Conference Session C4 Paper #2241 BULLET PROOF VESTS: THE EVOLUTION OF ARAMID FIBERS Jann Grovogui (jag168@pitt.edu), Rachel Rohr (rar97@pitt.edu) Abstract—The most basic form of protection for military and law enforcement members is the bullet proof vest. This paper will discuss both the properties of the materials used – past and present – in bullet proof vests, as well as the process used to test and develop this form of protection. It will then go on to analyze the flaws of currently used vests. Lastly, the ethics surrounding the protection offered to those who serve will be investigated. First, the paper will delve into the basic history and technological advances of body armor from the Greeks who used steel to 1965 when Kevlar® was first introduced [1]. Next, the National Institute of Justice’s standards at which manufacturers test bullet proof vests will be established, emphasizing the requirements of these vests. An analysis of the materials of which bulletproof vests are composed will be discussed next. The primary material being assessed will be Kevlar®; this paper will then compare the standard vest to Kevlar® treated with colloidal silica nanocomposites, which has proven more effective. In conclusion, the topic of ethics will be explored and a suggestion for the future will be presented. Currently, bullet proof vests simply protect against gunfire; they do not address threats from “knives and sharply pointed instruments, which are different types of threats” [2]. Research should now focus on not simply creating a strong bullet proof vest, but an all-around protective body armor. prevented by placing the densest materials available in front of the body [1]. In 1965, DuPontTM revolutionized the body armor industry. Protective gear could then be created through the weaving of high tenacity polymer fibers. These fibers shifted body armor focus from the macro to the microscopic scale. KEVLAR® AS A VIABLE MATERIAL The historic change from hard body armor – the large ceramic and metal plates – to soft body armor – the multilayering of textile material – took place because of that 1965 DuPont™ innovation: Kevlar® [1]. Kevlar® was discovered while scientists were searching for an improvement from the top man-made fibers at the time: nylon and polyester. Their current problems consisted of difficulties creating high tenacity fibers with their flexible-chain polymers. Using a new method of production, DuPont™ scientists were able to create “an almost perfect polymer chain extension.” By having a backbone with a para orientation of the benzene ring, as seen in Figure 1, the repetitiveness of the molecular backbone of the liquid crystalline polymer poly-b-benzamide formed rod-like molecular structures [4]. Key Words—Aramid fiber, Bullet proof vest, Colloid, High tenacity fabrics, Kevlar®, Silica nanocomposites, Soft body armor, Tensile strength BODY ARMOR BASICS With today’s advances in weaponry, it is essential to protect those who risk their lives when they put themselves in harm’s way. The most basic form of protection for military and law enforcement members is the bullet proof vest. It was reported that 99.4 percent of law enforcement officers nationwide wear body armor while on duty, even though only 59 percent of agencies require protective gear [3]. Because these trained professionals who work to protect the general population rely on these ballistic vests, furthering their development and using the most effective materials for the job must be a priority. Prior to the 1960s, body armor revolved around the concept of stopping close and long range threats using the same primitive technology that has been used for the last several thousand years. Since the practice of using metal shields by the ancient Greeks to the use of steel and ceramic plates during WWI and WWII, bodily threats were FIGURE 1 INITIAL POLYMER AND LAYERING OF KEVLAR® [4] The key to a liquid crystalline polymer is its “aligned molecule chains with crystal-like spatial regularity” [5]. The main success of the fibers made with this new polymer polyb-benzamide was because of this high orientation with strong interchain bonding. As opposed to the flexible chain polymers, an increase in concentration of liquid crystalline polymers leads to a parallel alignment of the rods, as seen in Figure 2, which is what leads to a high tenacity. The ability to create a high tenacity fiber was now much more easily accomplished. University of Pittsburgh Swanson School of Engineering April 14, 2012 1 Jann Grovogui Rachel Rohr protective that hard body armor. In fact, “Kevlar® fiber is five times stronger than steel on an equal weight basis, offering superior protection against fragmentation and ballistic threats” [8]. DuPont™ currently stresses the fact that “there is no such thing as completely ‘bullet proof’ armor,” and should instead be more accurately described as “bullet-resistant” [9]. These levels of resistance vary, and therefore not all vests can provide the same protection. Through careful studies in their Ballistic Labs in Virginia and Switzerland and as established by the standards from the National Institute of Justice, DuPont™ has discovered the various levels of their materials which can best protect against specific bullet types. Based on these varying levels of ballistic performance, the National Institute of Justice has classified body armor into five different types: FIGURE 2 DIFFERENCE IN RIGIDITY BETWEEN PREVIOUSLY-USED MAN-MADE FIBERS AND KEVLAR® [4] Using the same technology which created their first high tenacity polymer over the next few years, DuPont™ was then able to develop a fiber of poly-paraphenylene terephthalamide, as seen in Figure 3, which became their high-strength aramid fiber seen today. Type II-A protects against 9mm and .40 S&W caliber bullets Type II protects against 9 mm and .357 Magnum bullets Type III-A protects against higher velocity 9 mm and .44 Magnum bullets Type III protects against rifles Type IV protects against .30 caliber armor piercing bullets [10] By adjusting the layers of Kevlar in body armor as well as the density, these different types can be created. This variety is what allows men and women of different professions to all use Kevlar® bullet proof vests. As they enter different dangerous situations, they need the best protection for what harm they will most likely face. Type IIA body armor is often used by police officers while Type III is often used by military in tactical situations. In addition, Kevlar® is so popular because of its light weight and comfort. Law enforcement officers have relied on Kevlar® for more than 30 years. For the same time, every branch of the Armed forces has used Kevlar® vests. FIGURE 3 POLY-PARAPHENYLENE TEREPHTHALAMIDE POLYMER [6] Kevlar® and its aramid fibers, which can be seen in a variety of places including the military, automobiles, and fiber optics, is characterized by its unique properties which include: high tensile strength at low weight, low electrical conductivity, and flame resistance [4]. ADVANCING KEVLAR TECHNOLOGY Since its development in the 1960’s there have been numerous advancements made to improve the abilities of Kevlar. Many more types of high tenacity fibers have been developed such as Dyneema®,Twaron®, and several others [11]. These new advancements have either enhanced the strength to weight ratio of these individual fibers or improved other qualities such as resistance to heat [12]. However, one of the most impressive advancements has not been the development of a new fiber, but rather a way to improve the properties of all high tenacity fibers. This new technology involves the impregnation of colloidal silica into the fibers of vests, also referred to as shear thickening liquid [13]. A colloid is a “mixture in which a dispersed substance (which is solute-like) is finely divided in a dispersing Effectiveness in Bullet Proof Vests By 1973, Kevlar® could be seen in bullet proof vest designs for use in field trials. In 1976, a report was released which concluded that this new soft body armor was effective and ready for use [7]. Kevlar® so effectively “catches” a bullet because of its woven multilayer fabric. Each layer works together to engage a high-velocity projectile and attempt to stop it as quickly as possible [4]. “The engaged fibers absorb and disperse the energy of the impact, transferring it to other fibers at crossover points in the weave of the body armor” [8]. The subsequent layers absorb energy and reduce the force felt by the wearer. Though labeled soft body armor, it by no means is less 2 Jann Grovogui Rachel Rohr medium (which is solvent-like)” [14]. A colloidal mixture is any liquid that has with in it small spherical particles of radii between 1nm and 1000nm [14]. Colloids are incorporated into high tenacity fibers through a relatively short process, which involved first the soaking of fabrics in a basin filled with colloidal silica suspension. The material soaks for an hour before then being removed from the colloid. Excess liquid is then driven out of the fabric through a pressing process and then finally the fabric is baked at 80°C for an additional hour [11]. After this short process, the transformation is complete and the strength of the fibers are significantly improved. the inter-fiber friction, causing there to be more dispersion of forces. In order to test this, of course, experiments had to be performed. One such test was devised in order to test “neat” fibers–fibers that were not impregnated with the colloid– versus fibers treated with three different sized colloids (110 nm, 380nm, and 540nm) [11]. The tests that were performed included but were not limited to; ballistic tests and string pull tests. Ballistic tests are the most obvious test that would occur during testing of bullet proof vests. This involves the launching of a projectile into woven fibers and examining the impact the projectile has on them. In this experiment, clay was also placed behind the woven fibers so that the impact behind the cloth could be observed afterwards. In addition to the ballistic test, a string pullout test was performed. In an experiment like this, a machine is built to pull out the string on the frayed edges of woven fibers. This will test the inter-fiber friction which is usually a good determinant of how well a certain woven fabric will disperse a force put upon it. For a single string pull-out experiment there are usually six factors that affect the result of the test. These factors include: “…fabric style, material properties such as elastic modulus and strength of the yarn, fabric length, transverse load, surface treatment, and pull-out loading rate” [16]. In the case of vests impregnated with silica colloid, the colloid is the only difference between the neat and treated vests is the surface treatment. Therefore any difference in results will be due to the colloid because it is a surface treatment of the vest. FIGURE 4 Test Results (ABOVE) UNTREATED KEVLAR® MICROSCOPY IMAGE (BELOW) KEVLAR® TREATED WITH COLLOIDAL SILICA NANOCOMPOSITE [15] Due to the relatively new nature of shear thickening technology, there are very few experiments that have been performed. However, because of the potential of colloid impregnated ballistic fibers, it is important for scientists to continue their studies on this new technique in order to fully test the qualities that this material possesses. Without such research, it would be unethical to produce and use this fantastic material in bullet proof vests without knowing if it has certain flaws. Bok-Won Lee, Il-Jin Kim, and Chun-Gon Kim performed one experiment on the properties of silica colloid impregnated fibers. In this experiment, two tests that were performed were the string pullout and projectile tests. In the projectile test, an interesting result was found. Woven cloth treated with three colloid particle sizes were tested (approximately 100nm, 300nm, and 500nm) along with an untreated sample. These four fabric samples were clamped by the team on each edge to a frame and clay was used to back the samples in order to measure the back face deformation of the fabric. When a 5.52-gram projectile was launched at approximately 224 m/s at the fabrics, all the fabrics except for the cloth impregnated with the 100 nm colloid successfully arrested the projectile [11]. Despite the small size of the particles and the fact that they are immersed in a liquid, this technology is surprisingly effective and has incredible results. The first reason that this technology is effective is that the addition of a liquid into the fiber adds almost no weight or stiffness to the fabric [11]. In addition, the stopping power is greatly improved. For example, four layers of Kevlar® treated with 8 mL of colloidal silica have the same strength properties as 14 layers of dry Kevlar [15]. Shear Thickening Liquid Treatment The basic reason that the fibers are significantly enhanced when impregnated with silica is in part due to the mechanics behind how bulletproof vests operate. The way that these vests work is that when impacted by a bullet or other projectile, the fibers within them interact with each other and quickly disperse the concentrated force over a larger area of the vest [16]. The theory behind why silica colloids improve the stopping power of vests is that the colloid may improve 3 Jann Grovogui Rachel Rohr Another interesting finding from the results of this test showed that in general, as particle size decreased, energy dissipation increased; however, untreated cloth consistently dissipated the least energy. The general reason that smaller particles dissipate more energy is because there are more particles with more surface area to interact, which in turn causes more inter-fiber frictional force. Considering this concept, it is bizarre that not only would the 100 nm particles dissipate less energy than the 300nm and 500nm particles, but it actually weakened the fibers because the cloth was actually penetrated when impregnated by 100nm particles but dissipated over 90% of the projectiles energy when it was untreated [11]. This abnormality in this particular data proves that this technology needs to be further researched. Because so few studies have been done, it is unclear whether 100 nm particles are too small to have any positive affect on aramid fibers or if this data occurred because of an experimental flaw. Perhaps there are more weaknesses of shear thickening fluid that scientists are unaware of, and again this is why aramid fiber technology needs to be researched in order for us to be able to utilize this technology affectively. Another interesting result occurred in the string pullout test. As the strings were being pulled from the fabric, it was found that at low speeds, all four fabrics that were tested required nearly the same force to pull out the fibers. However, as the speed of pullout increased, the colloids begin to react to the speed. The special quality that shearthickening fluids such as this colloid have is that “during normal use, they flow as easily as conventional liquids,” but “when subjected to sudden stresses that make them flow at higher shear rates, they instantly turn rigid and act like a solid material” [13]. Because of this quality, there were certain speeds of pullout that were revealed in which the colloid switched from acting like a liquid to acting more rigid and solid-like. In addition, the different sized colloids reacted in this way at different speeds. For example, between 400 and 500 mm/min the 300nm colloid reached its shear thickening point and the resistance of the fiber it was reinforcing greatly increased making it the toughest fibercolloid combination. However, at about 1356 mm/min the 100 nm colloid reached it shear thickening point and the pullout force needed to pull the string increased by 89.2% making it the toughest fiber-colloid combination at this point [11]. This shows that different sized colloids may be more effective for stopping projectiles at different speeds. This knowledge is very important to ensure the safety of those wearing vests. This is because that could mean that a soldier protected by high velocity projectiles could be injured by something more slow moving such as an arrow. Because of intricacies such as this, more engineers need to perform follow up experiments in order that shearthickening technology can be fully understood and utilized in body armor. However, new aramid fiber technology is not the only aspect of body armor that needs to be improved. There are many factors that affect the durability and strength of body armor and can cause significant degradation. These factors cannot be controlled, but the need to create aramid fibers that are more resistant to these outside factors is vital for the full protection of those who use ballistic vests. DOWNFALLS OF CURRENT BALLISTIC VESTS Though ballistic vests have certainly achieved great advancements since steel and ceramic plates during the two World Wars, there are still many developments that need to be made. Ethically, these are issues that need to be focused upon immediately. Men and women rely on these vests daily to save their lives; research should therefore be done to make them as effective as possible. A number of problems can be addressed. Environmental Effects on Vest Quality Since wearers of bullet proof operate in all types of environments, vests need to be able to withstand the variety of elements these wearers face. Currently, Kevlar®, like all materials, has points where it can no longer be as effective. Providing the most protection at a neutral pH, Kevlar® significantly reduces in strength when exposed to strong acids and bases, as seen in Figure 5. It shows the break strength–which prevents a sample from failing when enduring loads–of Kevlar® remaining at different pHs [17]. FIGURE 5 EFFECT OF VARYING PHS ON KEVLAR® [4] The U.S. Department of Justice and National Institute of Justice report that temperature is also a worry with bullet proof vests. Although Kevlar® degradation is mostly a problem at extreme temperatures not faced on a daily basis, the extended period of time which ballistic vests are worn allows lower temperatures to be a problem as well. This is mainly due to the fact that vests have such a long time to endure such degradation; the typical life of a bullet proof vest is three to five years [7]. As exposure to high temperature continues, the tensile strength of a material, which is “the maximum stress that a material can withstand while being stretched or pulled before necking, which is when the specimen's cross-section starts to significantly contract,” is reduced [18]. 4 Jann Grovogui Rachel Rohr Prolonged exposure to UV and visible light additionally harms bullet proof vests; it can cause “loss of mechanical properties, depending on wavelength, exposure time, radiation intensity and product geometry” [4]. When the absorption spectrum of Kevlar® is overlapped with the sunlight spectrum, as shown in Figure 6, there is sufficient energy to break the chemical bonds of the fiber and therefore maximum degradation. For this reason, body armor should never be dried outdoors, yet this cannot always be avoided. The preliminary experiment described above lead to further experiments and to another performed by the National Institute of Standards and Technology. In this follow up experiment, the aim was to discover if there would be a dramatic degradation in aramid fiber strength when the fibers were woven as is found in bullet proof vests. Another aim was to discover why this effect was occurring, in order to find a way to prevent this reduction in strength. A machine was constructed that would apply a force consistently that would replicate a folding in woven aramid fibers. The machine ran fibers through either 5,500 cycles or 80,000 cycles of folding, which is an amount not too inconsistent with the estimate of folds stated earlier [20]. The results of this experiment showed that woven fibers folded 5,500 times showed a strength reduction of 14% and that those folded 80,000 times showed a strength reduction of 41%. In addition, when externally examined through a scanning electron microscope, no external damage was observed. This leads to the conclusion that folding causes internal damage of the fibers [20]. The internal damage that was caused was predicted to be an increase in the internal flaw density that all aramid fibers contain. These defects are due to tiny “needle like internal voids having approximately 2.4 nm diameters and length of 30 nm which are connected to each other through cracks or openings between micro fibrils” [21]. Folding creates an increase in the flaw density, which in turn causes a “higher probability of the fiber to form a critical flaw big enough to fracture the fiber as the tensile stress increases” [20]. FIGURE 6 UV AND VISIBLE LIGHT EFFECT ON KEVLAR® [4] Day-to-Day Degradation There are many factors, most of them being environmental, that affect the strength of bullet proof vests. One factor that is not environmental is the effect of folding on aramid fibers. The specific type of folding in body armor that can cause its degradation is the bending of the armor around joint areas that occur due everyday movement. In fact, a simple estimation is that “a body armor user might bend at the wait (e.g., when entering or exiting a vehicle) 4 times per hour, 40 hours per week, 50 weeks per year, which would result in 8,000 folding cycles per year, or 40,000 folding cycles over 5 years” [19]. This estimate is consistent with the daily activity that may be seen by a police officer; however this may not be consistent with the amount of activity that an active duty soldier would perform. In this case, a much higher activity level would be observed, leading to more movement and more eventual folding of body armor. Because the movement cannot be measured accurately based on a simple statistical analysis, the activity level of police officers will be considered. Now that it is seen how many times a piece of armor may be folded, it is safe to assume that this factor cannot be ignored and that a way to determine how much effect folding has on body armor but be found. One study was carried out by J.H. Kim, N. Brandenburgh, W. McDonough, W. Blair, and G.A. Holmes, in which 50 fibers of polybenzoxazole (PBO), a common aramid fiber, were folded once each. Before and after each fold, the single fibers were tested to find their strain-tofailure ratio. It was found that after just a single fold, there was a reduction in the strain-to-failure ratio by 10% [20]. FIGURE 7 EVIDENCE FOR THE DECREASE OF TENSILE STRENGTH AS CYCLES OF FOLDING INCREASE [15] As a result, it can be seen that the folding of aramid fibers through everyday use can cause a massive decrease in the strength of ballistic vests. This is a flaw that has not been overcome and is definitely one that should be looked into further. According to the calculations made, it could be possible for a vest to decrease in strength over the course of 10 years up to 41% and in the course of one year over 14% simply to the everyday movement [20]. Of course, these time estimates are based on the activity level of a police officer. As stated earlier, in the case of an active duty soldier, the level of activity would be much higher and thus 5 Jann Grovogui Rachel Rohr lead to a faster rate of body armor degradation, possibly within the time of a single tour of duty, leading to much less protection for those serving on the front lines. Because of this great weakness in the properties of aramid fibers, it is important for engineers to continue research and development in order to not let body armor wearers enter dangerous situations with the false assumptions that they are protected. In addition to problems with the material itself, a vital aspect of body armor that needs to be reevaluated is a relatively simple one: covering the body. Due to the need for movement, ballistic vests cannot provide complete protection. “In firearms assaults on officers, bullets may strike in vital regions not protected by body armor, notably the shoulder, underarm, and the gap between the front and back armor panels. If a bullet strikes close to the edge of the body armor panel, it can slide off the armor panel or backing and penetrate the torso” [2]. Because parts of the body are left exposed, multiple deaths occur each year even when body armor is worn, most of which include gunshots to the head or upper torso [7]. This separation forces wearers to choose one type of protection over the other. Bullet proof vests, which are characterized by superb protective abilities from gunfire, “may not be completely effective against attack by a knife or other sharp instrument, such as an ice pick” [7]. Unfortunately, bullet proof vests do not even protect against all bullets, let alone these other dangers. Five types of bullet proof vests exist because not one of these can protect against all potential projectiles. Though police typically face lower velocity 9mm bullets in their line of work (for which type IIA body armor is adequate), should a high-tense barricade confrontation arise, their daily bulletproof vests will not be suitable for the job. In these situations, “officers have died from wounds received from weapons or ammunition exceeding the rated protection of the armor” [10]. Leaving officers and other military personnel more susceptible to blunt force trauma, stabbings, and other projectiles for which their vests are not designed is therefore a huge ethical issue. Every day, Chief of Police and Commanding Officers send their men and women into harm’s way partly unprotected. Not only should these men and women understand that, but also developments should be made in body armor to allow them as much protection as possible. Lack of Education CONTINUING DEVELOPMENT Since so many actions and environments could deteriorate bullet proof vests, there is a strong need for users to be educated about proper use. Though all vest companies provide information about how to best maintain the quality of their products, those using them often do not take careful note [7]. For example, each model of armor has clear instruction about how to clean the components. Inserts of body armor should typically be cleaned with cold water and a sponge. If soap is used, it must be removed completely, as it “prohibits the accumulation of residual soap film, which can absorb water and reduce the protective properties” [7]. Directions are also clear to say that body armor should be regularly checked for signs wear; should the user choose to ignore this step, they may be entering harmful situations with potentially faulty defense. As of January 2012, soft body armor has saved the lives of more than 3,000 members of law enforcement alone since the 1970’s, let alone the military personnel who use the same body armor on a daily basis [22]. Soft body armor, which was developed through the use of Kevlar®, is used by these two groups because of its strength and comfort compared to alternative body armor materials, especially much heavier, less flexible hard body armor. Since the development of the first aramid fiber in 1965, numerous stronger fibers have been created such as Dyneema® and Twaron® which have led to body armor improvements [11]. However, developments cannot stop there. More research into possible fiber enhancements needs to be explored, such as the inclusion of sheer thickening fluid into the woven fabrics. Further, new research into maintaining the strength of fibers in all environments should be completed, allowing for maximum protection throughout a longer period of time. Temperature resistance, ability to withstand all acidities, endurance through exposure to UV and visible light, and flexibility while maintaining strength are all areas which need improvements. Ultimately, body armor comes down to saving lives. “Of the approximately 1,200 officers killed in the line of duty since 1980, more than 30% could have been saved by body armor” [4]. With continued developments, body armor can save an even great number of people who risk their lives to protect others. Lack of Coverage Protection Against Alternative Attacks Possibly the most significant topic of education is guaranteeing that ballistic vest users understand what exactly their vests protect against. Today, law enforcement and military troops face various types of threats. Companies have created protective vests for many of these; in addition to bullet proof vests, stab, bite, and blunt force trauma vests all exist. 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Available: http://galenet.galegroup.com/servlet/BCRC?srchtp=adv&c=1&ste=31&tbst =tsVS&tab=2&aca=nwmg&bConts=2&RNN=A148197353&docNum=A1 48197353&locID=upitt_main (2012). “Aromatic Substitution Reactions.” Michigan State University. [Online]. Available: http://www2.chemistry.msu.edu/faculty/reusch /virttxtjml/benzrx1.htm (2011). “Kevlar® Reference Designs for Vests made with DuPont™ Kevlar®/Kevlar® XP™.” DuPont. [Online]. Available: http://www2.dupont.com/Kevlar/en_US/assets/downloads/DSP_ KevlarXP_ReferenceDesigns_K23338.pdf ACKNOWLEDGMENTS We would like to thank Nick Andes for helping us to develop our conference paper, as well as our Co-Chair Caroline Repola. Also, thank you to Hans Mattingly for his feedback throughout this process. 7