Effects of Applied Pressure on Densification During

Sintering in the Presence of a Liquid Phase

by W. D. KINGERY, J. M. WOULBROUN, and F. R. CHARVAT
Ceramics Division, Department of Metallurgy, Massachusetts Institute of Technology, Cambridge, Massachusetts and
Technology Department, Union Carbide Metals Company, Niagara Falls, New York

Experimental measurements of the effects of an

applied pressure on sintering of powdered materials containing a liquid phase indicate that the
applied pressure c a n b e effective b y : ( a ) increasing the extent a n d rate of particle rearrangement, ( b ) increasing the rate of solution at particle
contacts, a n d (c) causing plastic flow within the
solid particles. Which of these processes predominates depends o n the characteristics of each
particular system a n d o n the level of applied
pressure.

(c) is a liquid in which the solid is partly soluble, rapid

densification is obtained first b y rearrangement of the solid
particles under the forces of capillary action b y sliding over
one another with little friction between them, and second b y
solution at the contact points and precipitation elsewhere.
Theoretical and experimental studies have permitted evaluation of the effects of particle size, surface tension, and solubility, which are the major factors influencihg the process
rate.2*3 Recently, i t has been shown that the requirement
of the presence of a liquid phase was overly restrictive; a
solid surface (adsorbed) layer was found effective in significantly increasing the sintering rate i n the tungsten-nickel
system.
Since the driving force resulting from liquid surface tension tends t o compress the solid particles, increased solubility results at the contact area and the rate of densification
during the rearrangement process is

1. Introduction
the sintering of crystalline materials, densification occurs b y diffusional processes under the influence
of surface energy as a driving force. The rate at
which this process can take place is limited b y the diffusion
coefficients. To achieve high final densities, extremely
small particle size starting material and high sintering
temperatures are required. Two general approaches have
been taken to form dense products more effectively. One is
to adjust the composition so that a small amount of liquid
phase is present at the sintering temperature; a second
approach is the application of pressure at the sintering
temperature
The effectiveness of a liquid phase in increasing the sintering rate depends on the introduction of new densification
processes. When a liquid is added which ( a ) is present
in sufficient amounts at the sintering temperature, ( b ) completely wets and penetrates between the solid particles, and
URING

AV/VO

t+u

(1)

Av/vo = fractional volume shrinkage.

t = time.
1 y = exponent near unity.

For spheroidal grains diffusion in the liquid phase still

limits the densification rate during the solution-precipitation
process and the rate of densification is given by

Al/lo = fractional linear shrinkage.

k , and k2 = geometrical constants.
6 = thickness of liquid film between solid grains.
D L = diffusion coefficient in liquid.
CO = solubility of solid in liquid.
Vo = molar volume of dissolving material.
yLv = liquid-vapor surface energy.
r = initial particle radius.
R = gas constant.
I = absolute temperature.

Presented at the Sixty-Fourth Annual Meeting, The American

Ceramic Socicty, New York, N. Y., April 30, 1982 (Symposium on
Kinetics of Ceramic Reactions, No. 6-2s-62). Received April
9, 1962; revised copy received March 28, 1963.
A portion oE this work was donc at the Massachusetts Institute
of Technology w i t h the support of the United States Atomic Energy Commission under Contract No. AT(30-1)-2574.
Part of this paper was taken from a thesis submitted by J. M.
Woulbroun in partial fulfillment of the requirements for the
Master of Sciciicc degree in Ceramics, Massachusetts Institute of
Tcchnologp.
The writers are, respectively, professor of ceraniics and
graduate studcnt, Ceramics Division, Department of Metallurgy,
Massachusctts Institute of Technology, and section manager of
ceramics, Technology Department, Union Carbide Metals Comof Union Carbide Cormration.
.Danv.~,( aTlivision
) G. C. Kuczynski, Self-Diffusion in Sintering of Metallic
Particles, J . Metals, 1 [a]; Trans. A I M E , 185 [2] 169-78

These relations have been experimentally verified in a number

of systems.
The effect of applied pressure on densification is additive
with the pressure derived from the capillary forces. An

W. D. Kingery, Densification During Sintering in the Presence of a Liquid Phase: I, Theory, J . A p p l . Phys., 30 [3] 301306 (1959); Ceram. Abstr., 1960, July, p. 171c.
( a ) W. D. Kingery and M. D. Narasimhan, Densification
During Sintering in the Presence of a Liquid Phase: 11, Experimental, J . A p p l . Phys., 30 [3] 307-10 (1959); Ceram. Abstr.,
1960, July, p. 171d.
(b) W. D. Kingery, E. Niki, and M. I). Narasimhan, Sintering
of Oxide and Carbide-Metal Compositions in Presence of a Liquid
Phase, J. Am. Ceram. Soc., 44 [1]29-35 (1961).
J. Wulff, J. H. Brophy, and L. A. Shepard, The Nickel Activated Sintering of Tungsten; p. 113 in Powder MetallurgyProceedings of an International Conference, New York, 1960.
Edited by Werner Leszynski. Interscience Publishers, New
York, 1961. 847 pp.; Ceram. Abstr., 1962, August, p. 203b.

(1949).
( b ) W. D. Kingery and M. Berg, Study of the Initial Stages of

Sintering Solids by Viscous Flow, Evaporation-Condensation, and

Self-Diffusion, J . Appl. Ihys., 26 [lo] 1205-12 (1955); Ceram.
Abstv., 1956, February, p. 45c.
(c) J . E. Burke, Role of Grain Boundaries in Sintcring,

J. A m . Ceram. Soc., 40 [3] 80-85 (1957).

( d ) R. L. Coble, lnitial Sintering of Alumina and Hematite,
J. Am. Cevam. Soc., 41 [2] 55-62 (1958).
( e ) R. L. Coble, Sintering Crystalline Solids: I, Intermediate
and Final State Diffusion Models, J. Appl. Phys., 32 [5] 787-92
(1961); Ceram. Abstr., 1961, November, p. 274s.

391

392

Journal of The American Ceramic Society-Kingay

et al.

Vol. 48, No. 8

applied pressure, P , during the solution-precipitation process,

can be written

atomized copper particle size 40 to 60yo<200 mesh (both

supplied by Charles Hardy, Inc., New York). The fraction
of liquid present was determined from the equilibrium phase
diagram for the copper-bismuth system.11

The effects of hot-pressing crystalline powders have been

mostly discussed on the basis o plastic flow. Murray,
Livcy, and Williams5 observed that densification occurred
much more rapidly with applied pressure than in normal sintcriiig and interpreted this in terms of a different mechanism
than volume diffusion. Based on flow characteristics of a
I3ingham solid,6 they arrive a t a rate equation for hotpressing

(2) Sodium Chloride-Water Compacts

(4)
p =

7 =

relative density.
viscosity

In its integrated form

log (1 -

p) =

-kPt

+ log ( 1 -

po)

(4a)

where po = relative density at t = 0. This equation has

been found to agree with experiments on aluminum oxide,
[used silica,8 and powdered metal^.^ In the development
ol equation (4) it is assunied that the applied pressure is
much largcr than the surface energy compressive force and
that the yield point for creep deformation is low. These
requirements will be met for the materials and conditions investigated here, but they may not always be true for fine
particle size materials and low temperatures.
Feltenlo has reported that the initial part of densification
during hot-pressing cannot be adequately represented by
equation (4) A complex rearrangement process apparently
occurred which required particles sliding over one another and
involved concentrated stresses at particle contact points,
particle Iragmentation, and other similar mechanisms These
processes accounted for a large fraction of the observed total
density change, as has also been found For the initial stages
of densification in the presence of a liquid. For a particular
powder thc fractional shrinkage could be descrihed by a
relation of the form

was a fractional expnncnt varying between 0.1 7 and

During later stages OF the process, after rearrangciiient was assumed completed, the density change followed
equation (4).
I n thc present study the writers have investigated thc
cffect of applied pressure on the densification rate when a
liquid phase is present

whcrc

IZ

0jX

II. Experimental Measurements

Experimental determinations of the densification rate
werc made with mixtures of copper-bismuth, ice-methanol,
and sodium chloride-water in a temperature range corresponding to the presence oE a liquid phase In each of these
systems the solid is partly soluble in the liquid
(1 ) Copper-Bismuth Compact
The apparatus uscd to hot press copper-bismuth samples
consisted of a resistancc wound electric furnace which contained a graphite die Temperature measurements werc
madc with thermocouples Unpressed samples were introduced into the die, heated to fiOOC, and pressure was
applied with a hydraulic press Compositions of 100%
copper (no liquid), 92% copper-8 wtyo bismuth (7 5 vol%
liquid), and 84y0 copper-16 wt% bismuth (15 vol% liquid)
werc mixed for 4 hours, heated and pressed, density was
determined after 15, 60, and 240 minutes at temperature and
pressure The bismuth powder was <325 mesh, and the

The sodium chloride-water experiments were carried out

a t room temperature utilizing compositions containing up to
10 wtyo water and compacted a t pressures of 10,000, 20,000,
and 40,000 psi with a hydraulic press in a 3/8-in.-diameter
metal die. Shrinkage was recorded continuously by measuring the die plunger movement. Final densities were determined from the weight and dimensions of the resulting compacts, but a t the higher pressures and larger water contents
some of the liquid was exuded from the samples.
A few measurements were made with Mallinckrodt analytical reagent grade NaCl; most of the measurements were
made with -200 mesh crushed single crystal chips obtained
from The I-Iarshaw Chemical Company, Cleveland, Ohio.

(3) Ice-Methanol Compacts

Pressing experiments in the ice-methanol system were
carried out in a cold test room at an ambient temperature
of -22(jC. Dies 3 in. in diameter were used and load was applied with dead weights on a lever-arm assembly. Higher
pressures were obtained in a hydraulic die. Continuous
shrinkage measurements were made with a precision depth
gage micrometer. All measurements were made using ice
particles produced by an impact grinder and having a particle
diameter of approximately 20g. Mixtures were prepared
using reagent grade methanol to give 0, 10, and 2070 liquid
a t -26C according to the phase diagram.I2 Pressure
used covered the range up to 1000 psi; densification periods
from 25 to 140 hours were investigated.
111.

(I)

Results and Discussion

Copper-Bismuth Compacts

The copper-bismuth compacts containing 15 volyo liquid

gave variable and erratic results, probably because of inhomogeneities resulting from the mixing process. Data
for the 0 and 7.5 volyo liquid samples are plotted in Fig. 1
as log (1 - p ) vs. time. As found by Felten,Io a plasticflow relation (equation (4a))represents experim.enta1 results
only after an initial period of rapid consolidation. The
major effect of the liquid was t o increase the fractional
densification that occurs during the initial consolidation.
The later stages of the densification process corresponding
to plastic deformation of the grains are not much affected
by the presence of a liquid. As illustrated in Fig. 2, a sub-

5 P. Murray, D. T. Livcy, and J. Williams, Hot Pressing of

Ceramics; pp. 147-71 in Ceramic Fabrication Processes, (W. D.
Kingery, editor). Technology Press of Massachusetts Institute
of Technology and John Wiley & Sons, Inc., New York, 1958.
235 pp.; Ceram. Abstr., 1958, May, p. 123h.
6 J. K. Mackenzie and I<. Shuttleworth, Phenomenological
Theory of Sintering, Proc. Phys. Soc. (London), 62 [360B]
833-52 (1949); Ceram. Abstr., 1950, May, p. 108e.
7 G. E. Mangsen, W. A. Lamhertson, and B. Rest, Hot Pressing of Aluminum Oxide, J . Am. Ceram. Soc., 43 [2] 55-59

(1960).

8Tliomas Vasilos, Hot Pressing of Fused Silica, J . Am.

Ceram. Soc., 43

[lo] 517-19

(1960).

J. Williams, Hot Compacting of Metal Powders, Symposium on Powder Metallurgy, 1954, Spec. Rept., No. 58, Iron
Steel I&., pp. 112-24 (published 1956). 390 pp.
10 E. J. Felten, Hot Pressing of Alumina Powders at Low
Temperatures, J . Am. Ceram. Sor., 44 [El 381-85 (1961).
11 A. C. Vaughn, Bi-Cu Bismuth Copper; p. 1178 in Metals
9

Handbook. Edited by Taylor Lyman. The American Society

of Metals, Cleveland, Ohio, 1948. 1332 pp.
12 G. BaumC and W. Borowski, Systems CHSOH-H~O,J .
Chim. Phys., 12,276 (1914).

DensiJication During Sintering

August 1963

393

0.50 7

0.20

- 0.10
Q

0.05

---_.

0 01O
0

Time (minute)
Fig. 1.

Correlation between log ( 1 - p ) und time for copper-bismuth

compacts hot-pressed a t 60OoC.

Fig. 3. Correlation between log ( 1 - p ) and time for room-temperature

sodium chloride-water compacts pressed a t 10,000 psi.

0.20

Fig. 2.

0.0% HZ0

Copper-bismuth compact containing 7.5% liquid at 600C

pressed for 4 hours at 1000 psi. (KzCr207 etch, X185.)

stantial amount oC dcformation of the solid has actually

occurred.

(2) Sodium Chloride- Water Compacts

The experimental studies of the sodium chloride-water
compacts wcrc carried out a t much higher pressures than
those used for the copper-bismuth system. At the lowest
pressure (1 0,000 psi) the dry sodium chloride samples reached
a relative dcnsity of 82% after about 5 hours with almost
the entire densification occurring in the first 2 minutes.
As shown in Fig, 3, there was increased initial consolidation
with increasing amounts of liquid, but the rate of densification became uniform and independent of liquid content after
5 to 10 minutes. That is, the primary effect of the liquid
phase was to increase the initial particle rearrangement and
consolidation. For the sodium chloride-water system, an
additional feature was that continued densification took
place in the presence of a liquid. Liquid films on the surface of the sodium chloride particles apparently allowed
plastic deformation to occur that was absent in the dry
powder. This presumably results from the elimination of an
atmosphere-contaminated surface layer described in deformation experiments on alkali halides by Gorum et 01.~

0.002
0

10

20

30

40

50

60

70

Time (minute)
Fig. 4.

Correlation between log ( 1 - p ) and time for room-temperature

sodium chloride-water compacts pressed at 20,000 psi.

When the pressure was increased to 20,000 psi, similar

results were found (Fig. 4) except that complete densification
was achieved in a very short time when 10 wt% water was
employed. As the pressure was further increased to 40,000
psi, the liquid had much less effect (Fig. 5) and the samples
became completely dense and transparent after 2 to 4 hours.
Observations of microstructure indicated that a t this pressure
there was considerable grain fracture as well as plastic
deformation.
In previous studies3 of liquid phase sintering, kinetics
corresponding to equation (3) have been observed. For

13 A. E. Gorum, E. R. Parker, and J. A. Pask, Effect of Surfacc

Conditions on Room-Temperature Ductility of Ionic Crystals,
J . Am. Ceram. SOC.,
41 151 161-64 (1958).

Journal of The American Ceramic Society-Kingery

394

et al.

Vol. 46, No. 8

0.0% H20
1.0%H20

5.0% HzC

Time (hour)
Fig. 8.

Log fractional shrjpkage of ice-methanol compacts plotted vs.

log time.

40

(minute)
Fig. 5.

Correlation between log ( 1 - p) and time for room-temperature

sodium chloride-water compacts pressed a t 40,000 psi.

Time (minute)
Fig. 6.

Log fractional shrinkage o f sodium chloride compacts vs. log time

pressed a t 10,000 psi.

samples with 5% water pressed at 10,000 psi this relation

seems to hold during the first half minute as indicated in
Fig. 6. For higher pressures and larger water contents, the
effect, if it occurs a t all, is so rapid as not to be observed with
the writers experimental technique. Although the data
shown in Fig. 6 suggest that solution-precipitation processes
may be a contributing factor in the rapid consolidation
process, this cannot be regarded as demonstrated.

EL+.-

0,260

-1

Empirically it was observed that straight lines were obtained when log density was plotted as a function of log
time (Fig. 7). The various factors contributing to the
early stages of the process make any proposed mechanisms
speculative.

(3) Ice-Methanol Compacts

Measurements in the ice-alcohol system were carried out
at much lower pressures than those employed for the other
systems studied. Under these conditions, the total fractional
densification was smaller and the rate was slower. Typical
data for samples containing 10 and 20 vol% liquid are
illustrated in Fig. 8. These data are similar t o results found
for straight liquid phase sintering3 and are characterized by
an initial rapid rearrangement followed by a solution-precipitation process, and finally by a much slower solid-state
process such as plastic deformation. For the 10% liquid, a
plot of the fractional shrinkage vs. log time gives a slope
of 1/3 corresponding to equation (3).
In equation (3) taking kl = 1/2, kp = 1, 6 = lo-? cm,
D =
cm2 sec-l, CO = 0.1,
= 26 erg ernw2,P =
3.5 X lo6 dyne emw2,and r = 20p, a rate constant K =
0.0048 can be calculated. Plotting AZ/& vs. t I 3for shrinkage
values from 0.8 to 8 hours gives a straight line relation with a
slope equal to 0.0016. This is the experimental rate constant I< and is to be compared with the calculated R
= 0.0048. Agreement within a factor of three is as good as
can be expected from the rough estimates for material
constants and geometrical factors.
(4) General Discussion
In each case investigated, the major effect
of applied pressure during the densification of
a solid-liquid system was to increase the initial
rearrangement consolidation. In this part
of the densification process, particles move
into a denser configuration ; shearing stresses
cause fracture or plastic flow at particle
corners allowing rearrangement and greater
density; some particles fracture under high
stresses, and solution at high pressure contact
points allows sliding of one particle over another. The combination of these processes is
markedly enhanced by the application of
an exterior pressure.
When an external pressure is not applied,
the presence of a small amount of liquid at the
contact points between particles results in a
normal compressive force driving them to-

August l!X%

A dsorfition of Admixtures on Portland Cement

gether. This force is greatest with very fine particles and for
a small amount of liquid phase. It is not large for the 10
to 20p particle size used here. More important, it does not
lead to shear stresses between particles causing extensive
rearrangement.
The shear stresses resulting from an externally applied pressure are, in contrast, most effective
in rearranging particles relative to one another.
The level of applied pressure (and resultant shear stress)
is critical in determining the extent of rearrangement. It
also determines the subsequent mode of deformation. At
low values, as in the ice-methanol system, i t leads to solutionprecipitation processes similar to those found without
externally applied pressure. At higher values, as in the
copper-bismuth and NaC1-water systems, it causes plastic
deformation not otherwise found.

395

IV. Conclusion
Experimental investigation of the hot-pressing of copperbismuth compacts, sodium chloride-water compacts, and
ice-methanol compacts in the presence of a liquid phase
indicates that applied pressure is most effective in giving
rapid densification by the rearrangement of particles relative
to one another. Once this process has been completed,
densification continues by plastic deformation of individual
grains fixed in position relative to their neighbors. In the
ice-alcohol system evidence for a solution-precipitation
process was also found.
Acknowledgment

S. Sarian did the experimental measurements on sodium chloride pressing at the Metals Research Laboratories, Union Carbide
Metals Company.

Adsorption of Admixtures on Portland Cement

by B. BLANK, D. R. ROSSINGTON, and 1. A. WEINLAND
State University o f New York College of Ceramics at Alfred University, Alfred, New York

In a n attempt to verify theories on the effect of

admixtures on portland cement, the adsorption
isotherms for calcium lignosulfonate and salicylic acid on cement have been determined. The
adsorption isotherms for these compounds on
3Ca0.SiOz,2Ca0.SiOz, 3CaO.AI2O3,and4Ca0'Al2O3.Fe2Oaand on a mixture of these components in the ratio 60/25/5/10 have also been
determined. Adsorption isotherms were determined at 24C by a spectrophotometric method,
using a Beckman DU spectrophotometer. As
a check on t h e method, previous work of Ernsberger and France on the adsorption of lignosulfonates on portland cement was repeated and
their results were confirmed. Results indicate
that in aqueous solution the constituents of portland cement mainly responsible for the adsorption of the two compounds studied are the hydration products of 3Ca0.AI2O3and 4Ca0.AI203.Fe203. Salicylic acid adsorption on cement compounds does not fit the Langmuir form. However, adsorption of salicylic acid on type I portland
cement, for equilibrium concentrations above
0.005%, fits the form. Calcium lignosulfonate
adsorption on type I portland cement, 3Ca0.Si02,
2 C a 0 .SiOz, and partly on 4Ca0.A1203.FePO~
fits
the Langmuir form, Adsorption isotherms of
salicylic acid on the major cement compounds
were determined from ethyl alcohol solution to
eliminate the hydration of the compounds occurring in aqueous solution. The adsorption of
salicylic acid on the materials studied was found
to b e in t h e order :
:3C:i0.SiOz > 2CaO.SiO2 > type Iportland cement >
4Ca0.Al2O3.Fee03= 3CaO.Al208 = 0
The effect of water on the adsorption of salicylic
acid from ethyl alcohol solution was studied. It
was found that the smaller the amount of water
present, above a minimum value, the greater was
the adsorption on 3 C a 0 .A1203,2CaO.SiO2, and

3 C a 0 .%On. I n t h e case of 4Ca0 .Al2O3.Pe2Oa

the adsorption of salicylic acid was proportional to
the amount of water present at all concentrations
studied. It is observed in certain cases that it i s
probably not surface adsorption but a compoun-d formation with salicylic acid.

1. Introduction
cement is a product of nonequilibriuni cooling
of a sintered mass in the system CaO-Al203-Si02 with
iron and magnesium impurities. The four major constituents are tricalcium silicate (3Ca0. SiOZ), dicalcium silicate (2Ca0.SOz), tricalcium aluminate (3Ca0. A1~03),and
tetracalcium aluminoferrite (4Ca0 .Alz03.FenO3) ; it is conventional to abbreviate these formulas CaS, C2S, C3A, and
C4AF, respectively. These compounds are found in ASTM
type I portland cement in the following percentages:
ORTIAND

C3S

c2s

C3A
C4AF

45-60
20-30
5-10
8-15

Organic materials have long been used to modify the physical

and chemical properties of cement pastes. The reduction of

Presented at the Sixty-Fourth Annual Meeting, The American

Ceramic Society, New York, N. Y . , May 1, 1962 (Basic Science
Division, No 7-B-62). Received November 7, 1062; revised
copy received March 30,1963.
Based in part on a thesis submitted by B. Blank in partial fulfillment of the requirements for t h e degree of Master of Science
in ceramic technology, State University of New York College of
Ceramics at Alfred University.
At the time this work was done, the writers were, respectively,
graduate student, assistant professor of physical chemistry, and
associate professor of chemistry, Department of Physical Science,
State University of New York College of Ceramics at Alfred
University. B. Blank is now a graduate student, Department of
Mineral Technology, University of California and research associate for the Lawrence Radiation Laboratory, University of
California, Berkeley, California.