SOME

REGULAR FEATURES

OF P O R O U S P A R T S
E.

M.

IN T H E S I N T E R I N G

FROM HIGH-MELTING-POINT

Prshedromirskaya

and

V.

M.

COMPOUNDS

Sleptsov

Institute of Materials Science, A c a d e m y of Sciences of the UkrSSR

Translated from Poroshkovaya Metallurgiya, No. 4,
pp. 11-15, April, 1966
Original article submitted October 22, 1965
One of the most important stages in the manufacture of porous materials from h i g h - m e l t i n g - p o i n t compounds
is their sintering, which gives the m a t e r i a l s the necessary strength. By varying the temperature and duration of sintering it is possible to influence the p e r m e a b i l i t y and dimension of pores in the required direction. Many factors
can affect the sintering speed of parts from the above materials: the size grading of the powder, the temperature of
sintering, the additions, etc.
In the work being described we investigated the process of sintering of some carbides and borides of h i g h - m e l t ing-point metals and the kinetics of the activated sintering of carbides. An increased interest in activated sintering
is due to the fact that by using it more efficient production processes can be developed and, in particular, the sintering temperature can be reduced [1-4].
The process of sintering was investigated in a resistance furnace with a graphite heater in a hydrogen a t m o sphere. Spheroidized powders of h i g h - m e l t i n g - p o i n t compounds (TIC, WC, ZrB 2, TiB 2) made by the methods d e scribed in [10] were used to make 8-10 mm diameter, 12-15 mm long specimens under a pressure of 10 k N / c m 2.
The i n i t i a l porosity of specimens was 45-49%. A 5% aqueous solution of potyvinyl alcohol was used as the plasticizer. The activating addition was c o b a l t chloride (up to 3%), which was introduced by depositing a film of this
m a t e r i a l on the surface of i n i t i a l grains. The chlorine contained in the compounds affects the sintering process,
since at low temperatures m e t a l chlorides are produced which are then p a r t i a l l y decomposed during the sintering.
The atoms of the m e t a l are condensed at points with m i n i m u m free energy, which produces a gradient of concentration of the metals and nonmetals on the surface and accelerates the diffusion processes [5].
The specimens were placed in a furnace, previously heated to 700-800~
where they were held for 30 rain
and then rapidly heated to the required temperature. This is necessary because in this way the imperfections of the
crystalline structure are e l i m i n a t e d at low temperatures, and their contribution to the increase of the mobility of
atoms during the subsequent isothermal sintering is insignificant [6]. During the heating, cobalt chloride, distributed
as a thin f i l m on the carbide particles, becomes decomposed at temperatures of 650-1300~ into cobalt and chloride.
The first stage of sintering (800-1200~
forms the chlorides of the corresponding m e t a l while during the second stage
(to 2000~ the sintering is considerably affected by the cobalt. Because of a considerable increase in the vapor pressure of cobalt at temperatures above 2000~ [9] the liquid phase evaporates, as is indicated by the absence of cobalt
in specimens. In this case the sintering takes p l a c e in a solid phase.
Figure 1 gives the e x p e r i m e n t a l data on the variation of porosity during the sintering of WC, TiC, ZrB2, and
TiB 2. The curves show that an increase of heating time slowly reduces the porosity. After the introduction of the
activation agent (Fig. l a ) , an intense shrinkage takes p l a c e which reduces the porosity by about 20% Our research
involved the investigation of the kinetics of the compaction of titanium carbide specimens with grain sizes of
- 4 2 0 + 177 ~, with and without an addition of cobalt chloride at various sintering temperatures. This produced
the dependence of the porosity on t i m e at various sintering temperatures (Fig. l a ) . These curves can be used to d e termine the average rate of reduction of porosity for each time interval.
As a m o d e l of a porous body we used a static mixture of isomeric and isodiametric particles of the substance
with cavities and the following equation derived in paper [7]:
d;

dt

(1)

ro

269

20

z/g

60

80 r, rain

20

xr

60

80 ~ rain

Fig. 1. Dependence of porosity on the duration of sintering for various t e m p e r a tures, a: 1) WC, size g r a d i n g - 7 4 + 44 g, 2300 ~
3% COC12; 2) TiC, size grade
- 4 2 0 + 177 p, 2450 ~
3% CoC12; 3 ) T i C , size g r a d i n g - 4 2 0 + 177 p , 2300 ~
g% CoC12; 4) w e , size g r a d i n g - 7 4 + 44 g, 2300 ~ 5) TiC, size g r a d i n g - 4 2 0 +
177 p, 2450 ~ 6) TiC, size g r a d i n g - 4 2 0 + 177 p, 2300 ~ 7) WC, size grading
- 7 4 + 44 p, 2100 ~ b: 1) TiB2, size g r a d i n g - 1 7 7 + 149 g, 2250 ~ 2) TiB2,
size g r a d i n g - 1 7 7 + 149 p, 2100 ~ 3) ZrB 2, size g r a d i n g - 1 7 7 + 149 p, 2150 ~
4) ZrB2, size g r a d i n g , - 1 7 7 + 149 g, 2000 ~

where C is the second viscosity, a is the surface tension, P is the porosity,

and r 0 is the average particle radius.

3.10-o N s e c / m z
123~

From this relation we determine the value of the second viscosity

for various temperatures and sintering durations. Figure 2 gives the e x p e r i m e n t a l curves of the dependence of the second viscosity on the porosity for various sintering temperatures with and without the activating
agent.

/2
0,8

20

30

gO

p,%

Fig. 2. Dependence of the second viscosity on porosity for various sintering

temperatures: 1) TiC, size grading
--420 + 177p + 3% COC12, 2450 ~
2) TiC, size grading--420 + 177 p
+ 3%COCI 2, 2300~
3) TiC, size gradi n g - - 4 2 0 + 177 p, 2450 ~ 4) TiC,
size grading--420 + 177 p, 2300 ~

The effect of the activating additions on the acceleration of diffusion "flow" of titanium carbide is shown by the values of the coefficients
of shear viscosity ~ which were calculated by us on the basis of the ratio
derived in paper [7]:

p ( 3 - - p)
n = 4(1 - - p ).(1 - - 2 9 ) "

(2)

Figure 3 shows the variation of shear viscosity with the rate of

shrinkage of titanium carbide obtained from the e x p e r i m e n t a l data. This
diagram shows that by using m activating agent the sintering of titanium
carbide can be carried out at lower temperatures (curves 1 and 2).

The extrapolation of the 7? (t) curves to zero time by the method of least squares produced ~ 0 and, subsequently, from [8]:

A _u

~1o

-T e

nr

(3)

The values of the activation energy of the compaction process; in this equation ~ 0 is the shear viscosity at t = O,
U is the activation energy of the compaction process, A is a constant, R is the gas constant, and T is the temperature.
In the table we give the calculated values of the i n i t i a l shear viscosity of titanium carbide for various temperatures
with and without the activating agent.

270

~1~.10- 8
Nsec/m z

1,42
1,0
0,61
0,398
0,421
0,35
0,22

0,178

ln--~-

2473
2573
2723
2823
2473
2573
2723
2823

10,93 I
10,53
lO,O
9,54
9,72 Sintering with activating agent
9,5
>>
>>
9,0
>}
>>
8,73

go

Note

12'

2
s#--Y

I i

20

#a

da

8a Groin

Fig. 3. T i m e dependence of ttie second viscosity

for various temperatures: 1) TiC, size grading
- - 420 + 177 /1 + 3% CoC12, 2450 ~ 2) TiC,
size grading--420 + 177 g + 3~ CoCt2, 2300 ~
3) TiC, size g r a d i n g - 4 2 0 + g, 2450 ~ 4) TiC
size grading--420 + 177 ~, 2300 ~

1. Low-temperature sintering in the temperature range 650-1300~ in

which chlorine plays the major part in the activation of the process of sintering, forming chlorides of metals concerned while the ~ansfer of mass to the
contact between the particles is effected by the gaseous phase. In this case,
no shrinkage or reduction of the porosity of parts is observed.

r i g o/[q

Using the relation (3) we plotted the dependence of ln(n0/T) on 1 / T

(Fig. 4) for titanium carbide with some cobalt claloride added, and without this
addition. In the former case U = 149 kffmol and in the second case their v a l ue was 224 kJ/mol. Thus, the additions of cobalt chloride activate the sintering process of porous parts made from h i g h - m e l t i n g - p o i n t carbides. The m e c h anism of formation of contacts between the spherical particles in the presence
of cobalt chloride can be divided into three stages:

I/

T, ~

Fig. 4. Dependence of the logarithmic sintering speed on the r e ciprocai temperature: 1) TiC,
size grading--420 + 177 ~;
2) TiC, size grading--420 +177 #,
+ 3~ CoC1 a.

2. 8intering in the presence of a liquid phase in the temperature range

1500-2000"C. The mechanism of shrinkage and the formation of contacts is
in this stage easily explained by the action of capillary forces. At the contacts of spherical particles a film of molten cobalt forms a meniscus in the
shape of bridges resembling the so-called "nodoids." The pulling c a p i l l a r y
forces act in these areas. It is shown in papers [11, 12] that the pulling force
acting on two particles of radius R touching each other is:

1)+2~Rsinq).sin(cpq_O)J '
F=~ [ ~R ~sin sqo (1Q2 QI

(4)

where o is the surface tension of the c o b a l t m e l t on the liquid--gas interface, 0 is the l i m i t i n g angle of wetting,
is the angle depending on the amount of liquid phase, and Pz and Pz are the radii of curvature of the liquid.
Because of the presence of the liquid c o b a l t between the film particles the friction between them sharply d e creases and the m o b i l i t y increases, leading to the displacement of particles and, as could be expected, to shrinkage
of the part.
The contacts between the particles are formed at this stage of sintering by the recrystallization of the m a t e r i a l
of spherical particles through the liquid phase. The rate of recrystallization is particularly high at the points of contact with m a x i m u m amount of liquid phase. With the sintering temperature rising above 2000~ when the vapor
pressure of cobalt sharply increases and the amount of the liquid phase becomes almost negligibIe, the c a p i l l a r y
forces joining the particles reach their m a x i m u m values and Eq. (4) changes to:

F=

~/?~ cos O~

This is accompanied by a further compaction of the part and a reduction of its porosity.

271

3. When the liquid phase completely disappears through the

evaporation of cobalt and its partial diffusion into the high-meltingpoint compound, the contacts previously formed become generally
stronger owing to the recrystallization of the material and the evaporation of additions which make the grain boundaries brittle.

P,%

jr""

l/U

The listed factors improve the strength of the part and its density
during
sintering, but some of the pores, especially the fine pores,
t~Olee.,content, mass %
become closed, reducing the effectiveness of porous materials. The
Fig. 5. Dependence of porosity on the filler
methods used in manufacturing porous parts from high-melting-point
content (NH4C1) for titanium carbide size
compounds must ensure that the pores remain unbroken during the
grading--q4 + 44 it.
sintering and that an increase of strength takes place. By adding
5-30% of a filler which completely evaporates during sintering [8]
it is possible to control the permeability and the dimensions of pores. Figure 5 shows the dependence of porosity on
the filler content (NH4C1) for titanium carbide. The graph shows that an increase of the filler content increases tile
porosity by 30% of its initial value.
Jr/

I0

15

20

25

30

35

SUMMARY
The investigation being described was concerned with the processes of sintering of some materials made from
carbides and borides of some high-melting-point metals (TIC, WC, ZrB z, TiB2). The kinetics of the activated sintering of titanium carbide was investigated. The data obtained show the dependence of porosity on sintering time
and give the values of the secondary and shear viscosities of titanium carbide for various temperatures and durations
of sintering. The activation energies of sintering were calculated for titanium carbide to which some cobalt chloride
was added, and without this addition.
LITERATURE
I.
2.

3.
4.
5.
6.
7.
8.
9.
10.
11.
12.

CITED

V.S. Rakovskii, Proceedings of the Seventh All-Union Scientific Research Conference on Powder Metallurgy,
Erevan (1962), p. 3,
I.M. Fedorchenko, N. A. Filatova, M. A. Dmitrieva, and N. P. S1eptsova, Poroshkovaya metallurgiya, No. 3,
52 (1962).
M. Sivachek, Poroshkovaya metallurgiya, No. 5, 71 (1964).
I . T . Smith, J. of Appl. Physics, 36._, No. 2, 595 (1965).
A . D . Panasyuk and P. S. Kislyi, Poroshkovaya rnetallurgiya, No. 4, 18 (1965).
I . M . Fedorchenko, Poroshkovaya metallurgiya, No. 3, 17 (1962).
V . V . Skorokhod, Poroshkovaya metallurgiya, No. 2, 14 (1961).
K. Agte and K. Otsetek, Cermet Filters [in Russian], Sudpromgiz, Leningrad (1959).
F . I . Pererman, A. Ya. Zvorikin, and N. V. Oudima, Cobalt [in Russian], Izd. AN SSSR, Moscow-Leningrad
(1949).
V.M. Sleptsov, E. M. Prshedromirskaya, and Yu. P. Kukota, Poroshkovaya metallurgiya, No. 9, 11 (1965).
Yu. V. Naidich, I. A. Lavrinenko, and V. Ya. Petrishchev, Poroshkovaya metallurgiya, No. 2, 50 (1965).
Yu. V. Naidich and I. A. Lavrinenko, Poroshkovaya metallurgiya, No. 10, 61 (1965).

A l l a b b r e v i a t i o n s of p e r i o d i c a l s i n t h e a b o v e b i b l i o g r a p h y a r e l e t t e r - b y - l e t t e r t r a n s l i t e r a t i o n s of t h e a b b r e v i a t i o n s a s g i v e n i n the o r i g i n a l R u s s i a n j o u r n a l . S o m e o r al l o f t h i s perioclical l i t e r a t u r e m a y w e l l b e a v a i l a b I e in E n g l i s h t r a n s l a t i o n . A c o m p l e t e l i s t of t h e c o v e r - t o c o v e r E n g l i s h t r a n s l a t i o n s a p p e a r s a t t h e b a c k of t h e f i r s t i s s u e of t h i s y e a r .

272