CLASSIFICATION OF TYPES OF REACTION OF POWDER PARTICLES WITH A

SUBSTRATE DURING THE APPLICATION OF A COATING

Yu. A. Kharlamov UDC 621.793.7

Up to now analyses of the physlcochemlcal phenomena accompanying the formation of flame-

sprayed coatings (FSCs) have been carried out only for certain particular cases, conditions,
and stages of propagation of reactions of particles with a substrate [1-6]. Special experi-
ments have provided evidence that particles being spray-deposlted can assume various shapes
as a result of spreading and solidification occurring simultaneously with a variety of physi-
cochemlcal processes [2, 7-12].
The large diversity of possible conditions of reaction of particles with a substrate
leads to marked differences in the character of formation of flame-sprayed coatings. It is
therefore necessary to classify types of reaction of particles with a substrate, taking into
account the conditions of their collision, the parameters of their thermal and thermomechanl-
cal reactions, and the structure and properties of their materials. Without such a clas-
sification it is extremely difficult to investigate the conditions of formation of FSCs of
different types and determine their optimum processing parameters.
The mechanical, mechanochemlcal, thermophyslcal, and other phenomena taking place during
the formation of flame-sprayed coatings vary depending on the parameters of the ther-
momechanlcal reaction of particles with a substrate, the nature of the ambient atmosphere,
and the properties of the materials. They include melting, solidification, elastic and
plastic deformation, diffusion or anomalous mass transport, exothermlc reactions, hydrody-
namic spreading and pileup effects, brittle rupture, and exoelectronic emission. Processes
whose qualitative and quantitative characteristics exert a strong influence on the contact
reaction between the particle and substrate materials and on the formation of a bond between
them must be regarded as control processes. Together with these, there are associated pro-
cesses, which have but little effect on the formation of coatings. A change in conditions of
the reaction of particles with a substrate and in their state parameters may bring about
critical states and transitions from some control processes to others, with sharp differences
in all their characteristics. It is this point that constitutes the fundamental distinction
between control and associated processes in the formation of flame-sprayed coatings.
According to modern theories, the physlcochemlcal processes of rupture and bonding of
materials are similar in character, and consequently a classification of types of reaction of
particles with a substrate can be based on the following principles [13, 14]. A system of
particles reacting with a substrate (SPS) is regarded as an open thermodynamic system ex-
changing energy and material with its ambient atmosphere. All processes of contact reaction
between the particle and substrate materials are initiated and develop as a result of two
basic phenomena: activation, i.e., increase in the free energy of the materials of the SPS,
and passivatlon, i.e., decrease in the energy. In accordance with the first principle of
thermodynamics, the energy of the thermomechanical reaction of the particles with the sub-
strate (including the thermal and kinetic energies of the particles) Wp, which is the source
of the total activation GAp, is mainly expended in heating the substrate Q (thermal activa-
tion G~) and also partially stored by the materials of the surface layers AE (structural
activation GAs), i.e., Wp - Q + AE - G,p- The main components of passivation Gpa., are the
energy Gd dissipated by the part being treated (the substrate and coating being formed) and
the energy G, stored by the materials of the SPS, i.e., Wp - G d + G, - Gp~.,.
All the various processes occurring during the reaction of the particles with the sub-
strate can be divided into three main groups: normal processes, accompanied by the formation
of strong bonds betweenthe particles and the substrate; weak reaction phenomena, charac-
terized by the formation of weak bonds between the particle and substrate materials (low

Voroshilovgrad MachineConstructlon Institute. Translatedfrom Poroshkovaya Metallur-

giya, No. 1(301), pp. 18-22, January, 1988. Original article submitted August 7, 1985.

0038-5735/88/2701-0017512.50 9 1988 Plenum Publishing Corporation 17

 Activation intensity CA= ? f ~, ~, :, At,, )
I insufficient n~ excessive
CA << Gsb ~A G s b ~ >~ ~ sb
I Weak or no bonding Strong Weak bonding,
t bonding- - das~%ge
'I . . . . .
F-
1
I I
, ,7

I +
r !-i
9 0
0 ", tt4
0 q~ __ .
.r.I
~ 9 9 0
0 -~ , o.
@ .~ ~ o
0
I-
N "", ~ 9 ;

~ ~ -~ o o-~
~ 'i
9 ! o i?rj o
i tt '*"' 9 . . t
[ I
I ~___,i,L,_I_i~
~1 I I II I
.....
I !
'_~'_1I . ~, ~l -~, l _ _ _ t l i o
'-~ I ----- ~ - - ~lint. structu-
React lOSS
~ ,ral trans.
9 1
......... IOf Dartzc~es
~eaction with .- _ _ land substrat~
~1 thermal structural I ,tm. (O~, CO, suDs~ra~e
- v [surface laye2
ana seconear~c sca-~-~'~-
102 ~ H20-.-): structure r~
r t'= ~ i ~~ " ~ II Ldsorptlon,dlf . .maueriais
. . ,~Izatlon,poly-_.
~ Activation
L ' types ~h 9 " n~ catal- (bond forma-Lmo rp nic
iUSlOl .
rsis, chem. tion a. ~ r a n s l o r m a -
' ~ " ~ = ~ t i o n s . chem.
9eactions [react., etc. )
Passivation mechanisms Gp = ~y (At, M)

Fig. i. General classification of types of r e a c t i o n of p o w d e r particles with substrate.

a d h e s i o n a l s t r e n g t h ) o r t h e i r a b s e n c e ; and damage b u i l d u p p h e n o m e n a , w h i c h l e a d t o t h e rup-

t u r e o f t h e s u r f a c e l a y e r o f t h e s u b s t r a t e and p a r t i c l e s or to the formation of defects in
t h e s u r f a c e l a y e r o f t h e s u b s t r a t e and i n t h e c o a t i n g b e i n g f o r m e d .
Normalization of the reaction of the particles with the substrate is a result of the
t h e r m o d y n a m i c n a t u r e o f t h e s e p r o c e s s e s and t h e i r a b i l i t y t o s e t up s p o n t a n e o u s l y , under
certain conditions, stable, ordered states - energetically stable electron configurations
between the atoms of the surfaces being joined together [1]. As a c o n s e q u e n c e o f t h i s ,
s o l i d - p h a s e w e l d i n g o f t h e m e t a l ( o f t h e s u b s t r a t e and p a r t i c l e s ) takes place. When t h e
stability conditions are not realized, chemical bonds at contact sites are not formed or are
broken.
All types of structural c h a n g e s and r e a c t i o n b e t w e e n s u c h c o n t a c t s u r f a c e s a t l a r g e
external differences have a single nature, linked with the energies involved in the activa-
t i o n and p a s s i v a t i o n of the materials (Fig. 1). The i n t e n s i t y of activation GA - ~(Vp, Tp,
T,, A t , M), w h e r e Vp i s t h e p a r t i c l e velocity; Tp and T., t h e p a r t i c l e and s u b s t r a t e t e m p e r a -
tures, respectively; A t , t h e a t m o s p h e r e ; and M, t h e m a t e r i a l .
The m a i n a c t i v a t i n g factors are contact heat exchange between the particles and s u b -
s t r a t e and c o n t a c t e l a s t o p l a s t i c deformation. The h e a t i n g o f t h e s u b s t r a t e u n d e r a p a r t i c l e
brings about thermal activation of their reaction processes. The p r o c e s s e s o f s t r u c t u r a l
activation a r e d e t e r m i n e d by t h e k i n e t i c s o f n u c l e a t i o n and m i g r a t i o n o f c r y s t a l s t r u c t u r e
imperfections in the contact deformation zone. The k i n e t i c s of these processes in turn is
linked with the energetic s t a t e o f a t o m s , w h i c h d e p e n d s on t h e r m a l a c t i v a t i o n [13].
Activation i n d u c e s i n t h e s u r f a c e l a y e r s o f t h e m a t e r i a l s i n c o n t a c t an a n o m a l o u s ,
nonequilibrium, unstable state. From t h e p o i n t o f v i e w o f t h e r m o d y n a m i c s i t i s n a t u r a l f o r
these materials t o t e n d t o p a s s i n t o a more e q u i l i b r i u m s t a t e . Because of this, during the
reaction of the particles with the substrate activation processes are always followed by

18
 Between primary
materials(PM)
Bond /
Activation formation /
~ ) \ Through secondary
/ "'.... .k structures (SS)
Transformati~nSe (~,~,T
sAt,M) Reacti0n~ / GASPS~
, G sb
Wear - secondary
(SS, PM) \ structures (SS)
~+E~U/+AE~ a s s i v a t i o ~
% ........
Rupture ~ uamage - pr~---
mary
Cp= ~j ~.t ,M)
GJSPS27 Gsb~k....
Fig. 2. Model of b o n d formation b e t w e e n particles and substrate.

~adh
Gp6 Coh
2 CPU
~ Gp5 3
I Gp~
| Gp~

GpI, 2 = ~ ~ I
I I ~
/rl ff I ~ il -
, I -i-\

Fig. 3. General diagram of variation of adhesional strength of

coatings with intensity of activation: 1-3) welding of PM with
thermal activation and plastic deformation (i), plastic defor-
mation (2), and thermomechanlcal activation (3); 4) welding
through oxide film with thermomechanical activation.

passivat!on processes. It is possible to distinguish three main groups of passivation reac-

tions in the surface layers of the materials: formation of chemical bonds between the mate-
rials in contact; internal structural transformation of the surface layers; and reaction with
the active elements of the ambient atmosphere. All three passivatlon processes compete with
one another, each occurring under strictly defined conditions.
Normal processes of reaction of the particles with the substrate are characterized by
the fact that activation of the surface of the substrate (and in the case of deposition of
solid particles, also of their surfaces) manifests itself in the rupture of metal-oxygen
atomic bonds in an oxide or a complex, chemical adsorption, and the formation of atoms with
unsaturated bonds on the reacting surfaces, while passivatlon manifests itself in the forma-
tion of atomic bonds between the particle and substrate materials. Weak reaction phenomena
are characterized either by small numbers of ruptured metal-oxygen atomic bonds, or restora-
tion of ruptured bonds, or saturation of ruptured bonds as a result of reaction with the
ambient atmosphere.
In an analysis of passivation processes it is necessary to distinguish between cases
where they occur on the suhstrate/particle contact surfaces and on the free surfaces. The
reason for this is that parts of the surface outside the contact zone are also subjected,
although to a smaller extent, to thermal and mechanical activation. The particles experience
thermal activation until they react with the substrate. During the reaction of activated
surface metal layers with active elements in the ambient high-temperature atmosphere, very
fine single- or heterophase objects may form. When this cannot be allowed, coating deposi-
tion is performed in a vacuum or a protective atmosphere.

19
 A necessary condition for the normalization of processes of reaction between the par-
ticles and the substrate is a dynamic equilibrium between the activation and passtvatton
processes such that the effective energy of activation lies within the limits of values of
energy required for the formation of strong bonds, i.e., G ~ f - Gsb.
During a normal reaction of the particles with the substrate, predominantly structural
activation ensures stable mechanochemical processes. Thermal activation as a rule promotes
the development of stable thermochemical processes similar to those occurring during the
machining of materials [13, 1 4 ] . During the collision of a particle with the substrate
structural and thermal activation take place simultaneously, and their separation is ar-
bitrary, although in certain ranges of collision conditions the effect of either structural
or thermal activation o n w e l d t n g p r o c e s s e s may p r e d o m i n a t e . Damage, w h i c h may b e due t o
various causes (deformation, heating, processing heredity), appears at an excess of activa-
tion energy.
That the different processes of reaction of the particles with the substrate are related
t o one a n o t h e r i s b o r n e o u t b y t h e e x i s t e n c e o f c r i t i c a l points of transition from normal
p r o c e s s e s t o damage b u i l d u p a n d weak r e a c t i o n phenomena a n d a l s o o f t h r e s h o l d v a l u e s o f Vp,
Tp, Ts, a n d c o n c e n t r a t i o n of active elements in the atmosphere, as well as of critical values
of mechanical and thermophysical properties of the reacting materials.
As a r e s u l t o f s u c h a g e n e r a l a n a l y s i s o f s y s t e m a t i c i n v e s t i g a t i o n s , physical models
have been constructed of the processes of bond formation between the particles and the sub-
strate. T h e y d e s c r i b e ( F i g . 2) t h e i r r e v e r s i b l e processes of conversion of the thermal and
kinetic energy of the particles i n t o t h e e n e r g y o f i n t e r n a l p r o c e s s e s i n t h e SPS s y s t e m b y
various mechanisms.
This general classification does not conflict with existing theories concerning the
bonding of metals during solid-state welding and the need for the occurrence of the following
processes: formation of physical contact, activation of contact surfaces, and volume reac-
tion.
The principle of the general law of formation of flame-sprayed coatings consists in the
following: For all combinations of materials and ambient atmospheres there exist ranges of
substrate and particle temperatures and collision velocity within which the indicators of
coatings being formed (adheslonal strength oadh, coheslonal strength Ocoh, the coefficient of
powder utilization, and others) are stable and much higher than they are outside these ranges
(Fig. 3). The boundaries of the ranges (region III) are determined by critical values of
activation and passlvatlon energies corresponding to the conditions of formation of physical
contact and protective secondary structures. On their determination will depend the subse-
quent formulationof problems on the optimization of FSC application processes. A physical
mechanism of the general law is provided [13-15] by the universal phenomenon of struc-
turoenergetlc adaptation of materials (SEA). The principle of SEA is that, under normal
conditions of reaction of the materials, stable, ordered, dissipative structures are formed
in the contact zone possessing the property of minimum entropy generation.
The general classification of types of reaction of particles with a substrate makes
possible a more rational approach to analysis of existing and search for new ways of regulat-
ing the processes of reaction of materials in the formation of flame-sprayed coatings.

LITERATURE CITED
1. V. V. Kudlnov, Plasma-Sprayed Coatings [in Russian], Nauka, Moscow (1977).
2. M. Kh. Shorshorov and Yu. A. Kharlamov, Physlcochemlcal Principles of Gas-Detonation
Spray-Deposition of Coatings [in Russian], Nauka, Moscow (1978).
3. G. G. Maksimovlch, V. F. Shatinskll, and V. I. Kopylov, Physicochemical Processes in
Plasma Spray-Deposition and in the Rupture of Materials with Coatings [in Russian],
Naukova Dumka, Kiev (1983).
4. E. M. Ivanov, Engineering Calculation of Thermophyslcal Processes in Plasma Spray-Dep-
osition [in Russian], Saratov Univ. (1983).
5. A. Ya. Kulik, Yu. S. Borlsov, A. S. Mnukhln, and M. D. Nikltln, Flame-Spraying of Com-
posite Powders [in Russian], Mashlnostroenie, Leningrad (1985).
6. Yu. S. Borisov and A. L. Borlsova, Plasma-Sprayed Powder Coatings [in Russian], Tekh-
nlka, Kiev (1986).

20
 7. Yu. A. Kharlamov, M. S. Hassan, and R. N. Anderson, "Electron-mlcroscoplcal investiga-
tion of powder particles spray-deposlted onto a solid surface," Poroshk. Metall., No.
12, 40-45 (1979).
8. Yu. 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:
Surface Contamination. Genesis, Detection and Control (K. L. Mittal, ed.), Plenum
Press, New York (1979), p p . 4 0 7 - 4 4 1 .
9. Yu. A. Kharlamov and M. S. Hassan, "Behavior of the oxide film on monocrystalllne sili-
con during the plasma spray-deposltlon of nickel and aluminum powders," ~lektron. Obrab.
Mater., No. 4, 33-35 (1981).
10. Yu. A. Kharlamov, "Cleaning the basis metal of surface films in the spray-deposltlon of
powders," Poroshk. Metal1., No. II, 41-47 (1983).
11. G. M. Kallnln, I. S. Lupakov, V. M. Ivanov, and V. I. Bodnarchuk, "Electron-mlcroscopi-
cal investigation of plasma spray-deposlted oxide particles," Fiz. Khlm. Obrab. Mater.,
No. 2, 139-141 (1986).
12. B. I. Makhorln, N. V. Grevtsev, V. D. Zolotukhln, et al., "Reaction of liquid metal
drops with a baffle," Fiz. Khlm. Obrab. Mater., No. 1, 45-51 (1976).
13. B. I. Kostetskll, I. G. Nosovskll, A. K. Karaulov, et al., Surface Strength of Materials
in Friction [in Russian], Tekhnlka, Kiev (1976).
14. B. I. Kostetskii, "Classlflcatlon of types of surface rupture and general principles of
friction and wear," Vestn. Mashlnostr., No. II, 10-13 (1984).
15. W. Eberllng, Structure Formation in Irreversible Processes [Russian translation], Mir,
Moscow (1979).

BORON NITRIDE CERAMICS: PROBLEMS AND DEVELOPMENT PERSPECTIVES

L. N. Rusanova, A. G. Romashln, G. I. Kullkova, UDC 621.315.61

and O. P. Golubeva

Boron nitrlde is a material of exceptionally high heat resistance. Of the known refrac-
tory compounds only some two dozen have melting points lying in the range 2900-3300~ The
decomposition temperature of boron nltride is about 3000~ and it is therefore important to
explore the possibilities of producing boron nitrlde base constructional materials for pre-
cision metallurgy, the space, atomic, and fine chemical technologies, and other new branches
of engineering.
Boron nltride, BN, is a structural analog of carbon. Like carbon, it has a lamellar
hexagonal graphltellke modification (Fig. la) and two dlamondlike - a sphalerite-type cubic
(Fig. Ib) and a wQrtzlte-type hexagonal (Fig. ic) - modifications. Each of these crystal-
lographic structures has a number of unique physlcochemlcal properties, and is of con-
siderable interest to materials scientists.
The sphalerlte and w~rzlte forms of boron nltrlde are characterized by a tetrahedral
distribution of atoms in their lattices and also by a high density of packing of atoms, which
accounts for the high hardness of these modifications and their extensive use as abrasive
materials.
The hexagonal graphitelike form of b o r o n nltrlde consists of a system of plane parallel
layers arranged precisely one above another, with the boron and nitrogen atoms alternating in
the direction of the c axis (Fig. la). The layers are constructed of regular benzene ring
type hexagons with angles of 120 ~ between the bonds, so that each atom of one kind is sur-
rounded by three close neighbors of the other kind. In this structure the boron-nitrogen
chemical bonds have a heterodesmic character because of a strong covalent reaction within
each monolayer and a weak Van der Waals reaction between the layers [i]. It is in this

Obnlnsk. Translated from Poroshkovaya Metallurglya, No. I(301), pp. 23-31, January,
1988. Original article submitted November 26, 1986.

0038-5735/88/2701-0021512.50 9 1988 Plenum Publishing Corporation 21