Forensic polymer engineering

Last updated
Appearance of real linear polymer chains as recorded under liquid medium using an atomic force microscope Single Polymer Chains AFM.jpg
Appearance of real linear polymer chains as recorded under liquid medium using an atomic force microscope

Forensic polymer engineering is the study of failure in polymeric products. The topic includes the fracture of plastic products, or any other reason why such a product fails in service, or fails to meet its specification. The subject focuses on the material evidence from crime or accident scenes, seeking defects in those materials that might explain why an accident occurred, or the source of a specific material to identify a criminal. Many analytical methods used for polymer identification may be used in investigations, the exact set being determined by the nature of the polymer in question, be it thermoset, thermoplastic, elastomeric or composite in nature.

Contents

One aspect is the analysis of trace evidence such as skid marks on exposed surfaces, where contact between dissimilar materials leaves material traces of one left on the other. Provided the traces can be analyzed successfully, then an accident or crime can often be reconstructed.

Methods of analysis

IR spectrum showing carbonyl absorption due to oxidative degradation of polypropylene Irspec1.jpg
IR spectrum showing carbonyl absorption due to oxidative degradation of polypropylene

Thermoplastics can be analysed using infra-red spectroscopy, ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy and the environmental scanning electron microscope. Failed samples can either be dissolved in a suitable solvent and examined directly (UV, IR and NMR spectroscopy) or be a thin film cast from solvent or cut using microtomy from the solid product. Infra-red spectroscopy is especially useful for assessing oxidation of polymers, such as the polymer degradation caused by faulty injection moulding. The spectrum shows the characteristic carbonyl group produced by oxidation of polypropylene, which made the product brittle. It was a critical part of a crutch, and when it failed, the user fell and injured herself very seriously. The spectrum was obtained from a thin film cast from a solution of a sample of the plastic taken from the failed forearm crutch.

Microtomy is preferable since there are no complications from solvent absorption, and the integrity of the sample is partly preserved. Thermosets, composites and elastomers can often be examined using only microtomy owing to the insoluble nature of these materials.

Fracture

Fractured products can be examined using fractography, an especially useful method for all broken components using macrophotography and optical microscopy. Although polymers usually possess quite different properties to metals, ceramics and glasses, they are just as susceptible to failure from mechanical overload, fatigue and stress corrosion cracking if products are poorly designed or manufactured.

Scanning electron microscopy or ESEM is especially useful for examining fracture surfaces and can also provide elemental analysis of viewed parts of the sample being investigated. It is effectively a technique of microanalysis and valuable for examination of trace evidence. On the other hand, colour rendition is absent in ESEM, and there is no information provided about the way in which those elements are bonded to one another. Specimens will be exposed to a partial vacuum, so any volatiles may be removed, and surfaces may be contaminated by substances used to attach the sample to the mount.

Examples

Many polymers are attacked by specific chemicals in the environment, and serious problems can arise, including road accidents and personal injury. Polymer degradation leads to sample embrittlement, and fracture under low applied loads.

Ozone cracking

Ozone cracking in Natural rubber tubing Ozone cracks in tube1.jpg
Ozone cracking in Natural rubber tubing

Polymers for example, can be attacked by aggressive chemicals, and if under load, then cracks will grow by the mechanism of stress corrosion cracking. Perhaps the oldest known example is the ozone cracking of rubbers, where traces of ozone in the atmosphere attack double bonds in the chains of the materials. Elastomers with double bonds in their chains include natural rubber, nitrile rubber and styrene-butadiene rubber. They are all highly susceptible to ozone attack, and can cause problems like vehicle fires (from rubber fuel lines) and tyre blow-outs. Nowadays, anti-ozonants are widely added to these polymers, so the incidence of cracking has dropped. However, not all safety-critical rubber products are protected, and, since only ppb of ozone will start attack, failures are still occurring.

Chlorine-induced cracking

chlorine attack of acetal resin plumbing joint Chlorine attack1.jpg
chlorine attack of acetal resin plumbing joint

Another highly reactive gas is chlorine, which will attack susceptible polymers such as acetal resin and polybutylene pipework. There have been many examples of such pipes and acetal fittings failing in properties in the US as a result of chlorine-induced cracking. Essentially the gas attacks sensitive parts of the chain molecules (especially secondary, tertiary or allylic carbon atoms), oxidising the chains and ultimately causing chain cleavage. The root cause is traces of chlorine in the water supply, added for its anti-bacterial action, attack occurring even at parts per million traces of the dissolved gas. The chlorine attacks weak parts of a product, and, in the case of an acetal resin junction in a water supply system, it is the thread roots that were attacked first, causing a brittle crack to grow. The discoloration on the fracture surface was caused by deposition of carbonates from the hard water supply, so the joint had been in a critical state for many months.

Hydrolysis

Most step-growth polymers can suffer hydrolysis in the presence of water, often a reaction catalysed by acid or alkali. Nylon for example, will degrade and crack rapidly if exposed to strong acids, a phenomenon well known to people who accidentally spill acid onto their tights.

Failed fuel pipe at right from road traffic accident Plate7new.jpg
Failed fuel pipe at right from road traffic accident

The broken fuel pipe caused a serious accident when diesel fuel poured out from a van onto the road. A following car skidded and the driver was seriously injured when she collided with an oncoming lorry. Scanning electron microscopy or SEM showed that the nylon connector had fractured by stress corrosion cracking due to a small leak of battery acid. Nylon is susceptible to hydrolysis in contact with sulfuric acid, and only a small leak of acid would have sufficed to start a brittle crack in the injection moulded connector by a mechanism known as stress corrosion cracking, or SCC.

Close-up of broken fuel pipe Broken fuel pipe.jpg
Close-up of broken fuel pipe

The crack took about 7 days to grow across the diameter of the tube, hence the van driver should have seen the leak well before the crack grew to a critical size. He did not, therefore resulting in the accident. The fracture surface showed a mainly brittle surface with striations indicating progressive growth of the crack across the diameter of the pipe. Once the crack had penetrated the inner bore, fuel started leaking onto the road. Diesel is especially hazardous on road surfaces because it forms a thin oily film that cannot be seen easily by drivers. It is akin to black ice in lubricity, so skids are common when diesel leaks occur. The insurers of the van driver admitted liability and the injured driver was compensated.

Polycarbonate is susceptible to alkali hydrolysis, the reaction simply depolymerising the material. Polyesters are prone to degrade when treated with strong acids, and in all these cases, care must be taken to dry the raw materials for processing at high temperatures to prevent the problem occurring.

UV degradation

IR spectrum showing carbonyl absorption due to UV degradation of polyethylene Irspec2.jpg
IR spectrum showing carbonyl absorption due to UV degradation of polyethylene

Many polymers are also attacked by UV radiation at vulnerable points in their chain structures. Thus polypropylene suffers severe cracking in sunlight unless anti-oxidants are added. The point of attack occurs at the tertiary carbon atom present in every repeat unit, causing oxidation and finally chain breakage. Polyethylene is also susceptible to UV degradation, especially those variants that are branched polymers such as LDPE. The branch points are tertiary carbon atoms, so polymer degradation starts there and results in chain cleavage, and embrittlement. In the example shown at right, carbonyl groups were easily detected by IR spectroscopy from a cast thin film. The product was a road cone that had cracked in service, and many similar cones also failed because an anti-UV additive had not been used.

See also

Related Research Articles

<span class="mw-page-title-main">Polymer</span> Substance composed of macromolecules with repeating structural units

A polymer is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass, relative to small molecule compounds, produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures rather than crystals.

<span class="mw-page-title-main">Forensic engineering</span> Investigation of failures associated with legal intervention

Forensic engineering has been defined as "the investigation of failures—ranging from serviceability to catastrophic—which may lead to legal activity, including both civil and criminal". The forensic engineering field is very broad in terms of the many disciplines that it covers, investigations that use forensic engineering are case of environmental damages to structures, system failures of machines, explosions, electrical, fire point of origin, vehicle failures and many more.

<span class="mw-page-title-main">Corrosion</span> Gradual destruction of materials by chemical reaction with its environment

Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials by chemical or electrochemical reaction with their environment. Corrosion engineering is the field dedicated to controlling and preventing corrosion.

<span class="mw-page-title-main">Polymer degradation</span> Alteration in the polymer properties under the influence of environmental factors

Polymer degradation is the reduction in the physical properties of a polymer, such as strength, caused by changes in its chemical composition. Polymers and particularly plastics are subject to degradation at all stages of their product life cycle, including during their initial processing, use, disposal into the environment and recycling. The rate of this degradation varies significantly; biodegradation can take decades, whereas some industrial processes can completely decompose a polymer in hours.

<span class="mw-page-title-main">O-ring</span> Mechanical, toroid gasket that seals an interface

An O-ring, also known as a packing or a toric joint, is a mechanical gasket in the shape of a torus; it is a loop of elastomer with a round cross-section, designed to be seated in a groove and compressed during assembly between two or more parts, forming a seal at the interface.

<span class="mw-page-title-main">Polyoxymethylene</span> Engineering thermoplastic polymer

Polyoxymethylene (POM), also known as acetal, polyacetal, and polyformaldehyde, is an engineering thermoplastic used in precision parts requiring high stiffness, low friction, and excellent dimensional stability. As with many other synthetic polymers, it is produced by different chemical firms with slightly different formulas and sold variously by such names as Delrin, Kocetal, Ultraform, Celcon, Ramtal, Duracon, Kepital, Polypenco, Tenac and Hostaform.

Failure causes are defects in design, process, quality, or part application, which are the underlying cause of a failure or which initiate a process which leads to failure. Where failure depends on the user of the product or process, then human error must be considered.

In organic chemistry, ozonolysis is an organic reaction where the unsaturated bonds are cleaved with ozone. Multiple carbon–carbon bond are replaced by carbonyl groups, such as aldehydes, ketones, and carboxylic acids. The reaction is predominantly applied to alkenes, but alkynes and azo compounds are also susceptible to cleavage. The outcome of the reaction depends on the type of multiple bond being oxidized and the work-up conditions.

Failure analysis is the process of collecting and analyzing data to determine the cause of a failure, often with the goal of determining corrective actions or liability. According to Bloch and Geitner, ”machinery failures reveal a reaction chain of cause and effect… usually a deficiency commonly referred to as the symptom…”. Failure analysis can save money, lives, and resources if done correctly and acted upon. It is an important discipline in many branches of manufacturing industry, such as the electronics industry, where it is a vital tool used in the development of new products and for the improvement of existing products. The failure analysis process relies on collecting failed components for subsequent examination of the cause or causes of failure using a wide array of methods, especially microscopy and spectroscopy. Nondestructive testing (NDT) methods are valuable because the failed products are unaffected by analysis, so inspection sometimes starts using these methods.

<span class="mw-page-title-main">Stress corrosion cracking</span> Growth of cracks in a corrosive environment

Stress corrosion cracking (SCC) is the growth of crack formation in a corrosive environment. It can lead to unexpected and sudden failure of normally ductile metal alloys subjected to a tensile stress, especially at elevated temperature. SCC is highly chemically specific in that certain alloys are likely to undergo SCC only when exposed to a small number of chemical environments. The chemical environment that causes SCC for a given alloy is often one which is only mildly corrosive to the metal. Hence, metal parts with severe SCC can appear bright and shiny, while being filled with microscopic cracks. This factor makes it common for SCC to go undetected prior to failure. SCC often progresses rapidly, and is more common among alloys than pure metals. The specific environment is of crucial importance, and only very small concentrations of certain highly active chemicals are needed to produce catastrophic cracking, often leading to devastating and unexpected failure.

In materials science, environmental stress fracture or environment assisted fracture is the generic name given to premature failure under the influence of tensile stresses and harmful environments of materials such as metals and alloys, composites, plastics and ceramics.

<span class="mw-page-title-main">Embrittlement</span> Loss of ductility of a material, making it brittle

Embrittlement is a significant decrease of ductility of a material, which makes the material brittle. Embrittlement is used to describe any phenomena where the environment compromises a stressed material's mechanical performance, such as temperature or environmental composition. This is oftentimes undesirable as brittle fracture occurs quicker and can much more easily propagate than ductile fracture, leading to complete failure of the equipment. Various materials have different mechanisms of embrittlement, therefore it can manifest in a variety of ways, from slow crack growth to a reduction of tensile ductility and toughness.

<span class="mw-page-title-main">Fractography</span> Study of the fracture surfaces of materials

Fractography is the study of the fracture surfaces of materials. Fractographic methods are routinely used to determine the cause of failure in engineering structures, especially in product failure and the practice of forensic engineering or failure analysis. In material science research, fractography is used to develop and evaluate theoretical models of crack growth behavior.

Applied spectroscopy is the application of various spectroscopic methods for the detection and identification of different elements or compounds to solve problems in fields like forensics, medicine, the oil industry, atmospheric chemistry, and pharmacology.

<span class="mw-page-title-main">Forensic materials engineering</span>

Forensic materials engineering, a branch of forensic engineering, focuses on the material evidence from crime or accident scenes, seeking defects in those materials which might explain why an accident occurred, or the source of a specific material to identify a criminal. Many analytical methods used for material identification may be used in investigations, the exact set being determined by the nature of the material in question, be it metal, glass, ceramic, polymer or composite. An important aspect is the analysis of trace evidence such as skid marks on exposed surfaces, where contact between dissimilar materials leaves material traces of one left on the other. Provided the traces can be analysed successfully, then an accident or crime can often be reconstructed. Another aim will be to determine the cause of a broken component using the technique of fractography.

<span class="mw-page-title-main">Ozone cracking</span> Cracks in many different elastomers due to ozone attack

Cracks can be formed in many different elastomers by ozone attack, and the characteristic form of attack of vulnerable rubbers is known as ozone cracking. The problem was formerly very common, especially in tires, but is now rarely seen in those products owing to preventive measures.

<span class="mw-page-title-main">Environmental stress cracking</span> Brittle failure of thermoplastic polymers

Environmental Stress Cracking (ESC) is one of the most common causes of unexpected brittle failure of thermoplastic polymers known at present. According to ASTM D883, stress cracking is defined as "an external or internal crack in a plastic caused by tensile stresses less than its short-term mechanical strength". This type of cracking typically involves brittle cracking, with little or no ductile drawing of the material from its adjacent failure surfaces. Environmental stress cracking may account for around 15-30% of all plastic component failures in service. This behavior is especially prevalent in glassy, amorphous thermoplastics. Amorphous polymers exhibit ESC because of their loose structure which makes it easier for the fluid to permeate into the polymer. Amorphous polymers are more prone to ESC at temperature higher than their glass transition temperature (Tg) due to the increased free volume. When Tg is approached, more fluid can permeate into the polymer chains.

Polymer stabilizers are chemical additives which may be added to polymeric materials, such as plastics and rubbers, to inhibit or retard their degradation. Common polymer degradation processes include oxidation, UV-damage, thermal degradation, ozonolysis, combinations thereof such as photo-oxidation, as well as reactions with catalyst residues, dyes, or impurities. All of these degrade the polymer at a chemical level, via chain scission, uncontrolled recombination and cross-linking, which adversely affects many key properties such as strength, malleability, appearance and colour.

<span class="mw-page-title-main">Photo-oxidation of polymers</span>

In polymer chemistry photo-oxidation is the degradation of a polymer surface due to the combined action of light and oxygen. It is the most significant factor in the weathering of plastics. Photo-oxidation causes the polymer chains to break, resulting in the material becoming increasingly brittle. This leads to mechanical failure and, at an advanced stage, the formation of microplastics. In textiles the process is called phototendering.

Maciej S. Kumosa is a materials scientist and academic. He is a professor in the Department of Mechanical and Materials Engineering at the University of Denver, and the Director of the Center for Novel High Voltage/Temperature Materials and Structures (HVT).

References