Embrittlement of Nylon in Arid Environments

Steven Bowling 28 Foxwood cct.
Wakerley QLD 4154
28/5/2013
Professor D.J. Mee Head School of Mechanical & Mining Engineering University of Queensland Queensland 4072
Dear Sir, I hereby submit my Thesis titled Embrittlement of Nylon in Arid Environments for consideration as partial fulfillment of the Bachelor of Engineering degree. All the work contained within this Thesis is my original work except where otherwise acknowledged. I understand that this thesis may be made publicly available and reproduced by the University of Queensland unless a limited term embargo on publication has been negotiated with a sponsor.
Yours sincerely
Steven Hugh Francis Bowling Student ID: 40789972
Embrittlement of Nylon in Arid Environments Steven Bowling
Acknowledgements
First and foremost Id like to express my gratitude to my supervisor Assoc Prof Rowan truss, for guiding and mentoring me throughout the duration of my thesis. I have also appreciated the time Glenda Zemanek took teaching me to use the optical microscope and lending me the micrometre callipers. Also Id like to thank Ron Rasch for the excellent SEM session and for showing me the preparation procedures and giving me a tour of the Hawken SEM facility. Im also appreciative of Rob Lude for supplying the Nylon 66 samples which provided the inspiration and basis for this thesis.
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Summary
Nylon 66 parts have been fracturing prematurely while in service in Perth, Australia. This thesis investigates the causes behind their failure using a deductive investigate method similar to that used in polymer forensics. Numerous possible failure modes were explored in the literature, then optical microscopy and scanning electron microscopy (SEM) was performed. Results showed brittle fracture, and supported generalized embrittlement rather than hypothesis of stress concentrations and poor design. It is likely the hygroscopic behaviour of Nylon played significant role in their failure, although further information about these samples and their service conditions is required to be certain.
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Table of Contents
Acknowledgements ..................................................................................................................... i Summary ..................................................................................................................................... ii 1.0 Introduction ..................................................................................................................... 1
1.1 Background .................................................................................................................... 1 1.2 Aim ................................................................................................................................. 1 1.3 Introduction to Nylon..................................................................................................... 1 1.3.1 History ..................................................................................................................... 1 1.3.2 Chemistry and Synthesis ......................................................................................... 1 1.4 Investigative method ..................................................................................................... 4 1.5 Part specifications and nomenclature ........................................................................... 7 2.0 Fractography .................................................................................................................... 8
2.1 Effect of water content on fracture surface ................................................................ 12 3.0 Possible Failure Modes .................................................................................................. 14
3.1 Oxidation ...................................................................................................................... 14 3.2 Hydrolysis ..................................................................................................................... 15 3.3 Hygroscopic Behaviour ................................................................................................ 17 3.3.1 Rate of moisture diffusion ..................................................................................... 17 3.3.2 Solar radiation and moisture loss.......................................................................... 23 3.3.3 Outdoor exposure tests......................................................................................... 24 3.3.5 Degradation caused by humidity .......................................................................... 25 3.4 Environmental stress cracking ..................................................................................... 26 3.5 Other Chemical attack ................................................................................................. 27 3.5.1 Smog and ozone .................................................................................................... 27 3.6 Manufacturing faults .................................................................................................... 28 3.7 Design ........................................................................................................................... 30 3.8 Ductile-to-Brittle Failure Transition ............................................................................. 31 3.9 Mechanical Overload ................................................................................................... 32 3.10 Low Temperatures ..................................................................................................... 32 3.11 Fatigue........................................................................................................................ 33 3.12 Thermal fatigue .......................................................................................................... 34 3.13 Plasticizer loss ............................................................................................................ 34
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3.14 Thermal degradation.................................................................................................. 35 3.15 Thermal oxidative ...................................................................................................... 35 3.16 Temperature and moisture combined ....................................................................... 36 4.0 Environment .................................................................................................................. 36
4.1 Introduction ................................................................................................................. 36 4.2 Rainfall.......................................................................................................................... 37 4.3 Humidity ....................................................................................................................... 38 4.5 Solar exposure.............................................................................................................. 40 4.6 UV Radiation ................................................................................................................ 41 4.7 Temperature cycling .................................................................................................... 42 4.8 Acid Rain....................................................................................................................... 43 5.0 Optical Microscopy Inspections..................................................................................... 44
5.1 Morphology .................................................................................................................. 44 5.2 Factors Effecting Fracture ............................................................................................ 46 6.0 Scanning Electron Microscopy ...................................................................................... 49
6.1 Summary of Procedure ................................................................................................ 49 6.2 Results .......................................................................................................................... 49 7.0 8.0 9.0 Summary ........................................................................................................................ 56 Conclusions .................................................................................................................... 56 Recommendations ......................................................................................................... 58
10.0 References ..................................................................................................................... 61 11.0 Appendix ........................................................................................................................ 69
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Table of Figures
Figure 1 Nylon Synthesis (Adilia, 2006) ...................................................................................... 2 Figure 2 Nylon 6,6 repeat unit and the secondary bonding between polymer chains .............. 2 Figure 3 Stress-Strain graph for dry and conditioned Nyon 66 (BASF, 2003) ............................ 3 Figure 4 Nylon interacting with water (Howe, 2012) ................................................................. 3 Figure 5 General steps involved in failure analysis (Jensen, 2012) ............................................ 5 Figure 6 Basic Dimensions of sample ......................................................................................... 7 Figure 7 Dimensions of backbone cross section ........................................................................ 7 Figure 8 Nomenclature labelled on unbroken sample. On the rear side of each protrusion are 2 small flanges running the length, one on each side. ............................................................... 7 Figure 9 Scanning Electron Microscope (Calvier, 2008) ............................................................. 8 Figure 10 Images show the mirror region at point A with brittle morphology like ridges radiating out from this origin. (Dasari, 2006) ............................................................................. 9 Figure 11 Hackle morphologies (ASM, 2003) ............................................................................. 9 Figure 12 Low magnification SEM micrographs of impact-fracture surfaces of nylon 66. The smooth region at site A is the crack initiation site and the region labelled B represen ts hackle morphology. (Dasari, 2006)............................................................................................. 9 Figure 13Schematic of a craze (Halary et al. 2011) .................................................................. 11 Figure 14 Figure A: Brittle fracture Hackles in Nylon 66, the arrow points in the direction of crack origin. Figure B: Ductile bands in Nylon fracture. (Dasari et al. 2008) ........................... 11 Figure 15 Left: fatigue fracture surface (Brydson, 1999) Right: fatigue crack showing beach marks (Marissen et al. 2005) .................................................................................................... 12 Figure 16 Fracture surface of Nylon 66 at different moisture levels. (a) 0%RH (b) 50%RH (c) 100%RH (Bretz at al. 1979) ....................................................................................................... 12 Figure 17 (a) Fatigue fracture at 50%RH (b) fatigue fracture at 100%RH, the arrest lines are believed to be striations ........................................................................................................... 13 Figure 18 Hydrolysis of Nylon (New World Encylopedia, 2008)............................................... 15 Figure 19 Loss of tenacity of Nylon (N) fibres as a result of exposure to 10% sulphuric acid, compared with PET (T) (ASM, 2013) ........................................................................................ 15 Figure 20 (a) Is a microscopic image of the fracture surface, ch stands for chamfer which acts as a notch. c stands for cusp which protruded up from the sample and was torn in a ductile manner. Image (b) is an SEM micrograph which shows the curved arcs. Image (c) is
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a schematic of the fracture surface, while (d) is a composite of micrograph images to provide better resolution. (Lewis, 2006) ............................................................................................... 16 Figure 21 Dimensions of backbone cross section .................................................................... 18 Figure 22 Water absorption at relative humidity for Nylon. (Brydson, 1999) ......................... 19 Figure 23 Diffusion coefficient for Nylon at various water content. Untreated Nylon is marked (o) ................................................................................................................................ 20 Figure 24 Nylon 55 moisture absorption rate at 23c and 40-80%RH for Nylon with a shape factor =2000 (ASM, 2013) ...................................................................................................... 21 Figure 25 (BOM, 2013) ............................................................................................................. 21 Figure 26 Rate of moisture loss of Nylon over Drierite desiccant (DuPont , 1995) ............... 22 Figure 27Moisture gain in wt% over time (Jia et al. 2004) ....................................................... 23 Figure 28 Effect of outdoor exposure on the percentage loss of breaking strength for Nylon (shown as blue diamond), compared with other polymers. Red triangles is polyester, while the pink squares and green circles are UVR finished Nylon and polyester respectively. (Vikas et al. 2010) ................................................................................................................................ 25 Figure 29 Tensile strength with ageing time for Nylon in 100% relative humidity and argon. Plot A has a linear time scale and plot B is a logarithmic scale. (Bernstein et al. 2005) .......... 26 Figure 30 Chemicals which cause Nylon to permanently loose stiffness and become weak. (DuPont, 2005).......................................................................................................................... 27 Figure 31 Ozone levels at Caversham in Perth (DEP, 1996) ..................................................... 28 Figure 32 Non-hygrscopic resins only collect moisture on the outside of the pellet, whereas hygrscopic resins collect water on the inside as well. (Shah, V. 2007) .................................... 29 Figure 33 Stress concentration factor with fillet radius (DuPont, 1995) ................................. 30 Figure 34 Dimensional changes of Polyamides with varying moisture content (Hoffman, 2000) ......................................................................................................................................... 30 Figure 35 Ductile-Brittle transition ........................................................................................... 31 Figure 36 Effect of Temperature and Moisture on the Modulus of Nylon 6 and Nylon6,6 (Intech, 2012) ........................................................................................................................... 33 Figure 39 TGA of Nylon 66(Perkin Elmer, 2011). ...................................................................... 35 Figure 40 DSC of heat stabilized polyamide 66. (Crompton, 2010) ......................................... 36 Figure 41 (BOM, 2013) ............................................................................................................. 37 Figure 42 Mean relative 9am humidity for 1981-2010 ............................................................ 38
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Figure 43 Mean daily solar exposure (MJ/m2) ......................................................................... 40 Figure 44 Mean daily sunshine hours for Perth airport. Light bars are data for 1993-2013 and dark bars are for the year 2012 only ........................................................................................ 41 Figure 45 UV only (SoDa, 2013) ................................................................................................ 41 Figure 46 Temperature differences for Perth Airport (BOM, 2013) ........................................ 42 Figure 47 Radiation fluxes per unit area of Earths surf ace for a simple greenhouse model (Jacob, D. 1999) ........................................................................................................................ 43 Figure 48 Fracture surface no. 1 of sample C .......................................................................... 44 Figure 49 Fracture surfaces C2, E and B ................................................................................... 45 Figure 50 Images of fracture surfaces are labelled with the designated part letters for each piece they occurred on. ............................................................................................................ 46 Figure 51 Samples G and C with weld lines highlighted ........................................................... 47 Figure 52 Fracture surface of sample H. Fracture occurred close to the base of protrusion rather than at the hypothesised locations of stress concentrations. ...................................... 48 Figure 53 Fracture surface C1 ................................................................................................... 49 Figure 54 SEM photo on the left shows hackle morphology, sample on the right shows much finer ridges called mist. Both photos were taken on surface C1 with same magnification. .. 50 Figure 55 Zoom on the mirror region of surface C1 shows an inhomogeneity. ...................... 50 Figure 56 Spectral results of inhomogeneity on fracture surface C1. The spectra show the inhomogeneity is not pure Nylon 66; rather it has minerals in it. ........................................... 51 Figure 57 Ductile region of sample C1, showing small inhomogeneity ................................... 52 Figure 58 Spectral results of inhomogeneity in ductile cups on sample C1 ............................ 52 Figure 59 Sample A fracture surface of thin protrusion. .......................................................... 53 Figure 60 Sample A ................................................................................................................... 53 Figure 61 Fracture surface C2 ................................................................................................... 54 Figure 62 Voids on the mirror region of sample E. .................................................................. 55 Figure 63 Voids in the mirror region of sample E ..................................................................... 55 Figure 64 (Toray, 2013)............................................................................................................. 59 Figure 65 CES materials section chart ...................................................................................... 59 Figure 66 CES materials selection chart ................................................................................... 60
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1.0 Introduction
1.1 Background
Nylon 6,6 clips used near a road close to Perth airport, Australia have been fracturing prematurely during service. Rob Lude, the director of Plastic Essentials has sent 8 fractured samples along with 3 unbroken samples for investigation.
1.2 Aim
The aim of this thesis is to investigate the cause/s of failure behind the fractures of these Nylon 66 samples. Ideally the cause should be determined, or narrowed down as far as possible based available information about these samples, resources, time and information about Nylon failures in general.
1.3 Introduction to Nylon

1.3.1 History
Nylon was discovered in 1934 by Wallace Hume Carothers (1896 1937) while he was working at DuPont (Smith, 1985). Instead of using the glycols and forming polystyrene, Carothers and his team used amides in place of the glycols and ended up with polyamide. Carothers boss, Elmer K. Bolton played a key role in the discovery and later came up with the name Nylon. Nylon started to be produced industrially by 1938, and the new Nylon stockings were a sensation at the Worlds Fair (CHF). So successful they were that years later in 1945 riots broke out when DuPont was unable to keep up with demand (Smith, 1985).
1.3.2 Chemistry and Synthesis

The term Nylon refers to thermoplastic polymers from the polyamide family. Nylon 6,6 is copolymer, its two monomers each contain 6 carbon atoms which what the 6,6 designation refers to. As its a polyamide its made from an amide hexamethylene diamine - and the other monomer can be adipoyl chloride or Adipic acid. The two monomers combine in a polycondensation reaction, the condensate depends on the second monomer used, for example the reaction with adipoyl chloride results in an HCl condensate. This
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process is a step-growth polymerization, although nylon can also be made using chaingrowth polymerizations; in which case lactams would be used (Odin, 1981)
Figure 1 Nylon Synthesis (Adilia, 2006)
When the two monomers react, a pair of electrons on the nitrogen attacks the carbon on the part of the carboxylic acid group (Aharoni, 1997). A new dimer forms which then reacts with more amine and acid chloride monomers and so on the chain grows (Taylor, 2003). The amide unit on the chain plays a very important role in the materials properties. The nitrile groups are highly polar so strong intermolecular forces develop in the form of hydrogen bonding between chains as shown in figure 6. This results in increased strength, crystallinity and glass transition temperature.
Figure 2 Nylon 6,6 repeat unit and the secondary bonding between polymer chains
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The hydrogen bonding of the amide group is not only Nylons strength, but its Achilles heel as well. The consequences of it could potentially be very relevant to this thesis. Water is also a polar molecule and will hydrogen bond to these nitrile groups; this makes Nylon hygroscopic (Snape, 2008). The absorbed water molecules increase the free space in the polymer matrix allowing the chains to move about more freely so the water essentially acts as a plasticizer. Nylon may pass tests for ductility in a humid test facility, but then when shipped to dry climates for use can become brittle over time as the water migrates out. Nylon can absorb up to 9% of its weight in water (Matweb, 2012) so its effect on the polymer poses a challenge to manufacturers and users of nylon. The rate of moisture absorption is time, relative humidity and temperature dependant. The effect of moisture on Nylon is so pronounced that materials data sheets usually have two values for Nylon mechanical properties one for dry and one for wet (conditioned) (Snape, 2007).
Figure 3 Stress-Strain graph for dry and conditioned Nyon 66 (BASF, 2003)
Figure 4 Nylon interacting with water (Howe, 2012)
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1.4 Investigative method

The ideal approach to a case such as this is the investigative methods used in polymer forensic engineering because it avoids subjective assumptions and instinctual bias in favour of critical analysis of all possible options and deductive reasoning to derive conclusions. Analogously, a criminal investigator must question all suspects rather than simply trying to prove the investigators instinctual suspicions. Polymer forensics is the investigation or study of a polymer failure which led to loss of productivity, damage to the environment, property, harm to people etc. The goal is to determine the cause of why the product failed, did not meet specifications or did not perform as intended. Similar to criminal forensics, polymer forensics seeks to find, collect and analyse evidence which might provide a clue as to the suspect failure mode. (Neil, 2012) It is often used in industry to settle disputed between two or more parties; disputes can arise when a product or structure fails and results in loss to either party. For this reason it is often practiced by insurance companies evaluating claims, or from attorneys in liability suits. (Thompson, 2012) Research of similar failures is important to this investigative method as it can provide useful insight into cause, although no two failures are ever exactly alike. In this case the failure did not lead to catastrophic consequences such as loss of life, or even significant productivity loss but to determine the failure the same methods will still be applied in order to rigorously determine the cause (Lewis, 2010).
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Figure 5 General steps involved in failure analysis (Jensen, 2012)
Therefore order to best ascertain the cause of failure, the failure analysis should be conducted in a deductive procedure rather than simply running with the most intuitive cause. It is best to consider all possibilities and then eliminate each one until the most likely cause/s remains. This way investigators can be certain the process has been thorough. In order to structure this deductive logic, a basic fault tree was constructed as part of the preliminary report shown on the following page.
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1.5 Part specifications and nomenclature

An outline of major dimensions is provided in figure 6. The backbone has a T-shaped cross section with dimensions in figure 7. A digital vernier calliper: Mitutoyo Absolute Digimatic was used for measurements.
Figure 6 Basic Dimensions of sample
Figure 7 Dimensions of backbone cross section
The nomenclature used to describe different parts of the samples is shown in figure 8.
Figure 8 Nomenclature labelled on unbroken sample. On the rear side of each protrusion are 2 small flanges running the length, one on each side.
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2.0 Fractography
Fractography of polymers is a relatively new field which involves the study of fracture surfaces as a critical tool for failure analysis (Parrington, 2002). Examining material fracture surfaces can reveal information about failure mechanism, location of origin of fracture, sequence of events, directions of crack propagation, environmental interactions, material defects and information about stresses which occurred in the material. Hence, fractography is vital for this thesis. Factors which can significantly affect fracture morphology in thermoplastic polymers include: loading rate, temperature, moisture content and degree of crystallinity. (Greenhalgh & Hiley, 2007) Common analysis techniques include optical microscopy (OM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) - for greater resolution of fine structures. Nowadays modern SEMs have sufficient resolution to study the fine structure of surfaces which used to be studied with TEM. Atomic force microscopy (AFM) may also be used to provide high resolution without the use of a vacuum. (Sawyer et al. 2008)
Figure 9 Scanning Electron Microscope (Calvier, 2008)
A few main macroscopically evident regions are worth studying for comparison to the micrographs obtained in the lab (section 5). The smooth mirror region surrounding the crack initiation site is often called a mirror region and is from the slow crack growth phase.
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Adjacent to this is the mist region, where the crack transitions from slow to fast growth and begins to branch, this is evidenced by fine ridges or mist. (Parrington, 2002)
Figure 10 Images show the mirror region at point A with brittle morphology like ridges radiating out from this origin. (Dasari, 2006)
As the crack accelerates and propagates further away from the initiation site, ridges or hackles are formed; generally the fracture surface becomes rougher away from the point of origin (Sawyer et al. 2008). These ridges are an important morphology for this investigation because they radiate out from the fracture origin, thereby revealing its location. In SEM image on the right of figure 10 it is easy to see these lines radiating out from the origin at point A.
Figure 11 Hackle morphologies (ASM, 2003)
Figure 12 Low magnification SEM micrographs of impact-fracture surfaces of nylon 66. The smooth region at site A is the crack initiation site and the region labelled B represents hackle morphology. (Dasari, 2006)
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The basic fracture mechanics description is, Where KIC is the fracture toughness, and Y is the geometry factor, f is the stress at fracture and ac is the critical crack size. The crack size at the moment of instability is expected to be smaller at high stresses than at low stresses, this means the size of the mirror region is inversely proportional to the square of the fracture stress. Theoretically the magnitude of stress at fracture could be approximated by measuring the size of the mirror region (ASM, 2003) however in practice the effects of temperature and environment would have to be known and accounted for. This is not possible for this thesis as the times of fractures were not recorded, so local environmental conditions at the exact time of fracture remain unknown. Still this theory is worth considering when examining the fracture surfaces. The fracture strength is dependent on material flaws, and as no two samples are exactly alike it is not a well-defined bulk property and the flaws mean theoretical strength limits are never attained (Strobl, G. 2007). Modelling the fracture of polymers can be quite complex, it depends on intermolecular forces such as van der Waals, intermolecular covalent forces, and crystallinity. Although with an estimate of bond energies and intermolecular forces, estimates of theoretical strengths can still be attained (Strobl, G. 2007) In the centre of the mirror region is a small inhomogeneity which can provide the crack nucleation site (Ehrenstein, 2008). The mechanism for fracture in glassy thermoplastics is called crazing. Despite being macroscopically brittle, on the microscopic level polymers are ductile. This is fortunate because crazing means the toughness is not simply dependent on overcoming the energy barrier to from new surfaces. When the craze begins to form, polymer fibrils across the new surface support the load. Voids form at the tip of the crack, and the material between the voids is drawn analogously to many tiny tensile tests each of them absorbing energy as they are drawn out. The final fracture will take the path of least resistance: down mid-rib of the craze. These crazes are thin, planar defects so they form a very smooth flat region described above as the mirror region; in this region remnants of the craze may be found. (ASM, 2003)
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Figure 13Schematic of a craze (Halary et al. 2011)
Figure 14 Figure A: Brittle fracture Hackles in Nylon 66, the arrow points in the direction of crack origin. Figure B: Ductile bands in Nylon fracture. (Dasari et al. 2008)
Ductile polymer morphology is usually not as smooth, but has tearing marks and cups. Sometimes fibrils can be seen protruding from ductile ridges, a remnant from the tear. It is often clearly visible without microscopic inspection due to stress whitening. Discoloration in polymers can have a few causes; white discolouration is probably caused by crazing or crystal formation from cold drawing (ASM, 2003). As the sample is cold drawn polymer chains can line up and crystals grow which refract light differently and cause discoloration. Small crystalline regions can also align up and the many boundaries between amorphous and crystalline regions will scatter light and increase opacity. The other explanation is crazing, when a semicrystalline polymer such as this is cold drawn the amorphous spaces in-between crystals are strained causing small cracks or fissures to form. This causes density differentials to increase, and along with it the bending and scattering of light. Our perception of this reflected light is a whitening of the sample. (Rostaro et al. 2000).
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In contrast to these morphologies, a mechanical fatigue fracture surface would be more regular, consisting of beach marks or clam shell marks due to the arrest lines from repetitive loading (Brydson, 1999).
Figure 15 Left: fatigue fracture surface (Brydson, 1999) Right: fatigue crack showing beach marks (Marissen et al. 2005)
2.1 Effect of water content on fracture surface

A study by Bretz et al. 1979 made some interesting comparisons between Nylon 66 brittle fracture surfaces for various moisture contents. Their findings are potentially useful because the moisture content of the samples at time of fracture is unknown. Perhaps their Fractography can shed light on how the moisture content effect fracture morphology beyond the intuitive expectations due to moistures plasticizing effect. (Bretz et al. 1979)
Figure 16 Fracture surface of Nylon 66 at different moisture levels. (a) 0%RH (b) 50%RH (c) 100%RH (Bretz at al. 1979)
Their studies focussed on fatigue, they found fatigue crack growth rates for Nylon in equilibrium with 50%RH to be 2.5 times slower than for those at 0% or 23%RH. They found that tightly bound water, with a maximum of one water molecule per 2 amide groups, toughens the Nylon; while loosely bound water (saturation) weakens it. They noticed
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a transition from terminal unstable crack growth for water contents less that 3wt% to a tearing mode of failure at saturation. They discovered in their fatigue tests that samples in 0%RH, 23%RH and 50%RH failed via rapid unstable crack propagation, while the sample in 100%RH failed in a more stable manner, albeit still rapidly.
Figure 17 (a) Fatigue fracture at 50%RH (b) fatigue fracture at 100%RH, the arrest lines are believed to be striations (Bretz et al. 1979)
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3.0 Possible Failure Modes

This section contains a review of current literature on the major possible failure modes, and some investigation, discussion and calculations to complement and relate the literature to this case.
3.1 Oxidation
Ultra-violet rays can cause free radicals to form which react with oxygen and lead to chain scission and subsequently loss of molecular weight. This alters the mechanical properties of the polymer, often leading to loss of strength, impact resistance and embrittlement. (Massey, 2007) Heat will also cause degradation via a similar mechanism; its quite possible that during moulding the polymer melt was overheated for example. Anti-oxidants are added usually to polymers to prevent oxidation; although its possible for these to fail or not be added by mistake. These samples do appear to contain carbon black, an additive which improves UV resistance and weathurability (Wellman, 2009). To determine if the Nylon has oxidised, a characterisation technique such a Fourier Transform Infra-red spectroscopy (FTIR) can be used. Oxidation will produce bonds like C=O which will show up as an extra peak on the IR spectra. Another way to detect if UV radiation has led to chain scission and loss of molecular weight is with a simple melt viscosity test, the longer the polymer chains the greater the entanglements and hence viscosity. Studies have shown the presence of TiO2 considerably enhances the degradation of Nylon in sunlight (Lock, 1973). Titanium dioxide is a naturally occurring oxide with a wide range of applications from paint to sunscreen. Its plausible a worker has sunscreen residue on their hands after applying it, and then proceeded to handle the Nylon parts perhaps during installation.
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3.2 Hydrolysis
Most step-growth polymers will hydrolyse in water; this reaction is presented in figure 18. Nylon 66 is particularly susceptible to hydrolysis in the presence of an acid, so Nylon products will fail by fracture when exposed to even minor quantities of acid. The acid depolymerizes the Nylon meaning the molecular weight rapidly drops, and along with it the toughness. Cracks then form and the product fails (Lewis, 2006).
Figure 18 Hydrolysis of Nylon (New World Encylopedia, 2008)
Figure 19 Loss of tenacity of Nylon (N) fibres as a result of exposure to 10% sulphuric acid, compared with PET (T) (ASM, 2013)
There is a relatively famous polymer forensics case in which a leaky battery dripped acid on the fuel line of a van and the fuel pipe was hydrolysed. The broken pipe started leaking diesel fuel onto the road, which caused the following car to lose traction and slide, it collided head on with a semi-trailer and the female occupant sustained serious injuries. (Lewis, 2006) (a) (b)
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(c)
(d)
Figure 20 (a) Is a microscopic image of the fracture surface, ch stands for chamfer which acts as a notch. c stands for cusp which protruded up from the sample and was torn in a ductile manner. Image (b) is an SEM micrograph which shows the curved arcs. Image (c) is a schematic of the fracture surface, while (d) is a composite of micrograph images to provide better resolution. (Lewis, 2006)
Figure 20(c) displays a schematic of the fracture surface. The crack originated near the erosion zone at the point marked o, then travelled around leaving curved marks called arcs. These are similar to beach marks found in fatigue surfaces, each successive arrest in the crack front leaves a new mark. The larger arcs were from engine start-up while the smaller ones from engine movement during vehicle operation. The crack fronts met on the other side of the sample and a single crack advanced to the tip of the cusp until the pipe hung on by only a small tab, this then tore in a ductile fashion. The samples for this thesis were located near a road, so battery acid is one possibility (especially after an accident has occurred) although acid can come from a variety of sources including cleaning products, industrial chemicals and even acid rain.
A study into polyamide degradation found acid rain to cause changes in Nylons breaking strength, elongation and molecular weight losses. They also observed a synergistic effect between light and acid rain, leading to even greater loss in breaking strength and molecular weight as a result of chain scission (Kyllo, K. 1984). (See section 4.8 for acid rain in Perth)
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3.3 Hygroscopic Behaviour

As covered in the introduction (section 1.3) Nylon is a hygroscopic material; this is due to the presence of hydrogen bonds (Miri et al. 2006). When in humid conditions Nylon will absorb up to 9% of its mass in water; this water acts as a plasticizer. Then when the nylon is in an arid environment, this water will migrate out over time thus leading to embrittlement. This section focuses mainly of diffusion rates and diurnal humidity fluctuations, though moisture is a common theme throughout this thesis.
3.3.1 Rate of moisture diffusion

Data abounds on rate of moisture sorption and desorption for Nylon, however the rate is dependent on a couple of factors including relative humidity and equilibrium moisture content. So there is a large variation in rates found in literature, furthermore is also dependant on the specific part due to the effects of shape factor (surface area to volume ratio), so generic literature values can be of little use. Equations and constants have been developed to help estimate rate of water absorption for Nylon 66 components.
Where D is the diffusion constant (m2/s) and C is the water present at a distance x from the samples surface at time t. The water absorption rate (%) after a given time t, is given by: ( ) Where
is the equilibrium water absorption, V (m3) is the volume and S (m2) is the surface
area of the sample. The time to reach equilibrium water absorption is given by, ( ) Where is the shape factor,
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S is the surface area and V is the volume.
Figure 21 Dimensions of backbone cross section
The thicker section of the sample with the T-shaped cross section will be used for calculations. Due to the cross section remaining uniform throughout the length, in a Tshaped prism, the shape factor can be obtained easily from cross sectional area and perimeter using micrometre callipers as,
and still retains the shape factor units of m-1. The diffusion coefficient (D) for Nylon 66 at 20C and 60%RH is 3.4810-11m2/s (Toray, 2013), and the equilibrium moisture content is approximately 2.5wt% (see figure 22). D is actually a function of moisture content, however a single value is used in the literature by the slope of the initial linear region of a Q/Q E vs. , where Q is the mass of water lost or gained by time t, over thickness L. Q E is for equilibrium water mass (Asada, T. 1963; Kawasaki, K. 1964)
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Figure 22 Water absorption at relative humidity for Nylon. (Brydson, 1999)
The time to reach 80% of equilibrium water absorption with a surrounding environment is therefore given by, ( )
The time to reach 100% equilibrium (2.5wt %) is therefore 12.35hrs. This is unexpectedly rapid, further calculations show this is primarily due mainly to the high shape factor. If a shape factor value of 500 is trialled then time to reach full equilibrium works out to be 40hrs. In other words, these samples gain moisture rapidly due to their high surface area-to-volume ratio (as they are small and have complex geometry). Another reason for the fast diffusion rate is the diffusion coefficient varies amongst the literature; the value used above from the materials supplier was quite high. Kawasaki and Sekita, 1964 found a much slower diffusion rate of (assuming average moisture content of 2wt %). or roughly
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Figure 23 Diffusion coefficient for Nylon at various water content. Untreated Nylon is marked (o) (Kawasaki, K. Sekita, Y. 2003)
If their value is used then the time to reach 80% equilibrium works out to be, ( )
Clearly there is massive variation in rates of absorption and desorption in the literature, beyond even that expected from varying shape factors. The diffusion coefficient from the materials suppliers is lower than most, and its possible they are bias about a product they want to sell. Despite Kawasaki and Sekita to giving a more rigorous justification for their coefficient values, theirs remains abnormally high. Tests on these specific parts would need to be performed in order to be certain of desorption rates.
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Figure 24 Nylon 55 moisture absorption rate at 23c and 40-80%RH for Nylon with a shape factor =2000 (ASM, 2013)
The first set of results show that Nylon 66 with a high shape factor will re-absorb water from the environment in a matter of hours. Humidity data recorded by BOM at 10min intervals throughout the day was used to plot the chart in figure __. A polynomial of the 6 th order was used as a trend line.
110
100 90 80 %RH 70 60 50 40 30 20 0:00 8:00 Time of Day
Figure 25 (BOM, 2013)
24hr Humidity for 20/05/2013
16:00
0:00
Evidently humidity fluctuates with the diurnal cycle. This curve is typical of humidity in Perth; a similar sinusoidal cycle repeats itself, although the curve will shift up or down depending on the month and the period will change.
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The rate of moisture loss is not equal to the rate of absorption, even for thin samples and the use of a desiccant the rate of loss is still measured in days (figure __). Additionally, the high shape factor of these parts would mean they lose moisture more rapidly as well.
Figure 26 Rate of moisture loss of Nylon over Drierite desiccant (DuPont, 1995)
This means the Nylon does not dry out and crack from a diurnal cycle, it needs extended dry periods to loose moisture. Even then, one 5-hour period of rain and the sample can return to 80% equilibrium. If Kawasaki and Sekitas results are more accurate, then the yearly humidity would need to be considered. Mean annual humidity for Perth also follows a sinusoidal fluctuation, although the wave period is year. On average the dry months are about half of November and March, and all of December, January and February. In Perth the summer months have low humidity, and January and February average only 23days of rain for the month (see section 4.2); so based on these calculations and data it is both possible, and most likely these parts failed in the summer months. When the correct diffusion coefficient for these samples is obtained, further comparisons with climate can be made.
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Figure 27Moisture gain in wt% over time (Jia et al. 2004)
It must be noted that other factors will affect the rate of moisture loss including temperature, sunlight and even wind. Also because the samples are black, sunlight can raise their temperature above ambient and accelerate moisture loss beyond that which is expected of the temperature recordings from weather stations.
3.3.2 Solar radiation and moisture loss

As sunlight hits the polymer samples, their temperature is elevated; this in turn drives moisture out more rapidly. The heat transfer, Q, from radiation is given by,
Where is the Stefan-Boltzmann constant, T is the absolute temperature, A is the surface area and is the emissivity. Polymers on average have an emissivity of 0.91, although the carbon black filler in these Nylon parts would make their emissivity around 0.95 (Beardmore, R. 2013). This means most of the solar radiation is absorbed. To calculate more accurately, shape factor F, must be taken into consideration, along with the radiation lost from remittance,
4 QB B FAB AAATA BABTB4
So the net gain the absorbed minus the emitted. There would also be loss via convection. In addition to this, sunlight dries the outer surface of the polymer thereby creating a gradient to drive diffusion towards equilibrium. In overcast regions of the world, condensation such as dew may remain on the polymer longer and prevent or reverse drying.
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Contrariwise, the higher temperatures from sunlight will soften the polymer. So the carbon black can help prevent fracture from low temperature.
3.3.3 Outdoor exposure tests

Nylon degrades from heat, UV rays and other elements. Usually lab tests isolate one or two factors and study those; however multiple factors can interact in a complex manner, so analogously the whole is not the sum of its parts. Outdoor exposure tests are used to study the combined effect of degradation in order to more closely model reality. Assuming ordinary atmospheric conditions (23C/60%RH), the equilibrium water absorption term in the table is 2.5% for nylon 66.
Type Category Unit Exposure time
Tensile strength Tensile breaking elongation Flexural strength MPa In a dry state Equilibrium water absorption In a dry state Equilibrium water absorption In a dry state MPa Equilibrium water absorption In a dry state Equilibrium water absorption In a dry state Equilibrium water absorption In a dry state Equilibrium water absorption
Nylon 66 (CM3001-N) 0 years

80 50 100 200 115 65 2.8 1.4 50 300 119 100
1 year
67 48 12 35 110 62 2.6 1.4 4010 110 104
1 year and 9 months

56 46 6 30 80 2.4 1.4 5030 114 103
Flexural modulus Izod impact strength Rockwell hardness
GPa
J/m R scale
Table 1 Nylon 66 properties for exposure durations of wet and dry samples (Toray, 2013)
While most of the properties in this study remained relatively constant, one surprising find was wet Nylon 66 looses 82.5% of its tensile breaking elongation in the first year, but in the following 9 months this only climbs to 85% loss of original (Toray, 2013). So degradation plateaus somewhat after the first year. Ideally longer studies should be done, although there is an issue of practicality for experiments spanning many years.
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Other studies support the view of a plateau, one theory for this prosed by Vikas et al. (2010) is that the outer layer degrades then has a shielding effect, preventing the inner material from degrading to a similar extent.
Figure 28 Effect of outdoor exposure on the percentage loss of breaking strength for Nylon (shown as blue diamond), compared with other polymers. Red triangles is polyester, while the pink squares and green circles are UVR finished Nylon and polyester respectively. (Vikas et al. 2010)
3.3.4
Miscellaneous effects of water
Nylon is subjected to stress ageing, whereby if help at a stress below the yield point a temporary hardening occurs. Bubeck and Kramer 1971 found the kinetics of stress ageing to be markedly increased with moisture content. They also found the breakup of the stress aged structure is accelerated by moisture. (Bubeck, R. Kramer, E. 1971) Water will also affect Nylons acoustic, electrical, chemical and optical properties (Jai, N. Kagan, V. 2001)
3.3.5 Degradation caused by humidity

In a catch-22, Nylon degrades via a hydrolysis pathway from extended exposure to high humidity. This is the reverse of the synthesis reaction, and is widely accepted as the known textbook pathway for humidity degradation. An accelerated ageing study using a time-temperature superposition and Arrhenius plot found the rate of loss of tensile strength of Nylon in 100%RH to be significantly higher than thermal-oxidative ageing. The study also revealed a link between oxidation and hydrolysis previously unknown to researchers. When both oxygen and humidity were present the rate
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of degradation was considerably higher than for humidity alone (in the presence of argon). (Bernstein et al. 2005)
Figure 29 Tensile strength with ageing time for Nylon in 100% relative humidity and argon. Plot A has a linear time scale and plot B is a logarithmic scale. (Bernstein et al. 2005)
3.4 Environmental stress cracking

Environmental stress cracking (ESC) mode of failure accounts for 15-30% of all thermoplastic failures, making it the most common form of unexpected thermoplastic brittle failures (Mark, 2004). ESC can cause the polymer to fail at stresses substantially lower than the fracture or yield stress. Solvent can enter a small crack where it is absorbed and softens the crack tip, thus allowing the crack to advance more easily and propagate to failure (Young, 2011). Typical chemicals which can cause ESC in Nylon include; acetone, methanol, cyclohexanone, n-butanol (Wright, D. 1996), detergents (Bounamous, B. 2009), LiCl and LiBr (Kenney, M. 1985). Nylons also become brittle in the presence of metal halide solutions such as calcium, magnesium, lithium and zinc, chlorides, bromides, iodides and perchlorates (Wright, D. 1996).
If the fracture surfaces were uncontaminated from handling then a sample could be taken from the crack tip and tested for the presence of unwanted solvents. The environment in which the Nylon was used could also be examined for any potential chemicals.
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3.5 Other Chemical attack

Exposure to certain chemicals can lead to temporary or permanent loss of mechanical properties. Chemicals which Nylon 66 is not resistant to include: Chromic acid, Ethanoic acid, Potassium permanganate, Phenol, Nitric acid and Hydrogen peroxide.
Figure 30 Chemicals which cause Nylon to permanently loose stiffness and become weak. (DuPont, 2005)
Nylon will also experience a temporary loss of stiffness, which is regained upon evaporation of the following common solvents: acetone, ethyl alcohol, ethylene dichloride, isopropyl acetate, methyl alcohol, methyl acetate, methyl ethyl ketone and trichloroethylene. (DuPont, 2005)
3.5.1 Smog and ozone

A study by Mead et al. (1982) into the effects of humidity, smog and ozone of Nylon 66 found Nylon exposed to smog for six months lost 63% of its tensile strength compared to 7% loss in ozone (Mead et al. 1982). Perth is notorious for smog; thick smog has grounded planes at Perth airport (Rimrod & Pickard, 2011) near where the samples were in service. The department of environmental protection and the state energy commission of Western Australia carried out a 4 year study called the Perth photochemical smog study (PPSS). The study found Perths daily smog is
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closely linked to an offshore wind pattern, where the sea breeze causes recirculation of pollutants over Perth (DEP, 1996). Phil Morgan from the department of environmental protection claims Perths air is among the worst in the world (Loweth, A. 2000). Mr Morgan claims that during the summer, the levels of photochemical smog occasionally breach the National air quality standards. Photochemical smog is a noxious mixture of Aldehydes, Nitrogen oxides, Peroxyacetyl nitrates (PAN), Tropospheric ozone and volatile organic compounds. These are all highly reactive and oxidising. (DEP, 1996)
Figure 31 Ozone levels at Caversham in Perth (DEP, 1996)
The nearest monitoring station for the PPSS was Caversham, approximately 5kms from Perth airport. Figure 31 shows ozone fluctuations over the year, peaking in the summer
3.6 Manufacturing faults

There are a wide range of manufacturing faults that could cause embrittlement. One way to eliminate manufacturing would be to get in contact with the manufacturer and discuss if there have been other faults with the batch, testing of other samples in the batch could be performed or data could be gathered on the performance of other batches in the same environment.
If the evidence is pointing to a manufacturing fault these are a few causes to consider which include; Contamination Re-grind levels Low mould temperatures or high Lack of moisture conditioning High moisture content in the resin Weld lines
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melt temperatures Incorrect cooling channels Screw retraction time can effect homogeneity of toughness (DuPont, 1995 )
Poor quality raw material (resin) Small gate Voids which can cause loss of structural integrity of the part
The hydroscopic behaviour of Nylon means drying prior to moulding is particularly important. For non-polar polymers such as PVC, PE or PS they have a low affinity for moisture so will only contain moisture on the surface. Conversely Nylon pellets will rapidly absorb moisture in a matter of hours. If moisture is trapped in the resin pellet, and not completely removed by the dryer prior to moulding then two major issues can arise. The first is void, bubble and splay deformities; these are generally caused by trapped gas. The gas can be air, water trapped in the pellet, volatiles from the resin, decomposing by-products or in the case of a vacuum void there may not be any gas. If water is trapped in the resin pellets, then heating during moulding could cause the water to vaporize and form a gas bubble in the melt which solidifies upon cooling. (Bozzelli, 1986)
Figure 32 Non-hygrscopic resins only collect moisture on the outside of the pellet, whereas hygrscopic resins collect water on the inside as well. (Shah, V. 2007)
The other major problem is hydrolysis, to which Nylons are particularly susceptible. If the material is processed while still wet, then the condensation polymerization reaction which formed the Nylon can reverse itself. This results in a loss of molecular weight, as longer chains are broken down into smaller molecules, this in turn results in severe loss of mechanical properties. This process is not reversible, meaning re-grinding and re-moulding the material will not recover it.
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3.7 Design
If the design incorporates a small fillet radius it produces a sharp corner in which stress concentrates. Stress concentration factor is a function of fillet radius over thickness. Nylon has a high notch sensitivity (Matweb, 2012) so this is especially important when designing Nylon parts.
Figure 33 Stress concentration factor with fillet radius (DuPont, 1995)
Another design issue is the placement of weld lines in areas of high stress. Weld lines occur when two solidifying melt fronts meet. The weld line is an area of weakness as the polymer chains do not interpenetrate well, so they must be carefully positioned. Finite element analysis could be performed to determine if these line up with areas of stress concentration, and moulding software used to reposition them.
Loss of water content causes shrinkage which can sharpen a tight fillet radius even further. Dimensional change can be significant for Nylon 66, reaching 2% dimensional change at 7wt% moisture content.
Figure 34 Dimensional changes of Polyamides with varying moisture content (Hoffman, 2000)
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3.8 Ductile-to-Brittle Failure Transition

The ductile and brittle failure stresses of Nylon both decrease over time, although the brittle failure stress decreases more rapidly than the ductile failure stress. This produces a transition region where the dominant failure mode switches from ductile to brittle.
Figure 35 Ductile-Brittle transition
It is possible the Nylon samples have crossed this transition region, and this could be the cause of their brittle fracture. Another theory is that moisture effect this transition, this is plausible because water affects almost every aspect of Nylons mechanical behaviour. For example, lack of moisture in the Nylon could shift the line down or left so the transition to brittle occurs after less time in service.
Unfortunately after extensive searching, a ductile to brittle transition graph for Nylon 66 (like the one in figure 35) was not found. Constructing one of these charts for Nylon 66 and investigating the effect of relative humidity or moisture absorption would help prove or disprove this failure theory. However this is not straightforward and would require time and extensive experimental resources. Furthermore, the time that samples spent in service is unknown.
Due to the long time required to perform ageing tests at service temperature, ageing may be accelerated at high temperature then time-temperature superposition used to generate long term data by shifting the curve. Common shift factors include Williams-Landel-Ferry and Arrhenius law.
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3.9 Mechanical Overload

Failure can often be a simple case of subjecting the components to stresses greater than they were designed for. The stresses in service can be difficult to predict so usually a safety factor in incorporated, though this still may not compensate for excessively high stresses in service. To model areas of high stress and behaviour under load, it is recommended that a 3D CAD model should be obtained or drawn and then input into a finite element analysis software such as strand7. When load is applied during modelling, areas of high stress can graphically displayed using colour coding. Based on the design of parts and most likely loading scenarios, this engineer supposes that stress would concentrate in the two prongs, as they have less cross sectional area on which to distribute load. The usual failure mode for Nylon under high stress is yielding, so the brittle nature of these fractures would still need to be explained.
3.10 Low Temperatures

Polymers like Nylon lose their ductility at low temperature and become brittle. Nylon 6 has a glass transition temperature (Tg) of roughly 50C. This means it gains much of its modulus below this temperature, so during service at room temperature Nylon is in its glassy state. However as the temperature keeps falling further below the glass transition, the modulus still keeps increasing slightly as well. If the modulus is too high then the polymer is still and inflexible so could fracture in a brittle fashion. Section 4 outlines temperatures for Perth airport.
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Figure 36 Effect of Temperature and Moisture on the Modulus of Nylon 6 and Nylon6,6 (Intech, 2012)
3.11 Fatigue
The main types of fatigue in polymers are mechanical and thermal. Mechanical fatigue can occur when Nylon is subjected to a lifetime of loading cycles. For Nylon, the lifetime is mainly determined by the time under load, rather than the number of loading cycles (Scheirs, 2000). Jai and Kagan (2001) found the absorbed moisture to decrease fatigue crack growth rates, they claim this is due to water enhancing chain mobility. Conversely Toray (2013) found the endurance limit for Nylon 66 is actually lower at higher moisture contents; table 3 shows a reduction in 30Hz endurance limit of 60% for Nylon at 2.5wt% moisture content.
Moisture content (wt%) 0 2.5 Temperature (C) 73 73
Table 2 (Toray, 2013)
Endurance limit (MPa) 35 21
Exposure to seawater and other salt solutions can affect the fatigue life of Nylon 66; researchers found a 10% loss of strength compared with ambient air environments (Kenny et al. 1985). Perth sits on the coast and experiences regular sea breezes, although contact with salt water unknown.
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Rajeesh et al. provided an interesting schematic for crack propagation and molecular orientation when comparing effect of humidity on the flexural fatigue and indentation hardness of Nylon 6. Greater moisture contents increase polymer chain mobility which helps inhibit crack propagation.
Figure 37 (Rajeesh et al. 2009)
3.12 Thermal fatigue

When a polymer is respectively stressed, such as in cyclical loading, some of the inelastic deformation energy is transformed into heat and the temperature climbs. If the rate of heat transfer to the surroundings is less than the rate of generation then the materials properties can decline with raising temperature until it fails (ASM, 2003). Because Nylon is a thermoplastic, the heat would most likely just raise it above the glass transition temperature and make brittle fracture even less likely. However changes in temperatures from diurnal cycles or other means could produce residual stresses in the material which can accelerate premature fracture.
3.13 Plasticizer loss

The plasticizer added to the nylon may have degraded or leached out, leaving the Nylon brittle and susceptible to cracking. No information is available at this point on the type of plasticizer used in these samples.
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3.14 Thermal degradation

Overheating Nylon during moulding will cause crosslinking to occur and produce involatile char (Holland, B. 2000). Thermalgravimetric analysis (TGA) of Nylon 66 shows it undergoes thermal degradation beginning at 480C (Perkin Elmer, 2011).
Figure 38 TGA of Nylon 66(Perkin Elmer, 2011).
3.15 Thermal oxidative

Thermal oxidative degradation is essentially thermal degradation in the presence of oxygen (e.g. air). FT-IR spectroscopy and differential scanning calorimetry (DSC) is also used to investigate thermal oxidative degradation. A DSC scan of Nylon 66 is displayed in figure __, the endotherm at approximately 260C is due to the crystalline melting. The temperature oxidation begins is around 305C here an exothermic reaction shifts the baseline. The oxidation peak is around 330C (marked OPT on the chart). (Crompton, 2010)
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Figure 39 DSC of heat stabilized polyamide 66. (Crompton, 2010)
For more on oxidation see section 3.1.
3.16 Temperature and moisture combined

While temperature and moisture both have a similar effect on Nylon increasing ductility and reducing strength; Jai and Kagan (2005) found that temperature and moisture combined did not result in more ductility that would allow it to deform further prior to failure. Rather, the material failed sooner which suggests moisture and high temperatures combined can deteriorate the Nylon (Jai, N. Kagan, V. 2001)
4.0 Environment
4.1 Introduction
This section will analyse the environmental conditions of the service parts. Conveniently the Bureau of Meteorology (BOM) has a monitoring station at Perth airport, in close proximity to where the samples were in service. The monitoring station is site number 009021 at a
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latitude of 31.93 S and longitude of 115.98 E, and elevation of 15m and data recording since 1944. (BOM, 2013)
4.2 Rainfall
According to the Kppen-Geiger climate classification the climate of Perth is a classic example of a Mediterranean climate (Kottek et al. 2006). It is temperate to subtropical; summers are hot and dry while the winters are cool and wet (BOM, 2013). This high level of rainfall during the winter months (>150mm rain) makes Perth the 4th wettest capital city in Australia. Conversely the summers have very low rainfall (approximately 10-15mm rain), figure 41 shows the summer months of January and February average only 2-3 days of rain for the month. Usually this sporadic summer rainfall occurs in rapid thunderstorms, interspersed by long dry periods.
Figure 40 (BOM, 2013)
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4.3 Humidity
Figure 41 Mean relative 9am humidity for 1981-2010
Reflecting the mean average rainfall data, the mean average relative humidity for Perth also reaches a maximum in winter (80% RH) and a minimum in summer (50% RH). 1980-2010 data in figure 42 represents a typical year for Perth airport, evidently some years are drier, 2010 is one example. As far into the year the data extends it, it already appears to be abnormally low, though it is still not significantly lower than 50%RH.
Initially the mean 9am humidity data appears to counteract the prevailing theory of this thesis about Nylons hygroscopic behaviour. However, mean 3pm RH data presents a
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different view; humidity reached 35% in the summers between 1981 and 2010, and did not even reach 60%RH average for the wet winter months. Clearly there are large fluctuations in humidity over the period of the day. In the morning when sunlight strikes dew the humidity spikes, and by the afternoon evaporation of condensation has long since dried it out.
Comparing to the dry year in 2010 the average 3pm humidity drops to almost 25%RH average for the start of the year and although remaining data for the year is not yet released to the public, the winter appears to average 50% which is equivalent to the summer average for mean 9am RH for 1981-2010.
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In addition to this, 2011 saw an all-time humidity record for Perth where RH reached 10% on 1/12/2011. Worth noting also is 2012 was a record year for highest humidity. (BOM, 2013)
4.5 Solar exposure

Solar exposure is the total solar energy radiating onto 1m2 of horizontal surface. The daily values given in figure 43 are the total solar exposure for the day, typical values for global exposure range from 1 to 35MJ/m2. The figures __ and __ show Perth receives high levels of solar radiation, especially in the summer months. The effect of this radiation heating the black polymer and accelerating moisture desorption is explored in section 3.3.2.
Figure 42 Mean daily solar exposure (MJ/m )
During the summer Perth is exposed to >10hrs of sunshine per day. The Campbell-stokes recorder measures only the duration of bright sunshine, which is less than visible sunshine, so dawn and dusk are not recorded.
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Figure 43 Mean daily sunshine hours for Perth airport. Light bars are data for 1993-2013 and dark bars are for the year 2012 only
4.6 UV Radiation
As covered in section 3.1 of the literature review, UV rays cause polymer to degrade and lose molecular weight. Figure 45 shows global UV radiation data, Perth is in the 160-170J/cm2 band.
Figure 44 UV only (SoDa, 2013)
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4.7 Temperature cycling

To study the natural temperature variations of the diurnal cycle a plot of the difference between mean maximum and mean minimum temperatures was generated for each month in figure 46. Mean annual temperature differences for Perth airport
16 14 12 10 T (C) 8 6 4 2 0 11/11
12/11
2/12
4/12
5/12
7/12
8/12
10/12
12/12
1/13
Date (mm/yy)
Figure 45 Temperature differences for Perth Airport (BOM, 2013)
The largest temperature variations occur in the summer months; this could be attributed to the drier climate in those months. The cloud cover creates a miniature greenhouse effect, acting as a blanket and reducing radiation escape from the ground and air below the cloud. At night the loud cover absorbs then re-emits the long wave radiation from the earth. This is a function of temperature as per the Stefan-Boltzmann law describing black- body radiation. (Frierson, D. 2012)
Where J* is the emissive power or irradiance and has dimensions of energy flux (energy per unit time per unit area) and is the Stefan-Boltzmann constant which as derived from other constants as,
Where h is Planks constant, k is the Boltzmann constant and c is the speed of light in a vacuum.
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Figure 47 shows the radiation fluxes for this simple greenhouse model. Summer nights in Perth lack sufficient low altitude warm temperature cloud cover to provide any substantial back radiation.
Figure 46 Radiation fluxes per unit area of Earths surface for a simple greenhouse model (Jacob, D. 1999)
4.8 Acid Rain

Like many Australian cities, Perth is sparsely populated; and the city also has no other major population centres nearby. Typically then one would expect the precipitation to be close to 5 (unpolluted acidity); however areas which contain smelters, power stations and other industrial activities will usually record higher readings (CSIRO, 2011). The area surrounding Perth airport is mostly residential, and some industry. The nearest power station is the coal and gas-fired Kwinana Power Station located approximately 20kms away, its 4 turbines generate approximately 420MW of electricity (Verve, 2013). If the samples show signs of Hydrolysis then a study into the acid rain at Perth airport would be recommended in order to determine if this is the cause.
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5.0 Optical Microscopy Inspections

5.1 Morphology
A Wild M8 stereo optical microscope was used to examine the fracture surfaces of the broken samples A to G. Micrographs were taken using a Leica DFC295 digital camera fitted to the microscope. Section 2.0 of literature review provides some comparative information on polyamide Fractography. This fracture surface in figure 48 is classic brittle fracture; there are fine ridges radiating from the crack initiation site thereby indicating the origin. In the bottom left corner of figure 48 is a very smooth region which is the mirror zone, adjacent to this can be seen very fine ridges or mist. Further out, as the crack became faster and more violent the ridges become rougher and large hackles were formed. The morphology of this facture surface is indicative of classic brittle fracture. C1
Figure 47 Fracture surface no. 1 of sample C
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Although most of the fracture surface is characteristic of brittle fracture, there is a ductile tearing region seen in figures 49 and 49 as the region which appears to have been stress whitened. This region does not mean the overall fracture is ductile, but is probably where the remaining connecting portion was torn off. The protrusion adjacent to the white ductile tearing zone supports this theory. There are a number of other samples displaying similar fracture surfaces. C2
Figure 48 Fracture surfaces C2, E and B
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5.2 Factors Effecting Fracture

A potentially important observation was made during inspection, the fractures on the small prongs all originated from the same edge. This suggests a possible design flaw or local stress concentration. E G F1
F2
Figure 49 Images of fracture surfaces are labelled with the designated part letters for each piece they occurred on.
Without more information on the service conditions of these parts, it remains uncertain how they are loaded. Although based on the design, it is reasonable to assume the hooks are loaded in tension. If this is the case then the bottom side of the sample in figure __ will be loaded in compression and the top side in tension. The flange seen in figure 50 (opposite the origin) would be on this side in compression; this explains why the fracture originated on the opposite side. That does not explain why it originated from the same edge for each sample, but what could explain that is the sharp fillet radius. Although difficult to display, from handling the parts it
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is clear the sharpest corner on the whole sample occurs on the inside of the box-shaped hole to the side of the hook. This edge is significantly sharper than the rest, and is the same edge in which all above fractures originated. This observation could be explained by the high notch sensitivity of Nylon (see section 3.7). Additionally, the presence of the box-shaped hole has meant the two prongs carry the entire load. As they have a small area on which load is distributed, the resulting stresses are higher this would compound the problem further. In a number of the samples there can be seen a transition in the morphology occurring roughly 2/3rds of the way into the crack. This location corresponds to the presence of a weld line, which may be the cause of this transition.
Figure 50 Samples G and C with weld lines highlighted
Despite these sharp edges, weld lines or thin prongs there are fractures which seem to have no simple cause and fracture in unlikely places; so this suggests the samples were just very brittle at the time of failure. Figure 52 shows a fracture which occurred at the base of protrusion from the backbone. This is a thick section with no sharp edges or weld lines. This also doesnt explain the fractures of the thicker t -shaped cross section backbone. Considering their frequency it is indicative again of the samples being very brittle rather than some design issue.
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Figure 51 Fracture surface of sample H. Fracture occurred close to the base of protrusion rather than at the hypothesised locations of stress concentrations.
Overall the evidence from this lab seems to support general embrittlement, the fracture surfaces are classic brittle fracture and not limited to areas of stress concentration or sharp edge.
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6.0 Scanning Electron Microscopy

A scanning electron microscope (SEM) was used to inspect the fracture surfaces. The section contains procedure, results and critical discussion and analysis.
6.1 Summary of Procedure

To ensure correct fitting in the SEM, chosen samples were cut down to approximately 510mm size using a fine hacksaw. They were washed with ethanol to clean them, and then mounted to Aluminium SEM stubs using 5 min Araldite. An SPI sputter coater was used to coat the top fracture surface and sides of the samples by first exchanging the gas in the vacuums chamber with argon then using platinum in the plasma state to coat the top and two sides of the samples. The stubs were mounted in the SEM and calibrated using the copper mount. The SEM used was a Philips XL30 with a Lanthanum hexaboride (LaB6) emitter. The accelerating voltage was set to 15kV, and spot size set to 5 then micrographs were taken of the fracture surfaces.
6.2 Results
Figure 52 Fracture surface C1
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Figure 53 SEM photo on the left shows hackle morphology, sample on the right shows much finer ridges called mist. Both photos were taken on surface C1 with same magnification.
The hackles and ridges were traced back to the mirror region, there an inhomogeneity was noticed. It was hypothesized that this inhomogeneity could be the origin of fracture; however a further zoom showed the fine ridges do not originate there. In fact they appeared to avoid this region suggesting it may be tougher than the surrounding Nylon. Spectra results of the inhomogeneity in figure 56 reveal it is not composed of pure Nylon 66, rather minerals are present.
Figure 54 Zoom on the mirror region of surface C1 shows an inhomogeneity.
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Figure 55 Spectral results of inhomogeneity on fracture surface C1. The spectra show the inhomogeneity is not pure Nylon 66; rather it has minerals in it.
A further zoom on the mirror region showed the presence of small voids similar to those in figure 62. The ductile region of the surface was also explored; this is not the fracture origin so its morphology tells us little about the true nature of the fracture. While photographing the ductile cups a small inhomogeneity was noticed. The lines radiating out from this inclusion suggest it was already present prior to fracture.
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Figure 56 Ductile region of sample C1, showing small inhomogeneity
This inhomogeneity shows a straight edge and appears to have a layered sheet structure. The spectral results showed this was not Nylon 66. Only the carbon, oxygen and platinum (coat) correspond with Nylon; however the oxygen peak on the spectra is larger than the carbon. Also the presence of large magnesium and silicon peaks suggest this is an inorganic mineral inclusion, perhaps clay. The sheet structure suggests it may be a sheet silicate. This inhomogeneity would have been the origin of fracture for that local ductile cup only. However its presence tells us something about the quality of the Nylon. If further inorganic mineral inclusions can be found in brittle crack origins it may be theorized that its presence contributed to the brittle behaviour of these fracture, however no such inclusions were found.
Figure 57 Spectral results of inhomogeneity in ductile cups on sample C1
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Sample A revealed a similar overall morphology as the other brittle fractures. The hackles and mist were traced back to fracture origin which was obstructed by Nylon, this may have occurred post-fracture during handling or while still in service. The reason for the fracture origin location remains unknown. The theory discussed in section 3.7 about the high notch sensitivity of Nylon and the sharp fillet radius labelled stress concentration was not confirmed. The weak weld lines (see section 3.7) were not the point of origin either.
Figure 58 Sample A fracture surface of thin protrusion.
On further inspection of the samples, there is another possible location of stress concentration. The sharpest corner on the sample appears to be at the edge of the boxshaped hole on the protrusions (see figure 50). The sharp edge would actually be to the left of the one labelled stress concentration in figure 59. In addition to this, upon further analysis on the SEM images, it appears the obstruction may not be the fracture origin at all. The fine ridges pass this obstructed region and continue on.
Figure 59 Sample A
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Unfortunately this observation was not made during the SEM session so no higher magnification images of the mirror region are available. Based on projection of the direction of fine ridges, its plausible the fracture origin was in the south-west corner of figure 60 - the corner with the highest notch radius on the whole sample, and this is on the protrusions, which due to the box-hole have the smallest cross section on which to distribute mechanical load thereby furthering the stress concentration.
Figure 60 Fracture surface C2
In all the mirror regions of the samples, small voids were observed (see figure 62). 3 voids were measured, they were: 485nm, 589nm and 820nm. The average size was approximately 600nm, and they were spaced 5-10m apart. Figure 63 shows these voids on the mirror region of sample E, the small cracks which can be seen are from the Pt coating cracking from the concentrated electron beam. Its possible these voids occurred during moulding. If a small amount of water was trapped in the resin then it may vaporize upon heating, form a bubble and then solidify into a void upon cooling. It is unlikely these voids were caused by insufficient plastic; they are too small, too numerous and too evenly distributed throughout the part. If the resin pellets did contain water prior to moulding it is likely to be a minor quantity as Nylon pellets would almost certainly undergo a drying process prior to moulding. If a hopper drier was used then the degree of drying achieved will be dependent on moisture levels in the intake air, so a seasonal variation can often be seen, and high quality drying is rarely achieved. With the use of a dehumidifier then manufacturers claim less than 0.02wt% moisture content (Kenplas, 2013), although its plausible even this would be enough moisture to cause these tiny voids, especially considering the volume expansion to steam.
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Voided areas have a greater susceptibility to fracture, and when too numerous can leave the moulded part brittle (Bryce, D. 1997). Unfortunately voids were not spotted in any region besides the mirror. This is partly because they are only visible at >1000x magnification, becoming clear at 16,000x, and the largest
void spotted was less than a micron in diameter. Its also possible the micro cups in figure 57 were local voids which stretched and warped during the ductile tearing.
Figure 61 Voids on the mirror region of sample E.
Figure 62 Voids in the mirror region of sample E
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7.0 Summary
Nylons chemistry, synthesis, general properties and behaviour were introduced and the limited information available on these parts was collated. Then literature on numerous possible failure modes was examined including: oxidation, hydrolysis, ductile-brittle transition, fatigue and design flaws. The optical micrographs revealed the origin of fracture; and this seemed to confirm the hypothesis about stress concentrations and design. Micrographs showed clear signs of brittle fracture, although revealed little about cause of fracture. The SEM micrographs revealed some interesting inclusions; spectral analysis showed these were not Nylon but rather they were likely of inorganic mineral composition. These Nylon 66 samples all showed signs of classic brittle fracture.
8.0 Conclusions
There are a few main factors which could be the cause of failure, or could be contributing factors which combine to cause failure. These include; Exposure to arid environment for extended durations, Nylon is hygroscopic and becomes brittle why dry. Sharp fillet radius, Nylon has high notch sensitivity. Poor design, location of sharp notch radius is on the section with smallest cross sectional area on which to distribute load mean higher stresses. Micro voids, probably caused by water in the resin pellets, can lead to embrittlement. These voids are also a sign that water was present during moulding which can lead to degradation, although there was only a tiny quantity present. The second and third factors listed help explain why the fractures on the prongs originated on the same corner every time, but they dont explain other fractures of thick sections with
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no stress concentrations. Because of this, the theory only explains the origin of fracture location, not the reason these parts were brittle to begin with so it can be ruled out. The evidence collect does not support the hypothesis of stress concentrations or poor design as the sole cause of failure, rather it is indicative of generalized embrittlement. The cause of this embrittlement remains unknown; however an interesting observation was made just prior to the culmination of this thesis. When handling the parts and attempting to fracture them by hand, it proved impossible. The samples were extremely flexible and would bend back upon themselves (>160 flexion) without fracturing, even a previously fractured sample (definitely in service) was impossible to break. Humidity on this day was 94%RH. This seems to reinforce the profound effect of Nylons hygroscopic behaviour, based on the research in this thesis it is highly probable the samples were simply dry, became brittle, and fractured.
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9.0 Recommendations
From the information available, the fault seems to be primarily due to inadequate material selection. While the sharp edges contributed to failure locality, these were not the cause of premature failure. Additionally, re-tooling the die to enlarge the sharp fillet radius would be costly. Perhaps the easiest solution to prevent further failures would be an alternative material, and then simply send any old Nylon 66 parts in stock to humid areas of the country for service. Possible additions to reduce the effect of Nylon 66 hygroscopic behaviour include: Addition of a reinforcement water absorption capacity and rate of sorption both decrease with increasing glass fibre content. Additionally, glass filled Nylons have been found to retain more of their properties at all moisture levels than unfilled Nylons (ASM, 2003) Nylon-rubber blends have improved ductility at low moisture contents. (Murphy, J. 2001) Nano particle clay reduces Nylons moisture absorption capacity, and the diffusion coefficient (Brady & Parsi, 2011) Further additions of plasticizers, these will not migrate out in dry conditions like water. Although the possibility of over plasticizing them should be investigated. Increasing crystallinity may help because water is absorbed into amorphous regions only Crosslinking improves dry tensile strength (Brydson, 1999)
If none of the above are possible then perhaps consider an alternative choice of polymer. If Nylon was needed for a particular reason then possibly an alternative type of Nylon may suffice. While water is absorbed into other Nylons and plasticizes each of them, they dont all share the same capacity for moisture absorption. From figure __ its evident Nylon 66 is the second worst performing in terms of moisture absorption, so its properties will change much more significantly than a Nylon 11 or 12 when subjected to changing relative humidity. Those Nylons generally have inferior mechanical properties to 66, so it is a question of performance or longevity.
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Figure 63 (Toray, 2013)
Although it is still extremely difficult at this point to make a proper materials selection - as information on the parts and their service function is still lacking - a general comparison of various Nylons was conducted using the materials selection software CES. Based only on fracture toughness and price, Nylon 66 seems a very good choice.
Figure 64 CES materials section chart
Conversely, when selecting based on water absorption, the PA66s are high up on the chart. Surprisingly the cast PA6 has a low water absorption, and still very high tensile strength. Figure 65 shows it performs quite well with fracture toughness as well similar to PA66
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(moulding). Perhaps a cast PA6 wouldnt be a bad choice, the graph in figure 64 may have used toughened PA6, it does not specify.
Figure 65 CES materials selection chart
Once the application of these samples is known, a full materials selection could be conducted to select the alternative polymer. As part of that, equations can be derived to give certain weighting to various properties such as price, moisture absorption, modulus, fracture toughness then all included on the chart for selection. If further investigation into these fractures is conducted the following are recommended: Collect information about the samples: o Part function o Specific grade of Nylon, and any additives or fillers used o Time spent in service prior to fracture
o Time of fracture, even the approximate time of year they failed o Local environment (exposure to the elements such as direct sun or rain, surrounding properties and use, any pesticides or chemicals nearby etc.) Investigate the ductile-brittle transition of Nylon 66, and the effect of moisture Conduct finite element analysis (FEA) to examine stress concentrations
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10.0 References
Adilia, J. Coutlee, S. 2007. Polymer Synthesis Lab, accessed online 20th September 2012 http://www.wellesley.edu/Chemistry/Chem105manual/Lab6/lab06.html Aharoni, A. 1997. n-Nylons, their synthesis, structure, and properties, J. Wiley & Sons, ISBN 0471960683, 9780471960683 BOM, 2013. Climate statistics for Australian locations, Australian Government Bureau of Meteorology, accessed online 20th April 2013 http://www.bom.gov.au/climate/averages/tables/cw_009021_All.shtml Asada, T. Ongi, S. 1963. The diffusion coefficient for the nylon 6 and water system, Journal of Colloid Science, Volume 18, Issue 8, October 1963, Pages 784-792, ISSN 0095-8522 ASM, 2003. Characterization and Failure Analysis of Plastics, ASM international, ISBN 1615030735, 9781615030736 BASF, 2003. Mechanical performance of polyamides with Influence of moisture and temperature accurate Evaluation and better understanding Accessed online 23rd February 2013 http://www2.basf.us//PLASTICSWEB/displayanyfile?id=0901a5e180004880 Baumer, G. 1990. The Effect of Moisture Conditioning on the Performance of Impact Modified Nylons, Journal of Reinforced Plastics and Composites May 1990 vol. 9 no. 3 240250 Bernstein, R. Derzon, D. Gillen, K. 2005. Nylon 6.6 accelerated aging studies: thermal oxidative degradation and its interaction with hydrolysis, Polymer Degradation and Stability, Volume 88, Issue 3, June 2005, Pages 480-488, ISSN 0141-3910 Bounamous, B. Chaoui, K. 2009. Degradation and Failure of Some Polymers (Polyethylene and Polyamide) for Industrial Applications, Springer Science & Business Media B.V. 183194
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Bozzelli, J. 1986. Eliminate Bubbles, Voids, Sinks & Blisters, ULIDES, accessed online 15th May 2013, http://articles.ides.com/processing/jb_sinks_bubbles.asp Bretz, P. Hertzberg, R. Manson, J. 1981. Influence of Absorbed Moisture on Fatigue Crack Propagation Behavior in Polyamides, Journal of Materials Science, vol. 16, Part 1: Macroscopic Response, pp. 2061-2069 Bretz, P. Hertzberg, R. Manson, J. 1979. Fatigue crack propagation in crystalline polymers: effect of moisture in nylon 66, Journal of Materials Science, October 1979, Volume 14, Issue 10, pp 2482-2492 Bryce, D. 1997. Plastic Injection Molding: Material Selection and Product Design Fundamentals, SME, ISBN 0872634884, 978087263488 Brydson, J. 1999. Plastics Materials, Elsevier, 7th Edition. Bubeck, R. Kramer, E. 1971. Effect of Water Content on Stress Aging of Nylon 610 Journal of Applied Physics, Vol. 42 Chanda, M. Roy, S. Industrial Polymers, Specialty Polymers, and Their Applications, Volume 73 of Plastics Engineering, CRC Press Clavier, Ron. 2008. Characterization and Analysis of Polymers, John Wiley & Sons. Chemical Heritage Foundation (CHF), 2010. Wallace Hume Carothers, Synthetic polymers, accessed 13th September 2012, http://www.chemheritage.org/discover/onlineresources/chemistry-in-history/ Corti, T. Peter, T. 2009. A Simple Model for Cloud Radiative Forcing, Atmosphere Chemistry and Physics Journal, Vol. 9 Crompton, T. R. 2010. Thermo-oxidative Degradation of Polymers, Smithers Rapra Technology
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Ayers, G. 2011. Acid Rain, Commonwealth Scientific and Industrial Research Organisation (CSIRO), Australia Advances Dasari, A. Yu, Z. Yang, M. Zhang, Q. Xie, X. Mai, Y. 2006.Micro- and nano-scale deformation behavior of nylon 66-based binary and ternary nanocomposites, Composites Science and Technology, Volume 66, Issue 16, 18 December 2006, Pages 3097-3114, ISSN 0266-3538 Department of Environmental Protection (DEP), Western Power Corporation, 1996. The Perth Photochemical Smog Study, Department of Environment and Conservation, accessed online 20th May 2013 http://goo.gl/cqf37 DuPont, 1995. Zytel Nylon Resin Moulding Guide, DuPont Engineering Polymers DuPont, 2005. Filament Performance in Brushes, DuPont Filaments, USA, accessed online 29th February 2013 http://www2.dupont.com/Filaments/en_US/assets/downloads/Paintbrush/Filament%20per formance.pdf Ehrenstein, G. 2008. Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc. El-Mazery, C. Correc, O. Colin, X. 2012. A new kinetic model for predicting polyamide 6-6 hydrolysis and its mechanical embrittlement, Elsevier, Polymer Degradation and Stability 97 (2012) 1049-1059 Ezrin, M. 1996. Plastics Failure Guide: Cause and Prevention, SPE books, Hanser Verlag, ISBN 1569901848, 9781569901847 Frierson, D. 2012. Fundamentals of Global Warming Science: Radiation, University of Washington, Department of Atmospheric Sciences, accessed online 20 th April 2013 http://www.atmos.washington.edu/~dargan/587/587_2.pdf Greenhalgh, E. Hiley, M. 2006. Fractography of polymer composites: current status and future issues, Imperial College, London, UK
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Halary, J. Laupretre, F. Monnerie, L. 2011. Polymer Materials, John Wiley & sons Inc. Holland, B. Hay, J. 2000. Thermal Degradation of Nylon Polymers, Polymer International, Vol. 49 Howe, B. 2012. Dry vs. Conditioned Polyamide (Nylon) Explained, EL IDES, accessed online 3rd October 2012 http://www.ides.com/articles/dry_conditioned.asp Intech, 2012. Effects of Temperature and Moisture, Intech Power-Core, Accessed online 10th October 2012 http://www.intechpower.com/material-information/effects-oftemperature-and-moisture Jacob, D. 1999. Introduction to Atmospheric Chemistry, Princeton University Press Jia, N. Howard, A. Kagan, F. Kagan, V. 2004. Effects of Moisture Conditioning Methods on Mechanical Properties of Injection Moulded Nylon 6, Journal of Reinforced Composites, Vol. 23 no. 7 729-737 Jai, N. Kagan, V. 2001. Mechanical Performance of Polyamides with Influence of Moisture and Temperature Accurate Evaluation and Better Understanding Plastics failures and Prevention, William Andrew Publishing Jansen, J. A. 2002. Characterization of Plastics in Failure Analysis, Failure Analysis and Prevention, Vol 11, ASM Handbook, ASM International, 2002, p 437459 acessed online 25th September 2012 http://products.asminternational.org/hbk/do/highlight/content/V11_2002/D05/A04/index. htm Kagan, V. Jia, N. Fraenkel, H. 2004. Effects of Moisture Conditioning Methods on Mechanical Properties of Injection Molded Nylon 6, Journal of Reinforced Plastics and Composites May 2004 vol. 23 no. 7 729-737 Kawasaki, K. 1964. Sorption and diffusion of water vapor by nylon 6, Journal of Polymer Science, John Wiley & Sons, Inc.
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Kawasaki, K. Sekita, Y. 2003. Sorption and diffusion of water vapor by nylon 6, Journal of Polymer Science, John Wiley & Sons, Inc. Kenney, M. Mandell, J. McGarry, F. 1985. The effects of sea water and concentrated salt solutions on the fatigue of nylon 6,6 fibres, Journal of Materials Science, Volume 20, Issue 6, pp 2060-2070 Kenplas, 2013. Dehumidifier, Plastics Machinery, Kenplas Industry Limited, Hangzhou Kenplas Machinery Ltd. Kottek, M. Greiser, J. Beck, C. Rudolf, B. Rubel, F. 2006. World Map of the Kppen-Geiger climate classification updated, Meteorologische Zeitschrift, Vol. 15, No. 3, 259-263 Kyllo, L.1984. Acid rain degradation of nylon (polyamide, photodegradation), Dissertations Publishing, USA Lasoski, S. Cobbs, W. 1959. Moisture Permeability of Polymers. I. Role of Crystallinity and Orientation, Journal Of Polymer Science Vol. XXXVI, Pages 21-33 (1959) Lewis, P. Gagg, C. 2010. Forensic Polymer Engineering: Why Polymer Products Fail in Service Woodhead Publishing Lewis, P. Hainsworth, S. 2006. Fuel Line Failure from stress corrosion cracking, Engineering Failure Analysis,13 (2006) 946-962 Loweth, A. 2000. Perth's air is among the worst in the world, PM, ABC radio transcript, accessed online 3rd May 2013 http://www.abc.net.au/pm/stories/s153517.htm Matweb, 2012. Material Property Data, MatWeb, LLC. Accessed 15th August 2012 http://www.matweb.com/search/search.aspx Mead, J. Mead, K. Auerbach, I. Erickson, R. 1982. Accelerated Aging of Nylon 66 and Kevlar 29 in Elevated Temperature, Elevated Humidity, Smog, and Ozone, Ind. Eng. Chem. Prod. Res. Dev. 1982, 27, 158-163
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Miri, V. Persyn, O. Lefebvre, J. Seguela, R. 2006. Effect of water absorption on the plastic deformation behavior of nylon 6, European Polymer Journal, Volume 45, Issue 3, March 2009, Pages 757-762, ISSN 0014-3057 Murphy, J. 2001. Additives for Plastics Handbook, 2nd Edition, Elsevier Lock, L. Frank, G. 1973. A Study of Some Factors Affecting the Photodegradation of Textile Yarns Part II: Nylon 66 and Polyethylene Terephthalate Yarns, Textile Research Journal Vol. 43 Mark, H. F. 2004. Encyclopaedia of Polymers Science and Technology, 3rd Ed. Vol 12. John Miley & Sons Inc. Marissen, R. Lange, R. Biels, S. Hinkel, P. Nowack, H. Massey, L. 2007. The Effects of UV Light and Weather on Plastics and Elastomers, 2nd Edition, William Andrew Inc. Neil, G.T. 2012, Forensic engineering and failure investigations enhance safe operation and preserve assets, PennWell Corporation, Tulsa, Oil & Gas Journal110. 6 (Jun 4, 2012): B4 -B9 Odian, B. 1981. Principles of Polymerization, 2nd edition, John Wiley & Sons, Publishers, New York, 1981, p. 12. Parrington, R. 2002. Fractography of metals and plastics, Practical Failure Analysis, Vol. 2(5), Accessed online 23rd April, 2013 http://www.asminternational.org/pdf/Fract_PFA.pdf Perkin Elmer, 2011. Characterization of Polymers Using TGA, accessed online 15th May 2011 http://www.perkinelmer.com/CMSResources/Images/44132088APP_CharacterizationofPolymersUsingTGA.pdf Rajeesh, K. Gnanamoorthy, R. Velmurugan, R. 2009. Effect of humidity on the indentation hardness and flexuarla fatigue behaviour of polyamide 6 nanocomposite, Materials Science and engineering, Elsevier Rostaro, D. Rostaro, M. Rostaro, D. 2000. Concise Encyclopedia Of Plastics, Springer
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Rimrod, F. Pickard, L. 2011. Planes grounded, traffic gridlock as smog wreaks havoc across Perth, Newspaper Article, WA today, accessed online 20th May 2013, http://www.watoday.com.au/wa-news/planes-grounded-traffic-gridlock-as-smog-wreakshavoc-across-perth-20110517-1eqib.html Sawyer, L. Grubb, D. Meyers, G. 2008. Polymer microscopy, Springer Scheirs, J. 2000. Compositional and Failure Analysis of Polymers: A Practical Approach, John Wiley and Sons, ISBN 0471625728, 978047162572
Shah, V. 2007. Handbook of Plastics Testing and Failure Analysis, Third Edition, John Wiley & Sons, Inc. Smith, K. Hounshell, D. 1985. Wallace H. Carothers and Fundamental Research at Du Pont, Science, New Series, Vol. 229, No. 4712 (Aug. 2, 1985), pp. 436-442 Snape, M. 2008. Nylon 6 & 6/6 (part 1), UL IDES, accessed online 2nd October 2012 http://www.ides.com/articles/design/2008/sepe-part-98.asp Snape, M. 2007. Fixing Brittle Plastic Nylon Product With Water, UL IDES, accessed online 2nd October 2012 http://www.ides.com/articles/design/2007/sepe_05.asp SoDa, 2013. Yearly Mean of Irradiance in the World, Mines ParisTech, Armines, accessed online 20th April 2013 http://www.soda-is.com/eng/map/maps_for_free.html Strobl, G. 2007. The Physics of Polymers, Springer, 978-3-540-25278-8 Taylor, P. 2003. The Mechanism and Synthesis, Royal Society of Chemistry, ISBN 085404695X Toray, 2013. Physical Properties Water absorption rate, Toray industries In. accessed online April 9th 2013 http://www.toray.jp/plastics/en/products/amilan/technical/tec_003.html
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Verve, 2013. Kwinana, Verve Energy, accessed online 1st May 2013 http://www.verveenergy.com.au Vikas, S. Thakare, B. Singh, G. Verma, M. 2010. Effect of outdoor exposure and accelerated ageing on textile materials used in aerostat and aircraft arrester barrier nets, Indian Journal of Fibre & Textile Research Vol.36, June 2011, pp 145-151 Wellman, 2009. Wellman engineering resins design guide, Engineering Resins Division, accessed online April 9th 2013, http://www.wellmaner.com/assets/files/design-guide.pdf Whelan,. 1994. Polymer Technology Dictionary, Springer, ISBN 0412581809, 9780412581809 Wright, D. 1996. Environmental Stress Cracking of Plastics, iSmithers Rapra Publishing Yarnsand Fibers, 2006. Nylon Chain Report, Global Staistical Compendium, accessed online 20th September 2012 http://www.yarnsandfibers.com/ir/report/nylon_chain_report2006.htm Young, J. Lovell, R. 2011. Introduction to Polymers, 3rd Edition, CRC Press, Taylor & Francis Group LLC
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11.0 Appendix
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Embrittlement of Nylon in Arid Environments

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Steven Bowling 28 Foxwood cct.

Wakerley QLD 4154

Steven Hugh Francis Bowling Student ID: 40789972

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

10.0 References ..................................................................................................................... 61 11.0 Appendix ........................................................................................................................ 69

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

1.3 Introduction to Nylon

1.3.2 Chemistry and Synthesis

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 1 Nylon Synthesis (Adilia, 2006)

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 4 Nylon interacting with water (Howe, 2012)

Embrittlement of Nylon in Arid Environments Steven Bowling

1.4 Investigative method

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 5 General steps involved in failure analysis (Jensen, 2012)

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

1.5 Part specifications and nomenclature

Figure 6 Basic Dimensions of sample

Figure 7 Dimensions of backbone cross section

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 9 Scanning Electron Microscope (Calvier, 2008)

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 11 Hackle morphologies (ASM, 2003)

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 13Schematic of a craze (Halary et al. 2011)

Embrittlement of Nylon in Arid Environments Steven Bowling

2.1 Effect of water content on fracture surface

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

3.0 Possible Failure Modes

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 18 Hydrolysis of Nylon (New World Encylopedia, 2008)

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

3.3 Hygroscopic Behaviour

3.3.1 Rate of moisture diffusion

Embrittlement of Nylon in Arid Environments Steven Bowling

S is the surface area and V is the volume.

Figure 21 Dimensions of backbone cross section

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 22 Water absorption at relative humidity for Nylon. (Brydson, 1999)

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

24hr Humidity for 20/05/2013

Embrittlement of Nylon in Arid Environments Steven Bowling

Embrittlement of Nylon in Arid Environments Steven Bowling

Figure 27Moisture gain in wt% over time (Jia et al. 2004)

3.3.2 Solar radiation and moisture loss

Embrittlement of Nylon in Arid Environments Steven Bowling

3.3.3 Outdoor exposure tests

Nylon 66 (CM3001-N) 0 years

1 year and 9 months

Flexural modulus Izod impact strength Rockwell hardness

Embrittlement of Nylon in Arid Environments Steven Bowling

Miscellaneous effects of water