Development of A Novel Method To Shape From Ceramics For Personnel Armor and SOFC Applications

EMTEC CT-83-I
Development of a Novel Method to Shape From

Ceramics for Personnel Armor and SOFC Applications
By:
Dr. Dan Edson
Dr. Suv Sengupta
Dr. J. Richard Schorr
MetaMateria Partners
1275 Kinnear Road
Columbus, OH 43212
April 2006
Final Phase I Report
Distribution of this repo rt is unlimited.
Prepared for Edison Material Technology Center

(EMTEC)
3155 Research Blvd.
Dayton, OH 45420-4006
Neither this report nor any part thereof may be reproduced or transmitted in any form or
by any means, electronically or mechanic al, including photocopying, microfilming, and
recording, or by any information storage and retrieval system without permission in writing from
the Director Core Technology Programs of the Edison Materials Technology Center (EMTEC).
This Technical Report has been reviewed and is approved for publication.
___________________________
Percy J. Gros, Jr.
Director Core Technology Programs
EMTEC
Copyright ©2006, EMTEC, 3155 Research Blvd., Dayton, Ohio 45420-4006

Project CT-83
EMTEC Phase I Final Report
EMTEC Phase I Final Report .................................................................................................. 1

EMTEC Phase I Final Report .................................................................................................. 1
Introduction ..........................................................................................................................1
Work Plan ............................................................................................................................ 5
Task 1: Development of Excera’s Proprietary Preform Misture and Al2O 3
Colloid/Suspensions......................................................................................................... 5
Task 2: Development of Plastic Preforms Using Modified Casting Process.................. 5
Task 3: Investigate Effect of Plastic Deformation ...........................................................6
Task 4: Make Test Pieces for Evaluation by Production Partners................................... 7
Task 5: Evaluation of Part Quality/Properties/Performance............................................ 7
Task 6: Process Cost Estimate .........................................................................................7
Task 7: Reporting.............................................................................................................8
Results and Discussion......................................................................................................... 8
I. EXCERA ARMOR PREFORMS ............................................................................ 9
II. ALTERNATE EXCERA COMPOSITIONS.........................................................31
III. RUTGERS NANOSTRUCTURED COMPOSITE ARMOR ............................... 32
IV. FUEL CELL COMPONENTS ..............................................................................36
Manufacturing Cost Estimate– Task 6 ...........................................................................38
Conclusions ........................................................................................................................40
References ..........................................................................................................................40
MetaMateria Partners/Excera Materials Group

Project CT-83
EMTEC Phase I Final Report
Introduction
Many of today’s high-tech applications for ceramic materials require that the components
are high in density, often approaching fully dense.1,2 The traditional method to obtain high
density ceramic materials is to press or cast a part to shape, often with the aid of some
organic binder material to supply green strength, and then heat the part to an elevated
temperature for an extended period of time. Usually a glassy-phase or other liquid-phase
promoter is added to enhance the sintering and densification. Exotic, high-purity ceramic
materials that are desirable due to high strength and high melting-temperature properties
have proven to be difficult to sinter and densify using the traditional method, especially
since these sintering aids can not be employed as they are often detrimental to the properties
of the sintered part. Exceptionally high temperatures, often exceeding 2000°C, and the
assistance of pressure are needed to fully densify technologically important materials such
as boron carbide and silicon carbide. High temperature and high pressure processing
methods are costly with steep investment requirements and energy demands.
The amount of densification required during sintering is directly related to the green density
of the part prior to sintering. A part that has a 50% green density (relative to full theoretical
density) must increase in density 100% while a part that has a green density of 67% only
needs to increase 50% to become fully dense. During sintering, large pores usually can not
be removed, but instead are persistent through the sintering process. Pores usually act as
stress concentrators in parts and often lead to premature mechanical failure and lower
observed strengths. Large pores in the sintered part are associated with regions of low
particle packing in the green part. So, both high green density and homogeneous particle
distribution is important to produce parts that exhibit both high density and small defects.
MMP had developed a colloidal casting approach to make near-net shaped ceramic parts that
is aqueous-based and uses only a small amount of organic. This fabrication method is called
MMCP (MetaMateria Colloidal Process) and is being used to produce a variety of ceramic
components from various ceramic powders including Al2O 3, NiO, YSZ, CGO, SOFC
cathode materials and others. Some of the SOFC components that have been made using
MMCP are shown in Figure 1. MMCP offers processing advantages versus other traditional
ceramic forming methods like dry pressing, slip casting and wax-based injection molding
such as the ability to cast complex shapes, aqueous-based, low-temperature, low-pressure,
low organic content, high particle homogeneity and mixing and minimal particle orientation
preferentiality. A flow diagram of MMCP is shown in Figure 2. The two primary
limitations of MMCP are the observation of rogue pores and that the density of the green
part is limited by the solids loading of the MMCP slurry.
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Figure 1. Alumina SOFC parts cast using MMCP.
The presence of random and visually apparent rogue pores is especially detrimental to the
strength and mechanical properties of the final ceramic parts. In an attempt to eliminate
these pores, a 12.8 mm diameter green part was placed in a uniaxial die and pressed. The
thickness of the part decreased significantly. The experiment was repeated with a second
part and the thickness was measured to decrease from 10.41 mm to 9.05 mm, as shown in
Figure 3. The part did not exhibit cracking suggesting that after drying, parts made by
MMCP retain appreciable plasticity. The decrease in thickness correlates directly to a
significant increase in green density. Through the use of pressure assistance, it was
proposed that the two primary limitations of MMCP could be overcome. This plasticity may
also lend itself to other forming methods that are similar to those traditionally used in metal
fabrication, such as rolling or stamping.
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Powder Water Organic Additives
Mix
Suspension
Cast
Coagulation
Dry
Sinter
Figure 2. Process flow diagram of MMCP.
Figure 3. Plastic alumina pellet made by casting and then deformed under pressure.
To exploit this new technology two focus areas were identified; ballistic armor and solid
oxide fuel cells. Ceramic inserts for ballistic armor must be strong, hard and lightweight.
Boron carbide, which is the third hardest bulk material and has a density of only 2.52 g/cc, is
the material of choice for inserts for personnel armor. Boron carbide does not readily sinter
under standard processing conditions, but instead requires high temperatures and pressures
to reach high density.3 High density is required to attain the required mechanical properties
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to defeat ballistic threats. While not as demanding as boron carbide, YSZ used in SOFC
electrolytes must also be strong and fully dense for use in electrolyte supported cells.
Pinholes and pores in the electrolyte will provide a gas path for the fuel to mix with air in
the cell. YSZ requires temperatures of about 1600°C to become fully dense. Likewise,
alumina manifold components are also sintered to about 1600°C to impart high strength,
good thermal shock resistance and low gas transport. By increasing the green density of the
part, the amount of densification work required during sintering is reduced.2 This reduction
enables shorter sintering cycles and/or temperatures which allows for less expensive, lower
temperature furnaces or higher product throughput.
MMP has teamed with two commercial partners to move the pressure assisted MMCP (PA-
MMCP) technology into the market place; Excera Materials Group and NanoDynamics
Incorporated.
Excera Materials Group, Inc. is a company located in Worthington, OH and founded to

commercialize their novel metal infiltration technology for making unique ceramic/metal
composite (ONNEX) materials. The ONNEX material has interwoven ceramic and metallic
networks. The structure is produced by immersing a porous ceramic preform into a molten
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metal bath which causes a transformation reaction. These materials are targeted at
applications such as personnel armor and brake linings. Excera has some 21,000 square feet
that is configured to allow preparation and evaluation of a wide range of composite
materials, including preparation and forming of parts in both air and in controlled
atmospheres and equipment for characterization of these materials with respect to
microstructure, porosimetry and select mechanical properties (e.g., hardness, elastic
modulus, Poisson’s ratio).
Excera’s pilot production facility includes four unique processing furnaces capable of daily
making several hundred pounds each of their ONNEX composite materials. The furnaces
are equipped for real-time monitoring and logging of key process variables.
Excera currently purchases ceramic armor preforms from a company in Georgia. These are
made by injection molding; however, Excera is very interested in an alternative, lower cost
method for making these preforms.
NanoDynamics Incorporated (NDI) was founded in 2002 to develop and manufacture high
performance nanomaterials, components and systems based on these technologies.
NanoDynamics plans to introduce a commercial microtubular SOFC product (RevolutionTM)
into the market in 2006. This complete power plant is a highly efficient, fuel flexible solid
oxide fuel cell developed for portable applications including electronics, defense, safety,
signage, personal transportation, and outdoor appliances. It does not require a separate
reformer and can be operated at temperatures significantly below that of other SOFC
systems. The estimated market for the portable advertising and signage application is 25,000
units/year and early applications for portable systems are estimated to be more than $300
million.
NDI has some 50,000 sq. ft. of product development and manufacturing space. Its
principals have, cumulatively, several decades of direct fuel cell experience. The base
SOFC technology was acquired from a European firm.
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Work Plan
The work plan for the Phase I project was broken into seven Tasks.
Task 1: Development of silica/boron carbide and Al2O 3 colloid/suspensions
Task 2: Development of plastic preforms using modified casting process
Task 3: Investigate the effect of plastic deformation
Task 4: Make test pieces for evaluation by Production partners
Task 5: Evaluation of part quality/properties/performance
Task 6: Process Cost estimate
Task 7: Reporting
From the proposal:
Task 1: Development of Excera’s Proprietary Preform Misture and Al2O3

Colloid/Suspensions
One of the advantages of MMCP is that a high level of homogeneity can be
maintained using a suspension. Typically, suspensions of high solid loadings
(>50+vol %) are used in this process. The green density typically reflects the solids
loading of the suspension. Two types of suspensions will be produced in this
program. A proprietary suspension will be produced as preforms for armor plates
and a high solids loading Al2O3 suspension will be used for fabrication of SOFC
manifold parts.
The suspensions will be prepared by adding suitable amount of the ceramic
(proprietary or Al 2O3) powder to a solution containing water and additives. The
maximum amount of organic additives will be less than 5 wt %. Care will be taken
to minimize any bubble formation. The temperature of the suspension and pH will
be adjusted to achieve best possible dispersion. Viscosity of the suspension will be
monitored during dispersion of the ceramic particles. Elimination of any bubbles is
critical in this process, as these would manifest themselves as voids in the solid
preform. The composition of the suspension will be adjusted to produce a plastic
preform that can easily be deformed.
The output of Task 1 will be process information for making concentrated
suspensions of the powders to be used for the desired parts.
Task 2: Development of Plastic Preforms Using Modified Casting Process

Several pellets as well as slabs will be fabricated in Task 2 and these will be used to
investigate the effect of deformation on the density and microstructure after plastic
deformation. The composition of the suspension will also be modified in order to
improve the plasticity of the preforms.
Parts produced by using colloidal casting will be partially dried. In the proposed
approach, our objective is to remove the maximum amount of water at this stage
while maintaining the desired plasticity required for further plastic deformation. Our
preliminary experiments indicate that most of the water may be removed without
sacrificing plasticity.
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Furthermore, removal of water is more difficult at the high green density and fine
pore size obtained after deformation, which can cause cracking during drying.
Drying is a critical step in colloidal processing of bulk materials. It is a multistage
process that involves capillary driven fluid flow, viscous deformation of the body,
evaporation, and diffusion. Removal of liquid from the bulk body often leads to
problems with dimensional control. Drying of a green body prepared by using
colloidal processing techniques can be divided into three stages: (i) constant-rate
period (CRP), (ii) first falling-rate period (FRP1), and (iii) second falling rate period
(FRP2). In the CRP, the drying rate is controlled by the external conditions. Liquid
is supplied by capillary driven transport to the external surface (s) of the green body,
where the evaporation takes place. As drying proceeds, the large pores drain as
1,2
liquid is drawn to smaller pores with higher suction potential.
The drained pores may penetrate far into the interior of the green body, provided the
rate of capillary redistribution of the liquid exceeds the evaporation rate. The
transition to the FRP1 occurs when the liquid can no longer be supplied to the
external surface(s) at a rate equivalent to the evaporation rate observed during CRP.
As further evaporation occurs, the liquid resides in the isolated pockets, thereby
marking the transition to FRP2. In FRP2, the remaining liquid is removed by vapor-
phase diffusion.
Most of the shrinkage occurs during the first stage of drying. In this period,
evaporative processes lead to an increase in the colloid volume fraction in the layers.
Consolidation persists until the particle network can completely support the drying
stress imposed by the capillarity. The microstructure of the preform will be studied
by using scanning electron microscope (SEM).
The output of Task 2 will be process information regarding conditions under which
high density parts can be formed into desired shapes.
Task 3: Investigate Effect of Plastic Deformation

In Phase I of the proposed EMTEC program, we will only investigate the potential
for using plastic deformation by using pressing (forging) in order to plastically
deform the solid preform produced as a result of Task 2. In Phase II other plastic
deformation processes, like rolling, drawing will also be investigated.
Our objective in Task 3 is to obtain maximum deformation without increasing
defects. In Phase I, we will focus on deformation under uniaxial loads. Ideally, as
the plastic preform is densified, pores are expected to collapse or be reduced,
resulting into a more uniform and homogeneous microstructure. As pores are
reduced, a decrease in volume is also expected.
Evolution of the microstructure as a function of deformation rate and total
deformation will be investigated. A small hot stage to heat the preform and the die
will also be used to investigate the effect of temperature; however, the maximum
temperature will be limited to 50-60°C so that the sample always stays below the
decomposition temperature of the additives (organics). The microstructure will be
studied using scanning electron microscopy techniques. The final preform (after
deformation) will be sintered to a desired density and the microstructure of the final
preform will be investigated.
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The output of Task 3 will be an understanding of the plastic deformation properties

and properties of the densified materials.
Task 4: Make Test Pieces for Evaluation by Production Partners

Once a better understanding of the deformation process and the process parameters
are established, samples suitable for infiltration by Excera and manifolds for
NanoDynamics will be developed.
Plates (4″x 4″x 0.175″ ) will be prepared for evaluation by Excera using proprietary
suspensions. Special proprietary shaped parts for manifolds will be developed for
NanoDynamics by using Al2O 3 suspensions. The shapes required by NanoDynamics
will be identified in the earlier stage of the program. We envision special dies will
need to be constructed for deforming the plastic green bodies particularly for
NanoDynamics.
The final preform (after deformation) will be sintered to high density (~80-85 % of
the theoretical) for the proprietary preform desirable for infiltration and (~95 % of
the theoretical) for the SOFC components.
The proprietary tiles will be transformed into a metal/ceramic composite by Excera
using their molten conversion process. The output of Task 4 will be parts that can be
evaluated by our Partners.
Task 5: Evaluation of Part Quality/Properties/Performance

The mechanical properties as well as the microstructure for both the armor tiles as
well as the manifolds will be tested. The armor tiles will be laid-up in a standard test
pattern for ballistic testing. The test panels will be sent to UDRI Impact Physics lab
for ballistic testing. All ballistic testing will be performed to determine V50 data for
the M855 round. Manifolds will be tested by NanoDynamics in one of their test
cells.
The output of Task 5 will be comparative performance and properties of parts tested.
Task 6: Process Cost Estimate

With the help of its partners, MetaMateria will develop an overall manufacturing
cost estimate for making parts using its forming technology. A paper study will be
conducted to assess the benefits versus the cost for the proposed manufacturing
approach, as compared with alternative processes, such as injection molding
currently be used to make preforms for Excera.
This task will result in each of the process steps being defined, including the
materials and equipment required. Cost estimates for the materials and equipment
will be obtained. This information will include the impact of higher volumes. A
process flow diagram will be used to define the manufacturing operations, which will
include labor and manufacturing overhead costs. Reasonable projections can then be
made of the cost and selling price for parts.
The output of Task 6 will be a process cost model.
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Task 7: Reporting
Reports will be submitted as required by EMTEC. Upon completion of the project a
final report will be prepared, which will include technical breakthroughs,
experimental results, test results, the cost estimate, future recommendations, and
proposed commercialization approach.
Results and Discussion

When the project was proposed, two different applications were suggested for PA-MMCP;
armor preforms for Excera that contain a proprietary powder mixture and dense parts for
SOFC applications made from alumina. At that time, the Excera composition was very well
defined with the powder composition anticipated to be a “drop-in” addition with little
expectation for development work. Since Excera had attained the desired properties from
their transformed ONNEX material and were filling orders, they were primarily interested in
a lower-cost preform production method. The alumina composition was based on the
powders that MMP uses in MMCP to cast parts that are fired to full density.
After work began, several significant challenges to the scope of the project were
encountered. The initial development work focused on the armor preforms since Excera
was shipping large amounts of product and the path to commercialization was perceived
shorter. The work on the SOFC applications was minimized since a specific part had not
been identified. After the initial work with pressing small pellets, it was determined that
PA-MMCP is not well suited to parts with complex shapes. This observation suggested that
alumina SOFC parts probably would not benefit from the added processing steps of PA-
MMCP. SOFC work instead focused on processing YSZ plates for electrolyte supported
cells. Still, the work lacked a specific market pull product since NDI utilizes an anode
supported cell technology. In the Third Quarter of the project after an EMTEC review, the
decision was made to focus primarily on the armor aspects of the project. SOFC
applications would be pursued as identified.
At about the same time as the shift away from SOFC applications, NDI licensed a
technology from Rutgers University. This new technology is a low cost method to produce
a metastable powder precursor which when processed at elevated temperatures produces a
nanostructured composite material. The technology was developed by a group at Rutgers
that focuses on the science and development of ceramics in armor applications. Based on
the early results at the university, the technology was licensed for development as a new,
light-weight vehicular ballistic armor. Since MMP was working with Excera on ballistic
armor, NDI felt that the development work should be conducted at MMP. EMTEC agreed
to the addition of making armor preforms with powder from the Rutgers technology under
the program.
The other deviation in materials came early in the program when the Army changed the
ballistic specifications for personnel armor. This change from the SAPI to the ESAPI
specification required improvements to be made to the state-of-the-art Excera composition
to attain the higher required properties. To this end, work was done on variations in the
initially proposed composition, around which the bulk of the project work was conducted,
and in looking at other alternative compositions.
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The Results and Discussion section is organized into the work on each of these materials
subsets. The bulk of the work was conducted around the primary Excera composition, so
this work is presented first. In the development of the PA-MMCP process during Phase I,
every aspect of the process was investigated, often in an iterative manner in conjunction
with other stages in the process. The results from the Excera work will be presented in
terms of the processing steps. The relevant Task is listed for each process step as it is
introduced. The second material discussed will be the alternate armor compositions which
were of interest to Excera. Development work on the Rutgers Technology will be discussed
next and finally the SOFC work with YSZ for planar supports. The specific Task
correlation is not listed for the latter three materials, but is similar based on the processing
steps to the work on the Excera armor preforms.
I. EXCERA ARMOR PREFORMS
Batch Composition – Tasks 1, 2

The initial powder composition of the Excera armor was provided to MMP at the beginning
of Phase I. During the course of the project, Excera adjusted the batch details to improve the
mechanical properties of the transformed plates and to investigate various interactions of the
ONNEX process. All ceramic powders incorporated into the Excera armor preforms were
supplied by Excera.
The initial composition, termed BC1, is the same as that used by Excera at the beginning of
the program to make preforms using the wax-based injection molding process which PA-
MMCP is being developed to replace. This composition was a pre-existing, proprietary
mixture labeled BC-1. MMP was able to take this composition and use PA-MMCP to cast
4” x 4” plates with high green densities.
The second composition, BF1, is a variation on BC1. This composition was investigated to
determine if by lowering the grain size the mechanical properties could be improved. The
concept of reducing critical flaw size is based in the well-known Griffith’s flaw theory for
5
brittle failure of ceramic materials.
Much of the work at the end of Phase I focused on a third composition, BF2.
Dispersion – Tasks 1, 2
PA-MMCP is an aqueous-based process that uses a small amount of organic to impart green
strength and plasticity to the cast part prior to sintering. Through the use of organic
additives that act as dispersants, the solids loading of the slurry can be maximized which, in
turn, decreases the amount of pressure-assisted densification that is required. In order to
make parts with high green densities, a process to produce a stable suspension with high
volume loading of ceramic particles was developed.
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Suspensions based on the BC1 composition were produced to determine the attainable solids
loading using three additives when coupled with the other components necessary for
colloidal casting. An aqueous slurry with a solids volume loading of about 65% and about 4
weight percent of organics was developed.
Parts Fabrication – Tasks 2, 4

Four different sizes of sample were fabricated for study; half-inch diameter, one inch
diameter, 4” x 4” square plates and full size ESAPI plates. The half-inch diameter samples
were cut as plugs from a larger sheet formed by pouring the slurry. The one inch samples
were cast into one inch diameter plastic molds by pouring of the slurry. The larger 4” x 4”
were formed by injecting the slurry into a closed die, as were most of the ESAPI plates.
Figure 4 shows photographs of the 4” x 4” plates. A green ESAPI plate formed by injection
is shown in Figure 5. Some work was also done with slump forming of a sheet that was
formed by pouring into a rectangular mold, solidification, slumping to the curved shape of
the mold, and drying. A small 4” x 4” sample slumped very well and dried to the shape of
the mold, while a larger sheet exhibited drying cracks following slump forming. The level
of organic plays an important, though not completely understood, role in preventing
cracking during the drying process.
Figure 4. Photograph of green and sintered 4” by 4” tiles.
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Figure 5. Photograph of green ESAPI plate made by MMCP.
Prior to this program, a part the size of the Excera ESAPI plate had never been attempted
using MMCP. Proving that larger parts could be made was important in order to
demonstrate the applicability of the process to manufacturing the proposed parts. The
modified ESAPI breast plate die (see Figure 6) was delivered to MMP by Excera at the end
of the Fourth Quarter at which time MMP began working to incorporate the die into the PA-
MMCP shape forming process. The ESAPI plate is much larger than any part previously
cast by MMCP. Several different approaches to injection were attempted to produce defect-
free preforms. The primary hurdles to overcome in casting parts were die filling and die
cooling.
The slurry for the 4” x 4” plates are injected using a small ram injector. The capacity of the
small ram is such that seven injections were required to fill the entire ESAPI die. As one
would anticipate, the part exhibited large voids, most likely introduced between injections
when the injector was separated from the die cavity. Outside of those voids, the die
exhibited complete filling. A picture of the part after removal from the die is shown in
Figure 5. The part exhibited good green strength. The production of the part proved that
MMP would be able to make parts with larger dimensions. The part was not CIP’ed or
transformed. Instead it was used to mold face and back CIP mandrels from carbon fiber
composite for use in a CIP bag to support subsequent parts during the pressing operation.
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Based on the earlier limited success of the ram injector used for injecting the initial plate, a
larger ram injector system was sourced and procured. The issue of die cooling was also
addressed before the fourth plate was attempted. The slurry was mixed and injected using
the large ram injector in a single injection step. The die was then disassembled and the plate
was removed from the die and placed in a custom contoured drying rack to maintain shape
while drying. The part was cracked during die removal because of inadequate die
lubrication. The die was reoriented vertically for two additional injections which helped
limit the formation of surface pores between the part and the internal top surface of the die
caused by trapped air on the die.
Figure 6. ESAPI injection die with cooling water from chiller following injection.
Drying – Task 2
PA-MMCP is an aqueous fabrication process. In order to eliminate the variability caused by
different residual water contents and to maximize the green density following the pressing
step, all of the parts were dried to similar water contents, usually five weight percent of the
ceramic mass. Drying curves such as the example shown on Figure 7 were measured to help
estimate the drying time necessary to reach the optimal water content at pressing. The
curves are S-shaped with an almost linear central region when water content is plotted
versus the square root of time. This linearity suggests a diffusion controlled process in this
region. The samples show similar drying behavior. Drying is also important in that the
stresses that develop during the drying process can cause cracking if the part does not
possess enough green strength. Improving the drying process to be repeatable on a
manufacturing scale will be a continuing challenge for this technology at these high green
density levels.
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25
20
Water Content (%)
15
10
0
0 1 2 3 4 5 6 7
Drying time (hr^0.5)
Figure 7. Drying curve for thick plates with composition.
Pressing – Task 3
The pressure-assisted aspect of the PA-MMCP is the primary consideration under
development in this program. Much work was focused on this area. The water content at
pressing, organic content, and number of pressing cycles all influence the green density
following pressing.
Figure 8 shows the effect of water content on the density when a sample is pressed a single
time. As shown in the figure, water plays an important role in the level of densification that
is attainable by pressing. At lower organic additive levels, the pressed density exhibits a
maximum with decreasing water content. Pressed, green densities as high as 82% were
observed. Two competing processes are believed to affect the level of densification when a
sample is pressed with residual water. The pores must be free of water so that the particles
can rearrange to a smaller volume by moving into the void space. To attain a density of
82% with about 4 weight percent organic (~8 volume percent) requires that only about 10
volume percent is filled with water, which correlates to about 5 weight percent. However,
water also acts as a plasticizer to allow the particles to rearrange more easily at a lower
applied stress. Adding organic plasticizer should decrease the amount of pressure required
for densification. However, organic additives will also occupy pore volume, thus reducing
the attainable density, and are more difficult to remove from the structure than water.
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85 Level 1
Density (Percent Theoretical)
Level 2
80
Level 3
75
70
65
60
0 5 10 15 20 25 30 35 40
Water Content (Volume Percent)
Figure 8. Density as a function of water content for pressed pellet made by colloidal casting
at three different additive concentrations.
The amount of pressure during pressing has a direct impact on the density, as shown in
Figure 9. Three samples were measured at each load. Density increases with increasing
load. The parts with the highest densities were pressed at the highest loads. Since very high
loads are not practical based on the size of the preforms for which this process is being
developed, the effect of multiple pressings at lower pressures was investigated. The
influence of repeated pressing on deformation is shown in Figure 10. A single pellet was
pressed six times at 2000 pounds load, followed by four times at 4000 pounds load and
finally five times at 6000 pounds load. The pellet was removed from the die after each cycle
and the dimensions of the pellet were measured using calipers. The pellet was compressed a
total of 19% in the axial direction and was unchanged in dimension in the radial dimension
since it was confined within the die. The density of the pellet increases from about 63% to
about 77% of theoretical. Each subsequent pressing cycle at the same load decreases the
thickness of the pellet by a decreasing amount, while increasing the load causes a more
significant decrease in thickness.
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76
Density (Percent Theoretical)
75
74
73
72
71
70
0 1000 2000 3000 4000 5000 6000 7000 8000
Load (Pounds)
Figure 9. Density as a function of load for pressed BC1 parts.
11.0
10.5
Thickness (mm)
10.0
9.5
9.0
8.5
0 2000 4000 6000 8000
Load (Pounds)
Figure 10. Thickness of a single pellet which was pressed repeatedly as a function of
pressing load.
Large capacity presses require considerably more capital investment than lower capacity
presses. To improve the economics of the technology, the pressing pressure must be
reduced as much as possible while still attaining the required level of green density. Based
on the success of multiple pressing cycles, rapid cyclic pressing (RCP) was investigated. A
series of one inch diameter BF2 samples were prepared and dried to about five weight
percent residual water. The samples were then placed in a steel uniaxial die and rapidly
pressed to loads of 1000, 3000, 5000 and 10000 pounds for one cycle or 1000 cycles. Each
cycle alternated from full load to 80% of full load. Additional samples were pressed 10 and
100 cycles at the 5000 pound load. The samples were then completely dried and the density
was calculated geometrically. The density of the samples as a function of pressure is shown
in Figure 11. At the lowest pressure, there is not a significant increase in density after 1000
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cycles. The amount of improvement in density increases with increasing pressure between
the samples that experienced one pressing cycle and the samples that experienced 1000
cycles. The sample pressed at 6000 psi for 1000 cycles is 3.5% more dense than the single
pressed sample (in terms of absolute density). The sample pressed at 12000 psi and 1000
cycles is 4.0% better. The 1000 cycle sample at 3600 psi is more dense than the single
pressed sample at 6000 psi and the 1000 cycle sample pressed at 6000 psi is 1.2% more
dense than the single cycle sample at 12000 psi.
78%
76%
Gre en Density (% theoretical)
1 cycle
1000 Cycles
74%
72%
70%
68%
66%
0 2000 4000 6000 8000 10000 12000 14000
Pressure (psi)
Figure 11. Green density of BF2 samples after rapid cyclic pressing.
The densities of the samples pressed at 6000 psi using RCP are shown in Figure 12 as a
function of the number of cycles, on a log scale. The density is unchanged between the
sample pressed one cycle and ten cycles. The density is higher for the sample pressed for
100 cycles and highest for the sample pressed for 1000 cycles with the densities of the three
samples falling on a straight line when plotted versus the log of the number of pressing
cycles.
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74.5%
74.0%
73.5%
Density (% theoretical)
73.0%
72.5%
72.0%
71.5%
71.0%
70.5%
1 10 100 1000
Number of pressing cycles
Figure 12. Density of samples pressed at 6000 psi using rapid cyclic pressing.
All of the 4” x 4” plates and ESAPI plates that have been densified were pressed in a cold
isostatic press (CIP) on a toll basis. Since water transfers pressure uniformly, CIP does not
face the same limitations in scaling that standard presses do. However, CIP requires more
complicated handling in packaging the parts before processing such that none of the CIP
liquid comes in contact with the part. Based on the risk of bag and seal failure, CIP
inherently risks lower yields than uniaxial pressing.
The impact of different organic content of the slurry on the pressed density was investigated
as a function of residual water content using the BF2 composition. The organics used in the
PA-MMCP process can be classified in terms of traditional binders and plasticizers and
dispersants. A series of samples with varying amounts of binder and plasticizer were made
and are denoted by compositions 1, 2, 3 and 4. The relative amounts of binder and
plasticizer for each composition are given in Table I. The amount of water in each slurry
was adjusted so that the ceramic solids loading was about 57 volume percent. Half-inch and
1 inch samples were prepared. Some of the half-inch samples were pressed a single time to
about 32,000 psi at various stages of residual water content. The final density was then
calculated after being fully dried from the geometry of the samples and the mass. The mass
of the organics as calculated based on the slurry composition was removed from each
sample mass so that comparisons between the different compositions could be made. The
green density as a function water content during pressing is shown in Figure 13. The
pressed density of Composition 1 samples decrease with decreasing water content.
Composition 3 exhibited the least impact of decreasing water content on pressed density.
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Table I
Relative amounts of binder and plasticizer in compositions 1, 2, 3 and 4.
Composition Binder Plasticizer

1 1x 0x
2 1x 1x
3 1x 2x
4 2x 2x
75
74
De nsity (% theore tica l)
73
1
72 2
71 3
4
70
69
68
0 2 4 6 8 10 12 14
Water content (wt% versus dry)
Figure 13. Density as a function of residual water content for BF2 samples containing
different amounts of binder and plasticizer.
The remaining half-inch diameter samples were pressed three times while drying. The
samples were pressed to a pressure of about 14,000 psi. After completely drying, the
densities of the samples were calculated geometrically. Again the mass of the organics was
subtracted from the density calculation to enable comparison of the green densities. The
density as a function of composition is shown in Figure 14. The pressed density increases
with increasing amount of plasticizer and decreases with increasing amount of binder.
Again, comparison of the values in Figure 13 and 14 suggests that similar density values can
be attained with lower applied pressures if repeated pressings are employed.
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74.0
73.5
73.0
72.5
72.0
71.5
71.0
0 1 2 3 4 5
Sample Composition
Figure 14. Density as a function of organic composition for samples that were pressed
multiple times during drying.
MMCP is a near-net shape forming process that takes a slurry through a solidification
process step where the organic additives form a rigid structure that gives the part immediate
green strength. This solidification step is thermally induced and reversible. The impact of
the rate and intensity of the thermal change during the solidification step on the pressed
density was investigated. Five different cooling methods were identified and are referred to
as A, B, C, D, and E. The qualitative level of thermal quench associated with the five
methods increases from A to E. Two cooling times were measured for each of the methods
C, D and E. A single batch containing 65 volume percent solids was made and cast into 16
1-inch diameter samples by pouring. Two samples were exposed to each of the given
cooling methods and allowed to dry under ambient temperature and humidity conditions to a
target of 5 weight percent water (versus dry) as calculated based on the mass as cast and
slurry composition. Each sample was uniaxial pressed three times with a twenty second
hold at pressure to a pressure of about 8200 psi. The samples were then allowed to finish
drying in an oven at 100°C. The density of each sample was calculated based on the fully
dry mass and measured sample dimensions. The density as a function of cooling method is
shown in Figure 15. An appreciable variation in density is observed based on the cooling
method and time. The methods with the intermediate level of quench rate result in the
highest densities following pressing.
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79%
78%
77%
76%
75%
74%
73%
72%
71%
70%
69%
68%
A 3 hr B 3 hr C 30 min C 3 hr D 5 min D 30 min E 5 min E 10 min
Cooling Method
Figure 15. Density following uniaxial pressing of coarse mix samples dried to 5 weight
percent water that were solidified by various cooling methods.
The impact of pressing on the size of pores is shown in Figure 16. The optical micrograph
on the left shows the cross section of a sample that was dried without pressing while the
micrograph on the right shows a similar sample that was pressed with 5 weight percent
residual water. Several large pores can be seen in the micrograph of the sample that was not
pressed. Similar pores are not observed in the sample after pressing.
Figure 16. Micrograph of dried armor preforms. Sample on left was not pressed while
sample on right was pressed.
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The elimination of large rogue pores were also observed in the samples when examined
using SEM. Figure 17 shows SEM micrographs of a one inch diameter sample formed by
pouring. Large, spherical pores with diameters over 100 microns are observed. Smaller,
irregular voids are also prevalent in the micrographs. Figure 18 shows SEM micrographs of
a sample with identical composition that was dried to 5 weight percent water content and
pressed in a uniaxial die to about 6000 psi for 3 pressing cycles. None of the large spherical
pores are present in the micrographs. Also, only a few irregular shaped voids can be seen.
These voids are much smaller than those that are present in the unpressed sample. Figure 19
shows SEM micrographs for a sample that was pressed using filtration pressing at about
2500 psi. The micrographs do not exhibit the spherical pores observed in the micrographs
of the unpressed sample. The size and number of the irregular shaped voids lies between
that of the unpressed sample and the sample pressed after partial drying at more than twice
the pressure. PA-MMCP appears to be very effective at eliminating large spherical pores
and significantly reduces the number and size of the smaller irregular pores.
Figure 17. SEM micrographs of unpressed green sample.
Figure 18. SEM micrographs of green sample pressed to 6000 psi for 3 cycles.
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Figure 19. SEM micrographs of green BF2 sample processed by filtration pressing at 2500
psi.
Filtration pressing combines aspects of forming, drying and pressure densification in the
same processing step. A design of experiment (DOE) for filtration pressing was developed
to study the effects of binder identity, binder content, plasticizer content, pressure, hold time
and number of pressing cycles. After pressing the samples were heat treated over night to
remove the organics since it is impossible to determine how much organic may have been
removed with the water during the pressing step. The mass of the samples was measured
after drying and after the heat treatment. The samples which contain lower levels of
organics gained mass during the heat treatment while the samples with higher levels of
organic lost mass. These changes in mass indicate a level of interaction between the
components in the batch during heat treatment. The densities of the samples ranged from
65% to 74% of theoretical. Based on the analysis of the DOE, only binder content, pressure
and number of cycles significantly affect the pressed density. Increasing the amount of
binder decreases the density, while increasing the load and number of pressing cycles
increases the density, over the ranges studied. From the mathematical fit of the data, over
the range studied, increasing the pressing load 1000 pounds has the same impact as
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increasing the number of pressing cycles by six. These results suggest that filtration
pressure may be a viable forming method for preform manufacture.
Mercury porosimetry was used to measure the porosity of the least dense, Sample 6 (pressed
at 1000 pound load), and most dense, Sample 19 (pressed at 4000 pound load), from the
filtration pressing experiment. The total intruded volume for Sample 6 is 0.2004 cc/g while
that of Sample 19 is 0.1321, which give percent theoretical densities similar to those
measured using the Archimedes calculation. The change in intruded volume per change in
pressure is shown as a function of pore size in Figure 20. The same data is shown in Figure
21 as pore number fraction versus pore size. From the plot in Figure 20, it can be seen that
the majority of the difference in density is related to the presence of 1 to 5 micron pores.
The pore number fraction plot in Figure 21 shows that the sample pressed at higher pressure
to higher density has a larger percentage of its porosity in the smaller pore size range.
Figure 20. Pore size distribution dV/dP versus pore size for two samples formed by filtration
pressing.
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Figure 21. Pore number fraction versus pore size for two samples formed by filtration
pressing.
Organic Removal – Task 4

Organics are added to the ceramic slurry for three reasons: promote dispersion of the
particles, provide green strength to the part after part formation, and allow plastic
deformation and densification of the parts during post-forming operations. However, after
these functions are complete, the organic additives must be removed prior to aluminum
infiltration. The traditional method of organic removal is elevated temperature
degradation/oxidation by placing the dry green part in a furnace and heating to between 200°
and 500°C.1,2 Organic removal is very dependant on the nature of the organics, interactions
between different organics or with ceramic powders, and the porosity microstructure.
Waxes, similar to those used in traditional injection molding, melt prior to being removed
during thermal treatment, which may result in slumping of the part if it is not fully
supported. In addition to slumping, defects that may arise during organic removal include
cracks, blisters, internal voids and pores. As the level of organics within the part increases,
the tendency for these defects also increases. The low level of organic additives in PA-
MMCP is one of the major advantages over the wax-based injection molding process.
Initially, the impact of binder removal was not considered to be an issue with respect to the
organic additives used by the MMCP process. The level of additives is relatively low and a
simple isothermal hold at several hundred degrees effectively removes all of the organics
without impacting the integrity of the final sintered parts for other powder compositions.
The initial work with the BC1 composition resulted in transformed parts that exhibit similar
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properties to the parts made using the wax-based injection molding process. However,
subsequent work with the smaller particle size mixes was severely limited in the ability to
infiltrate with metal.
Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) measurements
were made on the pressed and dried green BF2 preforms to help determine the optimum
organic-removal thermal cycle. Samples were measured in both oxidizing and reducing
atmospheres. The DTA and TGA curves for the sample heated in air are shown in Figure
22, while the curves for the sample heated in flowing argon are shown in Figure 23. The
samples were heated at a rate of 10 K/min. Both of the TGA curves show about 4% weight
loss at 550°C. Inflection points in the lower temperature region of the TGA curve for the
sample heated in air occur at temperatures of about 163, 187, 227, 300, 370, 555 and 635°C.
The weight loss for the sample heated in argon is similar, but shifted a few degrees toward
higher temperatures. Both of the samples exhibit significant weight gain at temperatures
above 550°C, though the sample treated in argon lags the sample treated in air by about
75°C for similar weight gains. The shape of the TGA curves are different between the two
treatment conditions at temperatures above 800°C, but both samples experience continued
increases in mass through the temperature region. The weight loss in the low temperature
region correlates to the removal of adsorbed water and the added organics, while the weight
gain at higher temperatures suggests the formation of an oxide on the particle surfaces.
Based on the TGA curves, treatment temperatures should be limited to limit the formation of
the oxide layer. Also, flowing argon does not appear to be adequately reducing to prevent
oxide formation.
112 7
110 6
108 5
4
106
Weight (%)
3
104
DT
2
102
1
100
0
98 -1
96 -2
94 -3
0 200 400 600 800 1000 1200
Temperature ( oC)
Figure 22. Combined DTA and TGA curves for BF2 sample in air.
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114 2
112
1
110
0
108
Weight (%)
-1
106
DT
104 -2
102
-3
100
-4
98
-5
96
94 -6
0 200 400 600 800 1000 1200
o
Temperature ( C)
Figure 23. Combined DTA and TGA curves for BF2 sample in flowing argon.
The DTA curves for the samples treated in air and argon are also similar, except for the
temperature region from about 420°C to 620°C and a small region around 280°C. The
initial endothermic reaction correlates to the removal of adsorbed and absorbed water. The
next region of each of the curves shows the oxidation and removal of the organics, which is
exothermic. The region of the curves above 500°C coincide with the mass increase in the
TGA curves and are attributed to the exothermic formation of the oxide layers on the
surfaces of the particles. The oxidation of the sample in air shows strong exothermic peaks
and more rapid weight gain than the oxidation of the sample in flowing argon. The DTA
curve for the sample treated in air returns to neutral more quickly than the same curve for
the sample treated in argon, which correlates well with the observed weight increases in the
TGA curves as a function of temperature and suggests the same mechanism is being seen in
the two measurements. The exothermic nature of the oxide formation suggests that the
oxide layer is very stable and difficult to remove.
Prior to these measurements, the binder used in MMCP was removed by having a hold
during the sintering cycle. As can be seen by the curves, mass loss and an exothermic peak,
which is most likely associated with organic removal, occurs as high as about 550°C. This
result was very surprising. If organics are still present in the parts during metal infiltration,
this infiltration may be hindered.
Following the DTA and TGA measurements, a series of 4” by 4” plates were prepared and
delivered to Excera for transformation. Eight plates underwent the pressing operation (CIP)
which resulted in calculated green densities of about 71% theoretical. Two plates were
delivered that were dried without being pressed which exhibited green densities of about
65% theoretical. Using the inflection points of the TGA curve as a guide, samples were
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Project CT-83
treated with various treatment cycles in an effort to determine a successful debind cycle for
the BF2 mix parts. Samples were heated with a hold at 170°C followed by another hold at
either 300°C, 320°C, 400°C or 425°C. Each increase in hold temperature resulted in
additional weight loss. However, each of these samples still failed to transform in the metal
bath. Next, one sample was cut in half with one half heated in air to 400°C while the other
half was heated to 400°C in vacuum. Both halves were then dipped for transformation. The
sample that was treated in vacuum exhibited several millimeters of transformation while the
sample heated in air did not exhibit any transformation. Vacuum, or more highly reducing
conditions, coupled with higher temperatures during binder removal should further increase
the amount of infiltration. Excera has successfully transformed a parts based on the BF2
mix made using their traditional injection molding process, so it is expected that once the
favorable conditions are determined, the MMP samples should also successfully transform.
To better understand the contributions of the individual components to the DTA and TGA
curves, the mass change as a function of temperature was measured on individual bulk
samples. Samples of the binders, plasticizer, and each of the sample powders were placed
ceramic in crucibles and heated and held at various temperatures in air. After each hold the
samples were removed to measure the change in mass. The samples were then returned to
the furnace set at a higher temperature. The change in mass is shown in Figure 24. The
changes in the mass of the two binders are very similar to each other and to the change in the
mass of the plasticizer. It is suggested that the amount of organics should be minimized to
reduce the difficulties associated with organic removal and limit the amount of residual ash
remaining in the samples after thermal treatment.
0% 30.0%
Binder #1
Binder #2
Plasticizer
-20% 25.0% Fine B4C #1
Fine B4C #2
Coarse B4C
Organic Mass Change (%)
-40% 20.0%
B C Mass Change (%)
4
-60% 15.0%
-80% 10.0%
-100% 5.0%
-120% 0.0%
-140% -5.0%
0 100 200 300 400 500 600 700
o
Temperature ( C)
Figure 24. Change in mass during thermal treatment of components in PA-MMCP batch.
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Final Processing – Task 4

All aspects of the infiltration and transformation processing steps in the molten aluminum
bath were conducted by Excera at their facility in Worthington, OH. These processes for the
parts made using PA-MMCP were similar to the steps used in transforming parts made using
the wax-based injection molding process.
Part Evaluation and Ballistic Test – Task 5

Following transformation, Excera non-destructively analyzes each of their breastplates to
ensure that no large defects are present which may compromise the performance of the plate.
This measurement is done using X-ray radiography. The X-ray radiographs for a
transformed BC1 sample are shown in Figure 25. The small dark dot in the lower left-center
is an artifact of the measurement. The four separate radiographs show overlapping regions
of the sample. No pores or cracks are apparent. A composite X-ray radiograph of a partially
transformed BF1 sample is shown in Figure 26. The difference in density is readily
observed in the radiographs showing the extent of the infiltration from the perimeter of the
sample. A crack can also be seen.
Figure 25. X-ray radiograph of a BC1 sample following transformation.
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Figure 26. X-ray radiograph of a partially transformed BF1 sample.
Figure 27 shows the microstructure of a transformed cermet. The microstructure of a

standard Excera sample is shown in Figure 28. The microstructures are quite uniform. No
large void regions are apparent.
Figure 27. Micrographs of sample 3A following transformation.
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Figure 28. Micrograph of sample transformed part.
The mechanical properties that are routinely measured by Excera are modulus of rupture
(MOR), Young’s modulus and Rockwell hardness-C (HRC). The transformed density has
also been observed to be an important predictor of mechanical properties. These properties
are listed in Table II for a standard Excera sample, four different BC1 PA-MMCP samples
and a section of a BF1 PA-MMCP sample following transformation. The density of MMP
sample listed as BC1 #2 is significantly lower than those of the other samples and the values
of the mechanical properties are also much lower. The density, MOR and Young’s modulus
values for sample MMP BC1 #1 are higher than those reported for the standard Excera
sample. The values from the table clearly show that similar mechanical properties to those
of the wax-based forming process can be attained using PA-MMCP to make preforms. The
MOR value for the partially transformed MMP BF1 sample is about 40% higher than the
MOR values for the samples made using the BC1 composition. The finer particles appear to
significantly improve mechanical properties, which is expected from decreasing the limiting
5
flaw size.
Table II
Density and mechanical property data for transformed PA-MMCP and Excera samples.
Transformed Young's
MOR
Sample Density Modulus HRC
3 (MPa)
(g/cm ) (GPa)
Excera 2.89 163 ± 21 276 ± 2 58.7 ± 2.2
MMP BC1 #1 2.92 172 ± 24 282 ± 5 na
MMP BC1 #2 2.69 67 ± 17 216 43.7 ± 3.7
MMP BC1 #3 2.88 124 ± 10 258 ± 20 54.5 ± 4.2
MMP BC1 #4 2.83 134 ± 17 272 ± 3 55 ± 5
MMP BF1 na 260 na na
One of the initial tiles made during the second quarter with the BC1 composition by pour
casting was successfully tested against a ballistic threat (bullet) by Excera. The tile was
packaged in the ballistic tile composite matrix that provides front and backing material to
the tile. The tile package was tested against and stopped a single 164 grain AP M2, 0.308”
diameter round with a hardened steel core fired at a distance of 17 feet from a 308
Winchester Ruger No. 1 rifle at a measured muzzle velocity of 2249 feet per second. This
result is similar to that of other Excera standard transformed tiles made by Excera using their
conventional process for making preforms. Since ballistic testing is a pass-fail
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measurement, it is impossible to predict if a bullet with a muzzle velocity of 2400 feet per
second would have penetrated the tile. A photograph of the tile package after the test is
shown in Figure 29.
Figure 29. Photograph of PA-MMCP BC1 tile in ballistic packaging material following
successful ballistic test.
II. ALTERNATE EXCERA COMPOSITIONS

One of the benefits of PA-MMCP is the ability to easily adjust the composition of the batch
solids. Two different series of batch changes were investigated.
A series of compositions were prepared where grit replaced some of the ceramics in the BC1
powder. This set of samples was chosen to show that alternate compositions could be
prepared using the pressure-assisted MMCP process. The solids loading of the slurries was
61% and the organic content 4 weight percent. Following casting, the samples were partially
dried and then pressed three cycles in a uniaxial die. The mass of each sample was
measured prior to pressing and the change in thickness was calculated by measuring the
sample thickness. A change in sample thickness as a function of water content present in the
part during pressing is shown in Figure 30 for each of the three presses. The figure
demonstrates that the densification benefits of PA-MMCP are not limited to the other
compositions that have been investigated.
A strong correlation between water content and reduction in part thickness can be seen.
Some of the scatter observed in the first press cycle can be attributed to small variations in
part thickness and diameter caused by casting and drying shrinkage being eliminated. Very
high green densities were attained following uniaxial pressing. These samples demonstrate
the compositional flexibility attainable by PA-MMCP.
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Reduction in Thickness (%) 10

First Press
8
Second Press
6 Third Press
0
0 5 10 15
Water content (wt%)
Figure 30. Change in part thickness as a function of water content during each of three
progressive pressings.
III. RUTGERS NANOSTRUCTURED COMPOSITE ARMOR

Rutgers University has developed a method to make a metastable ceramic precursor particle
that can be processed using traditional ceramic processing methods, but decomposes into a
nanostructured composite when heated. When consolidated using hot isostatic pressing
(HIP), the resulting composite demonstrates exceptional strength and hardness values.
Based on preliminary results for these values, NanoDynamics has licensed the technology
for development as the ceramic component of a vehicular ballistic protection system. This
new product will compete with hot pressed silicon carbide tiles for this application.
PA-MMCP was applied to making preforms for the nanostructured composite ceramic
armor. Rutgers University is currently the sole source of the precursor powder that will be
used in the development work. If the applicability of the technology indicates that it can
meet the specifications of the vehicular ballistic system, MMP and NanoDynamics will
work to scale up the process technology. The path to commercialization of the envisioned
product at the required production levels has already been deemed feasible with the
appropriate commercial partners having already been approached. The goals of this aspect
of the program are to develop the process by which the precursor powder will be formed
into a usable ballistic tile and to demonstrate that those tiles meet the required ballistic
specifications.
The flow chart for using PA-MMCP to make vehicular ballistic tiles from Rutgers ceramics
is similar to that of the Excera process. The identities of the additives being used for the
Rutgers armor are different from the additives developed for the Excera armor because of
different properties of the powders used in each preform. The flow chart deviation occurs in
the final stages, after MMP prepares the preform. Excera uses their patented ONNEX
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process to transform the preform into a metal-ceramic composite while the Rutgers process
uses HIP to produce a fully dense nanostructured ceramic composite.
Rutgers provided MMP with small amounts of initial materials to test the applicability of
MMCP to the powder. Since the Rutgers precursor material is still under development,
several compositions are being considered. These compositions will be referred to by the
relative amounts of the two phases in the nanocomposite. The three compositions are 80/20,
60/40 and 40/60. The precursor powder can also be provided in two particle size ranges, a
coarse unmilled state and a fine milled state.
The first set of samples that MMP made, labeled RA-01, contained unmilled 80/20 powder.
Based on earlier results, the 80/20 powder is not going to be considered for the ballistic
application, but was in stock for early development work. The powder produces a good
slurry at about 80 weight percent loading. Two 1” diameter samples were cast. The
samples were pressed to a pressure of about 8200 psi in a uniaxial 1-inch diameter, single
action die three times during drying. The reduction in part thickness as a function of water
content is shown in Figure 31. The observed changes in thickness decrease with decreasing
water content which are consistent with expected changes based on earlier work with the
Excera compositions. Following drying, the green densities of the samples were about 65%
of theoretical. Following a bisque sinter, the density decreased to about 64% of theoretical,
however the sintered sample did not exhibit any strength and disintegrated into powder with
handling. Increasing the solid loading of the slurry, the pressing pressure, and/or sintering
hold time do not significantly increase the strength of the samples made from the 80/20
unmilled powder. An increase in sintering temperature to about 1200°C did increase the
bisque sintered strength. However, this temperature resulted in a partial transformation of
the precursor powder into the composite as measured by XRD. This transformation must be
confined to the HIP step to maintain the desired nanostructure and limit grain growth.
Based on these observations it was concluded that the preforms can not be made solely from
unmilled powder due to an absence of sintering potential at low temperatures associated
with low specific surface area.
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25
Sample 1
20
Change in thickness (%)
Sample 2
15
10
0
0 5 10 15 20
Weight Percent Water (vs dry)
Figure 31. Change in thickness as a function of water content while pressing.
MMP next received a small supply of milled 80/20 powder. Two sets of samples were
produced. One set, labeled RA-04, contained only milled powder while the other set,
labeled RA-05, contained 70% unmilled powder and 30% milled powder. The solids
loading of the slurry made from entirely milled powder was much lower than the solids
loading of the slurry which contained both types of powder. The advantages of higher solids
loadings are reduced drying times, smaller die tooling, improved initial density and less
deformation during HIP. Small, half-inch diameter samples were made from these slurries.
The samples were pressed multiple times during drying and sintered at 1080ºC where
transformation was not expected. Each of the samples showed appreciable strength. The
samples did not exhibit any dimensional shrinkage during the thermal treatment. The
densities of the different samples are given in Table III.
The samples with the highest densities contain a mixture of milled and unmilled powder.
Since these samples also exhibit strength after heat treatment at 1080°C and the process of
milling the powder is time consuming, it appears desirable to make preforms for HIP from a
mixture of powders. However, similar samples have yet to be transformed and the ballistic
properties measured.
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Table III
Green and sintered densities and qualitative strength following heat treatment of samples
containing 80/20 powder produced by the pressure-assisted MMCP process.
Number Appreciable
Green Sintered
Sample Composition of strength at
Density Density
Pressings 1080°C
RA-01 Unmilled 3 65% 64% No
RA-04 Milled 3 65% 60% Yes
RA-05 70% unmilled 2 71% 70% Yes
RA-05 70% unmilled 3 76% 73% Yes
After demonstrating that PA-MMCP can be applied to the nanocomposite precursor powder,
MMP received 80 grams each of 60/40 and 40/60 milled powder. The samples were made
using slurry with about 69 weight percent solids. Four 20 gram samples 1-inch in diameter
of each composition were cast. The samples were pressed three times during drying in a
uniaxial press. A photograph of one set of the samples is shown in Figure 32. The samples
were bisque sintered to remove the organics and develop limited particle sintering to provide
strength. The samples were sent to be canned and HIP’ed. After the samples were HIP’ed,
they were returned to Rutgers for analysis. An SEM of one of the cross-sectioned samples is
shown in Figure 33. The microstructures of both sample compositions look similar. The
samples did not exhibit adequate densification at the HIP temperature. A higher processing
temperature must be used to obtain the required high density that is responsible for
imparting the outstanding mechanical properties. A micrograph of a sample heat treated at a
higher HIP temperature is shown in Figure 34. Samples which started as solid preforms
exhibit significantly higher densities after HIP treatment than samples which were placed in
the HIP can as loose powder.
Figure 32. Photograph of Rutgers armor samples before heat treatment.
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Figure 33. SEM micrograph of nanostructured composite after HIP treatment.
Figure 34. SEM micrograph of nanostructured composite after HIP treatment at higher
temperature from previous work at Rutgers University. Sample was etched after polishing.
IV. FUEL CELL COMPONENTS

Yttrium stabilized zirconia (YSZ) is an important ceramic material used in solid oxide fuel
cells (SOFC). One of the primary problems with YSZ is that it is difficult to make slurry
compositions that contain high solids loadings. MMP is developing a thin ceramic tape that
can be used in some SOFC applications. Even with only 5.5 weight percent organic, the
ceramic tape remains very flexible after two weeks of drying, as shown in Figure 35. The
dimensions of a bulk sample with the same composition were measured before and after
uniaxial pressing. The density increased from about 2.78 g/cm3 to about 3.22 g/cm3. This
correlates to an increase in green density from about 47% of theoretical to about 55% of
theoretical, an increase of about 16% versus the as-cast value. Sections of the tape were also
pressed and had reductions in thickness of about 11% with pressures of about 6800 psi. This
tape was made using only 1-5 micron particles. By adding smaller particles to fill the
interstices, it is anticipated that higher green densities will be attained.
36
Project CT-83
Figure 35. Picture showing flexible YSZ tape made using the MMCP process
37
Project CT-83
Manufacturing Cost Estimate– Task 6
The MMCP process can be easily visualized as having the following steps (and in contrast to
Injection Molding:
MMCP Injection Molding (IM)

Dry mix
Wet Mix Wet Mix
Heat Heat
Fill Die Fill Die
Chill Chill
Remove/Clean Remove/Clean
Dry
Densify
Organic removal Plasticizer Removal
The MMCP process produces a superior preform. The table presentation allows an evaluation of
where there are opportunities for cost reduction in the MMCP process as compared to the Injection
Molding process.
These are, by line item:
Dry Mix Same

Wet Mix Lower Cost Addends
Heat Lower Temperature Heating
Fill Die Lower Pressure
Slump Forming
New Markets
Chill Same
Remove/Clean Same (lower if slump)
Dry Lower Loss Rate
Densify
38
Project CT-83
The MMCP process needs to be scaled up in order to meet the production requirements of the armor
preform market. MMP sees this as happening in four stages. Each stage of the process was costed
with assumptions of staged success in the developmental program.
Stage Volume Strategy Primary

Developmental Need
for Next Stage
Current One at a time Current None
Low Volume 100 per month, Manufacture on site, Develop/prove slump
tolling price point using current drying forming
at <$200 pp “box” as modified, using Determine how density
current mold system can be improved
Purchase pilot scale during forming/drying
mixing equipment. Use to eliminate
technician labor for densification step
production. Contract Reduce die mass to
densification. increase rate of chill
step to improve die
turnover.
Method to pack/
transport product
(cardboard
separations).
Production Mixing/
De-aeration
Moderate 1000 per month, Offsite manufacture Develop/prove forced
Volume tolling price point satellite, purchase mixing drying step on slump
at <$100 pp. Labor equipment scaled at 1000 mold
calculates to 1 hour pounds per day. Multiple Automation process
per part at 40 parts dies, if possible slump design
per day. formers. Contract
densification.
High Volume >10,000 per month, Automation line, offsite
tolling price point and adjacent to user. If
at target densification still needed,
on site press
39
Project CT-83
Conclusions
PA-MMCP is a forming method that enables the manufacture of a high-density green
ceramic part through the application of pressure to a solidified body. This novel forming
combines the benefits of aqueous colloidal processing, thermosetting organics, low organic
contents and pressure densification to produce parts with high green densities and good
homogeneity while minimizing large internal pores. As with any forming method,
numerous interacting process variables affect the properties of the final part.
With funding from EMTEC, Phase I of Project CT-83 primarily investigated the
applicability and development of PA-MMCP toward the manufacture of high-density green
preforms for use by Excera Materials Group of Worthington, Ohio. These preforms are
further processed by Excera to produce a high strength, high toughness ceramic insert used
in personnel ballistic armor. Early in the program work, PA-MMCP was shown to produce
preforms that exhibit similar properties after final processing as preforms produced by a
wax-based injection molding operation. A PA-MMCP produced preform was successfully
demonstrated to stop a ballistic threat.
Other work in the program was aimed at using PA-MMCP to produce solid oxide fuel cell
components and ballistic armor for a vehicular application. SOFC development was very
limited because PA-MMCP does not readily allow for the same complex shapes that can be
produced using the MMCP process. Also, SOFC development is moving away from
electrolyte supported cells to anode supported cells where the requirements for high density
are not as stringent. Work with the vehicular armor preforms show promise, but additional
work is necessary to prove the new material in the application.
References
1. J.S. Reed, Principles of Ceramics Processing; Second Edition, John Wiley and Sons, Inc.,
New York, 1995.
2. T.A. Ring, Fundamentals of Ceramic Powder Processing and Synthesis, Academic Press,
Inc., San Diego, CA, 1996.
3. R.F. Speyer and E.A. Judson, “New Process Makes Complex-Shaped Armor a Reality,”
Amer. Ceram. Soc. Bulletin, 85 [3] 21-23, (2006).
4. http://www.exceramaterials.com/ Accessed 4/6/06.
5. Griffith, Philos. Trans. R. Soc. London, Ser. A, 221, 163 (1920).
40

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EMTEC CT-83-I

Development of a Novel Method to Shape From

Final Phase I Report

Distribution of this repo rt is unlimited.

Prepared for Edison Material Technology Center

Copyright ©2006, EMTEC, 3155 Research Blvd., Dayton, Ohio 45420-4006

EMTEC Phase I Final Report

EMTEC Phase I Final Report .................................................................................................. 1

MetaMateria Partners/Excera Materials Group

EMTEC Phase I Final Report

MetaMateria Partners/Excera Materials Group

Figure 1. Alumina SOFC parts cast using MMCP.

MetaMateria Partners/Excera Materials Group

Powder Water Organic Additives

Figure 2. Process flow diagram of MMCP.

MetaMateria Partners/Excera Materials Group

Excera Materials Group, Inc. is a company located in Worthington, OH and founded to

MetaMateria Partners/Excera Materials Group

From the proposal:

Task 1: Development of Excera’s Proprietary Preform Misture and Al2O3

Task 2: Development of Plastic Preforms Using Modified Casting Process

MetaMateria Partners/Excera Materials Group

Task 3: Investigate Effect of Plastic Deformation

MetaMateria Partners/Excera Materials Group

The output of Task 3 will be an understanding of the plastic deformation properties

Task 4: Make Test Pieces for Evaluation by Production Partners

Task 5: Evaluation of Part Quality/Properties/Performance

Task 6: Process Cost Estimate

MetaMateria Partners/Excera Materials Group

Results and Discussion

MetaMateria Partners/Excera Materials Group

I. EXCERA ARMOR PREFORMS

Batch Composition – Tasks 1, 2

MetaMateria Partners/Excera Materials Group

Parts Fabrication – Tasks 2, 4

Figure 4. Photograph of green and sintered 4” by 4” tiles.

MetaMateria Partners/Excera Materials Group

Figure 5. Photograph of green ESAPI plate made by MMCP.

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

Figure 7. Drying curve for thick plates with composition.

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

Figure 9. Density as a function of load for pressed BC1 parts.

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

Composition Binder Plasticizer

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

A 3 hr B 3 hr C 30 min C 3 hr D 5 min D 30 min E 5 min E 10 min

MetaMateria Partners/Excera Materials Group

Figure 17. SEM micrographs of unpressed green sample.

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

Organic Removal – Task 4

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

MetaMateria Partners/Excera Materials Group

Final Processing – Task 4

Part Evaluation and Ballistic Test – Task 5