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Ceramic-Polymer Composites for Ballistic Protection

Article  in  Advances in Applied Ceramics · April 2006


DOI: 10.1179/174367606X84440

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Ceramic–polymer composites for ballistic
protection
P. Colombo*1,2, F. Zordan1 and E. Medvedovski3
Armour systems require advanced solutions, relying on a combination of materials of different
natures to provide adequate ballistic protection and weight saving. For the first time in the present
study composite layered systems based on monolithic armour ceramic tiles joined with polymer
infiltrated ceramic foams have been designed and evaluated for lightweight ballistic protection.
Open cell silicon carbide foams of various cell sizes infiltrated with thermosetting or elastomeric
polyurethane were used for this design. The ballistic test results are discussed taking into account
the morphological characteristics and main physical properties of the materials used (facing
ceramic tile, ceramic foam and polymers), as well as test conditions. The proposed design may
be considered for structural and vehicular protection solutions, including blast protection.
Keywords: Armour, Ballistic protection, Ceramic foam, Composite

Introduction which are frequently used as matrixes for composites,


possess good mechanical properties and the possibility
The development of protection for stationary and of absorbing energy by various mechanisms under
mobile structures against ballistic impacts and explo- mechanical loads.8 The synergistic combination of
sives, as well as radiation, chemical and biological positive properties of lightweight ceramic foams and
agents, is an important task in defence applications. selected polymers may bring positive results in the case
Ceramic composites have a variety of applications in of the use of these materials as components of ballistic
diverse engineering areas where they are subjected to protection systems (see below). For instance, rubber
high mechanical and thermal loads. One of the encapsulation of cellular ceramics has been shown to
prospective applications of ceramic composites is as significantly increase the amount of impact energy
ballistic protection structures. absorbed.9 Layered composite designs consisting of
Ceramic based composites with high toughness are materials with different natures are effective for ballistic
usually reinforced by ceramic or metallic fibres, whiskers protection applications if they contain components
or particulates,1,2 or can be obtained from laminated possessing energy dissipation and absorption capabil-
ceramic layers.3 Another type of composite structure, ities. The aim of the present work was to explore the
labelled interpenetrating composites,4 consists of porous possibility of using layered composites consisting of
ceramic structures infiltrated with metallic or polymeric materials with different characteristics, including solid
materials,5 in which the 3D interconnected ceramic ceramics and ceramic foam–polymer structures, for
phase affords additional properties (for example increased ballistic protection.
stiffness, wear resistance and creep resistance) to the
infiltrating matrix material.
Besides possessing unique properties, such as high Selected composite system design
relative strength and stiffness, high wear resistance and A layered composite design was selected as being
hardness, ceramic foams have potential as impact energy potentially effective for ballistic protection from the
absorbers owing to their cellular structure.6 Indeed, a performance and manufacturing standpoints. This
recent study showed that when tested as components of design included the following two major components:
shields protecting spacecraft from hypervelocity a ceramic faceplate with high hardness and mechanical
impacts, microcellular ceramic foams displayed high properties, in order to brake and fragment the bullet and
performance against small high velocity projectiles.7 to dissipate its impact energy; and a backing material for
Some polymeric materials (in bulk or composite form), impact energy absorption and for stopping the bullet
and resulting fragments.
1 As the face component, ballistic grade high alumina
Dipartimento di Ingegneria Meccanica – Settore Materiali Università di
Padova via Marzolo, 9.35131 Padova, Italy ceramic tiles with high hardness and strength, relatively
2
Department of Materials Science and Engineering, Pennsylvania State low brittleness, optimised microstructure and ballistic
University, University Park, PA 16802, USA
3
Ceramic Protection Corporation Inc., 3905 32nd St NE, Calgary, Alberta, impact energy dissipation ability were used. Owing to
T1Y 7C1 Canada; now with Umicore Indium Products, 50 Sims Ave, their high ballistic performance, tiles with limited
Providence, RI 02909, USA thickness were used. The backing material was made
*Corresponding author, email paolo.colombo@unipd.it of silicon carbide foams infiltrated with different

ß 2006 Institute of Materials, Minerals and Mining


Published by Maney on behalf of the Institute
Received 11 March 2005; accepted 9 October 2005
78 Advances in Applied Ceramics 2006 VOL 105 NO 2 DOI 10.1179/174367606X84440
Colombo et al. Ceramic–polymer composites for ballistic protection

1 Optical micrographs of as received (non-infiltrated) SiC foam (20 ppi): a general view, b detail of hollow strut

polymeric materials. A ceramic foam based system performance (see Table 1). This ceramic material has
would absorb impact energy by crushing the ceramic relatively low brittleness (significantly lower than dense
foam and by friction of the ceramic phase with the carbide based ceramics), defined by combined values for
bullet, and the cellular ceramic structure would interfere hardness, fracture toughness and Young’s modulus,
with the propagation of the shockwave.10,11 Two types which may be considered as a positive factor for ballistic
of polyurethane (PU), thermosetting (cross-linked) and performance of ceramics, and optimised high ballistic
elastomeric, were selected in this experimental design as energy dissipation ability. The ceramic tiles were made
the polymeric material. Thermosetting PU is stiff and by a pressing technology using in-house manufactured
has high compression strength, while elastomeric PU has spray dried powders followed by firing at relatively low
very good damping capability and can retard the temperature (below 1550uC) without a grinding step
propagation of shockwaves in the system. after firing (i.e. as fired tiles were used). Owing to the
In the case of polymer infiltrated ceramic foams, these proven high level of ballistic performance of this ceramic
composites may be considered as ceramic reinforced material, a thickness of only 6.0–6.5 mm for the tiles was
polymers possessing significantly increased mechanical selected for the layered composite design. Tiles with a
properties, especially stiffness and hardness. The pro- format of 1006100 mm were used, however tiles with
posed design did not have aramid based (e.g. Kevlar, other dimensions (format up to 1506200 mm and
Twaron), laminated polyethylene (e.g. Spectra, Dyneema) thickness up to 15 mm) can be manufactured.
or other backing materials widely used for ballistic As cellular ceramics for subsequent infiltration, open
protection systems, i.e. the backing consisted solely of a cell silicon carbide SiC foams (manufactured by Foseco
polymer infiltrated ceramic foam to replace the ‘tradi- Metallurgical Inc., Cleveland, OH, USA, for use as
tional’ backing. This layered composite (alumina tile molten metal filters) with two different cell sizes (10 and
bonded with foam-based 3D composite backing) can be 20 ppi – pores per inch) were selected. Relative density
bonded to an aluminium or plastic sheet (board), a was about 0.13 for both materials. Foams with these
‘panel’ design which can be easily installed in any mobile pore sizes were chosen to facilitate infiltration of liquid
or stationary structure. polymers into these structures without applying external
pressure. The foam samples had dimensions of 1006
Experimental procedure 100620 mm in order to be compatible with the format
of the alumina face tiles. The ceramic foams were
Materials selection and manufacture manufactured by the replica technique, that is by
The ceramic tiles used as the face component of the coating a cellular polymeric sacrificial structure with a
armour design were made from AL98.5 alumina devel- ceramic SiC slurry, followed by burning off the preform
oped and manufactured commercially by Ceramic Pro- during sintering of the ceramic material.15 It has to be
tection Corporation (CPC, Calgary, AB, Canada).12–14 noted that, because of their application, the properties
The ceramic material has an Al2O3 content of approxi- of commercially available molten metal ceramic foam
mately 98.5 wt-%. It has a uniform fine crystalline filters are generally optimised for permeability and
microstructure consisting of corundum grains with a size thermal shock resistance rather than strength. Foams
of 3–5 mm (mostly isometric) bonded by an alkali earth– produced by other technologies,16 affording different
aluminosilicate glassy phase (see Fig. 1). Owing to their morphology and improved mechanical properties, could
microcrystalline structure, AL98.5 ceramics possess a also be infiltrated and tested for ballistics related
high level of physical properties (such as hardness, applications.
Young’s modulus, sonic velocity) and favourable values The following materials were used for PU prepara-
of some other characteristics relevant to ballistic tion. In the case of rigid (thermosetting) PU, isoexter

Table 1 Physical properties of pressed AL98.5 alumina ceramic tiles


Density 3.82–3.84
Open porosity ,0.1%
Vickers hardness HV10, kg mm22 1320–1400 (12.9–13.7 GPa)
Fracture toughness KIC*, MPa m21/2 3.0–3.3
Young’s modulus E, GPa 330–400
Sonic velocity c, m s21 10200–10800
Flexural strength, MPa 260–280
Brittleness factor B{, m21 420–4606106
Ballistic energy dissipation ability D{, s21 1.80–1.9561012
*Determined by indentation technique.
{
Calculated using the formula B5HvE/KIC2.
{
Calculated using the formula D50.366Hv6E6c/KIC2.

Advances in Applied Ceramics 2006 VOL 105 NO 2 79


Colombo et al. Ceramic–polymer composites for ballistic protection

2 SiC foam (20 ppi) infiltrated with thermosetting polyurethane: a general view; b detail of strut

3446 polyol (Coim, Offanengo (CR), Italy) and and MDI The projectile velocities were 990–1000, 840–890 and
Suprasec 2085 isocyanate (Huntsman Polyurethanes, 845–870 m s21 respectively, i.e. the velocity values were
Everberg, Belgium) were used as precursors, while in accordance with values normally used for ballistic
Caradol 30-02 polyol (Shell Italia, Milan, Italy) and testing and recommended by the NIJ standards. The
Suprasec 2444 isocyanate (Huntsman Polyurethanes, distance between the weapon and the target was 12 m.
Everberg, Belgium) were used for the elastomeric PU Trauma after shooting was measured using a Roma
preparation. Mixing and handling of the precursors were Plastilina modelling clay supporting the armour systems
conducted based on the directions from the suppliers. on the back; the trauma in the clay duplicated the
Infiltration of the porous ceramic foams with the trauma in the armour. A trauma pack (a block of Kevlar
polymer materials was carried out by a vacuum simulating an armour vest) was placed behind the clay in
infiltration technique. The ceramic foams were held order to capture the bullet in the case of penetration.
under low vacuum (rotary pump, <1022 torr) and then The damage zone of the ceramics and backing, including
infiltrated with a liquid mixture of the desired PU component fragmentation, were studied, as well as the
precursors (viscosity of liquids was of the order of 4 and bullets after shooting.
1 Pa s at 25uC for the thermosetting and elastomeric PU
respectively). A setting time of 10 min at ambient Results and discussion
temperature provided proper infiltration and curing of
the polymers. After curing, the infiltrated foams were Microstructural study of the non-infiltrated SiC foams
slightly sanded from the excess of polymer in order to (Figs. 1 and 2) showed completely open interconnected
achieve flat surfaces, required for proper bonding with porosity comprised of a web of ceramic hollow struts.
face ceramic tiles. Bonding of infiltrated foams with the The holes in the struts derive from burnoff of the
ceramic tiles was carried out in an autoclave at elevated polymeric sacrificial template during high temperature
pressure and temperature using specially selected adhe- sintering of the SiC powder coating. Morphological
sives and a previously developed procedure for the analysis of the infiltrated foams revealed that it was
bonding of armour ceramics with backing materials. The possible to completely infiltrate the ceramic foam
ceramic tiles were preliminarily wrapped with prepreg structures with both elastomeric and thermosetting PU
(fibreglass) normally used for design and bonding of precursor solutions. However, owing to the higher
various armour systems. viscosity of the thermosetting PU precursor solution,
some trapped air was retained in the PU phase (see
Fig. 2a). It is worth observing that in some cases part of
Mechanical testing and microstructural analysis
the porosity inside the hollow struts was also infiltrated
The crushing strength of the foams, both non-infiltrated by the polymeric phase, as shown in Fig. 2b. In the
and infiltrated, was measured at room temperature by present study, no specific investigation was performed
compression testing, using an Instron 1121 UTM on the nature of the polymer/ceramic interface.
(Instron Danvers, MA, USA) with a crosshead speed Ceramic foams and foams infiltrated with selected
of 0.5 mm min21, on samples of nominal size of polymers were mechanically tested in order to compare
20620620 mm cut from larger specimens. Each data the influence of foam macrostructure and type of
point represents an average value of 5 to 10 individual polymer on the mechanical properties of the interpene-
tests. trating composites, and to interpret their behaviour in
Elastic modulus was measured using a non-destructive ballistic testing. The mechanical test results are reported
dynamic method based on the impulse excitation of in Table 2.
vibration (Grindosonic, J. W. Lemmens, Leuven, As received ceramic foams displayed limited strength,
Belgium), in accordance with ASTM E1876, on samples typical of cellular ceramics produced by the replica
of suitable geometry. technique, whereas foams infiltrated with polyurethane
Ceramic foam morphology was characterised using varied their strength according to the type of PU used.
optical microscopy and image analysis software (Image- Although the composite material produced using
Pro Plus, Media Cybernetics, Silver Spring, MD, USA). elastomeric PU did not display crushing strength
significantly different from that of the non-infiltrated
Ballistic testing ceramic cellular structure, using thermosetting PU
The ballistic performance of the selected systems was increased the compression strength of the foams
tested using a M16 weapon with 5.56645 mm SS109 significantly. The difference in behaviour of infiltrated
ammunition with a steel tip ball, 7.62651 mm NATO foams under mechanical loads is attributable to the
Ball Full Metal Jacket (FMJ) with a lead core, and variation in strength of the PU phase itself (see Table 2).
7.62663 mm Armour Piercing (AP) M2 FMJ with a The decrease in strength between the 20 ppi foam
tungsten carbide core. Depending on the ammunition, sample infiltrated with thermosetting PU and the pure
the bullet mass, velocity and energy were varied. The PU phase is probably related to a higher presence of
projectile velocity was controlled using a chronograph. voids in the polymeric phase. This could have occurred

80 Advances in Applied Ceramics 2006 VOL 105 NO 2


Colombo et al. Ceramic–polymer composites for ballistic protection

3 Stress–strain curves for SiC foams (10 ppi), as


received, infiltrated with elastomeric PU and infiltrated
with thermosetting PU

as a result of the smaller cell size of the ceramic foam


with respect to the 10 ppi sample. An increase in
stiffness was observed in the composites infiltrated with
thermosetting PU, but data could not be obtained for
those infiltrated with elastomeric PU owing to its
damping effect on the vibrations generated during
measurement.
When a non-infiltrated ceramic foam is subjected to
compressive loading, it deforms elastically up to a
maximum load (usually occurring at strain of about
5%), after which brittle crushing occurs with a more or
less sudden drop in stress, and the stress enters a plateau
region before increasing rapidly owing to densification
of the crushed debris17 (Fig. 3). Typically, after reaching
the peak load, the ceramic foam is subjected to
macroscopic cracking in the direction of the applied
stress, and if the loading ram is lifted the tested sample
falls apart in several large pieces18 (Fig. 4a).
The use of the thermosetting PU phase resulted in
modification of the behaviour of the ceramic foams
under compression. The stress–strain curves for infil-
trated ceramic foams did not show a drop in stress after
reaching peak load (Fig. 3), and the samples remained in
one piece (or fragmented into a very limited number of 4 a non-infiltrated SiC foam (20 ppi) after compression
pieces) after removal of the applied load. This behaviour strength testing (test stopped at relative deformation
may be explained by the binding effect of the of around 0.3%); b SiC foam (20 ppi) infiltrated with
interconnected polymeric phase (see Fig. 4b as an thermosetting polyurethane after compression strength
example). Cracking phenomena during loading seemed testing (test stopped at relative deformation of around
to occur mainly in the brittle ceramic phase (Fig. 4c). 0.3%); c SiC foam (20 ppi) infiltrated with thermoset-
Infiltration with thermosetting PU afforded the compo- ting polyurethane during compression strength testing
site structure much higher energy absorption, i.e. work (picture taken at deformation of around 0.14%; note
of fracture (the area underneath the stress–strain curve), crack formation in SiC phase)

Table 2 Physical and mechanical properties of as received and infiltrated ceramic foams

Average cell Bulk density, Compression Elastic modulus,


SiC foam size, mm g cm23 strength, MPa GPa

10 ppi, non-infiltrated 4.46¡1.17 0.437¡0.056 1.1¡0.3 1.80¡0.14


20 ppi, non-infiltrated 3.09¡0.61 0.402¡0.024 0.8¡0.1 1.74¡0.10
10 ppi with thermosetting PU 4.46¡1.17 1.093¡0.198 71.5¡4.5 3.69¡0.30
20 ppi with thermosetting PU 3.09¡0.61 1.180¡0.049 42.0¡1.5 7.11¡1.71
10 ppi with elastomeric PU 4.46¡1.17 1.023¡0.025 1.0¡0.2 …*
20 ppi with elastomeric PU 3.09¡0.61 1.044¡0.052 1.1¡0.1 …*
Elastomeric PU … 0.942¡0.098 … …*
Thermosetting PU … 0.962¡0.129 64.7¡2.1 1.79¡0.49
*Not determined owing to damping of vibrations by the elastomeric PU phase.

Advances in Applied Ceramics 2006 VOL 105 NO 2 81


Colombo et al. Ceramic–polymer composites for ballistic protection

6 Armour system with SiC foams (20 ppi) infiltrated with


thermosetting PU after ballistic testing with AP round:
5 Armour system with SiC foams (20 ppi) infiltrated with
a face view, b back view (fibreglass cloth prepreg
thermosetting PU after ballistic testing with 7.626
wrapping was removed to expose impact area)
51 mm NATO round: a face view, b back view (fibre-
glass cloth prepreg wrapping was removed to expose
impact area) pack (see Fig. 6). A similar system made from elasto-
meric PU could not stop the 7.62651 mm NATO round
in comparison with the non-infiltrated ceramic foam. or, especially, 7.62663 mm AP round (see Fig. 7 for
Owing to low strength and low Young’s modulus, the testing with the AP round). It can thus be noted that the
elastomeric PU infiltrating phase did not much influence difference in ballistic protection of the composites made
the stress–strain behaviour of the interpenetrating with two different types of PU is in good correlation
polymer–ceramic composite, but it helped in maintain- with their mechanical properties.
ing the tested sample in a coherent piece until large For the face ceramic tile, the observed fragmentation
deformations (.50%) were reached. and crack formation from ballistic impacts of the
A strong influence of the design and mechanical designed composites had a similar character to the high
properties of the composite components and, especially, alumina ceramics bonded to a Kevlar backing described
of the selected polymer nature on ballistic performance previously.12–14 The ceramic tile zone close to the impact
was observed. Preliminary testing of the system based on point consisted of chunks of various sizes and fine
the SiC foam infiltrated by thermosetting PU but powder with a locus of conoidal coaxial cracks and the
without a face alumina tile showed unsatisfactory presence of radial tensile and spall cracks. The backing
performance against the 7.62651 mm NATO projectile material consisting of SiC foam (both 10 and 20 ppi)
(testing of the infiltrated foam using an armour piercing infiltrated with thermosetting PU also fragmented into
projectile, i.e. with harder core and higher energy, was pieces of different sizes, but powder formation was
not undertaken). minimal. The reinforcement of thermosetting PU
In the case of the layered composite system (alumina achieved by the use of the SiC foams promoted the
tilezfoam) in which SiC foams were infiltrated with formation of large fragments upon impact. Destruction
thermosetting PU, the 5.56645 mm SS109 and 7.626 of the components of the composites and trauma were
51 mm NATO rounds were both stopped in the backing significantly lower in the case of the 5.56645 mm SS109
(see Fig. 5 as an example), while the 7.62663 mm AP projectile owing to its lower energy than the NATO and
round was stopped only in the first layers of the trauma AP projectiles. A comparison of ballistic performance of

82 Advances in Applied Ceramics 2006 VOL 105 NO 2


Colombo et al. Ceramic–polymer composites for ballistic protection

polyurethane has been evaluated as an armour system


for the first time. Fully infiltrated, 3D interpenetrating
ceramic–polymer composites were manufactured using
vacuum assisted processing. The composites consisting
of SiC foams and thermosetting (cross-linked) PU
demonstrated a relatively high level of mechanical
properties. Armour systems based on only 6 mm armour
tiles bonded with SiC thermosetting PU composite
backing could stop 5.56645 mm SS109 and 7.626
51 mm NATO Ball FMJ projectiles, so these systems
may have potential for ballistic and blast protection for
vehicular and structural applications. The use of
elastomeric PU as the infiltrating phase did not afford
the composite suitable properties to make it of interest
for ballistic protection applications. The preliminary
results obtained will lead to further exploration of a new
approach to the design of armour systems with lower
weight. The use of a backing system based on ceramic
foams infiltrated with proper PU (or some other suitable
material) would allow the replacement of expensive
polyaramid or polyethylene backing and would avoid
the need for a labour intensive lamination process.

Acknowledgement
Diana Essock of Foseco Metallurgical Inc., USA is
gratefully acknowledged for providing the SiC ceramic
foam samples.

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Advances in Applied Ceramics 2006 VOL 105 NO 2 83

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