POWDER METALLURGICAL MATERIALS, PARTS, AND COATINGS

FLAME-SPRAYED COATINGS WITH LOW-MELTING-POINT METAL UNDERCOATS

I. L. Kupriyanov, R. A. Azizov, UDC 621.762

V. A. Kot, and L. I. Sevkovskaya

The principal criteria determining the service performance and quality of a flame-
sprayed coating are its structural state, adhesion to its base, and the residual thermal
stress generated in it. A residual stress in a coating, of course, has a marked deleterious
effect on its operating properties, in particular wear resistance, fatigue strength, corro-
sion resistance, and adhesion [I, 2]. One of the key problems in the theory and practice of
flame spraying therefore is to reduce to a minimum the residual thermal stresses set up in
coatings.
In [3] it is noted that residual stresses in coatings can be decreased by employing
undercoats of low-melting-point metals. However, a survey of literature sources has shown
that this method has not yet been investigated fully. In this connection, the present work
was undertaken with the aim of establishing the basic laws of the generation of residual
thermal stresses in coatings on low-melting-point undercoats and of studying the effect of
these stresses on the operating characteristics of coatings, in particular their adhesion to
bases and wear resistance.
Flat type 45 (0.45% C) steel specimens were provided with 30- to 50-Dm-thick tin, cad-
mium, and zinc undercoats by immersion in molten metal under a layer of flux.
Type 65G (0.65% C-Mn) steel coatings were applied to the specimens in a (French-made)
SNMI apparatus with a Top-Jet/2 spray gun. The ~tructural state and phase composition of
coatings, with allowance for changes in their physicomechanical properties, are the basic
factors in the choice of spray-deposition conditions. Deposition under optimum conditions
results in the formation of coatings which are structurally homogeneous and free both from
defects such as pores, blowholes, cracks, and discontinuities at their phase boundaries with
low-melting-point undercoats and from intermeallic phases.
Metallographic examinations revealed that deposition was accompanied by vigorous pro-
cesses of thermal and physicochemical reactions between the molten particles being deposited
and the low-melting-point undercoats. This was indicated by the formation of a very well-
developed coating/undercoat interface with a virtually total absence of oxide inclusions
(Fig. la) and by the existence of an intermediate intermetallic zone in a region adjacent
to the zinc undercoat (Fig. ib).
A study, performed using a (French-made) MS-46 microanalyzer, of the element concentra-
tion distribution over the thickness of the coating-undercoat-base composite revealed the
presence of i0- to 20-~m -thick diffusion zones. The coatings were subjected to phase ana-
lyses in a DRON-3.0 diffractometer in Co K s radiation, as a result of which the following
intermetallic compounds were detected: FesZn2!, Fe3Zn10, and FeZn 7 on the zinc undercoat
and Fe~Sn, Fe2Sn, FeSn, and FeSn 2 on the tin undercoat. No chemical compounds were found on
the cadmium undercoat.
The stressed and strained state of the coatings on the low-melting-point undercoats was
studied by a method consisting in layer-by-layer removal of metal and recording specimen de-
flections [4]. A diagrammatic representation of the experimental apparatus employd is shown
in Fig. 2. A 4732F3 electric-spark machine was employed for removing 0.l-mm-thick coating,
undercoat, and base metal layers. Specimen strains were measured, using dial indicators,
with accuracy to • Bm.
On the basis of a formula relating residual stresses in a beam of constant cross sec-
tion and varying elastic modulus to its deflections [4], for a three-layer composite we can
write the following expression:

Belorussian Scientific Production Powder Metallurgy Association. Translated form Poro-

shkovaya Metallurgiya, No. 2(314), pp. 27-30, February, 1989. Original article submitted
December 29, 1987.

98 0038-5735/89/2802-0098512.50 9 1989 Plenum Publishing Corporation

 TABLE i. Comparison of Operating Characteristics of Coatings
with and without Low-Melting-Point Undercoats
Undercoat material Coating
Characteristics of coating without un-
Sn [ Cd Zn dercoat

Coefficient Ko 2,43 1,51 1,32 1

Adhesion, MPa a4,0 25, 1 21,8 17,3
Rel. wear resistance without
lubricant 1,44 1,35 I, 15 I
Re1. wear resistance with lubricant 1,38 1,30 1,12 1

Fig. i~ Microstructures of transition zones in coatings depo-

sited on tin (a) and zinc (b) undercoats.

8G [ # (a) o ]
a (a) = ~ N (a) da a~ (a) (h - O f (a) - g ( a ) ,f M (~) d~ , (i)
0

where N(a) = B(G)[h - a - e(a)] -I,

B (~) ] df(~)
M (~) - - A (~) (h ~ ~ - - e (a)) - - 3e (~) d$ '

A (a) = ll - - a + E~I 2 + E313, h = li + l, + I3,

(2)
B (a) = (h - - a - - e (a))3 - - (12 + 13 - - e (a)) 3 + [(l~ + l 3 - - e (a)) 3 - -

- - (/~ - - e (a))~] ~ + [(& - e (a)) 3 + e3 (a)l ~ ,

E, = E2/Et, E3 = EJE~, E(a) = E (a)!Ev

Here El, E2, and E 3 are the elastic moduli of the coating, undercoat, and base materials,
rspectively; gl, ~2, and ~a, the coating, undercoat, and base thicknesses, respectively; a,
the thickness of the material layer removed from a portion of length ~; and e(a), the speci-
men deflection.
The distribution of the residual stress in the coatings with the low-melting-point
undercoats had a fairly complex character (Fig. 3). The highest tensile stresses were exhi-
bited by the coatings without the undercoats~ It is interesting to note that within the
coatings there were zones with the maximum stress Oma x. It will be seen from the figure
that, with rising melting point of the undercoat material, these zones shifted toward the
base, and the value of Oma x increased. With the zinc undercoat, an additional tensile stress,
due to the formation of intermetallic compounds, was generated in the region of the coating
adjacent to the interface. The results obtained can be interpreted from the point of view
of relaxation of the residual thermal stresses in the coatings thanks to the presence of Very
ductile low-melting-point layers in the systems.
To a first approximation it may be assumed that relaxation of the stress comes to an end
at the instant when the undercoat passes, during cooling, from a ductile into an elastic
state, to which there corresponds [5] a critical temperature Tcr = Tm/3 (Tm is the melting

99
 [~
;~ ~/.." }&7:;-:~
...... ! ~ I ~
i:i:-:::~:i[/jY////,//////C-/J2
F Ii
....... ~ I 2

~ili:::::-;.~i ~::~si::!i.':~iiil ~}
,

n.;.,;, 6,8 a,m m

l~g. 2 Fig. 3
Fig. 2. Diagrammatic representation of apparatus for measuring specimen
deflection: I) site of material layer removal; 2) e~tension strip; 3)
support with bearing; 4 ) w i r e electrodel 5) base metal; 6) indicators;
7) undercoat; 8) coating.
Fig. 3. Distribution of residual thermal stress over thickness of coat-
ing, undercoat, and base: i-3) coatings with tin, cadmium, and zinc
undercoats, respectively; 4) coating without undercoat; 5) base without
coating. Zones: i) coating; II) ~ndercoat; III) base.

point of the undercoat material). In view of the fact that the negative gradient forming
during spraying continually lowers the undercoat temperature, it is possible to conclude that
there exists a critical coating thickness s and that at greater thicknesses the relaxing
action of the undercoat on the generation of the.residual stress becomes negligible. From
this it follows that the lower the melting point of the undercoat material, the larger is
s 9
Because of the fairly complex character of distribution of the residual stress in coat-
ings on low-melting-point undercoats, in a quantitative assessment of this stress it is con-
venient to introduce a coefficient K o defined by the expression
J

Ks = ~oiI% (3)
where,01 and ~i are, respeetlvely, the mean integral stresses in a coating without and with
a low-melting-point undercoat. Using Eq. (3) and o vs a curves (Fig. 3), in the present
work the following values of K o were obtained: K~ n = 2.43, K~ d = 1.51, and K~ n = 1.32.
These values of K O lead to the conclusion that the effectiveness of. an undercoat grows with
decreasing melting point of the low-melting-point metal.
Values of K o may be employed for establishing the relationship between the mean level
of the residual stress and the operating characteristics of coatings. In this work a study
was made of the wear resistance of thecoatings and their adhesion to bases. Adhesion deter-
minations were made using a (British-made) Instron-l195 tensile testing machine. Loads were
measured with an error of not more than • The rate of displacement of the measuring
pin within its holder was 0.5 mm/min. A (West German-made) Optima apparatus was used for
determining the wear resistance of the coatings. Before testing, the coatings were ground
to a surface roughness R z = 0.32-0.63 ~m. The mating part was a 10-mm-diameter ShKhl5 ball-
bearing steel sphere. Surface lubrication was with M-10G2 oil (GOST 8581-78 standard) fed
into the rubbing zone at a rate of 2 drops/min. Tests were carried out at a sliding velo-
city of 0.18 m/see, a specific load of 3.4 MPa, and a temperature of 323~
The results of this investigation (Table i) show that the residual thermal stress had
an adverse effect on the operating characteristics of the coatings. Incidentally, it will
be seen that the coefficient K o constitutes a reasonably objective criterion in an assess-
ment of the effectiveness of employing low-melting-point undercoats as a means of improving
the quality of flame-sprayed coatings.
In the light of the results of this work it may be concluded that the method under con-
sideration offers considerable promise, since it enables coatings to be applied having lower
residual thermal stresses and improved operating properties.

i00
 LITERATURE CITED

i. G. G. Maksimovich, V. F. Shatinskii, and V. I. Kopylov, Physicochemical Processes in the

Plasma Spray-Deposition and Rupture of Materials with Coatings [in Russian], Naukova
Durmka, Kiev (1983).
2. I . M . Fedorchenko, E. I. Ishchenko, and A. I. Bezykornov, "Residual stresses in plasma-
deposited coatings," in: Protective Coatings on Metals [in Russian], Vol. 14 (1980),
pp. 55-57.
3. A. A. Appen, Heat-Resisting Inorganic Coatins [in Russian], Khimiya, Leningrad (1967).
4. L. I. Dekhtyar ~, Determination of Residual Stresses in Coatings and Bimetals [in Russian]
Kartya Moldovenyaske, Kishinev (1968).
5. No V. Avdeev, Metal Deposition [in Russian], Mashinostroenie, Moscow (1978).

MECHANISM OF FORMATION OF CHROMIUM DIBORIDE-BASE GALVANOPHORETIC

COATINGS

Yu. Ao Guslienko, I. Mo Fedorchenko, UDC 621.762

and Io O. Shmatko

In [I] the mechanism of liquid-phase sintering of refractory compounds with good wett-
ability by a nickel-base galvanic sublayer (8 < 30~ was investigated. The possibility of
describing the process of liquid-phase sintering in obtaining galvanophoretic coatings by
the equation of M. Avra~mi for the processes of origin of a new phase were considered~ The
parameter ~u, the time of occurrence of the process under unsteady conditions, in this equa-
tion determines the length of the isothermal hold at the melting point of the galvanic sub-
layer to obtain structures with directed crystallization of the refractory phase. It has
been established that in this case structure formation may be divided into three stages, the
activation period, when solution in the liquid phase of fine crystals and accomodation of
the form of the coarse crystals of the refractory phase occur, the period of intense alloy-
ing, for which active and rapid origin and growth of refractory phase crystals is character-
istic, and the saturation period, during which significant changes in the galvanophoretic
coating do not occur despite the further increase in the time of the isothermal hold. The
first two stages are of important value for creation of a structure with directed crystal-
lization of the refractory phase. It was established that the time of unsteadiness and the
rate of origin of the crystals of the refractory phase depend substantially upon the quantity
of liquid phase, that is, upon the thickness of the sublayer. However, the kinetics of
growth of the new phaseduring liquid-phase sintering of galvanophoretic coatings and the in-
fluence of the galvanic sublayer material on this process have not been investigated.
In accordance with the method of [i] specimens with an iron-and a cobalt-containing
eutectic subayer were divided into groups in relation to the ratio of the thicknesses of the
phretic and galvanic layers K (Table i). As the result of the fact that the process of
liquid-phase sintering of ga!vanophoretic coatings with directed crystallization of the re-
fractory phase has been studied in detail for a CrB2-base galvanophoretic coating with a
nickel-containing eutectic, this system was selected as the standard in comparison with
chromium diboride-base galvanophoretic coatings with cobalt- and iron-containing eutectics.
For the systems with cobalt- and iron-containing eutectics galvanophoretic coatings were ob-
tained with directed crystallization of the refractory phase with K = 0.1-1.05. With K <
0.4 the refractory phase content in the coating is low and a galvanophretic coating structure
is formed with single CrB 2 inclusions randomly distributed in the coating thickness. With
K < 1.05 only a structure with refractory phase inclusions of different size and color occur
and as the result of these reasons the possibility of controlling the structure formation
process is completely absent.

Institute of Problems of Material Science, Academy of Sciences of the Ukrainian SSR.

Translated from Poroshkovaya Metallurgiya, No. 2(314), pp. 31-35, February, 1989. Original
article submitted July i, 1987.

0038-5735/89/2802-0101512.50 9 1989 Plenum Publishing Corporation I01