Relaxation times and energy barriers of rubbing-induced birefringence in glass-forming polymers

The relaxations of rubbing-induced birefringence (RIB) in several glass-forming polymers, including polycarbonate and polystyrene (PS) derivatives with various modifications to the phenyl ring side group, are studied. Significant relaxations of RIB are observed at temperatures well below the glass transition temperature T _g . The relaxation times span a wide range from ∼ 10 s to probably geological time scale. Physical aging effects are absent in the RIB relaxations. The model proposed for the interpretation of RIB in PS describes well the RIB relaxations in all the polymers investigated here. The energy barriers are of the order of a few hundred kJ/mol and decrease with decreasing temperature, in opposition to the trend of Vogel-Fulcher form for polymer segmental relaxations above T _g . The relaxation behaviors of different polymers are qualitatively similar but somewhat different in quantitative details, such as in the values of the saturated birefringence, the shape of the initial barrier density distribution functions, the rates of barrier decrease with decreasing temperature, and the dependence of relaxation times on temperature and parameter , etc. The RIB relaxations are different from any of the other relaxations below T _g that have been reported in the literature, such as dielectric relaxations or optical probe relaxations. A microscopic model for the relaxations of RIB is much desired.     

Substrate effect on mechanical relaxation of polystyrene in ultrathin films

Mechanical relaxation behavior in ultrathin polystyrene (PS) films supported on silicon oxide (SiO_x) and gold (Au) substrates has been studied by dynamic viscoelastic measurement. Based on the method, effects of free surface and substrate interface on the segmental dynamics were discussed. In the case of thin PS films with a thickness of approximately 200 nm, α_a-relaxation process corresponding to the segmental motion did not show any deviation from the bulk behavior. In contrast, for the films thinner than about 50 nm, the relaxation time distribution for the α_a-process became broader, probably due to a mobility gradient in the surface and interfacial regions. When we sandwiched an ultrathin PS film between SiO_x layers, another relaxation process, in addition to the original α_a-process, appeared at a higher temperature side that we assigned to the interfacial α_a-relaxation process. However, this was never seen for an ultrathin PS film between Au layers, implying that restriction from the substrate interface might be weak in this case.     

The polarized reflection and absorption spectra of perylene crystals in monomeric and dimeric forms

The electronic absorption spectra of perylene crystals in the α- and β-forms were measured by the normal incidence reflection method in the spectral region from 20 000 to 60 000 cm^?1. From the absorption spectrum polarized perpendicular to [1$\text{1}$0] axis of the α-form crystal, the bands around 24 000 cm^?1 were determined to be polarized along the long molecular axis. Two strong bands with different polarizations were observed around 50 000 cm^?1 for each of the α- and β-perylene crystals and were assigned to the transitions to the ¹B_2u and ¹B_3u states. The observed polarized absorption spectra as a whole were consistent with the theoretical results by Hummel and Ruedenberg and the reflection method was found to be suitable to the polarized absorption measurement of strong bands of crystals. The observed factor-group splittings were compared with the theoretical values, the oriented gas model being found to be applicable to the β-form crystal.     

Optical and Structural Modifications in Heavy Ion Irradiated Polystyrene

Samples of polystyrene (PS) have been irradiated with ⁶⁴Cu (50 and 120 MeV) and ¹²C (70 MeV) ion beams (fluence=10¹¹ to 10¹³ ions cm^?2) in order to study the induced modifications using UV‐VIS and FTIR spectroscopy. UV spectra of irradiated samples reveal that the optical band gap decreases from 4.36 to 1.46 eV in PS. The decrease in optical band gap is more pronounced with the Cu‐ion beam due to high electronic energy loss as compared to the C ion beam. The effect of low energy (50 MeV) Cu ions on the optical properties of PS is larger than that due to high energy (120 MeV) Cu ions. The correlation between the optical band gap and the number of six member carbon rings inside the largest carbon clusters embedded in the network of polystyrene is discussed. FTIR spectra reveal the formation of hydroxyl, alkene, and alkyne groups in the Cu‐ion irradiated PS. Changes in the intensity of the absorption bands on irradiation with C‐ion relative to pristine samples have also been observed and are discussed.     

Quantitative high temperature absorption spectroscopy of NCO at 305 and 440 nm

A spectral survey of NCO absorption near the P₂ + ^pQ₁₂ head of the [A²Σ + (00⁰0)←X²Π_i(00¹0)] band was obtained at 1450°K, 0.6 atm using a remotely located cw ring dye laser source and a shock tube. Mixtures of hydrogen cyanide, oxygen and nitrous oxide diluted in argon were shock heated to provide a reproducible steady-state concentration of NCO, and narrow-line absorption was measured in repeated experiments with the laser set at different wavelengths. The peak absorption was found at 440.479 nm (vac). The experimental spectrum was compared with a theoretical model to yield an average Voigt parameter a ? 0.1. Additional experiments, in mixtures of cyanogen, oxygen and nitrous oxide diluted in argon, provided a known plateau level of NCO, which was used to infer an absolute absorption coefficient β(1450°K, 0.60 atm) = 110(-50, +130) cm^-1 atm^-1 at 440.479 nm. This value of β corresponds to an oscillator strength of 0.0026 for the (00⁰0←00¹0) band.Similar experiments were conducted to monitor the absorption around the R₁ head of the [B²Π_i(10¹0)←X²Π_i(00¹0)] band of NCO, using a frequency doubled cw ring dye laser. The observed spectrum displayed strong broadening, indicating predissociation of the upper state. At the peak absorption wavelength (304.681 nm, vac), we inferred β(1470°K, 0.63 atm) = 40(-19, +48) cm^-1 atm^-1 and a ? 9. This value of β corresponds to an oscillator strength of 0.0031 for the (10¹0←00¹0) band.     

Beta-decay properties of exotic nuclei and the astrophysical r-process

The r-process abundances are evaluated with the use of three different β-decay models, i.e., the second version of the Gross Theory, the semi-Gross Theory and a QRPA approach. The necessary Q_β-values, as well as the neutron separation energies, are obtained from the TUYY, ETFSI and FRDM mass predictions. A comparison is made among the β-decay half-lives predicted by these β-decay models for the nuclei on a typical r-process path, as well as among the resulting r-process abundances.     

Far Infrared Spectroscopic Studies of Acetonitrile Vapour

Abstract

The infrared spectrum of acetonitrile vapour has been obtained in the range below 100 cm^?1. There is an absorption band located at 78 cm^?1 which is assigned to overlapping intermolecular vibrations of dimer molecules in equilibrium with the monomer species. The equilibrium constant calculated from the pressure dependence of the band intensity amounts to 42 ± 26 1·mol^?1.     

Fluorescence spectroscopy of potential electroluminescent materials: Substituent effects on DSB and segmented PPV derivatives

The absorption and fluorescence of substituted distyrylbenzene (DSB) derivatives and segmented poly(phenylene vinylene) (PPV) derivatives are characterized by long-wavelength absorption maxima and absorption coefficients of λ_a = 380–450 nm, ε = 20,000–60,000 M⁻¹ cm¹ and fluorescence maxima, quantum yields, and decay times of λ_r = 440–530 nm, Φ_f = 0.2–0.9, and Τ = 0.8–2.5 ns, respectively. Alkoxy substituents at the central phenylene ring of DSB groups increase the bathochromic shift in the spectra in comparison to DSB, without a significant decrease in the high DSB fluorescence quantum yield. Both phenyl and cyano substitutions at the vinylene bridge lead to a further bathochromic shift of the fluorescence and a decrease in the quantum yield to ca. 0.4. The DSB derivatives and the related segmented PPV derivatives show nearly the same absorption spectra, fluorescence spectra, and radiative rate constantsk _f= Φ_f/Τ, indicating the efficacy of the segmentation of the polymer chain. The radiative rate constants determined by the Φ_f and Τ values and by the Strickler/Berg formula are in reasonable agreement. This supports the possibility of interpreting the properties of the polymers in terms of their DSB units. The decrease in the emission anisotropy can be ascribed to multistep energy transfer processes between different oriented segments.     

Relationship between Hansen Solubility Parameters and Lewis Acid–Base Parameters of Polymers

Hansen solubility parameters and Lewis acid–base parameters are two groups of parameters that are used to characterize solvents, polymers, and the interactions between polymer matrix and additives. Although their definitions are very different, they can well explain the interactions in polymer composites. Therefore, some relations should exist between them. In this paper, the Lewis acid–base parameters of three polymers (PET, PS, and PVA) were measured by IGC technique. Including five other polymers (PE, PMMA, PC, PVC, and PVDF), the relationship between total Lewis acid–base intensity (K _a+K _b) and total polar intensity (δ² _p+δ² _h) of the eight kinds of polymers are discussed, where δ_p and δ_h are the polar components of the Hansen parameters. It is found that these polymers are all Lewis base polymers according to the values of K _b/K _a. Generally, a polymer with a larger (K _a+K _b) value possesses a higher (δ² _p+δ² _h) value.     

Low-frequency librational vibrations,boson peak,and interchain interactions in a vitreous polymer

The IR and Raman spectra of plasticized poly(methyl methacrylate) (PMMA) are measured and analyzed in the frequency range 10–120 cm^?1, in which the absorption and scattering due to the individual (85–90 cm^?1) and correlated librational vibrations (15–20 cm^?1, boson peak) preceding the appearance of relaxation dynamics manifest themselves. It is demonstrated that the presence of the boson peak as an indication of the solid-state behavior of the polymer material in the low-frequency spectra is associated with the correlation of librational vibrations not only inside macromolecules (in segments corresponding in length to the Kuhn segment) but also in segments of neighboring chains.     

Temperature-dependent photoluminescence from MEH-PPV and MEH-OPPV containing oxadiazole in the main chain

We report the temperature-dependent photoluminescence (PL) behavior of two poly (p-phenylene-vinylene) derivatives with different backbones, a homopolymer poly-[2-methoxy-5-(2^′-ethyl-hexyloxy)-1,4-phenylene-vinylene] (MEH-PPV) and a copolymer poly-{[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene]-alt-[2,5-diphenylene-1,3,4-oxadiazole-vinylene]} (MEH-OPPV). The PL peak positions of the MEH-PPV in both solid solution and film are blue shifted with increasing measurement temperature because the thermally induced torsion and libration modes reduce the conjugation lengths of the polymer, but the shift rate is smaller in the MEH-PPV film than that in the solid solution. The PL peak position of the MEH-OPPV film is independent of measurement temperature because there is a large dihedral angle between the adjacent monomer units. The large dihedral angle increases the conformational disorder to eliminate the effect of the disorder induced by the thermally induced torsion and libration modes on the conjugation lengths of the MEH-OPPV. PACS 73.61.Ph; 78.55.Kz     

FIR spectra of saccharides and polysaccharides

Measurements of the FIR absorption spectra of polysaccharides and their constituent monoand disaccharides have been made between 30 and 650 cm⁻¹, using FTS. Some of the structure of the saccharides is found to show up in the polymers.     

Low-frequency lattice vibrations of δ-GaSe compared to ϵ- and γ-polytypes

Raman spectra of the new polytype δ-GaSe are given in the low-frequency region (ω < 60 cm^-1) and their relation to lattice vibrations of the simpler polytypes γ, ? is discussed. A simple lattice dynamical model is used to describe the phonon modes in all 3 modifications. First observation of Davydov splitting in ?-GaSe is reported. Particular weakness of one component of this doublet is shown to be a consequence of the specific “molecular” nature of layer crystal.     

Improving the performance of a far-infrared quantum-ring-based photodetector utilizing asymmetric multi-barrier resonant tunneling

In this paper, a novel structure for quantum ring inter-subband photodetectors (QRIP) is proposed to reduce its dark current. Some additional layers including asymmetric multi-barrier resonant tunneling (AMBRT) in absorption region layers are exploited to provide near unity tunneling probability for generated photocurrents and completely reject thermally generated electrons. AMBRT structure consists of three asymmetric AlGaAs barriers and two InGaAs wells which are designed for operation wavelength of generated photocurrents by absorption of 20 μm. Simulation results show that AMBRT can considerably reduce the dark current compared to previously proposed resonant tunneling structure about three orders of magnitude. As a consequent, higher specific detectivity for AMBRT-QRIP is obtained in the order of ∼10¹¹ cm Hz^1/2/W at 100 K.     

Ground state of π-conjugated polymer chains forming an intermolecular charge-transfer complex as probed by Raman spectroscopy

The intermolecular charge-transfer complex (CTC) between the conjugated polymer MEH-PPV and the low-molecular organic acceptor trinitrofluorenone (TNF) has been studied by Raman and optical absorption spectroscopy. On mixing MEH-PPV with TNF, an absorption band due to the CTC appeared in the optical gap of the polymer, whereas, in the Raman spectra, characteristic bands of the polymer are shifted and their widths and intensities change. The low-frequency shift of the strongest band at 1580 cm^?1 in the Raman spectrum of the polymer, assigned to the symmetric stretching vibration of the phenyl group, is shown to be due to electron density transfer from the π-conjugated system of the polymer to the acceptor and is as large as 5 cm^?1, which corresponds to a charge transfer on the order of 0.1e ^?1. Even at a low acceptor concentration (one TNF molecule per 10 monomer units of the polymer), most Raman-active conjugated chains are involved in the CTC. It is suggested that conjugated segments of the polymer can form a CTC of variable composition MEH-PPV: TNF = 1: X, where 0.1 ≤ X ≤ 0.5 (for each monomer unit of the polymer), and one TNF molecule can thereby interact with two conjugated segments of MEH-PPV. The conjugated polymer chains involved in the CTC can become more planar, and their interaction with the local environment can noticeably change; however, their conjugation length, most likely, remains unaltered.     

Exciton fission in excimer-forming crystal dynamics of excimer build-up

The optically induced fission of singlet excitons in both α- and β-perylene crystals is investigated at room temperature. In the monomeric β-perylene the fission thresold coincides with the energy of two triplet excitons whereas it is blueshifted by ～3500 cm^-1 in the excimer forming α-crystal. This indicates that the excimer is formed prior to the fission of the initially excited monomer state and it implies that the rate of excimer formation is exceeding 10¹² s^-1. Theoretical estimates led to k_exc ≈ 10¹²-10¹³ s^-1. Analysis of the experimental data shows also that two adjacent perylene molecules in the α-crystal, each of them in the T₁ electronic state, are bound with the binding energy B_2T1 ≈ 350 cm^-1.     

Pressure broadening of the NO2 hyperfine multiplet at 93 GHz

Line shapes of the hyperfine NO₂ 26(1,25)←25(2,24) rotational transition have been measured at pressures below 3 torr with a bridge spectrometer originally designed for direct absolute absorption studies. The multiplet consists of six lines with δF=δJ=δN=1 in the vicinity of 93,445 MHz. The same line-broadening parameter of 3.7 MHz/torr and the same maximum absorption of 1.8×10^-5 cm^-1 have been found for all 6 lines. The maximum absorption of the strongly overlapped multiplet at a pressure of 10 torr was measured to be 1.06×10^-4 cm^-1, in good agreement with the theoretical value. The interference effect of the overlapping lines turns out to be below ?10%, so that a simple superposition of lorentzian shapes is a good approximation for this case. The remaining difference can be compensated for by the introduction of an overlap parameter for each line.     

Isotope effects in the infrared spectra of the polar and nonpolar isomers of N2O dimer

The rotationally resolved spectra of ¹⁵N¹⁵N¹⁶O dimer for the polar and nonpolar isomers are studied in the region of the N-N stretching fundamental of the monomer (∼2150 cm⁻¹) using a rapid-scan tunable diode laser spectrometer to probe a pulsed supersonic jet expansion. These spectra are very similar to the corresponding spectra of the normal species, (¹⁴N¹⁴N¹⁶O)₂. Structural parameters and vibrational shifts obtained here are compared with those of the normal species and ab initio values. These results confirm that the nonpolar isomer has a centrosymmetric slipped-antiparallel structure while the polar isomer consists of two slipped and (approximately) parallel monomer units.     

An investigation on the variations in properties of Ni+ irradiated ZnO thin films

ZnO thin films, irradiated by 80 MeV Ni⁺ ions, were analysed with the help of different characterization techniques like X-ray diffraction, optical absorption, transmission, photoluminescence (PL), electrical resistivity, photosensitivity (PS) and thermally stimulated current (TSC) measurements. Crystallinity and absorption edge were hardly affected by irradiation. PL spectrum of pristine sample showed a broad peak at 517 nm, whereas irradiated film had two emissions at 517 and 590 nm. Intensity ratio between these two emissions (I₅₁₇/I₅₉₀) decreased with the fluence, and finally at a fluence of 3×10¹³ ions/cm², the emission at 517 nm completely disappeared. Electrical resistivity of the sample irradiated with a fluence of 1×10¹³ ions/cm² drastically increased. However, on increasing the fluence to 3×10¹³ ions/cm², resistivity decreased, probably due the onset of hopping conduction through defects. PS also decreased due to irradiation. TSC measurements on pristine sample could reveal only one defect level at 0.6 eV, due to interstitia1 zinc (Zn_I). But, irradiation at a fluence of 1×10¹² ions/cm², resulted in three different defect levels as per TSC studies. Interestingly, the sample irradiated at a fluence of 3×10¹³ ions/cm² had only one defect level corresponding to a deep donor. The possible origin of these defect levels is also discussed in the paper.