Materials Research Bulletin 38 (2003) 1939–1948

Fabrication of b-sialon powder from kaolin

X.-J. Liu*, X.W. Sun, J.J. Zhang, X.P. Pu, Q.M. Ge, L.P. Huang
Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, PR China
Received 27 February 2003; received in revised form 2 September 2003; accepted 5 September 2003

Abstract

b-Sialon powder was fabricated by carbothermal reduction–nitridation of natural Chinese Yixing kaolin at
1300–1550 8C in nitrogen atmosphere, using carbon black as a reducing agent. The effect of reaction
temperature, holding time, nitrogen flow rate and the amount of carbon black on the synthesis of b-sialon powder
and its solid solution degree (z value) have been investigated systematically. The phases of the reaction products
are identified by XRD. The results indicate that the products of reaction are more sensitive to the reaction
temperature than holding time. Nearly all b-sialon is produced at a temperature of 1450 8C for 6 h. Higher
temperatures lead to the presence of SiC phase. A slight amount of carbon favors the carbothermal reduction of
kaolin and excess carbon results in the conversion of b-sialon to SiC. The z value of b-sialon (Si6
zAlzOzN8
z)
rises with the duration of holding time and varies from 2 to 2.8 as the holding time varies from 2 to 6 h at
1450 8C.
# 2003 Elsevier Ltd. All rights reserved.

Keywords: A. Ceramics; B. Chemical synthesis; C. X-ray diffraction; D. Phase transitions

1. Introduction

The b phase of sialon (b-sialon) is a very promising material because it has potential uses for various
engineering ceramics and refractories. b-Sialon is a material that has high strength, good thermal-shock
resistance, resistance against corrosion and erosion, and, particularly, superiority to silicon nitride in
sinterability and oxidation resistance [1,2].
b-Sialon is generally prepared by sintering mixtures of Si3N4, Al2O3, AlN and SiO2 at T > 1500 8C
[3,4], but also carbothermal reduction and nitridation of synthetic Al2O3/SiO2 mixtures, or of natural
aluminosilicate minerals are used as starting materials for the synthesis of sialon ceramics [5–16].
Simultaneously, aluminothermic reduction and nitridation of aluminosilicates are also reported to
produce sialon ceramics [17–19]. Recently, fly ashes and talc and halloysite clay mine schists have been

*
Corresponding author. Tel.: þ86-21-52412990; fax: þ86-21-52413903.
E-mail address: xjliu@mail.sic.ac.cn (X.-J. Liu).

0025-5408/$ – see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2003.09.018
1940 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948

used as starting materials to synthesis a/b-sialon’s by carbothermal reduction and nitridation [20–23].
Lee and Cutler [5] were the first to report the carbothermal reduction and simultaneous nitridation of a
kaolin/carbon mixture to form b-sialon powder, for instance according to:
3ðAl2 O3  2SiO2  2H2 OÞ þ 15C þ 5N2 ðgÞ ! 2Si3 Al3 O3 N5 þ 15COðgÞ þ 6H2 OðgÞ
Various aspects of this synthesis method for b-sialon powder have been studied by several investigators
[5–16]. This method has the potential of being an economical production process, utilizing
inexpensive and abundant natural raw materials, but the task of preparing pure, monophasic b-sialon
powder by this route is difficult because this reaction goes through a number of consecutive and
parallel steps.
Van Dijen et al. [11] carried out a detailed study using clay–carbon mixtures to determine the effect
of some reaction variables, including the nitrogen flow rate, temperature, and pellet size, on the
reaction rate. They reported that a mixture of b-Si3N4, Al2O3, and AlN was obtained when the carbon
content was stoichiometric and the nitrogen flow rate was high and that a mixture of b-Si3N4 and AlN
formed instead of single phase b-sialon when the carbon content was much higher than the
stoichiometric values. Yoshimatsu et al. [12] reacted mixtures of natural kaolin and carbon black
between 1350 and 1500 8C and reported that the amounts of 15R, SiC and AlN phases formed were
considerable at 1500 8C when the carbon content of the starting mixture was 20.37 wt.%. Lee et al. [7]
used Korean kaolin and graphite as starting materials to produce b-sialon powder by heating the
mixture at 1350 8C for 10 h in an 80% N2–20% H2 atmospheres and observed small amounts of Al2O3,
AlN, and 15R together with b-sialon in the reaction product. Lee and Cutler [5] used sedimentary
kaolin and commercial carbon black as starting materials to form b-sialon in nitrogen and obtained a
single phase b0 powder at <1450 8C and a mixture of SiC and AlN at >1450 8C. It is reported that the
addition of too little carbon results in Al2O3 and sialon, and too much carbon results in sialon and 15R
phase. The carbon content must be controlled within 0.5% to obtain sialon free from either Al2O3 or
15R phases. Hoch and Nair [13] prepared b-sialon powder by reaction nitridition of ultrafine
homogeneous mixtures of Al(OH)3 and SiO2 gel prepared by the alkoxide process with anhydrous
ammonia at 1000–1500 8C. They obtained single phase b-sialon only when the Si:Al starting ratio was
1:1 and b-sialon þ Al2 O3 when the Si:Al ratio was 1:2. Cho and Charles [14] prepared b-sialon by
reacting kaolin–carbon mixtures at 1400–1500 8C in flowing nitrogen and obtained single phase b-
sialon powders only when the kaolin/carbon ratio in the starting mixtures was accurately controlled.
When the carbon content in the starting mixture was 13.8 wt.%, the reaction product was mainly b0
with small amounts of X, Al2O3, and aluminum oxynitride. As the carbon content increased, the
amounts of X, Al2O3, and aluminum oxynitride phases decreased and at 19.4 wt.% C, none of these
phases was detected by XRD analysis, although a small amount of 15R phase was detected. A further
increase of carbon content increased the amount of 15R phase formed. A very high carbon content
(23 wt.%) resulted in a mixture of b-Si3N4 and AlN with a small amount of 15R phase rather than
single phase b0 .
So far, there has been limited investigation on the fabrication of single phase b-sialon from natural
aluminosilicate minerals. In this study, however, Chinese Yixing kaolin was used as raw material to
produce single phase b-sialon powder by carbothermal reduction and nitridation. The influence of
reaction temperature, holding time, N2 flow rate and the amount of carbon black on the formation of b-
sialon powder and its solid solution degree (z value) have been investigated in detail. The particle size
distribution of b-sialon powder is also reported.
 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948 1941

Table 1
Chemical composition of kaolin
Oxide Al2O3 SiO2 Fe2O3 TiO2 CaO MgO K2O Na2O LOIa
Content (wt.%) 32.05 48.70 0.87 0.92 0.24 0.16 0.41 0.33 15.28
a
Loss on ignition.

2. Experimental procedure

The raw material used in this study was Chinese Yixing kaolin that was commercially available from
Yixing Town of Jiangsu Province in China. X-ray diffraction showed that the kaolin consisted mainly of
halloysite. Table 1 gives the composition of the kaolin, based on elemental chemical analysis for Si and
Al and on X-ray fluorescence (PW2404 X-ray Fluorescence Analysis, Philips) for the other elements.
The kaolin ores were crushed and milled to pass a 200-mesh screen. Carbon black with a specific
surface area of 45.2 m2 g
1 was used as a reducing agent. The kaolin was mixed with 2% of Fe2O3 in
weight as a catalyst, in the form of Fe(NO3)3 solutions, to accelerate the carbothermal reduction and
nitridation of kaolin. The content of carbon black used was more or less the stoichiometric amount
necessary for the above chemical reaction equation. The mixture was ball-milled in water medium for
24 h in a plastic container. After having been subsequently dried and uniaxially pressed into cylindrical
pellets, they were then simultaneously reduced and nitrided for 2–6 h at 1300–1550 8C under a
controlled flow of N2 atmosphere in a vertical graphite furnace. The phase composition of the reaction
products was identified by X-ray powder diffraction (XRD, Guinier-Hägg camera) with CuKa radiation
and Si as the internal standard. The cell parameters of b-sialon were calculated by the PIRUM program.
The z value of the b-sialon phase was the mean of za and zc calculated from the cell parameters by the
equations [9]:
a ¼ 7:603 þ 0:0296z ð—Þ c ¼ 2:907 þ 0:0255z ð—Þ
The particle size distributions of b-sialon powder were measured using laser particle size analyzer
(LS230, Beckman Coulter Co., USA). As shown in Fig. 1, it was obvious that the particle sizes were
slightly reduced during the carbothermal reduction–nitridation reaction.

Fig. 1. Particle size distributions of Yixing kaolin and as-prepared b-sialon powder.
1942 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948

3. Results and discussion

3.1. Effect of reaction temperature and holding time

The stoichiometric mixtures were reduced and nitrided at 1300–1550 8C for 2–6 h under N2
atmosphere of 2.5 l min
1. The XRD patterns of the synthesized product were shown in Fig. 2. The
resultant compositions at different reaction temperature with various holding times are displayed in
Fig. 3, which were estimated from the XRD patterns. As was shown in Fig. 2b, kaolin phase
disappeared when the mixtures were reacted at 1300 8C for 2 h, which demonstrated that kaolin had
been transformed into mullite before reactive temperature of 1300 8C is reached. The major phases
present were mullite along with b-sialon as the minor phase. The holding time did not change the
composition of the reaction product but only their proportions (see Figs. 2b and 3a). Increasing the
reaction temperature to 1350 8C (as shown in Figs. 2c and 3a) the amount of mullite decreased and that
of b-sialon increased and further increased with the prolongation of the reactive holding times. In
addition, trace amounts of alumina were present at 1350 8C. At 1450 8C, b-sialon was the dominant
product with small amounts of Al2O3 and the b-sialon content increased with increasing reaction
holding times (see Figs. 2d and 3b). The conversion of the reactant to b-sialon was complete and the
resultant product was mostly b-sialon when the mixtures had been carbothermal reduced at 1450 8C for
6 h. If the reaction temperature was raised to 1550 8C for 2 h, a small amount of SiC phase was present
associated with a large proportion of b-sialon, as indicated in Fig. 2e. The phase compositions at
different reaction temperatures disagree with that of Cho et al. who reacted kaolin–carbon mixtures
containing a stoichiometric amount of carbon at 1400–1500 8C in flowing nitrogen. They reported the
product formed at 1400 8C contained the phases b0 , mullite, aluminum oxynitride, b-SiC, and 15R. At

Fig. 2. XRD patterns of the resultant product fabricated from kaolin at 1300–1550 8C for 2–6 h under nitrogen atmosphere of
2.5 l min
1. That of kaolin also is present for comparison. (&: Kaolin, *: mullite, *: b-sialon, ~: Al2O3, ~: SiC.)
 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948 1943

Fig. 3. The phases at different reaction temperature with various holding times, estimated from the XRD results.

1450 8C, b0 phase was the dominant product with small amounts of aluminum oxynitride and 15R. At
1500 8C, the reaction product consisted of 15R, b0 , and AlN [14]. However, Panda et al. [15] have
shown that mullite, silicon oxynitride and X-sialon phases are present at low temperatures (1550 and
1600 8C), while b-sialon, Al2O3, AlN, and SiC are present at high temperature (1650 and 1700 8C) in
the carbothermal reduction of kaolinite under nitrogen atmosphere. The discrepancy of the resultant
phase compositions between these studies and the present work might result from the difference in
starting material and reaction temperatures. From these experimental results, it can be concluded that
the carbothermal reduction reaction of kaolin is mainly completed when the temperature is held at
1944 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948

Fig. 4. Nitrogen percentages refer to the theoretical nitrogen uptake of b-sialon synthesized at 1450 8C for various holding
times.

1450 8C for 6 h, and higher temperatures lead to the presence of SiC phase. It seems from the results of
the present experiment that the formation of b-sialon powder is more sensitive to reaction temperature
than holding time and the amount of b-sialon rises from 31 to 92% when the reaction temperature
changed from 1300 to 1450 8C for 6 h, as illustrated in Fig. 3c. All nitrogen percentages refer to the
percentage of theoretical nitrogen uptake of b-sialon powders synthesized at 1450 8C for various
holding times were given in Fig. 4, which showed the reduction–nitridation reaction of kaolin had been
gradually finished and the nitrogen percentage was progressively close to the theoretical ones with
increasing the holding time.
b-Sialons are phases of hexagonal crystalline structure derived from b-Si3N4 corresponding to the
formula Si6
zAlzOzN8
z, where z is the degree of b-Si3N4 solid solution, ranging from 0 to 4.2
generally [24,25].
At z ¼ 2, the formula is Si4Al2O2N6 and the theoretical nitrogen percentage is: N ¼ 30 wt.%
at z ¼ 3; Si3 Al3 O3 N5 ; N ¼ 24:7 wt:%
at z ¼ 0; Si3 N4 ; N ¼ 40:0 wt:%
The chemical analysis showed that the nitrogen content of b-sialon prepared at 1450 8C for 6 h was
22.1 wt.% which was about 90% of the theoretical nitrogen uptake.

3.2. Effect of carbon content and nitrogen flow rate

The effect of carbon content on the carbothermal reduction–nitridation of kaolin was investigated in
detail under the same conditions (nitrogen flow rate of 2 l min
1 and reaction temperature of 1450 8C
for 6 h). When the carbon content was less 10% of the stoichiometric amount, the reaction product was
b-sialon with a little mullite, which showed the carbon content was not enough to finish the reduction
reaction. Mullite phase disappeared and the reaction was thoroughly completed at stoichiometry or
when 5% excess carbon was used. The latter (5% excess carbon) produced a little more b-sialon
powder than the former. With further increase of carbon content to over 10%, a small amount of silicon
carbon (SiC) was present in the product along with b-sialon. The present results are consistent with that
of Gilbert and Mosset [20]. They prepared b-sialon from coal-mine schists by carbothermal reduction
 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948 1945

under nitrogen and showed that the reaction led to mullite even at 1500 8C if the carbon percentage was
too low (10 mass%). The preparation of b-sialon as a unique phase was possible with 30 mass% of
carbon at 1400 8C. If the carbon content was too high (40 mass%), SiC was formed in large amounts,
whatever the temperature and the reaction time [20]. These results together with the results of the
present experiment indicate that a slight amount of carbon favors the carbothermal reduction of kaolin
and excessive carbon results in the conversion of b-sialon to SiC.
In the carbothermal reduction–nitridation of kaolin, the role of N2 gas is dual. A small portion of N2
takes part in the reaction as a reactant and the greater portion of N2 is used as a carrier to carry the
produced CO(g) (see Section 3.3) away in order to suppress forming SiC phase. For rapid formation of
b-sialon CO(g) must be efficiently removed from the sample. The flow rate of N2 can be controlled by
gas flow meter to regulate the partial pressure of N2 in the system conveniently.
The resultant products of 1450 8C for 6 h at different N2 flow rate were identified by XRD. At low
flow rates, the concentration of N2 in the system is low, and thus, the reaction rate of kaolin reduction
and nitridation is slow, which results in the reaction being not thoroughly completed and mullite
generally emerging. Simultaneously, at higher reaction temperatures, lower flow rate of N2 would bring
about the appearance of SiC, which results from higher partial pressure of SiO(g). The latter is one of
the intermediate compounds for the fabrication of b-sialon from kaolin [9,14,16]. Zheng and Forslund
show that an elevated nitrogen pressure effectively suppressed SiC formation [9]. At lower
concentration of N2 gas, N2 can not remove SiO(g) efficiently so that the partial pressure of SiO(g)
rises. To a certain degree, SiO(g) can be transformed into SiC phase as follows:
SiOðgÞ þ 2C ! SiC þ COðgÞ
The nitrogen flow rate not only influences the reaction rate, but also changes the phase compositions of
the reaction products. In order to advance the syntheses of b-sialon and to prevent the presence of SiC,
the nitrogen flow rate must be retained at higher levels, i.e. a high gas flow rate must be used. The
experimental results showed the flow rate of N2 at 2 l min
1 was appropriate to the preparation of
monophasic b-sialon powder by the carbothermal reduction and nitridation of Chinese Yixing kaolin.

3.3. Formation mechanism and z value of b-sialon

Kaolin, a formula of Al2O32SiO22H2O, contains two crystalline waters, which can be affirmed by
its differential thermal analysis (DTA) curve. Cho and Charles [14] reported that kaolinite loses
chemical water at about 450 8C to form metakaolinite. However, the present experiment shows from the
DTA curve of kaolin an endothermic peak emerges at about 570 8C due to loss of one water molecular
and an exothermic peak presents at about 980 8C due to loss of another water molecular, as indicated in
Fig. 5. The process can be described as follows:
Al2 O3  2SiO2  2H2 O ! Al2 O3  2SiO2 þ 2H2 O
With increasing the reactive temperature, kaolin can be mullited:
3ðAl2 O3  2SiO2 Þ ! 3Al2 O3  2SiO2 ðmulliteÞ þ 4SiO2 ðcolloidÞ
In order to confirm this, a mixture of kaolin and carbon black in stoichiometric proportions was reacted
at 1300 8C for 2 h in Ar rather than N2 atmosphere. The XRD analysis demonstrated the produced batch
was composed of mullite associated with heavy background spectrum (see Fig. 6), which indicated
1946 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948

Fig. 5. DTA curve of kaolin.

colloidal SiO2 present. Above 1300 8C, the mullite product was reduced and nitrided to b-sialon having
a lower z value. The reaction can be written as:
3Al2 O3  2SiO2 þ 10SiO2 þ 27C þ 9N2 ! 3Si4 Al2 O2 N6 ðz ¼ 2Þ þ 27CO
or
2ð3Al2 O3  2SiO2 Þ þ 9C þ 3N2 ! Si4 Al2 O2 N6 ðz ¼ 2Þ þ 5Al2 O3 þ 9CO
b-Sialon fabricated from kaolin at 1350 8C in our case had z value of 2, which agreed with that of
Mukerji and Bandyopadhyay’s results [6]. The z value may depend mainly on the starting mixtures and
their reaction conditions. Yoshimatsu et al. [12] prepared b-sialon powder having a value of z ¼ 3:0 by
heating mixtures of Al2O3SiO22H2O and carbon in N2 at 1470 8C. Lee et al. [7] prepared b-sialon
powder having a value of z ¼ 2:5 by heating mixtures of Korean kaolin and graphite at 1350 8C for 10 h
in an 80% N2–20% H2 atmosphere. Mazzoni and Aglietti [16] reported that z values between 2.5 and
3.5 were obtained for the cyanite-andalusite minerals. The present study reveals the duration of the
holding time contributes to the rise of z value and z value changes from 2 to 2.8 as the holding time
varies from 2 to 6 h at 1450 8C, as illustrated in Fig. 7. This could result from the fact that b-sialon with

Fig. 6. XRD pattern of the produced batch at 1300 8C for 2 h in Ar condition.

 X.-J. Liu et al. / Materials Research Bulletin 38 (2003) 1939–1948 1947

Fig. 7. The z value of b-sialon prepared at 1450 8C as a function of the holding time.

lower z value can further react with produced alumina to form b-sialon having a higher z value at higher
temperature. The longer the duration of holding time is, the more the alumina is incorporated into the
cell of b-sialon and the higher z value. The reaction that takes place is as follows:
3Si4 Al2 O2 N6 ðz ¼ 2Þ þ 3Al2 O3 þ 3C þ N2 ! 4Si3 Al3 O3 N5 ðz ¼ 3Þ þ 3CO

4. Conclusions

Single phase b-sialon powder can be produced by carbothermal reduction–nitridation of cheap,

natural kaolin at
1450 8C for 6 h, using carbon black as a reducing agent, under nitrogen atmosphere
and a gas flow rate of 2.5 l min
1. The reaction is sensitive to the reaction temperature in comparison
with holding time. The reaction is finished when the reaction temperature is held at 1450 8C for 6 h, and
the nitrogen content of the corresponding product is 22.1 wt.% that is about 90% of the theoretical
nitrogen uptake. Excessively high reaction temperatures lead to the presence of SiC phase. A slight
amount of carbon, e.g. excess 5%, favors the carbothermal reduction of kaolin and excess carbon, e.g.
excess 10%, results in the conversion of b-sialon to SiC. In order to advance the syntheses of b-sialon
and to prevent the presence of SiC impurity, the nitrogen flow rate must be retained at a high level, e.g.
a flow rate of 2 l min
1. The duration of the holding time contributes to the rise of z value and z value
varies from 2 to 2.8 as the holding time varies from 2 to 6 h at 1450 8C.

Acknowledgements

Authors would like to acknowledge ‘‘The Science & Technology Development Foundation of
Shanghai Municipality’’ of the People’s Republic of China for its financial support (Grant No.
015211068, 0152 nm 031).

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