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NRC Publications Archive Archives des publications du CNRC Rigid ballistic composites (Review of literature) Utracki,

NRC Publications Archive Archives des publications du CNRC

Rigid ballistic composites (Review of literature) Utracki, Leszek A.

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Conseil national de recherches Canada Institut des matériaux industriels National Research Council Canada Industrial

Conseil national de recherches Canada

Institut des matériaux industriels

National Research Council Canada

Industrial Materials Institute

Research Council Canada Industrial Materials Institute Rigid ballistic composites (Review of literature) Leszek A.

Rigid ballistic composites

(Review of literature)

Leszek A. Utracki

NRC/IMI/Advanced Materials Design

31.10.2010

Institute Rigid ballistic composites (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

INTRODUCTION

Rigid ballistic composites, 31 October 2010

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.

updated versions of those developed for the Korean War. In 1969, American Body Armor™, Inc. was

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.

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/cm 2 . 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.

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.

A new breed of armor may contain a

Since the 1970s, several new fibers and construction methods for bulletproof fabric have been

developed besides

Twaron ® , Pinnacle Armor's Dragon Skin ® body armor, INNegRITY Innegra S and Toyobo's

Zylon ® .

Kevlar ® , e.g., DSM Dyneema ® , Honeywell's GoldFlex ® and Spectra ® , Teijin

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

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 )

(kg/m 3

Tensile strength

Failure strain

E(GPa)

(MPa)

(%)

Kevlar ® Laminate PE Laminate

9

1160

450

9

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 (m 3 /g), respectively. Similarly, the deformation-divided-by-thickness for

these two composites was about 3 and 5, respectively. The ratio of V 50 to

determined for Kevlar ® and PE composites as 73.3 and 95.2 (m 3 /kg), respectively. Numerical

simulations of the ballistic performance were in good agreement with the observations.

Rigid ballistic composites, 31.10.2010

Rigid ballistic composites, 31.10.2010 Structural fiber sizing ARL hybrid fiber sizing Ballistic fiber sizing The US

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

Stephanie Kwolek invented Kevlar ® crystalline aromatic polyamide, a fiber gram-for-gram five times stronger than

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.

Rigid ballistic composites, 31 October 2010

The chemical composition of aramid, PBO

and M5 fiber

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.

is shown left.

Kevlar ® is an

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.

and stiffer in the axial than in the transverse direction. The PPTA aramid stretched fibers are

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

Rigid ballistic composites, 31.10.2010

Recently Li et al. [2008] functionalized Kevlar ® 1680 monofilament with phosphoric acid, H 3 PO 4 . 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

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].

(with

IM7

The

specimens

have

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.

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

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 Thickness Breaking Strength: Length & Width

35

x 35 Length & Width

31 x 31 Length & Width

23.0 (mils) 0.58(mm

12.0(mils) 0.30(mm)

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

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

(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).

Mark IV is being evaluated by the U.S. Army in the Enhanced Combat Helmet

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

is

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.

and more effective protection of vehicle and body armor. DuPont high performance fiber technology. M5 the

DuPont high performance fiber technology. M5

the

®

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, H 3 PO 4 . 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

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

Table 4. Advanced Fiber Mechanical Properties 23

Fiber/

Strength (j)

Failure Strain

Modulus (E)

Strain wave velocity (m/s)

(denier)

(GPa)

(i) (%)

(GPa)

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

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/m 2

8.3 oz/ sq. yd

Width:

60

inch

71 inch

Denier

930 dtex

1000

Weave:

 

Plain

Plain

Construction Thickness Breaking Strength: Length/Width

27

x 27 Length & Width

31 x 31 Length & Width

0.36 mm

0.38 mm

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 90 o ) 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/m 2 ), or T750 (plain weave; 3360 dtex; 460 g/m 2 ) 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.

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.

Kolon developed Heracron ®

27, 28

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 160 o C; tensile strength = 590 MPa; modulus = 19 GPa; elongation at break = 7.2 %; dielectric constant = 2.2 and dielectric loss = 0.0002. 29, 30, 31

Making fabrics

Rigid ballistic composites, 31 October 2010

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

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.

Table 7. Comparable properties of high performance fibers.

36

7 compares performance of Dyneema ® to other fibers. Table 7. Comparable properties of high performance

Patented ballistic armor

Rigid ballistic composites, 31 October 2010

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 23 o C) 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.

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

Patent

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

ArmorFelt TM [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.

Stress is on the well-performing needled felt:

of its path. Stress is on the well-performing needled felt: 7,727,914 also discusses flexible, penetration resistant

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

Pat.

comprising a number of layers including continuous filament yarns, having an areal density of less than about 4.4 kg/m 2 . 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

Rigid ballistic composites, 31.10.2010

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

polypyridobisimidazole fibers, and mixtures thereof. The special emphasis has been placed on the filaments made

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 V 50 (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

V 50

 

# layers

dtex

# layers

dtex

kg/m 2

m/s

1 550

31

--

--

4.3

517

2 550

21

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

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.

a light weight. 43

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

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. 0/45/90/45/0 o (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/m 2 , 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 25 o C) 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 90 o ) 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 V 50 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.

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, T g > 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.

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 properties

Kyo and Asai, 1978

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, heat and chemical resistance

Chiba et al., 1978

PPS with polyphthalamide (PPA)_

heat and chemical resistance, HDT, mechanical properties

Chen and Sinclair, 1990

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 and chemical stability

Ishio and Kobayashi, 1992

PPS, either PA-66 or PA-MXD6 and Mg(OH) 2

tensile strength, arc tracking, and heat resistance

Dubois et al., 1993

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 or EPDM)

impact strength at low-T, Rilsan™

Arraou, 1986

5.

PA/PAI Blends

PAI with PA-66 or PARA and inorganic filler

moldings with high mechanical performance

Toray Ind., 1979

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™, blended with either PA or PARA

thermal aging behavior

Angeli, 1992

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

Density (kg/m 3 )

1130

1140

1040

1020

1100

1080

1060-1120

T g (°C), T m (°C)

57

57

42

37

 

50

145

220

255

184

180

295

215

240

HDT (°C)

80

105

55

140

90

95

150

H 2 O absorption at 23 o 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.

Rigid ballistic composites, 31 October 2010

Table 11. Typical properties of PA-11 49

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.

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

INTERPHASE

Mold Temp. Range (°C)

40 - 60

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.

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 studieson the interphase will be divided into four sections: Compatibilization Fiber sizing Shear sensitive coupling

Compatibilizationwill be divided into four sections: Computational studies Fiber sizing Shear sensitive coupling Computational studies

Fiber sizinginto four sections: Computational studies Compatibilization Shear sensitive coupling Computational studies 5 1 During

Shear sensitive couplingComputational studies Compatibilization Fiber sizing Computational studies 5 1 During the last two decades the

Computational studies 51

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

Rigid ballistic composites, 31.10.2010

change

conformation.

the

computed

structure,

the

order

of

interface

shells,

or

the

macromolecular

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 for analyzing the mechanical properties of polyimide (PI) with dispersed silica particles, whose radius ranged from r = 1 nm to 1 µm. 59

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

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, T g . For CPNC with the matrix T g ≤ RT (room temperature), addition of clay enhances the mechanical properties. However, when the matrix T g 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.

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 V 50 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, V 50 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 V 50 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 V 50 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.

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

(ToF-SIMS) imaging

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

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.

The macromolecule (M w = 100 kD, degree of polymerization DP = 918) had a

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 H 2 SO 4 . 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.

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 NH 3 , 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 (H 3 PO 4 ) at different concentration. 77

strength was constant up to 40 wt% H 3 PO 4 , but the maximum of oxygen functional groups was

obtained using 20 wt% H 3 PO 4 . Composites prepared from optimally functionalized fibers, and

various combinations of epoxy/hardener were studied.

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 H 3 PO 4 -functionalized fibers, what in

11 The mechanical properties were further

The monofilament tensile

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.

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

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 30 o C 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.

time of fiber reinforced polymeric composites.

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). The properties of two epoxies with similar chemical structures were controlled by varying the molecular weight between cross-links, M c . Two rubber-toughened epoxies with different nominal rubber particle sizes (10–40 and 1–2 m) were used. The changes of M c 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

81

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

The

composites were designed for Composite

ester/E-glass composites. 82

the

Combat Systems (FCS) . The authors the stressed that the interphase may control CIA performance,

stressed that the interphase may control CIA performance, viz. strength, durability,

fatigue life, as well as

micromechanical energy absorbing capability during a ballistic event. Immediately after drawing the E-glass fibers (16.9 µm diameter) the sizing was 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.

equipment to demonstrate their behavior in composites. The Figure above shows two atomic force microscopy (AFM)

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 1.1x10 3 (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 0 o to a plateau ranging from 30 to 150 o . 84 Similar conclusion could be drawn from the recent studies

0 o to a plateau ranging from 30 to 150 o . 8 4 Similar conclusion

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

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 Fe 3 Al alloy. The ceramic layers were made off yttrium stabilized zirconium oxide [YSZ = zirconium-oxide, ZrO 2 , whose crystal structure is stable at RT by addition of yttrium oxide, Y 2 O 3 ]. 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.

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

layer of acceleration-rate-sensitive microcellular foam. The origin of strain hardening behavior might be deduced
layer of acceleration-rate-sensitive microcellular foam. The origin of strain hardening behavior might be deduced

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,

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

It has been known that gel made of 2-to-1 (by volume) combination of

as children toys. 98

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 210 o C. 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/mlclothing against blunt trauma. Its other properties are: Shear Hardness: 65 - 81 Operating temperature range:

Shear Hardness: 65 - 81trauma. Its other properties are: Density: 0.5 - 0.65 g/ml Operating temperature range: -55°C to 120°C

Operating temperature range: -55°C to 120°Care: Density: 0.5 - 0.65 g/ml Shear Hardness: 65 - 81 Repeat washing: 40 washes at

Repeat washing: 40 washes at 40°C65 - 81 Operating temperature range: -55°C to 120°C Tensile strength: 1MPa according to the standard

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

values are about 3-orders of magnitude smaller. 1 0 1 BG main drawbacks are: the lack
values are about 3-orders of magnitude smaller. 1 0 1 BG main drawbacks are: the lack

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

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.

Again, formation of local dynamic crosslinks is responsible. Stress-strain hardening of suspensions – introduction A
Again, formation of local dynamic crosslinks is responsible. Stress-strain hardening of suspensions – introduction A

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

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

Krieger and Choi studied the viscosity behavior of sterically stabilized PMMA spheres in silicone oil. 104 In high viscosity oils, thixotropy and yield stress was present. In most systems the lower

Newtonian plateau was observed for the reduced shear stress value:

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.

(d is

σ

r

σ

12

d

3

/ RT > 3

Rigid ballistic composites, 31.10.2010

Utracki derived the following relation for dilatant flows: 105

(
(
) ( ) 0
)
(
)
0

1

a exp

0

2 a { 2  a } 1 (  ) 11 2
2 a
{
2
a
}
1
(
)
11
2

m

1

m

2

where a i are equation parameters whereas τ 1 and τ 2 are relaxation times of segment and cluster, respectively. The first square bracket describes the dilatancy, the second the pseudoplasticity. The left Figure illustrates the dependence for different values of a 0 .

Assuming uniform particle size distribution Ookawara and Ogawa derived a dependence predicting a linear increase of viscosity with shear rate, increasing with the square of volume fraction of particles. Furthermore, the viscosity linearly depends on density and an average particle diameter. 106

PSEUDOPLASTIC-DILATANT FLOWS 1 10 o -1 a o = 1.0 10 a o = 0.1
PSEUDOPLASTIC-DILATANT FLOWS
1
10
o
-1
a o =
1.0
10
a o = 0.1
a o = 0.01
-3
a o = 0.001
10
a o = 0.0
η = a 1 = 0;
a 2 = 0.1;
= 1.0;
m 2 = 0.8
-5
m 1
10
10 -6
10 -2
10 2
10 6

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.

by the STF is probably due to an increase in the yarn pullout force upon transition
by the STF is probably due to an increase in the yarn pullout force upon transition

Rigid ballistic composites, 31 October 2010

As shown above, the spheres were not monodispersed, thus the maximum packing volume fraction for the suspension φ max > 0.62. The flow curves (see right Figure) for two silica 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 suspension shows the onset of dilatancy at about 400 (1/s) – well below the rate of shear at the

.

ballistic event, estimated as:

γ 10

of shear at the . ballistic event, estimated as: γ  10 4 10 5 (

4

10

5

( 1 / s)

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. The authors also prepared STF with acicular CaCO 3 crystals. 3 Similar flow curve as the one shown above for φ = 0.62 of silica was obtained for φ = 0.51. The data points of energy 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 SiO 2 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 H 2 O.

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 80 o C. 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.

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

q. chaps, r. pants s, gloves, t. sail cloth, etc . 1 0 9 The experience
q. chaps, r. pants s, gloves, t. sail cloth, etc . 1 0 9 The experience

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

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

+ nil

+ K-STF

Layer areal density (g/m 2 ) load at 20 mm, Spike (N) load at 20 mm, Knife (N) Energy absorbed:18 gauge HN (J) Energy absorbed:22 gauge HN (J) V 50 (m/s)

180

210

216

35

160

180

80

120

120

8

76

62

11

39

36

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.