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Forensic polymer engineering

From Wikipedia, the free encyclopedia

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.

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.

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  • A cut above the rest? - Manufacturing lawnmowers (1/2)
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  • Nanofiltration and Reverse Osmosis in Water Treatment - Course Introduction

Transcription

We regard ourselves as being pioneers in our type of industry and pioneers in developing new manufacturing techniques and taking them to their ultimate. Flymo's success in developing air-cushion mowers has come from this attitude, evidence in their injection moulding techniques and in centralising their polymer processes on one site for automatic manufacture. Polymers are figuring more and more in new products and concepts and a knowledge of polymer engineering is absolutely essential. When competition is fierce and margins are slim, the use of polymers has given this particular company an added advantage both in terms of design for function and ease of processing to shape. In a moment we'll be looking at the application of both ideas to a specific product. We'll also be looking at the way polymer processes can be readily adapted for rapid, automatic production. As the series progresses we'll come to many factories like this one to look at both good practice and new ideas in action. The start of any design exercise is selecting the right material for the job. This is an example of one of the earliest air-cushion lawnmowers made. It was heavy, it was rather noisy in use because of the steel vibration, and it was relatively unattractive. It had problems with corrosion initiated by impacts caused by stones being thrown up against the side of the hood. It's pretty basic in its construction. The steel hood had a great number of limitations which included such things as the number of operations that had to be carried out once it was pressed to make it acceptable for assembly. For example, things like these lugs that locate the handle had to be attached on by welding, holes that had to be drilled and tapped and so on. The painting process was expensive and time consuming and we found that the demand was being stifled because of the manufacturing problems associated mainly with the deck. The next material Electrolux tried was GRP, here being used to produce motor car bodies. Being lighter than steel and less noisy, it gave the designers more freedom. But it still had limitations. It needed trimming and painting and a number of parts still had to be produced separately and then attached, so increasing assembly costs. But above all, production rate was too slow and couldn't meet demand. So what was the solution? Fortunately in the early '70s, Borg-Warner, Corporated in America came up with a grade of ABS thermoplastic which offered us a number of interesting properties for hood manufacture. So what are these properties? Well, the hood must be light enough to ride the air cushion without using a high-powered motor. It must also be stiff enough to support the motor internally. And tough enough to withstand external impacts as well as internal impacts from objects thrown up by the spinning blade. The problem is that a material like polystyrene is brittle. But if rubber particles are added to the polymerisation stage, a material with much improved properties results. The polybutadiene particles increase the toughness of the material and if a mixture of styrene and acrylonitrile monomer is used for the reaction the resultant polymer is known as acrylonitrile butadiene styrene or ABS. This is how the raw material arrives in the factory in a one-ton container. This bin is actually worth £1,200. In its virgin state, the raw material comes in the form of granules. It's worth twice as much as polypropylene and over five times as much as mild steel. So at this cost, what are the advantages? The big advantage to the user is that the part is much lighter and he's able to manoeuvre it over the lawn very much easier. The advantages to us, the manufacturers, of course, are even greater. The processing is much easier with ABS. As you can see, all these fairly intricate details can be moulded into the hood design to enable the assembly to be made cheaply and quickly. We use a stylo acrylonitrile to give us transparency in this lens application here. There are other polymers such as polyamide 6 and 66, polypropylene of various types, high-density polythene, polycarbonate and a number of other minor ones. So Flymo have chosen a particular set of polymers for their specific properties in their main product. The main component is the ABS hood and it is essential to know how the finished component behaves under in-service conditions. The most critical test is to withstand flying objects thrown up by the blade onto the inside of the hood. Steel ball bearings are loaded into a pipe which leads to the underside of the mower. 50 such balls will be shot successively into the spinning blade by compressed air. Production testing is conducted on an audit basis from regular production runs and a small sample are tested to destruction. If the material behaves in a brittle fashion and the ball penetrates the hood, the failure will mean that the entire batch of that particular run will have to be rejected. This is the result of the test. And on the inside edge of the hood you can see the indentations produced by the impact from the ball bearings. There's also quite a lot of damage to the metal blade of the impellor. On the outside edge of the hood you can see the phenomenon known as strain whitening which is produced by a ductile response of the ABS. So we've looked at the advantages of polymers in design for function and how these designs are tested. But what about the process they chose to produce the ABS hood? They needed precise detail and rapid production which they felt was only provided by injection moulding. This is one of 57 injection moulding machines used by Flymo to make their products. At the moment it's making one of their largest volume products, the hood for the Minimow. The projected area of the hood is relatively large so they need a 500-ton locking force machine to make it. Granules of ABS are added to the hopper. From there it is both mixed and heated to temperature by the shearing action of the screw. Aided by electrical heating, it reaches about 130 degrees centigrade above its glass transition temperature where its consistency is toffee-like. As the material moves down the barrel, it pushes the screw back until there is enough material ready for injection. At that point the screw behaves as a ram. The polymer viscosity drops to that of a thin syrup. The gate is opened and the molten polymer pushed through into the cool, steel mould. After cooling it can be removed ready for the next stage in the cycle. Such a machine can mould a variety of different shapes simply by changing the tool. It's this facility which allows a company to make a whole range of different products. This is one of the largest mouldings produced by Flymo, in this case for a two-wheeled, rotary mower. There's some intricate detail, particularly around the support for the impellor blade and this particular moulding also incorporates a re-entrant angle at the start of the grass-collecting duct. Yet the whole moulding only weighs 20 kilograms. It replaced an aluminium die casting which weighed over three times as much. This is the metal mould from which the hood was made. Hot molten polymer is squirted down the central runner and subdivided via 12 gates to the periphery of the mould itself. The grass-collecting duct forms a re-entrant angle at this point where a massive retractable core can be operated by a joint motor at the outside edge of the tool. The combination in improved production rate using injection moulding together with the weight saving led to a plastic moulding which was less than a quarter of the price of its aluminium equivalent. This tool is actually quite simple in concept. A much more complex problem arises when a moulder wishes to produce more than one component from just one tool. At Flymo they solved this problem using a technique known as computer aided design to produce three components in this one tool. Essentially the problem is one of achieving a uniform flow of polymer into the three quite different shaped cavities in the tool. The solution to the problem was to calculate the right gate size to feed polymer into each of the three different cavities. The success of this technique applied to this particular problem can be judged by the fact that the very first production run was entirely successful. But of course tool design is only one aspect of injection moulding. Injection moulding machines have to work efficiently and effectively throughout 24 hours of the day in a much larger manufacturing environment. Production runs from each mould may vary from 2,000 to 20,000 or more. So an important aspect of smooth production is the ability to change moulds relatively quickly and adjust the conditions for each moulding. Once a machine has been set up for a specific moulding, by fine tuning of the temperature, the position, the pressure, the timing and all the other variables which affect the mould cycle, conditions can be reset automatically using this program card which can be inserted into the microprocessor control console like this.

Methods of analysis

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

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

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

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

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

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

References

  • Peter R Lewis and Sarah Hainsworth, Fuel Line Failure from stress corrosion cracking, Engineering Failure Analysis,13 (2006) 946–962.
  • Lewis, Peter Rhys, Reynolds, K, Gagg, C, Forensic Materials Engineering: Case studies, CRC Press (2004).
  • Wright, D.C., Environmental Stress Cracking of Plastics RAPRA (2001).
  • Ezrin, Meyer, Plastics Failure Guide: Cause and Prevention, Hanser-SPE (1996).
  • Lewis, Peter Rhys, Forensic Polymer Engineering: Why polymer products fail in service, 2nd Edition, Elsevier-Woodhead (2016).
This page was last edited on 10 May 2024, at 00:26
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