Primary chemical events in ion bombarded polystyrene films: An infrared study

Puglisi, Orazio; Licciardello, A.; Pignataro, S.; Calcagno, L.; Fóti, G.

doi:10.1080/00337578608206108

Cited by 32 publications

(15 citation statements)

References 7 publications

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“…These studies have all indicated major physical and chemical property changes in the surface regions of the polymers, which may or may not be permanent, depending on the fluence. In most cases, there are significant changes in the mechanical (Lee et al, , 1997Nishimiya et al, 1991;Lee, Lee, & Mansur, 1992;Ochsner et al, 1993;Rao, Wang, & Lee, 1993;Rao et al, 1995;Tretinnikov & Ikada, 1998), chemical (Puglisi et al, 1986;Nishimiya et al, 1991;Lee et al, 1993Lee et al, , 1997Š vorčík et al, 1998;Tretinnikov & Ikada, 1998), electronic (Forrest et al, 1982;Venkatesan et al, 1983;Liu, Liu, & Zhai, 1989;Lee et al, 1993;Š vorčík et al, 1997), diffusion (Calcagno et al, 1993), optical (Calcagno, Compagnini, & Foti, 1992;Rück, Schulz, & Beusch, 1997), and rheological properties (Calcagno, Compagnini, & Foti, 1992) of ion-bombarded polymeric samples. These changes are obviously a result of the increased crosslinking and unsaturation occurring in these polymers.…”

Section: B Atomic Ion Bombardment Of Polymersmentioning

confidence: 99%

Cluster secondary ion mass spectrometry of polymers and related materials

Mahoney

2009

Mass Spectrometry Reviews

283

329

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Cluster secondary ion mass spectrometry (cluster SIMS) has played a critical role in the characterization of polymeric materials over the last decade, allowing for the ability to obtain spatially resolved surface and in-depth molecular information from many polymer systems. With the advent of new molecular sources such as C(60)(+), Au(3)(+), SF(5)(+), and Bi(3)(+), there are considerable increases in secondary ion signal as compared to more conventional atomic beams (Ar(+), Cs(+), or Ga(+)). In addition, compositional depth profiling in organic and polymeric systems is now feasible, without the rapid signal decay that is typically observed under atomic bombardment. The premise behind the success of cluster SIMS is that compared to atomic beams, polyatomic beams tend to cause surface-localized damage with rapid sputter removal rates, resulting in a system at equilibrium, where the damage created is rapidly removed before it can accumulate. Though this may be partly true, there are actually much more complex chemistries occurring under polyatomic bombardment of organic and polymeric materials, which need to be considered and discussed to better understand and define the important parameters for successful depth profiling. The following presents a review of the current literature on polymer analysis using cluster beams. This review will focus on the surface and in-depth characterization of polymer samples with cluster sources, but will also discuss the characterization of other relevant organic materials, and basic polymer radiation chemistry.

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Section: B Atomic Ion Bombardment Of Polymersmentioning

confidence: 99%

Cluster secondary ion mass spectrometry of polymers and related materials

Mahoney

2009

Mass Spectrometry Reviews

283

329

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“…Altough it has been shown that the changes induced by irradiation depend on the energy deposition process, a detailed description of the relevance of the different energy deposition mechanisms (elastic versus inelastic) in the modification processes is still lacking (Puglisi et al 1986;Fink et al 1994). According to our results, comparing the effect of Ar and H irradiation on the absorption coefficient it seems that the spectral changes of this organic material are mainly due to elastic collisions.…”

Section: Experiments With Polystyrenementioning

confidence: 99%

Space weathering of asteroidal surfaces

Kaňuchová

Baratta²,

Garozzo³

et al. 2010

A&A

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Context. The surfaces of airless bodies in the Solar System are continuously altered by the bombardment of micrometeoroids and irradiation by solar wind, flares, and cosmic particles. Major effects of this process -space weathering -are darkening and "reddening" of the spectra of surface materials, as well as a "degrading" of absorption features. Aims. We studied the changes induced by energetic ion irradiation in the ultraviolet-visual-near-infrared (UV-Vis-NIR) (0.2-0.98 μm) reflectance spectra of targets selected to mimic the surfaces of airless bodies in the inner Solar System. Our chosen targets are olivine pellets, pure or covered by an organic polymer (polystyrene), which is transparent before irradiation. Polystyrene is used as a template for organic matter of low volatility that can be present on asteroidal surfaces. Moreover we measured the changes induced by ion irradiation in the absorption coefficient of the polymer. The purpose was to have a tool to better compare laboratory with observed spectra and distinguish between planetary objects with pure silicate surfaces and those whose surface is covered by organic matter exposed to cosmic ion bombardment. Methods. The samples were irradiated in vacuum, at room temperature, with 200 keV protons or 200-400 keV argon ions. Before, during, and after irradiation diffuse reflectance spectra were acquired. Polystyrene films were also deposited on quartz substrates and irradiated while transmittance spectra were recorded. Results. We measured the variations of the absorption coefficient of polystyrene as a function of ion fluence. We showed that after ion irradiation the diffuse reflectance spectra of the samples covered by organics exhibit a much more significant variation than those of pure silicates. The spectra of targets made of olivine plus polystyrene can be fitted by using the measured absorption coefficient of polystyrene. Conclusions. The results obtained for pure olivine extend to the UV the spectral range of previous experiments. The data concerning the absorption coefficient of polystyrene are available on our web site (http://web.ct.astro.it/weblab/dbindex.html) and can be used to compare laboratory with astronomical spectra. This will possibly allow us to obtain information about organic matter on the surface of a given object, as well as on the relevance of the exposure to cosmic ions (space weathering).

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“…A few γ versus reactor irradiation comparisons have been published. , However, logically, most of the high LET data come from ion irradiations. A very significant number of papers deal with PS irradiated at high LET, but, unfortunately, there are only some partial reviews. – Without being exhaustive, we can mention different groups that have been active in this domain: Bell laboratories, , Oak Ridge, , Notre Dame, ,, Berlin, , Catania, – and GSI. – Our group has also contributed to the study of LET effects in PS – with an approach very similar to the one used for polyolefins , and PVDF . In fact, these works cover very different situations in terms of ion masses, ion velocities, and dose range.…”

Section: Introductionmentioning

confidence: 99%

“…The LET effect on the yield of dihydrogen emission was studied by several teams. ,, The most recent work mentions an increase of a factor 30 with respect to electron irradiation when LET reaches 10 MeV·cm 2 ·mg −1 . Methane, acetylene, and benzene are also significantly produced at high LET. , At the molecular level, Fourier transform infrared spectroscopy (FTIR) was widely used, ,,, and FTIR results will be deeply analyzed in the core of the article. In all polymers, it is now well established that specific unsaturated bonds, alkynes and in some cases allenes, are observed above a LET threshold .…”

Section: Introductionmentioning

confidence: 99%

“…In PS, Z. Zhu et al have determined a LET threshold value of ∼8 MeV·cm 2 ·mg −1 for alkyne formation. The detection of cross-linking at the molecular level by FTIR has been debated, ,, but it is difficult to get rid of ambiguities (see the Appendix). Martínez-Prado et al reported a Nuclear Magnetic Resonance (NMR) experiment on PS massively (320 MGy) irradiated by 1.5 MeV protons.…”

Section: Introductionmentioning

confidence: 99%

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Irradiation of Atactic Polystyrene: Linear Energy Transfer Effects

et al. 2008

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Atactic glassy polystyrene (PS) has been irradiated in anoxic conditions by electron and ion beams. The induced modifications were followed, in situ, by Fourier transform infrared spectroscopy (FTIR). In-film modifications and hydrocarbon gas release were followed. In-situ measurements allowed one to avoid any spurious oxidation of the films after irradiation and also permitted studying in detail the evolution with dose of the FTIR spectra. The data were quantitatively analyzed, and we present a complete analysis of the effects of the Linear Energy Transfer (LET) on the radiation chemical yields of several radiation-induced modifications (alkynes, allenes, alkenes, benzene, and disubstituted benzenes). For a better understanding of the LET effects, the in-film modifications are compared to H2 release data from the literature and to our measurements of hydrocarbon gaseous molecule yields obtained by us. The overall destruction yield becomes very significant at high LET, and the radiation sensitivity of this aromatic polymer merges with typical values of aliphatic polymers: the radiation resistance conferred at low LET to polystyrene by the phenyl side groups is lost at high LET. This loss of radiation resistance equally affects the aromatic and aliphatic moieties. Monosubstituted alkynes are created above a LET threshold, whereas the other radiation-induced modifications are observed in the whole LET range. Several observations indicate that the phenyl ring is broken at high LET. Comparison of the alkyne yield in PS, polyethylene, and polycarbonate as well as the formation of nitrile bonds in poly(vinylpyridine- co-styrene) are consistent with a cleavage of the phenyl ring as the prominent source of alkynes. As the competing damage mechanisms do not have the same LET evolution, the relative importance of a specific modification on the global damage depends on LET. Some (benzene and disubstituted benzenes) dominate at low LET, while others (in-film alkyne and acetylene release) dominate at high LET.

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Primary chemical events in ion bombarded polystyrene films: An infrared study

Cited by 32 publications

References 7 publications

Cluster secondary ion mass spectrometry of polymers and related materials

Cluster secondary ion mass spectrometry of polymers and related materials

Space weathering of asteroidal surfaces

Irradiation of Atactic Polystyrene: Linear Energy Transfer Effects

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