SUPA Forensics Fiber Analysis • Natural fibers: fibers derived entirely from animal or plant sources • Man-made fibers: fibers derived from either natural or synthetic polymers; the fibers are typically made by forcing the polymeric material through the holes of a spinneret • Polymer: a substance composed of a large number of atoms. These atoms are usually arranged in repeating units or monomers • Molecules: two or more atoms held together by chemical bonds • Macromolecule: a molecule with a high molecular mass • Monomer: the basic unit of structure from which a polymer is constructed Natural Fibers Natural Fibers Are ... • Nonthermoplastic – do not soften when heat is applied • Particularly susceptible to microbial decomposition (mildew & rot) – cellulose based • decomposed by aerobic bacteria & fungi – protein based • decomposed by bacteria and molds • moths, carpet beetles, termites, silverfish Natural Fibers • Classified according to their origin – vegetable or cellulose based – animal or protein based – mineral class • asbestos WOOL Microscopic images of wool fibers Wool Cotton Cotton • Cotton fiber, once it has been processed to remove seeds and traces of wax, protein, etc., consists of nearly pure cellulose, a natural polymer. • Cotton production is very efficient, in the sense that ten percent or less of the weight is lost in subsequent processing to convert the raw cotton bolls (seed cases) into pure fiber. • The cellulose is arranged in a way that gives cotton fibers a high degree of strength, durability, and absorbency. Cotton Micrograph Spider Silk Spinnerets http://science.howstuffworks.com/spider2.htm Spider Silk Spinnerets • Scientists don't know exactly how spiders form silk, but they do have a basic idea of the spinning process. Spiders have special glands that secrete silk proteins (made up of chains of amino acids), which are dissolved in a waterbased solution. The spider pushes the liquid solution through long ducts, leading to microscopic spigots on the spider's spinnerets. Spiders typically have two or three spinneret pairs, located at the rear of the abdomen. Artificial Fibers and Polymeric Fibers Polymers Long strings of repeating chemical units – poly (many) – mer (unit) Fibers are Polymers Cellulose Based Fibers • Cotton • Jute – sacks & bags • burlap – backing for tufted carpets & hooked rugs • Oriental rugs – twines & ruff cordage Protein Based Fibers • More vulnerable to environmental degradation than cellulose based fibers • Wool (sheep) • Mohair (goat) – fiber structure similar to wool • half the scales of wool • scales lie flat (smooth surface) • <1% of fibers have a medulla • Silk Helical Proteins • Based on alpha-keratin A Hair Fiber Sheet Proteins • Based on beta-keratin Mineral Polymers • Asbestos – any of several minerals that readily separate into long, flexible fibers • Chrysotile (hydrous magnesium silicate) – Mg3Si2O5(OH)4 – formerly used in • shingles • insulation • cement pipes Man/Woman-Made Fibers Man-Made Fibers • Regenerated Fibers – derived from naturally occurring polymers • rayon • acetate • Synthetic Fibers – made of polymers that do not occur naturally • polyesters • polyamides Polymers are fibers too! • Polymers arranged in fibers like this can be spun into threads and used as textiles. The clothes you're wearing are made out of polymeric fibers. So is carpet. So is rope. Here are some of the polymers which can be drawn into fibers: Polyethylene • Polypropylene • Nylon • Polyester • Kevlar and Nomex • Polyacrylonitrile • Cellulose • Polyurethanes Polyesters • Polyethylene terephthalate (PET) – X=O – can be melt-spun into very practical and cheap fibers • Dacron • Clothing, furnishings, carpets, tire cord PET Polyamides • Polyhexamethylene adipamide (Nylon 6,6) – X= NH – synthesized from adipic acid and hexamethylenediamine – each contain six carbon atoms • Nylon 6 or Nylon 6,6 • Apparel, carpets, and tire cord Nylon 6,6 Hx of Nylon • Nylons are one of the most common polymers used as a fiber. • Nylon is found in clothing all the time, but also in other places, in the form of a thermoplastic. • Nylon's first real success came with it's use in women's stockings, in about 1940. They were a big hit, but they became hard to get, because the next year the United States entered World War II, and nylon was needed to make war materials, like parachutes and ropes. But before stockings or parachutes, the very first nylon product was a toothbrush with nylon bristles. http://www.pslc.ws/mactest/nylon.htm NYLON examples Fishing net rope backpack Dog harness Nylon Polarizing microscope image of a nylon fiber. TEM Nylon 6 SEM Nylon 6 400 mcm Nylon strength • In that case I suppose I can tell you that fibers have their drawbacks. While they have good tensile strength, that is, they're strong when you pull or stretch them, they usually have bad compressional strength, that is, they're weak when you try to squash or compress them. Also, fibers tend to be strong only in one direction, the direction in which they're oriented. If you pull in them in the direction at right angles to their orientation, they tend to be weak • Nylons are also called polyamides, because of the characteristic amide groups in the backbone chain. • Proteins, such as the silk nylon was made to replace, are also polyamides. These amide groups are very polar, and can hydrogen bond with each other. Because of this, and because the nylon backbone is so regular and symmetrical, nylons are often crystalline, and make very good fibers Nylon 6,6 The nylon in the pictures on this page is called nylon 6,6, because each repeat unit of the polymer chain has two stretches of carbon atoms, each being six carbon atoms long. Other nylons can have different numbers of carbon atoms in these stretches. Making Nylon 6,6 Polyesters • Polyesters have hydrocarbon backbones which contain ester linkages, hence the name. Polyester as a fiber • The ester groups in the polyester chain are polar, with the carbonyl oxygen atom having a somewhat negative charge and the carbonyl carbon atom having a somewhat positive charge. The positive and negative charges of different ester groups are attracted to each other. This allows the ester groups of nearby chains to line up with each other in crystal form, which is why they can form strong fibers TEM Polyester Woven Aromatic Polyesters (Aramids) • Flexible CH2 groups replaced by rigid aromatic rings • High melting • Flame retardant clothing, bullet-poof vests, tire cord Nomex and Kevlar • Aramids are a family of nylons, including Nomex® and Kevlar®. Kevlar® is used to make things like bullet proof vests and puncture resistant bicycle tires. I suppose one could even make bullet proof bicycle tires from Kevlar® if one felt the need. Nomex and Kevlar • Blends of Nomex® and Kevlar® are used to make fireproof clothing. Nomex® is what keeps the monster truck and tractor drivers from burning to death should their fire-breathing rigs breathe a little too much fire. Thanks to Nomex®, an important part of American culture can be practiced safely. • Firefighters turnout gear Kevlar • Kevlar® is a polyamide, in which all the amide groups are separated by paraphenylene groups, that is, the amide groups attach to the phenyl rings opposite to each other, at carbons 1 and 4. Kevlar • Kevlar is the DuPont Company's brand name for material made out of synthetic fiber of polyparaphenylene terephthalamide which is constructed of para-aramid fibers that the company claims is five times stronger than the same weight of steel, while being lightweight, flexible and comfortable. • It is also very heat resistant and decomposes above 400 °C without melting Kevlar Hx and uses • It was invented by Stephanie Kwolek of DuPont from research into high performance polymers, and patented by her in 1966 and first marketed in 1971. Kevlar is a registered trademark of E.I. du Pont de Nemours and Company. • Originally intended to replace the steel belts in tires, it is probably the most well known name in soft armor such as bulletproof vests. • It is also used in extreme sports equipment, high-tension drumhead applications, animal handling protection, composite aircraft construction, fire suits, yacht sails, as an asbestos replacement, sometimes in loudspeaker cones, and recently, even in R/C model helicopter blades. Kevlar Nomex Nomex Cellulose • Cellulose is one of many polymers found in nature. Wood, paper, and cotton all contain cellulose. Cellulose is an excellent fiber. Wood, cotton, and hemp rope are all made of fibrous cellulose. • Cellulose is made of repeat units of the monomer glucose. This is the same glucose which your body metabolizes in order to live, but you can't digest it in the form of cellulose. Because cellulose is built out of a sugar monomer, it is called a polysaccharide. Cellulose Regenerated Fibers • Fibers consisting of both natural and artificial components Manufacture of Synthetic Fibers • Melted or dissolved polymer is forced through fine holes of a spinnerette – Similar to a bathroom showerhead • A fine filament is produced Manufacture of Synthetic Fibers • polymer molecules are aligned parallel to the length of the filament • crystallinity • imparts stiffness & strength Wood Cellulose Wet structure Synthetic fibers are the result of extensive research by scientists to increase and improve upon the supply of naturally occurring animal and plant fibers that have been used in making cloth and rope. In general, synthetic fibers, or man-made fibers, are created by forcing, usually through extrusion, fiber forming materials through holes (called spinnerets) into the air, forming a thread. Common synthetic fibers include: Rayon (1910) (an artificial fiber, but not truly synthetic) Acetate (1924) Nylon (1939) Modacrylic (1949) Olefin (1949) Acrylic (1950) http://en.wikipedia.org/wiki/Synthetic_fiber Polyester (1953) PLA (2002) Specialty synthetic fibers include: Vinyon (1939) Saran (1941) Spandex (1959) Vinalon (1939) Aramids (1961) - known as Nomex, Kevlar and Twaron Modal (1960's) PBI (Polybenzimidazole fiber) (1983) Sulfar (1983) Lyocell (1992) Fibers comparison methods Microscopic Comparison • • • • Color Diameter Lengthwise striations on surface Pitting with delustering particles – TiO2 – reduces shine Dye Composition • Visible Light Microspectrophotometry – non-destructive – fiber mounted on a microscope slide • Chromatographic separation of dye components – dye extracted from fiber with solvent – TLC of questions extract vs. control extract Manufacture of Synthetic Fibers Fiber Composition • Attempts to place fiber into both a broad generic class & a subclass • Many man-made fibers exhibit birefringence – light passing through fiber emerges as two rays • one parallel to fiber length • one perpendicular to fiber length • Table 8-2 Nylon 6 Nylon 6, 10 Collection of Fiber Evidence Collection of Fiber Evidence • Investigator must identify & preserve potential fiber “carriers” • Clothing items are packaged individually in paper bags – different items must not be placed on the same surface before being bagged • Tape lifts of exposed skin areas of bodies & inanimate objects Collection of Fiber Evidence • If fibers must be removed from an object – clean forceps – fold fiber into a small sheet of paper – store in paper bag Collection of Fiber Evidence • Fibers are gathered at a crime scene with tweezers, tape, or a vacuum. • They generally come from clothing, drapery, wigs, carpeting, furniture, and blankets. • For analysis, they are first determined to be natural, manufactured, or a mix of both. Narrow it down • Natural fibers come from plants (cotton) or animals (wool). • Manufactured fibers are synthetics like rayon, acetate, and polyester, which are made from long chains of molecules called polymers. • To determine the shape and color of fibers from any of these fabrics, a microscopic examination is made. Non-invasive first • Generally, the analyst gets only a limited number of fibers to work with—sometimes only one. • Whatever has been gathered from the crime scene is then compared against fibers from a suspect source, such as a car or home, and the fibers are laid side by side for visual inspection through a microscope. Microscopy • A compound microscope uses light reflected from the surface of a fiber and magnified through a series of lenses, while the comparison microscope (two compound microscopes joined by an optical bridge) is used for more precise identification. Spectrophotometry • Another useful instrument is the spectrometer, which separates light into component wavelengths. • In 1859, two German scientists discovered that the spectrum of every organic element has a uniqueness to its constituent parts. • By passing light through something to produce a spectrum, the analyst can read the resulting lines, called "absorption lines." That is, the specific wavelengths that are selectively absorbed into the substance are characteristic of its component molecules. • Then a spectrophotometer measures the light intensities, which yields a way to identify different types of substances. Microscope + Spectrophotometer = Microspectrophotometer • A combination of these instruments for the most effective forensic analysis is the micro-spectrophotometer. • The microscope locates minute traces or shows how light interacts with the material under analysis. • Linking this to a computerized spectrophotometer increases the accuracy. The scientist can get both a magnified visual and an infrared pattern at the same time, which increases the number of identifying characteristics of any given material Step 1 • The first step in fiber analysis is to compare color and diameter. • If there is agreement, then the analysis can go into another phase. • Dyes can also be further analyzed with chromatography, which uses solvents to separate the dye's chemical constituents. • Under a microscope, the analyst looks for lengthwise striations or pits on a fiber's surface, or unusual shapes--as with the one short and two long arms of the trilobal fibers in the Williams case. CASE STUDY Fibers and Probability Theory Wayne Williams Case • From 1979 to 1981, someone was killing Atlanta's youth. More than twenty-five black males, some as young as nine, had been strangled, bludgeoned or asphyxiated. A few females were killed and some children were just missing, but all potential leads turned into dead ends. The only real clue---which was valuable only if a suspect surfaced---was the presence on several of the bodies and their clothing of some kind of fiber threads. A few also bore strands of what was determined to be hair from a dog. These specimens were all sent to the Georgia State Crime Laboratory for analysis, and technicians there isolated two distinct types: a violet-colored acetate fiber and a coarse yellow-green nylon fiber with the type of tri-lobed (three branch) qualities associated with carpets. They searched unsuccessfully for the manufacturer. Wayne Williams Case • Since the unknown predator seemed to favor the Chatahoochee River, the police set up a stakeout. • On May 22, 1981, this strategy appeared to pay off. In the early morning hours, the stakeout patrol heard a loud splash. Someone had just thrown something rather large into the river. • On the James Jackson Parkway Bridge, they saw a white Chevrolet station wagon, and when they stopped it, they learned that the driver's name was Wayne Williams. He was a 23 year-old black photographer and music promoter. They questioned him, but when he said he'd just dumped some garbage they let him go. • (Later he would claim that he'd come there to see the stakeout, having heard about it from friends in the police force.) • Only two days later, the police found what they believed had been the source of the splash---the body of 27-year-old Nathaniel Cater. He was dredged up about a mile from the bridge, and despite his murderer's carefulness, a single yellowgreen carpet fiber was found in his hair. • The police got a search warrant for Wayne Williams' home and car, and the search turned up a valuable piece of evidence: The floors of Williams' home were covered with yellow-green carpeting, and he also had a dog. • Comparisons from the samples removed from the victims showed good consistency with Williams' carpet. • Although Williams claimed to have an alibi, the description he gave of his movements the night they found him on the bridge was partly false and partly unsubstantiated. Three separate polygraph tests indicated deception on Williams' part. • Then FBI experts analyzed samples from his rugs. With special equipment, and in consultation with Du Pont, they managed to ascertain that the fibers came from a Boston-based textile company. • The fiber was called Wellman 181B and it had been sold to numerous carpet companies. Each uses its own dye, so that made it possible to narrow down the likely source, which was the West Point Pepperell Corporation in Georgia. Their "Luxaire English Olive" color matched that found in Wayne William's home. • There were also similarities between the hair from Williams' dog and the dog hair found on several victims. Too good to be true • However, many other homes had this carpeting installed, too. • Thus, it had to be determined just how likely it was that Williams' carpeting was unique enough to persuade a jury of his connection to the murders. • The next step was calculating the odds. • A look into company records turned up information that they had only made that type of carpet during a one-year span of time, with over 16,000 yards of carpet distributed throughout the South. • In comparison with the total amount of carpet distributed across the country, this was a very small sample. That made the statistical probability of the carpet being in any one person's home to be slight, if it could be assumed that Luxaire English Olive had been fairly evenly distributed. • Altogether they figured that around eighty-two homes in Georgia were carpeted with Luxaire English Olive. That meant the odds were stacked against finding many homes in Atlanta: 1 in 7792. • To make their case, the prosecution relied on only two of the twenty-eight suspected murders---the one from the river, Nathaniel Cater, and another recovered in the same general area a month before, Jimmy Ray Payne • A single rayon fiber had been found on his shorts, which was consistent with the carpeting in Williams' station wagon. • In this second case, statistical probability was also employed. With Chevrolet's help, the investigators determined that there was a 1 in 3,828 chance that Payne had acquired the fiber via random contact with a car that had this carpeting installed. Math is good • When the odds in both cases were multiplied, the law of probability that both men could have picked up these fibers in places other than Williams' home and car came out to 1 in almost 30,000,000. That seemed pretty staggering. • The prosecution also introduced into evidence the fibers found on the bodies of ten of the other victims (allowed in Georgia courts), which also matched those in Williams' car or home. • These, they claimed, showed a pattern, and taken altogether, it increased the odds in the fiber evidence into numbers that no one could even comprehend. • In total, there were 28 fiber types linked to Williams. • In addition, several witnesses had come forward to place Williams with some of the victims, and others claimed to have seen suspicious scratches on Williams' arms. • After only twelve hours, the jury returned a guilty verdict, with two life sentences. The police announced that twenty-two of the unsolved murder cases were now closed, despite the fact that there was no real proof for those victims. • Subsequently the Williams conviction has become controversial. To understand this, let's look at how fiber analysis is done. Fiber Analysis • Cross transfers of fiber often occur in cases in which there is person-to-person contact, and investigators hope that fiber traceable back to the offender can be found at the crime scene, as well as vice versa. • Success in solving the crime often hinges on the ability to narrow the sources for the type of fiber found, as the prosecution did with their probability theory on the fibers in the Williams case. • The problem with fiber evidence is that fibers are not unique. • Unlike fingerprints or DNA, they cannot pinpoint an offender in any definitive manner. There must be other factors involved, such as evidence that the fibers can corroborate or something unique to the fibers that set them apart. For example, when fibers appeared to link two Ohio murders in the 1980s, it was just the start of building a case, but without the fibers, there would have been no link in the first place. Kristen Lea Harrison • In 1982, Kristen Lea Harrison was abducted from a ball field in Ohio and her body was found six days later some thirty miles away. She had been raped and strangled. • Orange fibers in her hair looked suspiciously like those that had been found on a twelve-year-old female murder victim from eight months earlier in the same county. • Since they were made of polyester and were oddly shaped (trilobal), forensic scientists surmised that it was carpet fiber. In addition, a box found near Kristin's body and plastic wrap around her feet indicated that the killer had once ordered a special kind of van seat, but then leads dried up. Kristen Lea Harrison • Some time later, a 28 year-old woman was abducted and held prisoner in a man's home. He tortured her and appeared to be intent on killing her. When he left, she escaped and reported him. • Police noticed that he had a van similar to the one into which Kristin had been forced. It proved to have orange carpeting that matched the fibers in her hair. The color was unique, which allowed scientists to trace it to a manufacturer who supplied information about its limited run. • Apparently only 74 yards of it had been shipped to that area of Ohio. That helped to narrow down possibilities. Other evidence established a more solid link and Robert Anthony Buell was eventually convicted.