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Rigid ballistic composites (Review of literature)


Utracki, Leszek A.

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Conseil national de National Research Council
recherches Canada Canada

Institut des matériaux Industrial Materials


industriels Institute

Rigid ba llist ic c om posit e s


(Review of literature)

Leszek A. Utracki
NRC/IMI/Advanced Materials Design

31.10.2010
Rigid ballistic composites, 31.10.2010

Contents
INTRODUCTION ....................................................................................................................... 3
Body armor ............................................................................................................................ 3
Composites for armor (vehicles) ............................................................................................. 4
REINFORCEMENT .................................................................................................................... 6
Kevlar’s .................................................................................................................................. 6
Twaron® ................................................................................................................................11
Making fabrics .......................................................................................................................13
Patented ballistic armor .........................................................................................................15
MATRIX ....................................................................................................................................18
INTERPHASE ...........................................................................................................................22
Computational studies ..........................................................................................................23
Compatibilization ...................................................................................................................26
Fiber sizing............................................................................................................................27
SHEAR SENSITIVE COUPLING...............................................................................................32
Strain hardening (SH) of foams and gels ...............................................................................33
Stress-strain hardening of suspensions – introduction ..........................................................37
Stress-strain hardening of suspensions – Wagner group ......................................................38
Stress-strain hardening of suspensions – others ...................................................................42
NANOTECHNOLOGY...............................................................................................................51
EVOLUTION OF HELMET TECHNOLOGY ..............................................................................54
SUMMARY AND CONCLUSIONS ............................................................................................60
Best performing materials .....................................................................................................61
Fibers and fabrics ..............................................................................................................61
Polymeric matrix ................................................................................................................62
Interphase .........................................................................................................................62
Stress or strain sensitivity ......................................................................................................62
Helmet or headgear ..............................................................................................................63
Final comments .....................................................................................................................64
APPENDIX 1 .............................................................................................................................65
APPENDIX 2 .............................................................................................................................67
REFERENCES .........................................................................................................................68
END 77

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Rigid ballistic composites, 31 October 2010

INTRODUCTION

There are three aspects to ballistic personal protections, each requiring different technologies:

1. Flexible body armor


2. Armored vehicles
3. Headgear

The first two aspects will be briefly discussed in the INTRODUCTION, while the third at the end
of this review. The text “in between” will summarize the information on reinforcing solids
(particles and fibers), on the matrix polymers, and on the interphase between these two.

Body armor

The first ballistic armor was invented in Korea in 1860s, right after the French campaign. The
Imperial Regent, Heungseon Daewongun, ordered development of a bullet-proof armor because
of the increasing threats from the West. The first vests, made of 30 folds of cotton, were used in
battles with US Navy in 1871. The US army captured one of the vests and took it to the US. It
was stored in the Smithsonian Museum until 2007 then returned to Korea. 1, 2

During the early 1880s, Goodfellow from Arizona investigated silk vests of 18 to 30 layers that
protect the wearers from arrows and bullets. Zeglen from Illinois used Goodfellow's findings for
developing a bulletproof vest made of silk fabric capable of stopping slow rounds from black-
powder handguns (in 1914 the vests cost $800 each). During World War I, the USA developed
several types of body armor, including the chrome nickel steel Brewster Body Shield, which
were clumsy and weighed 18 kg.

In the early stages of WWII the US Army designed heavy and mobility-restricting body armor for
infantrymen. Next was Nylon "flak jackets" for aircraft crews, expensive and inefficient for
stopping bullets. Similar developments took place in Canada, UK, Soviet Union and Japan. In
mid-1944 US military produced better vests, including the T34, T39 and the M12. For the
Korean War several new vests were produced, including the M-1951 that used fiberglass or
aluminum segments woven into nylon. However, the vest failed to stop bullets and fragments.
The Vietnam War vests were simply updated versions of those developed for the Korean War.

In 1969, American Body Armor™, Inc. was founded and


began production of a patented combination of quilted nylon
faced with multiple steel plates. This armor configuration was
widely marketed to American law enforcement agencies by
the Smith & Wesson as "Barrier Vest™". In the mid-1970s
DuPont introduced Kevlar fiber, which was woven into a fabric
and layered for lightweight, concealable body armor of
American law enforcement officers. Kevlar® soft armor,
developed for the American military in 1994, was able to stop
rifle caliber rounds. The newer Kevlar® Interceptor armor
issued by the United States military was intended to provide
shrapnel protection and 9 mm sub machine gun fire. Ceramic
plates, worn front and back, protect the vital organs from threats up to NATO rifle rounds. Vests
that combined stab and ballistic protection were developed in the 1990’s.

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Rigid ballistic composites, 31.10.2010

In the following publication by Egres et al., Nylon or Kevlar, dry and with shear thickening fluid
(STF) containing 20 – 28 wt% silica spheres in polyethylene glycol (PEG), were evaluated for
stab-wound protection at constant aerial weight. 3 Several ways the composites were arranged
with dramatic changes in the results. Thus, placing 4 layers of Kevlar® and a layer of STF
suspension gave 17.2 mm deep penetration in the witness clay, whereas soaking these 4 fabric
layers with STF reduced the penetration depth to 6.8 mm. A similar performance was obtained
for 120 as for 450 nm diameter silica spheres. At high velocity test the 8-layer Kevlar/STF far
outperformed 11 layers dry Kevlar, viz. 92% energy dissipated vs. 60% dissipated in the older
construction. At low velocity stabbing, the usually poor Kevlar® stab resistance was improved
from 25 to 42 mm penetration depth at the areal density of 0.06 g/cm2. The mechanism of
ballistic energy dissipation of STF impregnated fabrics appears to be “grabbing” the
yarns, preventing intern-yarn mobility at high strain rates – in other words, the
suspension behaves as liquid-like at low velocity, becoming solid-like at high velocity.

A new breed of armor may contain a magneto-rheological (MR) fluids body armor. 4 MR fluid
consists, e.g., of small iron particles suspended in silicon oil. The suspension transforms from
liquid to solid in milliseconds when a magnetic or electrical field is applied. The current causes
the iron particles to lock into a uniform polarity and stack on top of each other, creating an
impenetrable, solid cluster. How hard the armor becomes depends on the particle
concentration, strength of the magnetic or electrical field. Once the charge or magnetic field is
removed, the particles unlock, and the substance goes back to a liquid-like suspension. It is
expected that MR fluids will be incorporated into the Future Force Warrior (FFW) uniforms,
wired so an electrical current may pass through the fabric. The electrical current will be
controlled by the onboard computer system that will automatically charge the MR fluid when a
ballistic threat is detected. It will take 5 to 10 years to integrate today’s MR into fully bullet
resistant body armor.

Since the 1970s, several new fibers and construction methods for bulletproof fabric have been
developed besides Kevlar®, e.g., DSM Dyneema®, Honeywell's GoldFlex® and Spectra®, Teijin
Twaron®, Pinnacle Armor's Dragon Skin® body armor, INNegRITY Innegra S and Toyobo's
Zylon®.

Composites for armor (vehicles)

There are several articles on the ballistic performance of composites. For example, Faur-Csukat
studied the mechanical and ballistic behavior of carbon, glass (E and S type), aramid and
polyethylene fabric reinforced composites with different epoxies produced by hand lay-up
method. 5 The specimens were characterized by low and high velocity impact tests. They
absorbed a significant part of the kinetic energy of the projectile. In low velocity impact tests
(e.g., in drop-weight testers) the support conditions are crucial as the stress waves generated
outward from the impact point have time to reach the edges of the structural element, resulting
in a full-vibration response. For common epoxy composites, the transition to a stress wave-
dominated impact occurs at impact velocities between 10 and 20 m/s. In high velocity or ballistic
impact, the response of the structural element is governed by the ‘local’ behavior of the material
in the neighborhood of the impacted zone.

The ballistic performance of a composite focuses on the capacity of energy absorption of


structures during a high-velocity impact. For a given target-projectile combination, the ballistic
limit is defined as the lowest initial velocity of the projectile that will result in complete

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Rigid ballistic composites, 31 October 2010

penetration. The factors that affect ballistic performance are: material properties of
reinforcement; fabric structure; matrix mechanical properties; interaction of multiple plies –
number and order of layers; projectile geometry and its velocity. The majority of the kinetic
energy of the projectile is transferred to the yarns that are in direct contact with the projectile as
strain and kinetic energy, whereas, the contribution of the orthogonal yarns to energy absorption
is small. Fibers possessing high tensile strengths and high failure strains can absorb
considerable amounts of energy, thus the materials possessing high modulus and low density
disperse the strain wave more rapidly from the impact point, which distributes the energy over a
wider area and prevents large strain development from developing at the impact point.

For ballistic applications the fabrics have plain or basket weave, with the ‘‘cover factor’’ ranging
from 0.6 to 0.95. Stitching multiple fabric-plies increases the ballistic impact damage tolerances
of a carbon fiber/epoxy and the compression strength in ballistic impact increased by about
50%. The impact property and damage tolerance of composite laminates with different laminate
constitutions depends on matrix ductility. The composites thickness significantly affects the
energy absorption capacity during ballistic. Thus, the most efficient hybrid composites for
ballistic protection contain carbon (in the front part) and polyethylene (Dyneema®) fibers in rigid
and flexible epoxy matrices with laminates consisting of two separated types of fibers.
Composites with rigid epoxy matrix have lower energy absorption capacity than those with
flexible matrix, viz. ca. 30 vs. 36 (J), respectively. The basket wave fabrics resulted in structures
with 10% higher energy absorption than those with plain weave. With the increasing number of
plies the specific energy absorption ability of the composites increased, i.e., the efficiency of the
individual layers increased. It was established that glass, aramid and Dyneema® reinforcing
composites structures lead to high ballistic performance.

Table 1. Comparison of PPTA (Kevlar® 29) with UHMWPE (Dyneema®)

Materials Modulus Density Tensile strength Failure strain


E(GPa) (kg/m3) (MPa) (%)
Kevlar® Laminate 9 1160 450 9
PE Laminate 19.5 900 653 7

Colakoglu et al. studied ballistic properties of two composites containing Kevlar® 29 or


polyethylene (PE) fibers saturated with polyvinyl butyral (PVB). 6 Even when the bullet does not
penetrate the armor, the part of the body directly behind the point of impact usually receives a
“hammer-like” blow as a result of the deformation of the armor from the impact of the bullet. The
blow may produce bruises, lacerations of the skin and damage internal organs. Thus, the
authors investigated the ballistic performances of two different polymer matrix composites. In
addition to experimental tests they constructed a finite element model for the backside
deformation and penetration speed. It was found that PE fiber composite had better ballistic
limit, the backside deformation, and penetration speed than that of Kevlar® 29. Considering the
performance parameters listed in the Table 1, this observation was to be expected.

The back face deformation, both elastic and plastic, was measured from the witness paste. Its
value divided by the areal density for Kevlar® and PE composites at striker velocity of 450 (m/s)
was about 2.5 and 5.6 (m3/g), respectively. Similarly, the deformation-divided-by-thickness for
these two composites was about 3 and 5, respectively. The ratio of V50 to areal density was
determined for Kevlar® and PE composites as 73.3 and 95.2 (m3/kg), respectively. Numerical
simulations of the ballistic performance were in good agreement with the observations.

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Rigid ballistic composites, 31.10.2010

Structural fiber sizing ARL hybrid fiber sizing Ballistic fiber sizing

The US Army undergo significant equipment changes, e.g., weight reduction from 70+ ton ground
fighting vehicles (GFV) to < 20 tons Composite Armored Vehicle (CAV), without loss of personal
protection or performance. This only may take place by designing an advanced composite
armor that combines ceramics, metals and polymeric composites, using advanced materials
and mathematical modeling. Previously two types of composites have been developed: (1)
structural with high compressive strength and (2) ballistic with high projectile energy absorption.
As illustrated in the Figure above, the newly-developed third hybrid type combines both
functions. 7 Owing to sensitivity of information, rather sketchy image emerges what has been
done and how. For the new CAV, the polymeric composites contain ca. 50 vol% of glass fibers
(GF), rest being thermoset or thermoplastic polymer. The hybrid composites are designed
with strong fiber-matrix interfacial adhesion at structural loading rates, and weak
interfacial strength at ballistic loading rates. This is possible through innovative
manipulation of the chemical and physical interactions between the matrix and fibers.

Notice that the required behavior is reverse to that that offers good ballistic protection in flexible
personal armor. Now, not the STF behavior is required, but rather the shear-softening one. It is
also noteworthy that fabrics and matrix of the soft body armor are also part of the rigid armor
required for CAV protection – it is the way they are assembled that matters.

REINFORCEMENT

Kevlar’s

During the 1920s and 1930s DuPont carried out fundamental research that led to the invention
and commercialization of Neoprene synthetic rubber (1933), Nylon® linear polyamides (1938),
Teflon® fluoro-polymer resins, Kevlar® poly-p-aramid fibers (1971), Nomex® poly-m-aramid fiber
and sheets, Lycra® spandex fiber, Sontara® spun-laced fabric, Mylar® polyester film, Tyvek®
spun-bonded olefin, Cordura® nylon fiber, and Corian® solid surface material, etc. 8

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Rigid ballistic composites, 31 October 2010

The chemical composition of aramid, PBO


and M5 fiber is shown left. Kevlar® is an
aramid, an abbreviation for aromatic
polyamide. Chemically, it is a poly p-
phenylene-terephthalamide, or PPTA (amide
group shown in red rectangle). Poly(benzo-
bisoxazole), PBO, was invented at the USAF
research lab in the 1980s. PBO fibers have
high tensile strength, achieving better
penetration resistance than the HMWPE
fibers, but suffer from low compressive
strength. The decomposition temperature of
PBO is about 550°C, compared to 450°C for
aramid. The latest high strength polymer, M5,
will be discussed later.

The aromatic rings assure Kevlar’s thermal


stability, while the para (p) structure its
crystalizability. Like PA, Kevlar® filaments are
made by extruding a precursor through a
spinneret. The rigid flat rod p-aramid
molecules and the extrusion process make
Kevlar® fibers anisotropic – they are stronger
and stiffer in the axial than in the transverse
direction.

Stephanie Kwolek invented Kevlar® crystalline


aromatic polyamide, a fiber gram-for-gram five
times stronger than steel, with ca. ½ of
fiberglass density. 9 Kevlar® displays excellent
dimensional stability over a wide range of
temperatures for prolonged periods. Even at
160°C it shows essentially no embrittlement or
strength loss. Kevlar® fiber also has excellent
dimensional stability with a slightly negative
coefficient of thermal expansion (-0.2 10-6/°C).
The fibers do not melt or support combustion
and start decomposing at about 427°C.

The PPTA aramid stretched fibers are highly resistant to chemical attacks. Thus, the adhesion
with epoxy is poorer than that with inorganic fibers. Aramid/epoxy chemical interactions are
expected to be only secondary, strong enough to result in a thermodynamic fiber wetting. Fiber-
matrix physical interactions resulting from the thermal stress and Poisson contraction are not
strong enough to improve significantly the interfacial load transfer and may even be detrimental
to adhesion. Skin-core morphology of the aramid fibers may result in weaker properties in the
surface region that may form a cohesive weak boundary in the fiber-matrix interphase. These
observations suggest that to improve aramid-epoxy adhesion both the morphological and the
physiochemical modification of the interphase must be considered. 10

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Rigid ballistic composites, 31.10.2010

Recently Li et al. [2008] functionalized Kevlar® 1680 monofilament with phosphoric acid, H3PO4.
For the initial fictionalization of less than 40 % the monofilament tensile strength was constant.
For the optimal functionalization the fibers were tested in various combinations of epoxies and
hardeners. The mechanical properties were well enhanced. The interfacial shear strength and
inter-laminar shear strength were 76 and 79 MPa, respectively. Microstructure analysis revealed
better interfacial adhesion and the suitable toughness matching between ductile fiber and
toughened matrix, which resulted in high improvement of composite performance. 11

From 1970 to 2005, the helmet material technology changed little. The U.S. Army ballistic
helmets used woven aramids with a toughened polyvinyl butyral (PVB)/phenolic resin that often
failed to meet all the criteria. The combination of mass efficient ballistic and structural materials
provides a means of meeting the spectrum of performance specifications. Several helmet
prototypes with alternate design methods have been produced, e.g., stiffening the core ballistic
shell. Walsh et al. [2005] presented a preliminary normalized performance data on hybrid
structures, demonstrating the improved mass efficiency. A series of Kevlar® KM2 structures has
been hybridized using secondary structural materials, such as graphite-reinforced
polyolefin/polyamide (with Hercules IM7 graphite fibers). The specimens have been
characterized ballistically and structurally. The conclusion has been that thermoplastic based
systems can yield a 10 to 25% weight reduction over the conventional thermoset (PVB/phenolic)
materials, maintaining equivalent protection levels. The practical manufacturing methods for
producing these systems have been identified and preliminary prototypes of these new material
and system designs have been fabricated at relatively low pressures. 12 [The evolution of helmet
technology is presented on pg. 54].

There are several grades of Kevlar® available for ballistic applications: 13, 14, 15, 16

Kevlar® 29 &129 are tough yarns which are well suited for ballistic protection and are used both
in soft body armor applications such as ballistic vests and as robust reinforcements for variety of
hard armor applications, helmets, spall panels, ballistic blankets and electronic housing
protection. These Kevlar’s have been also used in industrial-type applications.

The thermal treatment of Kevlar® 29 fibers enhances its performance through two mechanisms:
(1) free-radical formation within the external skin region, resulting in the formation of interchain
crosslinks; and (2) hydrogen-bond disruption resulting in the destruction of the highly ordered,
pleated sheet configuration within the core region. Interchain covalent crosslinks improve the
compressive strength of the aramid fiber by augmenting its rigidity. Disruption of hydrogen-bond
within the core region slightly disorient the crystals and enhances the compressive properties of
Kevlar® by disrupting nearly perfect molecular alignment. 17

The tensile modulus and strength of Kevlar® 29 is comparable to that of glass (S or E), yet its
density is almost 1/2. Thus, Kevlar® may be substituted for glass where lighter weight is desired.
Kevlar® 49 or 149 cut the weight even further when the higher strength is accounted for. Tensile
properties of the three “standard” Kevlar’s are presented in Table 2. Table 3 compares the
properties of two ballistic Kevlar® fabrics.

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Rigid ballistic composites, 31 October 2010

Table 2. Tensile properties of common grades of Kevlar® PPTA

Grade Density (g/ml) Modulus (GPa) Strength (GPa) Elongation (%)


29 1.44 83 3.6 4.0
49 1.44 131 3.6 to 4.1 2.8
149 1.47 186 3.4 2.0

Table 3. The two Kevlar® ballistic fabrics may serve as examples:

Property Kevlar® 29 Style 735 Kevlar® KM-2 Style 705


Data at Kevlar Kevlar
FabricStyle735.com FabricStyle705.com
Finish Water repellent
Weight 14.70 oz. sq. yd 6.8 oz/sq. yd
Width: 50 & 63 inch 56.5";
Denier 1500 850
Weave: Basket 2x2 Plain
Construction 35 x 35 Length & Width 31 x 31 Length & Width
Thickness 23.0 (mils) 0.58(mm 12.0(mils) 0.30(mm)
Breaking Strength: Length & Width 1800(lbf/in) 880 and 950 (lbf/in)

Kevlar® KM2, is p-aramid fiber made in 400, 600 and 850 denier (denier is the total weight in
grams of 9 km of a filament). This high performance product was designed for ballistic
applications in soft and hard military products, e.g., for fragmentation protection. DuPont created
Kevlar® KM2 to achieve the performance goals defined by casualty reduction testing.

The transverse compressive behavior of the Kevlar® KM2 fibers is nonlinear and pseudo-elastic.
The original loading and unloading path is totally different, provided the maximum deformation
during these cycles does not exceed the maximum deformation the specimen has experienced
in the first loading cycle. The original loading and unloading cycle leaves a large residual strain
in the fiber of absorbed energy. Furthermore, KM2 fibers keep their mechanical properties in
their longitudinal direction despite of large residual strain in the transverse. Their transverse
compressive behavior is insensitive to loading rates, but the longitudinal tensions can stiffen the
transverse behavior at large deformations. To estimate the transverse Young’s modulus, a
relation was derived between transverse compressive load and deflection based on a classical
stress solution to this plane strain problem and the constitutive relation for transversely isotropic
materials. At low deformation the transverse compressive Young’s modulus was estimated at
1.34 ± 0.35 GPa. 18

Helmets and vests made with KM2 provide enhanced bullet and fragmentation resistance while
remaining comfortable and breathable. Its excellent thermal stability at temperature extremes,
water repellency, chemical stability, as well as inflammability and resistance to petroleum

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Rigid ballistic composites, 31.10.2010

products has made KM2 a high asset to the military. The KM2 fiber is a transversely isotropic.
Its tensile stress-strain response in the axial direction is linear and elastic until failure. However,
the overall deformation in the transverse directions is nonlinear and inelastic, although it can be
treated linearly and elastically at low strains. For a linear, elastic, and transversely isotropic
material, five material constants are needed to describe its stress-strain response. 19, 20

Kevlar® LT is a new yarn used in development of the lightest weight body armor products for
the market, to be mainly used in the civilian police products, providing comfortable, high level
protection.

Kevlar® K-159 was developed for correctional institutions as the first stab resistant fabric. This
new fiber, is 4 times thinner than typical ballistic yarns and used for an ultra-dense weave that
maintains a strength value five times stronger than steel on an equal weight basis.

Kevlar® Mark IV was recently developed for the use in hybrid personal protection and armoring
solutions. 21 Mark IV is being evaluated by the U.S. Army in the Enhanced Combat Helmet
(ECH) program. Kevlar® Mark IV is combined with a thermoplastic matrix, which provides more
protection per weight than existing aramid-phenolic composites. It can help to improve
performance and reduce helmet thickness and cost of ECH or other emerging military helmet,
including the Next Generation Helmet (solicitation issued 21.09.2009).

M5® fiber is not polyaramid (thus it is not Kevlar), but it is being developed by Magellan Systems
International (where DuPont is majority owner) using
DuPont high performance fiber technology. M5® is
the polyhydroquinone-diimidazopyridine (left is its
repeating unit), developed by Sikkema at Akzo
Nobel. Potentially it is an ultra-high strength, ultra-
high thermal and flame resistant alternative to the
existing advanced fibers. Its future applications may
include soft and hard ballistics protection, fire
protection, non-structural composites, and a host of
others. M5 is stronger than aramids (Kevlar®, Twaron) or UHMWPE (Dyneema®), it is the most
fire resistant organic fiber (better than Nomex®), less brittle than carbon fiber and will yield when
stretched. The US Army is experimenting with it in new, advanced composites for lighter and
more effective protection of vehicle and body armor.

M5 fibers are prepared by a condensation of tetra-amino pyridine with di-hydroxy terephthalic


acid using di-phosphorus pentoxide as a dehydrating agent. Then, the polymer mixture is
heated and extruded to form brightly blue fibers, which are extensively washed with water and
an alkaline removing the residual phosphoric acid, H3PO4. Finally, the fiber is heated and
stretched, aligning its macromolecules to optimal configuration. Its crystalline structure is
different from all other high strength fibers. The macromolecules have covalently bonded
backbone with a hydrogen-bonded network in the lateral dimensions. M5 fibers have an
average tensile modulus of 310 GPa (i.e., higher than 95% of the carbon fibers), and average
ultimate tensile strength ≤ 5.8 GPa (higher than Kevlar® or Twaron®, and on a par with Zylon®
PBO fibers). The ballistic impact performance of composites prepared from relatively poor M5
fibers (ultimate tensile strength = 3.9 GPa, elongation at break = 1.4%, and modulus = 271
GPa) was slightly inferior to aramid armor systems. However, M5 armor systems based on
these fibers have been shown to provide performance almost as good as the best composite
materials ever prepared for fragmentation protection. Thus, at the same level of protection the

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Rigid ballistic composites, 31 October 2010

fragmentation protective armor systems based on M5 might require 40-60% smaller areal
density than that based on Kevlar® KM2 fabric. 22
23
Table 4. Advanced Fiber Mechanical Properties
Fiber/ Strength ( ) Failure Strain Modulus (E) Strain wave velocity
(denier) (GPa) ( ) (%) (GPa) (m/s)
PBO 5.20 3.10 169 813
Spectra® 1000 2.57 3.50 120 801
Kevlar® KM2/600 3.40 3.55 82.6 682
Kevlar® KM2/850 3.34 3.80 73.7 681
Kevlar® 129/840 3.24 3.25 99.1 672
Kevlar® 29/1500 2.90 3.38 74.4 625
Kevlar® 29/200 2.97 2.95 91.1 624
Kevlar® 29/1000 2.87 3.25 78.8 621
Kevlar® 49/1140 3.04 1.20 120 612
Carbon fiber 3.80 1.76 227 593
E-Glass 3.50 4.7 74 559
Nylon 0.91 N/A 9.57 482
M5® Conservative 8.50 2.5 300 940
M5® Goal 9.50 2.5 450 1043
M5® (2001 Sample) 3.60 1.4 271 583

Having completed construction of its pilot plant in December 2004, Magellan is ramping up
production to between 20 and 60 metric tons of fiber annually. The DOD, which funded
Magellan R&D, will be the priority customer. Potential Army applications of the M5® fiber include
fragmentation vests and helmets, composites for use in conjunction with ceramic materials for
small arms protection and structural composites for vehicles and aircraft, for body armor of
soldiers and police, heat-resistant coats for fire fighters, and engineered composites for satellite
struts and aircraft wings. Only after meeting those critical markets will the company turn to
consumer products such as golf club shafts, bicycle frames and tennis rackets. As the Table 4
above shows, there is large difference between the performance obtained in 2001 for M5® and
the goal. Depending on the application, M5® could be interwoven with other fibers to boost their
performance. M5® doesn’t degrade with exposure to waters, acids or ultra-violet light, and its
ability to adhere to resins allows it to be used in composites. Competitors’ fibers may compete
on the basis of individual attributes, but none combine all its characteristics. 24

Twaron® 25

Twaron® 1000, 2040 are high performance p-aramid fibers supplied by Teijin Aramid®. In the
last 15 years of Twaron® being in the marketplace, many improvements in properties have been
made. Developments of finer filaments, uniquely combined with higher tensile properties,
resulted in the patented Twaron Microfilament® and have led to the newest types of Twaron®
yarns well adapted to the specific demands of hard and soft ballistic applications. Twaron T5713

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Rigid ballistic composites, 31.10.2010

was developed as a replacement for Kevlar® 29. Table 5 compares performance of two Twaron®
fabrics (see also Table 3).

Table 5. The two Twaron® ballistic fabrics may serve as examples:

Property Twaron® T5930-60 Twaron® T5713


Weight 6.0 oz sq. yd; 203 g/m2 8.3 oz/ sq. yd
Width: 60 inch 71 inch
Denier 930 dtex 1000
Weave: Plain Plain
Construction 27 x 27 Length & Width 31 x 31 Length & Width
Thickness 0.36 mm 0.38 mm
Breaking Strength: Length/Width 925/925 lbf/in 900/930 lb/in

Twaron® LFT AT is based on 930 dtex p-aramid fibers from Teijin Twaron Ballistic Engineering
in 2006. It shows excellent performance using laminating technology for hard armor
applications. The high tenacity Twaron ballistic fabrics were combined with an impact-resistant
polypropylene composite for soft armor application. However, there was a long way to go from
the initial idea to the final product. Countless runs followed by ballistic tests were required
before launching Twaron® LFT AT. The new plain weave, laminated material is capable
distributing deformation energy of a bullet over a larger area, thus reducing hematomas.

Teijin also developed a composite called Curv, consisting of an extended thin polypropylene
ribbon, which is woven and then laminated into a composite structure joined with Twaron woven
fabric, CT 707, in a specially developed pressing procedure. Its application is for hard shell
suitcases, under-seal of cars, shin protection in sports equipment, etc. For the ballistic
application the goal was reinforcement of the rather brittle Curv so that it is able to distribute the
energy of the impact over a larger area. Two layers of LFT AT reduced the bruises to the body
by almost 40%. The real aim was a compromise between maximum protection for the wearer
and portability of the vest. The LFT AT is more economical and lighter in comparison with shock
absorbers manufactured from neat aramid-laminates. Patents are pending. 26 Twaron® LFT GF
is a recent (2010) soft ballistic unidirectional laminate of 4 layers of Twaron (orientation 0 and
90o) between two PE films, designed for the use in bullet resistant vests. For helmets Twaron
fabrics: CT 736 (2x2 basket weave; 1680 dtex; 410 g/m2), or T750 (plain weave; 3360 dtex; 460
g/m2) are recommended by Teijin.

Heracron® polyaramid fibers from a Korean company, Kolon Inc. It has high strength, thermal
and chemical resistance, thus it may be used in ballistics. 27, 28 Kolon developed Heracron®
technology during 1979 to 1994 period, accumulating 25 related patents. Global
commercialization of Heracron® (filament and pulp) started in 2005. Two years later, a
disgruntled DuPont ex-employee, M. D. Mitchell, started consulting for Kolon, transmitting some
confidential information for what he was sentenced in 2009 to 1.5 years in prison.

Innegra™ S Fibers are highly oriented polypropylene fibers (>90% crystallinity), used for police
& military vests & helmets filament. Their properties are: denier = 12.5; density 0.84 g/mL;
melting at 160oC; tensile strength = 590 MPa; modulus = 19 GPa; elongation at break = 7.2 %;
dielectric constant = 2.2 and dielectric loss = 0.0002. 29, 30, 31

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Rigid ballistic composites, 31 October 2010

Making fabrics

Hexcel is the largest weaver of high performance yarns in the US for over 25 years. Hexcel
fabrics are woven from Kevlar®, Spectra®, Twaron® and other high performance fibers that offer
unmatched resistance to bullets, fragments, cuts, stabs and abrasions, while offering lightweight
strength and comfort. Police forces exposed to relatively high-mass/low-velocity bullets will use
a different fiber and different weave than military, which encounter relatively low-mass/high-
velocity bullets and fragments. The high strength fabrics woven from these fibers provide
ballistic and blunt trauma protection which has saved thousands of lives. Kevlar® fabric displays
excellent dimensional stability over a wide range of temperatures for prolonged periods. 32

Kevlar® KM2, made in 400, 600 or 850 denier, is a high performance product designed for use
in ballistic applications.

Kevlar® K-159 was developed for correctional institutions as the first stab resistant fabric. This
new fiber, which is 4 times thinner than typical ballistic yarns, is used for an ultra-dense weave
but still maintains a strength value that is five times stronger than steel on an equal weight
basis.

Kevlar® XLT is one of the newest yarns developed for body armor. This new yarn is available to
licensed companies through Du Pont.

Kevlar® A-200 and LT are new yarns that are used in the development of the lightest weight
body armor products. These new yarns are used in the civilian police products to provide
comfortable, high level protection.

Kevlar® Mark IV is a new poly(p-aramid) yarn in a thermoplastic resin matrix material, used in
the helmet design, being evaluated by the U.S. Army’s Enhanced Combat Helmet (ECH)
program. It provides more protection per weight than existing p-aramid-phenolic composites. 33

Spectra® 900 is the original gel-spun, extended-chain ultra-high molecular weight polyethylene
(UHMWPE) fiber was introduced by Honeywell’s Spectra® in 1985. Common to all Spectra®
fibers, with a high strength-to-weight ratio Spectra® 900 is 8 times stronger than steel. It is light
enough to float, has superior abrasion-resistance qualities, and is resistant to chemicals, water
and UV. Applications include safety products, such as cut-protective gloves and abrasion
resistant materials. Because of the hydrophobic character, it is an excellent product for marine
applications.

Spectra® 1000, the second generation family of Spectra fibers, was developed to provide higher
strength, higher modulus and improved creep properties, as well as enhanced ballistic
performance in armor. Spectra®1000 fibers have a high strength-to-weight ratio and are 10
times stronger than steel. It has superior abrasion resistance and has excellent resistance to
chemicals, water and UV. Applications include ballistic armor, cut-protective gloves and safety
products. 34

Similar to Spectra® in composition and performance are the Dyneema® fibers from DSM. The
Dyneema® fiber is gel-spun, multi-filament fiber produced from UHMWPE, with main
characteristics: high strength, low density, low elongation at break, and resistance to most
chemicals. Dyneema® fibers are produced in three strength ranges and several linear densities

13
Rigid ballistic composites, 31.10.2010

with a characteristic very low filament diameter. In Table 6, the tensile properties are correlated
with the fiber linear density.

Table 6. Tensile properties of three denier sizes of Dyneema® fibers.

Dyneema Tensile strength Tensile modulus Elongation


SK-XY N/tex g/den GPa N/tex g/den GPa at break
75, 78 3.4 – 4.0 38 – 45 3.3 – 3.9 112 – 1267 – 109 –
137 1552 132 3-4 %
60, 62, 65 2.5 – 3.4 28 – 38 2.4 – 3.3 67 – 102 759 – 65 – 100
1158
25 2.2 25 2.2 54 608 52

Dyneema® HB80, is the latest cross plied unidirectional fabrics (unidirectional, UD, means 75 –
90% of fibers run in one direction) composite meets the joint US Army and Marine challenge to
increase the fragmentation performance by at least 35 percent of advanced combat helmets. 35
In testing, helmets made with Dyneema® HB80 have demonstrated a minimum of 35 percent
increase in fragmentation performance when compared to the helmets currently used by the US
armed forces. Table 7 compares performance of Dyneema® to other fibers.
36
Table 7. Comparable properties of high performance fibers.

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Rigid ballistic composites, 31 October 2010

Patented ballistic armor

Number of ballistic-resistant constructions for hard or soft armor articles is described in several
U.S. Patents, viz. 4,403,012, 4,457,985, 4,613,535, 4,623,574, 4,650,710, 4,737,402,
4,748,064, 5,552,208, 5,587,230, 6,642,159, 6,841,492, 6,846,758, 7,700,503, 7,727,914,
7,762,175, and others. These usually describe sandwich structures made off high strength
fibers, felts or fabrics.

For example, patents 4,623,574 and 4,748,064 disclose composite structures comprising high
strength fibers embedded in an elastomeric matrix. Patent 4,650,710 discuses a flexible article
manufactured from several flexible layers, including high strength, extended chain polyethylene,
polypropylene, polyvinyl alcohol, and extended chain polyacrylonitrile (PAN) fibers coated with a
low modulus (< 41 MPa at 23oC) elastomeric material. 37

Patents 5,552,208 and 5,587,230 disclose articles comprising at least one network of high
strength fibers and a matrix composition that includes a vinyl ester and di-allyl phthalate. 38
Preferably, the article is made from at least one prepreg which includes at least two layers of the
high strength fiber network in the vinyl ester-containing matrix composition. The prepreg
element is made by applying a peroxide-curable mixture of epoxy vinyl ester, di-allyl phthalate
and a carbon-carbon saturated solvent (an alcohol that contains 1 to 5 carbon atoms) to the
high strength fiber network.

Patent 6,162,746 discloses a composite designed to be impact resistant to knife and ice pick
stabs, which comprises a number of woven layers selected from the group consisting of
extended chain polyethylene, aramid and polybenzoxazole (PBO) or polybenzothiazole fabrics
with a tightness factor of at least 0.75, and a number of layers of a network fiber. 39 Pats. No.
6,642,159 and later 7,762,175 discloses an impact resistant rigid composite having multitude of
fibrous layers with elastomeric layers there between. The composite is bonded to a hard plate to
increase protection against armor piercing projectiles.

Patent 7,700,503 describes a ballistic-resistant material composed of several layers: 1. first


exterior layer formed of a ballistic-resistant non-woven textile, 2. a second exterior layer formed
of a ballistic-resistant non-woven textile, and 3. an interior layer of ballistic-resistant woven tight
weave textile arranged between 1 and 2. 40 Stress is on the well-performing needled felt:
ArmorFeltTM [50% p-aramid, 50% extended chain UHMWPE, e.g., 50% 1.5 denier Kevlar® K29
+ 50% 3.6 denier Spectra® 1000with extra 30% performance over the average]. As shown
below, on impact Kevlar® fibrillates while UHMWPE deforms. The projectile energy is efficiently
dissipated by destabilization of its path.

Pat. 7,727,914 also discusses flexible, penetration resistant articles


comprising a number of layers including continuous filament yarns,
having an areal density of less than about 4.4 kg/m2. 41 At least one of
these layers should have a fiber with tenacity≥ 30 g/dtex 42
and a
continuous filament yarn having a linear density of less than about
1100 dtex. The first layers may be made from polybenzoxazole,
polybenzothiazole, polyareneazole, polypyridazole, or poly(pyrido-
bismidazole) fibers, while the continuous filament yarns are selected
from the group comprising polyamide, polyolefin, polybenzoxazole

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Rigid ballistic composites, 31.10.2010

fibers, polyareneazole, polypyridazole, polypyridobisimidazole fibers, and mixtures thereof.

The special emphasis has been placed on the filaments made from polyareneazole of the
chemical structure shown above. This polymer has one hetero-aromatic ring fused with an
adjacent aromatic group with nitrogen, sulfur, or oxygen atom, or NR a group with R being
hydrogen or alkyl or aryl attached to N. The number of repeating units ranges from about 10 to
25,000. To polyareneazole polymers belong polybenzazole, polypyridazole, poly(benz-
imidazole), polybenzobisimidazole, and polypyridobisimidazole. In the patent examples the
yarns of aramid [Kevlar®, tenacity of 25.2 g/dtex, elongation at break of 3.8%, and modulus of
575 g/dtex] and PBO [PBO Zylon, poly-p-phenylenebenzoisooxazole with tenacity of 37.8
g/dtex, elongation at break of 3.5%, and modulus of 1170 g/dtex] were used. Composition and
V50 (9 mm handgun) are listed in the Table 8– examples 1 & 2 are for the patent composites, C1
and C2 are comparative.

Table 8. Ballistic efficiency of PBO (Zylon) and PPTA (Kevlar®) fibers


for similar areal weights.

# Zylon Kevlar® Areal weight V50


2
# layers dtex # layers dtex kg/m m/s
1 31 550 -- -- 4.3 517
2 21 550 8 660 4.35 519
C1 -- -- 24 660 4.35 476
C2 18 1650 -- -- 4.25 478

US Pat. 7,762,175 describes lightweight, ballistic resistant armor incorporating two or more
connected but spaced apart, ballistic panels, having superior impact and ballistic performance at
a light weight. 43 The panels are spaced by air or by an intermediate material. When a high
speed projectile hits the first panel, the projectile is deformed, re-directed and slowed down
before reaching the second panel, where it is either slowed down further, or stopped. The
spacing reduces the back-face deformation compared to a configuration where multiple panels
are bonded together. The improved ballistic resistance allows weight reduction.

For example, the first panel comprises a number of consolidated fibrous layers, each made of
fibers having a tenacity of≥ 7 g/denier or and a tensile modulus of ≥ 150 g/denier. The fibers
are coated with a polymer. The fibrous layers are united into a monolithic structure by the

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Rigid ballistic composites, 31 October 2010

application of heat and pressure, to form the single, consolidated composite of fibers and the
matrix polymer. The second panel, connected to the first one, also comprises a number of
consolidated fibrous layers, each made of many fibers with a tenacity of≥ 7 g/denier or and a
tensile modulus of≥ 150 g/denie r. The fiber surface is coated with an elastomeric or rigid
polymer. The two (or more) panels are connected and spaced apart by about 6 to 13 mm from
each other. The spacing is achieved by placing a frame between the panels with air vents, or a
layer of open-cell foam of PU or PVC. Excellent ballistic resistance is achieved when individual
fibrous layers are cross-plied such that the fiber alignment direction of one layer is rotated at an
angle with respect to the fiber alignment direction of another layer, e.g. 0/45/90/45/0o (see also:
U.S. Pats. 4,457,985; 4,748,064; 4,916,000; 4,403,012; 4,623,573; and 4,737,402).

Each panel comprises a combination of fibers and a matrix. For sufficient ballistic resistance,
the fiber content preferably ranges from about 65 to 85 wt% plus the optional polymeric matrix
composition. The matrix may include additives such as fillers and reinforcements. The number
of layers in a single panel depends on the ultimate use. For example, in armor vests with the
areal density of 4.9 kg/m2, a total of at 22 layers may be used.

The preferred ballistic composite comprises: (a) a network of fibers having a tensile modulus of
at least about 500 g/denier and an energy-to-break of at least about 22 J/g; and (b) a matrix
consisting essentially of an elastomer, which substantially coats each of the individual fibers and
has a tensile modulus (at 25oC) of ≤ 41 MPa. The high tensile modulus fibers include extended
chain polyolefin fibers (UHMWPE, Spectra and Armor), and ultra-high molecular weight
polypropylene fibers or types (UHMWPP), p-aramid fibers (Kevlar®, Twaron®, Heracron®, and
Rusar), polyamide fibers, polyethylene terephthalate fibers, polyethylene naphthalate fibers,
extended chain polyvinyl alcohol fibers, extended chain polyacrylonitrile fibers, polybenzazole
fibers (PBO, Zylon) and polybenzothiazole fibers, and liquid crystal copolyester fibers.

Ballistic composite test packages were assembled from Spectra® Shield II SR 3124, where one
layer includes four plies of non-woven consolidated fibers (adjacent plies cross-plied at 0 and
90o) and water-based Kraton® block copolymer latex, the resin comprising about 16% of the 4-
ply layer. The assembled test packages were tested against 17 grain fragment simulating
projectiles (FSP) to determine the V50 of the molded panels. Excepting single example where
plywood was used as a spacer, air or foam spacing did not enhance the performance. Better
results were obtained for panels touching each other compared to a single molded panel of
equivalent weight. The ballistic performance of two panels with 1/4'' air gap was slightly better
(the first panel deformed and destabilized the bullet), but four half as thick panels kept 1/4'' apart
did not deform the bullet and was less effective than even a monolithic panel.

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Rigid ballistic composites, 31.10.2010

MATRIX

The synthetic thermoplastic polymers are divided into three categories: 44


1. Commodity resins (PE's, PP, styrenics, acrylics, PVC),
2. Engineering resins (PA, PEST, PC, POM, PPE), and
3. Specialty resins (PSF, PPS, PES, PAE, PEK, PEEK, PEKK, PI, PEI, PAI, PAr, PARA, PEA,
LCP, PHZ, etc.).
Thermoset polymers constitute ca. 13% of the plastics mass.

The five large-volume commodity polymer families are: polyethylenes (PE), polypropylenes
(PP), styrenics (PS), acrylics (PMMA), and vinyls (PVC). They represent 71% of all plastics and
their world market share remains stable.

The five engineering polymer families are: polyamides (PA), thermoplastic polyesters (PEST),
polycarbonates (PC), polyoxymethylene (POM or acetal), and polyphenyleneether (PPE). They
constitute about 13% by volume and 34% by value of the plastic's consumption.

The specialty polymers are characterized by high mechanical properties and high continuous
use temperature 150≤ CUT(°C) ≤ 500; their consumption amounts to about 3 %. Th ey are
expensive, produced in relatively small quantities either for specific applications or expecting a
market niche. Their glass transition temperature, Tg > 200°C and modulus > 3 GPa. To this
category belong: polysulfone (PSF), polyphenylsulfide (PPS), polyethersulfone (PES),
polyarylethers and ketones (PAE, PEK, PEEK, PEKK), polyimides (PI, PEI, and PAI),
polyarylates (PAr), polyarylamides (PARA), polyetheramide (PEA), liquid crystal polymers
(LCP), polyphosphazene (PHZ), and several others. PEEK was the polymer of choice in body
armor patent US Pat 7,413,809. Excellent properties were reported for PEEK with nano-
particles, such as tungsten di-sulfide (≤ 2 wt% WS 2) fullerene, fly ash (maximum strength for
about 20 wt%) or mica (best for ca. 10 wt%). 45, 46

Evidently, in addition to neat polymers there are numerous blends prepared to address some
specific lacunae of the basic resin. Table 9 lists PA-blends with specialty polymers (most are
commercial). Polyamides (PA-, followed by the number of carbons in a di-amine and di-
carboxylic acid, e.g., PA-66 patented in 1937 by Carothers, commercialized by du Pont two
years later as Nylon™, an aggregate of New York and LONdon. PA-11 was commercialized in
1955, PA-12 in 1966, PA-612 in 1970, and PA-46 in 1987. Liquid crystal aromatic polyamides
(PARA), poly(meta-phenylene isophthalamide), Nomex™, and poly(p-phenylene
terephthalamide), Kevlar™-49, were commercialized in 1961 and 1965, respectively.
Amorphous aromatic polyamide, Trogamid™, was introduced in 1969, and polyphthalamide,
Amodel™, in 1991.

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Rigid ballistic composites, 31 October 2010

Table 9. PA blends with specialty polymer [Utracki, 2002] 17

Composition Comment Reference


1. PA/PSF Blends
PSF with PA-11 for improved impact properties Nield, 1971
PA/PSF with poly(sulfone-g-lactam) processability and mechanical properties McGrath and Matzner, 1972
PA-6/PSF processability, thermal & mechanical Kyo and Asai, 1978
properties
PARA/PES HDT = 172°C & mechanical properties Hub et al., 1986
PA-46/PES mechanical and thermal properties Koning and Vroomans, 1992
PARA/PES mechanical and thermal performance Bapat et al., 1992
PAES or PES blended with PA-6T6 high heat resistance and stiffness Weber and Muehlbach,
1993
2. PA/PPS Blends
PARA with a small amount of PPS moldability, HDT, & impact strength Shue and Scoggins, 1981
PA-46 with PPS impact and mechanical properties, HDT, Chiba et al., 1978
heat and chemical resistance
PPS with polyphthalamide (PPA)_ heat and chemical resistance, HDT, Chen and Sinclair, 1990
mechanical properties
PPS with PPA and GF mechanical properties Davies, 1990
PPS/PA with EPDM and MA compatibilized-cum-impact modified Yu and Beever, 1992
PPSS with either PA or PEST mechanical properties, HDT, dimensional Ishio and Kobayashi, 1992
and chemical stability
PPS, either PA-66 or PA-MXD6 and tensile strength, arc tracking, and heat Dubois et al., 1993
Mg(OH)2 resistance
3. PA/Phenoxy Blends
PA-6 with Phenoxy excellent ESCR Schober, 1973
PA-66 with Phenoxy and SEBS tensile and impact strength Freed, 1975
PA with PEST, Phenoxy and MBS tensile and impact properties Robeson, 1988
4. PA/PEA Blends
PA-12 with PEA tough, flexible, heat and hot oil resistant Sumitomo Chem., 1984
PEBA/PA and (ABS, MBS, NBR, SBR impact strength at low-T, Rilsan™ Arraou, 1986
or EPDM)
5. PA/PAI Blends
PAI with PA-66 or PARA and inorganic moldings with high mechanical Toray Ind., 1979
filler performance
PI, PA, PAI or PI + PA and aromatic PI miscible blends for selective permeation Ekiner and Simmons, 1993
6. PA/PEI Blends
PEI with PA or PEST processability Giles and White, 1983
PEI with PA-6 and PEI-b-PA impact strength Robeson and Matzner, 1984
PEI with PA-6 or PA-66 compatibilized by nonyl-phenolic Gallucci, 1988
PEI with PA-12 reduced shrinkage and water absorption Giles, 1987
Copolyesteretherimide, PEEI Lomod™, thermal aging behavior Angeli, 1992
blended with either PA or PARA

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Rigid ballistic composites, 31.10.2010

PA’s are characterized by the presence of amide groups (-CO-NH-). They may be divided into
three categories: aliphatic (such as PA-6 or PA-12), semi-aromatic (e.g., PA-63T), and aromatic
(i.e., polyaramids such as Kevlar® or Nomex®) where the amide linkages, R-CO-NH-R, are
directly attached to two aromatic groups. Depending on the regularity of structure, PA’s may be
either crystalline or amorphous – the latter being transparent and susceptible to solvent attack.
47

As shown in Table 10, polyamides are tough, strong, and impact resistant, have low friction
coefficient and abrasion resistance, are easy to process, and have fair resistance to solvents
and bases. However, they also suffer from several drawbacks, out of which the moisture
absorption and susceptibility to hydrolysis (especially by acids) is a major one. The molecular
weight of the attacked polymer decreases and then cracks are formed. PA-6 is affected by
moisture more than more hydrophobic higher PA’s, such as PA-12. High temperatures may also
degrade the polymer. Furthermore, PA’s are susceptible to oxidation and UV degradation;
hence stabilization is required. Another disadvantage is a large, in-mold shrinkage caused by
crystallization.

Table 10. Comparative Properties of PA’s

PROPERTY PA-6 PA-66 PA-11 PA-12 PA-46 PA-610 PA-63T*


Tensile Modulus (GPa) 1.4 2.0 1.0 1.6 1.7 1.5 ≥ 2.8
Tensile Stress (MPa) 40 65 50 45 59 40 ≥ 75
Maximum Elongation (%) 200 150 500 300 60 500 50-150
3
Density (kg/m ) 1130 1140 1040 1020 1100 1080 1060-1120
Tg (°C), 57 57 42 37 50 145
Tm (°C) 220 255 184 180 295 215 240
HDT (°C) 80 105 55 140 90 95 150
o
H2O absorption at 23 C (%) 9.5 8.0 1.9 1.4 6.8 3.5 7.5

Note: *PA-63T is an amorphous product of co-polycondensation of terephthaloyl di-methyl ester with


2,2,4-and 2,4,4-trimethylhexamethylenediamine, which is chemically named as poly(trimethyl-
®
hexamethylene-terephthalamide), sold by Evonik Degussa AG as Trogamit T

Polyamide 11, Nylon 11, PA-11 or poly(ω-amino-undecanoic acid) is derived from vegetable
oil. It is produced by Arkema under the trade name Rilsan®. It is an important commercial
polyamide with excellent piezoelectricity and mechanical properties and thus widely used in a
wide range of industrial applications from automotive to offshore. PA-11 has multiple crystal
forms dependent on the thermal treatment. Its PNC with clay and carbon nanotube (CNT) have
been reported. For example, incorporation of 2 wt% exfoliated clay increased yield strength by
32 and modulus by 60%. 48 Properties of PA-11 are similar to those of PA-12, although it has a
lower environmental impact, its production consumes less energy and it has superior thermal
resistance. It has low water absorption, good dimensional stability and the best impact strength
of all PA’s. It is used in high-performance applications such as automotive fuel lines, pneumatic
airbrake tubing, electrical anti-termite cable sheathing, oil and gas flexible pipes, sports shoes,
electronic devices, catheters, micro switches, protective coverings, cable ties for electrical
installations and automotive industries, sports shoe soles, fuel, lubricant, vacuum and air brake
lines, hydraulic pressure hoses, etc. Typical properties of PA-11 are listed in Table 11.

20
Rigid ballistic composites, 31 October 2010
49
Table 11. Typical properties of PA-11
Property Value
Density (g/ml) 1.06
Surface Hardness RR78
Tensile Strength (MPa) 48
Flexural Modulus (GPa) 0.34
Notched Izod (kJ/m) 0.1
Linear Expansion (/°C x 10-5) 13
Elongation at Break (%) 330
Strain at Yield (%) 25
Max. Operating Temp. (°C) 70
Water Absorption (%) 0.3
Oxygen Index (%) 22
Flammability UL94 HB
Volume Resistivity (log ohm.cm) 10
Dielectric Strength (MV/m) 25
Dissipation Factor 1kHz 0.2
Dielectric Constant 1kHz 3.9
HDT @ 0.45 MPa (°C) 140
HDT @ 1.80 MPa (°C) 47
Material. Drying hrs @ (°C) 2 @ 90
Melting Temp. Range (°C) 200 - 260
Mold Shrinkage (%) 1.5
Mold Temp. Range (°C) 40 - 60

Polyamide-12, Nylon 12, PA-12 or poly(ω-dodecanolactam) is flexible polymer, with good


abrasion resistance, Izod impact strength, elongation at break, resistance to chemicals and low
hygroscopicity. To its disadvantages belong: cost, the reduced heat distortion temperature,
increased coefficient of linear expansion and poor electrical characteristics. Its typical properties
are listed in Table 12. The polymer is available from Evonik as Vestamid® L, from Ube America
Inc. as Ubesta®, from Arkema as Rilsan®, etc.

PA-12 is being used for the manufacture of damping cogwheels, protective coverings, ski boots,
tubing and profiles for the automotive industry. Flexible piping for air ducts and petrol and oil
pipes for the automotive and machine building industries. Flexible cover caps. Sealing rings,
sheet gaskets, diaphragms, cable fasteners, soles for sports shoes and others.

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Rigid ballistic composites, 31.10.2010

Table 12. Typical properties of PA-12 19


Property Value
Density (g/ml) 1.03
Surface Hardness RR80
Tensile Strength (MPa) 25
Flexural Modulus (GPa) 0.4
Notched Izod (kJ/m) 0.07
Linear Expansion (/°C x 10-5) 12
Elongation at Break (%) 300
Strain at Yield (%) 37.5
Max. Operating Temp. (°C) 70
Water Absorption (%) 0.2
Oxygen Index (%) 21
Flammability UL94 V2
Volume Resistivity (log ohm.cm) 11
Dielectric Strength (MV/m) 55
Dissipation Factor 1kHz 0.08
Dielectric Constant 1kHz 3.8
HDT @ 0.45 MPa (°C) 135
HDT @ 1.80 MPa (°C) 50
Material. Drying hrs @ (°C) 2 @ 90
Melting Temp. Range (°C) 190 - 200
Mold Shrinkage (%) 1.4
Mold Temp. Range (°C) 40 - 60

INTERPHASE

The goal of this review is for improved performance of military helmets – improvement in the
sense of better protection and durability at lowest weight and cost. One desires a tough
construction that would not shatter on low speed impact, but under high velocity bullet or
shrapnel become more rigid, more energy absorbent. Thus, the composite should have some
rate sensitivity. After the brief review of the matrix and reinforcing materials, the next part will
focus on the interphase between these two materials, including the methods that offer rate
sensitive response.

In any bi-phase system there are three phases! For example, in immiscible polymer alloys and
blends (PAB) the interphase thickness ranges from 2 (highly immiscible) to 60 nm (reactively
compatibilized). Similarly in PNC’s, the crystalline clay solidifies the first 6 nm of the matrix, and
reduces segmental mobility for up to 120 nm. 50 In either of these systems the total volume of
the interphase may be larger than that of either the matrix or dispersed phase.

Thermodynamics requires that surface energy be minimized, thus the highly mobile, low
molecular weight fractions and contaminants migrate to the interphase reducing its energy,
which in turn reduces the interphasial adhesion and strength. To compensate for this effect, one
must provide a mechanism strengthening the interphase – either by chemical or physical
means.

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Rigid ballistic composites, 31 October 2010

The chemical method relies on the chemical reaction that create covalent, ionic or hydrogen
bonding interphase between the two principal ones. Compatibilization of PAB or PNC is
accomplished chemically either by addition of reactive compatibilizer or by adding low molecular
weight reactive species that in-situ create compatibilizing macromolecules. Fiber “sizing” is also
a form of compatibilization where specific fiber is chemically treated to make it more compatible
with the matrix and more resistant to degradation during the lifetime of the composites (e.g.,
making glass fiber, GF, hydrophobic to prevent the degrading moisture attack).

The physical methods of compatibilization may involve roughening of fibers, adsorption and
solidification of matrix segments on highly surface active crystalline solid, on epitaxial
crystallization, on the use of strain-sensitive systems, etc.

The discussion on the interphase will be divided into four sections:

Computational studies
Compatibilization
Fiber sizing
Shear sensitive coupling

51
Computational studies

During the last two decades the understanding of the solid/polymer interactions expanded due
to the advancement of the simulation techniques via the Monte Carlo (MC) or molecular
dynamic (MD) methods, as well as the rapid progress of the nuclear magnetic resonance (NMR)
techniques. Computations (and experiments) show that macromolecules are greatly affected by
the solid surface energy – their molecular arrangements, conformations and dynamics are
strongly perturbed with respect to the isotropic bulk. MC has also been used for simulation of
tensile impact of unidirectional composites. 52

MC simulations have been carried out on or off the lattice. On-lattice computations, with
polymeric chains represented as random, self-avoiding walks, are more economic, but not as
realistic as the out-of-lattice methods. 53 MC and MD simulation have been used in studies of
static and dynamic properties of composites. For example, mathematical modeling of
organoclays and PNC has been used to describe structure and energetics of organic molecules
in the vicinity of 1:2 layered silicates. 54, 55 Vacatello 56 carried out MC simulations for dense
polymeric melt with solid, spherical nanoparticles. The model incorporated off-lattice
approximation and conformational distribution of the simulated chains, similar to that of real
polymer, with the Lennard-Jones 6-12 potential. The results showed that at the interface the
polymer segments are densely packed in form of ordered shells around the nanoparticles,
analogous to the layer formation near planar solid surface. The thickness of the shells was
approximately 1.35 nm. According to a MD model, the mechanical reinforcement originated in
the formation of long-lived transient polymer-particle networks composed of macromolecular
loops and bridges. The interphase volume should be smaller than that of the bulk phase and
that the reinforcement-polymer interactions must be strong. The reinforcement originates in the
volume expansion of reinforcing phase caused by tension of the compatibilizing molecules. 57
These calculations well simulate the structure and dynamics of the polymer/solid surface
system. The results, determined by topology and entropy, are applicable to diverse situations.
The presence of preferential interactions between polymer and a solid should not significantly

23
Rigid ballistic composites, 31.10.2010

change the computed structure, the order of interface shells, or the macromolecular
conformation.

During the last few years the MC/MD computation was extended to simulation of the mechanical
properties of composites. The multi-scale procedure starts with (1) atomic/molecular dynamics
modeling of the particles and their interactions; (2) construction of a representative volume
element (RVE); and (3) computation of macroscopic behavior of the composite from RVE, using
either classical continuum expressions or a finite element method (FEM). Originally Odegard et
al. applied this approach to systems containing carbon nanotubes. 58 Later, the model was used

radius ranged from r = 1 nm to 1 µm. 59


for analyzing the mechanical properties of polyimide (PI) with dispersed silica particles, whose

Sheng et al. 60 applied the multi-scale modeling strategy to clay-containing polymeric


nanocomposites (CPNC). (1) At nano-scale the interactions between matrix and nano-particles
were computed; (2) At micron-scale, the clay particles were considered either exfoliated or
intercalated, forming stacks; (3) At a length scale of millimeters, the structure was assumed to
be of a matrix with dispersed in it high aspect ratio particles. The new model correctly predicted
the elastic moduli for CPNC with MXD6 (PA produced from m-xylenediamine by Mitsubishi Gas

modulus with the orientation and volume fraction of clay platelets (φf ≤ 0.1). 61
Chem. Co.) or PA-6 matrix. More recently, 3D FEM was used to predict variation of the relative

Multi-scale modeling was also applied to damage in ceramic and polymeric composites. 62 The
fracture behavior in fully exfoliated CPNC was recently modeled using MD. 63 The system was
subjected to tension in the z-direction. The simulation indicated that addition of clay platelets
may improve the polymer fracture strength. The effect depends on the magnitude of
polymer/clay interactions, the relaxation time of polymer chains, and the polymer glass transition
temperature, Tg. For CPNC with the matrix Tg ≤ RT (room temperature), addition of clay
enhances the mechanical properties. However, when the matrix Tg is above RT (e.g., vitreous
epoxy or polystyrene), clay addition does not toughen the polymers, thus creation of a stress
relaxation mechanism might be necessary. For example, this might be accomplished by the use
of elastomeric intercalant, or by addition of a compatibilizer/coupling agent.

The MC/MD findings might be confirmed by the solid-state Magic Angle Spinning (MAS) NMR
spectroscopy. The chemical shift, Cs, dipole-dipole interactions, and J-coupling are capable to
elucidate electronic structure surrounding the nuclei, inter-nuclear distances and orientation.
More recently the two-dimensional (2D) NMR spectroscopy has been developed for studying
the geometry of the molecular dynamics and interactions. 64, 65 The homo- and hetero-nuclear
2D correlated solid state NMR provided invaluable information on the organic-inorganic complex
structures. 66, 67

There are several computational studies of the behavior of fiber-reinforced composites under
load. One important aspect that emerges from the high velocity deformation studies is the
coupling of the mechanical response with the temperature rise and resulting local changes in
material properties. For example, under the ballistic velocity of V = 1.1 km/s impact of a
tungsten projectile onto an aluminum (Al) block the temperature reached 1800 K (confirmed
experimentally). 68 In a standard helmet tests the velocities are not as high, but at the same time
the thermal conductivity of Kevlar® composites is significantly lower than that of Al, viz., 2 ± 1
vs. 250 W/mK, respectively. Thus, this aspect may be important when selecting the material.

24
Rigid ballistic composites, 31 October 2010

Recently, Phoenix et al. proposed a new interference model for the ballistic response of a
hybrid, two-layered, flexible body armor. 69 Since the stacking order of layers that has different
mechanical properties affects the V50 limit velocity for penetration, the authors applied the
analysis to a two-layer system consisting of fabrics of Kevlar® 29 and Dyneema®. Early
experimental results of 1992 showed the difference in the V50 by about factor of two for the two
possible stacking orders. The new model extends previous work by addressing interference
factors in terms of instantaneous material inflow to the impact cone using a convolution over
current local strain around the projectile edge during its deceleration. The current model is more
complete and produces velocity, strain, and deformation histories either to perforation or to
halting the projectile. In the new model, V50 differences with stacking order and with layer
bonding versus no bonding are even larger. However, back-face deflections turn out to be
minimally affected. Calculations are fast and post-processing figures may be obtained in less
than a minute using MATLAB on a laptop.

The new model predicts the ballistic response of a hybrid, two-layered, flexible body armor
system, where the individual layers are not bonded together and differ considerably in their
mechanical properties. Such systems are used in body armor for public safety officers and
security personnel as well as in airline cockpit doors, helicopters, and the doors of automobiles
and light trucks. It has been postulated that placing the stiffer and lighter fibrous polyethylene
layer on the strike face led to an interference effect whereby the naturally occurring impact cone
of the polyethylene layer clashed with that of the Kevlar® layer. This would result in impact cone
interference and a shift in load from Kevlar® to the top polyethylene. The paper introduces a
new version of the single-layer model that responds instantaneously (in terms of material inflow
velocity) to the changing tension around the projectile edge as it decelerates and it applies the
new version to the two-layer, interfering system to study analytically the negative effects of such
interference on V50 performance and back-face deflection.

The most important result is that the model predicts properties for a hybrid system, allowing it to
be largely expressed in terms of a single-layer problem and thus greatly reducing the number of
needed independent parameters, but allowing for detailed calculation of ply strains from the
effective property solution depending on true material wave-speed ratios. Note that effective
parameters are considerably different among cases of layers strongly bonded together versus
interfering layers, non-interfering layers, and systems based on just one of the materials at the
same overall fabric areal density. Future work will extend the model to stacked biaxial fabrics
and to the systems with small air gaps between layers which reduce V50 as the spacing
increases.

The Jones-2010 review of the interphase design and formation in fiber-reinforced composites
provides a suitable closure to this section. 70 The author discusses carbon and to a lesser extent
the glass fiber surface treatment and coating as the mechanism of interphase formation.
Adsorption of sizing polymers is a key part for securing good interaction between reinforcing
fiber and polymeric matrix. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging
was used to analyze solid surfaces and to identify the locus of failure and confirm the nature of
the interphase. In the case of glass fibers the hydrolysis of the silane coupling agent is critical.
The surface chemistry of the glass controls the degree of polymerization of the polysiloxane and
hence the interaction with the matrix polymer whether it be thermoplastic or thermoset. For
completeness a brief review of the surface treatments of advanced polymer fibers was included.
The role of the interphase in the micromechanics of the failure of composites is also modeled
and discussed in an attempt to provide design guidelines for the composite manufacture. The
micromechanical modeling showed that the thermomechanical properties and thickness of the

25
Rigid ballistic composites, 31.10.2010

interphase have a major impact on the stress transfer between fiber and resin, even when the
thickness of an interphase is only 5 nm. The well-designed interphase should match the matrix
mechanical properties, but have a slightly lower yield stress so that energy is absorbed by
elastic–plastic deformation, not debonding.

Compatibilization

The strongest bond is that between carbon-carbon atoms, thus the crystalline form of C has the
highest modulus. Accordingly, providing a direct covalent bond across the interphase may lead
to the strongest, most rigid, but brittle composite. Macromolecules in the melt are entangled and
may crystallize on solidification, thus analysis of their tensile behavior at the atomic level is
difficult. However, the stress-strain of a single polystyrene (PS) chain in a solvent has been
measured. 71 The macromolecule (Mw = 100 kD, degree of polymerization DP = 918) had a
contour length of 284 nm. While stretched by the ends, it first uncoiled with little resistance than
upon stretching it deformed elastically by about 21% before breaking. The elastic deformation
originated mainly from changes of the internal C-C bond angles, not from their elongation. The
bonds, each about 0.14 nm long, break when stress exceeds a critical value with little (is any)
effect of the deformation rate. Thus, if the stress hardening of a system is desirable, uniformly
strong covalent bonding across the interphase is not.

Evidently, for covalent bonding both the matrix and the reinforcement must be reactive. Ajji and
Brown in their chapters 4 and 5, discuss the compatibilization of PAB by addition and reaction,
respectively. 72 Considering the great diversity of the matrix/reinforcement combinations and
numerous possible compatibilization methods makes a general discussion meaningless. Thus,
the rest of this section will consider a limited case: Kevlar® fibers in polyamide (PA) matrix, the
later selected from the list of processable (thermoplastic) PA in Appendix 1.

The processability requirement means that the PA of choice will be either linear (e.g., PA-11) or
semi-aromatic (e.g., PA-63T), thus reactive by the presence of chain end amine or carboxylic
acid groups or by the limited trans-reaction of the amide groups, hydrolytically catalyzed. The
problem rests with making Kevlar® reactive.

Kalantar and Drzal offer an early review of Kevlar-epoxy


matrix bonding. 10, 73 The authors concluded that in spite of
a considerable number of publications on aramid fiber
composites and extensive efforts for improving aramid-
epoxy adhesion, up to date, the efforts grossly failed. One
reason for it is the highly conjugated nature of the PPTA
molecules, the others: presence contaminating salts and
the skin-core fiber morphology, created during filament
spinning from 20 wt% PPTA solutions in a concentrated
H2SO4. Lack of sulfonation during the process by itself
indicates chemical inertness of PPTA. Thus, promising
coupling agents for PPTA are not easily found.

Three methods of PPTA surface treatment are possible: (1)


radio frequency plasma treatment, (2) bromination, and (3)
phosphoric acid treatment.

26
Rigid ballistic composites, 31 October 2010

Re (1). Allred et al. reported that Kevlar® fibers treated with radio frequency (r.f.) plasma in the
presence of NH3, resulted in a two-fold increase in the interlaminar peel strength of treated
Kevlar® 49-epoxy composites with failure mode changing from interface failure to mixtures of
fiber and matrix failure. 74

Re (2). Wu and Tesoro investigated selected reagents and conditions for surface-controlled
heterogeneous reactions on Kevlar® filaments and fabrics. They used a wet chemistry
approach, brominating Kevlar® fibers, subjecting them to ammonolysis, nitration, and then
reduction to amine functional groups on the fiber surface. Modification of filaments has been
attained without impairment to fiber properties. The presence of amino groups improved peel
strength and apparent interlaminar shear strength in epoxy laminates, suggesting a significant
role of covalent bonding in improving adhesion between PPTA and the matrix. 75 Chemical
treatment of aramid surface was also carried out by chloro-sulfonation. 76

Re (3). Li et al. functionalized Kevlar® 1680 fibers (diameter, 12 µm, monofilament strength, 2.0
GPa) with phosphoric acid (H3PO4) at different concentration. 77 The monofilament tensile
strength was constant up to 40 wt% H3PO4, but the maximum of oxygen functional groups was
obtained using 20 wt% H3PO4. Composites prepared from optimally functionalized fibers, and
various combinations of epoxy/hardener were studied.11 The mechanical properties were further
enhanced when 40 wt% DGEBF (diglycidyl ether of bisphenol F, epoxy value 0.54) was added
to DGEAC (diglycidyl ester of aliphatic cyclo, epoxy value 0.85) and reacted with 4,4 -
diaminodiphenylmethane (DDM) hardener and DETDA (a mixture hardener of two di-ethyl
toluene di-amines). The improvement was attributed to the interfacial adhesion between
functional groups of the matrix polyamide and those of the functionalized PPTA fibers, as well
as to a good match of toughness of fiber and matrix. The interfacial shear strength (IFSS) and
interlaminar shear strength (ILSS) were 76 and 79 MPa, respectively, and the fiber strength
conversion ratio of Naval Ordnance Laboratory (NOL) Rings reached 95%. The microstructure
analysis revealed that the increased concentration of polar functional groups on the fiber
surface, enhanced interaction between resin matrix and H3PO4-functionalized fibers, what in
turn resulted in greatly improved mechanical properties. Compared to various combinations of
epoxy and hardener, Kevlar® fiber composite of DGEAC/DGEBF/DDM/DETDA system exhibited
excellent mechanical properties.

Fiber sizing

Sizing refers to deposition of a specific substance on a fiber to modify its surface properties and
protect it during processing. Sizing is used in papermaking, textile manufacturing, composite
production and other domains. For example, yarn sizing reduces its breakage, thus assures
production without stops of the weaving machine. Sizing improves the strength, abrasion
resistance and the hairiness. Several types of water soluble polymers are used for textile sizing,
viz. modified starch, polyvinyl alcohol (PVAl), carboxy-methyl cellulose (CMC), acrylates, etc.
Usually, in addition wax is added for reduction of the abrasiveness of the warp yarns.

It is noteworthy that frequently sizing agent is extracted before product goes to market or before
it enters the production line, thus it does not bond covalently to the fiber. Even in cases when is
not to be removed (see below) it forms a protective layer that offers additional resistance in
standard pull-out tests, but does not exceeds the tensile strength of the fiber.

27
Rigid ballistic composites, 31.10.2010

Sizing is essential for the manufacture of glass fibers (GF) as well as for improved performance
of their composites. GF are abrasive and without sizing would turn each other to dust.
Furthermore, without sizing it would be difficult to make glass rovings and virtually impossible for
anyone to use it. GF sizing agents are mixtures of several chemicals comprising: (1) film-
formers, (2) coupling agents and (3) other functional chemicals. Often the film-former is
chemically similar to the matrix polymer. It is designed to protect and lubricate fibers and hold
them together before processing, and then facilitate their separation when contacted by resin,
thus ensuring good filament wetting. The GF coupling agent (usually an alkoxy silane) bonds
the fiber to the matrix. In addition, sizing may include lubricating and antistatic agents as well as
other additives. Optimized sizing works well with a specific resin, e.g., the one designed for
polypropylene (PP) will not work for PA. Similarly, the one for anhydride-cured epoxy should not
be used for amine-cured epoxy composites. Frequently glass manufacturers offer "tri-
compatible" products (e.g., polyester, vinyl ester and epoxy), or even "multi-compatible" sizing
agents. Optimized sizing is essential for the recently developed long fiber-reinforced
thermoplastic (LFRT) composites with PP matrix, to be used for automotive applications. 78

Early studies on the interphases properties of composites discuss E-glass-fiber/epoxy-amine

displacement rates in the range of 230 to 2450 µm/sec. 79 The data reduction related the force
systems. For example, Tanoglu et al. used a new dynamic micro-debonding method at

vs. displacement response to interphase shear stress/strain response. The obtained curves and
interphase shear moduli were determined for the average shear rates of 215-3278 (l/s). The
results showed that the interphase shear modulus depend on the sizing agent and strain rate,
but it always was lower than the matrix modulus. The two sized fiber systems exhibited the
highest strain rate sensitivity, with modulus increasing about threefold over the range studied.
Using the dynamic mechanical analysis and the time-temperature superposition principle, the
master curves of flexural storage modulus vs. strain rate were constructed.

From the cumulative damage principle, Tang et al. derived a fatigue model for predicting the life-
time of fiber reinforced polymeric composites. 80 The model parameters are: applied maximum
stress, stress amplitude, loading frequency, residual tensile modulus, and material constants.
The residual modulus for a given maximum applied load after N loading cycles may be
predicted for the three environments combined. Fatigue data for glass fiber/vinyl ester
composites were used for verification of the model. The specimens at 30oC were subjected to
tension-tension stress at four levels and two frequencies. In freshwater and saltwater the vinyl
ester/E-glass fiber composite lost 25 and 30% of tensile strength, and 15% and 11% of tensile
modulus, respectively. Thus, the loss in residual tensile strength and modulus in freshwater and
saltwater was similar, but larger than that in air. Numerical analysis was applied for determining
the material constants. The fatigue model agrees well with the experimental data and it may be
used to predict the fatigue life-time and the residual tensile modulus of the polymeric
composites subjected to an applied load in different environments.

The cyclic fatigue resistance of a silane-bonded epoxy/glass interface in moist air was studied
using the double cleavage drilled compression test (see the reference for the method details). 81
The properties of two epoxies with similar chemical structures were controlled by varying the
molecular weight between cross-links, Mc. Two rubber-toughened epoxies with different nominal
rubber particle sizes (10–40 and 1–2 m) were used. The changes of Mc had little effect on the
cyclic fatigue resistance of the epoxy/glass interface, but incorporation of rubber particles
significantly improved the resistance. Incorporation of rubber particles smaller than the plastic
zone size found ahead of the propagating crack gives a significant improvement in the cyclic
fatigue resistance of the interfaces through the additional energy absorbing mechanisms of

28
Rigid ballistic composites, 31 October 2010

cavitation and shear yielding. Smaller particles gave the greatest improvement of fatigue
resistance (75% improvement) compared to non-modified epoxy. Adjustment of the number of
silane bonds between the neat epoxies and the glass had little effect, suggesting that the
energy dissipated through the breaking of the interface bonds accounts for only about 10–15%
of the total energy necessary to drive the crack. Therefore, this term is negligible compared to
the energy dissipated though plastic deformation and other inelastic mechanisms.

Jensen et al. developed a multicomponent


GF sizing formulations for pultruded vinyl
ester/E-glass composites. 82 The
composites were designed for Composite
Integral Armour (CIA) in the Future
Combat Systems (FCS). The authors
stressed that the interphase may control
CIA performance, viz. strength, durability,
fatigue life, as well as the
micromechanical energy absorbing
capability during a ballistic event.

fibers (16.9 µm diameter) the sizing was


Immediately after drawing the E-glass

deposited from aqueous emulsion


comprising 4.4 wt% film former and 0.6
wt% propyl-tri-methoxy-silane coupling agents (methacryl-, amino-, and gycidox- or MPS, APS
and GPS). The film formers were thermoset systems: di-glycidyl ester of bis-phenol-A (DGEBA)
epoxies, unsaturated bis-phenol-A vinyl ester and polyesters. The emulsion was stabilized by
Pluronic surfactant. The sized fibers were formed into tows each having 2052 filaments, dried
and spun into bundles of 38 tows. Next, the cylindrical pultruded rods were formed with 50 vol%
of GF in vinyl ester/styrene thermoset matrix.

For determining the void content the specimen density was measured by immersion method,
the interlaminar shear strength (ILSS) was calculated from the ASTM short beam shear test, the
dynamic-mechanical temperature scans were conducted on dry and wet samples for
determining “durability” (i.e., the ratio of wet-to-dry ILSS). The conclusion was based on the
ILSS and durability data as the moisture resistance was judged to be of crucial importance.
From the many combinations of silane and the film-former the most important conclusion was
that both of them must have chemical reactivity with the vinyl ester matrix. The coupling agent
reactivity toward the matrix decreased in the order: MPS > APS > GPS.

During GF manufacture a multicomponent sizing is applied to the fibers for protection against
damage during processing. 7 Conventional sizing incorporates silane coupling agents, which
enhance adhesion between GF and the matrix and durability of the composite. The silane forms
a nanometer sized interphase that surrounds GF. This structure is essential to composite
performance, but poorly understood and not optimized for static and dynamic responses. Yet,
there is new information that sizing may be tailored for high-energy absorption by designing
weak fiber-matrix interfacial interactions and for structural performance by strong fiber-matrix
interactions.

The Army Research Laboratory (ARL) searched for the fundamental understanding of GF sizing
that could suggest a new class of sizing agents with rate-sensitive bonding. The resulting
strategy comprises two elements:

29
Rigid ballistic composites, 31.10.2010

1. Mixed organo-functional silane coupling agents are


employed to vary the chemical reactivity toward the
polymeric matrix and produce bond strengths dependent on
the viscoelastic properties of the interphase. This
“viscoelastic switch” yields strong fiber-matrix interactions at
low strain rates (structural) and weak fiber-matrix
interactions (ballistic) at high strain rates.
2. The GF surface was modified using an inorganic-organic sol-
gel compound that not only acts as a silane-based, glass-
fiber sizing, but also increases GF surface roughness.

The result is an increased friction coefficient between fiber and


matrix during the fiber pullout stages of composite failure, further
resulting in enhanced energy absorption in the composite during
ballistic events. These results were first documented mechanically
on micro-scale model composite specimens. Subsequently, the
experimental inorganic-organic hybrid fiber sizing were scaled-up
and applied using commercial manufacturing equipment to
demonstrate their behavior in composites.

The Figure above shows two atomic force microscopy (AFM) micrographs – top: the nano-
textured GF surfaces produced on a commercial scale; bottom: a “standard” fiber. The fabrics
made from these textured fibers were used in manufacturing reinforced composites. Their
structural and impact energy responses are displayed in the center of the Figure on pg. 6; the
green bars represent the impact energy absorption and the orange ones the structural
performance of composites produced using state-of-the-art commercial sizing’s and the ARL
inorganic-organic hybrid sizing. These results show the traditional trade-offs found when using
commercially available fibers that have been coated with either a structural or ballistic sizing. In
comparison, these trade-offs are absent in the ARL inorganic-organic hybrid sizing, and the
structural and ballistic performance of the new sizing are both excellent. A 40% increase in the
energy absorption of composites fabricated with no loss in structural properties enables the use
of PMCs at reduced cost in ballistic applications where they have not been used previously.

It is noteworthy that standard GF/epoxy


composites show strain rate dependent
compression behavior. 83 The backing
plate for composite armor applications,
was studied at strain rates 10-4 to 1.1x103
(1/s), where the modulus and failure
strength increased with increasing strain
rate from 6 and 0.45 GPa to 10 and 0.7
GPa, respectively. Microscopic
observations showed that the composite
ductile failure constituted a matrix cracks
and through and in-between the fiber
layers. Crack deflections at rubber particle/matrix interface and particle pull-out contributed to
the composite toughness. As the above-right Figure demonstrates, the strain rate sensitivity of
composites depends on the fiber orientation angle, decreasing from the maximum value at 0o to
a plateau ranging from 30 to 150o. 84 Similar conclusion could be drawn from the recent studies

30
Rigid ballistic composites, 31 October 2010

on the mechanical behavior and failure mode of unidirectional fiber composites at low strain
rates. 85

Also carbon fibers (CF) are sized for better processability and composite performance. CF
sizing is applied to the fiber tow (ca. 12,000 filaments) to prevent abrasive contact damage. In a
recent patent from Mitsubishi Rayon, CF sizing agent comprised of water-soluble thermoplastic
resin (e.g., PVAl, PA, PU, polyacrylamide, acrylamide-vinyl acetate copolymer, polyacrylic ester
or methyl cellulose) and alkyl-imidazoline-based betaine-type amphoteric surfactant in a weight
ratio ranging from 6/1 to 1/3. Both sizing components should be water-soluble in a wide pH
range, and impart adequate coverage to CF, forming stable chopped carbon fibers, superior
workability and satisfactory uniform tow dispersibility in water over a wide pH range. 86

Recently Gan reviewed the interface of advanced composites. 87 Nanostructuring the composite
interface by introduction of nanopores and nanofibers has the key role in determining the
behavior. A nonlinear damage model for characterizing deformation of the polymeric
nanocomposites (PNC) was developed and its application to carbon nanotubes (CNT)-
reinforced and reactive graphite nanotube-reinforced epoxy composites was presented.
Formation of nanopores on metal surface may increase bonding strength of the metal/polymer
interface. Surface treated CNT are used in preparing nanoreinforced matrices. The nanofiber
reinforced epoxies containing reactive graphitized CNT as new adhesives can help to alleviate
the residual stress problem because they are more ductile than the conventionally used epoxy
adhesives. The progressive damage of interfaces in composites may also be evaluated by
nonlinear models.

For at least 20 years aramid fibers have been commercially sized. The composition of the
coating is considered confidential, but some information might be found in the literature. For
example, de Lange et al. analyzed Twaron® 2200 (1680 dtex, f1000) fibers. Three forms were
studied: without any finish (HM), with a standard finish (HMF) and with an adhesion activation
treatment (HMA). The standard finish consists of deposition of a non-ionic ethylene oxide and
propylene oxide that facilitates fiber processability and can easily be removed with alcohol. The
adhesion-active finish is based on an epoxy–amine system, e.g., glycerol diglycidyl ether as
epoxy and piperazine as amine, in the mass ratio of 9:1. This finish (which also contains some
oil) is to improve processability and performance of epoxy composites. After application (0.3
wt% epoxy–amine, based on yarn weight) and drying (2 s, 70°C), the adhesion -active finish was
cured on the yarn by drawing it over a hot metal plate (240°C) for 5 s. Since Soxhlet extraction
with ethanol easily removed the standard finish, ethylene and propylene oxides did not
chemically bonded to PPTA. Indeed, the bundle pull-out adhesion test from an epoxy matrix
indicated that HM and HMF fibers had similarly low adhesion to matrix. However, in such test
HMA performed better by ca. 40%. 88

More recently, Twaron® 2200 adhesion to epoxidized natural rubber (ENR) was enhanced by
dipping the activated HMA fiber in resorcinol-formaldehyde latex (RFL). 89 The authors used the
micro-bond pull-out test, mechanical characterization and scanning electron microscope (SEM)
in studies of the interphase properties. It was found that surface treatment is important for the
adhesion of aramid fibers to ENR. The interfacial shear strength between fiber and the matrix
was improved by morphological modification of its surface. By contrast with the de Lange et al.
findings 88, the tensile and impact strength of the Twaron/ENR composite showed that without
RFL treatment the HM and HMA fibers show a similar, poor adhesion to matrix, i.e., the
standard modification of the fiber surface and epoxy activation did not improved the composite
performance. However, HM or HMA treatment with RFL resulted in higher tensile and impact

31
Rigid ballistic composites, 31.10.2010

strength, caused by improved dispersion and interactions between Twaron® and ENR. The
authors suggested that both, the epoxy-based standard adhesion activation and RFL coating
should be used in the PPTA/ENR composites.

A closing note on sizing should include at least a mention of the emerging nanotechnology
application for the enhancement of ballistic performance of composites. More details will be
given in the final section of this review entitled NANOTECHNOLOGY (see pg. 51).

Siddiqui et al. studied the tensile strength of glass fibers sized with CNT–epoxy nanocomposite
coating. 90 The main idea was to create a self-healing interphase that would reduce the stress
concentrations and to improve reinforcing efficiency. Coatings made from neat epoxy and CNT
were deposited onto the individual GF or their rovings. Already at the level of 0.3 wt% CNT in
epoxy there was a significant increase in tensile strength of the single fiber for all gauge lengths
over the standard epoxy coating. The results on rovings also evidenced beneficial effects of
nanocomposite impregnation in tensile tests, viz. higher and more uniform strength. The authors
concluded: (i) The single fibers coated with the 0.3 wt% CNT–epoxy exhibit strength
improvement over fibers with a neat epoxy coating, suggesting that incorporation of CNT to
epoxy sizing enhances the crack healing. (ii) The effective crack length coefficient (obtained
from the crack length vs. gauge length) is inversely proportional to the fiber critical strength, thus
incorporation of CNT reduced the crack length indicating larger healing effect. (iii) The degree of
nanoparticles dispersion in the polymer coating strongly affects the healing effect. (iv) The glass
fiber bundles impregnated with CNT–epoxy nanocomposite led to much higher tensile strength
than those with neat epoxy coating, with accompanied change in the failure mode. The
enhancement of interfacial adhesion arising from the amino-functionalized CNT’s was partly
responsible for the beneficial effect of the nanocomposite on tensile strength of bundle fibers

Modern techniques are required for creating interphase regions, with which the performance of
unidirectional fiber composites can be improved. Gas phase plasma polymerization is a
potential new sizing approach, since the interlaminar shear strength properties can be adjusted
by careful control of interphase thickness and properties. The method may cause less damage
to fibers than the laser ablation assisted interphase formation. 91, 92

SHEAR SENSITIVE COUPLING

Rheology recognizes that all materials are time and rate of deformation sensitive, each within a
specific range of temperature (T) and pressure (P), determined by their chemical nature. Thus,
material sheared at constant speed may become less (thixotropy) or more (rheopexy) viscous.
Similarly, when sheared at increasing rate of deformation the material may became less
(pseudoplastic) or more (dilatant) viscous. This rheological terminology applies to liquid
systems, single or multiphase ones. In the literature there are two other nomenclatures. The first
evolved from the measurements of elongational viscosity, where entangled molecules
dramatically stiffen at high strains – the effect is known as strain hardening (SH). Its opposite,
the strain softening (SS), has only been recorded for filled polymers. The onset of SH or SS
limits the linear viscoelastic behavior. In another nomenclature the pseudoplastic and dilatant
terms are replaced by “shear softening fluid (SSF)” and “shear thickening fluid (STF)”,
respectively. The three terminologies are only approximately equivalent as the rheology speaks
in terms of rate of deformation in shear or elongation, the SH/SS system in terms of strain,
whereas the last one is concerned with “shear”, what may mean shear stress or the total shear

32
Rigid ballistic composites, 31 October 2010

strain. In the following text all three systems will be used, following the nomenclature in the
original publications.

Deformation of a solid material may also show diverse behavior. For example, the stress-strain
curves may show only elastic behavior and brittle fracture, or elastic and plastic with ductile or
strain hardening performance. For given external conditions of T and P, one is able to identify a
polymer showing any of these three characteristics, e.g., at ambient conditions PS would be
brittle, PA-6 ductile and PEEK strain hardening (SH). 93

Biermann et al. patented an impact resistant flexible body vest, comprising a flexible support
matrix and energy absorbing elements connected to the matrix. 94 The elements were made off
at least one ceramic material and at least one strain rate sensitive polymer. The impact resistant
device was to be worn as a body armor protecting the wearer from high velocity projectiles.
Each impact resistant element comprised ceramic layers alternated with Fe3Al alloy. The
ceramic layers were made off yttrium stabilized zirconium oxide [YSZ = zirconium-oxide, ZrO2,
whose crystal structure is stable at RT by addition of yttrium oxide, Y2O3]. In addition to ceramic
and metal layers, the impact resistant element comprised a strain rate sensitive polymer with
modulus ≥ 3 GPa at a strain rate of 1000 (1/s). PEEK was the preferred polymer not only as an
internal part of the multilayer elements, but also covering and protecting their surface. The vest
was made of two overlapping layers of interconnected energy absorbing elements, affixed to
ballistic aramid or polyethylene fabrics.

The present day technology rarely relays on a single-component or single-phase materials.


Thus, the rheological behavior, which reflects the material structure, in practice shows a more
complex behavior, where for example, a suspension at increasing deformation rate may be
Newtonian, then pseudoplastic, dilatant, pseudoplastic, finally reaching the lower Newtonian
plateau. The multi-phase systems are also know for their yield behavior, which make the
material double-sensitive to strain and to stress.

Strain hardening (SH) of foams and gels

Similarly like PEEK, poly(boron di-methyl siloxane), PBDMS is an interesting SH-sensitive


polymer. Hydrothane® (hydrophilic polyurethane, PU) shows strain and stress hardening effects.
Innace et al. tested the material in stress-relaxation
experiments in a range of deformation up to 25%.
The stress-strain curves (see left Figure) show that
SH is larger at higher deformation rate (triangles 10,
circles 1 mm-1). After separating the strain and time
effects the data followed predictions of the rubber
elasticity theory. Stress strain curves obtained at
different rates have been interpreted introducing
strain rate dependent scaling factors. 95 In PU as in
other elastomers the crosslink density controls the
molecular weight between crosslinks that determine
SH. In PEEK the crosslinking is achieved through
micro-crystals from which several macromolecules
emerge. Thus, for SH a network structure is
essential.

33
Rigid ballistic composites, 31.10.2010

Dennis and Russell patented a multi-layer, helmet with HYDROTHANE PU and its foamed
version showing SH. The outer and inner load-bearing semi-rigid layers, as well as the foamed
core were spray-deposited. 96 The patent specifies personnel-protective helmets against blunt
object impact and noise suppression. The contacting drops agglomerate forming a solid, semi-
rigid, load-bearing structure. In the preferred design, a central layer is formed of a suitable
shock-absorbing and sound-deadening soft, viscoelastic, microcellular foam. As distinguished
from the conventional helmet-making practices, no molding step was employed. The selected

energy dissipation characteristic of about tan δ = 0.7 and hardness of about 90 Shore A.
PU exhibited a rebound characteristic lying in the range of about 8% (ASTM D 2632-90), the

Spraying created foam shell about 1.6 to 3.2 mm thick. Thus, while the central layer is formed of
a soft, pliable, microcellular, viscoelastic foam, the inner and outer layers form relatively rigid
container encapsulating the central layer of acceleration-rate-sensitive microcellular foam.

The origin of strain hardening behavior might be deduced from the Sorrentino et al. model. 97
The authors described high strain rate compressive properties of PU foams with three
contributions to the nonlinear mechanical response: foam morphology, time-dependent polymer,
gas entrapped in the cells. The foam morphology contribution was estimated from a uniaxial
compression test at low strain rate. The time/temperature-dependent behavior of polymer was
evaluated by stress relaxation tests. The gas contribution was predicted by using a gas flow
model derived for scaled closed cells at the compression rate > 2 (1/s). As the left Figure above
shows, there are two principal contributions to SH polyurethane foams: the viscoelastic behavior
of the elastomer and gas compression in the foam enclosed cells. As the rate of compression
increased the PU viscoelasticity becomes more important. At low deformation rates the foam
morphology played some role, but at higher rates the gas escape from cell was slower than the
compression and scaled closed cell model worked well. Thus, taking into account the polymer
viscoelasticity and the contribution to the stress of the gas entrapped in the cells, the
compressive mechanical behavior over a wide range of strain rates was correctly described
(see right Figure above: points are experimental, lines computed).

Since the year 2000 Palmer and Green have been developing a new material for protecting
bodies from impact and injury, named d3o (dee-three-oh), produced in the company d3o Lab,
apparently associated with the University of Hertfordshire’s research and development centre,
and a design studio in London. Commercialized in 2005, d3o is a unique material made of
intelligent molecules, which flow when you move but on shock they lock together for body
protection, and then when the impact is over return to their original state. d3o has been
incorporated into sports clothing (outerwear in jackets and pants, base layers, and beanies have
been used by Olympic GS in racing suits for the US and Canadian teams), guards, gloves,

34
Rigid ballistic composites, 31 October 2010

protecting shells for electronic devices (Apple iPhone and iPod Touch), helmets and as building
blocks of molecular armor.

In Russia and China the similar substance called Handgum or Thinking Putty (off starch, PVAl
and water) is used for development of a small motility of fingers and anti-stress devices as well
as children toys. 98 It has been known that gel made of 2-to-1 (by volume) combination of
cornstarch and water might be poured, but when squeezed, the liquid morphs into a doughy
paste that can be formed into shapes, only to “melt” when the stress is relieved. People can run
across a pool of the gel, but sink once they stop.

Palmer and Green patented a family of commercially successful, energy absorbing materials
comprising: i) solid foamed synthetic polymer or elastomer such as PU, EPR or EPDM; ii)
polymer-based dilatant, different from i) incorporated and distributed through the matrix during
manufacture of i), e.g., known for the dilatant behavior poly(boron di-methyl siloxane) (PBDMS),
neat or filled with nano-particles; and iii) a fluid (e.g., foaming gas) distributed through the
matrix. 99 The dilatant content is 15 – 35 vol% of the composite, and the amount of fluid (in the
preferred case gas) 40 – 70 vol%. The composite may include fibrous and/or particular fillers,
plasticizers, lubricants, extenders, pigments, dyes, etc.

Applications include impact protection for objects, animals and humans, e.g., in protective pads
or clothing for humans and animals, in or as energy absorbing zones in vehicles and other
objects with which humans or animals may come into violent contact, and in or as packaging for
delicate objects or machinery. Specific examples of applications are in headwear and helmets;
protective clothing or padding for elbows, knees, hips and shins; general body protection, for
example for use in environments where flying or falling objects are a hazard, vehicle
dashboards, suspension bushes, upholstery and seating.

The following patent application enlarged the STF materials to non-foamed polymer blends. 100
The composites comprise: i) an elastomer and ii) a second dilatant polymer entrapped in a solid
matrix i) prior to foaming. The composite may be foamed or not. Other ingredients may also be
added, e.g. fillers, plasticizers, colorants, lubricants and thinners. The first material i) may be
EVAc or an olefin polymer, PP, LDPE, LLDPE or HDPE. The polymer i) may also comprise an
elastomer, natural or synthetic. Preferred elastomers include elastomeric PU, EVAc, silicone or
EPDM. The second material ii) is any polymer exhibiting dilatancy alone or in combination with
one or more other components, e.g. finely divided particulate material, viscous fluid, plasticizer,
extender, or their mixtures. The preference is for PBDMS or any number of polymers where
PBDMS is a constituent. The dilatancy may be enhanced by the inclusion of other components
such as particulate fillers including microspheres or micro-balloons, fibrous or platy particles or
their mixture. In PBDMS the dilatancy is related to the temporary borated cross-links formed
reversibly during high rates of deformation. In the PBDMS systems this effect inhibits the
siloxane chains from sliding during high rates of strain thus instantaneously inhibiting viscous
flow. In this condition the polymer will therefore behave more like an elastomer.

The preferred method of forming the blend is first to form microspheres of second material ii) to
prevent coalescence coated, e.g., with elastomer. These coated microspheres are then
introduced into the material i) which is either comminuted or molten. Subsequently the blend is
foamed into a closed-cell foam, with at least part of the dilatant ii) within cell walls. The foam
subjected to deformation recovers completely within≤ 5 s. Non -foamed composite is a mixture
of i) and ii), in the barrel of an injection molding machine including means for supplying a
blowing agent; bringing the material to an elevated temperature and an elevated pressure such

35
Rigid ballistic composites, 31.10.2010

that it is in molten form; supplying a blowing agent to the barrel; and reducing the pressure of
the heated composite thereby causing foaming. The weight ratio of ii) to i) is from 2.3 to 1; the
elevated temperature is from 170 to 210oC. Another production method involves incorporating
microspheres (e.g., EXPANCEL by Akzo Nobel) within one or both components of a mixture i)
and ii). The microspheres hermetically encapsulate a gas or vapor in a plastic shell.

The composite of the invention may include a textile, which enhances the abrasion resistance
and that to intrusion of sharp objects and/or assist in the attachment of the composite material
to other systems or products. A textile backing will also serve to limit the elongation of the
material and thereby provide durability. The textile may serve as an antiballistic or stab-proof
fabric in body armor with woven grades of Kevlar®. With potential applications ranging from
protective gear for the military, police, and firefighters to safety seats for cars that protect
against high-force impact to soundproofing, d3o attracts attention of NASA and Boeing. The
company discusses with the U.S. Army development of a protective suit to soften the impact for
troops when they hit the ground to dodge bullets.

The d3o is a non-toxic, dilatant, thermosetting plastic with shelf life > 4 years. It is lightweight,
flexible and malleable, until subjected to abrupt force, making it useful in protective clothing
against blunt trauma. Its other properties are:
Density: 0.5 - 0.65 g/ml
Shear Hardness: 65 - 81
Operating temperature range: -55°C to 120°C
Repeat washing: 40 washes at 40°C
Tensile strength: 1MPa according to the standard BS EN ISO 1798:2000.

Ballistic gelatin (BG) is a solution of 10% gelatin powder in water, which simulates the density
and viscosity of human muscle tissue. It is used as a standardized medium for testing the
terminal performance of firearms and ammunition. BG impact response is used for comparing
terminal ballistics. From the viscoelastic point of view, the gel has strain sensitivity, SH. As
shown below, the maximum of stress-strain curves at strain rates 2000 to 3200 (1/s) range from
2 – 6 MPa, whereas the quasi-static values are about 3-orders of magnitude smaller. 101

BG main drawbacks are: the lack of consistency of its viscoelastic properties caused by
variability during the fabrication, short shelf-life, and deterioration under prolonged usage even
at room temperature (RT). As a replacement for BG, Moy et al. developed physically associating

36
Rigid ballistic composites, 31 October 2010

gels (PAG), from commercial triblock copolymers polystyrene (PS) and polyisoprene (PI); viz.
80% triblock (PS-PI-PS) and 20% diblock (PS-PI). 102 One of the associating gels contains 15
wt% PS (PAG15) and the other gel 30 wt% PS (PAG30). The final gel contains 20 vol% of
polymer, the rest being mineral oil. Unlike the casting of the BG, the PAG solution was poured
into pre-heated aluminum molds allowing the solution to fill the mold to the desired shape. Two
specimen geometries were used with dimensions equal to that for the BG.

PAG may be tailored for the desired properties, has a narrow range of viscoelastic behavior,
storage at RT, and superior environmental stability compared to BG. However, like BG, the PAG
response and failure behavior at high rates are still not completely understood. In addition to
high rate experiments, stress-strain behavior of these materials at an intermediate strain rate
(1/s) was also obtained. In the Figure up right, the stress-strain behavior at the deformation rate
of about 2500 (1/s) are presented for BG, PAG15 and PAG30. The SH effect is well reproduced,
but the error bars especially for PAG30 are uncomfortably large. It is noteworthy that in di- and
three-block copolymers a great diversity of morphology has been predicted AND observed.
These structures depend on composition, but also on the shear and thermal history.

Strong shear thickening effects were reported for aqueous solutions of amphiphilic copolymers
of the type shown below. 103 Again, formation of local dynamic crosslinks is responsible.

Stress-strain hardening of suspensions – introduction

A typical example of dilatant or STF is that of semi-concentrated suspensions – here viscosity


increases as shear stress increases. The plot of shear stress versus shear rate is nonlinear with

by two parameters: the intrinsic viscosity, [η], and the maximum packing volume fraction, φmax,
shear stress increasing faster than the shear rate. The viscosity of suspensions is determined

at which the viscosity goes to infinity. For monodispersed hard spheres [η] = 2.5 and φmax, =
0.62. For polydispersed hard spheres, [η] = 2.5 and φmax, ≤ 0.96.

Krieger and Choi studied the viscosity behavior of sterically stabilized PMMA spheres in silicone

Newtonian plateau was observed for the reduced shear stress value: σ r ≡ σ 12 d 3 / RT > 3 (d is
oil. 104 In high viscosity oils, thixotropy and yield stress was present. In most systems the lower

sphere diameter, R is gas constant, and T is absolute temperature). However, when shear
stress was increased further, dilatant behavior was observed. Dilatancy was found to depend on
d, T, and the suspending oil viscosity. The authors reported small and erratic normal stresses.

37
Rigid ballistic composites, 31.10.2010
105
Utracki derived the following relation for dilatant flows:

( )( ) 1 a0 exp { 1  a1 } ( 2 )
2 a2 m1 − m2

0 1 

where ai are equation parameters whereas τ1 and


τ2 are relaxation times of segment and cluster,
PSEUDOPLASTIC-DILATANT FLOWS
1
respectively. The first square bracket describes 10 o
the dilatancy, the second the pseudoplasticity. The
left Figure illustrates the dependence for different
-1 a = 1.0
values of a0. 10 o
a = 0.1
o

Assuming uniform particle size distribution a = 0.01


o
Ookawara and Ogawa derived a dependence -3 a = 0.001
10 o
predicting a linear increase of viscosity with shear a = 0.0

η = a = 0; a = 0.1; m = 1.0; m = 0.8


o
rate, increasing with the square of volume fraction
of particles. Furthermore, the viscosity linearly -5 1 2 1 2
10 -6 -2 2 6
depends on density and an average particle 10 10 10 10
diameter. 106

Stress-strain hardening of suspensions – Wagner group


In 2003, Lee, Wetzel and Wagner, published an article on the ballistic impact characteristics of
Kevlar® fabrics impregnated with nano-sized silica spherical particles (120 or 450 nm diameter,
dispersed in ethylene glycol). 107 The authors reported that the composite material is flexible, yet
penetration-resistant. Fragment simulation projectile (FSP) (a chisel-pointed metal cylinder of
5.6 mm diameter, 1.1 g weight) ballistic penetration measurements at ca. 244 m/s demonstrated
penetration resistance improvement due to the addition of STF to the fabric, without any loss in
material flexibility. Energy absorption by the STF-fabric was proportional to the volume of STF.
Compared with neat Kevlar® fabrics of equivalent weight, the STF-impregnated fabric provides
nearly the same ballistic protection, yet is much thinner and more flexible. The performance
enhancement provided by the STF is probably due to an increase in the yarn pullout force upon
transition of the STF to its rigid state.

38
Rigid ballistic composites, 31 October 2010

fraction for the suspension φmax > 0.62. The flow curves (see right Figure) for two silica volume
As shown above, the spheres were not monodispersed, thus the maximum packing volume

fractions, φ = 0.57 and 0.62 show irreproducibility of the rheological response of the latter
composition. The irreproducibility stretching for one decade of the shear rate is caused by the
stochastic nature of aggregate formation of the polydispersed spheres. The less concentrated

ballistic event, estimated as: γ 10 4 10 5 ( 1 / s ) .


suspension shows the onset of dilatancy at about 400 (1/s) – well below the rate of shear at the

Egres et al. evaluated for stab-wound protection dry Nylon® or Kevlar® and these with 20 – 28
wt% STF. 3 At constant aerial weight composites were arranged by placing 4 dry layers of
Kevlar® and a layer of STF suspension (silica particles with diameter of 120 or 450 nm) or by
soaking these 4 fabric layers with STF. The depth of penetration in the witness clay was 17.2
and 6.8 mm, respectively. At high velocity test the 8-layer Kevlar/STF dissipated 92% energy
whereas 11 layer of dry Kevlar® (at the same aerial weight) dissipated 60%. Similarly, at low
velocity Kevlar® stab resistance improved by soaking from 42 to 25 mm clay penetration depth.

shown above for φ = 0.62 of silica was obtained for φ = 0.51. The data points of energy
The authors also prepared STF with acicular CaCO3 crystals. 3 Similar flow curve as the one

dissipated vs. areal density followed the same dependence. This opens a possibility of
replacing silica spheres with an organoclay.

The work directed by Wagner at the Dept Chem. Eng., U. Delaware resulted in several patents
listed in APPENDIX 2. The flexible ballistic protection technology may be summarized as
follows:

1. The protective sandwich is composed of high performance fabric and STF.


2. Several fabrics have been mentioned (e.g., nylon, polyolefin, polyester, or polyaramid),
but p-aramid, Kevlar® KM2 or Twaron® are preferred.
3. STF is made off solid particles (oxides, calcium carbonate, synthetic or natural occurring
minerals, polymer particles or their mixture) suspended in liquid, [e.g., ca. 50 – 57 vol%
446 nm of SiO2 particles, Shokubai, KEP-50, Nissan Chemical] dispersed in ethylene
glycol or silicone oil such as phenyl-tri-methicone (1,1,5,5,5-hexamethyl-3-phenyl-3-
[(trimethylsilyl)oxy]trisiloxane). The onset of shear thickening occurs at the rate of shear
between 100 and 1000 (1/s).
4. For depositing STF on a fabric, a co-solvent and surfactant must be added and the
suspension sonicated. The preferred co-solvent was ethanol, but due to flammability it is
being replaced by H2O.
5. The preferred surfactants are those that have a hydrophilic/lyophilic balance, HLB ≈ 15,
such as Pluronic or Triton.
6. The fabric was submerged in the emulsion for 1 min and then drawn through a set of 2
rubber nip-rollers to remove excess fluid. The sheet was then dried at 80oC. The final
weight of the deposited STF was 24%.
7. Originally, the technology was developed for flexible protective clothing, i.e., for
dissipating the kinetic energy of a moving object. The invented system comprised a
fabric and fluid STF, with particles suspended in a solvent (behaving as liquid) during
service.
8. Recently, the technology was expanded to thermoset and thermoplastic rigid systems.
For example, a reactive polymer such as polyurethane, epoxy, crosslinkable PDMS or
elastomers might be mixed with STF at room temperature and then cured.

39
Rigid ballistic composites, 31.10.2010

9. Similarly, thermoplastics such as PO, PA, PMMA, PVC, PEST (e.g., PET), PC, etc.,
could be melt-compounded with STF, and then cooled down to generate the solid
polymer-STF composite. 108
10. Application of the developed protective barrier composites ranges from the use as a
flexible ballistic material for body armor, an airbag, bomb blanket, protective clothing,
tents, seats, cockpits, spall liner, rigid composite for vehicle armor, storage and transport
of luggage, transport of munitions, tank skirt, etc.
11. The material may be used in: a. belts and hosing for industrial and automotive
applications, b. Fiber optic and electromechanical cables, c. Friction linings (clutch plates
and brake pads), d. Gaskets for high temperature and pressure applications, e.
Adhesives and sealants, f. Flame-resistant clothing, g. composites, h. asbestos
replacement, i. hot air filtration fabrics, j. mechanical rubber goods reinforcement, k.
ropes and cables l. inside helmets m. fencing clothing n. motorcycle protective clothing
o. boots, p. gaiters, q. chaps, r. pants s, gloves, t. sail cloth, etc. 109

The experience is summarized in a recent review. 110 The left Figure above shows the effect of
latex concentration and shear stress on the flow behavior. Addition of particles to water

particle concentration approaches the maximum packing volume fraction, φmax, the fluid shows
increases the viscosity and eventually leads to onset of non-Newtonian behavior. When the

an apparent yield stress. Once the yield cluster is broken, the viscosity drops – a shear thinning
behavior. At higher stresses, shear dilatancy or thickening occurs – once the critical shear
stress is reached viscosity rises abruptly (sometimes discontinuously). Experiments and
simulations of the atomic and small-molecule liquids predict only shear thinning, at least until the
eventual onset of turbulence at flow rates that vastly exceed those of interest. However,
concentrated suspensions of non-aggregating solid particles in the appropriate range of shear
rate will always show (reversible) shear thickening. The mechanism of the shear thickening
depends on: particle volume fraction, size (distribution), shape, as well as those of the
suspending phase (viscosity deformation stress in shear or extension, steady or transient, time
and rate of deformation). 111, 112

In the right Figure above, changes of a suspension microstructure is schematically illustrated. In


concentrated dispersions strong hydrodynamic coupling between particles leads to the
formation of hydroclusters (marked orange) — transient concentration fluctuations that are
driven and sustained by the applied stress field. At equilibrium, random collisions among
particles make them naturally resistant to flow. But as the shear stress or shear rate increases,

40
Rigid ballistic composites, 31 October 2010

particles become organized in the flow, which lowers their viscosity – the shear thinning flow. At
yet higher shear rates, hydrodynamic interactions between particles dominate over stochastic
ones, a change that spawns hydroclusters— transient fluctuations in particle concentration
engendered by dissipative hydrodynamic interactions. The flow results in anisotropy in the
nearest-neighbor distributions that gives rise to clustering of particles and concomitant large
stress fluctuations that leads to high dissipation rates and thus a high viscosity. The difficulty of
particles flowing around each other in a strong flow leads to a higher rate of energy dissipation
and an abrupt increase in viscosity – the shear thickening flow. Evidently, the structures are
dynamic, erased by return to equilibrium.

Coating the particles with polymers or grafting them with “brushes” may prevent formation of
hydroclusters. Fluid slip, adsorbed ions, surfactants, polymers, and surface roughness all
influence the onset of shear thickening. Simple models based on the hydrocluster mechanism
have proven valuable in predicting the onset of shear thickening and its dependence on those
stabilizing forces. 113 When the repulsive force approaches 10% of the particle radius, the shear
thickening is effectively eliminated and the suspension flows with low viscosity. Manipulating
those nanoscale forces, the particles’ composition and shape, and properties of the suspending
fluid so as to control the sheer thickening, however, remains a challenge for the suspension
formulator.

At high particle densities, dispersions may undergo discontinuous shear thickening. Here,
increasing power to a rheometer might lead a dramatic increase of viscosity and large
fluctuations in stress, since the suspension refuses to flow any faster or solidifies. Samples that
exhibit strong shear thickening are particularly interesting as candidates for soft body armor.
Another active research topic concerns jamming transitions under flow. Concentrated
suspensions could be jammed at low and high shear stresses but flow in between. Evidence
also exists that dispersions may exhibit a second regime of shear thinning at the highest
stresses rather than continuing to resist the increasing shear rate. The effect may be related to
particle elasticity – at high stresses, particles elastically deform altering the rheology. The same
forces that drive the hydrocluster formation, may also lead to irreversible aggregation. That is,
particles forced into contact remain in contact even as the flow weakens. Such shear-sensitive
dispersions irreversibly thicken and thus are undesirable. Conversely, in dispersions composed
of particle aggregates or fillers such as fumed silica or carbon black, the extreme forces may
lead to particle breakage and thixotropy.

While most STF are based on glass spheres in PEG, there have been attempts to widen the
compositions to other solids and suspending liquids. One of the more interesting observations in
this domain is the publication by Rosen et al. on the use of 500 nm diameter kaolin clay

such a suspension at φ = 0.43 shear thicken at a shear stress of 12 Pa. Upon intercalating the
particles (kaolin is non-exfoliating clay) in glycerol. 114 Rheological measurements showed that

STF into Kevlar®, the composite shows a marked increase in spike and needle resistance, as
well as a reduction in yarn pullout. Quasi-static stab tests on four layers of Kevlar® impregnated
with the kaolin STF showed that the sample can prevent penetration of a standard spike at
loads up to 160 N while the neat fabric layers are penetrated at 35 N. Finally, the V50 velocity of
single-layer STF-treated Kevlar® fabric, using 0.22 caliber spherical steel projectiles, was found
to be about 50% higher than that of neat Kevlar® fabric, thus similar to the standard STF-Kevlar®
composite.

STF with kaolin (K-STF) offers additional protective benefits comparing to STF with spherical
particles (S-STF). For example, the K-STF exhibits continuous shear thickening whereas the S-

41
Rigid ballistic composites, 31.10.2010

STF exhibits a discontinuous one. In a K-STF treated Kevlar® fabric, the K-STF is dispersed
evenly, uniformly coating the tows. Over a range of quasi-static stab experiments, the K-STF
fabrics perform comparably to S-STF fabrics, and both perform better than untreated fabric. For
small diameter hypodermic needles (12-gauge), the flat particle K-STF slightly outperformed the
spherical (diameter: d = 450 nm) silica particle S-STF. This increase in performance may be due
to the shape or aspect ratio of the particle. As the Table 13 shows, under ballistic testing, the K-
STF fabrics performed better than neat fabric, but poorer than S-STF fabrics. Because K-STF
performs comparably to the S-STF in defeating stab and puncture threats, the clay-based STF-
fabrics may be a viable alternative to silica-based STF-fabrics. The raw materials for K-STF are
readily available, which could potentially make them more economic.

Table 13. Performance of neat Kevlar® 706 and saturated with K-STF or S-STF
Properties Kevlar 706 Kevlar 706 Kevlar 706 +
+ nil + K-STF S-STF
Layer areal density (g/m2) 180 210 216
load at 20 mm, Spike (N) 35 160 180
load at 20 mm, Knife (N) 80 120 120
Energy absorbed:18 gauge HN (J) 8 76 62
Energy absorbed:22 gauge HN (J) 11 39 36
V50 (m/s) 100 150 250

Stress-strain hardening of suspensions – others

The publications from the Wagner group provide the most comprehensive information on STF,
but are not unique. Composites usually consist of fiber or fabric reinforced plastics. Their
enhanced performance comes from the high strength fibers. The STF used in flexible protective
clothing include: dilatant polymer, gels, foams and suspensions of nano-sized solid particles.100,
109
Thus, as discussed before, Kevlar® impregnated with STF have been used for production of
flexible body armor. However, one of the disadvantages is the low viscosity of the suspending
fluid in the STF, which may leach out of the protective system.

Picken et al. patented a damage-resistant composite characterized by deformation or shear rate


depending stiffness, comprising: a reversible supra-molecular polymer, fiber reinforcement, and
nanoparticles with the aspect ratio p ≥ 10. 115 The patent is for damage tolerant, self healing
composites, able to resist multiple damages. The main application is for protective, hard shell
clothing of shin, elbow, wrist and knee pads as well as body armor.

The material has the following composition:

1. 35 to 55 wt% of the reversible supra-molecular polymer,


2. 25 to 60 wt% of reinforcing fibers,
3. 2 to 10 wt% of nanoparticles,
4. 0.2 to 7.5 wt% of surfactant (intercalant),
5. Conventional additives.

Re 1. The supra-molecular polymer is a material with properties that depend on the presence of
reversible supra-molecular interactions, such as, e.g.: (i) metal-hydroxide modified siloxane, viz.

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Rigid ballistic composites, 31 October 2010

boric-acid modified PDMS (BPDMS), 116 (ii) reversible metal ligand-based supra-molecular
polymers, 117 and (iii) reversible hydrogen bond based supra-molecular polymers. 118 Reversible
supra-molecular polymers may be linear or branched, polymers or oligomers, but with functional
end groups that form a reversible supra-molecular physical network. In combination with the
other components this leads to specific properties of the composite. Preferred reversible supra-
molecular polymers are based BPDMS. The boric-acid modification is usually performed by
heating boric acid and the siloxane at 150 to 250°C. The polymeric material has a dynamic
equilibrium reversible bonding of the end groups which leads to the formation of a dynamic
physical network, which results in highly elastic behavior especially at high deformation rates.

Re 2. The reinforcing fibers may be natural or synthetic, viz. glass, aramid, carbon, high-
molecular weight polyethylene, and others. They may be in any suitable form, such as loose
fibers, non-woven, woven, knitted, laminates, etc.

about 1 – 10 nm and the largest 0.1 – 1 µm, having high aspect ratio, e.g., p = 100 – 2500. This
Re 3. The nanoparticles are clays, nanotubes or nano-fibers with smallest size is in the range of

aspect ratio allows for a much lower loading of fillers, while obtaining the same or better
properties. The preferred nanoparticles are plate-like smectite clays such as montmorillonite
(MMT), beidellite, hectorite and saponite. The particles are usually not fully exfoliated and most
materials display a combination of dispersion states. Clay platelets are used because they are
more efficient than micro sized fillers, although they need intercalation and exfoliation.

Re 4 and 5. Additionally the composite may contain surfactants, other fillers, rubbery materials
and the like. Their amounts depend on the application of specific materials and may each be up
to about 5 wt% of the total composite. Surfactants can be used to improve adhesion, whereas
fillers and rubbers are added for modifying the mechanical properties.

Three samples were prepared using a glass fabric, pre-intercalated MMT (p ≈ 150) and
BPDMS. The composition (in wt%) is given in Table 14. The samples were prepared by first
blending the MMT and the BPDMS until a homogeneous. Subsequently the blend was pressed
into the glass fabric at a temperature of about 100°C and a pressure of about 50 kN. As shown
in the Table 14, sample 1 failed above impact energies of about 3 J whereas samples 2 and 3
could withstand multiple impacts of up to about 8 J, albeit with some fiber damage. Some weeks
after the tests, to a large extent the damage from the impact test had disappeared.

Table 14. Composition impact performance of BPDMS/GF composite with clay

Material MMT (wt%) GF (wt%) BPDMS (wt%) Impact energy (J)


Sample #1 0 57 43 3
Sample #2 2.15 57 40.85 8
Sample #3 4.30 57 38.70 8

A patent from École Polytechnique Federal, Lausanne (EPFL) describes composites having
tailored stiffness and damping performance with a STF at the interface between two elements
moving relatively to each other. The composite structure may be used in diverse applications
such as sports equipment, aeronautics, aerospace, consumer goods or in any other suitable
field where the dynamic properties of a structure need to be tailored. 119 STF is a concentrated,
stabilized dispersion of rigid sub-micron particles in a carrier fluid. It may be tailored such that its
storage and loss shear (or tension/compression) varies as a function of the amount of shear. By

43
Rigid ballistic composites, 31.10.2010

tailoring the STF composition and the geometry of the element containing it, the amount of
deformation required to activate the STF may be tailored. The thickness of the interfaces or
containment layers may be kept constant by using continuous or
discontinuous fibers, spheres, or any form of suitable spacer. The

φ = 0.518) of monodispersed, SiO2 spheres (500 nm diameter) in


STF described in an Example, was composed of 67.75 wt% (i.e.,

polyethylene glycol (PEG) with an average molar mass of 200


g/mol. The viscosity vs. deformation is shown in the left Figure.
Tests of compliance vs. frequency, or dynamic mechanical analysis
(DMA) may be used for determining the structure's dynamic
behavior in tension, compression or torsion.

Evolution of (a) storage modulus G’ and (b) loss modulus G” for the 15 wt% fumed silica

frequency at various level of strain amplitude, γo = 50 – 1000%.


suspension, as well as (c) G’ and (d) G” for the 67.75 wt% monodispersed silica suspension vs.

In a recent publication Fischer et al. also used hydrophilic fumed silica (Aerosil 200, from
Degussa Corp.), with 12 nm diameter of the primary (spherical) particles and a specific surface
area of approximately 200 m2/g. The primary particles formed large, unbreakable aggregates.
The carrier fluid was polypropylene glycol (PPG = H[OCH(CH3)CH2]17OH) with molar mass of

44
Rigid ballistic composites, 31 October 2010

ca. 1000 g/mol. The carrier fluid was added to the powder in a blender and mixed for 5 min. The
bubbles were eliminated by placing the resulting suspensions in a vacuum chamber for several

φ = 0.075). 120 As the Figures above illustrate, there is a significant difference in the rheological
hours. The suspensions used for this study had a solids concentration of 15 wt% (i.e.,

response to steady-state shearing; while the monodispersed spheres show a sharp change of
slope at the critical shear rate, the polydispersed ones show more controllable dependence. The
difference in the solid content is also noteworthy – one needs about 8 vol% of small particles for

evident in the shear moduli, G’ and G”. From the Delaware-Rutgers rule: * ( o ) = (  ) one
obtaining similar response as that for 52 vol% of the large ones. Similar difference is also

=
121
may correlate the rheological variables at the onset of SH: c c / c
.

Galindo-Rosales et al. studied the shear-thickening behavior of ca. 10 wt% (i.e., 5 vol%)
hydrophobic Aerosil R816 nanoparticles suspensions in polypropylene glycols (PPG) with
molecular weights of 400 and 2000. 122 The fumed silica had a primary particle diameter of 12
nm and it was rendered hydrophobic by replacing hydroxyl groups (in Si-OH) by alkyl -C16H33.
The article reports on the rheology of the dispersions, the effect of concentration, and the
method of preparation. The dynamic rheometry indicates that Aerosil® R816 particles formed
non-flocculated suspensions in PPG. Steady flow curve shows shear-thickening behavior
between two shear-thinning regions, with the maximum viscosity at the shear rate 77 and 56
(1/s) for PPG 400 and 2000, respectively. The transient rheological response has been
analyzed using a protocol proposed in 1986 by Cheng. It has been found that, within the
reversible shear thickening region, all the constant structure curves overlap, suggesting that the
response at a certain shear rate does not depend significantly on the previous state. However,
the larger the molecular weight, for the same amount of solid phase, the bigger is the effective
volume fraction which implies lower values of critical shear rates and higher viscosities. Thus,
this procedure may be used for distinguishing flocculated and non-flocculated suspensions.

As discussed above, the modern flexible armor is made mainly from STF-Kevlar® composites,
where STF is a suspension of ca. 55 wt% silica in PEG. In the case of STF with monodispersed
silica particles, on steady-state shearing, STF shows instantaneous spike in viscosity above a
critical shear rate (depended on SiO2 sphere diameter and concentration). Fabrication of STF-
Kevlar® composites requires STF preparation, dilution, and then impregnation with Kevlar.

Mahfuz et al. used silica particles dispersed in a mixture of PEG and ethanol by sonication (55
wt% SiO2 in PEG). 123 Two types were studied: 30 nm crystalline silica and 7 nm amorphous
one. Kevlar® fabric was impregnated with the suspension producing flexible armor. For
improved bonding between silica and PEG, the particles were treated with, amino-propyl-tri-
methoxy silane, Gelest-SIA0591.0 (see left schematic below), what significantly improved
performance of the composites, e.g., the limiting energy for zero-layer penetration jumped from
12 to 25 (Jcm2/g). The source of this improvement has been traced to the formation of siloxane
Si-O-Si bonds between silica and PEG and superior coating of Kevlar® filaments with particles.

FT-IR, SEM, and x-ray photo-emission spectroscopy were used for analyzing chemical bonds,
composition, and degree of dispersion responsible for the improvement. The experiments have
demonstrated that functionalization of silica followed by direct dispersion into PEG/ethanol
resulted in superior composites having high spike resistance. Durability of the armor composites
was tested using a rippling and shaking method. It was observed that after 72 folding and 72
shakes, the loss in areal density was 5%, with the same single layer of penetration as before.
As documented by the penetration depth in the right Figure below, the best performance was

45
Rigid ballistic composites, 31.10.2010

obtained for the functionalized (silated) 30 nm SiO2 particles – no penetration for impact energy
below 25 (Jcm2/g) and then only a single layer penetration up to the limit of the test tower (70
Jcm2/g).

(a) Silane coupling agent and functional groups, NIJ penetration depth tests of Kevlar®
(b) formation of Si-O-Si bonds on substrate composites
surface

Table 15. Comparative properties of Kevlar® KM2 and Heracron

Property Values for Kevlar® KM2 Values for Heracron®


Linear density (denier) 600 1500
Breaking tenacity (cN/tex) 247.1 203.1
Breaking strength (N) 165 340
Elongation at break (%) 3.80 3.30
Modulus (cN/tex) 5560 6357
Yarn count(yarn/inch) 28x28 17x17

Lee et al. investigated the effect of the particle size of silica in STF-impregnated woven fabrics
on their ballistic performance. 124 Rigid, spherical silica particles with average diameters of 110,
280 and 540 nm and surface area ca. 50, 30 and 15 m2/g, respectively, were dispersed in PEG
(mol. wt. = 200) at concentration of 65 wt% solid content. At constant silica concentration the

square of the particle diameter: γc ∝ 1 / d 2 . A similar dependence was also found for the
critical rate of shear for the onset of stress hardening was found to be inversely proportional to

concentration dependence – higher the silica content lower the critical deformation rate in shear
or elongation. 125 Two types of polyaramid fabrics were impregnated with STF: Kevlar® KM2 and
Heracron® (condensation product of p-phenylene di-amine and terephthaloyl chloride), the latter
produced by the Korean company, Kolon Inc. 126 The material very much resembles Kevlar®, but
as Table 15 shows, the fibers are heavier and stiffer.

46
Rigid ballistic composites, 31 October 2010

0.002
As illustrated in the left Figure, the Heracron® fabric
impregnated with STF having the smallest silica
Clay deformation per weight

effect Heracron
effect Kevlar
spheres (d = 110 nm) formed the smallest
0.0015
deformation in the witness clay, thus it showed the
highest energy dissipation. [It is worth recalling that
120 and 450 nm spheres gave the same results,
0.001
and then from between 7 and 30 nm spheres the
larger one gave better results, thus the optimum
size may be between 30 and 110 nm.]
0.0005

The results of the drop impact and yarn pull-out


tests indicated that fabric impregnated with STF
0
none 100 nm 300 nm 500 nm
having the smallest particles exhibits the largest
SiO size increase of inter-yarn friction at the onset of shear
2
thickening. The impregnation affects the interfacial
friction of filaments and yarns, which contributes to a larger transfer of the impact energy to
interaction of individual yarns in the fabric, resulting in significantly higher energy dissipation
with less transverse deformation. The influence of impregnation with STF on the ballistic
performance was found to be closely associated with the way the tested specimen is affixed –
the “boundary conditions”. The particle size and the boundary conditions are the dominant
factors that can be manipulated to fully utilize the benefits of impregnated fabrics for flexible
body armor. As the Figure shows, Heracron® performed significantly better than Kevlar®.

The shear thickening fluids are primarily densely


packed colloids or suspensions. Thus, Brown and
Jaeger reported on the rheometry of spherical particle

jamming behavior of 100 µm diameter glass spheres in


suspensions in Newtonian media near the critical

oil and cornstarch in water. 127, 128 The slope of the


shear thickening part of the viscosity curve is found to
increase dramatically with packing fraction and diverge
at a critical packing fraction c. This behavior is
reversible after removal of stress. The authors focused
on the stress-shear rate discontinuity and the
relationship to the yield stress. The latter phenomenon
limits STF efficiency at particle concentrations
approaching the critical for the onset of shear
thickening. As shown in the left Figure, the above the
critical deformation rate the stress jumps dramatically to another plateau at higher rates.

The rheological behavior of highly concentrated


suspensions is complicated by the yield stress. Its
origin rests in particle-particle interactions
engendered by chemical, electric, magnetic or other
forces. In the right Figure the open triangles show
the viscosity vs. shear stress dependence for
hydrophobic spheres in water – the upper
micrograph show particle string formation
responsible for the yield stress. The lower
dependence is for the same system, but after a

47
Rigid ballistic composites, 31.10.2010

surfactant was added – now there is no yield stress only the STF behavior. As seen in the lower
micrograph there are no strings of interacting spheres, able to form the hydroclusters.

The left Figure maps the general behavior of a


suspension caused by variation of shear stress and
volume fraction of suspended spheres. The shear
thickening occurs over an intermediate stress range
of stress, which varies little with volume fraction
when the yield stress is well below this range. For
stresses either larger than the upper limit of the
shear thickening region or smaller than the shear
thickening onset, shear thinning behavior is
observed. The behavior is similar to that found in
shear thickening colloids. The jammed region here

diagram, exceeding the yield stress leads to shear thinning flow. The critical volume fraction, φc,
is defined as the portion in the diagram below the yield stress. As in the usual jamming phase

is sharply defined, nearly the same in silicone oil or water, or when the particle size is doubled,

geometric packing. For glass spheres, an average value of φc = 0.573 ± 0.013 is consistent with
indicating that the value is not determined by fluid properties or particle diameter but by

0.57 for mechanically stable packing, or to random loose packing of 0.56 (random close packing
value is 0.64). If a mechanically stable packing exists, it must have a yield normal stress holding
itself up against gravity on the order of about 10 Pa.

According to Hassan et al. STF may also be observed in suspensions of hard metal oxide
particles in molten polymers. 129 The authors prepared STF by ultrasonication of 40 wt% of SiO2
particles (diameter d = 15 to 30 nm) dispersed in polyethylene glycol (molecular weight = 200
D). The as-prepared STF have been tested for their rheological and thermal properties, and

STF viscosity changed from η ≈ 5 Pas at γ ≈ 2 to 410 Pas at γ ≈ 12 (1/s) before a catastrophic
then used to impregnating Kevlar® and Nylon® fabrics, 29 and 25 wt% loading, respectively. The

drop. Continuous increase in sample’s viscosity at low and narrow shear rates range confirmed
that the sonochemical mixing improved the shear thickening effect. Indeed, TEM micrographs
showed fibers well coated with spherical silica particles.

Knife and quasi-static penetration tests were performed on the neat fabrics and STF/fabric
composite targets (areal density ca. 0.27 g/cm2) for both knife and engineered spike. The neat
Kevlar® target supported a small load of 85 N before allowing the spike to penetrate through the
target, while the STF/Kevlar® composite target supported a load of 573 N and was not
punctured. For the knife threat, STF/Nylon® composite target showed loading of 406 N to be
compared with 284 N obtained for neat Nylon target. The quasi-static loading results show a
major improvement in resistance of STF/fabric composite as compared to neat fabric for both
the spike and knife threats. STF/fabric composites targets exhibit better stab resistance as
compared to neat fabric targets. Evidently, STF with silica nanoparticles have enhanced the
fabric performance for body armor applications. In short, at low impact energy STF impregnated
fabrics have better penetration resistance then neat fabrics without affecting the fabric flexibility.

Torki et al. studied the mechanical


properties of Kevlar® impregnated with 34.2
wt% of PVB, or PVB with SiO2 or TiO2. 130
The average diameter of silica and titania
particles was 7 and 25 nm, respectively,

48
Rigid ballistic composites, 31 October 2010

and the amount introduced into PVB matrix ranged up to 7 wt%. Composites containing SiO2 or
TiO2 had higher mechanical properties than the one with neat PVB. When TiO2 particles were
added to PVB, the highest increase of storage modulus by about 54% was obtained at 5 wt%
loading, while for SiO2 it was of about 99% at 7 wt% loading. Similarly, impregnation of Kevlar®
with PVB + 5 wt% silica or titania increased the storage modulus by 98 and 65%, respectively.
As an example, the dynamic compressive moduli, E’, at 30oC and the glass transition
temperature, Tg, for the four compositions are shown in Table 16.

Table 16. Dynamic modulus and the glass transition temperature


for Kevlar® 129 composites
Sample E’ (MPa) Tg (oC)
PVB 51.22 31.73
PVB/Kevlar® 151.5 31.80
PVB/Kevlar®/TiO2 249.8 31.06
PVB/Kevlar®/SiO2 299.8 32.74

To close this part dedicated to STF it is appropriate to mention two theoretical studies. The first
by Krekelberg et al. applied a model of short-range attractive (SRA) colloidal fluid, in which the
interactions are limited to a few percentages of a particle diameter. 131 The model describes a
suspension of colloidal particles attracted to one another by the presence of non-adsorbing
polymers. The colloidal particles are spherical and their effective interactions consist of three

fraction and a long-range soft repulsion. The model has a fixed colloid volume fraction φc = 0.4,
parts: a repulsive core, a potential accounting for attractions proportional to the polymer volume

variable polymer concentration, φp = 0.0 – 0.4, and shear rate γ = 0.001 – 0.5. The free volume
of a single particle vf is a ‘‘cage’’ of connected space that the particle center could geometrically
access by translation if every other particles in the system were held fixed in its position. Thus,
the inter-particle repulsions prevent their centers approaching closer than the effective hard-
sphere particle diameter. The average free volume per particle was computed as a function of

concentration φp, i.e., increasing the strength of short-range attractions at constant φc, enlarges
shear rate and polymer concentrations. At low shear rates, vf increases with polymer

the local space available to particles. Thus, the short-range attractions lead to particle
clustering, which increases the populations of small and large free volumes. However, the
particles with larger vf control the average response.

In the context of STF the most interesting is the interrelation between shear rate and
suspension viscosity as well as the free volume. Computations lead to dependencies shown in
the two Figures below:

49
Rigid ballistic composites, 31.10.2010

It is apparent that increasing the attraction between colloidal particles (increasing φp, at constant
particle concentration, φc = 0.4) initially reduces suspension viscosity, and then increases it due
to aggregate formation that cause the yield stress. By contrast, the increase of ฀p

rate, γ . For low interparticle attractions, φp < 0.2, shearing has no effect on vf over the explored
systematically increases the free volume and the increase slightly depends on the deformation

range of shear rates. For more attractive particle systems, shear leads to small increases of vf.
Furthermore, the change in free volume is unable to explain the shear thinning and thickening
discussed above.

The objective of the last paper discussed in this


section was the development of an artificial
neural network model for analyzing the ballistic
performance of a system made from single layer
Kevlar® 29 fabrics, using the material properties
as inputs. 132 The results from fragment
simulation projectile ballistic penetration at 244
m/s were used for demonstrating the modeling
aspects of artificial neural networks (ANN). The
demonstrated in this paper ANN is based on the
propagation algorithm from MATLAB 7.1. In the
present research, comparisons were made
between the measured values of samples
selected for building the neural network model
and network predicted results. The developed
predictive model provides excellent correlations
with experimental data. The optimized networks can be used for design, development of ballistic
protection fabrics without going for further destructive tests. The results show that the ANN can
be successfully used in modeling material properties of ballistic fabrics with similarity and better
accuracy compared to traditional fiber science study methods.

The schematic representation of the ANN developed for Kevlar® is shown above. There are
eight input and two output variables – all need to be used “training” the model with minimum,
maximum, mean values and their standard deviation.

50
Rigid ballistic composites, 31 October 2010

Specific modulus (CN/Tex) — Elastic modulus per mass density of a material, or the
stiffness to weight ratio (specific stiffness).
Specific tenacity (CN/Tex) — Force required to break the fabric during tensile
testing. Specific tenacity is the force divided by the linear density of the material at
break.
Density (g/mL) — Fiber density = ratio of mass to volume of the fiber measured using
density gradient column.
Warp yarn (denier) — Warp, in fabrics refers to yarns running lengthwise.
Weft yarn (denier) — Weft, in fabrics refers to yarns running widthwise between
warp yarns.
Impact or striking velocity (m/s) —Velocity of a projectile or missile at the instant of
impact.
Penetration depth (cm) — A measure of how deep the projectile or missile can
penetrate into a material.
Dissipated energy (J) — Energy that is dissipated through the protective cloth layers
due to the impact of the projectile or missile.

The ANN performance may be judged by the linear correlation between the predicted (y) and
measured (x) relative or scaled values and the correlation coefficient squared:

Penetration depth (cm): y = 0.0002 + 0.9995x; r2 = 0.9995


Dissipated energy (J): y = 0.0002 + 0.9995x; r2 = 0.9996

NANOTECHNOLOGY

The polymer nanocomposites (PNC) are 30 years old. 50 The two principal components of PNC
are the polymeric matrix and nano-sized particles. Virtually all polymers (thermoplastic,
thermoset and elastomer) have been modified by addition of nano-particles. Of the latter the
most frequently used are clays and more recently nanotubes. The key for the PNC performance
is the random distribution of individual nano-particles throughout the matrix – possible ONLY at
low concentration; for most commercial clays it ranges from 1.1 to 3.6 wt% inorganic content.

Ostermayer et al. tested PA-6 based PNC for the ballistic impact protection using commercially
available materials, Ube 1015B (PA-6 matrix) and 1015C2 PA-6 with ca. 2 wt% MMT. The
velocity at which 50% of 0.22~cal. fragment simulator projectiles penetrated the unmodified
PA-6 and 0.5 mm aluminum witness plate was V50 = 436 while that of PNC was 338 ft/s. Thus,
incorporation of organoclay reduced the impact resistance of PA-6. 133 This unexpected effect
(tensile modulus of 1015C2 G = 4.1 while that of 1015B Go = 2.7 GPa) is most likely caused by
C12 paraffinic chain attaching PA-6 macromolecules to MMT. On high velocity impact the
paraffin may act as a lubricating plasticizer.

Reports from different branches of science suggest that reduction of particle size leads to
enhanced, not reduced STF. For example, the recent article reported that nano-crystalline
metals show >10-fold increase of strain-rate sensitivity in comparison to the conventional
coarse-grained counterparts. 134 The effect may originate in the increased specific surface area,
As, thus stronger interactions between nano-particles (for MMT As = 750 – 800 m2/g).

As in 2004 Savage wrote, there are few examples of PNC used in defense applications – these
materials development rely on commercial forces with little support from the defense

51
Rigid ballistic composites, 31.10.2010

establishments. 135 The author collected numerous examples of the possible applications of
nanotechnology in defense, viz. carbon fibers and nanotubes in electrically conductive and
energy storage applications, solid lubricants, chemical sensors, nano-foams in shock absorbers,
microwave absorbers, UV resistant coatings, fire retardants, etc. The review compressed the
use of nanoparticles for ballistic protection to ½ of a page. An interesting suggestion was the
use of electro-spun fibers as a replacement of the traditional high performance fibers/fabrics
such as Kevlar®. The only practical use of nano-particles (?) in ballistic protection mentioned in
the report was the STF system developed in Wagner’s laboratories.

Nanotechnology has a promising future in the area of protective clothing, due to their
extraordinary physical, chemical, mechanical, and electrical properties. Thilagavathi et al.
summarized the applications of nanotechnology in producing lightweight and comfortable
protective clothing for the military personnel as well as in sensor, energy storage, conductivity,
and decontaminant fabrics. 136 The review focuses on fibers and fabrics with emphasis on
micro- and nano-fibers. The protective clothing made up of these fibers and their composites
give high performance, functionality, comfort, and larger life span with less weight, size,
maintenance and cost. Nanostructures and nanocomposites are being developed for the
following defense applications:

Lightweight protective clothing with STF, as described by the Wagner group


Flexible antiballistic textiles
Chemical and biological warfare protection fabrics
Adaptive suits from switchable fabrics for improved thermal control and camouflage.
Micro-sensors for body and brain sensing, environmental and situational awareness,
integrated into a smart suit or a smart helmet
Wearable and/or flexible displays for visual feedback auxiliary supports: flexible/rigid
textiles for additional strength, exoskeletons, and robotics to assist the human tasks.

Recently, Gordeyev and Crawley summarized the EU situation as far as the Personal Protective
Equipment (PPE) for first responders (military, police, firefighters, and bio-chem responders) are
concerned. 137 The estimated EU market is about €9.5-10 billions. Protective textiles have been
identified as one of six lead markets for Europe with technological and market developments
offering the opportunity to renew the traditional industry. The protective materials market is
driven by developing standards to improve the effectiveness of PPE in response to emerging
security threats and challenges.

The technological assessment of nano-enabled technologies in the PPE sector has been
divided into four sub-sectors: (1) detoxification and decontamination; (2) protection from
impact such as knives, ballistic projectiles, and firearms; (3) fire resistance/retardancy; and (4)
integration of information and communication technologies (ICT) devices. In these materials the
nano-enabled functionality may offer superior qualities over existing technologies. Examples
include:

Prototype protective vests made using carbon nanotube yarns and inorganic fullerenes
with superior ballistic protection yet at a fraction of the thickness (and therefore weight) of
current materials;
Quantum Tunneling Composites offering “smart” functionalities such as a flexible control
interface allowing the user to illuminate sections of clothing for high visibility purposes;
Magnesium oxide nanoparticles loaded into nano-fibers providing effective detoxification
and decontamination coupled with ability to be incorporated into cloths;

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Rigid ballistic composites, 31 October 2010

Use of nanoparticles in shear thickening and electro-rheological fluids providing


advanced ‘liquid’ amours changing their rigidity when required.

Despite considerable progress in nanomaterials and nanotechnologies for security applications,


the majority of experts involved in preparation of the report concurred that significant effort is still
required for these results to become technically and commercially viable.

Protection from impact requires light weight gear allowing for extreme mobility, a high degree
of protection, increased breathability and user comfort. Current technologies such as aramids
(Kevlar®), PBO (Zylon®) and UHMWPE (Dyneema®, Spectra®) fibers and ceramics despite their
high theoretical strength do not provide sufficient impact resistance, which depends mainly on
distribution of defects in bulk materials. For example, Zylon® vests were used in the US in the
late 1990’s but experienced continued failures, ultimately resulting in the death of a police
officer. At present UHMWPE seems to take over a major part of the market currently covered by
the aramid fibers. The experimental M5 fiber seems promising as well. Nevertheless, there is a
market opportunity for new technologies to enhance performance of the existing solutions.

Since 2004, the inorganic fullerenes, IF, (boron carbide and silicon carbide fullerenes are five
times stronger than steel) became the promising shock absorbing materials. ApNano,
commercialized the inorganic fullerene material technology and supposedly they are developing
body armor under the name ‘NanoArmor’. 138 Tungsten and molybdenum di-sulfite, WS2 and
MoS2 nanotubes are ultra-strong impact resistant materials for the production of bullet proof
vests, helmets, car bumpers, high strength glues and binders. These unique nanotubes are up
to 4-5 times stronger than steel and about 6 times stronger than Kevlar®. The nanotubes have
high aspect ratio (length L ≈ 150,000 and diameter D ≈ 30-180 nm mean that p ≈ 833 – 5000),
which gives them their unique tensile strength (21 GPa) and chemical properties. Zhu from the
University of Nottingham subjected a sample of the ApNano material to shocks generated by a
steel projectile traveling at velocities of up to 1.5 km/s. The material withstood the shock
pressures generated by impacts of up to 250 tons/cm2. The material proved to be so strong that
after the impact the samples remained essentially identical compared to the original. A study by
Martin from École Central de Lyon tested the new material under isostatic pressure and found it
to be stable up to at least 350 tons/cm2. 139

At an early stage of development, researchers in Australia examine the theoretical potential of


carbon nanotubes (CNT) in anti-ballistic applications. 140 They concluded that ballistic resistance
capacity is greater when a bullet hits the centre of a single nanotube and that those with a larger
radius can withstand a higher bullet speed. They theorize that body armor made from six layers
of 100 m carbon nanotube yarns (ca. 600 m thick), may bounce off a bullet with muzzle
energy of 320 J. Extending this theory they suggested that CNT body armor could have a
constant ballistic resistance even when bullets strike at the same spot; the studied CNTs
withstood a bullet at almost the same speed as the first impact after a short time interval.

Yarns of multi-walled carbon nanotubes (MWNT) with promising mechanical properties have
been produced on an experimental scale for making bullet proof vests as strong as existing
products, in addition offering 48% reversible damping and much higher thermal, creep and
chemical resistance. Despite considerable concerns regarding practical implementation of CNT
and IF ballistic and dynamic properties they appear to be the most promising materials for the
10 years distant future. The introduction of improved conventional ballistic fibers and/or ceramic
whiskers could lead to an important breakthrough in the field of ballistic protection on a shorter
timescale. So-called ‘liquid’ armor with STF may provide such functionality for low end of

53
Rigid ballistic composites, 31.10.2010

ballistic velocities required for applications such as protective helmets, boots/footwear, gloves
and face protection (such as goggles, masks, and shields). 141 Electro-rheological fluids which
change their rigidity in response to an electric charge have also been suggested for protection
applications.

The European review on the role of nanoparticles in protective equipment ends with the outlook
for the near future. 137 Research needs for assessing the bullet impact on CNT under different
loading conditions has been identified for applications such as bullet proof vests and explosion
blankets. Research areas in protective clothing for impact protection should include: inorganic
fullerenes, shear thickening fluids, electrorheological fluids, and carbon nanotubes for ballistics.

EVOLUTION OF HELMET TECHNOLOGY

As shown in Table 17, the helmet technology has changed little since the replacement of steel
by aramids in the 1970s, in the Personal Armor System for Ground Troops (PASGT). 142 These
U.S. Army helmets used woven aramids with a thermoset (toughened phenolic) resin, while
current research explores the use of thermoplastics. Although thermoplastic/aramid systems
have been evaluated for specialty applications, they have often failed to meet all stringent
criteria. The combination of mass efficient ballistic and independent structural materials provides
means of meeting the spectrum of helmet specifications. In addition, several helmet prototypes
explore alternate designs for selectively stiffening the core ballistic shell. Preliminary data
demonstrate the improved mass efficiency of the hybrid ballistic material solutions.

The improved PASGT offered the protection level (50% ballistic limit now 610 m/s), area of
coverage (0.14 m2) and better fit (1st to 99th percentile of the U.S. military population).
However, it had low resin content (ca. 20 wt%), multi-ply fabric architecture and high porosity.
With its standard wall thickness of 9 mm (KM2 fibers reduced it to 7.6 mm), it barely meets the
practical requirements. Beginning in the early 1990s, the aim was reduction of the weight by at
least 25%. Materials such as Spectra® Shield or Kevlar® Mark III used alternate resin systems,
fabrics or laminates. Both were successfully molded into PASGT geometry and found to meet
the ballistic and weight goals, but failed the durability requirements.

Table 17. Historical perspective of U.S. Army helmet design and materials

The new advanced combat helmet (ACH) and the modular integrated communications helmet
(MICH) use high strength Kevlar® K129, reduced phenolic resin content (thus higher fiber

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Rigid ballistic composites, 31 October 2010

content for the same weight), shell thickness of 7.8 mm, modified edge cut for protecting lower
surface, and a new suspension system for better comfort and trauma reduction. Another is the
lightweight Marine Corps helmet, based on Twaron® and a phenolic resin.

The Army Research Laboratory, ARL, has proposed an incremental


approach that will first establish thermoplastic-based matrices as viable
candidates for fabricating helmet shells. The advantage of this approach is
the ability to reap the near-term benefits of commercially available
thermoplastic matrix aramids, such as Tepex® PA (ballistic laminate of
Kevlar® fabric and PA-66 used in automatic helmet forming process for
Norwegian Army) and Kevlar® Mark III (coated fabric pre-laminated material)
as well the ability to “spiral in” new fibers such as M5®. The Future Force
Warrior (FFW) is a major element of the Army transformation. The new
“headgear” architecture, together with the integrated electronic sensors and
other devices, will demand a balance between the enhanced functionality
and the overall weight of the helmet. The FFW ensemble is divided into two
parts: “neck up” which includes all the systems and functions associated
with the headgear, and “neck down,” which encompasses the uniform and
other equipment attached to the soldier’s body and extremities. An early
prototype of this type of integrated system, known as Scorpion, is shown in
the right Figure. Weight reductions will be achieved by miniaturizing the
electronics, power, packaging of these sub-systems and use better
materials.

The “headgear” has an effective 13 mm air gap between the inner shell wall and the soldier’s
head, which accommodates most deflections during projectile arrest. Fabrics, although
ballistically resilient at aeral densities around 0.975 g/cm2, tend to deform significantly. The
fragment or bullet could conceivably be arrested by the fabric, but the resulting deformation
could still result in a fatal injury. The thermoset composites such as PVB-phenolic-aramid
reduce the transient deformation. “Ear-to-ear” loads of 2 to 3.5 MPa must be withstood by the
helmet for several cycles. During the development of an effective thermoplastic-based aramid
ballistic recipe, it was determined that transient deflections are the limiting factor. To preserve
the ballistic benefits of aramid with thermoplastic matrix and minimize the potential for skull
trauma, it will be necessary to combine them with other materials that exhibit greater stiffness
against static and dynamic loading.

Thermoplastic matrix aramid systems have excellent, mass-efficient ballistic properties.


However, the thermoplastic matrix is typically 30% to 60% less rigid than even toughened
thermoset (e.g., phenolic) matrix. This has significant implications for the overall static structural
stability and resilience of the thermoplastic aramid shell, as well as the dynamic deflections
associated with a ballistic event. The design goal was to obtain an areal density of 1.75 psf for
these panels. Therefore, a ply orientation scheme was determined from which a preliminary
weight for the skins could be calculated. From there, the number of plies of Kevlar-thermoplastic
was determined to obtain the desired areal density. Hard thermoset or graphite/epoxy skin on
polyolefin-KM2 shell has also been used to obtain the desired rigidity. For assuring the desired
areal density the application of rigid skin, demanded that some KM2 layers be removed. The
graphite-epoxy and the KM2-polyolefin gave excellent results.

A year later ARL announced a new step toward development of the new “headgear”. 143 Two
types of materials have demonstrated the potential for significant weight savings. The first

55
Rigid ballistic composites, 31.10.2010

involved a high performance laminate of cross plied unidirectional layers of high strength fibers
with a compliant resin matrix. The commercial
Spectrashield® or Dyneema® composites use the
UHMWPE fibers with thermoplastic elastomer matrices.
The second class of ballistic laminate materials involved
woven fiber reinforcements with compliant thermoplastic
matrices (see right photograph).

Aramid fibers such as Kevlar® or Twaron® allow for a


direct comparison of the influence of the matrix materials
on key parameters such as ballistic mass efficiency,
structural and dynamic deformation, and processing
conditions. Continued application of heat and pressure improves adhesion of the thermoplastic
to the woven Kevlar® fabric. It is critical that a rigid structural skin (IM7 graphite/epoxy skin) well
adheres to the more compliant ballistic composite, which by itself (even at room temperature)
would not pass the cyclic compression test.

Initially, helmets have been monolithic, made from steel and later from aramid/phenolic
composite. However, as emphasis on producing lighter helmets increases, the more ballistically
efficient fibers and thermoplastic resin systems are inherently “softer” than the old thermoset
systems, and less material is used. Several thermoplastic-based candidates have been
identified for FFW. The lighter, more compliant thermoplastic matrices require additional
modification to address the durability and trauma concerns. The mass-efficient ballistic
properties of the Kevlar/polyolefin composites might be successfully employed by hybridizing
the shell with a carbon-based structural composite “skin” and a “stiffener” – see the photographs
below.

The stiffener: (1) provides selective stiffening, minimizing parasitic weight; (2) eliminates need to
drill holes into helmet for attaching suspension and liner; (3) minimizes part count and enables
cost-effective helmet production.

COMPARISON of present vs. future

Four years ago in an unclassified review presentation from the ARL, Walsh et al. summarized
the results of the new headgear development using combinations of the matrix (PE, PA, TP-
elastomer and epoxy), fiber (aramid, carbon, glass and UHMWPE) and architecture (woven
fabric, cross plies and stitch bond). 143 The work resulted in designing the headgear as a hybrid.
In Table 18 the performance of new FFW headgear is compared with that of PASGT.

56
Rigid ballistic composites, 31 October 2010

Table 18. Comparison of the structure and performance of two US Army headgears.

Property FFW PASGT


Fabric 600 Denier Kevlar® KM2 19 Ply S735 Kevlar
Matrix polyolefin PVB phenolic
Skin graphite overwrap None
Areal density (psf) 1.75 2.3
17 grain V50 (fps) ~2261 ~2100

The authors summarized their most significant results in the graph shown below. Evidently, the
best ballistic material (of all discussed!) is KM2/18 wt% TP (polyethylene) – it has the highest
ballistic resistance at the lowest flex modulus. FFW has a rigid skin and inner stiffener, the latter
playing several roles, viz. improving the headgear stiffness and fatigue resistance, provides the
space between the energy-absorbing composite and facilitating fitting the helmet to different
head size.

In the late 2009 officials from Product Manager Soldier Protective Equipment announced
ordering 200,000 Enhanced Combat Helmets (ECH) that depend on UHMWPE. 144 After two
years of development at a cost of $10.6m, testing of prototypes from four companies (i.e., Mine
Safety Appliances Co. of Pittsburgh, Pa.; BAE Systems Aerospace & Defense Group Inc. of
Rockville, Md.; Genex Corp. of Zeeland, Mich.; and Ceradyne Inc. of Costa Mesa, Calif.) was
scheduled to begin in 2009, and start fielding by mid-2010. “The first time in nearly three
decades, soldiers and Marines will not wear helmets made of ballistic fibers such as DuPont’s
Kevlar. The new plastic, used commercially in everything from artificial hip replacements to
police body armor, offers more protection from fragmentation in explosions and the ability to
stop some small arms”.

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Rigid ballistic composites, 31.10.2010

It’s unclear what kind of rifle round the new helmets will stop. For nearly two years, though,
finding a new helmet that can stop a 7.62mm round — the caliber of ammunition used in the
AK47 assault rifle favored by combatants in Afghanistan, Iraq and elsewhere — has been a top
priority. It is expected that the new helmet offers at least 35 percent more protection against
fragmentation, handgun and small-arms fire. Army officials would not discuss specific
ammunition the new ECH will stop, but confirmed it will stop penetration by at least some rifle
rounds. “We would like to achieve 7.62mm, but the protection level will be finalized during
testing”.

Army officials acknowledged that wearing a helmet capable of


preventing penetration by rifle rounds could save lives, but would
also mean increased risk of head and neck trauma because of the
force of a bullet hitting the headgear. The ECH will look very much
like the present ACH headgear, but it will be “a little bit thicker”. In
2009 GENTEX Corp. received a $1.8 million contract for the
production of developmental test units for ECH. 145 The ECH will
maintain the current weight while providing a 35% increase in
ballistic protection against fragmentation. Alternatively, the new
helmet will match the ballistic fragmentation resistance of ACH
helmets with ca. 20% lower weight. The prototype must successfully
pass a battery of ballistic, non-ballistic and user tests. The ECH
design incorporates advanced processing and material technologies
including DSM Dyneema® latest unidirectional (UD) composite. The new materials and
processing technologies will not only increase ballistic protection, but will facilitate future
advances in head protective systems. The ECH consists of a ballistic protective shell, pad
suspension system, and 4-point chinstrap/napestrap retention system. The ECH is compatible
with other components of infantry combat equipment such as Body Armor Systems, protective
spectacles/goggles and/or prescription glasses, night vision equipment and a camouflage fabric
helmet cover. 146

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Rigid ballistic composites, 31 October 2010

In January 2010 it was announced that test versions of the Marine Corps’ new plastic helmet
have failed to protect against bullets, blunt force, or both. 147 Equipment officials would say only
that all five of the test helmet models, made by four companies, failed in either ballistic or non
ballistic testing. The non ballistic tests examined the impact of blunt force trauma to the helmets
from blast waves, rolled-over vehicles and fragmentation. The test failures have set the program
back, postponing the Corps’ plans to field the new helmet this year. Creating a lightweight
helmet that will stop a rifle round is difficult. Last May, the U.S. Army recalled 44,000 ACH, after
the Program Executive Office raised concerns about their ballistic protection. 148 The case is
being investigated by the Department of Justice. According to an All Army Activities message
released May 14, 2010. “There is evidence that ArmorSource and Rabintex ACHs were
produced using unauthorized manufacturing practices, defective materials and improper quality
procedures which could potentially reduce ballistic and fragmentation protection.” The recall
constitutes about 4 percent of ACHs currently in the Army’s inventory. The Army adopted the
ACH design in 2002, replacing PASGT helmet. ArmorSource was one of four companies
selected to produce the ACH, and, by March 2009 the company has delivered over 70,000 ACH
helmets. Gentex Corporation, another manufacturer of the ACH faced a similar recall of 34,218
helmets last year. The other two manufacturers are BAE Systems and MSA.

Australia, after studying four different helmet designs, accepted one from an Israeli firm and
introduced it as the Enhanced Combat Helmet (ECH). 149 The helmet is a modified version of
RBH 303 used by the Israeli armed forces. The main modifications are improved ballistics
protection, changes to the padding system, the elimination of the front brim, a reduction in ear
coverage to enable troops to use “Active Noise Reduction” equipment and addition of “extra
large” size that weights 1.2 kg, but apparently many Australian have big heads.

DuPont Armor Technology Center focuses on next-generation protection for U.S. Military.
Center will test DuPont™ Kevlar® Mark IV and other advanced ballistics materials to develop
hybrid personal protection and armoring solutions. 150 Mark IV is being evaluated for the ECH
program. Kevlar® Mark IV is a thermoplastic resin matrix material that provides more protection
per weight than existing aramid-phenolic composites. It may improve performance, reduce
helmet thickness and cost of the current ECH and potentially other emerging military helmet
designs, including the Next Generation Helmet (solicitation issued on September 21, 2009).

Similarly, DSM launched Dyneema® HB80, cross plied


unidirectional fabrics (UD) composite that meet the joint US
Army and Marine challenge to increase the fragmentation
protection by at least 35 percent of advanced combat helmets.
35
Dyneema® – the highest ballistic performance UD material is
being manufactured at the company’s North Carolina plant, for
ECH. As the pre-launch material, Dyneema® X31, the product
has undergone extensive testing by several helmet manufacturers. In testing, helmets made
with Dyneema® HB80 have demonstrated at least 35 % reduction of fragmentation effects,
comparing to the helmets currently used by the US armed forces.

Ten years ago Fink published “Performance metrics for composite integral armor” where he
discusses the need to reduce weight of armored vehicles from about 70 tons to 15 tons. Such a
dramatic change requires the use of composite integral armor (CIA) made of several layers of
different materials. 151 However, the publication focuses on the myriad design requirements
which serve multi-functional roles including: ballistic, structural, and others. His list of
performance criteria and critical aspects are quoted below. Even if the theme of concern is the

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Rigid ballistic composites, 31.10.2010

armored vehicle, a similar set of criteria will be pertinent when developing other armor items,
such as helmet.

Ballistic Performance

Single-Hit V50
Multi-Hit V50 Sympathetic Damage
Dynamic Deflection
Triple-Point
Ballistic Damage Resistance
Post-Ballistic Damage Tolerance
Ballistic Shock
Spall/Secondary Projectiles

Structural Performance

Static Performance Variables (Strength, Stiffness)


Low-Velocity Impact Damage Resistance
Low-Cycle and Pulse-Vibration Fatigue
Damage Tolerance
Critical Defect Size/Location

Other Competing Metrics

Areal Density
Reparability
Manufacturability
Manufacturing/Assembly Costs
Fire/Smoke/Toxicity
Thermal & Electromagnetic Shielding/Signature
Internal Space Claim
Joint Design/Fit Tolerances

SUMMARY AND CONCLUSIONS

This review is based on the public, accessible, non-classified information. Judging by the easily
detectable urgency in some of the reports coming from ARL, other military establishments and
from suppliers, there is extensive confidential information as well. Keeping this in mind let us
see what one may learn from research publications, patents and general web information.

The ballistic personal protection has been divided into three types: (1) Flexible body armor, (2)
Armored vehicles, and (3) Headgear, previously known as helmet. Nowadays, all of them involve
multilayered structures comprising polymer composites. The technologies are summarized in
Table 19, below.

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Rigid ballistic composites, 31 October 2010

Table 19. Comparison for ballistic protection in three types of armor.

Components Flexible body armor Armored vehicles Headgear


Construction Flexible, multilayered 5-layer structure: Helmet made of skin,
®
Kevlar fabric (ca. 76 polymer matrix ballistic composite,
wt%) coated with 24 composites (PMC) stiffener, mouth-
wt% of suspensions of Outer Face-sheet, guard, and strap-
SiO2 spheres in PEG or Alumina Armor Tiles, harness
phenyl-tri-methicone EPDM, Structural
Composite with 50 vol%
of fibers strongly
bonded to matrix,
Phenolic Inner Liner and
4 layers of adhesive
® ®
High performance Kevlar , Twaron , Ceramic and/or metal Unidirectional fabrics:
®
components Dyneema , Innegra™, tiles, fibers with special Kevlar® Mark IV or
etc. sizing that delaminates Dyneema®HB80 with
under impact, 20% polyethylene
matrix
Shear sensitive fluid Shear thickening, STF Shear softening, SSF It shows SSF behavior
Rigid outer skin none Thin PMC protecting CF & epoxy
tiles

Best performing materials

Fibers and fabrics

Polyaramid category has been dominated by Kevlar®’s (USA), Twaron®’s (Japan), and more
recently Heracron® (So. Korea). The technology continuously evolves, thus DuPont renews its
Kevlar® grades. For ballistic applications KM2 remains the workhorse, with Kevlar® LT and
Kevlar® Mark IV being recent additions. The latter grade has been specifically developed for the
new headgear. It is noteworthy that in body armor application thicker Heracron® fibers
outperformed Kevlar® KM2 at constant areal densities. The Heracron® fibers are stiffer than
KM2, what for the headgear application should not make much difference.

Polyolefin category is represented by the gel-spun UHMWPE fibers, Dyneema® from DSM and
Spectra® from Honeywell. Innegra™ S fibers (introduced by INNegRITY™ in 2007) are
inexpensive, highly oriented polypropylene fibers used for police & military vests & helmets. Of
the three types, the clear winner in the performance category is Dyneema® HB80 with 35%
better performance than Kevlar®, in the economy is Innegra™ in combination with Kevlar® or
Dyneema®.

Other fibers, such as PBO, M5, polyarenazoles, etc. still suffer the pains des nouveau-née.

Non-woven textiles (e.g., 1:1 Kevlar® + Spectra®) have been reported 30% ballistically more
efficient than fabrics. This may be due to their ease to pull out, similar (but to smaller degree) as
the one observed for the new unidirectional UD-fabrics. To the non-woven, stitched or needled
textile or felt belong materials produced by carding, air laying, randomizer roll, cross-lapping, lot

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Rigid ballistic composites, 31.10.2010

merge and/or slurrying. Usually, these are bonded together by needle-punching entanglement
of fibers, but may be resin-encapsulated, adhesively or thermally bonded, and/or laminated. To
this category belong ArmorFeltTM (50% p-aramid, 50% UHMWPE), Kevlar®, Twaron®,
Dyneema® Fraglight, Spectra®, Zylon®, etc., as well as their blends. The non-woven fabrics are
known as ballistic-resistant materials for garments (vests, helmets, body armor and the like) and
equipment (shielding, coverings, shrouds, etc.). 40

Polymeric matrix

Polymers are divided into: (1) commodity, (2) engineering and (3) specialty categories, with cost
and performance going in the same order. In combination with fibers or fabrics, polymers from
each category have been used for ballistic protection.

Re (1). There are recent reports about use of polyethylene with Kevlar® (immiscible system). On
impact the fibers are liberated to deform absorbing more energy.

Re (2). In this category only polyamides (PA) and their blends were looked at. PA-11, PA-12
and PA-63T may be worth scrutiny. The drawback of PA is their hygroscopicity. Water acts as a
plasticizer softening the polymer, increasing chain mobility what may lead to recrystallization
and hydrolysis that reduces PA molecular weight. As a result, the property of the composite will
vary with season and with time. Evidently, smaller is the number of hygroscopic amide groups,
less hygroscopic is the polymer. Of blends, PA/PO type may be of value as these systems have
low moisture absorbance and will not solidly bond to aramid fibers.

Re (3). Because of the cost and low production volume PEEK and PPS and their various blends
are interesting. They are high temperature polymers with excellent mechanical properties. In
addition, on impact PEEK was reported to show strain thickening behavior.

Interphase

Interphase is crucial for the performance of composites. Three methods have been used for its
modification: compatibilization, sizing and physical modification. Changes to the interphase may
engender either strain thickening (STF) or softening (SSF) fiber behavior. The GF sizing is the
best described, but little has been published about sizing of aramid or olefin fibers

Stress or strain sensitivity

For the rheologists, these sensitivities belong to the non-linear viscoelastic category. In
particular, the STF is known as dilatant and SSF as pseudoplastic fluid. The behavior is often
complicated by the presence of the yield stress in several of its forms (tensile, apparent,

particles), is broken when stress exceeds a critical value (yield stress, σy), then the system
dynamic, etc.). Yield, which originates in a 3D aggregate of interacting bodies (drops, gels, solid

becomes pseudoplastic and at certain critical level of strain (γSH) the strain hardening (dilatancy
or STF) behavior may be seen. The following systems are known as STF:

1. Suspensions of solid particles near their maximum packing volume fraction: φSH < φM. Since
the latter quantity depends on the shape and polydispersity, so does the former. For the
ballistic application in flexible body armor, silica spheres, glass fibers, and clays have been
used. The most advanced and advantageous is the use of nearly-monodispersed glassy or

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Rigid ballistic composites, 31 October 2010

ceramic spheres. From various studies it seems that the highest ballistic efficiency might be
expected for the average sphere diameter 30 < d (nm) < 100. For the reason of expected
multiple impact, fragility of fibers and exfoliated platelets need to be examined. Kaolin,
which is non-exfoliable crystal, worked quite well.

2. Gels and foams containing crosslinked macromolecules may also show the STF behavior.
However, because of low modulus ballistic gels are used to simulate human body reaction
to projectile. On the other hand, HYDROTHANE PU foam with STF behavior has been
used in helmet construction.

3. Some polymers are also known to show the STF behavior, e.g., poly-ether-ether-ketone,
PEEK (Tg = 143 and Tm = 343°C). However, the “obvious” combination of PEEK with solid
particles may not work as the stress field around solids affects the stress field and in
elongational flow is known to result in stress softening. On the other hand, since these
experiments were carried out with low concentration of solids, the effect near ฀M may be
totally different. Evidently, PEEK may only be used with high temperature fibers, not PE or
PP. Excellent properties were obtained using PEEK with≤ 2 wt% tungsten disulfide (WS 2)
fullerene and other nano-particles.

Pseudoplasticity or the strain softening (SSF) behavior is the regular molten polymer behavior.
In ballistic applications to armored vehicles SSF has been generated by reducing the chemical
interactions between fiber and matrix. However, since the composite also must have structural
properties, the fiber sizing resulted in formation of small knobs or bumps on the surface.

Helmet or headgear

When in 1970 steel helmet was replaced by the one made of rigid Kevlar/PVB/phenolic
composite, the change was a simple substitution. Nowadays the change is to provide better
protection at lower mass by means of at least partially thermoplastic materials. The Future
Force Warrior (FFW) headgear has multiple functionalities: protection, communication center,
mounting platform for plethora of devices, etc.

Reading the accessible information one gets a feeling that the military technology is undergoing
a fundamental change. For example, the dramatic reduction of weight of ground fighting
vehicles (from > 70 to < 20 ton) precipitated research into multi-material composites that serve
structural function, but on impact acts as an anti-ballistic protective structure. Similarly, in the
past helmet was constructed from rigid thermosets, which for some patented designed on
impact showed the STF behavior, i.e., became stiffer. However, for the newest (still
experimental) FFW headgears the philosophy is reversed; the ballistic protection is offered by
the incompatible Kevlar® (KM2 or Mark IV) in polyolefin matrix, which under impact let the fibers
to stretch absorbing more energy. The “structural” function is given to the “skin” and stiffening
frame made of graphite-or-carbon fiber-or-carbon nanotubes in epoxy. The most recent
information is that replacement of Kevlar® by the unidirectional Dyneema® HB80 UHMWPE/PE
composite at the same areal density offers better ballistic protection by 35%, or inversely –
keeping the same ballistic protection permits reduction of weight by 20%. The finalized
headgear design should go to production and distribution in 2011.

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Rigid ballistic composites, 31.10.2010

Final comments

This review, limited to documents in public domain, reveals great concern about the protective
equipment, high economic impact and technical complexity. There is a waste array of available
materials and their number is continuously growing. Military research organization influence
R&D activities in large industrial organization that leads to new advancement in technology,
e.g., witness by Dyneema® HB80 or Kevlar® Mark IV.

There are two noteworthy issues:

1. PBO fibers have been virtually abandoned owing to irreproducibility of performance – the
irreproducibility was related to polymer hygroscopicity and small spinning defects,
which resulted in a failure to protect the body. These errors are prone to occur more
frequently in material approaching the ultimate performance, in materials where
randomness has been eliminated (e.g., compare STF silica/PEG systems with
polydispersed and monodispersed diameter spheres). The use of the unidirectional fabrics
that can be assembled into oriented layers helps preventing the random failure.

2. Another material aspect that may be important is the temperature rise during the ballistic
impact. Only one article could be found discussing this point and the reported effect was
staggering temperature increase to 1800 K. It seems odd that US Army is in great favor
with Dyneema® PE fiber that melts at ca. 135oC. Is the temperature rise a myth or reality?
Thermodynamically, for high speed event the absorbed impact energy (more-or-less
adiabatically in poorly conducting polymers) is converted to heat within the deformed
(absorbing) mass of material. Thus the larger part of the protecting structure deforms during
the event, the smaller is the temperature increase, but clearly the temperature increase
exists and for PE fiber the margin for melting is quite small. High temperature specialty
resins or even PP should do better than PE.

The progress has been assisted by the growing use of mathematical modeling, which in some
cases (e.g., after “calibration” that fits the available data to a model) offers precise predictions of
in-field experience. Some of the programs mentioned in this review seem efficient and simple to
use.

GOOD LUCK

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Rigid ballistic composites, 31 October 2010

APPENDIX 1

Typical properties for Polyamides (Nylons). www.ides.com/generics/Nylon/Nylon_typical_properties.htm


Polyamide Density Flow Flexural Tensile Tensile Rockwell Notched DTUL @ DTUL @ CLTE, Flow
(g/cm³) Rate Modulus Strength Elongati Hardness Izod 66 psi 264 psi (cm/cm/°C )
(g/10 (MPa) (MPa) on (%) Impact (0.45 (1.8 MPa)
min) (J/m) MPa) (°C ) (°C )
HPPA 1.42 to 1.72 -- 9600 to 150 to 265 2.2 to 2.8 -- -- 254 220 to 245 0.000010 to
19100 0.000019
Nylon 1010 1.03 to 1.76 -- 500 to 1740 34.0 to 230 2.0 to 110 109 14 75.0 to 120 50.0 to 190 0.000010 to
0.000013
Nylon 11 1.02 to 1.09 -- 152 to 1570 29.9 to 70.7 2.0 to 56 77 to 109 16.0 to 114 143 to 180 39.2 to 177 0.000084 to
0.00011
Nylon 12 0.978 to 1.23 -- 110 to 2310 24.8 to 58.9 0.60 to 68 79 to 115 16.0 to 163 78.7 to 175 40.0 to 168 7.5E-6 to 0.00023
Nylon 12 1.00 to 1.03 7.0 to 20 80.0 to 8.00 to 48.6 25 to 400 -- 170 51.0 to 116 45.0 to 45.1 0.00018 to
Elast. 1720 0.00024
Nylon 46 1.17 to 1.79 -- 350 to 30.0 to 214 0.56 to 53 90 to 100 40.0 to 100 289 to 291 155 to 291 0.000017 to
11600 0.000085
Nylon 6 0.00167 to 4.0 to 20 2.00 to 36.7 to 106 0.40 to 50 110 to 123 34.3 to 145 to 224 47.7 to 211 3.0E-6 to 0.00019
28.3 8630 92.9
Nylon 6 Alloy 1.03 to 1.14 -- 2650 to 74.6 to 84.8 10 to 84 -- 37.4 to 60.0 to 210 50.0 to 190 0.000019 to
3030 78.2 0.00017
Nylon 6 Elast. 1.01 to 1.46 6.0 to 7.0 110 to 1400 14.8 to 117 45 to 250 74 to 120 42.7 to 39.0 to 230 35.0 to 48.7 0.000086 to
1070 0.00016
Nylon 6/3T 1.12 -- -- 89.8 to 90.0 7.4 to 51 -- -- 139 to 141 119 to 120 0.000050 to
0.000051
Nylon 6/6T 1.16 to 1.54 -- 2900 to 99.6 to 280 1.8 to 3.3 -- -- 120 to 280 100 to 290 0.000015 to
7300 0.000026
Nylon 6+ABS 1.06 to 1.08 6.0 to 8.0 1570 to 33.0 to 53.5 3.0 to 100 105 9.70 to 747 88.0 to 200 50.0 to 152 0.000079 to
2310 0.00010
Nylon 610 1.06 to 1.15 -- 1820 to 47.1 to 61.8 2.4 to 100 112 to 116 37.4 to 150 to 181 50.0 to 68.1 0.000078 to
2340 52.6 0.00020
Nylon 612 1.02 to 1.35 -- 300 to 8490 26.0 to 173 2.0 to 62 113 to 118 29.0 to 132 to 220 50.7 to 203 0.000014 to

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Rigid ballistic composites, 31.10.2010

89.0 0.00017
Nylon 66 1.07 to 1.37 -- 2.40 to 42.2 to 91.2 0.70 to 110 to 122 4.50 to 179 to 260 58.5 to 257 1.5E-6 to 0.086
50000 700 13300
Nylon 66 1.13 to 1.14 10 2000 to 50.0 to 88.6 19 to 180 -- 37.4 to 130 to 245 65.0 to 225 0.000017 to
Alloy 3110 69.0 0.000065
Nylon 66/6 1.10 to 1.41 -- 1760 to 50.5 to 91.0 1.5 to 50 112 to 120 27.0 to 162 to 238 59.6 to 257 0.000012 to
8460 70.9 0.000096
Nylon 1.38 to 1.72 -- 9300 to 210 to 260 2.5 to 3.0 -- -- 245 224 to 255 0.000015
66+Nylon 20000
6I/6T
Nylon 66 1.28 to 1.85 -- -- 145 to 300 1.5 to 3.0 -- -- -- 230 to 250 0.000010 to
+Nylon 6I/X 0.000020
Nylon 9T 1.14 -- 3000 90 15 118 20 -- 135 --
Nylon 1.10 to 1.46 -- 2110 to 68.0 to 180 2.5 to 22 -- 53.0 to 219 203 to 215 174 to 200 0.000020 to
Copolymer 10400 0.000040
Nylon, 0.998 to 1.34 0.52 to 787 to 9660 40.2 to 116 1.5 to 61 110 to 121 7.00 to 102 95.5 to 248 51.3 to 222 0.000061 to
Unspecified 6.5 0.00014
Nylon + PP 0.957 to 1.05 1.1 to 7.5 869 to 2200 22.0 to 51.0 5.0 to 88 -- 107 to 801 60.0 to 195 54.5 to 55.8 0.00004
Nylon + PPE 1.08 to 1.27 4.0 to 40 1910 to 43.8 to 68.6 7.0 to 100 110 to 115 40.0 to 214 134 to 190 115 to 145 0.000079 to
2380 0.000091
Nylon + TPE 1.07 to 1.13 3 438 to 469 51.7 to 58.1 300 to -- 85.4 to 859 -- -- --
500
PARA 1.35 to 1.77 -- 8230 to 109 to 280 0.60 to 120 to 121 65.0 to 170 234 to 238 215 to 231 9.5E-6 to
24100 2.7 0.000051
PPA 1.10 to 1.80 20 to 310 1310 to 50.6 to 263 1.0 to 5.7 108 to 125 14.7 to 146 276 to 320 105 to 294 0.000013 to
14200 0.000023

66
Rigid ballistic composites, 31 October 2010

APPENDIX 2.

Prof. Norman J. Wagner et al. patents on shear thickening fluids, STF

1. Wagner; Norman J., Wetzel; Eric D., Advanced body armor utilizing shear
thickening fluids, International Application filed May 18, 2004 PCT/US 2004/015813
2. Wagner; Norman J., Wetzel; Eric D., Conformable ballistic resistant and protective
composite materials composed of shear thickening fluids reinforced by short fibers,
US Pat. Appl., 20050004413, Feb. 9th, 2005
3. Wagner; Norman J., Wetzel; Eric D., Advanced body armor utilizing shear
thickening fluids, US Pat. Appl., 20050266748, December 1, 2005.
4. Green, John Henry; SommerG2
5. Marc Martin; Spahr, Douglas Eric; Wagner, Norman Joseph, Designed particle
agglomeration, US Pat. Appl., 20050106310, May 19, 2005
6. Wagner; Norman; Kirkwood; John E.; Egres; Ronald G. JR, Shear thickening fluid
containment in polymer composites, US Pat. Appl., 20060234572, October 19,
2006.
7. Wagner; Norman J., Wetzel; Eric D., Advanced body armor utilizing shear
thickening fluids, US Pat., 7,226,878 B2 June 5th, 2007.
8. Wagner; Norman J.; Nam; Caroline H., Process for coating a shear thickening fluid
onto a material, WO/2007/146703, 21.12, 2007.
9. Wagner; Norman J.; Nam; Caroline H., Emulsification of concentrated dispersions of
colloidal and nanoparticles, US Pat. Appl., 20070282053, December 6, 2007
10. Wagner; Norman J., Wetzel; Eric D., Conformable ballistic resistant and protective
composite materials composed of shear thickening fluids reinforced by short fibers,
US Pat. Appl., 20090004413, January 1, 2009
11. Wagner; Norman J., Wetzel; Eric D., Advanced body armor utilizing shear
thickening fluids, US Pat., 7,498,276 B2 Mar. 3th, 2009.
12. Wagner; Norman J.; Nam; Caroline H., Emulsification of concentrated dispersions of
colloidal and nanoparticles, US Pat. Appl., 2010/0093240 A1, April 15, 2010

67
Rigid ballistic composites, 31.10.2010

REFERENCES

1
http://www.newworldencyclopedia.org/entry/Ballistic_vest
2
http://www.worldlingo.com/ma/enwiki/en/Ballistic_vest#Overview
3
R. G. Egres Jr., M. J. Decker, C. J. Halbach, Y. S. Lee, J. E. Kirkwood, K. M. Kirkwood, N. J.
Wagner, E. D. Wetzel, Stab resistance of shear thickening fluid (STF)–Kevlar composites for
body armor applications, ADM001736, Proceedings for the Army Science Conference (24th)
Held on 29 November – 2 December 2005 in Orlando, Florida.
4
http://www.tacticalwarfightergear.com/tacticalgear/catalog/Army_Technology.php
5
G. Faur-Csukat, A study on the ballistic performance of composites, Macromol. Symp., 239,
217–226 (2006).
6
M. Colakoglu, O. Soykasap, T. Özek, Experimental and numerical investigations on the ballistic
performance of polymer matrix composites used in armor design, Appl. Compos. Mater., 14,
47–58 (2007).
7
B. A. Cheeseman, R. Jensen, Ch. Hoppel, Protecting the future force: Advanced materials and
analysis enable robust composite armor, AMPITAC Quarterly, 8 (4), 37 – 43 (2010).
8
http://www2.dupont.com/Directories/en
;US/Products_Services_Index/Performance_Fibers_Fabrics/Fibers.html.
9
History of Kevlar from the official DuPont site. (URL: www.heritage.dupont.com) Kevlar The
Wonder Material The Lawrence Berkeley National Laboratory is operated by the University
of California for the United States Department of Energy. (URL:
www.lbl.gov/MicroWorlds/Kevlar/).
10
J. Kalantar, L. T. Drzal, The bonding mechanism of aramid fibres to epoxy matrices; Part 1 A
review of the literature, J. Mater. Sci., 25, 4186-4193 (1990).
11
G. Li, C. Zhang, Y. Wang, P. Li, Y. Yu, X. Jia, H. Liu, X. Yang, Z. Xue, S. Ryu, Interface
correlation and toughness matching of phosphoric acid functionalized Kevlar fiber and epoxy
matrix for filament winding composites, Composites Sci. Technol., 68, 3208–3214 (2008).
12
S. M. Walsh, B. R. Scott, D. M. Spagnuolo, The development of a hybrid thermoplastic
ballistic material with application to helmets, ARL-TR-3700, December 2005.
13
S. L. Goodwin, N. J. Abbott, Kevlar Properties Investigation High Speed Abrasion Resistance,
Afwal-Tr-80-3004, February 1978 - January 1980 Final Report 1980.
14
J. F. Graham, C. McCague, O. L. Warren, P. R. Norton, Spatially resolved nano-mechanical
properties of Kevlar-49 fibers, Polymer 41 4761–4764 (2000).
15
T. J. Mulkern, M. N. Raftenberg, Kevlar KM2 yarn and fabric strength under quasi-static
tension, ARL-TR-2865, October 2002.
16
http://www2.dupont.com/Kevlar/en_US/uses_apps/helmets.html
17
J. W. Downing, Jr., J. A. Newell, Characterization of Structural Changes in Thermally
Enhanced Kevlar-29 Fiber, J. Appl. Polym. Sci., 91, 417–424 (2004).

68
Rigid ballistic composites, 31 October 2010

18
M. Cheng, W. Chen, T. Weerasooriya, Experimental investigation of the transverse mechanical
properties of a single Kevlar_ KM2 fiber, Internl. J Solids Structures, 41, 6215–6232 (2004).
19
http://www2.dupont.com/Kevlar/en_US/products/life_protection/kevlar_km2.html; Mechanical
Properties of Kevlar® KM2 Single Fibre, J. Eng Materials Technology, April 2005, Volume
127, Issue 2, pp.197-204.
20
M. N. Raftenberg, M. Scheidler, T. J. Moynihan, C. A. Smith, Plain-Woven, 600-Denier
Kevlar KM2 Fabric Under Quasistatic, Uniaxial Tension, ARL-TR-3437 March 2005.
21
http://www2.dupont.com/Kevlar/en_US/uses_apps/helmets.html
22
P. M. Cunniff, M. A. Auerbach, High performance “M5” fiber for ballistics/structural
composites; http://web.mit.edu/course/3/3.91/www/slides/cunniff.pdf.
23
P. M. Cunniff, M. A. Auerbach, E. Vetter, D. J Sikkema, High performance “M5” fiber for
ballistics/ structural composites, http://web.mit.edu/course/3/3.91/www/slides/cunniff.pdf
24
http://www.m5fiber.com/magellan/about_m5.htm
25
Teijin leaflet 2010, Twaron® Ballistic material handbook; ballistics@teijinaramid.com
26
http://armorco.com/shop/category.aspx?catid=2
27
www.ikolon.com/eng/index.html
28
http://www.bis.doc.gov/news/2010/doj03182010.htm
29
B. Morin, B. Adams, B. Follo, D. Salem, Weight Reduction and Cost Savings Using Hybrid
Composites Containing High Modulus Polypropylene Fiber, American Composites
Manufacturers Association, COMPOSITES & POLYCON 2009 Tampa, FL USA, January 15-
17, 2009.
30
Innegra S high performance fiber Presentation, 2010, INNegRITY, LLC
31
B. G. Morin, Polypropylene fiber for reinforcement of matrix materials, US Pat., 7,704,595,
April 27, 2010, to Innegrity, LLC (Greer, SC).
32
http://www.hexcel.com/Markets/Ballistics/
33
http://www2.dupont.com/Kevlar/en_US/news_events/article20090929.html
34
http://www51.honeywell.com/honeywell/news-events/press-releases-
details/6.22.10SpectraMaterialsProtectIndianPolice.html
35
http://www.dyneemamatters.com/HB80/files/DSM%20DYNEEMA%20LAUNCHES%20DYNEEMAR
%20HB80.pdf
36
R. L. Lane, High performance fibers for personnel and vehicle armor system, AMPTIAC
Quarterly, 9 (2), 3 – 9 (2005).
37
G. A. Harpell, I. Palley, S. Kavesh, D. C. Prevorsek, Ballistic-resistant fabric article, US Pat.,
4,650,710, March 17, 1987; to Allied Corp.

69
Rigid ballistic composites, 31.10.2010

38
L. C. Lin, L. G. Wilson, A. Bhatnagar, H. L. Li, High strength composite, US Pat., 5,587,230,
December 24, 1996, to AlliedSignal Inc
39
A. Bhatnagar, B. D. Arvidson, Impact resistant rigid composite and method for manufacture,
US Pat., 6,642,159, November 4, 2003, to Honeywell International Inc
40
H. L. Thomas, Jr., Layered ballistic-resistant material, US Pat., 7,700,503, April 20, 2010.
41
M. J., Chiou, Flexible penetration resistant article, US Pat., 7,727,914, June 1, 2010.
42
Denier is a weight in grams of 9 km of a continuous fiber or yarn: 1 denier = wt. in g/9 km =
1/9 tex. Decitex is a unit of the linear density of a continuous filament or yarn, equal to 1/10th
of a tex or 9/10th of a denier
43
A. Bhatnagar, D. A. Hurst, B. D. Arvidson, L. L. Wagner, Spaced lightweight composite
armor, US Pat. 7,762,175, July 27, 2010.
44
L. A. Utracki, Introduction to Polymer Blends, Chapter 1 in Polymer Blends Handbook. L. A.
Utracki, Ed., Polymer Blends Handbook, Kluwer Academic Pub., Dordrecht (2002).
45
M. Naffakh, A. M. Díez-Pascual, C. Marco, M. A. Gómez, I. Jiménez, Novel Melt-Processable
Poly(ether ether ketone)(PEEK)/Inorganic Fullerene-like WS2 Nanoparticles for Critical
Applications, J. Phys. Chem. B, 114 (35), 11444–11453 (2010).
46
M. R. Parvaiz, S. Mohanty, S. K. Nayak, P. A. Mahanwar, Polyetheretherketone (PEEK)
Composites Reinforced with Fly Ash and Mica, J. Min. Mater. Charact. Eng., 9(1), 25 – 41
(2010).
47
H. Mark, N.M. Bikales, C. G. Overberger, G. Menges and J. I. Kroschwitz, Eds., Encyclopedia
of polymer science and engineering, 2-nd ed., 11, 315 – 489, John Wiley & Sons, New York
(1988).
48
T. X. Liu, K. P. Lim, W. C. Tjiu, K. P. Pramoda, Z. K. Chen, Preparation and characterization
of nylon 11/organoclay nanocomposites, Polymer, 44, 3529-3535 (2003); S. Huang, M.
Wang, T. Liu, W.-D. Zhang, W. C. Tjiu, C. He, X. Lu, Morphology, Thermal, and
Rheological Behavior of Nylon 11/Multi-Walled Carbon Nanotube Nanocomposites Prepared
by Melt Compounding, Polym. Eng. Sci., 49:1063–1068 (2009).
49
http://www.azom.com/details.asp?ArticleID=882
50
L. A. Utracki, Clay-containing Polymeric Nanocomposites, book 786 pg, RAPRA, Shawbury,
Shrewsbury, Shropshire UK (2004).
51
L. A. Utracki, “Mechanical properties of clay-containing polymeric nanocomposites”, in
Handbook of Polymer Nanocomposites, Rakesh Gupta, Elliot Kennel and Kwang-Jea Kim,
Eds., CRC Press, Boca Raton, FL (2009).
52
Z. Wang, J. Yuan, Y. Xia, A dynamic Monte-Carlo simulation for unidirectional composites
under tensile impact, Compos. Sci. \Technol., 58, 487 – 495 (1998).
53
K. Binder, Ed., Monte Carlo and molecular dynamics simulations in polymer science, Oxford
University Press, New York (1995).

70
Rigid ballistic composites, 31 October 2010

54
G. Tanaka, L. A. Goettler, Predicting the binding energy for nylon 6,6/clay nanocomposites by
molecular modeling, Polymer, 43, 541-553 (2002).
55
D. Brown, P.Mélé, S. Marceau, N.D. Albérola, A molecular dynamics study of a model
nanoparticle embedded in a polymer matrix, Macromolecules, 36, 1395-1406 (2003).
56
M. Vacatello, Monte Carlo simulations of polymer melts filled with solid nanoparticles,
Macromolecules, 34, 1946 (2001).
57
S. Sen, J.D. Thomin, S. K. Kumar, P. Keblinski, Molecular Underpinnings of the Mechanical
Reinforcement in Polymer Nanocomposites, Macromolecules, 40, 4059-4067 (2007).
58
G. M. Odegard, T. S. Gates, L. M. Nicholson, K. E. Wise, Equivalent-Continuum Modeling
With Application to Carbon Nanotubes, NASA/TM-2002-211454; Equivalent continuum
modeling of nano-structured materials, Comp. Sci. Tech., 62, 1869–80 (2002).
59
G M. Odegard, T. C. Clancy, T. S. Gates, Modeling of the mechanical properties of
nanoparticle/polymer composites, Polymer, 46, 553-562 (2005).
60
N. Sheng, M. C. Boyce, D. M. Parks, G. C. Rutledge, J. I. Abes, R. E. Cohen, Multiscale
micromechanical modeling of polymer/clay nanocomposites and the effective clay particle,
Polymer, 45, 487-506 (2004).
61
K. Hbaieb Q. X., Wang Y.H.I. Chia, B. Cotterell, Modelling stiffness of polymer/clay
nanocomposites, Polymer, 48, 901-909 (2007).
62
R. Talreja, Multi-scale modeling in damage mechanics of composite materials, J. Mater. Sci.,
41, 6800-6812 (2006).
63
Mo Song, L. Chen, Molecular Dynamics Simulation of the Fracture in Polymer-Exfoliated
Layered Silicate Nanocomposites, Macromol. Theory Simul., 15, 238-245 (2006).
64
A. Usuki, A. Koiwai, Y. Kojima, M. Kawasumi, A. Okada, Y. T. Kurauchi, O. Kamigaito,
Interaction of Nylon 6-Clay Surface and Mechanical Properties of Nylon 6-Clay Hybrid., J.
Appl. Polym. Sci., 55, 119 – 123 (1995).
65
M. J. Potrzebowski, What High-Resolution Solid-State NMR Spectroscopy can offer to organic
chemists, Eur. J. Org. Chem.; 1367 – 1376 (2003).
66
P. Sozzani, S. Bracco, A. Comotti, M. Mauri, R. Simonutti, P. Valsesia, Nanoporosity of an
organo-clay shown by hyperpolarized xenon and 2D NMR spectroscopy. Chem. Commun.,
1921–1923 (2006).
67
A. Comotti, S. Bracco P. Valsesia, Adsorption properties of nanoporous organoclay and NMR
characterization, AIZ Workshop, Alessandria, Italy; 2006.09.01-02.
68
S. Yadav, E. A. Repetto, G. Ravichandran, M. Ortiz, A computational study of the influence of
thermal softening on ballistic penetration in metals, Internl. J. Impact Eng., 25(8), 787-803
(2001).
69
S. L. Phoenix, A. K. Yavuz, Pankaj K. Porwal, New interference approach for ballistic impact
into stacked flexible composite body armor, AIAA J., 48 (2), 490 – 501 (2010).

71
Rigid ballistic composites, 31.10.2010

70
F. R. Jones, A review of interphase formation and design in fibre-reinforced composites, J.
Adhesion Sci. Technol., 24, 171–202 (2010).
71
K. Nakajima, T. Nishi, Nanoscience of single polymer chains revealed by nanofishing, The
Chemical Record, 6, 249–258 (2006).
72
A. Ajji, Interphase and compatibilization by addition, Ch. 4; S. Bruce Brown, Rective
compatibilization of polymer blends, in Polymer Blends Handbook, L. A. Utracki, Ed.,
Kluwer Academic Pub., Dordrecht (2002).
73
J. Kalantar, L. T. Drzal, The bonding mechanism of aramid fibres to epoxy matrices; Part 1 A
review of the literature, J. Mater. Sci., 25, 4186-4193 (1990).
74
R. E. Allred, E. W. Merrill, D. K. Roylance, Molecular Characterization of Composite
Interfaces, Plenum Press, New York (1985).
75
Y. Wu, G. C. Tesoro, Chemical modification of Kevlar fiber surfaces and of model di-amides,
J. Appl. Polym. Sci., 31, 1041 – 1059 (1986).
76
T. K. Lin, S. J. Wu, J. G. Lai, S. S. Shyu, The Effect of chemical treatment on
reinforcement/matrix interaction in Kevlar-fiber/bismaleimide composites, Compos Sci
Technol., 60, 1873–8 (2000).
77
G. Li, C. Zhang, Y. Wang, P. Li, Y. Yu, X. Jia, H. Liu, X. Yang, Z. Xue, S. Ryu, Interface
correlation and toughness matching of phosphoric acid functionalized Kevlar fiber and epoxy
matrix for filament winding composites, Compos. Sci. Technol., 68, 3208–3214 (2008)
78
K. Mason, Sizing up fiber sizings, Compos. Technol., April 2006.
79
M. Tanoglu, S. H. Mcknight, G. R. Palmese, W. Gillespie. Jr., Dynamic stress/strain response
of the lnterphase in polymer matrix composites, Polym. Compos., 22 (5), 621 – 635 (2001).
80
H. C. Tang, T. Nguyen, T.-J. Chuang, J. Chin, J. Lesko, H. F. Wu, Fatigue model for fiber-
reinforced polymeric composites, J. Mater. Civil Eng., 12 (2) 97 – 104 (2000).
81
J. R. Pelch, J. E. Ritter, A. J. Lesser, T. P. Russell, T. J. Lardner Fatigue resistance of silane-
bonded epoxy/glass interfaces using neat and rubber-toughened epoxies, J. Mater. Sci., 37,
3269 – 3276 (2002).
82
R. E. Jensen, S. H. McKnight, M. J. Quesenberry, Strength and durability of glass fiber
composites treated with multicomponent sizing formulations, ARL-TR-2655 (2002).
83
M. Guden, U. Yildirim, I. W. Hall, Effect of strain rate on the compression behavior of a
woven glass fiber/SC-15 composite, Polym. Testing, 23, 719–725 (2004).
84
A. Jadhav, High strain rate properties of polymer matrix composites, MSc Thesis, Louisiana
State University, 2003.
85
L. Sun, Y. Jia, F. Ma, S. Sun, C. C. Han, Mechanical behavior and failure mode of
unidirectional fiber composites at low strain rate level, J. Compos. Mater., 43 (22), 2623-
2637 (2009).

72
Rigid ballistic composites, 31 October 2010

86
Sugiura, N., Maki, N., Sizing agent for carbon fiber, method for sizing carbon fiber by said
sizing agent, sized carbon fiber and knitted or woven fabric using said carbon fiber ,
EP1445370, 18.06.2008.
87
Y. X. Gan, Effect of interface structure on mechanical properties of advanced composite
materials, Int. J. Mol. Sci. 10, 5115-5134 (2009).
88
P. J. de Lange, P. G. Akker, A. J. H. Maas, A. Knoester, H. H. Brongersma, Adhesion
activation of Twaron® aramid fibres studied with low-energy ion scattering and x-ray
photoelectron spectroscopy, Surface Interface Analysis, 31 (12), 1079 – 1084 (2001)
89
I. Ahmad, T. S. Chin, C. K. Cheong, A. Jalar and I. Abdullah, Study of Fiber Surface
Treatment on Reinforcement/Matrix Interaction in Twaron Fiber/ENR Composites, Am. J.
Appl. Sci., (Sp. Issue): 14-20 (2005).
90
N. A. Siddiqui, M.-L. Sham, B. Z. Tang, A. Munir, J.-K. Kim, Tensile strength of glass fibres
with carbon nanotube–epoxy nanocomposite coating, Composites, A40 1606–1614 (2009).
91
R. J. Zaldivar, J. Nokes, G. L. Steckel, H. I. Kim, B. A. Morgan, The effect of atmospheric
plasma treatment on the chemistry, morphology and resultant bonding behavior of a pan-
based carbon fiber-reinforced epoxy composite, J. Compos. Mater., 44 (2), 137 – 156 (2010).
92
C. D. Warren, F. L. Pauiauskas, R. G. Boeman, Laser ablation assisted adhesive bonding of
automotive structural composites, ORNL/CP-102637, 03 July, 1999.
93
J. W. Gillespie Jr, L. A. Carlsson, A. J. Smiley, Rate-dependent mode i interlaminar crack
growth mechanisms in graphite/epoxy and graphite/PEEK, Compos. Sci. Technol.,28, 1-15
(1987).
94
P. J. Biermann, J. C. Roberts, R. Reidy, Richard, Impact resistant flexible body device, US
Pat. 7,413,809, 19.08.2008.
95
S. Iannace, L. Ambrosio, A. D'amore, L. Nicolais, Nonlinear viscoelasticity of Hydrothane®, J.
Mater Sci.: Mater. Med., 7, 305-307 (1996).
96
M. R. Dennis, A. Russell A., Multi-layer, personnel-protective helmet shell with spray-
fabricated inner and outer structural layers, US Pat., 6,671,889, 01/06/2004.
97
L. Sorrentino, M. Aurilia, S. Iannace, A simple method to predict high strain rates mechanical
behavior of low interconnected cell foams, Polym. Test., 26 878–885 (2007).
98
http://ru.wikipedia.org/wiki/Handgum
99
R. M. Palmer, P. C. Green, Energy absorbing material, US Pat., 7,381,460, June 3, 2008.
100
P. C. Green, R. M. Palmer, Energy absorbing blends, US Pat. Appl., 20070029690, February
8, 2007.
101
J. Kwon, G. Subhash, Compressive strain rate sensitivity of ballistic gelatin, J. Biomech., 43,
420–425 (2010).

73
Rigid ballistic composites, 31.10.2010

102
P. Moy, T. Weerasooriya, T. F. Juliano, M. R. VanLandingham, W. Chen, Dynamic Response
of an Alternative Tissue Simulant, Physically Associating Gels (PAG), ARL-RP-136,
September 2006.
103
J. P. Caritey, C. Chassenieux, F. Lafuma, Françoise C. Le Chatelier-Brunet, P. Maroy, Anionic
amphiphilic copolymers and solutions comprising thereof, WO/2005/123788, 14.06.2005
104
I. M. Krieger, G. N. Choi, Proc. IX Int. Cong. Rheol., Mexico, 1984; Advances in Rheology,
B. Mena, A. Garcia-Rejon and C. Rangel-Nafaile, Eds., Univ. Nat. Autonom. Mexico (1984)
105
L. A. Utracki, in “Multiphase Polymers: Blends and Ionomers,” L. A. Utracki and R. A.
Weiss, Eds., Vol. 395, ACS Symp. Ser., Washington DC (1989)
106
S. Ookawara, K. Ogawa, Dilatant flow characteristics model of coarse particle suspensions
with uniform size distribution, Korea-Australia Rheol. J., 15(1), 35 – 42 (2003).
107
Y. S. Lee, E. D. Wetzel, N. J. Wagner, The ballistic impact characteristics of Kevlar® woven
fabrics impregnated with a colloidal shear thickening fluid, J. Mater. Sci., 38 2825 – 2833
(2003).
108
Wagner; Norman J.; Nam; Caroline H., Emulsification of concentrated dispersions of colloidal
and nanoparticles, US Pat. Appl., 2010/0093240 A1, April 15, 2010.
109
Wagner; Norman J., Wetzel; Eric D., Advanced body armor utilizing shear thickening fluids,
US Pat., 7,498,276 B2 Mar. 3th, 2009
110
N. J. Wagner and J. F. Brady. Shear thickening in colloidal dispersions, Physics Today, 62(10):
27-32 (2009).
111
H. M. Laun, R. Bung, and F. Schmidt, Rheology of extremely shear thickening polymer
dispersionsa) (passively viscosity switching fluids), J. Rheol., 35(6), 999-1034 (1991).
112
H. M. Laun and R. Bung, S. Hess, W. Loose, and O. Hess, K. Hahn, E. Hädicke, R.
Hingmann, and F. Schmidt, Rheological and small angle neutron scattering investigation of
shear-induced particle structures of concentrated polymer dispersions submitted to plane
Poiseuille and Coutte flowa), J. Rheol., 36(4), 743-787 (1992)
113
B. J. Maranzano, N. J. Wagner, The effects of particle size on reversible shear thickening of
concentrated colloidal dispersions, J Chem. Phys., 114(23), 10514 – 10527 (2001).
114
B. A. Rosen, C. H. Nam Laufer, D. P. Kalman, E. D. Wetzel, N. J. Wagner, Multi-threat
performance of kaolin-based shear thickening fluid (STF)-treated fabrics, SAMPE 2007
Proceedings, Baltimore, MD, 3-7 June 2007.
115
S. J. Picken, R. Marissen, V. Antonelli, G. W. Jansen, Damage tolerant composite material,
WO/2009/142491, 20.05.2009.
116
J. G. E. Wright, Process for making puttylike elastic plastic, siloxane derivative composition
containing zinc hydroxide, US Pat. 2541851, 02/13/1951.
117
U. S. Schubert, Ch. Eschbaumer, C. H. Weidl, Design of supramolecular metal complexing
polymers: synthesis, complexation and polymerization of 5,5"-bis-functionalized terpyridine
building blocks, Design Monomers Polym., 2(3), 185-189, (1999).

74
Rigid ballistic composites, 31 October 2010

118
R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer, J. H. K. Ky Hirschberg, R. F. M.
Lange, J. K. L. Lowe, E. W. Meijer, Reversible polymers formed from self-complementary
monomers using quadruple hydrogen bonding, Science, 278 (5343), 1601-1604 (1997).
119
Ch. Fischer, R. Neagu, P. E. Bourban, V. Michaud, C. J. G. Plummer, S. Lavanchy, J.-A. E.
Manson, Structures with adaptive stiffness and damping integrating shear thickening fluids,
WO2009053946 (A2), 2009-04-30.
120
Ch. Fischer, A. Bennani, V. Michaud, E. Jacquelin, J.-A. E Månson, Structural damping of
model sandwich structures using tailored shear thickening fluid compositions, Smart Mater.
Struct., 19, 035017 (7pp) (2010).
121
Ch. Fischer, C. J. G. Plummer, V. Michaud, P.-E. Bourban, J.-A. E Månson, Pre- and post-
transition behaviour of shear thickening fluids in oscillating shear Rheol. Acta, 46 1099–108
(2007).
122
F. J. Galindo-Rosales,·F. J. Rubio-Hernández, J. F. Velázquez-Navarro, Shear-thickening
behavior of Aerosil® R816 nanoparticles suspensions in polar organic liquids, Rheol Acta, 48,
699–708 (2009).
123
H. Mahfuz, F. Clements, V. Rangari, V. Dhanak, G. Beamson, Enhanced stab resistance of
armor composites with functionalized silica nanoparticles, J. Appl. Phys., 105, 064307
(2009).
124
B.-W. Lee, I.-J. Kim, C.-G. Kim, The influence of the particle size of silica on the ballistic
performance of fabrics impregnated with silica colloidal suspension, J. Compos. Mater.,
43(23), 2679 – 2698 (2009).
125
M. Chellamuthu, E. M. Arndt J. P. Rothstein, Extensional rheology of shear-thickening
nanoparticle suspensions, Soft Matter, 5, 2117–2124 (2009).
126
https://www.ikolon.com/eng/imd/heracron/heracron.html
127
E. Brown, H. M. Jaeger, Dynamic jamming point for shear thickening suspensions, Phys. Rev.
Lett., 103, 086001 [4 pages] (2009).
128
E. Brown, N. A. Forman, C. S. Orellana, H. Zhang, B. W. Maynor, D. E. Betts, J. M.
DeSimone, H. M. Jaeger, Generality of shear thickening in dense suspensions, Nature
Materials, 9, 220 – 224 (2010).
129
T. A. Hassan, V. K. Rangari, S. Jeelani, Synthesis, processing and characterization of shear
thickening fluid (STF) impregnated fabric composites, Mater. Sci. Eng. A, 527, 2892–2899
(2010)
130
A. M. Torki, I. Živković, V. R. Radmilović, Dynamic mechanical properties of
nanocomposites with poly (vinyl butyral) matrix, Int. J. Modern Phys.,B, 24, 805–812 (2010).
131
W. P. Krekelberg, T. M. Truskett, V. Ganesan, Relationship between shear viscosity and
structure of a model colloidal suspension, Chem. Eng. Comm., 197 (1), 63 — 75 (2010).

75
Rigid ballistic composites, 31.10.2010

132
G. B. Ramaiah, R. Y. Chennaiah, G. K. Satyanarayanarao, Investigation and modeling on
protective textiles using artificial neural networks for defense applications, Mater. Sci. Eng.
B, 168, 100–105 (2010).
133
D. Ostermayer, F. L. Beyer, P. G. Dehmer, M. A. Klusewitz, Measurement of V50 behavior of
a Nylon 6-based polymer-layered silicate nanocomposite, ARL-TR-2605, September 2001.
134
Y. Wei, A. F. Bower, H. Gao, Enhanced strain-rate sensitivity in fcc nanocrystals due to grain-
boundary diffusion and sliding, Acta Materialia, 56, 1741–1752 (2008).
135
S. J. Savage, Defence applications of nanocomposite materials, Swedish Defence Research
Agency Report FOI-R-1456-SE, ISSN 1650-1942, December 2004.
136
G. Thilagavathi, A. S. M. Raja, T. Kannaian, Nanotechnology and protective clothing for
defence personnel, Defence Sci. J., 58 (4), 451-459 (2008).
137
S. Gordeyev, T. Crawley, Protective Materials for Emergency Responders, Security Sector
Focus Report, April 2010.
138
http://www.weizmann.ac.il/ICS/booklet/20/pdf/reshef_tenne.pdf
139
B. Halford, Inorganic Menagerie – Unusual properties of nanotubes made from inorganic
materials offer intriguing possibilities for applications, C&EN, 83 (35), 30-33 (2005).
140
K. Mylvaganam, L. C. Zhang, Ballistic resistance capacity of carbon nanotubes,
Nanotechnology, 18, 475701 4 pp (2007).
141
M. Abrams, Nanoscale armour, Mech. Eng., 128, 34 -37 (2006).
142
S. M. Walsh, B. R. Scott, D. M. Spagnuolo, The development of a hybrid thermoplastic
ballistic material with application to helmets, ARL-TR-3700, December 2005
143
S. M. Walsh, B. R. Scott, D. M. Spagnuolo, J. P. Wolbert, Hybridized thermoplastic aramids:
enabling material technology for future force headgear, Army Science Conference, 30
November 2006.
144
Bobdina, New Army helmet to replace Kevlar with plastic can stop rifle rounds,
APACHECLIPS FORUM, 08-24-2009;
http://www.apacheclips.com/boards/showthread.php?3335-New-Army-helmet-to-replace-
kevlar-with-plastic-can-stop-rifle-rounds&s=f718fcfe8c6ab97e3cbb205db10f45ac
145
http://www.gentexcorp.com/default.aspx?pageid=2394
146
http://www.marcorsyscom.usmc.mil/sites/pmice/IndustryInfo/APBIMay10/USMC_ECH_2010.pdf
147
Amy McCullough, Plastic helmet prototypes fail tests, Marine Corps News, Monday Jan 11,
2010; http://www.marinecorpstimes.com/news/2010/01/marine_plastic_011110w/
148
http://defense-update.com/newscast/0510/army_recall_ach_helmets_17052010.html
149
http://en.wikipedia.org/wiki/Enhanced_Combat_Helmet
150
http://www2.dupont.com/Kevlar/en_US/uses_apps/helmets.html

76
Rigid ballistic composites, 31 October 2010

151
B. K. Fink, Performance metrics for composite integral armor, J. Thermoplast. Compos.
Mater., 13, 417 – 431 (2000).
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