Studies of the radiation chemistry and grafting of a fluoropolymer

The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

Predicting active material utilisation in LiFePO4 electrodes using a multi-scale mathematical model

A mathematical model is developed to simulate the discharge of a LiFePO4 cathode. This model contains 3 size scales, which match with experimental observations present in the literature on the multi-scale nature of LiFePO4 material. A shrinking-core is used on the smallest scale to represent the phase-transition of LiFePO4 during discharge. The model is then validated against existing experimental data and this validated model is then used to investigate parameters that influence active material utilisation. Specifically the size and composition of agglomerates of LiFePO4 crystals is discussed, and we investigate and quantify the relative effects that the ionic and electronic conductivities within the oxide have on oxide utilisation. We find that agglomerates of crystals can be tolerated under low discharge rates. The role of the electrolyte in limiting (cathodic) discharge is also discussed, and we show that electrolyte transport does limit performance at high discharge rates, confirming the conclusions of recent literature.

Legislative and security requirements of audit material for evidentiary purpose

This research used the Queensland Police Service, Australia, as a major case study. Information on principles, techniques and processes used, and the reason for the recording, storing and release of audit information for evidentiary purposes is reported. It is shown that Law Enforcement Agencies have a two-fold interest in, and legal obligation pertaining to, audit trails. The first interest relates to the situation where audit trails are actually used by criminals in the commission of crime and the second to where audit trails are generated by the information systems used by the police themselves in support of the recording and investigation of crime. Eleven court cases involving Queensland Police Service audit trails used in evidence in Queensland courts were selected for further analysis. It is shown that, of the cases studied, none of the evidence presented was rejected or seriously challenged from a technical perspective. These results were further analysed and related to normal requirements for trusted maintenance of audit trail information in sensitive environments with discussion on the ability and/or willingness of courts to fully challenge, assess or value audit evidence presented. Managerial and technical frameworks for firstly what is considered as an environment where a computer system may be considered to be operating “properly” and, secondly, what aspects of education, training, qualifications, expertise and the like may be considered as appropriate for persons responsible within that environment, are both proposed. Analysis was undertaken to determine if audit and control of information in a high security environment, such as law enforcement, could be judged as having improved, or not, in the transition from manual to electronic processes. Information collection, control of processing and audit in manual processes used by the Queensland Police Service, Australia, in the period 1940 to 1980 was assessed against current electronic systems essentially introduced to policing in the decades of the 1980s and 1990s. Results show that electronic systems do provide for faster communications with centrally controlled and updated information readily available for use by large numbers of users who are connected across significant geographical locations. However, it is clearly evident that the price paid for this is a lack of ability and/or reluctance to provide improved audit and control processes. To compare the information systems audit and control arrangements of the Queensland Police Service with other government departments or agencies, an Australia wide survey was conducted. Results of the survey were contrasted with the particular results of a survey, conducted by the Australian Commonwealth Privacy Commission four years previous, to this survey which showed that security in relation to the recording of activity against access to information held on Australian government computer systems has been poor and a cause for concern. However, within this four year period there is evidence to suggest that government organisations are increasingly more inclined to generate audit trails. An attack on the overall security of audit trails in computer operating systems was initiated to further investigate findings reported in relation to the government systems survey. The survey showed that information systems audit trails in Microsoft Corporation's “Windows” operating system environments are relied on quite heavily. An audit of the security for audit trails generated, stored and managed in the Microsoft “Windows 2000” operating system environment was undertaken and compared and contrasted with similar such audit trail schemes in the “UNIX” and “Linux” operating systems. Strength of passwords and exploitation of any security problems in access control were targeted using software tools that are freely available in the public domain. Results showed that such security for the “Windows 2000” system is seriously flawed and the integrity of audit trails stored within these environments cannot be relied upon. An attempt to produce a framework and set of guidelines for use by expert witnesses in the information technology (IT) profession is proposed. This is achieved by examining the current rules and guidelines related to the provision of expert evidence in a court environment, by analysing the rationale for the separation of distinct disciplines and corresponding bodies of knowledge used by the Medical Profession and Forensic Science and then by analysing the bodies of knowledge within the discipline of IT itself. It is demonstrated that the accepted processes and procedures relevant to expert witnessing in a court environment are transferable to the IT sector. However, unlike some discipline areas, this analysis has clearly identified two distinct aspects of the matter which appear particularly relevant to IT. These two areas are; expertise gained through the application of IT to information needs in a particular public or private enterprise; and expertise gained through accepted and verifiable education, training and experience in fundamental IT products and system.

EduBuilding: material selection from life cycle costing sensitivity

Life Cycle Cost Analysis provides a form of synopsis of the initial and consequential costs of building related decisions. These cost figures may be implemented to justify higher investments, for example, in the quality or flexibility of building solutions through a long term cost reduction. The emerging discipline of asset mnagement is a promising approach to this problem, because it can do things that techniques such as balanced scorecards and total quantity cannot. Decisions must be made about operating and maintaining infrastructure assets. An injudicious sensitivity of life cycle costing is that the longer something lasts, the less it costs over time. A life cycle cost analysis will be used as an economic evaluation tool and collaborate with various numbers of analyses. LCCA quantifies incurring costs commonly overlooked (by property and asset managers and designs) as replacement and maintenance costs. The purpose of this research is to examine the Life Cycle Cost Analysis on building floor materials. By implementing the life cycle cost analysis, the true cost of each material will be computed projecting 60 years as the building service life and 5.4% as the inflation rate percentage to classify and appreciate the different among the materials. The analysis results showed the high impact in selecting the floor materials according to the potential of service life cycle cost next.

Restructuring instructional material in vocational education to enhance learning

This paper reviews research findings regarding the design of instructional material and its effectiveness in facilitating learning. Firstly, a discussion of memory processes engaged in when learning from different types of instructional material is presented. Secondly, referring to empirical research, the implications of the above discussion for vocational education instruction, and in particular, for engineering graphics, CNC programming and learning to use equipment from manuals are presented.

A material model for flexural crack simulation in reinforced concrete elements using ABAQUS

This paper presents a material model to simulate load induced cracking in Reinforced Concrete (RC) elements in ABAQUS finite element package. Two numerical material models are used and combined to simulate complete stress-strain behaviour of concrete under compression and tension including damage properties. Both numerical techniques used in the present material model are capable of developing the stress-strain curves including strain softening regimes only using ultimate compressive strength of concrete, which is easily and practically obtainable for many of the existing RC structures or those to be built. Therefore, the method proposed in this paper is valuable in assessing existing RC structures in the absence of more detailed test results. The numerical models are slightly modified from the original versions to be comparable with the damaged plasticity model used in ABAQUS. The model is validated using different experiment results for RC beam elements presented in the literature. The results indicate a good agreement with load vs. displacement curve and observed crack patterns.

Analysis of micro-structural changes and measurement of their parameters of a food material

Food microstructure represents the way their elements arrangement and their interaction. Researchers in this field benefit from identifying new methods of examination of the microstructure and analysing the images. Experiments were undertaken to study micro-structural changes of food material during drying. Micro-structural images were obtained for potato samples of cubical shape at different moisture contents during drying using scanning electron microscopy. Physical parameters such as cell wall perimeter, and area were calculated using an image identification algorithm, based on edge detection and morphological operators. The algorithm was developed using Matlab.

The meaning of 'material prejudice'

As dictated by s 213 of the Body Corporate and Community Management Act 1997 (Qld), the seller of a proposed lot is required to provide the buyer with a disclosure statement before the contract is entered into. Where the seller subsequently becomes aware that information contained in the disclosure statement was inaccurate when the contract was entered into or the disclosure statement would not be accurate if now given as a disclosure statement, the seller must, within 14 days, give the buyer a further statement rectifying the inaccuracies in the disclosure statement. Provided the contract has not been settled, where a further statement varies the disclosure statement to such a degree that the buyer would be materially prejudiced if compelled to complete the contract, the buyer may cancel the contract by written notice given to the seller within 14 days, or a longer period as agreed between the parties, after the seller gives the buyer the further statement. The term ‘material prejudice’ was considered by Wilson J in Wilson v Mirvac Queensland Pty Ltd.

Queensland Court of Appeal opines on the meaning of 'material prejudice'

The decision of Wilson J in Wilson v Mirvac Queensland Pty Ltd was the subject of an article in an earlier edition of this journal. At that time, it was foreshadowed that the decision was to be taken on appeal. The decision of the Court of Appeal in Mirvac Queensland Pty Ltd v Wilson is considered in this article.