Selection and optimization of piezoelectric polyvinylidene fluoride polymers for adaptive optics in space environments

Various piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films depend on charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to deteriorate owing to strong vacuum UV, � -, X-ray, energetic particles and atomic oxygen exposure. We have investigated the degradation of PVDF and its copolymers under various stress environments detrimental to reliable operation in space. Initial radiation aging studies have shown complex material changes with lowered Curie temperatures, complex material changes with lowered melting points, morphological transformations and significant crosslinking, but little influence on piezoelectric d33 constants. Complex aging processes have also been observed in accelerated temperature environments inducing annealing phenomena and cyclic stresses. The results suggest that poling and chain orientation are negatively affected by radiation and temperature exposure. A framework for dealing with these complex material qualification issues and overall system survivability predictions in low earth orbit conditions has been established. It allows for improved material selection, feedback for manufacturing and processing, material optimization/stabilization strategies and provides guidance on any alternative materials.

Effect of simulated space environments on piezoelectric vinylidene flouride-based polymers

Piezoelectric polymers based on polyvinylidene flouride (PVDF) are of interest as adaptive materials for large aperture space-based telescopes. In this study, two piezoelectric polymers, PVDF and P(VDF-TrFE), were exposed to conditions simulating the thermal, radiative and atomic oxygen conditions of low Earth orbit. The degradation pathways were governed by a combination of chemical and physical degradation processes with the molecular changes primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure, as evident from depoling, loss of orientation and surface erosion. The piezoelectric responsiveness of each polymer was strongly dependent on exposure temperature. Radiation and atomic oxygen exposure caused physical and chemical degradation, which would ultimately cause terminal damage of thin films, but did not adversely affect the piezoelectric properties.

Piezoelectric vinylidene-fluoride based polymers for use in space environments

The effects of simulated low earth orbit conditions on vinylidene-fluoride based thin-film piezoelectrics for use in lightweight, large surface area spacecraft such as telescope mirrors and antennae is presented. The environmental factors considered as having the greatest potential to cause damage are temperature, atomic oxygen and vacuum UV radiation. Using the piezoelectric strain coefficients and bimorph deflection measurements the piezoelectric performance over the temperature range -100 to +150°C was studied. The effects of simultaneous AO/VUV exposure were also examined and films characterized by their piezoelectric, surface, and thermal properties. Two fluorinated piezoelectric polymers, poly(vinylidene fluoride) and poly(vinylidene fluoride-co-trifluoroethylene), were adversely affected at elevated temperatures due to depoling caused by randomization of the dipole orientation, while AO/VUV contributed little to depoling but did cause significant surface erosion and, in the case of P(VDF-TrFE), bulk crosslinking. These results highlight the importance of materials selection for use in space environments.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

Novel synthetic bio-mimic polymers for potential cell delivery therapy

Cell-based therapy is one of the major potential therapeutic strategies for cardiovascular, neuronal and degenerative diseases in recent years. Synthetic biodegradable polymers have been utilized increasingly in pharmaceutical, medical and biomedical engineering. Control of the interaction of living cells and biomaterials surfaces is one of the major goals in the design and development of new polymeric biomaterials in tissue engineering. The aims of this study is to develop a novel bio-mimic polymeric materials which will facilitate the delivery cells, control cell bioactivities and enhance the focal integration of graft cells with host tissues.

Value-adding to cellulosic ethanol: Lignin polymers

Lignocellulosic waste materials are the most promising feedstock for generation of a renewable, carbon-neutral substitute for existing liquid fuels. The development of value-added products from lignin will greatly improve the economics of producing liquid fuels from biomass. This review gives an outline of lignin chemistry, describes the current processes of lignocellulosic biomass fractionation and the lignin products obtained through these processes, then outlines current and potential value-added applications of these products, in particular as components of polymer composites. Research highlights The use of lignocellulosic biomass to produce platform chemicals and industrial products enhances the sustainability of natural resources and improves environmental quality by reducing greenhouse and toxic emissions. In addition, the development of lignin based products improves the economics producing liquid transportation fuel from lignocellulosic feedstock. Value adding can be achieved by converting lignin to functionally equivalent products that rely in its intrinsic properties. This review outlines lignin chemistry and some potential high value products that can be made from lignin. Keywords: Lignocellulose materials; Lignin chemistry; Application

Diels-Alder reactions as an efficient route to high purity cyclic polymers

A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels–Alder reaction yielding a high purity cyclic product.

Photoinduced conjugation of Dithioester- and Trithiocarbonate-Functional RAFT polymers with alkenes

We report the photoinduced conjugation of polymers synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization with a number of low molecular weight (functional) olefins. Upon irradiation of a solution of an aliphatic alkene and the benzyl dithioacetic acid ester (CPDA) or dodecyl trithiocarbonate (DoPAT) functional poly(alkyl acrylate) at the absorption wavelength of the thiocarbonyl group (315 nm), incorporation of the alkene at the polymer chain-end occurred. The most efficient systems identified with regard to the rate of reaction and yield were poly(butyl acrylate)/CPDA/ethyl vinyl ether (78% monoinsertion product after 1 h) and poly(butyl acrylate)/CPDA/1-pentene (73% insertion product after 7 h) at ambient temperature. An in-depth analysis of the reaction mechanism by 1H NMR and online size-exclusion chromatography-electrospray ionization tandem mass spectrometry (SEC/ESI−MSn) revealed that a possible [2 + 2] photoaddition mechanism of conjugation does not take place. Instead, fast β-cleavage of the photoexcited RAFT-end group with subsequent radical addition of an alkene was observed for all employed systems. The presented reaction thus provides a means of spatial and temporal control for the conjugation of alkenes to thiocarbonyl thio-capped macromolecules via the use of UV radiation.

Chain scission resists for extreme ultraviolet lithography based on high performance polysulfone-containing polymers

A series of polymers with a comb architecture were prepared where the poly(olefin sulfone) backbone was designed to be highly sensitive to extreme ultraviolet (EUV) radiation, while the well-defined poly(methyl methacrylate) (PMMA) arms were incorporated with the aim of increasing structural stability. It is hypothesized that upon EUV radiation rapid degradation of the polysulfone backbone will occur leaving behind the well-defined PMMA arms. The synthesized polymers were characterised and have had their performance as chain-scission EUV photoresists evaluated. It was found that all materials possess high sensitivity towards degradation by EUV radiation (E0 in the range 4–6 mJ cm−2). Selective degradation of the poly(1-pentene sulfone) backbone relative to the PMMA arms was demonstrated by mass spectrometry headspace analysis during EUV irradiation and by grazing-angle ATR-FTIR. EUV interference patterning has shown that materials are capable of resolving 30 nm 1:1 line:space features. The incorporation of PMMA was found to increase the structural integrity of the patterned features. Thus, it has been shown that terpolymer materials possessing a highly sensitive poly(olefin sulfone) backbone and PMMA arms are able to provide a tuneable materials platform for chain scission EUV resists. These materials have the potential to benefit applications that require nanopattering, such as computer chip manufacture and nano-MEMS.

Two-dimensional coordination polymers in rubidium and caesium complexes with orthanilic acid

The crystal structures of the rubidium and caesium complexes with 2-aminobenzenesulfonic acid (orthanilic acid), [Rb4(C6H6NO3S)4(H2O)]n (1) and [Cs(C6H6NO3S)]n (2) and have been determined at 200 K. Complex 1 has a repeating unit comprising four independent and different Rb coordination centres, (RbO8), (RbO7), (RbN2O4) and (RbO10), each having irregular stereochemistry and involving a number of bidentate chelate sulfonate-O,O’-metal and bridging interactions, giving a two-dimensional polymeric layered structure. Anhydrous complex 2 is also polymeric with the irregular (CsO7) coordination polyhedron comprising six sulfonate oxygen donors from three separate bidentate chelate sulfonate ligands and one monodentate bridging sulfonate oxygen, giving a two-dimensional layered structure.