CARBON 4 6 (2 0 0 8) 2 6 1–27 1

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The chemistry, morphology, topography of titanium

carbide modified carbon fibers

N.I. Baklanovaa,*, B.N. Zaitsevb, A.T. Titovc, T.M. Zimaa

a
Institute of Solid State Chemistry and Mechanochemistry SB RAS, Kutateladze st. 18, Novosibirsk 630128, Russian Federation
b
State Research Center of Virology and Biotechnology ‘‘Vector’’, Koltsovo, Novosibirsk Region 630559, Russian Federation
c
General Institute of Geology, Geophysics and Mineralogy SB RAS, Novosibirsk 630090, Russian Federation

A R T I C L E I N F O A B S T R A C T

Article history:
Received 2 August 2007
Accepted 19 November 2007
Available online 24 November 2007
Titanium carbide coatings were successfully applied on carbon fibers using reactive chem-
ical vapor deposition approach. Chemistry, morphology, and topography of the TiC modified
carbon fibers have been studied by scanning electron microscopy/energy dispersive spec-
troscopy, atomic force microscopy, and X-ray diffraction analysis. Uniform, adherent,
crack-free and non-bridging coatings were obtained. After application of the TiC coating
on carbon fibers, relief becomes more smooth and uniform. This is confirmed by decrease
of the roughness parameter and the average height value of relief, as well as by decrease
of scatter of measured heights. The coating consists of radially oriented crystals with high
aspect ratio. Crystals are aligned in rows which are parallel to fiber axis. An increase in the
tensile strength has been achieved by introducing the TiC coating on carbon fiber, the aver-
age strength and the Weibull modulus parameters were 2.55 GPa and 4.36 GPa, respectively.
The obtained results can be useful for the predictive design of the well-matched interphase
zone for composite materials reinforced by the TiC-coated carbon fibers.
 2007 Published by Elsevier Ltd.

1. Introduction posite materials it remains one of the weakest links in the

It is well established that the mechanical properties, thermal
and environmental stability of the carbon fiber-reinforced
composites, such as polymer composites, carbon/carbon
and ceramic matrix composites are strongly influenced by
the interfacial phenomena at the carbon fiber/matrix bound-
ary [1,2]. The interphase zone is formed in situ during com-
posite processing or specially designed by application of
coatings on reinforced fibers prior the matrix fabrication. In
essence, the interphase is a third phase of composite, the
chemical, structural, physical, and mechanical properties of
which are greatly differ from properties both matrix and fi-
bers. In addition, the local properties within the interphase
zone itself can also significantly vary. In despite of wide rec-
ognition that the interphase is a crucial component of com-
research of the matrix–interphase–fiber triad. This is because
of the functions and properties of nanoscale interphase are
not yet well-understood and generally very difficult to charac-
terize. It prevents detailed predictive design of well-matched
interphase zone for composite materials reinforced by fibers.
To establish a relationship between microscopic properties
of interphase and macroscopic mechanical properties of com-
posites it is necessary comprehensively to characterize inter-
phase in terms of elemental and phase composition,
morphology, texture, nanorelief with a heavy emphasis on
quantitative characterization. The nature of interphase with-
in a thickness less than 1 lm was not so frequently reported
in literature. This is because of the limitation of analytical test
methods which could be able accurately to measure the inter-
phase characteristics on nanoscale level. The development of

* Corresponding author: Fax: +7 383 3322847.

E-mail address: baklanova@solid.nsc.ru (N.I. Baklanova).
0008-6223/$ - see front matter  2007 Published by Elsevier Ltd.
doi:10.1016/j.carbon.2007.11.019
262 CARBON 4 6 ( 2 0 0 8 ) 2 6 1 –2 7 1
modern analytical methods, including high resolution elec-
tron microscopy and atomic force microscopy stimulated a
research on microstructure, topography, fracture, local
mechanical characteristics of interphase, local physical and
chemical properties, the direct measurements of adhesion
between fiber and matrix and helped to clarify a nature of
interphase in some extent [3–7].
As was mentioned above, in many cases, the interphase
zone is specially designed by application of coatings on rein-
forced carbon fibers prior the matrix fabrication. In modern
composites reinforced by carbon fibers the interfacial coating
must be oxidation resistant at high temperatures because car-
bon reacts with oxygen at temperatures as low as 400 C. As
interfacial coatings on carbon fibers, the refractory oxides, ni-
trides, and carbides, including titanium carbide have been
used by Fitzer et al. [8], Wang et al. [9]. Main reasons for pro-
posing of these materials were, firstly, the availability of easy
fabrication through CVD process, and secondly, the improved
oxidation resistance of coated carbon fibers in comparison
with uncoated ones. Recently, a number of the refractory car-
bides TiC, ZrC, HfC/SiC, TaC, SiC as barrier coatings on rein-
forced carbon fibers have been also proposed by Baklanova
et al. [10–12]. So-called reactive chemical deposition (RCVD)
earlier described by Schäfer [13] has been used for obtaining
carbide coatings on carbon fibers.
The aim of this work is to study of the TiC-coated carbon
fibers with an emphasis on chemistry of the fiber-coating
RCVD process, characterization of the surface morphology, lo-
cal characterization of surface topography, peculiarities of
nanorelief and local adhesion forces.
2. Experimental
2.1. Substrate and coating preparation
As the initial substances, continuous carbon fibers type ‘‘UKN-
5000’’ and ‘‘VMN-4’’ both (ex-PAN) supplied by ‘‘VIAM’’ (Mos-
cow) were used. Prior to coating, carbon fiber tows were
immersed for 24 h in 50:50 acetone/ethanol mixture for
removing a sizing agent, after that they were dried at ambient
temperature and then thermally treated in vacuum at 960 C.
For fabrication of the titanium carbide coating the cuttings
or/and powder of titanium (not less than 99.9% pure) as well
as fluoride-containing gases (CF4) and argon as carrier gas
were used as initial substances. The amount of metal used
was in large excess to carbon support (10:1 and more). The
coating process was carried out by using reactive chemical
vapor deposition (RCVD) technique and was similar to that
described by Baklanova et al. in [14]. The process was carried
out at 1200–1300 K for 0.5 h, with the total pressure in the sys-
tem being 102 Pa. The gas flow was maintained at 0.5 l/h. Inter-
action of gaseous fluorine-containing compounds with the
walls of the quartz reactor was minimized due to the special
metal tube made from inert material and inserted into reactor.
2.2. Sample characterization
The morphology and composition of the initial and coated
carbon fibers were examined by scanning electron micro-
scope (SEM: LEO 1430VP). Samples were coated with gold
(ca. 20 nm). Elemental composition of coating was carried
out using energy dispersive spectroscopy (EDS, Oxford). The
phases in coatings were characterized by X-ray diffraction
analysis (XRD) using monochromatic Cu Ka radiation with
DRON-3 diffractometer (Russia).
The topography and surface roughness of fibers was
examined by atomic force microscope (AFM) using Sol-
verP47Bio (NT-MDT, Russia). Carbon filaments were attached
to glass slide using two-sided adhesive tape. For all samples,
several images were recorded at different locations to verify
the reproducibility of the observed features. The topography
of samples was studied in contact and intermittent contact
modes using silicon cantilevers NSG11 (NT-MDT). During the
scanning, phase shifts, i.e. changes in the phase contact angle
of vibration with respect to the phase angle of freely oscillat-
ing cantilever, were recorded simultaneously with height
images.
A roughness and other statistical parameters of selected
areas were obtained using software of device. The AFM
images were flattened before analysis using second-order sur-
face subtraction. Parameters were calculated based on follow-
ing definitions. Mean roughness (Ra) is the arithmetic average
of the absolute values of the surface height deviations, Zij,
measured from mean plane:
Ny
1 X Nx X
Ra ¼ jzj:
Nx Ny i¼1 j¼1
Mean height (Rmean) is the arithmetic average of the absolute
values of the measured heights
Ny
1 X Nx X
Rmean ¼ Zij :
Nx Ny i¼1 j¼1
Maximum height roughness (Rmax) is the difference in height
between the highest and lowest points:
Rmax ¼ Zmax  Zmin :
Direct apparent adhesion force measurements on the initial
and coated carbon fibers were performed using standard
‘‘V’’-shaped silicon nitride cantilever (Veeco) with nominal
spring constant (K) 0.12 N m1 under ambient conditions at
room temperature. Adhesion between the Si3N4 tip and the
filament surface was measured by recording the deflection
of the flexible cantilever at the stage at which, during the
retraction regime of the force–distance curve, the tip became
detached from the surface. This ‘‘pull-off’’ deflection (current,
nA) was converted to a force of adhesion (nN) using sensor re-
sponse obtained from each force curve and the spring con-
stant of the cantilever. One hundred measurements for the
5 · 5 lm2 surface area on three filaments of the same kind
were carried out.
2.3. Tensile strength tests
Mechanical tensile tests of the desized initial and coated
fibers were conducted at room temperature using FM-4 (Hun-
gary) testing machine. Single fibers extracted from a tow were
fixed on paper frame using a hard resin. The gauge of 10 mm
 CARBON 4 6 (2 0 0 8) 2 6 1–27 1
in length was used. The diameter of each filament was mea-
sured in the middle of length by laser interferometry and
used for calculation of mechanical properties. Next, the lat-
eral sides of support frame were cut by a heated wire and
the load was applied at constant crosshead speed of
1.3 mm/min. About 50 filaments for each type of fibers were
tested. The average diameter for the desized fibers was deter-
mined to be 7.49 ± 0.06 lm.
3. Results and discussion
3.1. The formation of TiC coatings on carbon fibers by
RCVD
In course of experiments the fibers were gradually becoming
silver-grey in color, indicating the formation of new phase
identified by XRD to be TiC [JCPDS, File #3-1213]. Cuttings
and powder of titanium lost metallic luster and were becom-
ing slightly grey. According to XRD data, titanium carbide is
formed on the surface of titanium cuttings [JCPDS, File #1-
1222]. At longer time (4 h) deposition a mixture of titanium
carbide and titanium silicide, namely, Ti5Si3, was found
[JCPDS, File #8-41] on the surface of cutting and powder.
Well-developed violet crystals were detected on the inner
walls of quartz reactor. The composition of crystals was iden-
tified by XRD to be TiF3 [JCPDS, File #9-112].
The formation of the TiC coating on carbon fiber by RCVD
process can be described by the following scheme. The inter-
action of gaseous CF4 with titanium cuttings after admittance
of CF4 into reactor leads to the formation of titanium fluorides
according to the reactions:
2TiðsÞ þ CF4ðgÞ ¼ TiCðsÞ þ TiF4ðgÞ ; ð1Þ
ð4  nÞTiðsÞ þ nTiF4ðgÞ ¼ 4TiFnðgÞ ; ð2Þ
where n = 3, 2, 1, the relation between fluorides being deter-
mined by the temperature and pressure in the system. As
the self-consistent thermodynamic data for the Ti–TiF4 sys-
tem were not found in literature and therefore, the calcula-
tion of the gas phase composition in equilibrium with
titanium was impossible. Nevertheless, one could propose
that this composition can be represented by lower fluorides,
mainly, TiF3. Some literature data on thermodynamic calcula-
tions in the transition metal–halogen systems and experi-
mental results on RCVD in the transition metal–carbon–
halogen systems can be evidence in favor of the formation
of lower fluorides in this system. Actually, earlier it was
shown by Barkovsky and Tsyrelnikov [15] that the composi-
tion of the gas phase in equilibrium with metal zirconium
in the Zr(s)–ZrF4(g) system in the 1200–1600 K temperature re-
gion and at Ptotal = 10 Pa or less is represented by lower fluo-
rides, namely ZrF3 and ZrF2, with the partial pressure of
ZrF2 is by several orders of magnitude lower than that of
ZrF3. Similar to the Zr–ZrF4 system, the predominant gaseous
components in equilibrium with metal titanium appear to be
also lower titanium fluorides, mainly, TiF3.
The reaction of gaseous TiF3 with carbon occurs in the
zone of disposition of carbon fiber following by the formation
of TiC coating and gaseous TiF4 (reaction (3)), with the last
263
being recycled according to reaction (2) in zone of disposition
of titanium cuttings:
CðsÞ þ 4TiF3ðgÞ ¼ 3TiF4ðgÞ þ TiCðsÞ : ð3Þ
Thus, the formation of the TiC coating on carbon fiber is an
evidence of titanium transfer through the gas phase by lower
titanium fluorides according to reactions (2) and (3). The
observation of the violet well-developed crystals TiF3 on the
walls of reactor after cooling can be considered as a confirma-
tion of reaction (3).
As was mentioned above, for long-time deposition (4 h) the
formation of titanium silicide on the surface of cuttings was
detected by XRD. It could be as a result of side-interaction
of gaseous fluorine-containing compounds with quartz walls
of reactor, for example, according to following scheme:
SiO2ðs;wÞ þ 2CF4ðgÞ ¼ SiF4ðgÞ þ CO2ðgÞ ; ð4Þ
8TiðsÞ þ 3SiF4ðgÞ ¼ Ti5 Si3ðsÞ þ 3TiF4ðgÞ ; ð5Þ
2TiF4ðgÞ þ SiO2ðsÞ ¼ SiF4ðgÞ þ 2TiOF2ðgÞ : ð6Þ
Reaction (4) was studied by Vogt et al. [16] in detail. They
found that the interaction occurs with noticeable rate at tem-
peratures higher than 1200 K. In despite of safety precautions
to prevent the side-interaction of halogenides with quartz
walls in our experiments, reaction (6) cannot be entirely ex-
cluded and the presence of oxygen-containing gaseous com-
ponents must be taken into consideration.
Summing up, one can state that (i) the chemical transport
of titanium through the gas phase in the form of lower fluo-
rides leads to the formation of the TiC coatings on both types
of carbon fibers, (ii) the process is satisfactory described by a
set of reactions which are similar to those observed earlier in
the Zr–C–CF4 and Hf–C–CF4 systems under RCVD conditions,
(iii) the process can be complicated by side-interaction of gas-
eous fluorine-containing components with quartz walls.
3.2. Coating characterization
3.2.1. SEM/EDS analysis
SEM images of the initial carbon fiber type VMN-4 are repre-
sented in Fig. 1a and b.
The initial fibers exhibit groove-like features parallel to the
fiber axis. Each single fiber consists of very thin fibrils with a
diameter of about 100–200 nm and more. High-magnification
SEM micrograph of the surface of single fiber shows that it
has a block structure. There are slot-like pores with a size of
30–50 nm between fibrils. In turn, fibrils are composed of
blocks with ultra micropores of several nanometers in size.
Carbon fiber type UKN-5000 shows the same morphological
features (not represented here).
SEM images of the TiC-coated VMN-4 fiber are represented
in Fig. 2a–c.
From a survey image (Fig. 2a) one can see that the obtained
coatings are uniform along length and diameter, no any rough
defects were detected on the surface of filaments. Fibers are
not bridged by coating. No breakaway of coating was
observed. The application of coating results in smoothing of
relief of the initial fiber, decreasing in sizes of pinholes. The
coatings repeated a relief of the initial fiber (Fig. 2b), the thick-
ness was found to be around 150–200 nm. The coating ap-
pears to be grain-oriented and built from nanocrystals
264 CARBON 4 6 ( 2 0 0 8 ) 2 6 1 –2 7 1

Fig. 1 – SEM images of the initial carbon fiber type VMN-4: (a) survey image; (b) close view.

Fig. 2 – SEM images of the TiC-coated carbon fiber type VMN-4: (a) survey image; (b) cross-section; (c) close view.

which are directed normally to the surface of filament. With
increasing of deposition time till to 4 h, the crystals sizes of
coatings are increased.
The same morphological features were observed for the
TiC-coated UKN-5000 fiber (Fig. 3a and b). Sometimes, rough
defects as randomly arranged crystals can be seen on the sur-
face (Fig. 3a). They weaken the cross-section of the filaments
and can serve as routes for the fiber failure.
The EDX spectrum of the coated fiber is represented in
Fig. 4. The EDX analysis data show that titanium and carbon
are the main constituents of coating. In some cases, traces of
fluorine and oxygen were also detected in the coating but this

Fig. 3 – SEM images of the TiC-coated carbon fiber type UKN-5000.

 CARBON 4 6 (2 0 0 8) 2 6 1–27 1
Fig. 4 – EDS spectra of the coated carbon fiber.
is very rare occurrence. Several reasons can be as a route for
appearance of oxygen in the coating. Firstly, oxygen can orig-
inate from carbon fiber itself. Further, oxygen contamination
in the outgassing of the apparatus can contribute in the
appearance of oxygen within coating, as was noted by Naslain
et al. [17]. Finally, the appearance of oxygen within coating
can be due to the oxygen transfer from quartz walls on to car-
bon fiber through the gas phase according to reactions (4), (6)
and (7). This transfer is accompanied by a shift of TiCx compo-
sition to lower boundary of the homogeneity region:
TiCðsÞ þ TiOF2ðgÞ ! TiChOiðsÞ þ TiF4ðgÞ : ð7Þ
Earlier, we detected the presence of oxygen in the RCVD-de-
rived HfC coating on carbon fiber by X-ray photoelectron
spectroscopy [10]. One can note that the oxygen transfer
through the gas phase appears to be a common feature for
the processes with participation of halogenides of transition
metals in quartz apparatus (see, e.g. Refs. [13,14,18]), but it be-
comes essential only for long-time experiments.
The presence of F in the EDS spectrum of the coated car-
bon fiber (Fig. 4b) can be due to the adsorption of the gaseous
fluorine-containing compounds (titanium fluorides and/or
oxyfluorides) on the fiber surface with following slow hydro-
lysis during exposition to air [10,19]. To remove the adsorbed
compounds from the fiber surface, an additional heat-treat-
ment of the coated fibers must be undertaken.
3.2.2. AFM analysis
3.2.2.1. AFM analysis of the initial carbon fibers. Among the fi-
ber surface features involved in the interphase phenomena,
the surface roughness and adhesion is seen to be the crucial
ones. Fig. 5 presents AFM topographical images of the surface
of the initial carbon fiber type UKN-5000. As seen in Fig. 5a,
fiber has a well-developed relief. Section analysis shows that
a contour of cross-section is tortuous one. This is owing to the
fact that each single fiber is consisted of fibrils of 100–500 nm
in diameter, with fibrils being oriented parallel to the fiber axe
(Fig. 5b). The structure with ridges and grooves is mainly de-
fined by spinning procedure of precursors. The picture is typ-
ical for ex-PAN fibers and previously was observed by Donnet
and Qin [20,21]. The AFM data are in good accordance with
SEM analysis data of this work.
During scanning in the intermittent contact mode phase
shifts, i.e. changes in the phase angle of vibration with
265
respect to the phase angle of the freely oscillating cantilever,
are present as a phase image (Fig. 5c). Phase contrast image
revealed difference in the local surface properties of the ini-
tial carbon fiber. The difference can originate from the topo-
graphical peculiarities of the surface relief, namely, pores or
from the phases that are distinct by their viscoelastic proper-
ties. Harder and less viscoelastic phases will be brighter than
the softer, more viscoelastic phases. The comparison of the
AFM and SEM analysis data suggests that phase contrast is re-
lated to pores.
Fig. 6a presents AFM images of the surface of the initial
UKN-5000 after subtracting a second-order surface. Statistical
analysis of AFM image allowed us to determine some quanti-
tative characteristics of fiber surface, such as roughness, Ra,
and the arithmetic average of the absolute values of the mea-
sured heights, Rmean (Fig. 6b). Thus, the surface roughness
was found to be 53.9 nm over 3.5 · 3.5 lm2 scanned area. Note
that the roughness value increases with increasing analyzed
area. As can be seen from Fig. 6b, the height distribution for
the initial fiber is very broad, attesting to a wider scatter in
height and nonuniformity of relief.
Fig. 6c presents a cumulative function of the height distri-
bution. It follows from data that a half of measured heights
were less than or equal 190 nm.
According to AFM data, the initial carbon fiber type VMN-4
shows the morphological features similar to fiber type UKN-
5000 (Fig. 7a and b). The surface relief is a stepwise one. Each
filament VMN-4 consists of fibrils of 100–400 nm in diame-
ter, with fibrils being arranged parallel to the fiber axe. We ob-
served a great number of pores (Fig. 7b). For both type fibers
the roughness and the average height values determined over
the same in size scanned areas are close to each other.
3.2.2.2. AFM analysis of the TiC-coated carbon fibers. Fig. 8a–c
presents AFM images of the surface of the TiC-coated UKN-
5000 carbon fiber (deposition time is 0.5 h). It follows from
3D height image that the surface of the coated fiber is rather
uniform and repeats a relief of the initial fiber. Microstructure
features are clearly seen on the lateral mode image (Fig. 8b).
The coating is formed by the radial oriented crystallites, the
vertical size of which is about 100 nm, with crystals having
a high aspect ratio. They are tightly aligned in rows along
the fiber axe. Sometimes, one can observe the aggregates of
crystals of 300–500 nm in size.
266 CARBON 4 6 ( 2 0 0 8 ) 2 6 1 –2 7 1
Fig. 5 – AFM images of the initial carbon fiber type UKN-5000: (a) 3D height; (b) MAG; (c) phase contrast.
A comparison of the height and phase images suggests
that both the initial and coated carbon fibers have a devel-
oped porous structure, with pores being concentrated mainly
between fibrils (Fig. 8b). Fig. 9a and b presents the height and
phase images, respectively, for the same scanned area of the
surface of the TiC-coated carbon fiber type UKN-5000. Com-
parison of images suggests that dark areas marked by arrows
in Fig. 9b originate from large grains on the surface of fiber
(Fig. 9a). Phase shifts in AFM measurements are related not
only to the topographical features but also to the local
mechanical properties of the surface relief. One can discreetly
propose that the grains have mechanical properties which
differ from those of the main phase of coating. Because of
elastic modulus and stiffness of TiCx are greatly dependent
on composition [22] and decreased with decreasing of x and
with increasing of the oxygen content in titanium carbide,
one can also propose that these grains could be by-products
of the chemical transport in the Ti–C–F–SiO2 system. The
EDS data confirm this consumption. Indeed, on the separate
TiC-coated carbon filaments the traces of elemental oxygen
and fluorine were detected by EDS analysis (Fig. 4b). However,
it should be noted that direct measurements of local hardness
and elastic modulus of the coating by nanoindentation tech-
nique must be fulfilled in the future to clarify this issue.
Additional data on relief of the coated fibers can be
obtained from analysis of the cross-sections of filaments.
After deposition of coating the height step is significantly de-
creased (compare 200 nm vs. 60 nm). It can be resulted
from filling up the longitudinal grooves between fibrils by tita-
nium carbide. Relief becomes more smooth and uniform. This
is evidenced, at first, by diminishing of the roughness and the
average height values compared with those for the initial fiber
for the same scanned area (Figs. 10b and 6b), secondly, by nar-
rowing the height distribution for coated fibers. Thus, after
deposition of coating approximately a half of measured
heights were less than or equal 50 nm (Fig. 10c). One can note
that the profile line of cross-section of the coated fibers be-
comes rather tortuous one in comparison with that for un-
coated fiber. It might be associated with more coarse
crystallites of coating compared with particles of carbon core.
SEM analysis data confirm these observations.
AFM analysis on the TiC-coated fiber type BMN-4 revealed
the same features as for UKN-5000 fiber. Rather uniform coat-
ing is formed by titanium carbide crystallites with an ordered
arrangement along the fiber axis (Fig. 11).
3.2.3. Adhesion force measurements
Direct adhesion force measurements on both types of the ini-
tial and coated fibers were carried out to study the local
adhesion characteristics. A variety of cantilever force–dis-
placement response during the silicon nitride tip approach
and retraction of fiber surface was measured at constant
speed. As the cantilever tip is approaching to the fiber surface,
it begins to sense the attractive force from the fiber surface. It
causes the free end of cantilever to bend downward and jump
into contact with fiber surface. During retraction the cantile-
 CARBON 4 6 (2 0 0 8) 2 6 1–27 1 267

50

100
Rmean = 184.8 nm
40
Ra = 53.9 nm
75
30
Counts

50
20

25
10

0 0
0 100 200 300 400 0 100 200 300 400
Height, nm Height, nm

Fig. 6 – AFM image and statistical data for the surface of the carbon fiber type UKN-5000: (a) height image after subtracting of
the second-order surface; (b) height distribution; (c) cumulative function of height distribution.

Fig. 7 – AFM images of the initial carbon fiber type VMN-4: (a) the height image; (b) phase image.

ver tip and the fiber keep together by the adhesion force. with the fiber surface. The interaction between the tip and the
When the tensile load exceeds the adhesion, tip loses contact surface is a sum of van der Waals forces, ionic bonding
268 CARBON 4 6 ( 2 0 0 8 ) 2 6 1 –2 7 1

Fig. 8 – AFM images of the TiC-coated carbon fiber type UKN-5000: (a) 3D height image; (b) phase image.

Fig. 9 – The same scanned area of the surface of the TiC-coated carbon fiber type UKN-5000: (a) the height image; (b) the phase
image.

between the functional groups, electrostatic double layer
forces and capillary forces [23].
Summary of these measurements are represented in
Fig. 12. Each column represents an arithmetic average of three
the probable adhesive force values determined on three dif-
ferent filaments of the same types. In despite of scatter of
data, the tendency is that the adhesive force between the can-
tilever tip (Si3N4) and the TiC-coated carbon fiber is smaller
than the corresponding force between the same tip and the
uncoated fiber for both type fibers. For example, the average
probable adhesion force for uncoated UKN-5000 fiber is
63 ± 13 nN, whereas for TiC-coated 20 ± 1 nN. The correspond-
ing values for VMN-4 fiber are 22 ± l and 10 ± 1 nN, respec-
tively (Fig. 13).
It is interesting question why the application of coating on
carbon fibers leads to a decrease in adhesion force between
the fiber surface and the cantilever tip (Fig. 13). As was deter-
mined in this work, the initial and coated fibers have the sur-
face roughness on several tens of nanometers, with the
roughness of the coated fibers being significantly smaller than
that for the initial fibers. Based on this fact, one can propose
that ‘‘smooth’’ coated fiber would be attracted by the cantile-
ver tip worse than ‘‘rough’’ initial carbon fiber. Besides topo-
graphical features, the chemistry of the surface carbon fibers
can greatly contribute in a decrease of adhesion force.
The AFM results of this work can be summarized as fol-
lows. The initial carbon fibers of both types have the well-
developed surface relief. On the basis of the analysis of the
height and phase images one can conclude that the fiber have
fibrillar structure and pores of 30–50 nm in size are present
between fibrils. In turn, fibrils are composed from blocks. Sta-
tistical processing of AFM data allowed us to determine a set
of quantitative characteristics of the fiber surface, such as the
roughness, the average height, as well as the height distribu-
tion for scanned surface areas. It is shown that the roughness
of the initial carbon fibers is several tens of nanometers and
the average height is about 150–200 nm. The height distribu-
tion is characterized by a wide scatter of the measured height
values that can be an evidence of nonuniformity of relief of
the initial fibers.
 CARBON 4 6 (2 0 0 8) 2 6 1–27 1 269

160

100

120
Rmean = 53.5 nm
Ra = 14.6 nm 75
Counts

80
%

50

40
25

0 0
0 40 80 120 160 0 40 80 120 160
Heights, nm Heights, nm

Fig. 10 – AFM image and statistical data for the surface of the TiC-coated carbon fiber type UKN-5000: (a) height image after
subtracting of the second-order surface; (b) height distribution; (c) cumulative function of height distribution.

70
Uncoated
60
TiC-coated

50

40
F, nN

30

20

10

0
UKN-5000 VMN-4

Fig. 12 – The averaged adhesive forces for Si3N4 tip on the

Fig. 11 – AFM image of the TiC-coated carbon fiber type
VMN-4 (lateral mode).
After application of the TiC coating on carbon fibers, relief
becomes more smooth and uniform for both types of fibers.
This is confirmed by decrease of the roughness parameter
and the average height value, as well as by decrease of scatter
coated and uncoated carbon fibers.
of measured heights. The coating consists of radially oriented
crystals with high aspect ratio. Crystals are aligned in rows
which are parallel to fiber axis. It follows from the phase con-
trast data that the local mechanical characteristics of various
areas of the TiC coating are distinct from each other. Together
with pores, ‘‘soft’’ phases (by-products of the coating process)
270 CARBON
1 that those for the initial desized carbon fibers (2.47 ±
0.8
Σi 0.6
Wei(x)
0.4
0.2
0 as high carbon activity in the gas phase is maintained, solid
0 0.5 1 1.5 2 2.5 3 3.5
σ, GPa
Fig. 13 – Single-modal two-parameter Weibull cumulative
distribution plot of the ultimate strength of the TiC-coated
carbon fibers.
are detected in the TiC coating. The surface modification of
carbon fibers by titanium carbide results in a decrease of
adhesion between the fiber surface and the cantilever tip
regardless of type of carbon fiber. The topographical features
together with the chemistry of the surface modified carbon fi-
bers can contribute in a decrease of adhesion force.
3.3. Tensile strength tests
Mechanical properties of carbon fiber-reinforced composites
depend not only on the interfacial stress transfer capacity
but also on mechanical properties of fibers [2]. Tensile
strength of carbon fibers can be greatly influenced by coating,
especially ceramic coatings which are usually used to protect
carbon fibers from oxidation at high temperatures [8,9,24].
Therefore, it is very importantly to determine the tensile
properties of the coated fiber to evaluate their ability as rein-
forcement for composites. In this work, the single filament
tensile tests of uncoated and TiC-coated fibers were per-
formed at room temperature. Experimental data for the TiC-
coated fibers type UKN-5000 are represented in Fig. 13. The
strength data for individual fibers were analyzed using two-
parameter Weibull function
  m 
x
CDF ¼ 1  exp  : ber surface, including the roughness, the average height, as
h
Here CDF (cumulative distribution function) is the probability
of a fiber having a strength less than or equal to x, x is the
room temperature tensile strength (GPa); m and h are the Wei-
bull shape and scale parameters, respectively. The scale
parameter is a characteristic strength corresponding to
63.2% failed. The application of the single-modal two-param-
eter Weibull function to the failure of fibers implies that frac-
ture is governed by a single flaw population. Fig. 13 shows the
measured and calculated cumulative distribution functions
which characterize the frequency fracture as a function of fi-
ber strength. One can see that experimental data are well-de-
scribed by single-modal Weibull function. The Weibull
parameters extracted from these data are h = 2.55 ± 0.08 GPa
and m = 4.36 ± 0.10 GPa. The parameters are slightly higher
4 6 ( 2 0 0 8 ) 2 6 1 –2 7 1
0.12 GPa and 3.88 ± 0.11 GPa, respectively). The increase in
the fiber strength appears to be related to the elimination of
the surface flaws by TiC coating.
Earlier, it was reported by Himbeault et al. [24] and Aggour
et al. [8] that the fiber strength is greatly reduced by the TiC
coating, especially for the cases when carbon from the fiber
was consumed for carbide formation, e.g. in the CVD or LMTA
(liquid metal transfer agent) approaches. Aggour et al. [8]
found that by increasing the amount of excess carbon in
the feed gas used in the CVD process, the original strength
of fibers was maintained. It was proposed that unless such
4
carbon diffuses from the fiber through the carbide layer to-
ward the surface. Carbon diffusion toward the surface leads
to the formation of internal pores and thus the strength of
the carbon fibers is considerably reduced. Based on these con-
siderations one could propose that at least two reasons,
namely, usage of the carbon-containing gas (CF4) as a feed
gas in our experiments and healing of the large surface flaws
by the coating would result in the increase of the tensile
strength of filaments.
4. Conclusions
Chemistry, morphology, and topography of the titanium car-
bide modified carbon fibers have been studied in this work.
Major experimental results can be highlighted as follows:
Titanium carbide coatings were successfully applied on
carbon fibers using RCVD approach. The scheme describing
the reactions in the Ti–C–CF4 system has been proposed.
The process is complicated by side-interaction of gaseous
fluorine-containing components with quartz walls of reactor.
The main constituents of coating are titanium and carbon. In
some cases, oxygen and fluorine are present as contamina-
tion in the coating. The contamination of coating can be af-
fected by several factors, with side reactions of gaseous
components being considered as dominant ones.
Uniform, adherent, crack-free and non-bridging coatings
were obtained at rather low temperature. The study of the ini-
tial carbon fibers of both types by SEM and AFM showed that
they have fibrillar structure and, as a consequence, the well-
developed surface relief. Quantitative characteristics of the fi-
well as the height distribution for scanned surface areas were
determined by statistical processing of AFM data. The rough-
ness of the initial carbon fibers is several tens of nanometers
and the average height is about 150–200 nm. The height distri-
bution is characterized by a wide scatter of the measured
height values that can be an evidence of nonuniformity of re-
lief of the initial carbon fibers. After application of the TiC
coating on carbon fibers, relief becomes more smooth and uni-
form for both types of fibers. This is confirmed by decrease of
the roughness parameter and the average height value, as well
as by decrease of scatter of measured heights. The coating
consists of radially oriented crystals with high aspect ratio.
Crystals are aligned in rows which are parallel to fiber axis.
Local mechanical characteristics of various areas of the
TiC coating are distinct from each other. Together with pores,
 CARBON
‘‘soft’’ phases (by-products of the coating process) were de-
tected in the TiC coating. The surface modification of carbon
fibers by titanium carbide results in a decrease of adhesion
between the fiber surface and the cantilever tip regardless
of type of carbon fiber. The topographical features together
with the chemistry of the surface modified carbon fibers
can contribute in a decrease of adhesion force.
An increase in the tensile strength has been achieved by
introducing the TiC coating on carbon fiber, the average
strength and the Weibull modulus parameters were
2.55 ± 0.08 GPa and 4.36 ± 0.10 GPa, respectively. The increase
in the fiber strength appears to be related to the elimination
of the surface flaws by TiC coating. One can conclude that
the proposed coating process is promising because it im-
proves the mechanical properties of carbon fibers.
The obtained results can useful for the predictive design of
the well-matched interphase zone for composite materials
reinforced by carbon fibers.
Acknowledgement
The authors acknowledge the technical assistance of Mrs.
Tatyana Naimushina (ISSC SB RAS).
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