Powder Metallurgy and Metal Ceramics, Vol. 48, Nos.

9-10, 2009

SHRINKAGE OF METAL CERAMIC

BRIQUETTES DURING SINTERING

I. M. Fedorchenko1

The shrinkage of metal ceramic briquettes during sintering is still to be fully explained physically and
mathematically.
Frenkel [1] was the first to start the mathematical development of the sintering process and treated it as a
viscous flow of a crystalline body under surface tension. Frenkel explained later the physics of sintering [2] and
pointed out that the flow that governed sintering represented a bulk diffusion flow. In addition to the bulk sintering,
he also assumed that there was surface sintering. According to Frenkel [3], the faces of a crystal when heated
become naturally rough as a result of thermal fluctuations and seem to be covered with terraces of individual atomic
layers.
The experimental data of Dedrick and Gerds [4] and Shaler [5] do not support Frenkels assumption that
the mechanism whereby metal particles are sintered can be regarded as a viscous flow of the crystalline body.
Kuczynski [6] and Dedrick and Gerds [4] concluded that sintering resulted from bulk diffusion. However, the
conclusions made by Kuczynski and Dedrick and Gerds cannot apply to the actual conditions under which metal
powder briquettes are sintered since the experimental conditions did not cover sintering times and surface states
common for metal ceramic production practices. Pines [7] regards shrinkage as the diffusion of holes outside,
through the briquette. This idea has not been verified experimentally. Dawihl [8] attributed shrinkage to the
contraction of particles resulting from the recrystallization inside individual grains in which their shape becomes
more regular.
We have established [9] that the specific surface area of metal powders changes intensively when heated,
and the self-diffusion of atoms over particles is governed by the general equation of diffusion in metals. We assume
that the surface rearrangement of powder particles is critical for the shrinkage and sintering of metal powder
briquettes. Based on these assumptions, we performed experiments to study how the reduction in the specific
surface area of powders when annealed influenced the shrinkage of the briquettes and made an attempt to find a
relation between the shrinkage process and surface diffusion of atoms.

1. PRELIMINARY EXPERIMENTS AND SHRINKAGE HYPOTHESIS

To study how the specific surface area of the starting powder influences the shrinkage of metal ceramic
samples after sintering, we pressed 5 10 40 mm plane samples from iron powders of the same fractional
composition but different specific surface areas. The specific surface area was controlled by varying the annealing
temperature of the powder mixture or individual powder fractions. The specific surface area of the powder was
determined with Deryagins gas permeability method [10]. The samples were measured before and after sintering.
The reduction in the cross-sectional area of the samples was used to measure the shrinkage.

1Frantsevich Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Kiev,
Ukraine. This article by I. M. Fedorchenko was originally published in the Bulletin of the Academy of Sciences of
the USSR (No. 3, 1953, Division of Technical Science) and presented by Academician N. T. Gudtsov.
Translated from Poroshkovaya Metallurgiya, Vol. 48, No. 910 (469), pp. 922, 2009.

1068-1302/09/0910-0497 2009 Springer Science+Business Media, Inc. 497

 3 2
V, cm /g S, m /g
0.70 0.10
3.0 S
0.65 0.08 a
Shrinkage, %

2.0 0.60 0.06

V

1.0 0.55 0.04

0.50 0.02
0
o
0.010 0.015 0.020 0.025 500 700 900 1100 C
2
Specific surface area, m /g
b
Fig. 1 Fig. 2 Fig. 3
Fig. 1. Shrinkage of iron briquettes as a function of the specific surface area of the starting powder
Fig. 2. Specific surface area and bulk volume of 0.06 mm iron powder as a function of annealing
temperature
Fig. 3. Schematic of surface changes of powder particles during annealing: a) surface change of one
particle; b) surface change at the interface of two pressed particles (areas from which atoms moved
during heating are shaded; the particle outline after annealing is crosshatched with one line and the area
to which the atoms moved is crosshatched with two lines)

The results are presented in Fig. 1. The experimental data show a linear relationship between the specific
surface area of the starting powder and shrinkage of the samples sintered: the greater the specific surface area of the
powder, the greater the shrinkage of the sample after sintering, fractional composition being the same. Thus, the
reduction in the specific surface area of powder particles that form briquettes is one of the major causes of
shrinkage at the initial stage of sintering of metal ceramic briquettes. This is also the case for the specific surface
area and bulk volume of the powder.
Figure 2 shows our dependence of the specific surface area and bulk volume of 0.06 mm iron powder on
annealing temperature. Both curves have the same trend. The bulk volume decreases with reducing specific surface
area.
This phenomenon permits a new explanation for shrinkage and decrease in porosity during sintering.
Balshin, Wulff, Hutting, etc., suppose that shrinkage results from atoms moving over the surface of particles from
pores toward contact areas.
This explanation cannot be agreed with. The diffusion of atoms toward contact areas with increasing
temperature should lead to structural strengthening of the contacts. Since shrinkage can proceed when particles
come closer to one another at contact areas, this structural strengthening will prevent shrinkage. A pore cannot be
contracted when atoms move to a contact gap because if the pore volume reduces at places to which atoms have
arrived, it would increase the same way at places from which they have left. If the atoms leave a pore and move into
a contact gap, the pore volume will only increase but not decrease.
Let us consider how the surface of a metal particle changes during annealing. The specific surface area of
the particle decreases in this process because atoms go from peaks (since these atoms have high energy potential) to
valleys. Figure 3a schematizes the surface change of the particle when annealed; the areas from which atoms moved
in the annealing process are slightly shaded, the new outline of the particle after annealing is crosshatched with one
line, and the areas to which the atoms moved from peaks are crosshatched with two lines. The overall size of the
particle at peaks decreases as atoms move, and the volume of the powders after annealing should also decrease
because of closer packing of the particles.

498
 There is no reason to expect that the compaction process during sintering of pressed powders would
fundamentally differ from that of nonpressed powders. Figure 3b schematizes the interface of two pressed particles.
Since their surfaces are rough, the contact area can be represented as a juncture of two comb surfaces whose peaks
are partially deformed and compressed and partially free. The atoms on peaks have higher energy potential as a
result of both work hardening caused by pressing and their geometrical position. During heating, atoms should
move from peaks to neighboring valleys between adjacent peaks and from the extreme peaks to neighboring, larger
pores to form free-volume areas between two previously close-packed particles. As they form, powder particles can
come closer to each other, which leads to the total shrinkage of a metal ceramic body during sintering.
The reduction of a metal oxide film that has a greater volume than the relevant pure metal should bring the
same result. Since there is always an oxide film over particles before pressing, most surface areas will not form
metal contacts (as confirmed by the low strength of green briquettes) and the atoms at peaks will move
independently.
Where the oxide film fails during pressing and a metal contact forms (shown with an arrow in Fig. 3)
involving mutual attraction of atoms on adjacent surfaces, the atoms will be less free to move into neighboring
valleys. Why they flow from contact areas to neighboring pores can be explained as follows.
The surface tension forces on free surfaces and attraction forces between atoms at interfaces between clean
surfaces of particles can be added and replaced by the general force. Under this force, which is transferred through
contact surfaces, the metal is pressed from contact areas into pores as though a heated body is subjected to external
pressure of the same value. Since the total area of clean metal contact surface is small, especially at the beginning of
sintering, stresses on contact areas may be higher than the yield stress of the heated metal.
The surface tension forces and attraction forces between atoms at contact areas of particles are obviously
the main forces that make powder particles come closer to each other in briquettes as free-volume areas form at
contact areas during heating. Although all these forces are not high but are concentrated on small contact areas, they
may cause high local stresses sufficient for the metal to gradually flow outside the contract areas and fill the pores.
Therefore, shrinkage (this paper does not consider the sintering process as a whole) can be represented as
the following overlapping stages: 1) atoms move from particle peaks to valleys (pores), and free-volume areas form
at contact areas as a result; 2) powder particles come closer together (shrinkage) as free-volume areas form under
surface tension forces and attraction forces between atoms on approached surfaces; 3) contact surface expands
further because of plastic deformation of contact areas and pressing of the metal into pores under the above-
mentioned forces.
The entire process is based on the movement of atoms from peaks and contact areas into valleys and pores.
This shrinkage mechanism should be the major contributor during sintering when surface irregularities that prevent
closer approximation of particles dissolve.
At quite high temperatures and longer holding, a different shrinkage mechanism may be assumed, which
results from bulk self-diffusion of atoms. However, the contribution of this process to the total shrinkage is
obviously small. We ascertained this after comparing the samples pressed from iron powders of the same fractional
composition but preliminary annealed at 900 and 1200C. After sintering for 2 h at 1200C, the briquettes from the
former powder showed 34% shrinkage, while those from the other powder had almost zero shrinkage. The
conditions of bulk diffusion were the same during sintering in both cases. However, the briquettes from the powder
annealed at 1200C and with the minimum surface showed almost zero shrinkage. Therefore, surface but not bulk
diffusion is the major contributor to shrinkage in these sintering conditions.
If powder briquettes are sintered in the presence of a liquid phase in pores, shrinkage should increase when
the liquid-phase metal actively dissolves surface peaks of solid particles.

2. PROBLEM RELATING TO THE SHRINKAGE OF BRIQUETTES IN SINTERING

Since metal powder particles have rough and irregular surface in the initial state, their surface interfaces
also have many irregularities, peaks, and valleys after briquettes are pressed. These peaks and places where the
spatial lattice is distorted by pressing constitute point diffusion centers containing a certain number of activated

499
atoms with higher energy potential. During heating, the atoms tend to leave these places and move along the surface
to neighboring voids and valleys.
When the surface becomes smoother, the volume occupied by each particle in a briquette decreases. The
decrease in the volume of individual particles leads to the total contraction of the briquette. The extent to which the
volume of a particle decreases is determined by the amount of metal moved from peaks to valleys. As a first
approximation, we assume that the volume of the atoms moved is equal to the volume of shrinkage (they are not
actually equal but are in some relationship). As we assumed that shrinkage occurs when the particles become
smoother during surface diffusion from the point centers, the shrinkage process should be governed by the same
diffusion equation as the reduction of the specific surface area. These processes can be characterized by diffusion
coefficients: Ds is surface diffusion and Dsh is shrinkage diffusion.
In our previous paper [9], we obtained the following equation to find Ds*:
P
C= , (1)
4Ds t
where C is the concentration of the diffusing substance, which is equal to the ratio between the number of atoms on
actual specific surface area after heating and the number of atoms on ideal specific surface area; P is the amount of
substance in diffusion sources, which is equal to the mass of atoms moved on surface when heated; Ds is the
coefficient of surface diffusion; and t is time, sec.
To find the shrinkage diffusion coefficient Dsh from this equation, we should substitute C and P into it,
which are experimentally determined using data on the shrinkage of briquettes during sintering. The substitution of
experimental C and P makes unnecessary the accurate determination of the factor of proportionality between Ds and
Dsh. The C and P quantities reflect the total changes in the concentration and amount of the substance in diffusion
sources, which resulted in shrinkage. Therefore, the Dsh values will also characterize the final result from the
movement of all atoms during sintering.
For the shrinkage process, the concentration of atoms can be expressed as the concentration over space. If
we take the elementary volume of a briquette with a certain number of point diffusion sources, we will find an
increased number of atoms per elementary volume after shrinkage because the particles have come closer together.
Therefore, the concentration of diffused atoms for the shrinkage process can be measured as the ratio between the
number of atoms in the elementary volume of the briquette and the same elementary volume of compact metal.
Since the number of atoms in both volumes is proportional to the relative densities of the briquette and compact
metal, the concentration of atoms can also be expressed as the ratio of the relative densities:

C= 1, (2)
c
where 1 is the relative density of the elementary porous volume of the compact after sintering; c is the relative
density of the elementary volume of compact metal, which is equal to unity. The final relative density 1 is the sum
of the initial relative density 0 and density increment after sintering:
1 = 0 + .
Hence, the smaller the 0, the greater the number of atoms moved during sintering, the final density 1 being the
same.
The amount of the substance Ps in diffusion sources may be characterized by the number of atoms that
moved during heating. Since the movement of atoms into voids involves changes in density, the number of atoms
moved may be determined as the difference between the relative densities of the briquette before and after heating:
P = = 1 0. (3)

r2

* The factor e 4 Dt in the right-hand side of the equation differs little from unity and we neglected it as described in [9].

500
 Although the volume of atoms moved during heating will not actually be equal to the decrease in the
volume of the briquette, we may consider them to be equal as a first approximation as we are not interested in the
volume of all atoms involved in movement but the volume of atoms whose movement led to the total shrinkage
measured.
Substituting C and P into Eq. (1), we get
1
= , (4)
c 4Dsht
or, as c = 1,

= 4Dsh t , (5a)
1
or

= 4Dsh t . (5b)
0 +
Knowing experimental values of 1 and , we can use these equations to calculate the shrinkage diffusion
coefficient Dsh and then determine the shrinkage activation heat during sintering. If the shrinkage process obeys the
same laws as surface self-diffusion, the calculated activation heats should be close for both processes. With known
Dsh and Eq. (5b), we can also determine the change in the density of the briquette during sintering for preset
temperature and time. The density of the briquette after sintering will be as follows:
s = 0 + . (6)

3. PROCEDURE OF SHRINKAGE EXPERIMENTS

To verify the above ideas, we examined the shrinkage of briquettes from powders of different metals using
two methods: dilatometric analysis and micrometer measurement of the samples after sintering.
The samples were produced as cylinders 3.8 mm in diameter and 20 mm in length by double-action
pressing in a split die. They were sintered in hydrogen, which was deoxidized and dried by passing through a
furnace with incandescent copper chips and through calcium chloride, sulfuric acid, and phosphoric anhydride. We
used a differential method to measure how the samples shortened during sintering and displayed them at the
dilatometer screen under 118 to 400 magnification. Since samples with greater porosity can show additional
shrinkage under pressure of the dilatometer spring at high sintering temperatures, a reference sample was placed in
each experiment into an outside quartz tube near to the sample subjected to pressure of the dilatometer rod. The
shrinkage of the two samples was compared after sintering.
We conducted two series of sintering: a) sintering with continuous heating at a certain rate without holding
at the maximum temperature and b) sintering with isothermal holding lasting from 2 to 600 min. In the case of
isothermal sintering, the samples were heated to the holding temperature for 35 min by rapid movement of the
preheated furnace onto the quartz tube with samples.
Jet-milled iron, electrolytic copper, and carbonyl nickel powders were used to press the samples. The
powders had the following fractional composition: a) 0.06 mm (90%) and 0.15+0.06 mm (10%) electrolytic
copper; b) jet-milled iron (powder with two individual fractions was used: 0.15+0.06 mm and 0.06 mm), and
c) 0.06 mm carbonyl nickel.
The maximum relative error of determining the density was no more than 0.91%.

4. EXPERIMENTAL DATA ON SHRINKAGE IN SINTERING

Typical curves showing density as a function of continuously increasing temperature are shown in Figs. 4
and 5.
The briquettes made of carbonyl nickel and jet-milled iron show noticeable change in density
at corresponding temperature 0.4 (400450C) and of copper at 0.6 (550C). The shrinkage rate increases

501


0.9 3

3
0.8 0.8
2
0.7 2

0.6 0.7
1 1
0.5 o Temperature, C
o

Temperature, C
20 200 400 600 800 1000
20 100 200 400 600 800 1000 1200 0.6
0.4
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Corresponding temperature, Corresponding temperature,
Fig. 4 Fig. 5
Fig. 4. Change in density of briquettes during heating: heating rate is 34 C/min; the samples are
made of carbonyl nickel; 1) initial relative density 0.550; 2) 0.737; 3) 0.818
Fig. 5. Change in density of briquettes during heating: heating rate is 1.3 C/min; the samples are
made of 0.06 mm jet-milled iron; 1) initial relative density 0.676; 2) 0.779; 3) 0.861

1000oC 900oC

0.95 800oC

0.90
700oC
0.85
600oC
0.80 500oC

0.75 400oC

0.70
0 100 200 300 400 500 600 700
Holding time, min

Fig. 6. Change in density of briquettes during sintering with isothermal holding: the samples are made
from carbonyl nickel powder; the initial relative density is 0.74

with temperature. At about 900C, which corresponds to the critical point Ac3, the shrinkage of the briquettes made
of iron powder stops. With further increase in temperature, the density does not noticeably change up to 1100C.
For the copper powder samples, the shrinkage dependence loses its smoothness near the melting point
(1060C), which seems to result from a liquid phase formed from oxides and admixtures at this temperature. We
revealed the liquid phase after sintering at this temperature as black-blue sweating.
The presence of a liquid phase promotes the isolation of particles in dense briquettes and their shrinkage in
less dense briquettes. When iron powder is used with particles of different sizes, the trend of the shrinkage
dependences does not change but the absolute value of shrinkage is higher for fine powder.
Figure 6 shows typical density curves for isothermal sintering. The curves for other metals of interest are
similar. During the first 1012 minutes of holding, the density rapidly increases and then the process gradually
slows down. The shrinkage rate is higher for briquettes with lower initial density. The shrinkage rage increases with
temperature. Because of the allotropic transformation of iron, the density curve for sintering at 1000C is lower than
those for 900 and 800C.

502
 5. ANALYSIS OF EXPERIMENTAL RESULTS
The Dsh values were calculated from Eq. (5a), which shows the relation between the diffusion coefficient
and density of briquettes during sintering. If the shrinkage process is actually governed by the general diffusion
equation, the points on the lgDsh1/T graph should form a straight line. The verification of this condition showed
that it was valid. Figures 7 and 8 show some graphs to illustrate the temperature dependence of the diffusion
coefficient for different metals.
Q

Using the general temperature dependence of the diffusion coefficient D = Ae RT , we also determined the
shrinkage activation heats Qsh of the briquettes. According to the experimental conditions, the total probable error
in determining Dsh is 7.42% for the briquettes for iron powder, 10.65% for copper, and 4.84% for nickel powder.
The error in determining Qsh is much lower since it is an exponential quantity.
It is of practical interest to characterize the shrinkage of briquettes for two sintering stages: (i) heating to
preset temperature and (ii) holding. During heating, the diffusion rate of surface atoms is variable and increases
with temperature. Hence, the activation heat calculated for these heating conditions should differ from that for

lgD
lgD
5.0
Carbonyl Ni
3.5

5.5 4.0
0=0.550
0=0.737
6.0 0=0.818
4.5

Jet-milled Fe 5.0
6.5 2 min

5.5 10
0=0.676
7.0 30
6.0
0=0.779 120
7.5 o 6.5 240
Temperature, C o
Temperature, C
1300 1200 1100 1000 900 800 700 600 1000 900 800 700 600 500 540
8.0 7.0
6 7 8 9 4 10 11 12 7 8 9 10 11 12 13 14
4
1/T .10 1/T .10
Fig. 7. Temperature dependence of the diffusion coefficient for shrinkage during continuous heating:
the samples are made of carbonyl nickel and jet-milled iron powders
Fig. 8. Temperature dependence of the diffusion coefficient for shrinkage during isothermal holding:
the samples are made of carbonyl nickel powder; the initial relative density is 0.668

TABLE 1. Apparent Activation Heats and Coefficients A for the Shrinkage of Briquettes Heated
at a Rate of 34C/min in Comparison with Data for Powders [9]

Initial relative For briquettes For powder

Powder density of
briquettes, 0 Qsha, cal/g-atom A, cm2/sec Qsha, cal/g-at. A, cm2/sec

Carbonyl nickel 0.550 6960 7.39 105 6350 37.8 109

0.773 6060 3.36 105
0.818 5360 1.65 105
Jet-milled iron, 0.676 11,400 3.68 105 7840 7.14 109
0.06 mm 0.779 17,300 31.52 105

503
 TABLE 2. Activation Heats Q and Coefficients A for the Shrinkage of Briquettes in Isothermal Sintering

Initial Holding time, min

Characte-
Powder density of
ristic
briquettes 2 5 10 15 30 60

Carbonyl nickel 0.668 Qshr 11,245 11,048 8970 9956 6797

0.668 A 1133 105 483 105 109 105 77.3 105 8.9 105
0.740 Qshr 12,323 11,112 9712 7999 7640
0.740 A 1360 105 366 105 129 105 24.2 105 11.4 105
Electrolytic 0.529 Qshr 35,063
copper 0.529 A 809
0.716 Qshr 35,515 34,308 35,965 33,967
0.716 A 243 77 16.2
Jet-milled iron, 0.728 Qshr 21,050 20,143 20,332 19,542 19,883
0.06 mm 0.728 A 7001 105 2352 105 1312 105 629 105 259 105
Jet-milled iron, Not pressed Q sr 15,007 14,945 17,150
0.90 mm [9] Same A 2.495 107 0.853 107 1.013 107

Average Range of
Initial Holding time, min
Charac- Qshr, sintering
Powder density of
teristic tempera-
briquettes cal/g-at.
120 180 240 300 540 tures, C
Carbonyl nickel
0.668 Qshr 8084 7944 7055 7458 5001000
0.668 A 9.6 105 6.9 105 2.9
105 1.7 105
0.740 Qshr 7250 6774 6800 6419 5001000
0.740 A 5.3 105 2.5 105 2.0 105 1.1 105
Electrolytic 0.529 Qshr 32,355 35,086 35,634 34,670 600900
copper 0.529 A 18.9 17.2 18.8
0.716 Qshr 35,169 35,818 35,120 600900
0.716 A 8.97 7.48
Jet-milled iron, 0.728 Qshr 20,454 21,135 20,360 600900
0.06 mm 0.728 A 119 105 57.7 105
Jet-milled iron, Not pressed Q sr 16,390 18,210 16,000 600900
0.90 mm [9] Same A 0.606 107 0.576 107

isothermal holding (to differentiate them, we will further call the activation heat calculated for the shrinkage with
continuous temperature increase (heating) the apparent activation heat Qsha and for isothermal holding the real
activation heat Qshr).
Of interest is to determine A and Q from results of nonisothermal sintering, since in this case shrinkage can
be described as a diffusion process with its typical A and Q values.
To calculate Dsh for shrinkage during uniform heating, the sintering time of 1h was used as its accuracy has
no effect on the activation heat. The activation heats and coefficients A calculated with the least-squares method for
shrinkage during heating are summarized in Table 1 and for isothermal holding in Table 2.
The activation heats of the bulk self-diffusion of metals are several times higher than those of the shrinkage
of briquettes made of them; the latter are close to our [9] activation heats of the surface self-diffusion of atoms over

504
particles of metal powders. That these values are close confirms the assumption that the shrinkage of briquettes
when sintered results from diffusion processes occurring in surface layers of pressed particles.
Tables 1 and 2 show Q and A for the surface diffusion on powders for reference. The apparent activation
heats of nickel determined for the heating of briquettes and powders agree well. The values Q for the shrinkage of
iron powder briquettes are much higher than for the reduction of the specific surface area of the powder. This
increase in the activation heat for briquettes is probably because surface atoms are blocked during pressing and the
diffusion of hydrogen is difficult, which slows down the reduction of oxide films. The apparent activation heats for
the shrinkage of nickel briquettes are practically the same when the relative density varies from 0.550 to 0.818,
while Qsha of iron powder briquettes increases with density. This change seems to be associated with the
peculiarities of hydrogen diffusion in different metals. Hydrogen easily dissolves in nickel, harder in iron, and even
harder in copper.
The temperature dependence of the shrinkage diffusion coefficient for heating of iron powder briquettes is
peculiar in that the points corresponding to sintering at 950C do not form a straight line as a result of the
polymorphic transformation of iron at 906C.
The points on the curves of isothermal holding deviate from a straight line for the sintering of carbonyl
nickel powder briquettes at 1000C, starting from the holding time of 120, 240 min and more; the deviation begins
later for denser briquettes (120 min for 0 = 0.660 and 240 min for 0 = 0.740). The deviation in this case is
seemingly due to the depletion of surface particle layers by atoms with high energy potential as diffusion proceeds
rapidly at high temperatures. The deviation of points for denser briquettes at longer holding confirms that the
surface diffusion in briquettes slows down because of surface blocking. In isothermal sintering of iron and copper
powder briquettes, the real shrinkage activation heats Qshr remain unchanged for sintering times from 2 to 540 min;
their average values are 34,900 cal/g-atom for copper and 20,360 cal/g-atom for iron. Nickel powder briquettes
showed variable Qsh: it decreases from 1112 to 67 kcal/g-atom with increasing holding time. The decrease in Q
with time is probably due to the high oxygen and carbon content of carbonyl nickel. The rapid gas generation in the
initial sintering period retards the shrinkage process, which results in the increase in Q. After 1 h of isothermal
holding, the activation heat is close to the values determined for the reduction in the specific surface area.
The values of the real shrinkage activation heats of nickel, iron, and copper are placed in the order of
increasing heats of hydrogen dissolution in these metals.
According to Smithells [11], they are equal to 5400 cal/mole H2 for nickel, 15,600 cal/mole H2 for iron,
and 28,600 cal/mole H2 for copper.
The shrinkage activation heats are somewhat higher than the hydrogen dissolution heat in all the cases. This
indicates that shrinkage somewhat depends on the diffusion processes associated with the dissolution of hydrogen in
metals.
Since the number of atoms with high energy potential on powder particles is limited and decreases during
holding, the shrinkage process should cease with time. This is well displayed by the change in the coefficient A in
Table 2 and Fig. 9. The coefficient A can be regarded as that characterizing the number of atoms that can move
under appropriate activation energy. The A value is maximum within the first minutes of sintering and rapidly
decreases with holding time. The logarithmic plot of A versus time shows that they are in a strict hyperbolic
relationship. The ratio between the coefficient A and time t for briquettes can be represented by the following
simple experimental equations.
For iron powder briquettes with 0 = 0.768:
AFe = 0.1038t0.8567. (7)
For copper powder briquettes with 0 = 0.716:
ACu = 340t0.7845. (8)
For carbonyl nickel briquettes with 0 = 0.668 and 0.740:
ANi = 0.0315t1.315, (9)
where t is sintering time, min.

505
 Cu Ni Fe
1500 1000
5 4
A A .10 A .10
300 800

1000 600

200 400

500 200

100 0
0 100 200 300 400 500
0
0 100 200 300 400 500 600 700
0
0 100 200 300 400 500 600 700 min

Fig. 9. Coefficient A for copper, nickel, and iron briquettes as a function of isothermal holding time

The coefficient A should depend on the specific surface area of the starting powder and on the density of
briquettes before sintering. The larger the specific surface area of the powder, the higher the coefficient A should be,
and the denser the briquettes, the lower should it be. The ranges of variation in A depending on these factors are to
be experimentally examined further. The results permit calculating the shrinkage of briquettes when sintered. The
calculation is as follows. Equations (7), (8), and (9) are used to determine A for preset sintering time. The
experimental activation heat and coefficient A are put into the general equation for the temperature dependence of
the diffusion coefficient to determine Dsh for preset sintering temperature. Equation (5b) is used to determine the
increase in the relative density . Equation (6) gives the sought relative density of the briquette after sintering. In
calculating the density of copper and iron briquettes at sintering temperatures of 700 and 900C and holding times
from 2 to 540 min with this method, we found deviations between the calculated and experimental data for copper
(1.36) and iron (0.5%).
Because of the polymorphic transformation, the calculation constants for sintering of iron powder
briquettes should be different for temperatures above and below 950C. As the shrinkage of iron briquettes remains
practically unchanged between 950 and 1100C, the calculation can actually be performed for 950C and the result
will characterize the shrinkage up to 1100C. The shrinkage of -iron at higher temperatures is still to be examined.
The calculated and experimental data may differ if processes that influence the surface diffusion of atoms
and approaching of particles occur during sintering. These processes may result from a high oxidation level of the
powder, presence of unreducible oxides, insufficient reducing atmosphere, presence of components that cause rapid
gas generation, etc.
Our data permit quantitative characterization of the contribution of bulk and surface self-diffusion to the
shrinkage at preset sintering temperature and time. For this purpose, it will suffice to compare the coefficients of
surface and bulk diffusion calculated using Q and A. As an example, we will compare the coefficients of bulk and
surface self-diffusion for iron power briquettes for sintering at 900C.
Birchenall and Mehl [12] give the following values of Q and A for the bulk self-diffusion in -iron: Q =
= 73,200 cal/g-atom and A = 2.3 103 cm2/sec. Hence, the self-diffusion coefficient D = 0.65 1010 cm2/sec for
900C. The D values for surface self-diffusion in the shrinkage of briquettes calculated using the data of Table 2 are
summarized in Table 3.

TABLE 3. Surface Self-Diffusion Coefficients for Sintering of Iron Powder Briquettes at 900C

Isothermal holding time in

5 10 15 60 180 540
sintering, min

D, cm2/sec 1010 39,900 11,300 10,700 4400 2020 990

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 The surface diffusion coefficient is about 60,000 times higher for 5 min holding than the bulk self-diffusion
coefficient and 1500 times higher for 9 min holding.
Therefore, the contribution of bulk diffusion is practically zero in these conditions, and shrinkage is due to
surface diffusion.

CONCLUSIONS
1. In contrast to the existing idea that the shrinkage process results from the movement of atoms from pores
to contact areas, we have concluded that it results from the movement of atoms from peaks and their pressing out
from contact areas to neighboring valleys and pores.
2. We have shown that the shrinkage of one-component metal ceramic briquettes over a range of practically
relevant temperatures and sintering times results from the diffusion of atoms on rough surfaces of pressed particles.
This result partially agrees with Frenkels hypothesis of the surface mechanism of sintering. However, the
nature of this surface mechanism contradicts Frenkels hypothesis. According to Frenkel, the sintering process
results from atoms moving along crystallite surfaces and from natural roughness of the crystallite faces with
increasing temperature because of thermal fluctuations. Shrinkage actually proceeds because of the initial roughness
of powder particles. As the rough surfaces become smoother during sintering, the shrinkage process slows down.
3. We have determined the activation heats and diffusion constants for the shrinkage of one-component
briquettes from iron, copper, and nickel powders for sintering during heating and isothermal holding.
4. A method has been described to calculate the shrinkage of metal ceramic briquettes during sintering.
5. The contributions of bulk and surface self-diffusion to shrinkage has been compared quantitatively.
6. To apply the calculation method to the entire range of all practically relevant densities of briquettes,
surface states, and powder particle sizes, experimental Q and A data need to be collected and the range over which
they are constant should be determined.

The author is grateful to S. I. Gubkin, a full member of the Academy of Sciences of the Byelorussian Soviet
Republic, for valuable comments.

REFERENCES
1. Ya. I. Frenkel, Viscous flow in crystallites, Zh. ksp. Teor. Fiz., 16, No. 1 (1946).
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faces, Zh. ksp. Teor. Fiz., 16, No. 1 (1946).
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Physics, 20, No. 11 (1949).
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(1952).
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