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ISSN 0018-1439

Russian Original Vol. 15, No.2, March-April, 1981 "J1": . •. . .

September, 198r;·~i'/

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ACTIVATION-CHEMISORPTION MODEL OF THE PROCESS OF THE GROWTH OF
POLYMER FILMS IN A GLOW DISCHARGE

G. K. Vinogradov, Yu. A. Ivanov, UDC 537.525

and L. S. Polak

A two-step kinetic model of the process of the growth of thin polymer films in a low-
pressure glow discharge has been proposed. Under the conditions of a glow discharge
in mixtures of CH 4 (1-10 vol. %) with inert gases, the mechanism of film growth con-
sists of the activation of its surface layer primarily due to energy released when
positive ions recombine with electrons. 111is is accompanied by the elimination of
H atoms and functional groups from the macromolecules. Radicals arriving from the
gaseous phase are incorporated into the surface radicals formed in this manner.

The study of the formation of polymer films (PF) in a glow discharge is important both
for ascertaining the mechanisms of gas-phase and heterogeneous processes which take place in
a reduced-pressure low-temperature nonequilibrium plasma and for solving practical problems.
Despite the application of this process in various areas of modern technology [1, 2], its
mechanism is still a subject of debate [3-6]. With the aid of a specially developed electro-
static probe rrethod, in [7-9] we obtained qualitatively new experimental results, which could
not be described in the framework of the known mechanisms of film formation. In particular,
it was discovered that positively charged ions and neutral radicals simultaneously partici-
pate in the formation of polymer films in a glow discharge of constant current in mixtures of
methane with inert gases (Ar, Ne, Xe), the ions providing for "activation" of the surface layer
of the growing polymer film, and the free radicals being the "bricks," from which the polymer
film is constructed.
In the present work we shall propose a kinetic model of the process of film formation in
a glow discharge, which may be called an activation-chemisorption model. It is based on gen-
eral assumptions. We shall first examine these assumptions and evaluate the place and impor-
tance of each of them in the mechanism of the process. Then we shall analyze the possible
elementary rea.ctions which take place in the surface layer of a growing polymer film and de-
termine the ra.te of growth of the polymer film and its properties. On this basis we shall
derive an equ~tion for the rate of growth of a polymer film and analyze the expressions ap-
pearing in it in order to reveal the main channels of film formation under the experimental
conditions investigated.

General Assumptions
1. Under conditions in which, besides the neutral particles of various types, charged
particles of both signs or only positive ions can reach the surface of a growing polymer film,
the growth of the polymer film can proceed along several paths. First, active particles (which
have an internal energy sufficient for breaking chemical bonds) hit the surface of the growing
polymer film and create growth centers (GC) on it. The free radicals and molecules of the con-
version products of CH 4 with unsaturated bonds (as well as the corresponding ions and radical
ions) are incorporated into the polymer film at the growth centers. This assumption is an
hypothesis, which is based on experimental data that we obtained concerning the simultaneous
participation of both positively charged ions and neutral particles in the process of polymer
film formation. Second, the energy released upon recombination of the ions from the plasma
(and possibly also the deactivation energy of metastable electronically excited atoms) cause
dissociation of the adsorbed hydrocarbon molecules and inc9rporation of the radical formed
into the polymer film. The possibility of processes of this type was postulated in [3, 6].
Third, di- and trivalent radicals dropping from the plasma are inserted into the polymer film

A. V. Topchiev Institute of Petrochemical Synthesis, Academy of Sciences of the USSR.

Translated from Khimiya Vysokikh Energii, Vol. 15, No.2, pp. 153-159, March-April, 1981.
Original article submitted November 23, 1979.

120 0018-1439/81/1502-0120$07.50 © 1981 Plenum Publishing Corporation

 at C-C, C-H, and multiple bonds. Reactions of this type are known in polymer chemistry [10].
Fourth, hydrocarbon radical ions hit the surface of the polymer fJ.lm and recombine with elec-
trons. The energy released causes the elimination of hydrogen atoms (H) from the macromole-
cules of the polymer film and the incorporation of a radical at the free bond. This process
is a consequence of the first.
2. The growth centers are free valences in the surface layer of the polymer and can be
created upon the elimination of H atoms and functional groups from the macromolecules, upon
the cleavage of C-C bonds at the expense of the energy from the recombination of an ion with
an electron or the deactivation of an electronically excited metastable atom, and upon the
opening of multiple bonds in reactions with radicals and in reactions of the chain-transfer
type. The presence of free radicals in polymer films obtained by the plasma chemical method
has been confirmed experimentally [11-13]. The formation of growth centers due to the bom-
bardment of the surface of the polymer film by electrons and UV photons will be taken into
account, since it has been shown that these processes are ineffective in the plasma deposi-
tion of polymer films [12].
3. Polymerization of the type under consideration is classified among the heterogeneous
processes of the Eley-Rideal type, rather than the Langmuir-Hinshelwood type [14], i. e., we
shall not consider the reactions of two adsorbed particles (however, we shall take into ac-
count the recombination of two growth centers). Such a conclusion may be drawn, if we take
into account that the surface of a polymer film in contact with a plasma is subjected to con-
tinuous bombardment by highly energetic particles with a flux density on the order of 1016 _
1017 cm- 2 'sec- 1 • Under such conditions the adsorbed particles do not manage to approach one
another before they react with an ion, excited atom, or radical from the plasma.
4. The mechanism of the growth of a polymer film remains the same during the increase
of the thickness of the polymer film from several monolayers to several microns, and the poly-
mer film is horrogeneous, i.e" only the steady-state growth of the polymer film is considered.
This assumption is based on the fact that under steady-state conditions the rate of growth is
constant as the thickness of the polymer film varies in the range indicated [3, 4, 6].
5. Growth centers are created and most of them decay mainly in the surface layer of the
growing polymer film. It is a "forest" or bush of side chains and terminal repeating units
(groups) of the macromolecules. The maximum height of the "forest" and the maximum length
of its branches are equivalent to three to five elementary units. Stated differently, the
thickness of the surface layer, where the processes which determine the rate of polymeriza-
tion and the properties of the polymer film mainly take place, amounts to three to five mono-
layers. As the temperature is increased, the intensity of the motion of the branches in-
creases. Such a picture of the structure of the surface layer is due to the set of preceding
assumptions and makes it possible to explain the observed value of the rate of growth of a
polymer film and its decrease with increasing temperature of the polymer film.
6. Macroparticles from the gaseous phase do not reach the surface of a growing polymer
film. This assumption is valid for cases in which highly diluted mixtures of organic com-
pounds with inert gases are used, as well as in the case of the use of compounds which are
more inclined to undergo degradation than polymerization [15]. In these cases, processes of
gas-phase polyrrlerization are not observed. Macroparticles were not found in the gaseous phase
in any of the investigations known to us of reduced-pressure discharges in methane. For ex-
ample, only trace amounts of particles with a number of C atoms greater than three were dis-
covered in a mass-spectrometric study of an hf discharge in pure methane in [16]. The ab-
sence of macroparticles from the gaseous phase is also supported by the observations of the
polymer films obtained in the present work in optical and electron microscopes.
7. Degradation (loss of weight) of a polymer film occurs as a result of the elimination
of the terminal groups and side chains from the macromolecules. The elimination of H atoms
may be neglected here. Processes associated with degradation of polymer films were discovered
in [12, 5].
The step of the appearance of a growth center is clearly equivalent to the step of the
initiation of polymerization on the surface, and the reactions resulting in growth of the poly-
mer film may be either chain-propagation or chain-termination steps. In the gaseous phase
the processes of dissociation and ionization of the hydrocarbon molecules upon interaction
J with electrons, ions, and electronically excited metastable atoms of the inert gas correspond
j to initiation steps.
;

j 121
Brief Consideration of the System of Equations
The system includes the main, energetically possible reactions which determine the rate
of growth of the polymer film, the concentration of growth centers, and the rate of degrada-
tion of the pc,lymer film. We introduce the following notation for the particles participat-
ing in the reactions: M, a.monomer or CH 4 in our case; A, an atom of the inert gas; A*, an
electronically excited metastable atom; e, an electron; I, an ion of the inert gas (atomic
or molecular); PM, molecules of conversion products of M in the plasma containing multiple
bonds, e.g., C2H4 and C2H2 , which can be incorporated into the polymer film at growth cen-
ters, Rk , a free radical, where k denotes the valence of the radical (k = 1, 2, 3), e.g.,
CH 3 ; CH~, CH 3 , C2H~, etc.; Rk+, a singly charged radical ion having the valence k (k = 1,2,
3), e.g., clt 3+, CH~+, etc.; (~)s, a growth center on the surface, where s is a symbol for
surface; (RxH)s' terminal group or side chain of a macromolecule, which becomes a growth cen-
ter upon the elimination of an H atom; (Kx M)s and (R~A)s' a molecule of M- and an atom of A
physically ad!:.orbed on a growth center; (Rx-Ry), a C--{; bond between repeating units of a
macromolecule; Nx ' a macromolecule consisting of x repeating units. Let us consider the re-
actions on the surface which take place owing to the fact that streams of active particles
that interact with one another, with molecules of M and PM, and with the polymer film come
from the plasma in order to ascertain how the rate of growth of a polymer film is dependent
on the fluxes of these particles.
Radicals dropping from the plasma onto a growth center cause an increase in the mass
of the macromolecule by the value of the mass of the radical with the simultaneous destruc-
tion of the growth center (chain determination), i.e.,
(1)
or without deEtruction of the growth center, i.e.,
R2 + (Rx t ) ,_(Rx+t 1 ) •• (2)
Holecules of PH with double bonds (as well as PW) can be incorporated into the polymer film
at a growth center without destruction of the growth center:
PM+ (R x ' ). ~ (R r +2 ).,
t
(3)
Recombining with electrons on the surface of the polymer film, the radical ions, W, and PW
can be converted into radicals and participate in the corresponding reactions with growth
centers. The energy released upon the recombination of any ion with an electron can be used
to dissociate a molecule of H adsorbed on a nearby growth center. Then the radical formed
from M can be incorporated at the growth center, e.g"
I+e+(RxtM).~(Nx+t).+A+H. (4)
Let us consider the reactions which result in the destruction of a growth center with-
out increasing the mass of the polymer film. Growth centers can be destroyed in recombina-
tion reactions with one another, i.e.,
(Rx').+(Ru').-(Nx+~)., (5)
and upon the chemisorption of H atoms arriving from the gaseous phase, i.e.,
H+(Rx').-(Nx).. (6)
Growth centers can also be destroyed upon the physical adsorption of molecules of M and atoms
of A on them, and they can be trapped by the growing polymer layer and converted into long-
lived bulk radicals. The creation of growth centers occurs in reactions of the types
I+e+ (RxH).-(Rx') .+H+A (7)

M++e+ (Rx-R) .-(Rx') .+R'+M (8)

A'+(RxH) .-(Rx').+H+A. (9)
When C-C bondE are broken at the expense of energy released upon the recombination of charged
particles, radical ions and P~ ions can be incorporated into the polymer film:
(10)
R1++e+ (Rx-R~) .-(Rx').+ (N~+I)'
PM+ +e+(Rx-R~)-(Nx+~+2).
(ll)

122
,,
The energy from the recombination of charged particles can also be utilized for removing
atoms of A and molecules of M adsorbed on growth centers from them. Such desorption can
also occur under the action of electronically excited metastable atoms or as thermal de-
sorption. The energy from the recombination of charged particles can also be sufficient for
removing physically adsorbed particles from growth centers and for the simultaneous dissocia-
tion of a hydrocarbon ion; therefore, the incorporation of hydrocarbon ions into a polymer
film is also possible upon desorption from a growth center.
The recombination of growth centers with one another results in the formation of cross
linkages and multiple c---e bonds in the surface layer. Such bonds can also appear upon the
chemisorption of radicals which have an unsaturated bond. These bonds can be opened by
radicals and H atoms arriving from the gaseous phase, growth centers being created.
If the growth of a polymer film is accompanied by the passage of an electric current
through it (e.g., when a polymer film grows under surface potentials which differ from the
floating potential of the plasma or on an electrode), it can apparently have an influence on
the kinetics of its growth through thermal or electric perturbations of the surface layer.
For example, an increase in temperature causes an increase in the mobility of the branches of
the "forest," 'which inf luences the rate of chemisorption of H atoms, since it makes growth
centers located in deep layers of the "forest" accessible to them. A significant electric
field in a surface layer can influence the rates of ion and radical reactions. Such an in-
fluence on adsorption is known [17J.
We analyzed a scheme containing 138 energetically possible reactions on the surface of
a growing poly:ner film (some of them were described above) and derived an equation for the
rate of growth v of a polymer film on its basis. Without restricting the general nature of
the result, we take the dimensions cm- 2 for the concentrations of the adsorbed particles and
growth centers and the dimensions cm- 2 'sec- 1 for the fluxes of particles from the plasma onto
the surface of the growing polymer film. We shall denote the fluxes by the letter W. The
rate of growth v is quantitatively equal to the number of elementary units ("bricks") incor-
porated in 1 sec on a surface with an area of 1 cm 2 •
We write an expression for the rate of growth of a polymer film in the form of a sum of
terms correspo:lding to different modes of incorporation or elimination of molecular units
("bricks"):

where
II[ (R.,'},]=[ (Rxl ) . ] {W(R 1)k l +W(R')k.+W(R')k.+W(RI+)k88 +
(13)
+ W(R'+) 1£1.+ W (RH) 1£13+ W (PM) 1£,+ W ( PM +) 1£8,+ W(M+) (kl'+k l.)}
II[ (RxFI).] = [ (HxH).] {W (R') 1£.7+ WeB') 1£,8+ W(R2+) 1£\7+ W(R'+) 1£\8+ W(lVP) 1£\9+ W( PM+) k. o} (14)
II[ (H",-R~).J=[·(Rx-R~).]{W(R +)k to +W(R2+) (1£••+1£8.) +W(RH)k.7+W(PM t) (ktt+k•• )}
t (15)
II[ (Rx=R~),] =[ (Rx=R~).] {W(RI) 1£,.+ W(R') k77 + W(R') 1£••+ W( PM +) k•• }
i (16)
II[ (RxIM).]=[ (RxIM).] {WeI) (k,+k 3.)+W(RI+) (1£••+1£,0) + (17)
+W(R2+) (k••+ku)+W(HH) (k 30 +k u )+W(M+) (k'l+ku)+W(PM +) (k,.+ku)+WEA') (ku+k,.)}
II[ (R/A),] =l (R/A),] {W(RI+) kill + W(R'+) 1£112+ W(R'+) k lU + W (M+) (k w +k ll5 )+ W( PM +) (ktt.+k.tt7)} (18)
II [ (Rx-R),] =[ (Rx-R),] {W (/) 1£7,+ W(RI+) k H + W(R'+) 1£75 +W(RH) 1£7.+ W(M+) 1£8+ W( PM +) 1£78+ W(~') k 7.} ·(19)

Postulating that the conditions on the surface remain unchanged during the growth of the
polymer film, \~e may assume that the concentrations of the growth centers, as well as of the
C-H, C---e, C=c, and other bonds also remain unchanged. This makes it possible to introduce
several effective rate constants k*. For example, the effective rate constant for the crea-
tion of growth centers under the action of ions of the inert gas is k~ = [(Rx H)sJk 7 +
[(R - R )sJ2k 6 6 + [(Rx - Ry )sJk 73 + [~xM)s](k39 + k 97 ) + [(txA)s]k 9o .
x y
Let us consider the cases in which a) among the reactions which result in the destruc-
tion of growth centers, recombination reaction (5) may be neglected and b) the destruction
of the growth centers is entirely due to reaction (5). In case a) setting the rates of the
creation and destruction of the growth centers equal to one another makes it possible to ob-
j tain the expression
i (20)
j
.i

I;
~-----
123
 where
F.-W(I) kr"+W(RI+) k."+W(R'+) klT+W(R'+) k..+W(M+) k..+W( PM <) k..+ W(A·)k.+W(R') k..+W(R') k..+W(R') k..+W(H) k.. (21)
F,-W(R')k.+W(R")k..+W(M+)k..+W(PM +)k..+W(H)k.. (22)

The expression for F 2 was obtained under the assumption that the destruction of the growth
centers under steady-state conditions is due to reactions involving the formation of strong
chemical bonds, rather than the physical adsorption of atoms of A and molecules of H. Thus,
the reverse reactions involving the thermal desorption and removal of H and A from the growth
centers upon the impact of active particles were also not taken into account. In case b) it
is obvious that
[GC ]=(Ft!k.)"'. (23)
Let us ascertain which of the terms in expression (12) can correctly account for the
experimentally observed [7-9] dependences of the rate of growth of a polymer film on the tem-
perature of the growing polymer film, the flux density of the ions reaching the surface of
the polymer film, the total pressure in the discharge tube, the partial pressure of CH. in
the mixture, ccnd the radial coordinates (the distance from the axis of the positive column
of the discharge on a thin nonperturbing and massive plasma-perturbing substrate).
The decrease in the rate v with an increase in the temperature of the polymer film from
100 to 150°C, which corresponds to an activation energy of ~4 to 6 kcal/mole, cannot be
explained, if it is assumed that the growth of the polymer film is described mainly by ex-
pressions (14)-(17). The concentrations of the C-H, C-C, and C=C bonds in the surface layer
of t,he growing polymer film cannot vary appreciably in such a temperature range. At the
same time, the constants of the reactions appearing in these expressions apparently cannot
decrease with increasing temperature of the polymer film.
Expression (13) contains [GC] as one of the factors. The other factor cannot decrease
with increasing temperature of the polymer film. However, the concentration of growth centers
can decrease with increasing temperature of the polymer film in the following cases: [GC] =
F 1/F 2 and [GC] = (F 1/F s )1/2. This will be the case, if the demoninator increases with cons-
tant numerators.
Such an assumption could be plausible, if we would describe the physical model of the
surface layer of the growing polymer film in the form of a "forest," according to assumption
5. Then, in the first case, the destruction of the growth centers occurs mainly as a result
of the chemisorption of uncharged radicals. While this is an activationless process on the
upper branches, it takes place with an activation energy corresponding to the rotation of the
units comprisj_ng the branches on the lower branches. There should be an especially strong
temperature dependence in the framework of this model for the chemisorption of the lightest
radical, i.e., the H atom.
If the destruction of the growth centers occurs predominantly upon their recombination
with one another, the decrease in v with increasing temperature may be explained as an conse-
quence of the increase in the constant k~ for the recombination of the growth centers with
one another. In fact, in order for two growth centers to recombine with one another, it is
necessary for them to come sufficiently close to one another during the rotation of the
branches (segments).
The direct proportionality between the rate of growth of a polymer film and the flux den-
sity of the ions reaching its surface may be attributed to the predominance of either term
(13) or term (17) in expression (12). In addition, this means that the main channel for the
destruction of the growth centers is the chemisorption of neutral radicals, rather than the
recombination of the growth centers with one another. Otherwise, the rate of growth would be
proportional to the square root of the flux density of the ions reaching the surface.
The investigation of the radial distributions of the rate of growth on a plasma-perturb-
ing and a nonperturbing substrate in [18] showed that the rate of growth of a polymer film is
not determined by the flux of the molecules of H reaching the surface or, therefore, by ex-
pression (17). Under the experimental conditions we investigated the rate of growth is de-
scribed by the relation
v= ([W(I)k,'+ W(R H )k. s+W(RH)k>7+W(RH) k. s' +W(M+)k."+W( PM+ )k60'+W(A')ke']/[W(R')k,+W(H)ks]}
{W(R')k,+W(R Z )kz+W(R')k 6.+W( PM)k,}. (24)
This equation accurately describes the experimental results obtained. The quantitative evalua-
tion of v can be carried out on the basis of the following experimental data: The flux density

124
 of the ions in our experiments was "'10 16 cm- 2 'sec-\ thE! flux density of the radi-
cals was "'10 7 cm- 2 • sec - l . , and the rate of growth was v '" 10 A/sec, which corresponds to the
incorporation of "'10-16 units of the CH, CH 2 , and CH 3 types in 1 sec on 1 cm 2 . Writing Eq.
(24) in a simplified form, we obtain v = kW(R)[GC]. Assuming that k '" 10- 16 cm- 2 , we obtain
the value [GC] '" 101!! cm- 2 for the concentration of the growth centers in the surface layer
of the growing polymer film. On the other hand, if the growth centers are created under the
impact of ions alld are destroyed upon the chemisor~tion of H atoms, the evaluation of [GC]
in accordance wich the relation k 6W(H) [GCl = W(I)k 7 also yields a value of ~lOls cm- 2 , if
it is assumed that k; = 1 and k 6 '" 10- 16 cm- 2 . In fact, the ESR investigations showed that
in freshly prepared polymer films the concentrations of free radicals can reach 10 2 °_10 21
spins/cm 3 [12, 13]. In a recalculation for one monolayer of a polymer film this amounts to
10 13 _10 14 spins/monolayer. However, we recall that free radicals appear during the growth
of polymer films mainly in the surface layer of the polymer film (whose depth is three to
five monolayers) and that after the polymer film was been applied, the concentration of free
radicals in it d'2creases rapidly with time, especially if the polymer film is in contact
with atmospheric air. Thus, the estimate of the concentration in the surface layer of 10 14
spins/cm 2 is a IJwer estimate.
The activation-chemisorption model proposed in the present work for the process of the
formation of a p::>lymer film in a glow discharge accurately describes the experimental data
which we obtainei in [7-9] and does not contradict the experimental results known in the
literature. The elucidation of the limits of the applicability of this model will be the
subject of further investigations.

LITERATURE CITED
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merization and processing," J. Macromol. Sci.-Chem., 13, No.2, 575 (1976).
3. D. K. Lam, R. F. Baddour, and A. F. Stansell, "A mechanism and kinetics study of poly-
meric thin film deposition in glow discharge," J. Macromol. ScL-Chem., AIO, No.3, 421
(1976). -
4. J. M. Tibbit, R. Jensen, A. T. Bell, and M. Shen. "A model for kinetics of plasma poly-
merization," Macromol., 10, No.3, 647 (1977).
5. H. U. Poll, M. Arzt, andK.-H. Wickleder, "Reaction kinetics in the polymerization of
thin films on the electrodes of a glow-discharge gap," Eur. Polymer. J., 12, No.7, 505
1 (1976). --

I
6. H. Carcano, "Gas discharge polymerization," J. Chern. Phys., 61, No.9, 3634 (1974).
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~
.~
glow discharge," Khim. Vys. £nerg., 12, No.6, 542 (1978).
I
9. G. K. Vinogradov, Yu. A. Ivanov, andL. S. Polak, "Mechanism of plasma polymerization,"
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V. Topchieva Akad. Nauk SSSR, Moscow (1979), p. 64.
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125
 17. D. R. Frankel, "Surface states," in: Advances in the Investigation of the Surfaces of
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Plasma Chemistry [in Russian], Vol. 1, Nauka, Moscow (1979), p. 20.

DECOMPOSITION OF ~10(CO)6 IN THE NITROGEN PLASMA STREAM OF AN ULTRAHIGH-FREQUENCY

DISCHARGE

T. V. Rezchikova, V. N. Troitskii, UDC 66.088:621.762

N. V. Alekseev, and Yu. M. Shul'ga

The process of the decomposition of MO(CO)6 in a nitrogen plasma stream of a UHF

dischargE has been investigated. The phase composition of the pyrolysis products
has been studied by x-ray diffraction, thermogravimetric,and spectral methods.
Nonpyroghoric molybdenum powders with a mean particle diameter ranging from 220
to 360 A have been obtained. The total contents of carbon and oxygen in the molyb-
denum arE 0.2 and 1 wt.%, respectively. These values are ~5 times lower than their
concentrations in molybdenum in the case of the low-temperature pyrolysis of the
carbonyl.

The thermal decomposition of molybdenum carbonyl is widely utilized for obtaining pow-
ders, films, and coatings. The pyrolysis of MO(CO)6 for the purpose of obtaining powders is
generally carried out in a tubular 'quartz apparatus with electrically heated walls and is char-
acterized by a temperature level of 700-1500 o K for the process and a residence time of the
reactants in the apparatus of about 1 min. The yield of the molybdenum powder at 700 0 K is
86% [1-4J. The powders obtained have a particle diameter (the particles are practically
spherical) of ~l ~ and contain 1-3 wt.% carbon and 4-6 wt.% oxygen in the form of molybdenum
oxides. Appreciable lowering of the carbon content in the powder is observed in the case of
pyrolysis of the carbonyl in a weakly oxidizing medium. For the purpose of removing the car-
bon and oxygen, the powders obtained are subjected to prolonged (50-100 h) heat treatment
(100-1200 0 K) in a medium of dry or moist hydrogen. For subsequent use the purified powders
are subjected to grinding in order to destroy the conglomerates, fractionation, and some-
times isolation of particles.
Thus, the process of obtaining powders of molybdenum, as well as of other metals, by
pyrolysis of their carbonyls at moderate temperatures is characterized by: a restricted dis-
persity level of the powders obtained, a relatively high content of the carbon and oxygen im-
purities, and the need for prolonged operations for the subsequent treatment of the powders.
The purpose of the present work was to find a possibility to obtain relatively pure
molybdenum powders with a particle diameter equal to 0.01-0.1 ~.
Thermodynamic calculations were carried out in order to establish the nature of the in-
fluence of the temperature of the process on the composition of the pyrolysis products of
MO(CO)6' Table 1 presents the mole fractions of the condensed products in the Mo-C-o-N and
Mo-C-Q-H systems at atmospheric pressure with a ratio between the numbers of moles of nitro-
gen (hydrogen) and molybdenum carbonyl in the original mixture equal to 1000:1. The calcula-
tions show that single-phase molybdenum can exist only at high temperatures (2000-3000 0 K).
At temperatures below 2000 0 K molybdenum carbide is present in equilibrium, and temperatures
below 800 0 K the formation of molybdenum oxides and free carbon is possible. The presence of
hydrogen in the system significantly expands the temperature range for the possible forma-
tion of M0 2 C.
Thus, on the basis of thermodynamics, in order to obtain pure molybdenum it is necessary
to carry out the pyrolysis of the carbonyl at a temperature above 2000 0 K with subsequent
Institute of~New Chemical Problems, Academy of Sciences of the USSR. Translated from
Khimiya Vysokikh Energii, Vol. IS, No.2, pp. 160-164, March-April, 1981. Original article
submitted October 10, 1979.

126 0018-1439/81/1502- 0126$07.50 © 1981 Plenum Publishing Corporation