Ultrasonic degradation of poly(methyl methacrylate-co-alkyl acrylate) copolymers

The copolymers, poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA), of different compositions were synthesized and characterized. The effect of alkyl acrylate content, alkyl group substituents and solvents on the ultrasonic degradation of these copolymers was studied. A model based on continuous distribution kinetics was used to study the kinetics of degradation. The rate coefficients were obtained by fitting the experimental data with the model. The linear dependence of the rate coefficients on the logarithm of the vapor pressure of the solvent indicated that vapor pressure is the crucial parameter that controls the degradation process. The rate of degradation increases with an increase in the alkyl acrylate content. At any particular copolymer composition, the rate of degradation follows the order: PMMAMA > PMMAEA > PMMABA. It was observed that the degradation rate coefficient varies linearly with the mole percentage of the alkyl acrylate in the copolymer.     

Generation of microcellular poly(methyl methacrylate) by compressed gases

Abstract

Generation of microcellular poly(methy1 methacrylate) (PMMA) was studied in CO₂ and N₂O at pressures from 2 to 15MPa at three temperatures, 293.2K, 308.2K, and 323.2 K. The average diameter d and average number density N of voids generated by a rapid expansion of compressed gases in PMMA were measured by use of an optical microscope. Effects of gases, temperature, and pressure on the d and N values were examined. Even at pressure below glass transition pressure of PMMA with both gases, voids of diameter being as small as those found at high pressure, 15MPa, were obtained at each temperature. However, the void density of PMMA at lower pressure by both gases was not so good as those obtained at high pressures.     

多元丙烯酸酯泡沫制备中的溶剂效应

以季戊四醇四丙烯酸酯（PETA）为聚合单体,安息香乙醚为引发剂,通过紫外光引发生成凝胶,通过真空干燥得到PETA泡沫材料。通过理论计算和实验确定的多元丙烯酸酯交联聚合物的溶解度参数值为19.0左右,含有苯环的脂肪烃和酮类的溶剂会导致引发剂“失活”,而卤代烃、酯、醚和酰胺类溶剂能够保持引发剂的“活性”。     

多元丙烯酸酯泡沫制备中的溶剂效应

 以季戊四醇四丙烯酸酯（PETA）为聚合单体，安息香乙醚为引发剂，通过紫外光引发生成凝胶，通过真空干燥得到PETA泡沫材料。通过理论计算和实验确定的多元丙烯酸酯交联聚合物的溶解度参数值为19.0左右，含有苯环的脂肪烃和酮类的溶剂会导致引发剂“失活”，而卤代烃、酯、醚和酰胺类溶剂能够保持引发剂的“活性”。     

Muon spin rotation in liquid noble gases

A new mechanism of slow muon depolarization in liquid noble gases is suggested. The muon spin polarization in [A-μ-A]⁺ complexes is calculated. The results allow one to observe [A-μ-A]⁺ experimentally and to measure hyperfine interaction constants.     

Thin free arcs in alkali-seeded noble gases

Thin arcs (e.g. those observed in noble gas magnetohydrodynamic generators) are analyzed. The spatial distributions of the important plasma quantities are calculated by solving the appropriate balance equations. Solutions are obtained for cesium-seeded argon as well as for pure argon. The solutions yield characteristic radial dimensions which are in agreement with known experimental values. The effects of variations of important arc parameters are discussed in the case of cesium-seeded argon. It appears that the effects of the parameter variations can be explained to a large extent by a simplified expression for the radial dimension of the arc. Deviation from local thermodynamic equilibrium is only significant in the outer region of the arc and has practically no influence on the arc properties     

Molecular mobility in biodegradable poly( $ \varepsilon$ -caprolactone)/poly(hydroxyethyl acrylate) networks

Poly( e \varepsilon -caprolactone)/poly(hydroxyethyl acrylate) networks have been investigated by thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry (DSC). The introduction of hydrophilic units (HEA) in the system aiming at tailoring the hydrophilicity of the system results in a series of copolymer networks with microphase separation into hydrophobic/hydrophilic domains. Polycaprolactone (PCL) crystallization is prevented by the topological constraints HEA units imposed in such heterogeneous domains. Moreover, the mobility of the amorphous PCL chains is enhanced as revealed by the main relaxation process which becomes faster. The glass transition of PHEA-rich domains shifts to lower temperatures, as the total amount of PCL in the copolymer increases, due to the presence of PCL units within the same region. The behaviour of the copolymer networks swollen with different content of water has been investigated to analyze the interaction between water molecules and hydrophobic/hydrophilic domains and provide further insights into the molecular structure of the system.     

High pressure of solid noble gases in metals

The fact that noble gas ions implanted in metals with concentrations of a few percent precipitate at room temperature as solid bubbles under high pressure with a structure epitaxial with the host matrix (fcc or hcp) has been investigated recently. A brief survey of the results measured by transmission electron microscopy, glancing angle X-ray diffraction, energy-loss spectroscopy and positron annihilation is given. The main part of this paper deals with a study on⁸³Kr⁺ implanted in Al using Mössbauer spectroscopy. The results are as follows: the precipitates grow from 1.5 nm after implantation to 3.7 nm after 700 K annealing. The recoilless fractions can be fitted very well to a Debye model. On annealing. the characteristic Mössbauer temperature gradually decreases from 89 K to 64 K, the value for solid Kr at 1 bar. At the same time a decrease in the isomer shift is observed. Even after annealing at 700 K our experiments do not show melting in the temperature range 0–230 K.     

Novel MRI applications of laser-polarized noble gases

Gas-phase nuclear magnetic resonance (NMR) has great potential as a probe for a variety of interesting physical and biomedical problems that are not amenable to study by water or similar liquid. However, NMR of gases was largely neglected due to the low signal obtained from the thermally polarized gases with very low sample density. The advent of optical pumping techniques for enhancing the polarization of the noble gases³He and¹²⁹Xe has bought new life to this field, especially in medical imaging where³He lung inhalation imaging is approaching a clinical application. However, there are numerous applications in materials science that also benefit from the use of these gases. We review primarily nonmedical applications of laser-polarized noble gases for both NMR imaging and spectroscopy and highlight progress with examples from our laboratory including high-resolution imaging at millitesla applied field strength and velocity imaging of convective flow. Porous media microstucture has been probed with both thermal and laser-polarized xenon, as xenon is an ideal probe due to low surface interaction with the grains of the porous media.     

Low-energy librational excitations in vitreous poly(methyl methacrylate)

The infrared (IR) and Raman spectra of vitreous poly(methyl methacrylate) (PMMA) are measured and investigated in the frequency range 10–150 cm^?1. A comparison of the results obtained from IR and Raman spectroscopic measurements permits the assignment of the low-frequency anomaly (boson peak) observed in the spectra to librational vibrations occurring in a segment of the main chain that is comparable in length to the statistical chain segment. It is demonstrated that coherent librational excitations are associated with the relaxation processes proceeding in the polymers.     

Hot oxygen atom ballistics on Pt(111): collisional desorption of noble gases

Hot oxygen atoms formed by ultraviolet photofragmentation of chemisorbed O₂ on Pt(111) at T_s=20 K induced collisional desorption of coadsorbed noble gases. Angular distributions of desorbing Ar, Kr, and Xe were sharply peaked at 35° from the surface normal. Mean translational energies of the noble gases were in the 0.12 eV (1400 K) range. The O atom photofragments were found to chatter between the surface and the noble gases during the desorption process. The fastest O atom photofragments produced at 250 nm had an energy of at least 0.73 eV.     

Ionisation of noble gases by positron impact

The positron induced absolute single and double ionisation cross sections for the noble gases Ar, Kr and Xe have been determined in the energy region from below threshold to ∼1000 eV. With the use of an admixture of He to the target gas normalisation was performed by comparison to known single ionisation cross sections for He. Special interest has been taken in the energy gap of 6.8 eV below the direct double ionisation threshold energy, where only double ionisation with positronium formation is possible. This has been done to study the significance of double ionisation with Ps formation for the heavy noble gases. This revised version was published online in August 2006 with corrections to the Cover Date.     

Collisional polarizability anisotropies of the noble gases

We present a simple approximate calculation of the pair polarizability anisotropy β(R) of interacting inert gas atoms, including overlap effects. The overlap contribution to β(R) is found to be relatively long-range and to have an exponential form. We compare our results with recent ab initio Hartree-Fock calculations and experimental low density depolarized scattering spectra; agreement is excellent.     

High-repetition-rate femtosecond laser micromachining of poly(methyl methacrylate)

Investigations are performed to explore high-repetition-rate femtosecond laser ablation effects on the physical and chemical properties of poly(methyl methacrylate)(PMMA). A scanning electron microscopy(SEM) is used to characterize the morphology change in the laser-ablated regions. The infrared and Raman spectroscopy reveals that the fundamental structure of the PMMA is altered after laser ablation. We demonstrate the cumulative heating is much greater during high-repetition-rate femtosecond laser ablation, supporting a photothermal depolymerization mechanism during the ablation process.     

IR laser ablation of doped poly(methyl methacrylate)

We investigate the TEA CO₂ laser ablation of films of poly(methyl methacrylate), PMMA, with average M_W 2.5, 120 and 996 kDa doped with photosensitive compounds iodo-naphthalene (NapI) and iodo-phenanthrene (PhenI) by examining the induced morphological and physicochemical modifications. The films casted on CaF₂ substrates were irradiated with a pulsed CO₂ laser (10P(20) line at 10.59 μm) in resonance with vibrational modes of PMMA and of the dopants at fluences up to 6 J/cm². Laser induced fluorescence probing of photoproducts in a pump and probe configuration is carried out at 266 nm. Formation of naphthalene (NapH) and phenanthrene (PhenH) is observed in NapI and PhenI doped PMMA, respectively, with relatively higher yields in high M_W polymer, in similarity with results obtained previously upon irradiation in the UV at 248 nm. Above threshold, formation of photoproducts is nearly complete after 200 ms. As established via optical microscopy, bubbles are formed in the irradiated areas with sizes that depend on polymer M_W and filaments are observed to be ejected out of the irradiated volume in the samples made with high M_W polymer. The implications of these results for the mechanisms of polymer IR laser ablation are discussed and compared with UV range studies.     

Laser processing of poly(methyl methacrylate) Lambertian diffusers

Matrix-assisted pulsed laser deposition was used to deposit poly(methyl methacrylate) on silicon wafers and sodium silicate glass slides for the purpose of making optical diffusers. After deposition, the reflectance of the coated substrates was measured as a function of scattering angle. We found that the angular dependence of the reflectance could be described as the sum of two functions. First, a Gaussian describes the specular reflection of the underlying substrate that has been broadened by passage through the film. Second, a cosine function describes the reflectance contribution from the film itself. We found that by increasing the thickness of the deposited film that we could eliminate the specular reflection to obtain Lambertian diffusers. Since we can control the surface roughness by adjusting the ratio of the two matrices in laser processing, this deposition technique offers the possibility of producing a wide range of diffusers of different types.     

Configurational-conformational statistics of stereoirregular poly(methyl methacrylate)s

The mean-square radius of gyration of poly(methyl methacrylate) (PMMA) with Bemoullian statistics was theoretically investigated utilizing the method of periodic condition. The dependent curve of the characteristic ratio of mean-square end-to-end distance on periodic microstructure length increases monotonously with the length and goes gradually to its asymptotic value for atactic PMMA chains (P _m = 0.5). Conformational energies E _α ～1.3 kcal mol^?1 and E _β ～-0.6 kcal mol^?1 of the two-state scheme are acceptable, from which the derived meansquare end-to-end distance and mean-square radius of gyration conform to the experimental data. The ratio ?S²?/χ of atactic PMMA (P _m = 0.2) as a function of the degree of polymerization χ first increases with increasing chain length, then passes through a maximum at χ = 30, and finally decreases to its asymptotic value, which is in reasonable agreement with the experimental measurements reported elsewhere. The ratio ?S²?/χ as a function of stereochemical composition indicates that theoretical and experimental data are in accord for isotactic and atactic PMMA, but small-angle neutron scattering (SANS) measurements are higher than the calculated values for syndiotactic PMMA.     

Segmental Dynamics in net -poly(methyl methacrylate)- co -poly(n-butyl acrylate) Copolymer Networks

Dynamic mechanical spectroscopy and differential scanning calorimetry investigations of segmental dynamics are reported for net-poly(methyl methacrylate)-co-poly(n-butyl acrylate) copolymer networks. Three characteristic temperatures, namely, Vogel (T_∞), glass transition (T _g ), and crossover (T _c ), were used to define cooperativity range and a new reduced temperature parameter (Solidness, S). The results showed that broadness of the α -dispersion (glass transition) and cooperativity length scale at the glass transition temperature decreased with increasing butyl acrylate content and T _g -scaled temperature dependence of the relaxation time (fragility). However, the cooperativity range (T _c –T_∞), decreased with increasing fragility index. Furthermore, the solidness at T _g (S(T _g )) was nearly independent of chemical structure of the samples. Finally, a correlation was found between two measures of cooperativity length scale in the glass transition region, namely, average volume of cooperatively rearranging regions, V _CRR , and the number of basic units in an act of rearrangement in the glass transition region, Z(T _g ), determined from two completely independent experimental techniques.     

稀有气体纯质热物理性质的预测

根据量子力学和分子运动学理论,采用稀有气体的ab initio势能,分别计算了氦-4、氖、氩、氪和氙纯质在低密度时的热物理性质,包括第二维里系数,热扩散系数和热扩散因子,计算的温度范围为50—5000 K.预测结果具有较高的精度,与采用经验势能的计算结果相比,本文结果更接近实验数据和REFPROP 8.0的标准值,为相关的科学研究和工程应用提供了所需的基础数据. 关键词： ab initio势能')" href="#">ab initio势能 稀有气体 热物理性质     

Isotopic thermal diffusion factors of the noble gases

A new set of isotopic thermal diffusion factors for Ar, Kr and Xe is reported. The data have been obtained from thermal diffusion column measurements in a column previously calibrated with Ne gas, and complete the α_T data for the binary mixtures of noble gases given previously. The results lead to the conclusion that the thermal diffusion properties of the noble gases and their mixtures are well described by the law of corresponding states first proposed by Kestin, Ro and Wakeham. It is also concluded that the calibration technique used makes the thermal diffusion column a valuable instrument for the determination of the thermal diffusion factors of isotopic and non-isotopic dilute gas mixtures.