have been investigated. Due to its theoretical
composition of SiO2 (34.3%), MgO (44.1%), Fe2 O3
(6%), Al2 O3 (0.2%) and CaO (0.45%), serpentine is also
frequently used to manufacture forsterite-based refractory that contains about 85% of forsterite and 15%
magnesioferrite. This type of refractory is made from
serpentine, talc or olivineserpentine using high temperature (Song, 1978). When serpentine is used to make
forsterite, it needs to be calcinated to release its structural water that results in 12% volume reduction. From
the MgOSiO2 binary phase diagram and MgO
Al2 O3 SiO2 ternary phase diagram (Levin et al., 1964;
Carniglia, 1992), it was found that refractoriness for
serpentine is low. In order to form forsterite with serpentine as raw material, the ratio of MgO, Al2 O3 and

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T.W. Cheng et al. / Minerals Engineering 15 (2002) 271275

SiO2 need to be controlled under certain optimum

fractions. In particular, sucient magnesite must be
added to convert the low-melting metasilicate to the
high-melting orthosilicate. The literature is relatively
scarce in this eld. Carniglia (1992) has noted that forsterite basic refractories must be kept to the MgO-rich
side of the forsterite composition P58 wt% to ensure
the MgOMg2 SiO4 eutectic at 1850 C which governs
initial melting. The purpose of this research is to seek the
optimum ratio of magnesium-based compound, such as
MgO, MgCO3 or MgOH2 , for making synthetic forsterite, which involves a potential usage of the serpentine
waste in Taiwan.

2. Experimental procedures
Serpentine samples were collected from the undersize
(less than 6 mm) raw materials, where the oversize ones
were supplied to China Steel. Table 1 shows the chemical composition of the serpentine sample. After ground
to 74 lm, the samples were treated with a wet magnet
separator in order to remove the magnetite. The samples
were ltered and dried for subsequence experimental
usage. Thermogravitational and dierential thermal
analyses (TGA/DTA) were then used to evaluate the
samples thermal behavior. Blended samples with MgO,
MgCO3 , or MgOH2 powder in the ratio of 10%, 15%,
and 25%, respectively, were then ground for 30 min in a
ball mill. The ground samples were pressed into pellets
(1 cm diameter) and heated by a programmable control
electric furnace to 400 C for 1 h in order to release the
structural water. The temperature was slowly increased
at a heating rate of 10 C/min until certain temperatures,
(i.e. 780, 1250 and 1500 C) were reached. The desired
temperature was held for 30 min and then cooled to
room temperature. Following the high temperature
treatment process, samples were ground to 74 lm for
XRD (Rigaku D/MAX-VB diractometer with CuKa
radiation) determination and the phase transformation
characteristics were evaluated. The relative proportions
of the phases as a function of temperature, additional
percentage of magnesium-based compound, or sintering
time were estimated from the ratio In =Itotal where In is the

intensity of a chosen X-ray peak for each phase and Itotal

is the sum of the intensities of all peaks. The peaks used
 [forsterite (1 0 0)],
for the In =Itotal calculation were 2.45 A


14.30 A [clinochlore (0 0 1)], 2.87 A [enstatite (6 1 0)],
 [Cordierite (1 1 0)] and 2.10 A
 [magnesia (2 0 0)].
8.45 A

3. Results and discussion

3.1. DTA/TGA analyses of thermal behavior
Fig. 1 shows the DTA/TGA result of the serpentine
waste. An endothermic peak was found at temperatures
between 400 and 430 C with a slight weight reduction.
This is probably due to the heat eect caused by brucite
and other impurities (Huang, 1987). Fig. 1 also shows an
obvious endothermic reaction when temperature increased from 740 to 780 C, due to the release of
structural water. At temperature between 800 and 850
C, a small exothermic peak was found which represents
the destruction of serpentine crystalline structure and
the formation of forsterite and enstatite (see XRD results). This indicates that the structure of serpentine is
not perfect; otherwise, only forsterite is observed (Huang, 1987; Deer et al., 1992). For temperatures higher
than 850 C, TGA analysis shows no weight variation.
After comparing the test results with those obtained by
Nagamori et al. (1980), the serpentine in Taiwan has a
higher endothermic region (740780 C) than that of
serpentine found elsewhere (650750 C) (Nagamori
et al., 1980). This is probably due to the minor dierence
in their mineral composition. However, the weight reduction measured  12% was in good agreement with
that obtained by Nagamori et al. (1980).
3.2. XRD Determination of phase transfer
Fig. 2 shows the plot of In =Itotal versus sintering
temperature. The sintering time was half an hour and
10% MgO was added to the sample. It is obvious that

Table 1
Chemical composition of serpentine sample
Chemical composition

Wt%

SiO2
Al2 O3
MgO
CaO
Fe2 O3
MnO
TiO2
Ig. Loss

39.23
2.52
37.06
0.55
7.48
0.09
Tr.
12.14

Fig. 1. DTA/TGA result for serpentine in Taiwan.

T.W. Cheng et al. / Minerals Engineering 15 (2002) 271275

Fig. 2. Plot of In =Itotal versus sintering temperature for 0.5 h with additional 10% MgO.

the serpentine decomposed to free magnesia, and

transformed to forsterite in the range of 7801500 C.
The intensity peak of forsterite increases with raising
sintering temperature. Enstatite exhibits similar characteristic but shows a decrease in intensity at 1500 C.
For clinochlore and magnesia, the peak intensities decrease sharply as the sintering temperature increases.
After heating to 1500 C and with increasing MgO
content, the peak intensities of forsterite and magnesia
decreased gradually. However, there is an increase in
enstatite due to the re-crystallization of free magnesia
and silica to form forsterite and enstatite (Fig. 3). At this
temperature, strong contraction of the material was
observed depending upon the degree of serpentinization
of the raw materials. Enstatite crystal grew and the raw
materials were completely sintered. As seen in Fig. 4, the
peak intensity of forsterite increases inversely with the
peak intensity of enstatite. Similar results were also reported elsewhere (Pan, 1982).
Fig. 5 shows the XRD results of serpentine with the
addition of 25% MgCO3 . Forsterite appeared when the

Fig. 3. Plot of In =Itotal versus MgO% additional for sintering 0.5 h at

1500 C.

273

Fig. 4. Plot of In =Itotal for forsterite and enstatite versus sintering time
with additional MgO at 1500 C.

Fig. 5. Plot of In =Itotal versus sintering temperature for 0.5 h with

additional 25% MgCO3 .

samples were heated to 780 C along with clinochlore

and cordierite. As the temperature increased, the intensity of forsterite peak increased and its phase became
more prominent while those of other mineral phases
started to decrease. The intensity of enstatite peak decreased gradually with rising temperature. However,
with sintering time increasing from 30 to 60 min, the
intensities of forsterite peaks increased slightly (Fig. 6).
With increasing amount of MgCO3 added, the intensities of forsterite decreased due to formation of enstatite
at the sintering temperature of 1500 C.
Figs. 7 and 8 show the results obtained under the
same conditions as shown in Figs. 5 and 6 but with the
addition of MgOH2 instead of MgCO3 . Both conditions produced similar results, but with lower forsterite
intensity when MgOH2 was used. As can be seen, the
intensity of enstatite peak is related to the amount of
MgOH2 added. When retention time reached one
hour, enstatite peak intensity decreased for both
MgOH2 and MgCO3 additions (10%).

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T.W. Cheng et al. / Minerals Engineering 15 (2002) 271275

Fig. 6. Plot of In =Itotal for forsterite, enstatite and magnesia versus

sintering time with additional MgCO3 at 1500 C.
Fig. 9. Schematic owsheet of forsterite plant.

Fig. 7. Plot of In =Itotal versus sintering temperature for 0.5 h with additional 25% MgOH2 .

for MgO. A higher temperature is required in order to

decompose MgO that can then react with serpentine
completely to form forsterite. Because of the lower decomposition temperature of MgOH2 and MgCO3 ,
magnesium ions from MgOH2 and MgCO3 can react
with serpentine more easily and transform to forsterite.
Therefore, the addition of MgOH2 and MgCO3 are
better choices for making forsterite. Besides better forsterite phase, cheaper cost of MgOH2 and MgCO3
compared to that of MgO is another major consideration. Generally the particle sizes of forsterite for commercial usage range from 6 mm to 44 lm. The size of the
synthetic forsterite produced from waste serpentine can
be controlled by mineral processing operation (i.e.
pelletizing, comminution, screening, and classication).
A schematic owsheet for manufacturing the synthetic
forsterite powder plant is illustrated in Fig. 9.
4. Conclusions

Fig. 8. Plot of In =Itotal for forsterite, enstatite and magnesia versus

sintering time with additional MgOH2 at 1500 C.

From the results discussed above, it can be concluded

that the addition of MgOH2 and MgCO3 into serpentine crystal structure produces better forsterite. It is
probably due to the higher decomposition temperature

This work demonstrated that it is feasible to produce

forsterite using serpentine waste with the addition of
magnesium carbonate and hydroxide at certain ratios.
Forsterite and enstatite are formed from 780 to 1500 C
due to the decomposition of serpentine crystalline
structure. From XRD results, the peak intensity of
forsterite increased with rising temperature, implying
better forsterite crystal structure. The completeness of
forsterite crystal structure is directly related to the retention time. Among the three additives tested,
MgOH2 and MgCO3 are considered to be better
choices than MgO due to their lower cost and lower
decomposition temperature, thus resulting in lesser
amount of additive and lower reacting temperature between magnesium oxide and serpentine.

T.W. Cheng et al. / Minerals Engineering 15 (2002) 271275

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