TITANIUM CARBIDE COATINGS ON STEEL :

STUDY OF THE CONDITIONS OF ELABORATION

AND OF SUBSTRATE-COATING INTERACTIONS
A. Derre, F. Teyssandier, M. Ducarroir

To cite this version:

A. Derre, F. Teyssandier, M. Ducarroir. TITANIUM CARBIDE COATINGS ON STEEL : STUDY
OF THE CONDITIONS OF ELABORATION AND OF SUBSTRATE-COATING INTERACTIONS.
Journal de Physique Colloques, 1989, 50 (C5), pp.C5-445-C5-453. <10.1051/jphyscol:1989556>.
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 JOURNAL DE PHYSIQUE
Colloque C5, suppl6ment au n05, Tome 50, mai 1989

TITANIUM CARBIDE COATINGS ON STEEL : STUDY O F THE C O N D I T I O N S O F ELABORATION

AND O F SUBSTRATE-COATING INTERACTIONS

A. DERRE, F. TEYSSANDIER' and M. DUCARROIR'

E.T.C.A., 16 bis avenue Prieur de la CGte d'Or, F-94114 Arceuil Cedex,

France
'CNRS-IMP, UniversitB, avenue de Villeneuve, F-66025 Perpignan Cedex,
France
Resume

La tn6thodologie des plans d'exMrience a et6 appliqde au &p6t de Tic sur des aciers
hypoeutectoi'desfaiblement allies. Des d l e s descn'ptiis de I'epaisseur du revQtement et
de la variation de poids ont et6 obtenus et cor6kSs a des calculs thermodynamiques dans le
domaine exp6rimental envisage. Les surfaces de kponse correspondantes ont ete
utilisees pour etudier quelques proprietes. I1 a ete observe que pour une epaisseur
constante, le coefficient de frottement du couple Ticlacier varie fortement avec la
morphologie qui est fonction du mecanisme de dep6t.
Les valeurs elevees des microduretessont attribuees a un effet de taille de grains. Les
contraintes r6siduelles ont ete evaluees. I1a ete montr6 que la decarburation du substrat
dam les conditions geMralement utilis6es ne peut gtre completement evitee.

Abstract

The methodologyof experimental designs was applied to the deposition of Tic on weakly
albyed hypoeutectoYdsteels. Models describing the coating thickness and weight change
were obtained and correlated with thermodynamic calculations. The corresponding
response surfaces were used to study some properties of the deposits. The friction
coefficient of a titanium carbidelsteel couple has been observed to present a particularly
large variation with respect to the surface morphology, which depends on the experimental
conditions.
The highvalues of mimhardnesswich mere measured mere presumed to be induced by
a grain size effect. The residual stresses bere evaluated. It has also been Shown that
substrate decarburization cannot be completely avoided with the usual coating conditions
used by previous authors.

Titanium carbide has been used as wear protecting coatings for many years. Initially deposited on
cemented carbide cutting tools (inserts), its application field extended with the diversity of the materials used
as substrate. In particular, as an exemple a large range of steels are processed industrially by chemical
vapor deposition, in order to give them useful surface properties. Their main composition fields are
presented on the isothermal section of the iron-carbonchromiumphase diagram in fiiute 1. This is of course
a s i m p i i i diagram, since other minor alloying elements (V. W, Ni..) are also present "A" corresponds to
highly alloyed high carbon steels (too! steels) [I]. In the "B "field, the less alloyed hypereutectoi'd steels
correspond to the cold working steels, used to manufacture parts such as pumhes, extruding nozzles or
ceramic powders compactiqndie. Low alloyed hypereutedcii'd steels (the "C "field) are used for bearings[2].
The high albyed hypoeutedoidsteels of the "D" field are used to protect parts against chemical conosbn or
high temperature damage (valves, push-rods, cams,...). On the other hand, the low alloyed hypoeutectoi'd
steels ("E " ) a r e nowadays only rarely coated with titanium carbide. This kind of steel is widely used in
mechanical engineering, and such a p m s s i n g would increase the reliability of parts working under severe
conditions.
The purpose of this wrk is thus to study the coating conditions of titanium carbide on low carbon sbeei and
to determine the influence of various parameters on the properties of the coated substrates. This work also
deals with solidlgas reactions and diffusion phenomena occuring during coating.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1989556

 JOURNAL DE PHYSIQUE

2-EXPERIMENTAL DEVICE
The coatings ate achieved on inductively heated polished samples (diameter = 16mm, thickness = 5mm)
in a cold wall reactor. Temperature is measured by means of a thermocouple welded by spark discharge at
the bottom of a hole drilled into the steel. The flow rates of the permanent gases (hydrogen and methane) are
set by means of mass flowmeters. The molarfraction of the titanium tetrachloride is cont~lledby a dew point
evaporator [3]. At the end of the experiment, the sample is cooled under a hydrogen flow.

3- EXPERIMENTAL RESULTS AND DISCUSSION

3-1 Determination of the response surface

Most of the experimental situations require the examination of the effect5 of varying tvvo or more factors. It
has been shown [4 -51 that in order to obtain a complete exploration of such a situation it is not sufficient to
vary one factor at a time, but all combinations must be examined in o&rto elucidate the effect of each factor
and the possible ways in which one may be modified by the variation of the others. In this case a generally
useful technique is provided by factorial design. When the expeded number of experiments generated by the
choice of the factors is too high a fractional factorial design may be used.

This method has been described elsewhere [6] and applied to the present study with the following
observed responses :
- (Am) :weight variation of the sample .
- (e) :thickness of the coating measured by a spherical wear technique.
Among all the factors, temperature (T),total pressure (P), the initial molar fraction of methane in the gas
phase (X,J and duration of the deposit were previously determined to be preponderant parameters [6]
The response surfaces were then obtained according to an experimental design, proposed by HOKE IT].
The various levels selected for each of the four parameters are presented in table 1 ( Xc = 0 means that all
the carbon comes from the substrate). The resutting response surface can be described by a second degree
polynomial expression.
e =7.99+2.45 T + 1 . 8 t + 1 . 0 7 ~ ~ + 0 . 8 5 ~ + 1 . 1 7 ~ ~ + 0 . 7 6 ~ ~ ~ + 1 . 1 4 ~ ~

- 1.35~: +2.13$
The relative importance of the factors agrees wII with the results of the previous experimental design.
Some isoresponse surfaces are plotted against T,Xc,t for several total pressures (figure 2 and figure 3).
The surfaces representingthicknesses are almost flat because of the weak interactions between the T, t,
atxi Xc parameters. As they are parallel to the (111) plane the variation of one of them may be
counterbalanced by a variation of the opposite amount of one of the two others in order to obtain the same
thickness. Similar behavior is observed for mass variation under atmospheric pressure.
The shape of the surfaces under reduced pressure is no longer a plane as a consequence of a strong
coupling effect between two main parameters XcP.
Due to the difficulties encountered in explaining these results a composite response (R) has been
calculated (ratio of the mass variation, Am, to thickness, e) :
R=Me
Its variations are plotted versus T and t in figure 4.
If mass variation is only growth rate dependent , this ratio would be constant whatever the coating
conditions and would be equal to 2.5 according to the geometry of the sample and the titanium carbide
density.
~, ,h,k, -K?,u,,IH ,; c;;nfi;;md iixle; atmospheric pressure (figure 4a, X, = 0.1). Under reduced pressure, the
-I I-

ratio (R) is lower and can even be negative (grey part of the surface), which can be interpreted as the
simultaneous growth (experimentally observed) of a titanium carbide coating and a global weight loss of the
sample. This unexpected behavior is attribued to the formation of iron chloride FeCI2, due to a chemical
exchange reaction between titanium chlorides and steel. As a matter of fact thermodynamic equilibrium
calculations show the increasedformation of FeCI2 when pressure is decreasing. In an open system, this
formation of iron chloride is enhanced and leads to a global weight loss of the substrate-coating couple.

Titanium carbide as coating is mostly used for its tribological properties. Preliminary resutts have been
used to characterize the coatings in term of friction. Three series of coatings with a constant thickness (5pm)
were prepared under different conditions according to the previous response surface; their behaviors are
presented in figure 2a (series A, 6 and C). As scratch tests showed that the corrosion of the substrate was
responsible for poor adhesion, the total p ~ s s u r was e fixed at 1 atm in order to reduce the formation of iron
dichloride.
In the pin on disc type friction tests, the pin is composed of a 35 NCD 16 (9335) steel treated at 1800 MPa.
The samples "A", made without methane inthe gas phase, present a friction coefficient which, after trans*Non,
leads to a final friction coefficient of 0.25-0.3 (figure 5). The "B "series behave diffe~ntly,since the final friction
coefficient is 0.650.7 (figure 6).
This variation can be related to the surface morphology of the samples. The samples "A" are rather
smooth (Ra = 0.2 pm) (figure 5b), presenting a "paving block" structure. These blocks correspond to the
austenite grains at the beginning of the experiment. This particular relief resultsfrom the d i i i o n a l growth of
the titanium carbide. On the other hand, samples prepared under high methane molar fraction O(,= 0.1) differ
by the presence of an extra, much thinner relief (figure 6b). The fact that the "paving block" type of relief
remains seems to prove that the diffusional component of growth is still present under these conditions, at
least at the very beginning of deposition. The thinner relief can be assigned to the, growth mode using
methane from the gas phase. On the other hand, this last relief is responsible for a high friction
coefficient.
The third series of samples, "C", obtained for an intermediate molar fraction of methane, presents both
types of friictional behaviour (A and B) according to the samples. No intermediate friction coefficient (between
0.3 and 0.7) is observed.
This non-reproducibility can be interpreted as a competition between the two growth modes. This is
confirmed by the surface morphology (figure 7). In t hiscase the relief associatedwith the growth mode wiEn
using methane appears first on the thickest parts of the coating (in the middle of the "paving blocks"). So it
seems that the chosen coating conditions correspond to the boundary beyond which the growth mode from
the gas phase is preponderant. The presence or absence of the extra relief related to the preponderant
growth mode extensively modifies the friction coefficient. The non-reproducibility could thus be due to an
uncertainty in controlling the experimental parameters.

3-3 Microhardness promrties

A high surface hardness is one of the most attractive feature when coating metallic parts with ceramics
such as titanium carbide. In figure 8, the V i e r s hardnesses, are plotted against the indentationload for b w
coatings prepared under different conditions (T = 1050"C, P = 1 atm, t = 90mm, X,= 0 and 0.1). The measured
thicknesses are respectively 9 and 15 pm.
In order to measure only the properties of the deposit, the volume of the plastic zone developed under the
indenter must not exceed the thickness of the layer. As a rule of thumbthese requirements are met when the
indentationdepth (h) is less than a tenth of the coating thickness (e). This empirical rule has been confirmed in
the case of titanium carbide [8] and the corresponding validity range is presented in figure 7. The
microhardnessof both coatings are similar.

The measured values (3500kg/mm-~-100~)

seem rather high in comparison with most of the published
- other hand, the harriness of coatings at higher temperature (T = 1600'C) [3] decreases to
va!ues; On the
2200 kg mm-' under a load of 100 g. This wide range of variation may be related to the modificationof the
grain size from 100 pm at lEOO°C to 50 to IOOnm at 1050°C as demonstmted by SEM (figm 9) 2nd TEM
C5-448 JOURNAL DE PHYSIQUE

@gum10). This change of microstNchrre b mainly mponsiblefor boththe hardening of the material by grain
size effect and the scattered measurements found in the literature.

3-4 Residual stresses

Inadditon to the high hardness and the low friction coefficient of the deposit it is also necessaryto ensure a
good adhesion to the substrate. Large amounts of residual macro stresses stored in the coating can be
responsiblefor it flaking off. For these reasons sVesses have been measured by theX- ray d i c t i o n method
[91. The measurement of the lattice spaang dhkl with respect to the Jr angle bebeen the perpendicularto the
plane and the perpendicular to the surface, allows the calculation of the residual stress in the coating
(equation 1) assuming a plane stress state. Figure 11 shows the variation of the diffraction angle 20 versus

2, ,e - 2 e+, = - ----- -
+
cotg e+,
360
E
"
- q,sin2I
n
(equation 1)

With E = 455 GPa [lo] and v = 0.19 (Poisson's ratio) respectively, a compression stress of 2000 MPa is
obtained. A calculation based on the theory of elasticity and assuming a perfect adhesion at the interface [ I 11
allows us to conclude that the mismatch beween the thermal expansion ooeff'ints of steel ( a =12 10-6K- 1)
and titanium carbide (a = 7.4 lo4 K-l) is mainly responsiblefor the measured stresses .When the thiness
exceeds 10 pm the stress value d m p rapidly to 780 MPa. A partial relaxationof stms is observed when the
elastic energy stored in the film, and which increases with its thickness, is high enough to allow crack
propagation within titanium carbide. This cracking starts at the interface, as shown in the figure 12, and
induces considerable flaking off .

3-5 Modifications of the substrate composition

The main problem encountered when coating steel pieces with titanium carbide is the decarburization of
the subsrate [12-1Sj. This phenomenomhas been mentioned in the paragraph3-2. Inthe case of low alloyed
hypoeutectoidsteels, the change in compositionof the substrate is harmful since it provokes a severe drop in
the mechanical properties of the steel.
The direct measurement of decarburization by microprobe analysis leads to large discrepancies. This
decartxlrization has thus been qualitatively observed by Vickers indentations (bad 100 g). All the samples
were oil quenched at the end of the experiment in order to prevent further modification of the carbon
distribution by a nucleation and growth process. Figure 13 shows the resuk measuredon three samples 35
CD4 steel (4135) coat& with a methane molar fraction of 0,0.05 and 0.1 respectively (P = 1atm, T = 1050"C,
t = BOmn, XTiC14 = 8 1iT3). For X , = 0, the drop of hardrsssfmm the middle of t
k sutxtfate (x= 2.5mm) to tts
deposit interface (x = 0 mm) is considerable and the decarburization affects almost all the substrate
thickness (total thickness 5 mm). While an increase in the methane molar fraction (Xc = 0.05) reduces the
level and depth of decarburization, it does not completely prevent this phemmenom, even for the highest
concentration (0.1). Afurther increase in methane concentrationwould give homogeneous nudeation into
the reactor under atmospheric pressure.
As a consequence, substrate decarburization cannot be completely avoided within the studied
experimental field which corresponds to the conditions generally used.

The main factors controlling the chemical vapor deposition of titanium carbide on steel have been
determined by means of an experimental design. The role of the total pressure on steel corrosion has been
interpreted using thermodynamic equilibrium calculations. This corrosion is induced by the iron- titanium
chemical exchange by means of chlorides, and is enhanced under reduced pressure. Coatings of identical
thickness have been prepared according to the response surfaces previously determined. Their friction
coefficients are nevertheless strongly affected by the coating conditions, mainly by the methane molar
fraction. This variation can be explained as the result of a competition between Wo growth modes : carbon
coming from methane or from steel . Diffusion of carbon from the steel substrate cannot be completely
avoided under normal coating conditions, even by increasing the methane molar fraction until homogeneous
nucleation appears. The mismatch between the thermal expansion coefficients of steel and TIC induces
compressive stresses in the coating. This stress can be high enough to allow crack propagation within
titanium carbide and subsequent scaling.
This study has been completed recently and solutions allowing the preventionof steel decarburization
have been found [20]. These results will be presented in a further publication.

REEFERENCES
[l] T. SADAHIRO, S. YAMAYA, K. SHIBUKI, N. UJllE
Planseseminar, Reutte Tirol, Bettray 32 Vorabdnrck, (1977),Vol. 2,32, 1-13
[2] H.J. BOVING, H.E. HINTERMANN, G.STEHLE
Journal of the American Society of Lubrication Engineers, Septembre, (1981),
534-537
[3] F. TEYSSANDIER
TMse, Gtenoble, 31 Octobre (1986)
[4] R. PHAN TAN LUU, D. FENEUILLE, D. MATHIEU
"Methodologie de la recherche ex@rimentale", Cycle d'actualisation des connaissances
IPSOI, Universitt5, rue Henri Poincarr5,13397 Marseilles Cedex
[5] G. E. P. BOX, L. R. CONNOR, W.R. COUSIN, 0. L. DAVIES, F. R. HIMSWORTH, G. P.
SlLLlTrO
"The design and analysis of industrial experiments", 0. L. Davies editor. (1963)
[q A. DERRE, M. DUCARROIR, F. TEYSSANDIER
J. Electrochem. Soc., Vol. 136,No. 3,March (1989), 853-858
m A.T. HOKE
Technometrics, Vol. 17,No. 3,(1975),375
[8] E. HUMMER, A.J. PERRY
Thin Solid Films, 101, (1983),243-251
[sl G. MAEDER, J.L. LEBRUN, J.M. SPRAUEL
Materiaux et Techniques, Avril-Mai, (1981), 135149
[lo] G.V. SAMSONOV, J.M. BlNlTSKll
Refractory Compounds Handbook, Metallurgy, Moscow, (1976)
[I11 A. DERRE
"DeNt chimique en phase gazeuse de carbure de titane sur acier", TGse, Universite de
Perpignan, 24 Novembre (1 988)
[12] W. RUPPERT
GLASKI F.A. (Ed), Proceedings of the Ill InternationalConference on CVD, American Nuclear
Soc., Hinsdale, (19721,Salt Lake City USA, 34G351 + 754
[13] P.J.M. VAN DER STRATEN, G. VERSPUI
Philips tech. Rev. 40, (1982)'No.7.204-210
[14] A.J. PERRY, E. HORVATH
Metals and Materials, October, (1978),37-40
[15] K. ROSER
WAHL G. , BLOCHER J.M. ,VUILLARD G.E. (Eds), Proceedings of the Vlll International
Conference on CVD, Electrochem. Soc., Princeton, (1981),Paris FRANCE, 586-597
[16] P.P.J. RAMAEKERS, F.J.J. VAN LOO
BLOEM J. , VERSPUI G. , WOLFF L.R. (Eds), P w e d i n g s of the IV European Conference on
CVD, (1983), Eindhoven THE NETHERLANDS, 546-552
[lTj S.G. YOON, H.G. KIM, J.S. CHUN
Journal of Materials Science 22, (1987),2629-2634
[18] A.J. PERRY, E. HQRVATH
Thin Solid Films, 62,(1979), 133-143
[lq P.J.M. VAN DER STRATEN, M.M. MICHORIUS, G. VERSPUI
BLOEM J. , VERSPUI G. , WOLFF L.R. (Eds), P m e d i n g s of the IV European Conference on
CVD, (1983),Eindhoven THE NETHERLANDS, 553-567
1201 A. DERRE, F. TEYSSANDIER
Brevet NoF 88 10553,04Aoi3 (1 988)
 JOURNAL DE PHYSIQUE

Fiaure 1: isothermal section of the iron-carbon-chromium phase diagram at 1000°C

Table 1: variation range of the experimental parameters

LEVEL
-1 0 +1
Temperature T ("C) 950 1000 1050
Duration of the depositiont (mn) 30 60 90
Fraction of methane Xc 0 0.05 0.1
Total pressure P (atm) 0.005 0.07 1

(4 (b)
Fiaute 2: thickness i-sponse (5 pm) with respect to T, t and Xc; (a) P = 1 atm; (b) P = 5 atm
 90 90
30 t (mn> 30 t <mn>

(a) (b)
Fiaure 3: wight isoresponse (5 mg) with respect to T, t and Xc; (a) P = 1 atm; (b) P = 5 1 f l atm

90 90
30 t <mn) t <mn)

(a) (b)
Fioum 4: variation of the wight/thickness ratio with respect to T and t for Xc = 0.1; (a) P = 1 atm;
(b) P = 5 lom3atm

Fiaure 5: tribological study of samples "A" made without methane in the gas phase; (a) friction
coeffiientwith respectto the time; (b)surface morphology
C5-452 JOURNAL DE PHYSIQUE

Fiaure 6: tribobgical study of samples "B" achieved under high methane molar fraction; (a) friction
coefficient with respect to the time; (b)surface morphology

6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
Eg!n%Esurface morphology 1000
of samples "C" obtained for an 20 30 40 50 60 70 80 90 100
intermediate molar fraction of
methane Figure 8: Vickers hardness in respect with the indentation load
for two coatings achieved with (Xc = 0.1) or without methane
in the gas phase (Xc = 0)

Figure 9: microstructure of coating

Fag% 10: K~cE,+~WE of coating obtained at 16000~2(SEM)
obtained at 10WC (TEM)
 2
SIN Y
I I I I I
153
0,O 0,1 02 03 04 0,s 0,6

Fiaure 11:variation of the diffraction angle 28 versus sir?Y

Fiaure 12: crack propagation within titanium carbide coating

Fiaure 13: Vickers hardness of the steel substrate versus the

distance from the titanium carbidelsteel interface