Review: Different types of ordering

Homogeneous structures A_xB_y with identical A–A or B–B self‐coordination numbers T₁, T₂, T₃, of nearest, next‐nearest and third neighbors are selected. The maximum T_i values are 2 2 2 (1D row), 6 6 6 (2D hexagonal net) and 12 6 24 (3D cubic close‐packing). Reduced T₁ or T₂ values for A_xB_y can be related with attractive or repulsive A–A (or B–B) interactions. A single set of T₁ T₂ T₃; y/x values was obtained for y/x = 1–4 and 6. The y/x = 2 structures of three equivalent positions A, B and C are unfavourable for A = ⊕ and B = ⊖ charge or direction of magnetic moments. The spatial distribution of positive and negative potential near A⁺ and B⁻ positions gives rise to neutral C positions. Frustrated magnetic moments at C positions are disordered. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

高频介质阻挡放电烟气脱硫研究

采用高频介质阻挡放电的方式产生低温等离子体,研究在不加入NH₃的情况下流动态SO₂的去除情况.实验表明,在输入电压为12 kV,SO₂浓度为5400 mg/m³,气体流量为0.36 m³/h,相对湿度为55%时,脱硫率可达到70%以上;水气的存在对SO₂的去除有较大的促进作用,升高电压和增加O₂量对脱硫率的促进作用有限.对实验结果进行了解释,并提出了反应机理.     

Molecular motion and relaxation studies of aliphatic polyureas by thermal windowing thermally stimulated depolarization current technique

Molecular motion and relaxation studies using a thermal windowing thermally stimulated depolarization current (TW‐TSDC) were performed for aliphatic polyureas 7 and 9. Global thermally stimulated depolarization current gave three characteristic major peaks corresponding to the α, β, and γ relaxation modes at 78.5, −44, and −136°C for polyurea 7 and at 80, −50, and −134°C for polyurea 9, respectively. The α relaxation is related to the large‐scale molecular motion due to micro‐Brownian motion of long‐range segments. This relaxation is significantly related to the glass‐transition temperature. The β relaxation is caused by the local thermal motion of long‐chain segments. The γ relaxation is caused by the limited local motion of hydrocarbon sections. Temperature dependence of relaxation times was expressed well using Vogel–Tammann–Fulcher (VTF) expression. 3‐D simulation of dielectric constants of dielectric strength and loss factor were performed in the frequency range from 10⁻⁶ to 10⁴ Hz and temperature range from −150 to 250°C, using the relaxation parameters obtained from the TW‐TSDC method. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 88–94, 2000     

Solvent‐ and counterion‐specific swelling behavior of poly(acrylic acid) gels

The collapse of alkali metal poly(acrylate) (PAAM) gels was investigated for various water/organic solvent mixture systems: methanol (MeOH), ethanol (EtOH), 2‐propanol (2PrOH), t‐butanol (tBuOH), dimethyl sulfoxide (DMSO), acetonitrile (AcN), acetone, tetrahydrofuran (THF), and dioxane. In order to ascertain the counterion specificity in the swelling behavior, four kinds of alkali metal counterions were used: Li⁺, Na⁺, K⁺, and Cs⁺. Remarkable solvent and counterion specificities were observed for every counterion species and every solvent system, respectively. For example, in aqueous EtOH the dielectric constants (D_cr) at which collapse occurred were in the order PAACs < PAALi < PAAK < PAANa. On the other hand, the D_cr at which PAALi gel collapsed increased in the order tBuOH < dioxane < THF < MeOH < 2PrOH < EtOH < acetone < AcN < DMSO, where the D_cr ranged from about 39 to about 67. This was in contrast to our previous observation for a partially quaternized poly(4‐vinyl pyridine) (P4VP) gel, which collapsed in a much narrower D_cr region in similar mixed solvents. The present solvent‐ and counterion‐specific collapses are discussed on the basis of solvent properties such as the dielectric constant and Gutmann's donor number and acceptor number of a pure solvent. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2791–2800, 2000     

Influence of the stereochemical configuration on the radical polymerization of methacrylic monomers: cis‐ and trans‐(2‐cyclohexyl‐1,3‐dioxan‐5‐yl) methacrylate

The synthesis of two new isomeric monomers, cis‐(2‐cyclohexyl‐1,3‐dioxan‐5‐yl) methacrylate (CCDM) and trans‐(2‐cyclohexyl‐1,3‐dioxan‐5‐yl) methacrylate (TCDM), starting from the reaction of glycerol and cyclohexanecarbaldehyde, is reported. The process involved the preparation of different alcohol acetals and esterification with methacryloyl chloride of the corresponding cis and trans 5‐hydroxy compounds of 2‐cyclohexyl‐1,3‐dioxane. The radical polymerization reactions of both monomers, under the same conditions of temperature, solvent, monomer, and initiator concentrations, were studied to investigate the influence of the monomer configuration on the values of the propagation and termination rate constants (k_p and k_t ).The values of the ratio k_p /k_t ^1/2 were determined by UV spectroscopy by the measurement of the changes of absorbance with time at several wavelengths in the range 275–285 nm, where an appropriate change in absorbance was observed. Reliable values of the kinetics constants were determined by UV spectroscopy, showing a very good reproducibility of the kinetic experiments. The values of k_p /k_t ^1/2, in the temperature interval 45–65 °C, lay in the range 0.40–0.50 L^1/2/mol^1/2s^1/2 and 0.20–0.30 L^1/2/mol^1/2s^1/2 for CCDM and TCDM, respectively. Measurements of both the radical concentrations and the absolute rate constants k_p and k_t were also carried out with electron paramagnetic resonance techniques. The values of k_p at 60 °C were nearly identical for both the trans and cis monomers, but the termination rate constant of the trans monomer was about three times that of the cis monomer at the same temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3883–3891, 2000     

Kinetic and ESR studies on radical polymerization behavior of N‐(2‐phenylethoxycarbonyl)methacrylamide

Polymerization of N‐(2‐phenylethoxycarbonyl)methacrylamide (PECMA) with dimethyl 2,2′‐azobisisobutyrate (MAIB) was investigated in tetrahydrofuran (THF) kinetically and by means of electron spin resonance (ESR). The overall activation energy of the polymerization was calculated to be 58 kJ/mol. The initial polymerization rate (R_p) is expressed by R_p = k[MAIB]^0.3[PECMA]^2.3 at 60 °C. Such unusual kinetics may be ascribable to primary radical termination and to acceleration of propagation due to monomer association. Propagating poly(PECMA) radical was observed as a 13‐line spectrum by ESR under practical polymerization conditions. ESR‐determined rate constants of propagation (k_p, 4.7–10.5 L/mol s) and termination (k_t, 4.6 × 10⁴ L/ml s) at 60 °C are much lower than those of methacrylamide and methacrylate esters. The Arrhenius plots of k_p and k_t gave activation energies of propagation (24 kJ/mol) and termination (25 kJ/mol). The copolymerizations of PECMA with styrene (St) and acrylonitrile were examined at 60 °C in THF. Copolymerization parameters obtained for the PECMA (M₁) − St(M₂) system are as follows: r₁ = 0.58, r₂ = 0.60, Q₁ = 0.73, and e₁ = +0.22. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4264–4271, 2000     

Polymers from aryl cyclic sulfonium zwitterions—photosensitive materials cast from and developed in water

Upon photolysis or heating, aryl cyclic sulfonium (ACS) zwitterions polymerize by ring‐opening and loss of charge to yield nonionic polymers. These water‐soluble monomers potentially are useful for photolithography because they can be cast from and developed in water. The ACS zwitterion from bisphenol A, 1,1′‐[isopropylidenebis(6‐hydroxy‐3,1‐phenylene)] bis (tetrahydrothiophenium hydroxide) bis(inner salt) (1) is a negative‐tone, photosensitive material that after photolysis yields a crosslinked film. Unexposed regions are removed by water. The cured film has a low dielectric constant, high volume resistivity, a high degree of planarization, low residual stress, thermogravimetric stability, acceptable fracture toughness, and high hardness. These are desirable properties for a dielectric material used in microelectronic applications. However, a shortcoming of the material is its low T_g, at about 140 °C. A second ACS zwitterion, 1,1′‐[fluorenylidenebis(6‐hydroxy‐3,1‐phenylene)] bis(tetrahydrothiophenium hydroxide) bis(inner salt) (2) was prepared that yields a crosslinked polymer with a higher T_g of about 190 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1283–1290, 2000     

Synthesis and characterization of fluorinated benzoxazole polymers with high Tg and low dielectric constant

Next generation microelectronic packaging requirements are driving the need to produce increasingly lower dielectric constant materials while maintaining high thermal stability and ease of processing. Efforts have focused on the synthesis and analysis of new polymers with the goals of high thermal stability [degradation temperature (T_d) > 400 °C, low glass‐transition temperature (T_g) > 350 °C], low water uptake (<1%), solubility in selected organic solvents, dielectric constant less than 2.5, and low thermal expansion coefficient. These stringent combined goals have been largely achieved with flexible aromatic benzoxazole polymers. Intramolecular hydrogen bonding between pendant hydroxyl groups and the double‐bond nitrogen of the benzoxazole has been exploited to increase the polymer T_g, whereas the incorporation of perfluoroisopropyl units effectively decreases the dielectric constant. Out‐of‐plane impedance measurements on films of materials in this family (38–134 μm thick) have resulted in typical dielectric values of 2.1–2.5 at 1 MHz, depending on copolymer ratios and functionalizations. Results have been correlated with optical waveguide measurements of films 4‐μm thick to determine film anisotropy and the high‐frequency dielectric constant, and have been corroborated by in‐plane interdigitated electrode dielectric measurements on samples 0.75 μm thick. Candidate materials exhibited extremely low water uptake (0.2%) even after submersion in boiling water for several days. Dynamic mechanical analysis of the polymers enabled the determination of the influence of intermolecular hydrogen bonding on the T_g and loss tangent magnitude. Finally, the coefficient of thermal expansion has been examined and correlated with copolymer constitution. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1991–2003, 2000     

A process–structure–property study of anisotropic PMDA-ODA films

A practical methodology for the correlation and prediction of the process–property performance of advanced materials is developed. The model polymer studied is PMDA-ODA polyimide. The connecting link between the process and the properties is the structural state of the polymer. An essential ingredient for a quantitative characterization of the system is a knowledge of its phase state and intrinsic molecular properties. The intrinsic molecular properties define the limiting performance properties available to the polymer. Anisotropic films and sheets produced by five different fabrication processes are examined. Maps of the molecular symmetry axis, the orientation function, and the thickness distributions of two 50-in.-wide sheets fabricated differently are measured nondestructively for process comparison. Four other film fabrication processes are examined and their three-dimensional orientation states determined and correlated. A three-dimensional orientation function triangular plot permits simultaneous representation of the different fabrication processes on the same figure and allows the investigator to choose the most economic and efficient fabrication route. The structure–property study includes the structural correlation and intrinsic molecular property determination of the anisotropic coefficient of thermal expansion (CTE), the anisotropic mechanical moduli and compliances, and the anisotropic dielectric constants. 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 777–788, 1997     

ChemInform Abstract: Crystal Structure and Magnetic Properties of the Uranium Germanide U5Ge4.

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