COMPOSITES SCIENCE AND TECHNOLOGY

Composites Science and Technology 67 (2007) 26752682 www.elsevier.com/locate/compscitech

A mechanism study on preparation of rayon based carbon bers with (NH4)2SO4/NH4Cl/organosilicon composite catalyst system
Hui Li *, Yonggang Yang, Yuefang Wen, Lang Liu
Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, PR China Received 8 August 2006; received in revised form 17 December 2006; accepted 7 March 2007 Available online 20 March 2007

Abstract The mechanisms of the preparation of rayon based carbon bers with (NH4)2SO4/NH4Cl/organosilicon composite catalyst system were studied. The thermal behaviors of rayon bers that were treated with dierent catalysts were studied by thermogravimetrymass spectrometry (TGMS) and the surface of treated rayon bers was studied by scanning electron microscopy (SEM) analysis. Our data showed that the composite catalyst treated rayon bers underwent pyrolysis under lower temperatures and in a wider range of temperatures. Rayon based carbon bers prepared with dierent catalyst system showed dierent mechanical properties. The presence of (NH4)2SO4/NH4Cl/organosilicon increased the production of H2O, CO2, CO and decreased the production of tar, aldehyde, furan and phenol derivatives. The composite catalyst also promoted the pyrolysis reaction of rayon bers by lowering its activation energy. Organosilicon seemed to have two aspects of eects on the process of preparing rayon based carbon bers. It could enhance the penetrability of (NH4)2SO4/NH4Cl to the interior of rayon bers and protect the ber surface in the pyrolysis process. Moreover, organosilicon may participate in the crosslinking reactions of rayon bers and enhance the drawability of rayon bers in carbonization process. Our experiments demonstrated that (NH4)2SO4/NH4Cl/organosilicon was an eective composite catalyst system in the preparation of rayon based carbon bers. 2007 Elsevier Ltd. All rights reserved.
Keywords: A. Rayon based carbon bers; B. Thermal behaviors; D. TGMS; Pyrolysis; E. Carbonization

1. Introduction Rayon ber is one important raw material for the manufacture of carbon bers because of its availability, low cost, and non-melting character. Rayon based carbon bers have low thermal conductivity, low density and high break elongation characteristics, which allow them to be used in the aerospace industry as structural reinforcement for phenolic resin based ablative materials [1,2]. The preparation of rayon based carbon bers was carried out in two main stages, pyrolysis and carbonization. According to the widely accepted BroidoShazadeh mechanism [36] and TangBacon mechanism [7] and as shown in Fig. 1, pyrolysis of rayon bers typically leads
*

Corresponding author. Tel./fax: +86 351 7560941. E-mail address: lihui7677@hotmail.com (H. Li).

to a solid residue (char), high boiling volatiles (tar) and gaseous products. These products are formed by two competitive pathways. The rst pathway involves dehydration, rearrangement, formation of carbonyl groups, evolution of carbon monoxide and carbon dioxide, and formation of a carbonaceous residue. These reactions are accelerated in the presence of a variety of organic and inorganic catalysts, particularly Lewis acids, which catalyze the dehydration reactions. In the second pathway, which competes with the rst pathway, the thermal scission of glycosidic bonds between the glucopyranose units of the cellulose produces many oxygenated compounds. These oxygenated compounds account for the major weight loss of the solid residue. Therefore, control of reaction pathways in the initial stage of pyrolysis is important for preparing highquality rayon based carbon bers. Since catalysts accelerate the pathway of the pyrolysis reactions, it is essential

0266-3538/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.compscitech.2007.03.008

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CH2 OH H H OH H O H H O H2 O H H CH2 OH O

H. Li et al. / Composites Science and Technology 67 (2007) 26752682

CH2 OH O H H H H H O O H O

The (NH4)2SO4 and NH4Cl used were of p.a. grade (>99.0%) from Chemical-Reagents Corp., Tianjin, China. Organosilicon was prepared in our laboratory through a hydrolysis and condensation reaction.
n

OH

OH

n Pathway 2

2.2. Preparation of rayon based carbon bers The procedure is schematically presented in Fig. 2. First, the washed rayon bers were impregnated continuously with 1% w/w organosilicon acetone solution and dried in hot air. Then they were impregnated with 2% w/w (NH4)2SO4/NH4Cl solution. After drying in hot air, the bers were pyrolyzed in at 250 C for 1 h. Finally, the bers were carbonized under nitrogen at 700 C for 20 min and at 1300 C for 2 min. 2.3. Analysis methods

Pathway 1
CH2 OH H HO H H H O H2O O O O O

CH2 H O O H OH H

H H OH

CH2
H

O Tar

Char

+
CO, CO2, H2O

Flammable gases

Fig. 1. Scheme of the two competitive pathways during the pyrolysis of rayon bers.

to study the eects of catalysts on the pyrolysis of rayon bers. An eective catalyst should have the following functions [8]. First, the catalyst should decrease the pyrolysis temperature to a lower range. Second, it should be able to increase the amounts of water and carbon dioxide produced in the reaction. Finally, it should increase the amount of char formed. Many works have been carried out to search for a suitable catalyst on the pyrolysis of rayon bers [810]. In the previous works, the catalysts contain only one single compound. In this study, we investigated catalysts made of multiple components. Two dierent inorganic ammonium salts, (NH4)2SO4 and NH4Cl, were used in the catalyst system to improve the eciency of the catalyst. The combination might bring a synergistic eect on pyrolysis of rayon bers. We also used an organic compound, organosilicon, in the catalyst system. Organosilicon may play a special role in the process of preparing rayon based carbon bers. The purpose of this work is to illustrate the eects of (NH4)2SO4/NH4Cl/organosilicon composite catalyst on the preparation of rayon based carbon bers. 2. Experimental 2.1. Materials

2.3.1. Thermogravimetrymass spectrometric (TGMS) analysis The thermogravimetric analyzer of model SETARAM TGA92 was used. Pyrolysis was carried out under ultra high pure argon (99.999%) at a low pressure of 150 kPa. Approximately 10 mg sample was heated at 5 C/min from room temperature up to 600 C in the dynamic experiments. In order to obtain accurate results, the TG analyzer was calibrated using Alumel and Nickel Curie point standards. The mass spectrometer of MS OmniStar 200 made by Switzerland Balzers Inc. was used. Its ion source of electron impact was set at 70 eV electron energy. The connection between the thermobalance and the mass spectrometer was a stainless steel capillary, maintained at 150 C. The intensities of several selected ions were monitored. The
Rayon fiber

Treated with or ganosilicone

Treated with
(NH4)2SO4/NH4Cl

Pyrolyzed in air

Carbonized in nitrogen

The cellulosic material used in this work was the pure cotton-derived rayon bers, provided by the XF. Chemical-Fibers Corp., Hubei, China. The rayon bers were washed with warm distilled water to remove the impurities and dried in vacuum overnight.

Rayon based carbon fiber

Fig. 2. Preparation process of rayon based carbon ber.

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MS intensities were normalized based on the sample mass and calibrated based on the intensity of 38Ar isotope in the ushing gas. 2.3.2. Scanning electron microscopy (SEM) analysis To study the eects of organosilicon in the preparation of rayon based carbon bers, scanning electron microscopy (SEM) analysis was performed on model JEOL-35C (Japan). The SEM micrographs of the surfaces of rayon bers treated with (NH4)2SO4/NH4Cl and (NH4)2SO4/ NH4Cl/organosilicon were generated. 2.3.3. The diameter of rayon bers measurement The diameter of rayon bers was measured on a Nikon YS-2 light microscope (Japan). The light microscope was adjusted by a sta gauge. Each type of rayon bers was tested by 10 times and the reported diameter was the average of 10 measurements. 2.3.4. Mechanical property test The mechanical properties of carbon bers were tested on a SHIMADZU AG-1 mechanical test machine by the composite strand tensile test method [11]. 3. Results and discussion 3.1. Pyrolysis of rayon bers Thermogravimetric (TG) and the rst derivative thermogravimetric (DTG) curves of the pure rayon bers (original materials, designated as R) and the rayon bers treated with (NH4)2SO4/NH4Cl/organosilicon (designated as RSCO) are shown in Fig. 3. The untreated rayon bers, R, showed a starting pyrolysis temperature of around 280 C and a termination temperature of approximately 400 C with a sharp weight loss at 319 C. The rayon bers treated with (NH4)2SO4/NH4Cl/organosilicon, RSCO, showed a very dierent pyrolysis behavior. Although the pyrolysis reaction having the similar termi-

nation temperature, the major pyrolysis of RSCO started at around 180 C and the strongest weight loss occurred at 192 C, both temperatures were markedly lower than those of R. The pyrolysis of RSCO happened at a lower and wider range of temperature, which is very important for preparing rayon based carbon bers. In addition, RSCO had a smaller weight loss at 600 C than R. All of these observations indicated that the presence of (NH4)2SO4/NH4Cl/organosilicon enhanced the rst pathway (Fig. 1) and thus catalyzed the dehydration reaction of rayon bers. It is known that the thermal decomposed products of (NH4)2SO4 and NH4Cl, H2SO4 and HCl, are the active components of the catalyst system [8]. Production of H2SO4 and HCl determines the eectiveness of the catalyst. To exam the decomposition of (NH4)2SO4 and NH4Cl, the TG curves of (NH4)2SO4 and NH4Cl versus temperature was generated. As shown in Fig. 4, (NH4)2SO4 and NH4Cl appeared to decompose at dierent temperature ranges. NH4Cl decomposed from about 200 C to 310 C, and (NH4)2SO4 decomposed from 260 C to approximately 420 C. Therefore, the combination of (NH4)2SO4 and NH4Cl will bring a continuous production of H2SO4 and HCl at a wider range of temperature, likely from 200 C to 420 C, than the use of (NH4)2SO4 or NH4Cl alone. This is the reason why we selected two inorganic ammonium salts to be used in the catalyst system. 3.2. Kinetics of the pyrolysis of rayon bers The rate of the disappearance of rayon bers can be expressed by the following equation [12]: da E n AeRT 1 a dt 1

in which, a is the fraction of rayon bers pyrolyzed at any time t, n is the order of reaction, A is the frequency factor (min1), R is the gas constant (8.314 J/K mol1), T is the absolute temperature (K), and E is the activation energy

100

100
Differential weight remainded (%/ C) Weight remainded (%)

0 80

80 Weight remainted (%)

60

60

RSCO
192 C

40

40
RSCO

-2

NH4Cl

(NH4)2SO4

20

20

R 319 C R

0 0 100 200 300 400 Temperature (C) 500 600

0 100 200 300 400 Temperature (C) 500 600

-4

Fig. 3. TG and DTG curves of treated and untreated rayon bers.

Fig. 4. TG curves of (NH4)2SO4 and NH4Cl.

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H. Li et al. / Composites Science and Technology 67 (2007) 26752682

of the reaction (kJ/mol). Through mathematical manipulations, we obtained Eq. (2) as follows:   da E ln A 2 n ln1 a ln dt RT
1 Thus a plot of n ln1 a ln da against T should result dt E in a straight line of slope R and of intercept lnA for the correct value of n, which can be obtained by an iteration method. The value of ln da is obtained from DTG curve, dt while the value of ln(1 a) can be obtained from the TG curve. By an iteration method, the values of correlation coecient and standard deviation of linear regression obtained for dierent incremental values of n are shown in Fig. 5. As shown in Fig. 5a, when the order of reaction n was 1.1, the curve had the lowest standard error and the highest correlation coecient for pure rayon bers. Therefore, the pyrolysis of pure rayon bers was mainly a reaction of 1.1 orders. The best straight line of regression was illustrated in 1 Fig. 6, where n ln1 a ln da was plotted against T . By dt the slope of the straight line in Fig. 6a, the activation energy of the pyrolysis reaction of pure rayon bers was calculated to be 237 kJ/mol. By the same method, the kinetic parameters of RSCO were also obtained. As shown in Figs. 5b and 6b. The best

straight line was obtained when order of the pyrolysis reaction was 3.2. The activation energy of pyrolysis of rayon bers with catalysts was determined to be 94 kJ/mol, indicating that in the presence of (NH4)2SO4/NH4Cl/organosilicon, the pyrolysis reaction of rayon bers was greatly accelerated. 3.3. Thermogravimetrymass spectrometric analysis One of the most useful tools available for studying the pyrolysis products of rayon bers is the thermogravimetrymass spectrometric analysis. More than 20 types of pyrolysis products of rayon bers have been identied by TGMS in the past [8,10]. Studies of the production of the major products, such as H2O, CO2, CO, aldehyde derivatives, furan derivatives and phenol derivatives, are essential to understand the functions of catalysts on the pyrolysis of rayon bers. The dierential TGMS spectrum of R and RSCO is shown in Fig. 7. The spectrum was obtained by subtracting the average spectrum of R from the average spectrum of RSCO. It is clearly shown that the presence of (NH4)2SO4/ NH4Cl/organosilicon increased the peak intensities at m/z 15, 16, 18, 28, and 44, which were CH4, H2O, CO and CO2, respectively, and decreased the peak intensities at

1.002 0.14

0.99946 0.0118 Correlation coefficiency 0.99944 0.0116 0.99942 0.0114 0.99940 0.0112 0.99938 0.0110 0.99936 0.0108 0.99934 0.0106 0.99932 0.0104 0.99930 0.0102 1 2 3 4 5 6

Correlation coefficiency

0.999 0.996 0.993

Standard deviation

0.12 0.10 0.08 0.06

Standard deviation

0.990 0.987 0.6 0.8 1.0 1.2 1.4 1.6

0.04 0.02 1.8

Order assumed (n)

Order assumed (n)

Fig. 5. Variation of standard deviation and correlation coeciency with the reaction order of (a) R and (b) RSCO.

5 2.3 2.2

n ln(1 - a) - ln da/dt

n ln(1 - a) - ln da/dt

n=1.1 y=-46.51+28558.77x

2.1 2.0 1.9 1.8 1.7 1.6 1.5

n=3.2 y=-22.75446+11326.12x

1 0.00168 0.00171 0.00174

-1

1.4 0.00177 0.00180 0.00214 0.00216 0.00218 0.00220 0.00222

1/T (K )

1/T (k )

-1

Fig. 6. Variation of 1/T with nln(1 a) ln(da/dt) of (a) R and (b) RSCO.

H. Li et al. / Composites Science and Technology 67 (2007) 26752682

15 16 Abundance (a.u.) + 18 28 27 44 43 98 110 95 96 124 m/z 144
H CH 2 O O
O H

2679

CO2 + CO

C C C

29

57 68

84

Fig. 8. Scheme of the formation of CO and CO2.

Fig. 7. Dierential TGMS spectrum obtained by subtracting the average spectrum of R from the average spectrum of RSCO.

m/z 29, 43, 57, 68, 84, 95, 96, 98, 110, 124 and 144 that were from aldehyde, furan and phenol derivatives. 3.3.1. Water production during the pyrolysis of rayon bers The study of water production is very important for understanding the pyrolysis mechanism of rayon bers at low temperature. As shown in Fig. 1, the tar is formed from the primary hydroxyl group (CH2OH). If the primary hydroxyl group is eliminated by the formation of water before the thermal scission of glycosidic bonds takes place, the formation of tar will be avoided. Therefore, sucient dehydration by elimination reaction can inhibit the formation of levoglucosan, which is harmful for the preparation of rayon based carbon bers. The H2O (m/z 18) MS signal in arbitrary units (a.u.) measured by TGMS during the pyrolysis of rayon bers is shown in Fig. 9a. As shown, the loss of H2O occurred at two dierent stages. The rst peak was attributed to the loss of absorbed water. The second peak was formed due to the chemical loss of water, which was in the main thermal degradation region of rayon bers. It is also shown in Fig. 9a that the dehydration reaction of RSCO (second peak) occurred at a lower temperature than the dehydration of R. RSCO showed a relatively larger peak area than R. The lower dehydration temperature and larger H2O peak area of RSCO indicated that water elimination reaction of rayon bers was facilitated by the (NH4)2SO4/ NH4Cl/organosilicon catalyst. We also found that rayon bers treated with (NH4)2SO4/NH4Cl (designed as RSC) showed the similar water loss behavior as RSCO, indicating that the presence of organosilicon did not aect the formation of water. 3.3.2. The formation of CO and CO2 According to Tang and Bacon [7], the breakdown of cellulose ring results in the formation of CO and CO2, leaving a species containing four-carbon atoms (Fig. 8). The four-carbon species would repolymerize to a carbon polymer in suitable conditions. As an intermediate product, the amount of the four-carbon species could be used to represent the ultimate yield of carbon bers. Being a very short-lived radical species, the four-carbon species can not be monitored directly. As a rough estimate, the amount of CO and CO2 produced could reect the amount of the four-carbon species formed.

The MS signals of the ions of m/z 28 and m/z 44 in arbitrary units (a.u.) are shown in Fig. 9b and c. The yield of CO and CO2 was higher when rayon bers was treated with (NH4)2SO4/NH4Cl/organosilicon or (NH4)2SO4/NH4Cl than without catalyst (R), indicating that the (NH4)2SO4/ NH4Cl/organosilicon composite catalyst enhanced the formation of the four-carbon species, therefore increased the product in yield of carbon bers. 3.3.3. The formation of tar volatiles Levoglucosan (1,6-anhydro-b-D-glucopyranose) is the major component of tar, which is also one of the primary product of rayon bers pyrolysis. Levoglucosan has primary ionization fragment ions of m/z 39, 52, 53, 57, 60, 68, 73, 96 and 144. The m/z 68 and 96 ions show the strongest relative peak intensity, so the signals of m/z 68 and 96 were used to estimate the formation of levoglucosan [8]. As shown in Fig. 9d and e, catalyst (NH4)2SO4/NH4Cl/ organosilicon inhibited the formation of levoglucosan. The organosilicon itself appeared having no obvious eects on the pyrolysis process. As discussed earlier, the formation of levoglucosan in rayon ber pyrolysis was proposed by the scission of the 1,4 glucosidic linkage in the cellulose molecule. The tar was formed from the primary hydroxyl group of rayon bers. The thermal decomposed product of (NH4)2SO4, H2SO4, can react with the primary hydroxyl group ( CH2OH) to form a cellulose sulfate ester as shown in Fig. 10. The formation of sulfate ester and subsequent elimination prevented the primary hydroxyl group from the formation of tar. 3.4. The eect of organosilicon on the process of preparing rayon based carbon bers The eects of inorganic catalysts on the pyrolysis of rayon bers have been studied in the past [810]. However, the eect of organosilicon on the pyrolysis of rayon bers is still unclear. We therefore carried out experiments to investigate its eects on the pyrolysis of rayon bers. 3.4.1. Modication of rayon bers by organosilicon We rst examined the surface of organosilicon treated rayon bers under SEM. The SEM micrograph of the surfaces of RSC treated bers is shown in Fig. 11a and the SEM micrograph of the surfaces of RSCO treated bers is shown in Fig. 11b. It was clearly shown that (NH4)2SO4/ NH4Cl was well dispersed on bers in the presence of organosilicon. The phenomenon of ber coalescence (Fig. 11a) disappeared in the presence of organosilicon.

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H. Li et al. / Composites Science and Technology 67 (2007) 26752682

RSCO RSC R
H2O

b
R Abundance (a.u.)
CO

Abundance (a.u.)

RSC RSCO

100

200

300

400

500

600

100

200

300

400

500

600

Temperature (C)

Tempetature (C)

c
R CO 2

d
68

Abundance (a.u.)

RSC RSCO

Abundance (a.u.)

RSCO

RSC 0 100 200 300 400 500 600

100

200

300

400

500

600

Temperature (C)

Temperature (C)

e
96 Abundance (a.u.) R

RSCO

RSC 0 100 200 300 400 500 600

Temperature (C)

Fig. 9. MS response of (a) H2O, (b) CO, (c) CO2, (d) m/z 68 and (e) m/z 96 of TGMS analysis of R, RSC, and RSCO.

OSO3 H
CH 2 OH H H OH H O O H H H

CH 2
O H OH H H H O H

CH 2
O OH H H H O

n H2 SO4

OH

OH

OH

Fig. 10. Scheme of the formation of cellulose sulfate ester.

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Fig. 11. SEM micrographs of surfaces of rayon ber treated with (a) (NH4)2SO4/NH4Cl and (b) (NH4)2SO4/NH4Cl/organosilicon.

Organosilicon is widely used in textile treatment eld as a surface modier. The organosilicon used in this work was a siloxane prepolymer and had abundant hydroxyl-terminated functional groups. At room temperature, the OH group in cellulose structure may form intramolecular hydrogen bond and prevent the molecules of (NH4)2SO4/ NH4Cl from entering the inside of cellulose structure. As illustrated in Fig. 12, the intramolecular hydrogen bond will be destroyed when the rayon ber is treated with organosilicon, and new intermolecular hydrogen bond is formed simultaneously. Thus, the rayon bers are swelled in the catalyst solution and make it easy for (NH4)2SO4/ NH4Cl molecules to enter inside the rayon bers. As a result, the catalyst is dispersed on the rayon bers uniformly and the phenomenon of ber coalescence disappeared. To demonstrate the eects of organosilicon on the structure of rayon bers, the diameters of rayon bers treated with no chemicals, organosilicon, (NH4)2SO4/NH4Cl, and (NH4)2SO4/NH4Cl/organosilicon were measured. The result is list in Table 1. The diameter of rayon bers increased from 13.6 lm to 15.1 lm after treatment with organosilicon. The diameter of RSCO was 17.2 lm, which was larger than RSC. We also carried out experiment to determine how much catalyst was absorbed by rayon bers by weighing. We found that the dry weight of bers increased about 1.8% after treatment with RSC and increased about 2.9% after treatment with RSCO. These
(NH4)2SO4 /NH4Cl
H
O H O H H O cellulose HO O H (NH ) SO /NH Cl 4 2 4 4
O

data clearly showed that rayon bers were swelled by organosilicon. In addition, organosilicon possess outstanding thermal and oxidative stability because of the high bond energy (1014.2 kJ/mol) of SiO. When rayon ber is treated with organosilicon, the surface of rayon bers is protected and the pyrolysis reaction can happen from ber surface to ber core with a tempered speed. The surface protection by organosilicon will likely prevent the formation of the shin-core structure of carbon bers. 3.4.2. Drawability of rayon bers in carbonization process In the experiments of preparing rayon based carbon bers, an interesting phenomenon was observed when we applied a quite high tension on bers in the carbonization process. In general, the bers would be ruptured under so high tension. However, in the presence of organosilicon, such rupture was not observed and excellent rayon based carbon bers were obtained. We then studied the mechanical properties of prepared carbon bers. The mechanical properties are listed in Table 2. As shown in Table 2, the carbon bers made in the absence of catalyst is too brittle to test. However, the tensile strength reached 944 MPa for the carbon bers made in the presence of (NH4)2SO4/ NH4Cl inorganic catalyst system. Remarkably, through applying high tension to control the shrinkage (reduced from 5% to 2%) of bers in carbonization process, rayon based carbon bers, obtained in the presence of (NH4)2SO4/NH4Cl/organosilicon composite catalyst system, showed a tensile strength of 1535 MPa. As discussed previously, the four-carbon species is an import intermediate in the process of preparing rayon based carbon bers. The four-carbon species repolymerize to form carbon polymer. It has been accepted that the repolymerization process involves two alternative pathTable 2 Properties of rayon based carbon bers Fibers Shrinkage in carbonization process (%) Properties of carbon bers Tensile strength (MPa) 944 1535 Elastic modulus (GPa) Elongation (%)

H
O Treated with organosilicone H O

H O O

(NH4)2SO4 /NH4Cl

Fig. 12. Scheme of the formation of the swelled cellulose structure.

Table 1 The diameter of rayon bers Types of rayon bers Pure rayon bers (R) Treated with organosilicon Treated with (NH4)2SO4/NH4Cl(RSC) Treated with (NH4)2SO4/NH4Cl/organosilicon (RSCO) Diameter (lm) 13.6 15.1 16.1 17.2

R RSC RSCO

5 2

Too brittle to test 54.3 1.76 59.8 2.57

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H. Li et al. / Composites Science and Technology 67 (2007) 26752682

CH2 O
O H

CH 2OH H O H OH H H

OH2 C
O H H H OH H O H H O

+ HO
n

O H OH H H

OH

OH

OH

OH

Fig. 13. Scheme of the formation of crosslinked macromolecules.

ways, longitudinal polymerization and transverse polymerization [13]. The rayon based carbon bers obtained by longitudinal polymerization possessed excellent properties of high orientation degree and high tensile strength. Applying high tension on bers during the carbonization process is an eective way to ensure the repolymerization reaction following the longitudinal polymerization pathway. But in general, the high tension can not be applied on the bers due to the formation of broken lament, and sometimes the bers will rupture. One reason that we add organosilicon in the catalyst system is to enhance the drawability of rayon bers in the carbonization process. As proposed in Fig. 13, through the primary hydroxyl groups of the rayon bers, the terminal hydroxyl end groups of organosilicon could crosslink the macromolecules of rayon bers. In this way, the organosilicon acts as a bridge role in the crosslinking reactions. This is likely why a higher tension can be applied on the bers in the carbonization process, and the mechanical properties of rayon based carbon bers are improved when organosilicon is used in the catalyst. 4. Conclusions We studied the eects of a composite catalyst system made of (NH4)2SO4/NH4Cl/organosilicon on the preparation of carbon bers from rayon bers. We found that the pyrolysis temperature of rayon bers was shifted to a lower temperature and to a wider range by the composite catalyst. The catalyst also increased the amount of char residue formed at 600 C. The use of two ammonium salts led to a wider range of pyrolysis temperature than the use of (NH4)2SO4 or NH4Cl alone. We also found that, after treated with (NH4)2SO4/NH4Cl/organosilicon, the order of the pyrolysis reaction of rayon bers was increased from 1.1 to 3.2 while activation energy was decreased from 237 kJ/mol to 94 kJ/mol, indicating that (NH4)2SO4/ NH4Cl/organosilicon catalyzed the pyrolysis reaction of rayon bers. Moreover, the use of (NH4)2SO4/NH4Cl/ organosilicon resulted in the increase of the pyrolysis products of H2O, CO2, CO and the decrease of production of aldehyde derivatives, furan derivatives and phenol derivatives. The composite catalyst also inhibited the formation of tar.

Organosilicon seemed to have two ways to aect the process of preparing rayon based carbon bers. Organosilicon could enhance the penetrability of (NH4)2SO4/NH4Cl to the interior of rayon bers and protect the ber surface in the pyrolysis process. Moreover, organosilicon may participate in the crosslinking reactions of rayon bers and enhance the drawability of rayon bers in carbonization process. Our experiments demonstrated that (NH4)2SO4/NH4Cl/ organosilicon was an eective composite catalyst system in the preparation of rayon based carbon bers. With this catalyst system, the prepared rayon based carbon bers showed a tensile strength of 1535 MPa. References
[1] Plaisantin H, Pailler R, Guette A, Daude G. Conversion of cellulosic bers into carbon bers: a study of the mechanical properties and correlation with chemical structure. Compos Sci Technol 2001;61: 20638. [2] Donnet JB, Wang TK, Peng JCM. Carbon bers. 3rd ed. New York: Marcel Dekker, Inc; 1998. p. 312. [3] Shazadeh F, Bradbury AGW. Thermal degradation of cellulose in air and nitrogen at low temperatures. J Appl Polym Sci 1979;23:143142. [4] Hirata T. Isothermal pyrolysis of cellulose untreated and treated with some ame-retardants. J Polym Sci 1984;22:307189. [5] Shazadeh F. Introduction to pyrolysis of biomass. J Anal Appl Pyrol 1982;3:283305. [6] Pouwels AD, Eijkel GB, Boon JJ. Curie-point pyrolysis-capillary gas chromatography-high-resolution mass spectrometry of microcrystalline cellulose. J Anal Appl Pyrol 1989;14:23780. [7] Bacon R, Tang M. Carbonization of cellulose bersI (Low temperature pyrolysis). Carbon 1964;2:21120. [8] Statheropoulos M, Kyriakou SA. Quantitative thermogravimetricmass spectrometric analysis for monitoring the eects of re retardants on cellulose pyrolysis. Anal Chim Acta 2000;409:20314. [9] Shindo Akio, Nakanishi Yoichiro, Soma Isao. Carbon bers from cellulose bers. Appl Polym Symp 1969;9:27184. [10] Pappa A, Mikedi K, Tzamtzis N, Statheropoulos M. Chemometric methods for studying the eects of chemicals on cellulose pyrolysis by thermogravimetrymass spectrometry. J Anal Appl Pyrol 2003;67: 22135. [11] Donnet JB, Wang TK, Peng JCM. Carbon bers. 2nd ed. New York: Marcel Dekker, Inc; 1998. p. 3113. [12] Coats AW, Redfern JP. Kinetic parameters from thermogravimetric data. Nature 1964;201:689. [13] Bacon R, Tang M. Carbonization of cellulose bersII (Physical property study). Carbon 1964;2:2215.