CLEANING THE BASIS METAL OF SURFACE FILMS IN THE SPRAY-

DEPOSITION OF POWDERS

Yu. A. Kharlamov UDC 621.793.7

The collision of molten powder particles with the basis metal is accompanied by their
intense spreading, followed by solidification. It is considered that a strong pressure pulse
in the collision zone promotes purification of the basis metal surface and brings the material
being deposited into physical contact with the basis metal in 10 -9 sec [i, 2]. Practically,
of course, it is impossible to obtain absolutely pure (virgin) surfaces even on metals and
alloys heated in vacuum. On the surfaces of parts being spray-coated there may be various
kinds of contaminants held on them by forces of a chemical origin (e.g., oxide films) and
adhesional forces (films of greases, lubricants, remains of polishing pastes, and coolants,
abrasive particles, dust, and the like).
To enable a strong bond to form between a particle being deposited and the basis metal
in the collision zone, it is necessary to remove any surface films preventing the particle
and basis materials from coming into physical contact with each other. However, the charac-
ter of the interaction between particles being deposited and a film-coated surface has up to
now received virtually no investigation. As in practice it is not possible to obtain an ab-
solutely clean basis metal surface, it is important to study in some detail the interaction
of particles and a basis metal with a contaminated surface. This will enable researches into
ways of preparing the basis metal surface for deposition and methods of gasothermic spray-
deposition to be carried out on a sounder scientific basis. In this connection, the present
work was undertaken with the aim of studying the physical phenomena accompanying the spreading
of molten particles on the basis metal surface.

When a liquid has an inclined impact front (a wedge forms between its surface and the
surface of the solid target), a strong jet is produced, whose velocity is much greater than
the impact velocity. This phenomenon resembles that associated with the action of a cumula-
tive charge [3, 4]. Now during acceleration melted particles of a material being spray-de-
posited become spheroidized, and consequently they always form a surface inclined to the ba-
sis metal surface. During the collision of a spherical liquid drop a radial spreading velo-
city is recorded exceeding 5 to i0 times the collision velocity [3].
According to modern theories of collision of spherical drops of a liquid with a solid
surface, the initial instant of spreading of the liquid may be represented as shown in Fig.
i. The radius of the contact spot corresponding to this instant is [5]

r, = r,~ vdc,
(i)

where r d is the drop radius; Vo, the collision velocity; and C, the velocity of sound in the
material of the drop.
The velocity of a cumulative jet is [4, 6]

I~ ----Vo/sin ~ -}- Vo/tg a = VoC tg (a/2), (2)

where a is the angle of slope between the drop and basis metal surfaces.
From Fig. 1 it follows that sin a = rs/r d. Taking into account Eq. (i), we obtain

sin~ = Vo/C. (3)

Voroshilovgrad Machine Construction Institute. Translated from Poroshkovaya Metallur-

giya, No. i1(251), pp. 41-47, November, 1983. Original article submitted May 20, 1982.

904 0038-5735/83/2211-0904507.50 9 1984 Plenum Publishing Corporation

 #

Fig. i. Diagrammatic representation of

molten particle in contact with basis metal
at initial instant of spreading after col-
lision: I) shock wave front; 2) compression
zone in molten particle; 3) basis metal sur-
face; 4) free surface of molten particle.

Fig. 2. Zones of collision of plasma-deposited nickel particles with

silicon plate surface covered with water film. Magnification: a)
650; b) 2500; c) x500.
Substituting this value in Eq. (2), we get the following expression for determining the ve-
locity of the cumulative jet at the initial instant of spreading of the particle (drop):

(4)
Vj = C (1 -}- "1/1 - - (Vo/C)2).

This is in qualitative accord with the finding [6] that the maximum velocity of contin-
uous cumulative jets is only slightly greater than 2C. True velocities of cumulative jets
will be less than calculated ones owing to the effect of the viscosity of the material of the
particles and surface tension and also to energy losses in the disintegration of the radial-
ly spreading layer (division into small radial jets).
The stress set up by the spreading layer of particles on the surface of a smooth basis
metal can be determined in the same way as the stress in the boundary layer of a liquid stream
on a solid wall. For a turbulent boundary layer its magnitude can be assessed with the ex-
pression [7]

905
 Fig. 3. Zones of collision of plasma-deposited nickel particles
with silicon plate surface covered with mineral oil film. Magni-
fication: a) 200; b) 1600; c) •

gl (5)

where ~ is the coefficient of dynamic viscosity of a spreading molten particle on the basis
metal surface; U1, the velocity of the spreading laminar layer of a particle; and 61, the
thickness of the boundary laminar layer,

= -I/~T~Up
Uo. (6)

Here 1 is, in a general case, the length of a plate in a stream flowing past it, which in our
case may be taken to be equal to the maximum diameter of the contact spot of a spreading de-
posited particle; p, the density of the material of the spreading particle; and Uo, the
spreading velocity of the particle.
Molten metals and ordinary liquids have practically identical values of viscosity [8, 9].
Because of this, the frictional stress generated during the spreading of deposited particles
is of the same magnitude as that set up during the erosion of solid surfaces by drops of wa-
ter [3]. It can be taken that the spreading thin layer of the material of the particles will
entrain any surface films and transfer them to the peripheral zones of contact of the parti-
cles with the basis metal.
The validity of this physical model was confirmed by special experiments on model ma-
terials. An induction plasma unit and the experimental procedure described in [i0] were
employed. The bases were [iii] single-crystal silicon plate specimens, to which various con-
taminants were applied artificially. The collision velocity between the particles and bases
was comparatively low, less than 15 m/sec. Some of the single-crystal silicon specimens were
held in a water vapor atmosphere, after which nickel particles were deposited on them. A
condensed water vapor film on the silicon surface brought about marked changes in the charac-
ter of the interaction between the particles and the basis material (Fig. 2). In contrast to
a clean silicon surface [i0], in the zone of action of particles on the solid surface no vis-
ible signs of interaction between their materials were detected. The zone of action was a
circular spot with annular film rolls on its periphery, which had formed as a result of

906
 Fig. 4. Zones of collision of detonation-deposited copper parti-
cles with silicon plate surface, •
spreading of particles on the basis material surface. The impact and flattening of a parti-
cle were accompanied by their more intense disintegration, and in the vicinity of the inter-
action zone fine spherical particles were observed (Fig. 2a and b). Treatment of a wet sin-
gle-crystal silicon surface with the plasma jet led to the appearance of a film-- possibly
a result of oxidation of silicon -- on the basis. Specimens held in the high-temperature zone
for a longer time were able to acquire a film of considerable thickness (Fig. 2c). The pres-
ence of a water vapor film on the basis material surface at the instant of impact decreased
the amount of energy introduced by each particle into the basis material and lowered the lev-
el of shear stress in the latter. Shear was mainly localized in the thin separating layer.
At the same time, the energy of the molten particle was sufficient for cleaning the basis
material surface in the impact zone. In addition, the separating films facilitated the
spreading of particles by decreasing contact friction. Fine spherical particles appeared
around the impact zone of each particle as a result of instantaneous spreading and division
of the particle into separate ligaments and their subsequent spheroidization under the action
of surface tension forces.
A similar study was made of the character of interaction of nickel p@rticles with basis
material specimens coated with thin mineral oil films. In this case, too, electron micro-
scopical examinations of specimen surfaces revealed zones cleaned free from oil at the sites
of collision with particles (Fig. 3a and b), but these zones were irregular-shaped rather
than circular. This was apparently due to stronger adhesion of the oil film to the solid
surface. Apart from this, the possibility cannot be ruled out of such oil decomposing under
the action of a high-temperature gas stream. At a temperature of 250~ mineral oils retain
their physicochemical properties for periods measured in minutes. In the unit employed the
plasma temperature is 9000 • 1500~ At a certain distance from the reaction chamber orifice
the temperature is much lower, but still high enough to bring about a rapid physicochemical
transformation in a lubricant.
The micrographs in Fig. 3a and b were obtained after the deposited nickel particles
were partly etched away. Figure 3c shows a surface with an oil film photographed after sev-
eral particles collided with it; light-colored regions -- a result of cleaning of the sur-
face -- are visible at sites of impact action of the particles~ As can be seen, the energy
of a particle was insufficient to clean its whole zone of contact with the basis material.
The above experimental data lead to the following conclusion: Smooth (polished) surfaces
can readily be cleaned free from surface films (contaminants) because in this case more fa-
vorable conditions are created for the spreading of deposited particles and for the appear-
ance of shear stresses in surface contaminant films.
The action of a high-temperature gas jet may give rise to physicochemical transforma-
tions in a film covering a basis material and also to a chemical reaction between film de-
composition products and the solid surface. By varying the environment in which a surface
is prepared for spray-deposition, it should be possible to exercise control over the charac-
ter of these transformations in such a way as to create more favorable conditions for the
formation of a strong adhesional bond between the particles being deposited and the basis
material.
With comparatively thin contaminant films, the particles being deposited can induce self-
cleaning of a smooth basis material surface in the collision zones. The extent to which this

907
phenomenon will manifest itself will presumably grow with increasing particle velocity. In
order to enable basis materials to clean themselves free from films of liquid and viscous
substances, it will be necessary to determine optimum roughness requirements for their sur-
faces.
In experiments on the gas-detonation spray-deposition of a copper powder at a particle
propulsion velocity of 500 m/sec data were obtained indicative of a more intense action of the
spreading layer of deposited particles on the basis material surface (Fig. 4). The central
zone of collision of particles with the single-crystal silicon basis was undamaged, while the
annular peripheral zone surrounding it, whose radius was three to eight times that of the
central region, was characterized by surface layer damage resulting from brittle fracture
(Fig. 4a). The character of the interaction was found to depend on the thermal state of the
particles. From Fig. 4b it will be seen that, together with surface damage of the basis ma-
terial, there were also signs of collision of particles with a cleavage character of fracture,
which was typical mainly of unmelted particles.
The undamaged central portion was eccentric relative to the damaged peripheral zone,
which may have been due to an oblique collision of the particle with the basis material. In
addition, the peripheral zone clearly exhibited a radial jetlike character of damage. A
similar character of the spreading layer of deposited particles was observed also after their
solidification on the basis material.
All this is evidence that the particle spreading phenomenon on the basis material exerts
a pronounced influence on the mechanism of formation of a strong bond between the particles
and basis material. Calculations with Eqs. (5) and (6) show that in the spray-deposition of
molten copper particles at a layer spreading velocity of i000 m/sec a stress of 25 MN/m 2 is
set up on the surface. In these calculations it is taken that the viscosity of molten copper
superheated to a temperature 50~ above its melting point is 4.1.10 -3 N.sec/m 2, U l = Uo =
i000 m/sec, and the density of molten copper is 7.938.10 ~ kg/m 3 [ii]. The assumption that
the particle spreading velocity is i000 m/sec is reasonable in view of the fact that in gas-
detonation deposition powder particles are accelerated to a velocity of 500-900 m/sec.
These approximate calculations show that the stress generated on the surface of the
basis material as a result of the spreading of a molten drop is much less than the strength
of silicon, which cleaves, with little prior strain, under a load of i00 ~ / m 2 [12]. In view
of this, the disintegration of the surface layer of a silicon basis must be attributed to the
simultaneous action of several factors, such as the compressive stress in the center of col-
lision; Rayleigh surface waves propagating radially from the center of collision; frictional
stress set up during the spreading of a particle; and thermal stress set up by the emanation
of heat stored in a particle. However, a dominant role in the cleaning of the contact sur-
face of a basis material is played by the frictional stress, whose action results in removal
of surface contaminants and films.
If we assume that the particle spreading velocity is i00 m/sec, which is possible at low
velocities of collision of particles with a basis material (20-30 m/sec), and that all the
above-mentioned conditions remain unchanged, we obtain an estimated value of the tangential
stress of 2.5 ~ / m 2. Such a stress, while clearly insufficient to disintegrate the surface
layer of a basis material, enables the spreading layer of a particle to remove various sur-
face films having little adhesion to the basis material. Real basis materials have, of course,
surface irregularities causing perturbations in the stream which are sufficient for the for-
mation of a critical point, as a result of which a pressure

p=~v~ (7)

is generated [3], where V s is the spreading velocity of a particle. With copper, at a parti-
cle spreading velocity of i00 m/sec, a stress (80 MN/m 2) will be set up at surface irregular-
ities close to the shear stresses of metals (i00 MN/m2). However, at a particle spreading
velocity of 200 m/sec, which is also easily attainable in spray-deposition, the stress rises
to 320 MN/m 2. Such a stress readily breaks up surface films, which are then entrained under
the action of frictional forces by the spreading layer of particles and removed to the pe-
ripheral zone of contact between the particles and basis material.

908
 CONCLUSIONS
In gasothermic spray-deposition the surface of the basis material experiences self-clean-
ing as a result of the disintegration of surface films by frictional forces set up by the
spreading layer of particles and their subsequent removal to the periphery of the contact
zone. The intensity of self-cleaning of the surface of a basis material grows with increas-
ing velocity of the particles being deposited. The self-cleaning phenomenon occurring on
the basis material in the zone of collision with particles being deposited facilitates the
formation of physical contact with the powder particles subsequently interacting with this
zone on the surface of the basis material.
LITERATURE CITED
I. V. V. Kudinov, Plasma-Deposited Coatings [in Russian], Nauka, Moscow (1977).
2. M. Kh. Shorshorov and Yu. A. Kharlamov, Physicochemical Principles of Gas-Detonation
Spray-Deposition [in Russian], Nauka, Moscow (1978).
3. J. E. Field, "Investigations of high-velocity liquid impact and cavitation," in: Mechan-
ics, A Collection of Translations [in Russian], Moscow (1972), pp. 78-87.
4. G. I. Pokrovskii, Hydrodynamic Mechanisms [in Russian], Znanie, Moscow (1972).
5. R. G. Perel'man, V. I. Baulin, and Yu. D. Denisov, "Role of dynamic stresses in drop
impact erosion," Izv. Vyssh. Uchebn. Zaved., Mashinostr., No. 5, 64-70 (1973).
6. S. A. Kinelovskii and Yu. A. Trishin, "Physical aspects of cumulation," Fiz. Goreniya
Vzryva, 16, No. 5, 26-40 (1980).
7. G. N. Abramovich, Applied Gas Dynamics [in Russian], Nauka, Moscow (1976).
8. Large Soviet Encyclopedia [in Russian], Vol. 5 (1971), p. 604.
9. D. R. Wilson, Structure of Liquid Metals and Alloys [Russian translation], Metallurgiya,
Moscow (1972).
i0. V. A. Kharlamov, M. S. Hassan, and R. N. Anderson, "Cleaning and surface preparation
technology and other factors related to coatings produced by flame spraying,"in: Sur-
face Contamination, Vol. i, Plenum Press, New York--London (1979), pp. 407-442.
ii. P. P. Arsent'ev and L. A. Koledov, Metallic Melts and Their Properties [in Russian],
Metallurgiya, Moscow (1976).
12. Yu. L. Krasulin, Solid-Phase Reaction of a Metal with a Semiconductor [in Russian],
Nauka, Moscow (1971).

909