Initial stage of etching through pores in PET films irradiated by Ar ions

Changes in the diameters and depths of pores were studied in the process of etching polyethyleneterephthalate (PET) films irradiated by Ar ions having an energy of 1 MeV/n. Information about the pore diameters and lengths was obtained with JSM-840 and TEM-125 electron microscopes. The solutions of NaOH (0.5 mol/dm³ and 2 mol/dm³) were used as etchants. Etching was performed at 55 °C and 70 °C. Two methods of sensitization were used: the first one by UV illumination and treatment in dimethylformamide (DMF), the second method just by UV illumination. It was found that the diameters and the depths of pores are larger in films treated according to the first sensitization method. Etching duration (breakthrough time), which leads to through-going pores of the minimal radius, was established. After sensitization according to the first method the track etch rate grows quicker than the transverse etch rate. This gives a possibility to obtain through pores with diameters ranging from 50 nm to several micrometers.     

Neutron irradiation-induced dimensional changes in MEMS glass substrates

A study is made of radiation-induced expansion/compaction in Pyrex^® (Corning 7740) and Hoya SD-2^® glasses, which are used as substrates for MEMS devices. Glass samples were irradiated with a neutron fluence composed primarily of thermal neutrons, and a flotation technique was employed to measure the resulting density changes in the glass. Transport of Ions in Matter (TRIM) calculations were performed to relate fast (∼1 MeV) neutron atomic displacement damage to that of boron thermal neutron capture events, and measured density changes in the glass samples were thus proportionally attributed to thermal and fast neutron fluences. Pyrex was shown to compact at a rate of (in Δρ/ρ per n/cm²) 8.14 × 10⁻²⁰ (thermal) and 1.79 × 10⁻²⁰ (fast). The corresponding results for Hoya SD-2 were 2.21 × 10⁻²¹ and 1.71 × 10⁻²¹, respectively. On a displacement per atom (dpa) basis, the compaction of the Pyrex was an order of magnitude greater than that of the Hoya SD-2. Our results are the first reported measurement of irridiation-induced densification in Hoya SD-2. The compaction of Pyrex agreed with a previous study. Hoya SD-2 is of considerable importance to MEMS, owing to its close thermal expansivity match to silicon from 25 to 500°C.     

Gamma-rays irradiation effects on polysulfone at high temperature

The temperature dependence of the irradiation effects on polysulfone was studies by measuring the molecular weight, glass transition temperature, gel fraction and evolved gas. Polysulfone was irradiated with gamma-rays at room temperature, 100, 150, 180 and 210 °C. The change of molecular weight distribution and glass transition temperature showed occurrences of a main chain scission at room temperature and cross-linking at high temperature. The decrease of gel dose, the increases of gel fraction and total gas evolution with increasing temperature was observed. The evolution of CO, CO₂ and SO₂ gases increased at high temperature, while yield of evolved H₂ was independent of irradiation temperature. The probability of the cross-linking was clearly increased by irradiation at high temperature above 180 °C, though the chain scission was not changed very much.     

Radiation resistance of photodiodes based on indium monoselenides under γ-irradiation

The influence of γ-irradiation (E = 3 MeV) over a large dose range 0.14-140 kGy on the electrical and photoelectric parameters of p-n-InSe and intrinsic oxide-p-InSe photoconvertors has been investigated. The detected changes in current-voltage characteristics, photoresponse spectra, open-circuit voltage, and short-circuit current for the structures are explained by the formation of radiation-induced point defects. A comparison to silicon photodiodes irradiated at analogous conditions has been carried out. On the basis of the absence of essential changes of the characteristics of the homo- and hetero-junctions based on III-VI layered semiconductors even at the maximum irradiation doses these junctions are recommended as radiation-resistant photodetectors for operation under γ-irradiation.     

Effect of gamma irradiation on a polymer electrolyte: Variation in crystallinity, viscosity and ion-conductivity with dose

PEO(1 − x)NH₄ClO₄(x) samples with x = 0.18 are irradiated with gamma doses varying up to 50 kGy. DSC and XRD studies indicate, in general, a decrease in crystallinity with dose. Measurement of viscosity of aqueous solutions of the irradiated samples at the same concentration, shows that there is overall chain scission on irradiation, though there is evidence of some cross-linking also at higher doses. This is corroborated by FTIR measurements. The ion-conductivity shows a strong increase for irradiation dose 35 kGy. This suggests that there is a possibility of improving polymer electrolyte properties on gamma irradiation.     

Beneficial effect of gamma irradiation on the N-deacetylation of chitin to form chitosan

The effect of gamma irradiation on the N-deacetylation of chitin to form chitosan was studied. Chitin from crab shells was irradiated up to 20 kGy and N-deacetylated in aqueous NaOH solution (40% and 60% w/w) at 60 and 100 °C for 60 min. The degree of N-deacetylation (DD) of non-irradiated and irradiated samples was determined by IR-band ratio method. It was found that higher extent of N-deacetylation was achieved for the chitin samples irradiated up to 20 kGy doses as compared to non-irradiated chitin. The DD values of chitin, prepared from non-irradiated and 20 kGy irradiated chitins by N-deacetylation at 60 °C with 40% NaOH for 60 min, were found to be 38% and 60%, respectively. The increase in DD by irradiation was interpreted as a result of reduction in molecular weight of chitin. Low dose irradiation of chitin has provided the possibility of its N-deacetylation into chitosan at much milder reaction conditions.     

Ion track formation in low temperature silicon dioxide

Low temperature silicon dioxide layers (LTO), deposited on crystalline silicon substrates, and thermally densified at 750 °C for 90 min or 900 °C for 30 min, jointly with thermally grown silicon dioxide layers, were irradiated with low fluence 11 MeV Ti ions. A selective chemical etch of the latent tracks generated by the passage of swift ions was performed by wet or vapour HF solution. The wet process produced conically shaped holes, while the vapour procedure generated almost cylindrical nanopores. In both cases thermal SiO₂ showed a lower track etching velocity V_t, but with increasing the densification temperature of the LTO samples, the V_t differences reduced. LTO proved to be suitable for wet and vapour ion track formation, and, as expected, for higher densification temperatures, its etching behaviour approached that of thermal silicon dioxide.     

Experimental study of the response of radiochromic films to proton radiation of low energy

We have investigated the response of radiochromic films (MD-55 and HD-810) exposed to protons of 0.6 MeV. Each film is bombarded with a proton beam in an angular geometry, in such a way that the absorbed dose is related to angle. Depending on the energy and the angular fluence, the irradiated volume is total or partial. We compare the dose of these irradiated films with fully irradiated films exposed to γ radiation from a ⁶⁰Co calibrated source.     

Radiation cross-linking of small electrical wire insulator fabricated from NR/LDPE blends

A low voltage, radiation-crosslinked wire insulator has been fabricated from blends of natural rubber block (STR-5L) and LDPE with phthalic anhydride (PA) as a compatibilizer. Physical properties of the NR/LDPE blend ratios of 50/50 and 60/40 with 0.5, 1.0, and 1.5 wt% PA were evaluated. The gel content increased as the radiation dose increased. Tensile at break exhibited a maximum value of 12 MPa at 120 kGy for 1.0 and 1.5 wt% PA of both blend ratios. A higher PA content yielded a higher modulus for the same blend ratio. Blends of 60/40 ratio with 1.0 wt% PA and 0.8 wt% antimony oxide flame retardant gave the highest limiting oxygen index (LOI) of >30% at above 150 kGy. Other electrical properties of the wire insulator were investigated. It was found that an insulator fabricated from a PA content of 1.0 wt% in the NR/LDPE blend ratio of 50/50, after gamma ray cross-linked at a dose of 180 kGy in low vacuum (1 mm Hg), met the Thai Industrial Standard 11-2531 for low voltage wire below 1.0 kV. To comply with the standard for vertical flame test, a more suitable flame retardant was needed for the insulator.     

Evidence of nanostructure formation in Ge oxide by crystallization induced by swift heavy ion irradiation

Ge oxide films were irradiated with 150 MeV Ag ions at fluences varying between 10¹² and 10¹⁴ ions/cm². The irradiation-induced changes were monitored by FT-IR spectroscopy, atomic force microscopy, X-ray diffraction and photoluminescence spectroscopy. The FT-IR spectra indicate stoichiometric changes and an increase in Ge content on irradiation. X-ray diffraction shows a crystallization of the irradiated films and presence of both Ge and GeO₂ phases. The Ge nanocrystal size, as calculated from Scherrer’s formula, was around 30 nm. The morphological changes, observed in atomic force microscopy, also indicate formation of nanostructures upon ion irradiation and a uniform growth is observed for a fluence of 1 × 10¹⁴ ions/cm².     

Syntheses of amine-type adsorbents with emulsion graft polymerization of glycidyl methacrylate

Glycidyl methacrylate (GMA) which was precursor monomer for the synthesis of metal ion adsorbent was emulsified by surfactant of Tween 20 (Tw-20). The emulsion of 5% GMA in the water was stable for 48 h at Tw-20 concentration of 0.5%. Graft polymerization of GMA on polyethylene fiber was carried out in the emulsion state at various pre-irradiation doses. Degree of grafting (Dg) reached 103%, 301% and 348% for 1 h grafting at 40 °C with pre-irradiation of 10, 30 and 40 kGy, respectively. But the Dg was depressed when the pre-irradiation dose was over 50 kGy since cross-linking occurred simultaneously in the trunk polymer. Dg decreased with increment of Tw-20 concentration in emulsion of 5% GMA at pre-irradiation of 40 kGy. The three kinds of amine-type adsorbents were synthesized by reacting diethylenetriamine (DETA), triethylenetetramine (TETA) and ethylenediamine (EDA) with GMA-grafted polyethylene fiber. The synthesized EDA-type adsorbent had the highest selectivity against U ion and the distribution coefficient was 2.0 × 10⁶.     

Effect of swift heavy ion irradiation on the surface morphology of highly c-axis oriented LSMO thin films grown by pulsed laser deposition

A detailed investigation of the surface morphology of the pristine and swift heavy ion (SHI) irradiated La_0.7Sr_0.3MnO₃ (LSMO) thin film using atomic force microscope (AFM) is presented. Highly c-axis oriented LSMO thin films were grown on LaAlO₃ (1 0 0) (LAO) substrates by the pulsed laser deposition (PLD) technique. The films were annealed at 800 °C for 12 h in air (pristine films) and subsequently, irradiated with SHI of oxygen and silver. The incident fluence was varied from 1 × 10¹² to 1 × 10¹⁴ ions/cm² and 1 × 10¹¹ to 1 × 10¹² ions/cm² for oxygen and silver ions, respectively. X-ray diffraction (XRD) studies reveal that the irradiated films are strained. From the AFM images, various details pertaining to the surface morphology such as rms roughness (σ), the surface rms roughness averaged over an infinite large image (σ_∞), fractal dimension (D_F) and the lateral coherence length (ξ) were estimated using the length dependent variance measurements. In case of irradiated films, the surface morphology shows drastic modifications, which is dependent on the nature of ions and the incident fluence. However, the surface is found to remain self-affine in each case. In case of oxygen ion irradiated films both, σ_∞ and D_F are observed to increase with fluence up to a dose value of 1 × 10¹³ ions/cm². With further increase in dose value both σ_∞ and D_F decreases. In case of silver ion irradiated films, σ_∞ and D_F decrease with increase in fluence value in the range studied.     

Radiation-chemical synthesis of poly(vinyl alcohol) hydrogel containing dicyclohexano-18-crown-6

Radiation-chemical synthesis of poly(vinyl alcohol) hydrogels containing physically immobilized dicyclohexano-18-crown-6 was carried out. Remarkable gel fraction of 40-70% was observed at absorbed dose of about 5 kGy. Increasing degree of poly(vinyl alcohol) crosslinking led to growth of the efficiency of crown ether immobilization. Post-irradiation thermal annealing of the hydrogel samples at 120 °C for 0.5-5 h resulted in an increase of crown ether retention as compared with non-annealed samples by approximately 20% at the same absorbed dose. Preliminary results on a sorption behavior of the crown-containing hydrogels with respect to Sr²⁺ cations in 2.4 M HNO₃ solution are presented.     

Dose rate effects on the radiation induced oxidation of polyethylene

The yields and spatial distribution of the products arising from the in source oxidation of 50 μm LDPE films induced by 60-Co gamma radiations and by 300 kev electrons have been investigated as a function of the dose rate. The dose rate was found to have a strong influence on the reaction, the hydroperoxides and carbonyls yields at the lowest gamma dose rate of 0.04 kGy/h being decreased by a factor of about three with increasing the gamma dose rate up to 0.69 kGy/h and by a factor of about 30 when operating at the e-beam dose rate of 1.5 kGy/s. The carbonyls depth concentration profiles, the EPR measurements on radicals intermediates and the experiments of post-irradiation oxidation are consistent with the conclusion that, as far as the gamma irradiation is concerned, the observed dose rate effects cannot be imputed to oxygen diffusion control and/or to the chain branching via hydroperoxides decomposition coupled to the longer times between the initiation events. The hypothesis of the dose rate acting on the kinetic chain length of the radioxidation which in turn implies a substantially uniform distribution of radicals in the amorphous phase attained through spur expansion is proposed.     

Desorption of gold nanoclusters (2-30 nm) under low excitation of their electronic subsystem by Ar ions (14 keV/nm)

Gold nanodispersed targets with islands-grains sized 2-30 nm were irradiated by Ar⁷⁺ ions with the energy of 45.5 MeV and (dE/dx)_e = 14.2 keV/nm in gold. The desorbed gold nanoclusters were studied by TEM method. For all the targets desorption of intact gold nanoclusters is observed. However, for inelastic stopping of monatomic Ar ions in gold of 14.2 keV/nm desorption of nanoclusters is observed only up to ∼25 nm. The yield of the desorbed nanoclusters considerably decreases from 3 to 0.02 cluster/ion with the increase of the mean size of the desorbed nanoclusters from 3 to 14.2 nm. The results are discussed.     

Radiation-induced grafting of inorganic particles onto polymer backbone: A new method to design polymer-based nanocomposite

Polypropylene/polyhedral oligomeric silsesquioxane (PP/POSS) nanocomposites were prepared by in situ radiation-induced grafting of POSS onto PP. Radiation-induced grafting of POSS was confirmed by FT-IR spectroscopy. The mechanical property of PP/POSS nanocomposites increased with the increase in POSS content and with the increase in absorption dose up to 5 kGy, above which it started to decrease. The reduction of mechanical property at high doses can be attributed to the chain scission of PP by radiation. The degree of reduction in decomposition temperature of irradiated PP/POSS nanocomposites was found to be much less than that of neat PP due to the covalent grafting of POSS onto PP by radiation.     

Gamma irradiation-aided chitin/chitosan extraction from prawn shells

Chitin and chitosan were extracted from prawn shells. The influence of a 25 kGy irradiation dose on the deproteination process was investigated. The deproteination degree was followed by Lowry-Folin method. The demineralisation degree versus reaction time with 1 N hydrochloric acid solution was followed by atomic absorption spectrometry.Chitin and chitosan obtained were characterised by FTIR spectrometry. The influence of some parameters, such as reaction time, alkaline concentration and temperature on the deacetylation degree was also investigated. The deacetylation degree was evaluated by FTIR spectrometry using the bands at 1320 cm⁻¹ and 1420 cm⁻¹.It was found that the irradiation of the shells at a dose of 25 kGy reduces the time of the deproteination reaction by a factor of three, comparatively to the non-irradiated samples.     

Oxygen defects created in CeO2 irradiated with 200 MeV Au ions

CeO₂ films were irradiated with 200 MeV Au ions in order to investigate the damages created by electronic energy deposition. In the Raman spectra of the ion-irradiated films, a broad band appears at the higher frequency side of the F_2g peak of CeO₂. The band intensity increases as ion fluence increases. Furthermore, the F_2g peak becomes asymmetric with a low-frequency tail. In order to understand the origin of these spectral changes, an unirradiated CeO₂ film was annealed in vacuum at 1000 °C. By comparing the results for the irradiation and for the annealing, it is concluded that the broad band obtained for irradiated samples contains the peak observed for the annealed sample. The F_2g peak becomes asymmetric with a low-frequency tail by the irradiation as well as the annealing. Therefore, the above-mentioned changes in the Raman spectra caused by 200 MeV Au irradiation is closely related to the creation of oxygen vacancies.     

Irradiation induced dislocation loop and its influence on the hardening behavior of Fe-Cr alloys by an Fe ion irradiation

Nano indentation analysis and transmission electron microscopy observation were performed to investigate a microstructural evolution and its influence on the hardening behavior in Fe-Cr alloys after an irradiation with 8 MeV Fe⁴⁺ ions at room temperature. Nano indentation analysis shows that an irradiation induced hardening is generated more considerably in the Fe-15Cr alloy than in the Fe-5Cr alloy by the ion irradiation. TEM observation reveals a significant population of the a₀<1 0 0> dislocation loops in the Fe-15Cr alloy and an agglomeration of the 1/2a₀<1 1 1> dislocation loops in the Fe-5Cr alloy. The results indicate that the a₀<1 0 0> dislocation loops will act as stronger obstacles to a dislocation motion than 1/2a₀<1 1 1> dislocation loops.     

High gamma dose response of the electrical properties of polyethylene terephthalate thin films

Electrical properties of polyethylene terephthalate (PET), irradiated with gamma rays, have been investigated. The PET films were irradiated with high gamma dose levels in the range from 100 to 2000 kGy. The changes in the DC (σ_DC) and the ac (σ_ac) conductivities, with the dose, have been performed. The effect of gamma irradiation on the dielectric constant (ε′) and loss (ε″) has been determined. Also, the dose dependence of the frequency exponent index (S), the resonance frequency (Fc) and the hopping frequency (ω_P) have been obtained. The obtained results show that increasing gamma dose leads to slight increase in σ_DC, σ_ac and ε′, while no change was observed in ε″ value. Meanwhile, S, Fc and ω_P are inversely proportional to the dose. Accordingly, the study suggests the possibility of using PET films in electronic components (capacitors, resistors, etc.), especially that operate at high gamma dose environments for the frequency independent applications.