Materials Express

2158-5849/2020/10/2070/010
Copyright © 2020 by American Scientific Publishers
All rights reserved. doi:10.1166/mex.2020.1842
Printed in the United States of America www.aspbs.com/mex

Synthesis and characterization of

poly(carbomethylsilane) prepared by catalytic
polymerization with titanocene dichloride
as a catalyst
Jin-Shuh Li1, ∗ , Tai-Yi Hsu2 , Cheng-Hsiung Peng3 , Chyi-Ching Hwang1 , Kai-Tai Lu1 , and Tsao-Fa Yeh1
1
Department of Chemical and Materials Engineering, Chung Cheng Institute of Technology,
National Defense University, Taoyuan, 33551, Taiwan, ROC
2
Master Program of Chemical Engineering, Chung Cheng Institute of Technology,
National Defense University, Taoyuan, 33551, Taiwan, ROC
3
Department of Chemical and Materials Engineering, Minghsin University of Science and Technology,
Article

Hsinchu, 30401, Taiwan, ROC

IP: 5.10.31.211 On: Tue, 24 Oct 2023 06:45:50

Copyright: American Scientific Publishers
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ABSTRACT
This study used a one-pot approach to synthesize PCMS, a precursor for preparing SiC fibers, by the reaction
of DMDCS with Na using Cp2 TiCl2 as a catalyst. The synthesized PCMS precursors were identified and char-
acterized by FTIR, UV-Vis, NMR, GPC, STA TG-DSC, CAG and DSR. The highest catalytic performance of
Cp2 TiCl2 for the synthesis of PCMS was achieved with a Cp2 TiCl2 /DMDCS molar ratio of 1/30. Afterwards, the
synthesized PCMS precursors were dissolved in xylene to prepare PCMS fibers by electrospinning. The mor-
phologies of the prepared PCMS fibers were observed by FE-SEM. A PCMS solution concentration of 1.5 g/ml
was most suitable for electrospinning. The prepared PCMS fibers exhibited a uniform structure and a smooth
surface. Finally, the prepared PCMS fibers were cured and calcined to produce SiC fibers. The microstructures
of the prepared SiC fibers were characterized by XRD and FE-SEM coupled with EDS. The XRD analysis
indicated that the calcination temperature should be above 1100  C. The SEM image showed that the SiC
fibers prepared at a calcination temperature of 1100  C exhibited a smooth surface and a uniform diameter of
approximately 4 m. The EDS analysis indicated that a small amount of TiC was present in the prepared SiC
fibers, which effectively improved the mechanical properties of the SiC fibers.
Keywords: Polycarbomethylsilane, Titanocene Dichloride, Polymer Precursor, Electrospinning, Silicon Carbide.

1. INTRODUCTION research and development due to their many advantages,

Silicon carbide (SiC) fiber is a high-performance ceramic
material with carbon and silicon as the main compo-
nents, and its morphology can be divided into whisker and
continuous silicon carbide fibers. In recent years, silicon
carbide (SiC) fibers have gained increasing attention in
∗
Author to whom correspondence should be addressed.
such as light weight, high stiffness, and excellent heat and
chemical resistance. SiC fibers are currently widely used
as high-temperature-resistant and reinforcement materials
in advanced ceramic matrix composites and are applied
in the fields of aerospace and nuclear science as well as
the development of military weapons and equipment. In
addition, the application range of SiC fibers has gradually

2070 Mater. Express, Vol. 10, No. 12, 2020

Synthesis and characterization of poly(carbomethylsilane)
Li et al.
CH 3 CH3
+Na / Toluene
Cl Si Cl Si
-NaCl
CH3 CH3
Dimethyldichlorosilane Poly(dimethylsilane)
Fig. 1. Yajima process for the synthesis of SiC fibers.
expanded and includes the development of technologies
for the fabrication of advanced sports equipment, automo-
bile exhaust dust collection and other civilian industrial
fields [1–5].
SiC includes -SiC and -SiC, which depend on the
crystal structure. -SiC with a hexagonal crystal struc-
ture is commonly formed at temperatures higher than
1700  C, and -SiC with a cubic zinc-blende struc-
ture is formed at temperatures below 1700  C [6–9].
The polymer-derived method is the most commonly used
method for preparing SiC fibers [10–14]. SiC fibers can
be prepared from preceramic polymers by electrospin-
ning and calcination. Yajima et al. first produced SiC
fibers using a preceramic polymer polycarbomethylsilane
(PCMS) in the 1970s [15–17]. This preparation process
used liquid PCMS injected through a spinneret to produce
cured green (unfired) fibers that underwent a series of pro-
IP:amount
cessing steps, including a significant 5.10.31.211
of timeOn:
in Tue,
a 24 Oct
high-temperature furnace to convert the Copyright: -SiC Scientific
PCMS toAmerican
fibers. The PCMS precursor was synthesized byDelivered
heating byhighly
polydimethylsilane (PDMS) obtained from the dehalocou-
pling reaction of dimethyldichlorosilane (DMDCS) and
sodium (Na) in toluene at atmospheric pressure in argon
to 470  C [18], which was named the Kumada rearrange-
ment or Kumada reaction [19]. The Yajima process for the
synthesis of SiC fibers [20] is shown in Figure 1. How-
ever, the expensive multistep synthesis of PCMS precur-
sors is one of the disadvantages of the Yajima process.
A method for the one-step synthesis of the PCMS precur-
sor employs the Wurtz-Fittig reductive coupling reaction
of DMDCS with Na or Li in boiling toluene, benzene
or tetrahydrofurane [21, 22]. The selection of suitable
catalysts for this reaction has been the main focus of
past research. Tian et al. [23] used zirconocene dichlo-
ride (Cp2 ZrCl2 ) as a catalyst to synthesize a PCMS pre-
cursor from DMDCS by a one-pot process. The yield
of the PCMS product was approximately 91% based on
the weight of the DMDCS reactant, which was much
higher than the yield obtained in the Yajima process
(<50%). Less than 10% of PDMS was formed as an insol-
uble byproduct that condensed with sodium chloride and
residual sodium. There was no requirement for an addi-
tional Kumada rearrangement through PDMS. In addition,
titanocene dichloride (Cp2 TiCl2 ) can also be used as a cat-
alyst to synthesize PCMS precursors from DMDCS by
a one-pot method. A small amount of polytitanocarbosi-
lane (TiPCS) is formed during the reaction. The pyrolysis
Mater. Express, Vol. 10, 2020
Materials Express
Kumada
H
rearrangement
ΔT
H2 T ∼ 1100 °C
Si C SiC fibers
n n Ar
CH3
Poly(carbomethylsilane)
process of TiPCS produces TiC. The introduction of TiC
crystallites can effectively improve the mechanical proper-
ties of SiC fibers [24].
The electrospinning method is a fiber production method
that uses electric force to produce charged threads of poly-
mer solutions. Its main advantage is the ability to obtain
small diameter fibers [25, 26]. Because of this key char-
acteristic, electrospinning has been used to prepare SiC
fibers in a variety of ways [27–29]. PCMS is one of the
most widely used preceramic polymers to obtain SiC fibers
by electrospinning [28, 30]. Electrospinning is a relatively
simple process, but there are many parameters that affect
the quality of the fibers, such as solution viscosity, surface
tension, applied electric field (or voltage), flow rate and
relative humidity [31–33]. Fong et al. [34] observed that
beads and droplets were usually generated by solutions
Article
with low polymer concentrations, which was attributed to
the low 2023 06:45:50
viscosity. This low viscosity can be attributed to
Publishers
the surface tension and bending instability [34, 35]. For
Ingenta
concentrated (or too viscous) solutions, the droplet
dries at the needle tip before the initiation of fiber for-
mation [35]. Therefore, the viscosity of the polymer solu-
tion needs to be within a certain range to obtain fibers
by electrospinning. In addition, the surface tension of the
solvent is also an important factor. It is well known that
different solvents contribute to the different surface ten-
sions of polymer solutions. If the surface tension of the
polymer solution is high, Rayleigh instability can cause
the polymer solution to form droplets or beads [36–38].
Xylene and tetrahydrofuran (THF) are most commonly
used as solvents for electrospinning PCMS into fibers [27].
In addition, several polymer synthesis methods have been
developed and gained attention in the past [39–41].
This study used a one-pot approach to synthesize
PCMS, a precursor material for preparing SiC fibers,
by the reaction of DMDCS with Na using Cp2 TiCl2
as a catalyst. The synthesized PCMS precursors were
identified and characterized by Fourier transform infrared
spectrometry (FTIR), ultraviolet-visible spectrometry (UV-
Vis), nuclear magnetic resonance spectrometry (NMR),
gel permeation chromatography (GPC), simultaneous
thermogravimetry-differential scanning calorimetry (STA
TG-DSC), contact angle goniometry (CAG) and dynamic
shear rheometer (DSR). Afterwards, the synthesized
PCMS precursors were dissolved in xylene to prepare the
PCMS fibers by an electrospinning apparatus (ESA). The
morphologies of the prepared PCMS fibers were observed
2071
 Materials Express
by field-emission scanning electron microscopy (FE-
SEM). Finally, the prepared PCMS fibers were cured and
calcined to produce SiC fibers. X-ray diffraction (XRD)
was employed to examine the crystal structure of the pre-
pared SiC fibers. FE-SEM coupled with energy dispersive
spectroscopy (EDS) was used to reveal the morphology
and elemental composition of the prepared SiC
fibers.
2. EXPERIMENTAL DETAILS
2.1. Materials
Dimethyldichlorosilane [DMDCS, Si(CH3 )2 Cl2 , 99.5%],
titanocene dichloride (Cp2 TiCl2 , 97.0%), sodium (Na,
99.9%) and anhydrous toluene (C7 H8 , 99.9%) were
reagent grade and purchased from Sigma–Aldrich. They
were used to synthesize polycarbomethylsilane [PCMS,
(SiHCH3 CH2 )n ]. Reagent grade methanol (CH3 OH,
99.9%) and n-hexane [CH3 (CH2 )4 CH3 , 99%] were pur-
chased from Echo Chemical Co., Ltd. in Taiwan and
used in the purification process of PCMS. Reagent grade
xylene [C6 H4 (CH3 )2 , 99%] was also purchased from Echo
Chemical Co., Ltd. and used as a solvent to dissolve the
PCMS.
Article
2.2. Synthesis of Polycarbomethylsilane (PCMS)
IP: 5.10.31.211 On: Tue, 24
This study used a one-pot approach toCopyright: synthesizeAmerican
which is a precursor material for making SiC fibers.
200 ml of toluene, 0.01 mole of Cp2 TiCl2 and the required
amount (0.2, 0.4, 0.6, 0.8 or 1.0 mole) of Na were placed
in a 500 ml four-necked flask, heated to 100  C in an
oil bath under nitrogen atmosphere and vigorously stirred
until the sodium was completely dissolved. Afterwards, the
required amount (0.1, 0.2, 0.3, 0.4 or 0.5 mole) of DMDCS
was slowly added to the above solution under stirring.
After DMDCS addition, the mixture was maintained at
100  C and continuously stirred until the pH value was
7.0, and then hydrogen was introduced into the mixture
to obtain PCMS. The precipitate was removed by suction
filtration, and the PCMS was separated from the solvent
by rotary evaporation. Finally, the synthesized PCMS was
washed twice with n-hexane and dried at room tempera-
ture. The experimental conditions used to prepare PCMS
are shown in Table I.
Table I. Experimental conditions for preparing PCMS.
Molar ratio
Exp. of TiCp2 Cl2 Reaction Reaction
no. to DMDCS Na temperature
A1 1:10 Twice the mole 100  C Continue stirring
A2 1:20 number of DMDCS until the pH value
A3 1:30 of mixture is 7.0
A4 1:40
A5 1:50
2072
Synthesis and characterization of poly(carbomethylsilane)
Li et al.
2.3. Preparation of Silicon Carbide (SiC) Fiber
The purified PCMS was used as a polymeric precursor to
prepare the SiC fibers by electrospinning and calcination.
First, PCMS was dissolved in xylene to prepare test solu-
tions with concentrations of 1.3, 1.4, 1.5 and 1.6 g/ml.
The prepared PCMS solutions were individually loaded
into a 10 ml plastic syringe with a 1 mm stainless steel
18 gauge needle, and then the syringe was mounted on
an electrospinning machine to perform the electrospinning
process. The processing parameters were set as follows:
the voltage was 20 kV, the flow rate was 0.3 ml/h, and
the distance between the needle tip and the collector was
20 cm. The collected PCMS fibers were transferred into
an oven, heated to 160  C at a rate of 5  C/min in an air
atmosphere and maintained at 160  C for 6 h to promote
cure. Finally, the cured PCMS fibers were placed into a
high-temperature furnace, heated to 400, 800 or 1100  C
at a rate of 10  C/min in a nitrogen atmosphere and main-
tained at the respective temperature for 2 h to prepare SiC
fibers.
2.4. Characterization Equipment
The synthesized PCMS precursors were identified and
characterized by means of FTIR (Varian 640-IR), UV-Vis
(ChromTech CT-8600), NMR (Bruker AVIII 500 MHz),
GPC (Waters Alliance 2000), STA TG-DSC (Netzsch STA
449Oct
F3 2023 06:45:50
Jupiter®), CAG (Kino SL200B) and DSR (Haake
PCMS, Scientific Publishers
Delivered RheoStress
First, by Ingenta 600). The functional groups of the synthe-
sized product were analyzed using FTIR in the range
−1
4000–500 cm with a spectral resolution of 4 cm−1 . The
absorption spectrum of the synthesized product was mea-
sured using UV-Vis in the range 200–400 nm at room
temperature. Tetrahydrofuran (THF) was used as solvent.
The chemical structure of the synthesized product was
determined using 29 Si-NMR. Chloroform-d1 (CDCl3 ) was
used as solvent. The molecular weight of the synthesized
product was measured using GPC coupled with a light
scattering detector. The sample was dissolved in THF at a
concentration of 5.0 mg/ml. The measurements were car-
ried out at ambient temperature using THF as eluent at
a flow rate of 1.0 ml/min and polystyrene (PS) as stan-
dard for calibration. STA TG-DSC measurements were
carried out in a nitrogen atmosphere at a heating rate
of 10  C min−1 using the sample weight in the range
8–10 mg to study the thermal properties of the synthesized
product. The static contact angles of solutions with dif-
ferent concentrations prepared from the synthesized prod-
uct were measured on a stainless steel surface using CAG
equipped with a tilting base. The viscosities of the same
solutions were measured using DSR. Xylene was used
time
as solvent. The shear rate logarithmically increased from
1 to 10000 s−1 at 25  C. In addition, ESA (Foxconn Tech-
nology FES-COL) was used to prepare PCMS fibers, and
FE-SEM (JEOL JSM-6700) was employed to observe the
morphology of the prepared PCMS fibers. Finally, the pre-
pared SiC fibers were characterized by XRD (Bruker D2
Mater. Express, Vol. 10, 2020
Synthesis and characterization of poly(carbomethylsilane)
Li et al.
Materials Express
PHASER) and FE-SEM coupled with EDS. XRD was
employed to examine the crystal structure of the prepared
SiC fibers. FE-SEM coupled with EDS was used to reveal
the morphology and elemental composition of the prepared
SiC fibers.

3. RESULTS AND DISCUSSION

3.1. Characterization of the Synthesized PCMS
Precursors
Cp2 TiCl2 was used as a catalyst to synthesize the PCMS
precursors by a one-pot approach during dechlorination
of DMDCS with Na in boiling toluene. The purified
PCMS precursor synthesized with a Cp2 TiCl2 /DMDCS
molar ratio of 1/30 is shown in Figure 2. The precursor
appears as a yellow-brown solid polymer. Subsequently, Fig. 3. FTIR spectra of the products synthesized with/without catalyst
Cp2 TiCl2 .
the synthesized PCMS precursors were identified and char-
acterized by FTIR, UV-Vis, NMR, GPC, STA TG-DSC,
CAG and DSR. 1335 and 1020 cm−1 , respectively. The stretching and
bending vibrations of the Si–H bond are found at approx-
3.1.1. FTIR Analysis imately 2100 and 880 cm−1 , respectively. The Si–CH3
The functional groups of the synthesized product absorption peaks appear at 1273 and 781 cm−1 , respec-
were analyzed by FTIR. Figure 3(a) shows the FTIR tively, and the corresponding CH3 absorption peak appears
spectrum of PCMS synthesized using Cp2 TiCl2 as at approximately 2972 cm−1 . In addition, the titanocene
a catalyst. The stretching and bending vibrations of absorption band is located in the range 600–900 cm−1 .

Article
the Si–CH2 –Si bridges are observed at approximately These results are similar to the results of Cheng et al. [42].
IP: 5.10.31.211 On: Tue, Therefore,
24 Oct 2023 the 06:45:50
FTIR spectrum verified that the synthesized
Copyright: American Scientific Publishers
product was PCMS. Figure 3(b) shows the FTIR spectrum
Delivered byofIngenta
the product synthesized without Cp2 TiCl2 . Compared
with the FTIR spectrum of PCMS, the characteristic peaks
of Si–H at 2100 cm−1 and Si–CH2 –Si at 1335 cm−1 disap-
peared from the spectrum. Thus, the synthesized product
was not PCMS. The FTIR spectra of PCMS synthesized
with Cp2 TiCl2 /DMDCS molar ratios of 1/10, 1/20, 1/30,
1/40 and 1/50 are shown in Figure 4. The intensities of
the characteristic peaks of Si–H at 2100 cm−1 and Si–
CH2 –Si at 1335 cm−1 gradually decrease with decreasing
Cp2 TiCl2 /DMDCS molar ratio from 1/10 to 1/50 due to
the shorter polymer chain length.

3.1.2. 29 Si-NMR Analysis

The structure of the synthesized product was further con-
firmed by 29 Si-NMR. Figure 5 shows the 29 Si-NMR spec-
trum of PCMS synthesized with a Cp2 TiCl2 /DMDCS
molar ratio of 1/30 in CDCl3 . The strongest signal at
approximately −17 ppm is assigned to silicon bonded
to one hydrogen and three carbons (SiC3 H). The weaker
signal at approximately 0 ppm is assigned to silicon
bonded to four carbons (SiC4 ). The presence of these sig-
nals implies that PCMS was the main synthesis product;
however, there was still a small amount of [Si(CH3 )2 -
CH2 -SiHCH3 -CH2 ]n . In addition, the weakest signal at
approximately −37 ppm can be assigned to Si–Si bonds,
indicating an incomplete conversion of the silane to
carbosilane bonds. This observation is consistent with the
Fig. 2. Synthesized PCMS sample. report of Yajima et al. [17].

Mater. Express, Vol. 10, 2020 2073

 Materials Express
Fig. 4. FTIR spectra of PCMS synthesized with
Cp2 TiCl2 /DMDCS molar ratios.
3.1.3. UV-Vis Analysis
The absorption spectrum of the synthesized product
was measured by UV-Vis spectroscopy. Figure 6 shows
the UV-Vis spectrum of PCMS synthesized with a
Cp2 TiCl2 /DMDCS molar ratio of 1/30 in THF. Figure 6
shows the maximum absorbance at 267 nm (max =
267 nm) in the 200–400 nm region. Tian et al. [43]
Article
reported a similar experimental result.
IP: 5.10.31.211 On: Tue, 24 tively,
3.1.4. GPC Analysis Copyright: American Scientific
The weight average molecular weight (Mw ), number Delivered
aver- byare
age molecular weight (Mn ) and polydispersity index (PDI,
Mw /Mn ) of the synthesized product were determined
by GPC using polystyrene (PS) as a standard in THF.
Figure 7 shows the GPC curve of PCMS synthesized
with a Cp2 TiCl2 /DMDCS molar ratio of 1/30 in THF.
The Mw , Mn and PDI of PCMS were 2767 Da, 1608 Da
and 1.72, respectively. The PDI can be used as a param-
eter to determine whether the molecular weight distri-
bution is narrow or broad. If the PDI value is close to
1.0, the distribution is narrow, while larger values indicate
a broader molecular weight distribution. The PDI value
of the synthesized PCMS indicated a narrow molecular
weight distribution, which was lower than the PDI of a
29
Fig. 5. Si-NMR spectrum of the synthesized PCMS.
2074
Synthesis and characterization of poly(carbomethylsilane)
Li et al.
different
Fig. 6. UV-Vis spectrum of the synthesized PCMS.
typical step-growth polymerization (PDI = 2.0) [44]. The
low PDI also indicates that the chain length of the poly-
mer can be controlled to obtain a similar molecular weight
range.
The Mw and PDI values of PCMS synthesized with
Cp2 TiCl2 /DMDCS molar ratios of 1/50, 1/40, 1/30, 1/20
and 1/10 are shown in Figure 8. The Mw and PDI values
are in the range 1000–3750 Da and 1.11–2.57, respec-
Octand
2023decrease with increasing the Cp2 TiCl2 /DMDCS
06:45:50
Publishers
molar ratio from 1/50 to 1/10. The reported PDI values
Ingenta
smaller than those of PCMS synthesized by the Yajima
process through the thermal decomposition and conden-
sation of PDMS in an autoclave at 470  C for 14 h.
They are smaller because PCMS formed by decomposi-
tion of PDMS exhibits a cross-linked molecular structure
rather than linear chains [23]. The results obtained in this
study indicate that Cp2 TiCl2 plays the role of a catalyst in
the synthesis of PCMS. In addition, the yields of PCMS
synthesized with Cp2 TiCl2 /DMDCS molar ratios of 1/50,
1/40, 1/30, 1/20 and 1/10 are shown in Figure 9. The
values are in the range 75–90%. The highest yield was
observed for PCMS synthesized with a Cp2 TiCl2 /DMDCS
molar ratio of 1/30, indicating that the optimum catalytic
performance was achieved.
Mater. Express, Vol. 10, 2020
Synthesis and characterization of poly(carbomethylsilane)
Li et al.
Materials Express

Fig. 7. GPC curve of the synthesized PCMS. Fig. 9. The yields of PCMS synthesized with different
Cp2 TiCl2 /DMDCS molar ratios.

3.1.5. STA TG-DSC Analysis

The thermal properties of the synthesized product were
TG curve showed a weight loss of approximately 2.0%.
studied by STA TG-DSC analysis. Figure 10 shows
This outcome may be due to the release of residual carbon,
the TG-DSC curves of PCMS synthesized with a
hydrogen and their conjugates. The ceramic yield calcu-
Cp2 TiCl2 /DMDCS molar ratio of 1/30. The analysis of
lated from the TG curve was approximately 68.0%, which
these two curves can be divided into three stages: 25–
was close to the ceramic yield of commercial PCMS [45].
400  C, 400–800  C and 800–1100  C. During stage 1,

Article
the DSC curve exhibited an endothermic peak at approx-
imately 209  C, while the TG curve showed little weight 3.1.6. CAG Analysis
IP: 5.10.31.211 On:
change at this temperature. Therefore, this endothermic Tue, 24 Oct
The 2023
static 06:45:50
contact angles of the solutions with different
Copyright: American Scientific Publishers
PCMS. byconcentrations
peak can be attributed to the melting behavior ofDelivered Ingenta
prepared from the synthesized product were
Approximately 1.0% of weight loss is due to the desorp- measured on a stainless steel surface by CAG. The PCMS
tion of low molecular weight PCMS. During stage 2, the synthesized with a Cp2 TiCl2 /DMDCS molar ratio of 1/30
DSC curve exhibited a strong endothermic peak at approx- was dissolved in xylene to prepare test solutions with con-
imately 548  C, while the TG curve showed a rapid weight centrations of 0.5, 1.0, 1.2, 1.3, 1.4, 1.5 and 1.6 g/ml.
loss. This outcome means that the pyrolysis of PCMS Figure 11 shows the static contact angles of the seven
occurred within this temperature range to form the SiC prepared solutions and xylene. The static contact angle
ceramic. The weight loss was approximately 29.0%. Dur- increased with increasing PCMS concentration. In general,
ing stage 3, the DSC curve exhibited an exothermic peak when the static contact angle is greater than 90 degrees,
at approximately 890  C, which was due to the energy the polymer solution exhibits sufficient cohesion to achieve
released during the crystalline rearrangement process. The stable electrospinning for the generation of uniform fibers.

Fig. 8. Mw and PDI values of PCMS synthesized with different

Cp2 TiCl2 /DMDCS molar ratios. Fig. 10. TG-DSC curves of the synthesized PCMS.

Mater. Express, Vol. 10, 2020 2075

 Materials Express Synthesis and characterization of poly(carbomethylsilane)
Li et al.

(a) (b)

(c) (d)

(e) (f)

Fig. 12. The relationship between shear rate and shear viscosity of
PCMS solutions with different concentrations.

(g) (h)
solution increased with increasing PCMS solution concen-
tration. Increasing the viscosity favored the formation of
smooth fibers. However, when the concentration of the
PCMS solution reached 1.6 g/ml, electrospinning became
relatively difficult because the solution had difficulty pass-
ing through the syringe needle, as shown in Figure 13(d).
Fig. 11. The static contact angles of PCMS solutions with different
This difficulty is due to the high viscosity and the low sur-
Article

concentrations.
face tension of PCMS solutions with concentrations above
IP: 5.10.31.211 On: Tue, 24 1.6Oct 2023
g/ml, which06:45:50
is not conducive to the electrospinning
Therefore, PCMS concentrations in theCopyright:
range 1.3–1.6 g/ml Scientific Publishers
American process.
are considered suitable solutions for electrospinning. Delivered by Ingenta
3.3. Characterization of the Prepared SiC Fibers
3.1.7. DSR Analysis
The PCMS fibers prepared with a concentration of
The rheological properties of the synthesized prod-
1.5 g/ml were selected to produce SiC fibers because of
uct were tested by DSR. PCMS synthesized with a
their uniform structure and smooth surface. The prepared
Cp2 TiCl2 /DMDCS molar ratio of 1/30 was dissolved in
PCMS fiber were first cured at 160  C and then calcined at
xylene to prepare test solutions with concentrations of
400, 800 or 1100  C to produce SiC fibers. The microstruc-
1.3, 1.4, 1.5 and 1.6 g/ml. Figure 12 shows the rela-
tures of the prepared SiC fibers were characterized by
tionship between the shear rate and shear viscosity of
XRD and FE-SEM coupled with EDS. Figure 14 shows
the four prepared solutions. The shear viscosity decreased
with increasing shear rate, which is characteristic of shear
thinning or pseudoplastic behavior [46]. In addition, as
expected, the shear viscosity increased with increasing
concentration of PCMS solution at the same shear rate.

3.2. Characterization of the Prepared PCMS Fibers

PCMS synthesized with a Cp2 TiCl2 /DMDCS molar ratio
of 1/30 was dissolved in xylene to prepare test solutions
with concentrations of 1.3, 1.4, 1.5 and 1.6 g/ml. These
four solutions were used to produce PCMS fibers by the
electrospinning process. The morphologies of the prepared
PCMS fibers were observed by FE-SEM. Figure 13 shows
the FE-SEM images of the PCMS fibers prepared with
different PCMS concentrations. Figure 13(a) shows that
bead-shaped electrospun fibers were formed at the low
PCMS concentration of 1.3 g/ml. At PCMS concentra-
tions of 1.4 and 1.5 g/ml, smooth fibers were formed, as Fig. 13. FE-SEM images of PCMS fibers prepared with different
shown in Figures 13(b) and (c). The viscosity of the PCMS PCMS concentrations.

2076 Mater. Express, Vol. 10, 2020

Synthesis and characterization of poly(carbomethylsilane)
Li et al.
Fig. 14. XRD patterns of SiC fibers prepared at different calcination
temperatures.
the XRD patterns of the SiC fibers prepared at calcination
temperatures of 400, 800 and 1100  C in the range of 2
from 10 to 80 . The XRD pattern of the SiC fiber prepared
at 1100  C is given by curve (a) in Figure 14. The diffrac-
tion peaks at 35.74, 41.54, 60.14, 71.96 and 75.82
can be indexed as the (111), (200), (220), (311) and (222)
reflections of the cubic crystal structure of -SiC (JCPDS
No. 75-0254). In addition, the average crystallite size was
IP: 5.10.31.211 On: Tue, nium 24 Oct
10 nm, as calculated by the ScherrerCopyright:formula. However,
American Scientific
the SiC diffraction peaks of the products prepared
Delivered
and 800  C could not be detected, as apparent from the
curves (b) and (c) of Figure 14. Therefore, the calcina-
tion temperature for preparing SiC fibers should be above
1100  C. Figure 15 shows the SEM image of the SiC
fibers prepared at the calcination temperature of 1100  C.
The prepared SiC fibers exhibited a smooth surface and
a uniform diameter of approximately 4 m. Furthermore,
the elemental composition of the prepared SiC fiber was
measured by EDS. Figure 16 shows the EDS spectrum
of the prepared SiC fiber. The analysis results indicated
that the atomic ratio of C:O:Si:Ti was 62.5:4.2:32.5:0.8.
Excess carbon atoms as well as oxygen and titanium atoms
Fig. 15. SEM image of the prepared SiC fiber.
Mater. Express, Vol. 10, 2020
Materials Express
Fig. 16. EDS spectrum of the prepared SiC fiber.
were found to be present in the prepared SiC fiber. In gen-
eral, polymer-derived SiC fibers contained SiC microcrys-
tals, excess carbon, and silicon oxycarbide (SiOC) [47].
The excess carbon in the SiC fiber can be attributed to the
methyl groups in PCMS. Yajima et al. [18] found that a
small amount of excess carbon and high molecular weight
PCMS resulted in a high tensile strength of the PCMS
fibers after the curing process. The oxygen atoms that were
introduced to form a small amount of SiOC during the cur-
ing process were retained in the SiC fibers [48]. Ichikawa
et al. [49] found that the oxygen content affected the ten-
Article
sile strength of the SiC fibers to a small extent. The tita-
2023in06:45:50
atoms the SiC fibers were attributed to TiC, the
pyrolysisPublishers
product of a small amount of polytitanocarbosi-
at 400 by Ingenta
lane formed by the reaction of Cp2 TiCl2 and DMDCS. The
presence of TiC crystallites in the fibers can effectively
improve the mechanical properties of the SiC fibers [24].
4. CONCLUSIONS
In this study, SiC fibers were successfully prepared by
electrospinning and calcination of the PCMS precursor
synthesized by the reaction of DMDCS with Na using
Cp2 TiCl2 as a catalyst. The synthesized PCMS precursors
were identified and characterized by FTIR, UV-Vis, NMR,
GPC, STA TG-DSC, CAG and DSR. The PCMS fibers
were prepared and observed by ESA and FE-SEM. Finally,
the microstructures of the prepared SiC fibers were charac-
terized by XRD and FE-SEM coupled with EDS. Based on
the above experimental results and analyses, the following
conclusions can be made:
(1) Cp2 TiCl2 can be used as a catalyst in the dechlori-
nation reaction of DMDCS with Na in boiling toluene
for the synthesis of the PCMS precursor by a one-pot
approach. The highest yield of PCMS was obtained for
a Cp2 TiCl2 /DMDCS molar ratio of 1/30, indicating that
the optimum catalytic performance was achieved. The Mw
and PDI of the synthesized PCMS were 2767 Da and
1.72, respectively. The low PDI value indicated a narrow
molecular weight distribution of the synthesized PCMS
because PCMS exhibited a linear chain structure rather
than a cross-linked structure. In addition, the ceramic yield
2077
 Materials Express Synthesis and characterization of poly(carbomethylsilane)
Li et al.

measured from the TG curve was approximately 68.0%,
which was close to that of commercial PCMS.
(2) The PCMS synthesized with a Cp2 TiCl2 /DMDCS
molar ratio of 1/30 was dissolved in xylene to prepare
PCMS solutions with different concentrations. CAG and
DSR analyses indicated that the PCMS solution with a
concentration of 1.5 g/ml was most suitable for electro-
spinning. The prepared PCMS fiber exhibited a uniform
structure and a smooth surface.
(3) The prepared PCMS fibers were first cured at 160  C
and then calcined to produce SiC fibers. The XRD analysis
indicated that the calcination temperature should be above
 pp.229–234.
1100 C. The SEM image showed that the SiC fiber pre-
pared at the calcination temperature of 1100  C exhibited
a smooth surface and a uniform diameter of approximately
4 m. The EDS analysis indicated that titanium atoms
were present in the prepared SiC fibers. These titanium
atoms were attributed to TiC, which is the pyrolysis prod-
uct of a small amount of polytitanocarbosilane formed by
the reaction of Cp2 TiCl2 and DMDCS. The presence of
TiC crystallites in the fibers can effectively improve the
mechanical properties of the SiC fibers.
(4) The polymer-derived method is the most commonly
used method for preparing continuous SiC fibers. The
introduction of TiC crystallites can effectively improve the
Article
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Received: 12 May 2020. Accepted: 20 June 2020.
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