Applied research on organometallics and organic materials

This thesis submitted for the degree of Doctor of Science, University of Tasmania, is entitled \Applied Research on Organometallics and Organic Materials\". It represents work undertaken in the employment of the Commonwealth of Australia during the period 1951-78. The thesis resulted from a suggestion that some early work carried out by the author on compounds based on phosphorus silicon and tin could still be of interest to scientists associated with organometallic chemistry. The approval for the unlimited public release of some of this work has enabled it now to be included. Prior to joining Defence Standards Laboratories Department of Supply (now Materials Research Laboratories Department of Defence) early in 1951 studies for the Degrees of Bachelor of Science and Bachelor of Science with Honours were undertaken at the University of Tasmania. A short period of post graduate research at the University followed the completion of the academic requirements for an Honours Degree. At the Ministry of Supply Britainduring 1951-53work was undertaken on special organometallic compounds. The synthesis of a new series of ether-containing organophosphorus compounds was initiated in collaboration with the late A.H. FORD-MOORE a specialist in organophosphorus chemistry. This was followed at my suggestion by a detailed study of the structure-toxicity relationships of some silicon analogues of the organophosphorus compounds. In the early 1950's the chemistry of organosilicon compounds was at an early stage of development and this area of research was relatively unexplored. The interest generated in phosphorus and silicon chemistry in Britain stimulated further research on organometallics (and related materials) following my return to Australia. One of these activities was the synthesis of a new series of tetraorthoesters of titanium as these materials were of interest as vehicles for heat-resistant paints. This work was completed in 1957. At about the same period the author became involved with scientific studies associated with several atomic tests conducted at Maralinga South Australia and code named Operation BUFFALO. A further area of research on organometallics was initiated in - 1957 and this work on the chemistry and applications of organotin compounds has continued for twenty years. During this period other scientists at MRL have also been associated with some of the research activities. In the mid-1960's during a period of secondment to the US Army work was initiated on the development of high performance non-black ethylene-propylene diene elastomers using new synthetic materials that had been introduced in the USA during 1963-64. On return to Australia applied research on organotin compounds was continued as well as work on a wide range of organic materials mainly rubbers and plastics. These types of activities are still in progress. The original aim of our research activities on organometallics was to find new applications for these interesting and versatile chemicals. In the role of additives they have shown considerable promise in the modification of the properties of a wide range of organic materials such as: rubbers; plastics; adhesives; sealants; coatings; and fibres. In this thesis details are given of our efforts to modify organic materials by the addition of organometallic compounds. To record my continuing interest in applied research other items associated with organic analyses and organic materials are included. During the period 1951-74 the research was undertaken at Defence Standards Laboratories (DSL) first in Department of Supply and then in Department of Manufacturing Industry. On 19 September 1974 DSL'sincreasing role in scientific studies of defence materials was recognised by a change of name to Materials Research Laboratories (MRL) and the transfer of MEL from Department of Manufacturing Industry to Department of Defence. Summary details of research activities during the period 1951-78 are given at Appendix 1. The work reported in this thesis was initiated by the author and undertaken either alone or with the collaboration of other scientific staff. Where appropriate results have been published in the open scientific literature or in the form of Government reports with collaboration being recognised by co-authorship. Details of co-authors including their past and present designations and present positions are given at Appendix 2. Although the research described was conducted over a number of years it has all been concerned with the understanding of unexpected chemical phenomena and the development of new and improved organic materials of primary interest to the Defence Force of Australia as well as to the scientific community in general. All the work reported in this thesis is original and is now unclassified. Some previously unpublished work is also included. The nature of this work is indicated in the text together with details of official references to documents available from Materials Research Laboratories. To confirm the initiation of and participation in the reported research activities copies of some specific documentation relating to the work presented are also included. It is a pleasure to record that the late Arthur FORD-M00RE Chemical Defence Establishment Ministry of Defence Porton Britain was responsible for the stimulation of my interest in defence science in general and organometallic chemistry in particular. The example of his aptitude towards the solving of chemical problems his manipulative skill in the laboratory and his general philosophy to research provided the stimulus that was necessary to maintain a long-term continuing interest in organometallics and organic materials of defence Interest. None of the work presented in this thesis has previously been submitted for the Degree of Doctor of Science."