fibers

Article
Improvement in Carbonization Efficiency of
Cellulosic Fibres Using Silylated Acetylene
and Alkoxysilanes
Maria Mironova *, Igor Makarov , Lyudmila Golova, Markel Vinogradov, Georgy Shandryuk
and Ivan Levin
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991 Moscow, Russia;
makarov@ips.ac.ru (I.M.); glk@ips.ac.ru (L.G.); vin1989@ips.ac.ru (M.V.); gosha@ips.ac.ru (G.S.);
levin@ips.ac.ru (I.L.)
* Correspondence: mariamir@inbox.ru; Tel.: +7-495-647-5927




Received: 6 September 2019; Accepted: 25 September 2019; Published: 28 September 2019


Abstract: Comparative studies of the structure and thermal behavior of cellulose and composite
precursors with additives of silyl-substituted acetylene and alkoxysilanes were carried out. It is
shown that the introduction of silicon-containing additives into the cellulose matrix influenced the
thermal behavior of the composite fibers and the carbon yield after carbonization. Comparison of the
activation energies of the thermal decomposition reaction renders it possible to determine the type of
additive and its concentration, which reduces the energy necessary for pyrolysis. It is shown that the
C/O ratio in the additive and the presence of the Si–C bond affected the activation energy and the
temperature of the beginning and the end of the pyrolysis reaction.

Keywords: Cellulose fiber; Lyocell; N-methylmorpholine-N-oxide; silicon-containing additives;

thermal properties

1. Introduction
By means of the solid phase dissolution of cellulose in N-methylmorpholine-N-oxide (NMMO),
a direct solvent for cellulose, it is possible to obtain highly concentrated solutions and to spin the
Lyocell-type fibers [1]. Recently, these fibers have attracted a lot of attention, not only as an alternative
to rayon textile material, but also as precursors of carbon fibers [2].
The main problems of thermal transformation of cellulose fibers into carbon fibers are the
increase of the carbon yield and formation of the necessary structures that provide good mechanical
properties [3]. The theoretically possible value of the carbon yield in the carbonization process of
cellulose is 44.4% [4]. In order to get as close as possible to this value, it is recommended to use active
substances (the catalysts) that direct the process of pyrolysis towards the formation of carbon structures
and prevent the byproducts (e.g., levoglucosanes) caused by the removal of carbon in gas form [5,6].
Catalysts of pyrolysis and flame retardants can be applied by impregnation of the precursor fibers
with solutions of active substances followed by their drying [7,8]. The most widely used pyrolysis
catalysts for cellulose are ammonium chloride and ammonium sulfate. Recently, silicon-containing
catalysts have been proposed as an alternative to these active agents. Their use allows carbon fibers
with a mechanical strength of more than 1 Gpa to be obtained. In [9–14], predominant data were
given on the use of silicon-containing compounds for obtaining carbon fiber, in particular, in [10], the
application of Tetraethoxysilane (TEOS) makes it possible to obtain carbon fibers with a diameter of
5.5 µm, a tensile strength of 930 Mpa, and an elastic modulus of 38 GPa, with a carbon yield of ~14.5%.
The introduction of the pyrolysis catalysts and flame retardants into the polymer matrix can
be considered as an alternative method of their application, which achieves a better distribution

Fibers 2019, 7, 84; doi:10.3390/fib7100084 www.mdpi.com/journal/fibers

Fibers 2019, 7, x FOR PEER REVIEW 2 of 11

fibers with a diameter of 5.5 µm, a tensile strength of 930 Mpa, and an elastic modulus of 38 GPa,
with 2019,
Fibers a carbon
7, 84 yield of ~14.5%. 2 of 12
The introduction of the pyrolysis catalysts and flame retardants into the polymer matrix can be
considered as an alternative method of their application, which achieves a better distribution of the
of the substance
active active substance in the volume
in the volume of the
of the fiber andfiber and the
reduces reduces theof
number number of processing
stages of stages of processing
(Figure 1)
(Figure
[15,16]. 1) [15,16].

Figure 1. Basic stages

1. Basic stages of cellulose composite precursors and
and carbon
carbon fibers
fibers production. TEOS,
production. TEOS,
Tetraethoxysilane; VTEOS, Vinyltriethoxysilane; BTMSA,
BTMSA, Bistrimethylsilyl
Bistrimethylsilyl acetylene; NMMO,
N-methylmorpholine-N-oxide.

Silicon-containing
Silicon-containing compounds
compoundsasasadditivesadditives allow notnot
allow onlyonly
an increase in thein
an increase carbon yield during
the carbon yield
heat
duringtreatment of fibers,ofbut
heat treatment also but
fibers, to obtain
also tocarbon-silicon carbide fibers
obtain carbon-silicon [17],
carbide and [17],
fibers it is exactly this
and it is class
exactly
of fibers which is the most interesting for obtaining heat-resistant materials
this class of fibers which is the most interesting for obtaining heat-resistant materials [18].[18].
Thermogravimetry
Thermogravimetry AnalysisAnalysis (TGA)
(TGA) and and Differential
Differential Scanning
Scanning Calorimetry
Calorimetry (DSC) (DSC) methods
methods are are
widely
widely used to study the properties of carbon fiber precursors and to represent the conditions for
used to study the properties of carbon fiber precursors and to represent the conditions for
their
their production [19]. However,
production [19]. However, the the results
results ofof experiments
experiments cannot
cannot always
always be be interpreted
interpreted definitely.
definitely.
To
To obtain
obtainmore
moreaccurate
accurateinformation,
information,ititisisrecommended
recommendedtotoprocess
processthe results
the resultsmathematically.
mathematically. Thus, to
Thus,
determine the differences in thermal behavior, process staging, thermostability
to determine the differences in thermal behavior, process staging, thermostability of synthetic of synthetic polymers,
polysaccharides, cellulose fibers,
polymers, polysaccharides, and sofibers,
cellulose on, it is
andreasonable
so on, ittoisevaluate the kinetic
reasonable parameters
to evaluate of the
the kinetic
decomposition
parameters of the using the Broido method
decomposition using the [20–23].
Broido method [20–23].
The
The Broido formula allows for estimation of
Broido formula allows for estimation the activation
of the activation energy
energy of the thermal
of the thermal decomposition
decomposition
of
of cellulose
cellulose [24]
[24]
ln[ln(1/y)] = A − Ea /(RT ), (1)
ln[ln(1/y)]=A-Ea/(RT), (1)
Ì
where y = (Mt − Me )/M0 -Me , M0 is the mass of the initial sample, t is the sample mass at temperature
where y = (Mt − Me)/M0-Me, M0 is the mass of the initial sample, Мt is the sample mass at temperature
T in the TG experiment, Me is the final mass of the sample, Ea is the activation energy, T is the
T in the TG experiment, Me is the final mass of the sample, Ea is the activation energy, T is the
temperature, and R is the universal gas constant.
temperature, and R is the universal gas constant.
The purpose of this study was to compare the structure and thermal behavior of cellulose and
The purpose of this study was to compare the structure and thermal behavior of cellulose and
composite precursors containing silyl-substituted acetylene and alkoxysilanes additives, by the TGA
composite precursors containing silyl-substituted acetylene and alkoxysilanes additives, by the TGA
and DSC methods.
and DSC methods.
In this research, we report that the addition of silyl-substituted acetylene and alkoxysilanes into
In this research, we report that the addition of silyl-substituted acetylene and alkoxysilanes into
the cellulose matrix led to a decrease in the activation energy. Valuable information was obtained
the cellulose matrix led to a decrease in the activation energy. Valuable information was obtained
from the TGA; it is shown that 5% of the additive is sufficient to significantly increase the carbon yield
from the TGA; it is shown that 5% of the additive is sufficient to significantly increase the carbon
compared to cellulose during heat treatment of fibers to 1000 ◦ C.
yield compared to cellulose during heat treatment of fibers to 1000 °C.
2. Materials and Methods
2. Materials and Methods
Concentrated cellulose dopes were prepared according to the method described in [25] from
Concentrated
cellulose cellulose
of the Baikal dopes
Cellulose were
and prepared
Paper according
Mill (Russia) to theofmethod
(degree described
polymerization in 600,
was [25] from
H2 O
cellulose of the Baikal Cellulose and Paper Mill (Russia) (degree of polymerization was 600,
content ~8%, and α-cellulose content not less than 94%). As a solvent, N-methylmorpholine-N-oxide H2O
content ~8%, and α-cellulose content not less than 94%). As a solvent, N-methylmorpholine-N-oxide
with a Tm = 120–160 C (H2 O < 10%) (Demochem, China) was used. The silicon-containing additives
◦
withshown
are a Tm =in120–1601 °C
Table (H2O < 10%) (Demochem,
(Sigma-Aldrich, USA). China) was used. The silicon-containing additives
are shown in Table 1 (Sigma-Aldrich, USA).
For inhibition of the of thermo-oxidative degradation, 0.5% of propylgallate (Sigma-Aldrich, USA)
was introduced to solution.
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Table
Table
Table 1. 1.
1. The
TheThe main
main
main characteristics
characteristics
characteristics of of organosilicon
of organosilicon
organosilicon additives.
additives.
additives.

Viscosity, η,
Viscosity,
Viscosity,
3
The
TheCompound
The Compound
Compound Structural
Structural Formula
Structural Formula
Formula
Ò
Тm
Тm, °C
m
◦
m,, °C
C ТÒboil
Тboil
boil,, °C
boil °C
Density,
, ◦ C Density,
Density,
(T =
g/cmg/cm
g/cm333

25 C)◦ η,
η, mPa·s
mPa·s
mPa·s
(T
(T == 25
25 °C)
°C)
(T
(T = 20 ◦ C)
(T == 20
20 °C)
°C)

Tetraethoxysilane
Tetraethoxysilane
Tetraethoxysilane −82.5
−82.5
−82.5 170
170
170 0.9330.933
0.933 0.75
0.75 0.75
(TEOS)
(TEOS)(ID
(ID24848042)
(TEOS) (ID 24848042)
24848042)

Vinyltriethoxysilane
Vinyltriethoxysilane
Vinyltriethoxysilane
(VTEOS)
(VTEOS)(ID
(VTEOS) (ID
(ID <0
<0
<0 160
160
160 0.9100.910
0.910 0.7
0.7 0.7
24850510)
24850510)
24850510)
Bistrimethylsilyl
Bistrimethylsilyl
Bistrimethylsilyl
Bistrimethylsilyl
acetylene(BTMSA)
acetylene
acetylene (BTMSA)
(BTMSA) 22
22
22 136
136
136 0.7520.752
0.752 -- -
(ID
(ID 24851275)
(ID24851275)
24851275)

For inhibition of the of thermo-oxidative degradation, 0.5% of propylgallate (Sigma-Aldrich,

USA)As wasthe main objects
introduced under consideration, the fibers obtained from the filled cellulose solutions
to solution.
in the
AsNMMO
the mainwith a weight
objects under ratio of 95/5 and
consideration, the90/10
fibers(cellulose/organosilicone additive)
obtained from the filled cellulose were studied
solutions
(Table
in the 2).
NMMO with a weight ratio of 95/5 and 90/10 (cellulose/organosilicone additive) were
in the NMMO with a weight ratio of 95/5 and 90/10 (cellulose/organosilicone additive) were studied studied
(Table 2).
(Table 2).
Table 2. Designation of the composite fibers.
Table 2.
Table 2. Designation
Designation of
of the
the composite
composite fibers.
fibers.
Ratio of Components
Sample
0 Ratio95/5
of Components
95/10
Sample
Cellulose/TEOS 0 L Ò-5 95/5 Ò-10 95/10
Cellulose/VTEOS L VT-5 VT-10
Cellulose/TEOS
Cellulose/TEOS L Т-5 Т-10
Cellulose/BTMSA L L B-5 Т-5 B-10 Т-10
Cellulose/VTEOS
Cellulose/VTEOS L
L VT-5
VT-5 VT-10
VT-10
Cellulose/BTMSA L B-5 B-10
The cellulose and composite precursors were spun on a capillary viscometer equipped with the
fiberThe
winding system
cellulose Rheoscopeprecursors
and composite 1000 (CEAST,wereItaly)
spun(don=a 1capillary = 40) by a dry-jet
mm, l/dviscometer equipped wetwith
method
the with
a spinning
fiber windingspeed of ~100
system m/min.1000 (CEAST, Italy) (d = 1 mm, l/d = 40) by a dry-jet wet method
Rheoscope
with aThe
spinning
thermalspeed of ~100 of
behavior m/min.
the fibers was examined on a TGA/DSC combined thermal analysis
The
instrument,thermal behavior
Mettler
The thermal Toledo
behavior of the fibers
fibers was
was examined
of (Switzerland).
the examined on aa TGA/DSC
The measurements
on TGA/DSC combined
werecombined thermal
carried out analysis
in theanalysis
thermal temperature
instrument,
instrument, Mettler
Mettler
range of 30–1000 Toledo
◦ CToledo (Switzerland).
(Switzerland).
at a heating The
rate of 10 The measurements
◦ C/min.
measurements
The flow ratewere
were carried
of carried out in
outwas
the argon the
in the temperature
3 /min. Alumina
temperature
10 cm
range of 30–1000
crucibles of 70 µL°C heating rate of 10 °C/min. The flow rate of the argon was 10 cm333/min.
at aused.
were
AluminaThecrucibles
morphologyof 70 of
µLthe
were used.surfaces and cross-sections was studied by the scanning electron
fiber’s
The morphology of the fiber’s surfaces and cross-sections was studied by the scanning electron
microscope JSM U-3 (JEOL, Japan).
microscope JSM U-3 (JEOL, Japan).
The structure of the fibers was studied by the X-ray diffraction method on a 12-kW generator
The structure
The structure ofof the
the fibers
fibers was
was studied
studied by
by the
the X-ray
X-ray diffraction
diffraction method
method on
on aa 12-kW
12-kW generator
generator
Rigaku
Rigaku (Japan)with
(Japan) witha a rotating
rotating copper
copper anode
anode modemode
at at room
room temperature.
temperature. The The CuKα
CuKα radiationradiation
with aa with
Rigaku (Japan) with a rotating copper anode mode at room temperature. The CuKα radiation with
a wavelength λ = 0.1542 nm was used. Equatorial diffractograms of the fibers were obtained from
wavelength λ = 0.1542 nm was used. Equatorial diffractograms of the fibers were obtained from
parallel bundlesofoffibers
parallel bundles fibers(~100
(~100 pieces,
pieces, average
average diameter
diameter of monofilament
of monofilament 12 µm).
12 µm).
Interplanar distances were calculated using the Bragg
Interplanar distances were calculated using the Bragg formula: formula:
Interplanar distances were calculated using the Bragg formula:
dd= =
λ/(2sin(θ))
λ/(2 sin(θ)) (2) (2)
where λ is the wavelength of the X-ray radiation, and θ is the diffraction angle.
where λ is the wavelength of the X-ray radiation, and θ is the diffraction angle.

3. Results and Discussion

Cellulose and composite fibers were obtained by a dry-jet wet method. The SEM images of spun
fibers with different contents of silicon-containing additives are illustrated in Figure 2.
Fibers 2019, 7, x FOR PEER REVIEW 4 of 11

3. Results and Discussion

3. Results and Discussion
Cellulose and composite fibers were obtained by a dry-jet wet method. The SEM images of spun
Fibers Cellulose
2019, 7, 84 and composite fibers were obtained by a dry-jet wet method. The SEM images of 4spun
of 12
fibers with different contents of silicon-containing additives are illustrated in Figure 2.
fibers with different contents of silicon-containing additives are illustrated in Figure 2.

(a) (b)
(a) (b)

(c) (d)
(c) (d)
Figure 2. Microphotographs of surface and cross-section of cellulose (a), composite precursors 95%
Microphotographs of surface and cross-section of cellulose (a), composite precursors 95%
Figure 2. Microphotographs
cellulose + 5% BTMSA (b), 90% cellulose + 10% VTEOS (c), 95% cellulose + 5% BTMSA (d).
cellulose +
+ 5%
5% BTMSA (b), 90% cellulose ++ 10%
BTMSA (b), 10% VTEOS
VTEOS (c),
(c), 95% cellulose ++5%
95% cellulose 5%BTMSA
BTMSA(d).
(d).

AsAs shown, the

shown,
shown, the
introduction of silicon-containing
theintroduction
introductionofofsilicon-containing
silicon-containing
compounds
compounds
compounds
into
intointo
the the cellulose
cellulose
the matrix
cellulose
matrix
did not
matrix
did not
didlead
not
to lead
a to a significant
significant change change
in the in the
morphology morphology
of the of
fibers. the
Thefibers.
surfaceThe
and surface
cross and cross
section of section
both of both
cellulosic
lead to a significant change in the morphology of the fibers. The surface and cross section of both
andcellulosic
composite andfibers
composite
didfibers
notfibers did not contain
contain obvious defects. The cross-section was circular. The
cellulosic and composite did notobvious
containdefects.
obviousThe cross-section
defects. was circular.
The cross-section The average
was circular. The
average
diameter diameter of
of the obtained the obtained
fibers was fibers
15 towaswas 15
17 microns. to 17 microns.
average diameter of the obtained fibers 15 to 17 microns.
The structure of precursor fibers
The structure of precursor fibers was one was one
of ofthethe factors determining their properties, including
factors
factors determining their properties, including
mechanical and
mechanical thermal behavior [26]. isThat isbefore
whycomparing
before comparing theproperties
thermal properties of
mechanical and andthermal
thermal behavior
behavior [26]. That
[26]. Thatwhyis why the thermal
before comparing the thermal of cellulose
properties of
andcellulose
compositeand composite
fibers, their fibers, their
structure structure
was studied was studied with X-ray diffraction (Figure 3).
cellulose and composite fibers, their structure waswith X-raywith
studied diffraction (Figure 3).(Figure 3).
X-ray diffraction

(a) (b)
(a) (b)
Figure 3. Cont.
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5 of

(c)
Figure 3. Equatorial diffractograms of cellulose (1) (c) and composite fibers: (a) T-5 (2) and T-10 (3); (b)
VT-5 (2) and VT-10 (3); (c) B-5 (2) and B-10 (3).
Figure
Figure 3. 3. Equatorialdiffractograms
Equatorial diffractogramsofofcellulose
cellulose(1)
(1)and
and composite
composite fibers: (a)
(a) T-5
T-5 (2)
(2)and
andT-10
T-10(3);
(3);(b)
(b)VT-5
VT-5(2)
(2)and
andVT-10
VT-10 (3);
(3); (c)
(c) B-5
B-5 (2)
(2) and
and B-10
B-10 (3).
(3).
For all the samples studied, the main peaks are observed in regions 2θ~12.3° and 2θ~20.6° with
interplanar
ForFor distances
allall
thethesamplesof studied,
samples 3.61 and the
studied, 2.19main
the Å, respectively.
main peaks are
peaks The positions
are observed
observed of 2θ~12.3°
ininregions
regions these peaks
2θ~12.3 ◦ and
and refer to the
2θ~20.6
2θ~20.6°
◦
with
polymorphic
with interplanar
interplanar form cellulose
distances
distances of of II and
3.61
3.61 [27]. The
and2.19
2.19Å, intensities
Å, of the
respectively.
respectively. Thepeaks
The decrease
positions
positions of
ofthese with
these an refer
peaks
peaks increase
refertoto inthe
the
concentration
polymorphic
polymorphic ofform
form the additive,
cellulose II [27].which
cellulose IIThe indicates
intensities
[27]. ofathepartial
The intensitiespeaks disordering
of decrease
the peaks within
anthe basal
increase
decrease inplanes
with of the in
concentration
an increase
cellulose structure.
of concentration
the additive, whichof theindicates
additive, a partial
whichdisordering
indicates ainpartial
the basal planes of the
disordering cellulose
in the basalstructure.
planes of the
Unlikestructure.
Unlike
cellulose cellulose fibers,
cellulose fibers, inin which
which thethe carbon
carbon yield
yield tends
tends to
to be
be the
the minimum
minimum valuevalue with
with linear
linear
heatingUnlike
heating up to
up to cellulose
1000 °C,
1000 ◦ for almost
almost
C, fibers,
for all composite
all
in which composite precursors
the carbonprecursors
yield tendsthetoincrease
the increase of the
of
be the minimumthe carbon
carbon yield
valueyield was
with was
linear
observed,
observed, which
heating which
up to 1000can be
can be seen
°C,seen from
for from the
almostthe thermogravimetric
allthermogravimetric
composite precursors curves
curves in
the in Figure
Figure of
increase 4 obtained
4 obtained
the carbon at various
at various
yield was
temperature
temperature intervals.
observed, intervals.
which can be seen from the thermogravimetric curves in Figure 4 obtained at various
temperature intervals.

Figure 4.4.Thermogravimetry
Figure ThermogravimetryAnalysis
Analysis (TGA) curves
(TGA) of cellulose
curves and composite
of cellulose fibers: fibers:
and composite complete curves
complete
and parts ◦ C and 260–315 ◦ C. Atmosphere: argon
curves andofparts
the curves
of the in the temperature
curves ranges 30–260
in the temperature ranges 30–260 °C and 260–315 °C. Atmosphere:
Figure 4. Thermogravimetry Analysis◦ (TGA) curves of cellulose and composite fibers: complete
10
argon /min.
cm3 10 cm3Linear heatingheating
/min. Linear at a rate
at of 10 C/min.
a rate of 10 °C/min.
curves and parts of the curves in the temperature ranges 30–260 °C and 260–315 °C. Atmosphere:
argon 10 cm /min. Linear heating at a rate of 10 °C/min.
3
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When the samples were heated up to 200 °C, the fibers lost 8%–9% of their mass, which was
stipulated
When thewithsamples
the adsorbed water removal.
were heated up to 200 The
◦ C,highest rate lost
the fibers of weight
8–9% loss for cellulose
of their fiberswas
mass, which was
observed up to 100 °C. At further heating, VT-10 precursors lose water the most
stipulated with the adsorbed water removal. The highest rate of weight loss for cellulose fibers actively and this
process
was continues
observed up to up
100to◦ C.
160
At°C. The process
further heating, of removing
VT-10 waterlose
precursors from T-10the
water fibers
mostproceeds
activelyat the
and
lowest rate and ends at around 200
◦ °C. In the next stage of sample heating (in the
this process continues up to 160 C. The process of removing water from T-10 fibers proceeds at temperature range
200–340
the lowest °C), two ends
rate and competing reactions
at around 200 ◦ C.occured–dehydration and depolymerization
In the next stage of sample [28]. These
heating (in the temperature
reactions
range correspond
200–340 ◦ C), twoto the extremes
competing on theoccured–dehydration
reactions differential curves of and
the mass loss rate (DTG)
depolymerization (Figure
[28]. These5).
reactions correspond to the extremes on the differential curves of the mass loss rate (DTG) (Figure 5).

Figure 5. Mass loss rate (DTG) curves for cellulose and composite fibers.
Figure 5. Mass loss rate (DTG) curves for cellulose and composite fibers.
Although the course of the DTG curves is the same, the positions of the temperatures at the
Although
beginning theend
and the course ofdecomposition
of the the DTG curves is the same,
reaction, as wellthe positions
as the of the
maximum oftemperatures
the mass loss at the
rate,
beginning and the end of the decomposition reaction, as well as the maximum of the mass loss
differ. The temperatures corresponding to the extremum points and DTGmax values for all the testing rate,
differ. The
samples temperatures
are given in Tablecorresponding
3. to the extremum points and DTGmax values for all the testing
samples are given in Table 3.
Table 3. Parameters of the thermodestruction rate of cellulose and composite fibers: the temperatures
ofTable 3. Parameters
minimums and the DTG of values.
the thermodestruction rate of cellulose and composite fibers: the
temperatures of minimums and the DTG values.
Sample Tmax, ◦ C DTGmax, %/min
Sample Tmax, °С DTGmax, %/min
L 331 −1.74
T-5 L 331
332 −1.74
−2.02
T-10 T-5 332
335 −2.02
−2.49
VÒ-5 T-10 337
335 −2.35
−2.49
VÒ-10 344 −2.38
VТ-5 337 −2.35
B-5 328 −2.03
B-10 VТ-10 344
332 −2.38
−2.14
B-5 328 −2.03
B-10 332 −2.14
The temperature range of pyrolysis, determined from the first derivative of the TGA curves, was
used for estimation of the activation energy of thermal decomposition. According to [29], these values
The temperature range of pyrolysis, determined from the first derivative of the TGA curves,
allow us not only to estimate the energy necessary for the reaction, but also the possible nature of
was used for estimation of the activation energy of thermal decomposition. According to [29], these
the product obtained. For more accurate determination of the pyrolysis starting temperature, TGA
values allow us not only to estimate the energy necessary for the reaction, but also the possible
derivatives of a higher order could be used. The corresponding temperature dependences of the weight
nature of the product obtained. For more accurate determination of the pyrolysis starting
loss rate is presented in Figure 6, and calculated activation energy, as well as intrinsic points of the
temperature, TGA derivatives of a higher order could be used. The corresponding temperature
decomposition process, is shown in Table 4.
dependences of the weight loss rate is presented in Figure 6, and calculated activation energy, as
well as intrinsic points of the decomposition process, is shown in Table 4.
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Figure 6. Dependence ln(ln(1/y)) VS 1000/T for determining the activation energy of the thermal
Figure 6. Dependence ln(ln(1/y)) VS 1000/T for determining the activation energy of the thermal
decomposition.
decomposition.
Table 4. DTG data for cellulose and composite fibers.
Table 4. DTG data for cellulose and composite fibers.
Sample L (1) T-5 (2) T-10 (3) B-5 (6) B-10 (7) VT-5 (4) VT-10 (5)
Sample
Slope −26.14 L (1)−19.47 T-5 (2) −25.08T-10 (3)−19.4 B-5 (6)−20.6 B-10 (7)
−19.6 VT-5 (4)
−17.1VT-10 (5)
, ◦C
TonsetSlope 281 −26.14282 −19.47 292 −25.08 279 −19.4 279 −20.6 282 −19.6 287 −17.1
Trange , ◦C
Tonset , oC 281–306 281282–307 282292–317 292279–304 279279–304 279282–307 282287–312 287
Ea , kJ/molo 234 162 209 162 172 164 143
Trange, C 281–306 282–307 292–317 279–304 279–304 282–307 287–312
Weight loss, % 5.6 4.7 7 5.3 3.4 3.5 4.8
Е a, kJ/mol
Carbon yield at 234 162 209 162 172 164 143
Weight◦ loss, % 3.5 5.6 14.4 4.7 12.3 7 14.8 5.3 13.1 3.4 12.6 3.5 5.7 4.8
1000 C, %
Carbon yield at 1000°C, % 3.5 14.4 12.3 14.8 13.1 12.6 5.7

Thus, the lowest point of the pyrolysis starting (279 ◦ C) was for the precursors B-5 and B-10,
Thus, the lowest point of the pyrolysis starting (279 °C) was for the precursors B-5 and B-10, and
and the highest was for the sample T-10 (292 ◦ C). All other formulations were located inside this
the highest was for the sample T-10 (292 °C). All other formulations were located inside this
temperature interval. This means that depending on the nature of the additive, the thermal stability
temperature interval. This means that depending on the nature of the additive, the thermal stability
of the samples was slightly varied. Reducing the structural order in the system did not lead to a
of the samples was slightly varied. Reducing the structural order in the system did not lead to a
decrease in thermal stability. Hence, it can be assumed that the chemical interaction between the
decrease in thermal stability. Hence, it can be assumed that the chemical interaction between the
silicon-containing additive and the cellulose matrix, and the amount of the additive, plays a more
silicon-containing additive and the cellulose matrix, and the amount of the additive, plays a more
important role in the decomposition process than the crystalline structure. It is known that in the
important role in the decomposition process than the crystalline structure. It is known that in the
presence of water, organosilicon compounds are extremely unstable compounds, prone to hydrolysis
presence of water, organosilicon compounds are extremely unstable compounds, prone to
reactions, and subsequent condensation and polycondensation with the formation of oligomers and
hydrolysis reactions, and subsequent condensation and polycondensation with the formation of
polymers with siloxane bonds of a linear or cyclic structure [30,31]. In the studied cellulose solutions in
oligomers and polymers with siloxane bonds of a linear or cyclic structure [30,31]. In the studied
NMMO, water was present in an amount of ~10% to 13%. The introduction of tetraethoxysilane (TEOS)
cellulose solutions in NMMO, water was present in an amount of ~10% to 13%. The introduction of
to cellulose solutions in NMMO led to the formation of a discrete phase of polysiloxanes. The resulting
tetraethoxysilane (TEOS) to cellulose solutions in NMMO led to the formation of a discrete phase of
polysiloxane particles were uniformly distributed in the cellulose matrix. The vinyltriethoxysilane
polysiloxanes. The resulting polysiloxane particles were uniformly distributed in the cellulose
(VTEOS) molecule contains double bonds that can open and integrate into cellulose chains during
matrix. The vinyltriethoxysilane (VTEOS) molecule contains double bonds that can open and
thermolysis, ensuring the formation of Si–C bonds (as evidenced by IR spectroscopy). Bistrimethylsilyl
integrate into cellulose chains during thermolysis, ensuring the formation of Si–C bonds (as
acetylene (BTMSA) is chemically inert and does not chemically interact with the matrix when forming
evidenced by IR spectroscopy). Bistrimethylsilyl acetylene (BTMSA) is chemically inert and does not
the fiber.
chemically interact with the matrix when forming the fiber.
Based on the Broido method, the values of activation energy (Ea ) of the thermal decomposition
Based on the Broido method, the values of activation energy (Ea) of the thermal decomposition
for the spun fibers were calculated. The activation energy for Lyocell fibers was 234 kJ/mol, which
for the spun fibers were calculated. The activation energy for Lyocell fibers was 234 kJ/mol, which is
is closer to the values for the cellulose samples discussed in [32–34]. The activation energy of the
closer to the values for the cellulose samples discussed in [32–34]. The activation energy of the
thermal decomposition of T-5, VT-5, and B-5 practically coincided. Further increases in the content of
thermal decomposition of T-5, VT-5, and B-5 practically coincided. Further increases in the content
Fibers 2019, 7, x FOR PEER REVIEW 8 of 11

Fibers 2019, 7, 84 8 of 12
of these additives in the system led to a multidirectional change in the activation energy. The value
of Ea increased for silyl-substituted additives and decreased for BTMSA. The maximum value of 209
these was
kJ/mol additives in thefor
achieved system
T-10 led to a multidirectional
samples. It should be noted change in the
that thisactivation
value of E energy. The than
a is lower of Ea
valuethat
increased
obtained forfor silyl-substituted
cellulose fibers. additives and decreased for BTMSA. The maximum value of 209 kJ/mol
wasAlong
achieved
withfortheT-10 samples.
highest It should
activation be noted
energy that this
for T-10 value
fibers, Ea is lower
theofhighest massthanlossthat
rateobtained
was alsofor
cellulose(Table
recorded fibers.4). Lyocell fibers, on the contrary, were characterized by the lowest rate of mass loss.
Along
As a result, in with the highest range
the temperature activation energy
for which thefor T-10 fibers,
activation energythewas
highest mass loss
calculated, rate was
the largest also
mass
recorded
loss (Table
of 7% was 4). Lyocell
observed for fibers,
the T-10 onsample,
the contrary,
whilewere characterized
the BT-5 and B-10 by the lost
fibers lowest rate3.5%
about of mass loss.
of the
As a mass
initial result,only
in the temperature
(Table 4). At Trange= 1000for°C,
which
the the activation
carbon yield ofenergy was calculated,
the Lyocell the largest
fibers tended mass
towards
loss of 7%values.
minimum was observed for the T-10
The composite sample, T-5
precursor while the BT-5
samples anda B-10
had fibers
carbon lostof
yield about 3.5%
14.4% at of thesame
the initial
mass only (Table
temperature, which4).isAt theT= 1000 ◦ C, the
maximum carbon
value among yieldallofthe
thesamples
Lyocell fibers
studied. tended
The towards
minimum minimum
value
values.
(5.7%) wasThe composite
observed precursor
for VT-10 T-5Itsamples
fibers. had atocarbon
is important yield
note that of 14.4%
despite the at the same
chemical temperature,
nature of the
which isintroduced
additives the maximum intovalue among allmatrix,
the cellulose the samples studied.
the carbon The
yield minimum
initially value (5.7%)
increased wasaddition
with the observed
offor
5%VT-10 fibers. It is important
silicon-containing compounds, to note that
while despiteincrease
a further the chemical
in the nature
additive oftothe10%additives
led to aintroduced
decrease
ininto the cellulose matrix, the carbon yield initially increased with the addition of 5% silicon-containing
its value.
compounds, while aare
The DSC curves further
shown increase in the
in Figure 7. additive to 10% led to a decrease in its value.
The DSC curves are shown in Figure 7.

(a) (b)

(c)
Figure
Figure DSC
7. 7.DSC curvesfor
curves forcellulose
cellulose(1)
(1)and
andcomposite
compositefibers:
fibers: (a)
(a) T-5
T-5 (2), T-10
T-10 (3);
(3); (b)
(b)VT-5
VT-5(2),
(2),VT-10
VT-10(3);
(c)(c)
(3); B-5 (2)(2)
B-5 and B-10
and (3).
B-10 (3).Atmosphere:
Atmosphere:argon cm/min.
argon1010cm3 3 /min.Linear
Linearheating
heatingatata arate ◦
rateofof1010 C/min.
°C/min.

Table5 5summarizes
Table summarizesthe
themost
mostimportant
importantquantitative
quantitativeindicators
indicatorsofofDSC
DSCdata.
data.
Two temperature ranges can be distinguished for all samples (Table 5). The first one (30–178 ◦ C)
characterizes an endothermic effect, connected to the removal of water. The second one is the
thermal decomposition of cellulose (the temperature range of 286–376 ◦ C), accompanied by endo- and
exo-effects. The described ranges are well correlated with the TGA data.
Fibers 2019, 7, 84 9 of 12

Table 5. The main parameters of fibers obtained by DSC studies at a heating rate of 10 K/min in an inert atmosphere.

Òrange, Òmin Endothermic Òrange, Òmin Endothermic Òrange, Òmax Exothermic Òrange, Òmin Endothermic
Sample ◦C Endotherma, ◦C Endotherma, ◦C Exotherma, ◦C Endotherma,
◦C Effect, J·g−1 ◦C Effect, J·g−1 ◦C Effect, J·g−1 ◦C Effect, J·g−1

L 30–172 77 −162 288–345 326 −119 345–372 350 −25

Ò-5 30–178 112 −155 295–319 311 −22 319–355 347 56
Ò-10 30–177 111 −157 277–341 317 −66 342–351 348 8 351–376 354 −11
VT-5 30–174 106 −178 286–333 318 −74 333–352 348 18 352–370 354 −8
VT-10 30–177 99 −224 289–326 323 −95 326–345 341 62 345–376 351 −14
B-5 30–164 101 −139 281–312 305 −10 312–357 337 92
B-10 30–177 112 −166 289–325 312 −10 339–355 347 19
Fibers 2019, 7, 84 10 of 12

The adsorbed water is the most quickly removed from the cellulose fibers, a minimum of the
endotherm is observed at 77 ◦ C. The introduction of additives into the cellulose matrix leads to a change
in the kinetics of the water removal and the shift of the endothermal minimum to higher temperatures.
The dehydration and depolymerization reactions are accompanied by an endo-effect, which,
depending on the type of additive and its concentration, starts at temperatures of 277–295 ◦ C.
The endo-effect decreases dramatically for T-5, B-5, and B-10 fibers, while for silyl-substituted
additives it increases with increasing additive concentration, and for composite fibers of series B it
remains unchanged.
At higher temperatures, processes of gas formation (CO, CO2 , etc.) [35] and their interaction with
the transformed sample under study are observed, which are expressed as endo- and exo- peaks on the
DSC curves.
With an increase in the VTEOS content up to 10%, the thermal behavior of the system changes.
On the DSC curve (Figure 7, curve 3), there are also three peaks, but the maximums of the peaks
are shifted. Thus, the position of the endopeak corresponding to dehydration processes shifts to
323 ◦ C, while the position of the maximum of the exopeak shifts toward lower temperatures to 341 ◦ C.
The character of the curve also changes. The increased content of the additive leads to a significant
acceleration of the processes of structural rearrangements, as evidenced by the heat of the exo-effect
that has increased almost 4-fold. The results obtained, at first glance, are somewhat different from
the TGA data, according to which an increase in the VTEOS content in cellulose to 10% leads to a
decrease in the carbon yield. Apparently, the processes occurring in the heat treatment process are
more complex. It can be assumed that high heat release in the bulk of the sample initiates the flow of
deeper destruction processes leading to the mass loss.

4. Conclusions
Thus, the introduction of silicon-containing additives into the cellulose matrix leads to a decrease
in structure ordering and affects the thermal behavior of the resulting composite precursors. For all
composite fibers, the activation energy of pyrolysis is less than that for cellulose fibers. At the same
time, the reaction itself starts first for samples B-5 and B-10, and later on for T-10 fibers, i.e., the first
type of additive acts as a pyrolysis catalyst, and the second one as a flame retardant. The type of
observed peaks on the DSC curves for composite fibers cardinally changes from the endopeaks inherent
for cellulose fibers by the combination of endo- and exo- peaks. This may indicate the occurrence
of a number of complex chemical processes leading to an increase in the mass of the carbon yield at
temperatures up to 1000 ◦ C. Regardless of the type of silicon-containing agent, the maximum values of
the carbon yield are achieved with the introduction of 5% of the composite additive into the cellulose.
For further improvement of the values of fibers’ carbon yield, it is necessary to optimize the temperature
profiles and residence times. Additional impregnation of the discussed composite precursors with
ammonium chloride, diammonium phosphate, or other silicon-containing compounds also contributes
to an increase in carbon yield values and is the subject of further research. The resulting carbon fibers
from composite precursors based on cellulose in the future can be used to create composite materials
with unique engineering properties such as high thermal stability and mechanical values.

Author Contributions: M.M. and I.M. provided the idea for this study, proposed the experiments and wrote the
paper; I.M. analyzed the data; L.G. analyzed the data and reviewed the paper; M.V. produced the composite
samples; G.S. performed thermal analysis and discussed the data; I.L. investigated the structure of the fibers; M.M.
and I.M. edited the final paper.
Funding: This research was funded by RFBR according to the research project No. 16-33-60218 mol_a_dk.
Conflicts of Interest: The authors declare no conflict of interest.
Fibers 2019, 7, 84 11 of 12

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