Variations in Microgravity Liquid Phase Sintering

Randall M. German
San Diego State University
5500 Campanile Dr., San Diego, CA 92182, USA

John L. Johnson
Elmet Technologies LLC
1560 Lisbon St., Lewiston, ME 04240, USA

ABSTRACT

Considerable experience exists with sintering on Earth, but the behavior under reduced gravity conditions
is poorly understood. This study analyzes replica microgravity liquid phase sintering data for seven
tungsten alloys, sintered for three hold times to 10 h at 1500°C using 0.002% of standard gravity.
Equivalent sintering is performed on Earth. Microgravity sintering results in a lower density and more
shape distortion. For Earth-based sintering, minimized distortion is associated with low liquid contents to
avoid solid settling and slumping. Distortion in microgravity sintering involves viscous spreading of the
component at points of contact with the containment crucible. Microgravity sintering exhibits pore
coalescence into large, stable voids that cause component swelling. The microgravity sintering results
show good replication in terms of mass change and sintered density. Distortion is scattered but
statistically similar between the replica microgravity runs. However, subtle factors, not typically of
concern on Earth, emerge to influence microgravity sintering.

INTRODUCTION

During liquid phase sintering a component consists of solid, liquid, and vapor phases. Usually the wetting
liquid supplies a capillary force on the solid grains to densify the structure. Sintering on Earth induces
pore buoyancy and grain settling effects that are most evident with high liquid contents [1-3]. Gravity
segregates the solid grain structure to increase grain bonding and reduce diffusion distances, resulting in a
coarser grain size and denser skeletal structure that resists distortion [4-7]. Accordingly, gravity effects on
sintering depend on the component height, amount of liquid, grain size, constituent densities, initial
porosity, and dihedral angle, leading to differences in solid-liquid ratio along the vertical dimension with
concomitant changes in grain size and other parameters, including the rate of grain growth [3, 6, 8].
Sintering shrinkage reflects liquid capillary forces coupled with liquid lubrication to pull the solid grains
together, allowing liquid to flow and fill pores. The component is a viscous body that responds over time
to both capillary and gravity forces. The measured viscosity during liquid phase sintering depends on the
composition, but tends to range from 109 to 1011 Pa∙s [9, 10]. Gravity results in slightly anisotropic
shrinkage, sometimes where one dimension shrinks and the perpendicular dimension expands. Capillary
forces act to cause uniform shrinkage, but substrate friction resists shrinkage at the component bottom.
The combination of viscous flow, gravity, shrinkage, and substrate friction leads to loss of precision
during Earth sintering to produce “elephant foot” geometries [3]. Computer simulations include these
factors to explain distortion, densification, and final geometry [5, 11-15].

Early attention to gravity effects on sintering came from Lenel and coworkers [16, 17]. Subsequently,
several hundred articles emerged detailing sintered component density and dimensional uniformity as
related to gravity. Access to high temperature microgravity furnaces allowed for the removal of gravity
during sintering. Initially the conjecture was that without gravity, sintering would be more predictable
since grain compression, solid-liquid separation, pore buoyancy, and substrate friction would be
eliminated. The experimental results show a very different situation [18]. Seemingly subtle effects lead to
large changes during microgravity processing. Removing gravity simply allows small system variations to
dominate the sintering trajectory. The secondary factors, such as impurity reactions to produce gas
pockets, were always present, but were small in impact compared with gravity. With the removal of
gravity, these secondary factors emerge to dominate the behavior, leading to grain agglomeration, radial
liquid-solid separation, and generation of massive pores [19-22].

Sintering is a relatively slow process involving capillary forces acting of a viscous solid-liquid-pore
system, so meaningful experiments require more than the few seconds possible in drop towers or
parabolic aircraft. Because of limited furnace availability, experimental data are often without replication.

This study assesses replica microgravity experiments with respect to sintered density, component
dimensions, and component shape of tungsten heavy alloys. The experiments focused on extracting the
gravity role on densification and distortion using variations in the solid:liquid ratio (tungsten content),
dihedral angle (matrix composition), and sintering time. The alloys ranged from 35 to 88 wt.% tungsten,
with Ni-Fe or Ni-Cu additions forming the liquid phase. Different addition ratios – Ni:Cu = 6:4, Ni:Fe =
7:3, or Ni:Cu = 8:2, were used to adjust the dihedral angle, nominally giving averages of 70⁰, 45⁰, and
30⁰ [23, 24]. Alloys were sintered for 1773 K for 1, 180, or 600 min.

EXPERIMENTAL

The characteristics of the W, Ni, Fe, and Cu powders used in this study are summarized in Table 1. The
compositions shown in Table 2 were prepared by rod milling the W powder to a final 2 µm particle size
and turbulently mixing it with the desired Ni, Fe, or Cu powders for 20 min. The mixed powders were
compacted in thin rubber bags using cold isostatic pressing (CIP) at 200 MPa into cylinders
approximately 25 mm diameter by 175 mm long. To reduce oxygen contamination and provide strength
for launch, the CIP logs were presintered in dry hydrogen (dew point 243 K). For the W-Ni-Cu
compositions presintering was to 1273 K for 60 min, while for the W-Ni-Fe compositions presintering
was to 1673 K for 120 min. Both were performed in a pusher furnace using molybdenum trays.

Individual samples were dry machined from the presintered logs to form right-circular cylinders. As
identified in Table 2, from 9 to 15 cylindrical compacts were formed for each composition. The samples
were numbered, measured for mass, height (two locations), and diameter (four locations). For the 84 dry
machined samples, the mean diameter was 8.24 mm with a coefficient of variation of 0.35%. The mean
height was 8.25 mm and the coefficient of variation was 0.53%. The green density was calculated from
the mass and measured dimensions. For each alloy the coefficient of variation in green density ranged
from 0.5 to 5.3%. The W-Ni-Fe samples were nearly fully dense while the W-Ni-Cu samples were about
64% dense.

Table 1. Powder Characteristics

elemen vendor designation purity median surface apparent tap density,
t , size, area, density, g/cm3 g/cm3
% µm m2/g
W GTP M37 99.9 12 0.17 3.5 5.4
Ni Novamet 123 99.8 9 0.43 2.3 3.2
Fe ISP R1470 99.5 6 0.52 2.5 3.7
Cu ACuPowder 635 99.0 10 0.41 3.3 4.4

Table 2. Experimental Compositions, Densities, and Density Variation

composition, wt.% ratio theoretical number of mean coefficient of
density, samples green density, variation,
g/cm3 g/cm3 %
78W-15.4Ni-6.6Fe Ni:Fe = 7:3 15.4 15 15.3 0.8
65W-24.5Ni-10.5Fe Ni:Fe = 7:3 13.6 9 13.6 0.5
50W-35Ni-15Fe Ni:Fe = 7:3 12.1 12 11.9 0.8
35W-45.5Ni-19.5Fe Ni:Fe = 7:3 10.6 12 10.4 0.8
88W-9.6Ni-2.4Cu Ni:Cu = 8:2 16.9 12 10.9 1.2
88W-7.2Ni-4.8Cu Ni:Cu = 6:4 16.9 12 10.8 1.3
50W-30Ni-20Cu Ni:Cu = 6:4 12.2 12 7.2 5.3

For each composition two compacts were randomly assigned to the microgravity experiments and one
compact was randomly assigned to ground sintering. The remaining samples were employed for 45 and
120 min (in both microgravity and ground) sintering runs that were not replicated, or used for calibration
and qualification tests.

Each sample was placed in an individual alumina crucible for sintering. The crucibles were 99.9% pure
alumina with 10 mm inner diameter and 10 mm inner height. The gap between the sample and crucible
was intended to allow reshaping, and even spheroidization, without constraint from the crucible. The top
of one crucible was sealed by the stepped bottom of the next crucible and the top crucible was capped by
a stepped lid. Seven crucibles formed an assembly for insertion into a boron nitride sleeve (2 mm wall
thickness) that was triple contained in vacuum outgassed tantalum tubes, closed by electron beam welding
after overnight vacuum outgassing. The inside environment was static during the experiments since no
penetration of thermocouple, vacuum gauge, or pumping port was allowed through the tantalum
containment, so the inner vapor pressures were not known.
Microgravity sintering was performed on the space shuttle Columbia during flights STS83 and STS94.
Supplemental data were extracted from STS65. All sintering, including the ground experiments, relied on
the Large Isothermal Furnace (LIF) provided by the Japanese NASDA agency. Ground experiments were
conducted in the LIF at the Marshall Space Flight Center with the same sample preparation, stacking
sequence, and containment. For the ground experiments gravity was oriented along the sample axis. Upon
sample extraction this orientation was noted with the open end of the crucible marked “T” on each
sample. Flight STS83 was terminated early due to fuel cell failure, so the entire mission was replicated on
STS94, thus three of the experiments completed prior to return to Earth on STS83 were repeated on
STS94 along with experiments at 45 and 120 min. The repeat microgravity experiments on STS94
provided the unique opportunity to replicate 21 microgravity conditions. There was only one set of 21
ground experiments.

Heating to the sintering temperature was at 10 to 18 K/min to 1773 K, which was held for 1, 180, or 600
min. Thermocouples on the outside of the cartridge indicated a drift of about ± 1 K during the 1773 K
holds. Along the cartridge the temperature gradient was 8 K or less. The same sequence of stacked
samples was used in all experiments. After sintering, cooling was controlled at 3 K/min to 1693 K
followed by furnace cooling to room temperature. The total time liquid phase existed equals the hold time
plus about 22 min for the W-Ni-Fe composition or about 40 to 50 min for the W-Ni-Cu compositions
(lower Ni content melts at a lower temperature).

After return from space, the containment was removed and the samples were marked, photographed,
measured on a three-axis coordinate measuring machine (accurate to 0.01 mm), weighed (accurate to
0.002 g), and tested for density via Archimedes immersion analysis. Distortion was quantified based on
eight to eleven diameter measurements at approximately 0.5 to 1 mm incremental height spacing. On
samples that formed a dome or otherwise reshaped toward a sphere, a 45⁰ tangent to the corner was used
to define the transition from diameter to height. Distortion is given as the coefficient of variation, defined
as the diameter standard deviation divided by the mean diameter, as a percentage. Based on the
calculation procedure, full sample spheroidization corresponds to 9.4% distortion.

Samples were sectioned and examined for grain size distribution, pore size distribution, liquid separation
from the solid, contiguity, and Vickers hardness as previously described [25-29].

RESULTS

Distortion

For the ground experiments, gravity caused the samples to contact the crucible bottom. All samples with
less than 88 wt.% W slumped to also made radial contact with the crucible walls for all three sintering
times. The cross-section micrograph in Figure 1 is from 78W-15.4Ni-6.6Fe sintered on ground for 1 min.
The sample slumped to conform to the crucible and formed a thin liquid skin on the upper dome.

The experiment design anticipated the cylindrical samples might spheroidize during microgravity
sintering, so the crucibles were oversized to avoid constraint from the crucible, but five microgravity
samples (50W-35Ni-15Fe 180 min STS83 and STS94, 65W-24.5Ni-10.5Fe 180 min STS83, and 600 min
STS83 and STS94) swelled to press against the crucible walls. Many of the other microgravity samples
conformed to the crucible walls.
Figure 1. Cross-section micrograph of 78W-15.4Ni-6.6Fe sintered on the ground for 1 min. The compact
distorted and slumped to conform to the crucible while forming a liquid cap.

Comparisons of the distortion of replica samples after microgravity liquid phase sintering are shown in
Figures 2 and 3. Both 50W-30Ni-20Cu samples held for 1 min at 1773 K show similar shapes with
extensive reshaping, realizing melt formed at about 1356 K. Both samples have a flat face from contact
with the crucible top and bottom. Both 65W-24.5Ni-10.5Fe samples held for 1 min have rounded corners
but otherwise good shape preservation. This composition held for 600 min undergoes significant
distortion. At this long time, swelling induced contact with the top and bottom of the crucible as well as
the crucible wall.

The average sample radius after the two microgravity sintering runs exhibited a poor correlation of 0.23
(a significance of p = 0.05 requires a correlation of 0.43). Figure 4 scatter plots the average radius for the
two microgravity runs, giving a visual indication of the lack of correlation. The correlation improved to
0.38 when samples pressing against the crucible wall were removed from the analysis, but the reduced
number of observations still indicated no significant correlation. For comparison, Figure 4 also shows a
similar scatter plot of the two microgravity results versus the equivalent ground average radius. Since
several of the compacts swelled to press against the crucible walls, an effort was made to correlate radius
for ground and microgravity using just the 88W compositions with the least crucible contact. It failed to
detect a statistically significant correlation; however, the final average radii were similar at 3.63, 3.63,
and 3.67 mm.

The starting, ground, and two microgravity profiles of 78W-15.4Ni-6.6Fe samples after 600 min are
compared in Figure 5, The ground sample slumped to conform to the crucible and formed the liquid dome
as previously shown in Figure 1. The STS94 microgravity sample also expanded to contact the crucible
wall (5 mm radius). For the STS83 profile the data were converted into distortion, giving 5.3%.

Figure 5 also contains a scatter plot of distortion for the two microgravity runs. The correlation is
significant at 0.68 with an average difference between the two runs of 2.7%. For the unconstrained (radius
under 5 mm) microgravity samples, the mean distortion was 6.9% (STS83) and 5.6% (STS94), while the
6 ground samples not radially constrained by the crucibles (all were 88W) averaged 3.7% distortion.
 (a) (b)

Figure 2. Comparative photographs of 50W-30Ni-20Cu sintered for 1 min on a) STS83 with an average
diameter of 7.31 mm and b) STS94 with an average diameter of 6.15 mm.

(a) (b)

(c) (d)

Figure 3. Comparative photographs of 65W-24.5Ni-10.5Fe sintered for a) 1 min on STS83 with an

average diameter of 8.12 mm, b) 1 min on STS94 with an average diameter of 8.25 mm, c) 600 min on
STS83 with an average diameter of 9.54 mm, and d) 600 min on STS94 with an average diameter of 8.78
mm.
Figure 4. The left scatter plot compares the average radius for compacts sintered on the two microgravity
missions. The right scatter plot compares the average sintered radius from two microgravity studies with
the parallel ground sintering results.

Figure 5. The left plot shows measured sample profiles for 78W-15.4Ni-6.6Fe sintered for 600 min,
showing the starting profile and the shapes after ground and replica microgravity sintering. The crucible
radius at 5 mm constrained the ground and STS94 samples. The right scatter plot compares distortion for
14 samples that were not constrained by the crucible on the two microgravity flights.

Restricting the distortion analysis to just the 88W compositions that avoided crucible wall contact, gives
the summaries in Tables 3 and 4. The overall average distortion is 4.8% for these high tungsten samples.
For the 88W compositions the average distortion on ground (two compositions and three times) was
3.7%, compared with 5.2% on STS83 and 5.7% on STS94. Even when restricted to the 88W
compositions, the distortion failed to correlate between the two microgravity runs and between
microgravity and ground. The Ni:Cu composition induced dihedral angle difference was not significant.
Table 3. Time Dependent Density and Distortion for 88W-9.6Ni-2.4Cu
STS83 STS94 ground
time, density, distortion,% density, distortion, density,% distortion,%
min % % %
1 95.7 4.1 95.5 2.7 99.3 1.6
180 91.6 9.6 93.8 6.3 84.9 6.0
600 86.2 5.9 92.4 7.2 93.6 4.2

Table 4. Time Dependent Density and Distortion for 88W-7.2Ni-4.8Cu

STS83 STS94 ground
time, density, distortion,% density, distortion, density,% distortion,%
min % % %
1 98.0 1.1 98.6 3.9 97.0 1.7
180 98.5 5.0 98.1 8.8 100.0 3.6
600 99.9 5.4 98.6 5.0 98.1 4.8

Pore Coarsening

Large pores were observed in some microgravity samples. An example of a large pore connected to the
exterior surface is shown in Figure 6a for 88W-9.6Ni-2.4Cu from STS83 after 180 min. This pore opened
to the surface in the region of contact with the crucible. Large pores indicate trapped vapor. Figure 6b is a
perpendicular image of the same sample with a sketch of the crucible inner diameter added as the black
circle. Figure 6c is a single large pore in the cross-sectioned 50W-35Ni-15Fe sample sintered for 180 min
on STS83. The pore gas pressure pushed the sample outward to contact the crucible walls and ends,
constraining the shape and final density. Large pores form by coalescence. An example of pore
coalescence is captured in Figure 6d, corresponding to 88W-9.6Ni-2.4Cu sintered for 180 min on STS94.

Mass Loss

Since the samples were in multiple levels of containment, almost no mass change occurred during
sintering. On average the microgravity sintered samples were within 0.1% of the starting mass, biased to a
slight mass gain. On the other hand, the ground samples were also within 0.1% of the starting mass,
biased to a slight mass loss. The one exception was 50W-30Ni-20Cu sintered for 1 min in the ground
experiments which stuck to the crucible with an apparent 16% mass loss. The mass measurements were
performed using the same calibrated device, so the slight mass gain in microgravity versus the slight mass
loss on the ground is a significant difference.

Densification

The ground processed compositions averaged 97.2% density while the microgravity compositions
averaged 93.7% density (92.6% for STS83 and 94.8% for STS94). Scatterplots of the data are given in
Figure 7. The correlation between the two microgravity experiments using absolute density in g/cm 3 was
highly significant at 0.87. On average, the density as a percent of theoretical differed by 2.2% between
parallel microgravity results. The outlier corresponds to 65W-24.5Ni-10.5Fe sintered for 180 min. This
composition swelled from 13.2 g/cm3 after 1 min to 8-10 g/cm3 after 600 min, but was delayed in swelling
at 180 min in the STS94 run; 64.2% for STS83 and 98.2% for STS94. Three other compositions at 180
min and four compositions at 600 min exhibited more than 2% difference in microgravity sintered
density. Removing the anomalous result of the 65W-180 min sample gave microgravity sintered densities
differing on average by 0.6% with an improved correlation of 0.93 between STS83 and STS94.

(a) (b)

(c) (d)

Figure 6. a) Picture of a large pore trapped where the sample wetted the crucible for 88W-9.6Ni-2.4Cu
from STS83 after 180 min. b) The same compact shown looking along the crucible axis. The crucible
location is sketched by the 10 mm circle. The sample has partially spread to conform to the crucible.
c) Cross-section of 50W-35Ni-15Fe sintered for 180 min on STS83. A large spherical pore is evident, and
in cross-section the sample conformance to the crucible is visible by the outer profile. d) Cross-section of
88W-9.6Ni-2.4Cu sintered for 180 min on STS94. In this image two sets of large pores are undergoing
coalescence. The average diameter of the compact was 7.23 mm, but varied from 6.41 to 7.81 mm.

As shown in Figure 7, the fractional density from microgravity sintering did not correlate with the ground
results. The correlation of ground versus STS83 percentage of theoretical densities gave zero (0.00)
correlation. Likewise, the ground versus STS94 sintered densities gave a similar poor correlation (0.01).
The final densities of the ground samples generally increased over the starting density, giving shrinkage,
while the microgravity samples tended to swell. The samples showing the greatest difference between
microgravity and ground sintered density were 50W-35Ni-15Fe at 180 min and 65W-24.5Ni-10.5Fe at
600 and 180 min.

There is no significant relation between sintered density and distortion for the microgravity results. For
microgravity sintering the distortion was lowest at short hold times, namely 1 min, even for high liquid
contents. For example, 50W-35Ni-15Fe sintered for 1 min in microgravity had distortion of 2.2%
(STS83) and 1.0% (STS94). In the ground experiment for 1 min this same composition slumped to
conform to the crucible.

Figure 7. The left plot of the sintered density in g/cm 3 for the two microgravity missions shows a good
correlation, with one outlier corresponding to 65W-24.5Ni-10.5Fe sintered for 180 min. The right plot
shows a poor correlation between the two microgravity experiments and the parallel ground experiments.

Microstructure and Hardness

Figure 8 compares the microstructure for the 78W-15.4Ni-6.6Fe sintered 180 min on STS83 with the
microstructure from a similar position on the ground sample. The microgravity sintered sample lacks
grain settling, while the ground sample exhibits liquid separation.

(a) (b)

Figure 8. Comparative microstructures at the sample “top” for 78W-15.4Ni-6.6Fe sintered for 180 min on
a) STS83 and b) ground. The ground sintered structure shows solid-liquid separation, due to the solid-
liquid density difference of about 19 versus 10 g/cm 3.
Table 5 compares the microstructural parameters and microindentation hardness of replica 78W samples
sintered in microgravity for 180 minutes. The lower density for one of the samples resulted in a decreased
solid volume fraction, grain size, contiguity, and hardness.
Table 5. Measured microstructural parameters and Vickers hardness for replica 78W samples
sintered in microgravity for 180 minutes
solid liquid mean
volume volume grain Vickers
flight cartridge porosity fraction fraction size, µm contiguity hardness, HV
STS94 3 0.020 0.515 0.463 30.0 0.095 262.3 ± 11.0
STS94 5 0.004 0.536 0.462 31.1 0.17 268.8 ± 9.3

DISCUSSION

Small levels of distortion are common in liquid phase sintering on Earth. In this study the initial diameter
showed 0.35% coefficient of variation. In large-scale component production by liquid phase sintering,
dimensions are held to a small scatter via adaptive process control, delivering sintered variations of 0.02
to 0.2% [30]. Tighter dimensional control requires post-sintering grinding, machining, or coining.

During liquid phase sintering components exhibit viscous flow, which depends on the solid content and
the dihedral angle [31]. STS65 experiments found distortion of only 0.2% for a high solid composition of
98W-1.4Ni-0.6Fe after 120 min [23]. The two high solid content 88% tungsten alloys in this work also
showed good shape retention. For lower W contents, the low viscosity allowed conformance to the
crucible shape. For example, the STS65 sample of 78W-15.4Ni-6.6Fe distorted 5.1% when sintered 1 min
at 1780 K. This composition underwent more distortion when heated longer, conforming to the crucible
after 15 min. The surface energy of the tungsten-alumina interface is sufficiently low to induce compact
spreading on the alumina from random crucible contact in microgravity. Otherwise the samples would
spheroidize to minimize crucible contact.

Sintering on Earth consistently resulted in a higher relative density while microgravity sintering proved
less predictable. Statistical analysis of the microgravity sintered density (percentage of theoretical)
indicated that neither time, composition, nor flight were significant factors. For distortion, the only
significant correlation was between the two sets of microgravity results. There is no precursor ground
observation that enables accurate prediction of the microgravity behavior.

Composition-time combinations that sinter to a high density on Earth do not necessarily sinter to a high
density under microgravity conditions. Ground sintering tends to show densification and then distortion,
while microgravity sintering results in distortion and a lower density [26]. Schematically the difference in
sintering trajectories is given in Figure 9. Gravity helps resist distortion by adding compression to induce
grain bonding into a rigid solid skeleton, but in microgravity the sample changes shape without equivalent
densification.

No relation exists between sintered density and distortion. For some compositions, density decreased due
to swelling during microgravity sintering and usually distortion increased. For example, data for 88W
alloys show the ground sample densifies, then swells to distort. But the microgravity samples never reach
the same peak density, show pore growth, and distort. The difference in sintering trajectory is profound,
suggesting densification in microgravity is difficult; distortion occurs even when densification is
incomplete. Pore coarsening is suspected as an underlying explanation.

Figure 9. Outline of the key findings in terms of densification-distortion sintering trajectory. The ground
experiments generally give densification followed by distortion, whereas microgravity experiments give
less densification and often more distortion.

Large pores form by coalescence in microgravity since there is no buoyancy force causing the pores to
rise out of the component [32-35]. As pores merge, the internal vapor pressure decreases (pressure is
balanced by curvature, so the pore volume increases as the pore size increases), leading to swelling. In
several cases the internal pore gas pressure pushed the compact outward to contact the crucible, giving a
low density.

Swelling is most likely the result of residual impurities reacting to form insoluble vapor products, such as
CO, CO2, or H2O. Tungsten alloys have a propensity to swell during long sintering cycles [36], especially
if the vapor filling the pores is not soluble [37]. One factor of concern is oxygen in the powders. During
grain growth by solution-reprecipitation any residual oxygen is released into the liquid phase where it can
react with other impurities, such as carbon. The reaction product stabilizes pores. As vapor accumulates,
surface energy balances the pore pressure to determine the pore size. Using the example of 50W-35Ni-
15Fe shown in Figure 6c, the 7 mm diameter pore constitutes 35% of the volume. At 1773 K the gas
quantity needed to stabilize this pore against the surface energy (estimated at 2 J/m 2) is 1.2 10-8 mol. If
that is CO2, the corresponding mass is about 6 10-7 g. The sample mass is 5.27 g, so the contamination
level needed to stabilize this large pore corresponds to about 0.1 ppm. Such small contamination levels
are difficult to monitor and control. Indeed, the starting powders contained from 30 to 1000 ppm of
oxygen and carbon, most of which was removed by the presintering treatment. Pores are small early in
sintering, but over time coalesce while gas production acts to enlarge the pores. In microgravity, lacking
buoyancy-driven pore migration, the consequence is a loss of density while swelling induces distortion.
Thus, pores grow to reach substantial dimensions. Trivial impurity levels are sufficient to generate large
pores with concomitant loss of component shape and density.
Several seemingly small factors, normally ignored on Earth, caused the variations encountered in
microgravity sintering. Pore formation is suspected to arise from internal gas generation during sintering.
For example, the 88 wt% tungsten compacts started with about 64% density, densified, then swelled.
Long hydrogen presintering removes impurities, but this cycle was not applied to the crucibles, which
might have contaminated the compacts. Vapor pressure was not measured inside the cartridge during
sintering, so impurity generated vapor is only a conjecture to explain swelling. Based on crucible contact
from earlier microgravity experiments with a smaller gap between the sample and crucible, these
experiments used a larger gap, but it was still insufficient to avoid contact with the crucibles.

Microstructural parameters, including solid volume fraction, grain size, and contiguity, and hardness for
78W alloys relate to the sintered density. The mechanical properties, especially ductility, of tungsten
heavy alloys are highly sensitive to porosity [37]. Elimination of pores in microgravity sintering will be
critical to achieving properties expected from Earth-based sintering.

A predictable sintering trajectory is critical to extraterrestrial fabrication or repair efforts. The need is to
predict sintered dimensions in different gravity levels. Conjectures on how to attain desired features using
additive manufacturing or extraterrestrial fabrication in other gravity conditions face the problem of
deciding which sintering trajectory is relevant – gravity or microgravity or something in between. Ideally
a basis can be developed to predict sintered component attributes over a variety of gravitational
environments.

CONCLUSIONS

This study on repeatability of the sintering trajectory for microgravity liquid phase sintering relied on a
rare instance where several replica experiments were performed in space. Overall, the replica
microgravity samples showed reasonable similarities between the sintering experiments. The compacts
generally looked the same, exhibited consistent mass, reached similar densities, and had similar
microstructures and hardnesses, but final dimensions were scattered. Swelling and distortion continue to
be difficulties with microgravity sintering. Some compacts lost density and distorted during sintering, a
behavior most likely associated with gas production from carbon and oxygen impurities in the starting
powders. Random compact contact with the crucible, leading to partial conformance to the crucible, was a
major problem.

It is not possible to predict size, shape, density, microstructure or mechanical properties of components
liquid phase sintered in microgravity based on ground sintering behavior. Ground sintering of similar
samples in the same furnace configuration with the same heating cycle was unable to provide a basis for
predicting microgravity behavior. Gravity might induce gradients, but we have much experience with
gravity, allowing for repeatable sintering results. The microgravity results show reasonable replication,
but with larger than typical scatter between experiments, caused by subtle factors, such as low levels of
impurities that are not usually a concern during sintering on Earth.

ACKNOWLEDGEMENTS

Sample preparation and analysis involved support from Louis Campbell, Ronald Iacocca, Yixiong Liu,
Kathy Lu, Tracy Potter, Wuwen Yi, and Anish Upadhyaya. Technical support for the experiments came
from Thomas Pendergast (ground), and Roger Crouch and Donald Thomas (microgravity). Scientific
support came from Thomas Glasgow and program management from Gilbert Santoro and Richard
DeWitt. Current research is under NASA grant NNX14AB31G managed by James Patton Downey and
Biliyar Bhat of the Marshall Space Flight Center.

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Induced Microstructural Changes in Liquid Phase Sintering", Metall. Trans. A, 1988, vol. 19A,
pp. 1905-13.
4. R.M. German, "Limitations in Net Shaping by Liquid Phase Sintering", Advances in Powder
Metallurgy, compiled by L.F. Pease and R.J. Sansoucy, Metal Powder Industries Federation,
Princeton, NJ, 1991, vol. 4, pp. 183-94.
5. R. Raman and R.M. German, "A Mathematical Model for Gravity-Induced Distortion During
Liquid Phase Sintering ", Metall. Mater. Trans. A, 1995, vol. 26A, pp. 653-9.
6. D.F. Heaney, R.M. German, and I.S. Ahn, "The Gravitational Effects on Low Solid-Volume
Fraction Liquid Phase Sintering ", J. Mater. Sci., 1995, vol. 30, pp. 5808-1812.
7. A. Eliasson, L. Ekbom, and H. Fredriksson, "Tungsten Grain Separation during Initial Stage of
Liquid Phase Sintering", Powder Metallurgy, 2008, vol. 51, no. 4, pp. 343-9.
8. Y. Liu, D.F. Heaney, and R.M. German, "Gravity Induced Solid Grain Packing during Liqiud
Phase Sintering", Acta Metall. Mater., 1995, vol. 43, pp. 1587-92.
9. O. Gillia, C. Josserond, and D. Bouvard, "Viscosity of WC–Co compacts during Sintering", Acta
Mater., 2001, vol. 49, no. 8, pp. 1413-20.
10. R.M. German, P. Suri, N.B. Erhardt, and S.H. Chung, "Gravitational Effects on Distortion in
Liquid Phase Sintering ", Advances in Powder Metallurgy and Particulate Materials compiled by
W.B. James and R.A. Chernenkoff, Metal Powder Industries Federation, Princeton, NJ, 2004,
vol. Part 5, pp. 41-50.
11. R. Ganesan, A. Griffo, and R.M. German, "Finite Element Modeling of Distortion during Liquid
Phase Sintering ", Metall. Mater. Trans. A, 1998, vol. 29A, pp. 659-64.
12. R.M. German, S.J. Park, S.H. Chung, and J.L. Johnson, "Predictions of Tungsten Heavy Alloy
Density, Size, Shape, and Microstructure in Different Gravitational Environments", 2006
International Conference on Tungsten, Refractory Metals, and Hardmetals VI, compiled by A.
Bose and R.J. Dowding, Metal Powder Industries Federation, Princeton, NJ, 2006, pp. 71-82.
13. J.A. Alvarado-Contreras, R.M. German, A.L. Maximenko, and E.A. Olevsky, "Coupled
Densification - Shape Distortion Analysis of Liquid Phase Sintering Affected by Gravity",
Metall. Mater. Trans. A, 2014, vol. 45A, pp. 927-33.
14. J.A. Alvarado-Contreras, E.A. Olevsky, A.L. Maximenko, and R.M. German, "A Continuum
Approach for Modeling Gravitational Effects on Grain Settling and Shape Distortion during
Liquid Phase Sintering of Tungsten Heavy Alloys", Acta Mater., 2014, vol. 65, pp. 187-4.
15. H.L. Frandsen, E.A. Olevsky, T.T. Molla, V. Esposito, R. Bjork, and N. Pryds, "Modeling
Sintering of Multilayers Under Influence of Gravity", J. Am. Ceram. Soc., 2013, vol. 96, no. 1,
pp. 80-9.
16. F.V. Lenel, H.H. Hausner, E. Hayashi, and G.S. Ansell, "Some Observations on the Shrinkage
Behaviour of Copper Compacts and of Loose Powder Aggregates", Powder Metallurgy, 1961,
vol. 4, pp. 25-36.
17. F.V. Lenel, H.H. Hausner, O.V. Roman, and G.S. Ansell, "The Influence of Gravity in Sintering",
Trans. AIME, 1963, vol. 227, pp. 640-44.
18. R.M. German, "Pore Buoyancy and Grain Compression Contributions to Densification in Liquid
Phase Sintering", Proc. 4th Inter. Conf. Science, Technology and Applications of Sintering,
Institut National Polytechnique de Grenoble, Grenoble, France, 2005, pp. 303-6.
19. Y. Liu, R.G. Iacocca, J.L. Johnson, R.M. German, and S. Kohara, "Microstructural Anomalies in
a W-Ni Alloy Liquid Phase Sintered under Microgravity Conditions", Metall. Mater. Trans. A,
1995, vol. 26A, pp. 2484-6.
20. A. Kneissl and H.F. Fischmeister, "Materials Solidification and Ostwald Ripening of Near-
Monotectic Zinc-Lead Alloys", Sci., 1984, vol. 225, pp. 198-200.
21. J.R. Cahoon, M.C. Chaturvedi, and K.N. Tandon, "The Unidirectional Solidification of Al-4 Wt
Pct Cu Ingots in Microgravity", Metall. Mater. Trans. A, 1998, vol. 29A, pp. 1101-11.
22. Z. Cheng, P.M. Chaikin, J. Zhu, W.B. Russel, and W.V. Meyer, "Crystallization Kinetics of Hard
Spheres in Microgravity in the Coexistence Regime: Interactions between Growing Crystallites",
Physical Review Letters, 2002, vol. 88, no. 1-4, p. 15501.
23. P. Lu, R.M. German, and R.G. Iacocca, "Presintering Effects on Ground-Based and Microgravity
Liquid Phase Sintering", Metall. Mater. Trans. A, 2001, vol. 32A, pp. 2097-107.
24. R.M. German, "Microstructure of the Gravitationally Settled Region in a Liquid Phase Sintered
Dilute Tungsten Heavy Alloy", Metall. Mater. Trans. A, 1995, vol. 26A, pp. 279-88.
25. A. Tewari, A.M. Gokhale, and R.M. German, "Effect of Gravity on Three-Dimensional
Coordination Number Distribution in Liquid Phase Sintered Microstructures", Acta Mater., 1999,
vol. 47, pp. 3721-4.
26. R.M. German, S.J. Park, and J.L. Johnson, "Critical Learning from Microgravity Sintering of
Tungsten Alloys: Implications for Extraterrestrial Fabrication and Repair", Proceedings of the
16th International Plansee Seminar, compiled by G. Kneringer, P. Rödhammer, and H. Wilder,
Metallwerk Plansee, Reutte, Austria, 2005, pp. 672-83.
27. L.G. Campbell and R.M. German, "Gravitational Effects on Microstructures in Liquid Phase
Sintering", Advances in Powder Metallurgy and Particulate Materials, compiled by J. Engquist
and T.F. Murphy, Metal Powder Industries Federation, Princeton, NJ, 2007, vol. 8, pp. 8.10-8.28.
28. L.G. Campbell, J.L. Johnson, and R.M. German, "A Quantitative Model for the Effects of Gravity
on the Mechanical Behaviour of Tungsten Heavy Alloys", Proceedings of the 17th International
Plansee Seminar, compiled by L.S. Sigl, P. Roedhammer, and H. Wildner, Metallwerk Plansee,
Reutte, Austria, 2009, pp. RM69.1-12.
29. J.L. Johnson, L.G. Campbell, S.J. Park, and R.M. German, "Grain Growth in Dilute Sintered
Tungsten Heavy Alloys during Liquid-Phase Sintering under Microgravity Conditions", Metall.
Mater. Trans. A, 2009, vol. 40A, pp. 426-37.
30. R.M. German, Powder Metallurgy of Iron and Steel, 1998, Wiley, New York, pp. 22-29.
31. J.L. Johnson, A. Upadhyaya, and R.M. German, "Effect of Solubility on Shape Retention During
Liquid Phase Sintering", Advances in Powder Metallurgy and Particulate Materials, compiled by
M. Phillips and J. Porter, Metal Powder Industries Federation, Princeton, NJ, 1995, vol. 1, pp.
4.219-4.28.
32. Z. Xue, S.L. Noojin, J.G. Vandegrift, A.K. Kuruvilla, and J.E. Smith, "Microgravity Liquid Phase
Sintering and Pore Evolution", Mater. Trans. JIM, 1996, vol. 37, no. 5, pp. 1084-90.
33. S. Kohara and M. Hoshino, "Microstructural Changes in Liquid Phase Sintered W-Ni Alloys",
Advances in Powder Metallurgy and Particulate Materials, compiled by C. Lall and A.J.
Neupaver, Metal Powder Industries Federation, Princeton, NJ, 1994, vol. 3, pp. 295-302.
34. A. Upadhyaya, R.G. Iacocca, and R.M. German, "Gravitational Effects on Compact Shaping and
Microstructure during Liquid-Phase Sintering ", JOM, 1999, vol. 51, no. 4, pp. 37-40.
35. Y. He, S. Yi, and J.E. Smith, "Pore Metamorphosis during Liquid Phase Sintering in
Microgravity", J. Mater. Sci., 2005, vol. 40, pp. 4067-75.
36. R.M. German, A. Bose, and S.S. Mani, "Sintering Time and Atmosphere Influences on the
Microstructure and Mechanical Properties of Tungsten Heavy Alloys", Metall. Trans. A, 1992,
vol. 23A, pp. 211-9.
37. K.S. Churn and R.M. German, "Fracture Behavior of W-Ni-Fe Heavy Alloys", Metall. Trans. A,
1984, vol. 15A, pp. 331-8.