无加热氧碘化学激光器超音速喷管

针对氧碘化学激光器的金属喷管在使用过程中需加热保温且存在结构复杂、故障率高等问题,初步选择了几种可用于加工无加热喷管的非金属材料,并以kW级氧碘化学激光器为原型,以聚酰亚胺为例,对激光器运行条件下的喷管温度场进行数值模拟,以验证此种非金属无加热喷管的可行性。结果表明:与金属喷管相比,非金属喷管在不加热保温的情况下能够有效阻止热量传递,防止碘蒸气冷却凝结,满足激光器喷管的使用要求。     

Synthesis and Characterization of Borax-Polyimide for Flame Retardant Applications

Polyamide-borax composites were prepared from solution of polyimide and the borax using N-methyl-2-pyrrolidone as a solvent. The Polyimide-borax composites films (PI-BX) characterized by FTIR, SEM and x-ray. The borax content significantly influences thermal behavior of the polymeric films, such as glass transition and decomposition temperatures of polyimide-borax composites. The glass transition temperatures of the composites were higher than that of the original polyimide. The flammability properties of them were demonstrated by cone calorimeter and indicate that the borax composites have significantly decreased in heat release rate, and mass loss rate. The PI-BX composites appears very good the flame retardant properties.     

Ferromagnetic Intermolecular Interaction of N-Protonated Pyridylphenylcarbene

Abstract

The HCl and DCl salts of pheny1-4-pyridyldiazomethane were prepared and irradiated at 6 K to generate the carbenes. Their ESR spectra indicated presence of plural triplet carbenes with slightly-different zero-field splitting constants. Besides the triplet species, we found a quintet species whose signal intensity decreases with increasing temperature. The quintet spin state was concluded to be a ground state which was produced by an intermolecular ferromagnetic interaction of the triplet carbenes. The ferromagnetic interaction would be explained by the McConnell mechanism, judging from the crystal structure of the HCl salt of phenyl-4-pyridylketone.     

脉冲敲击技术对PI微球表面粗糙度的影响

作为点火靶重要候选靶丸之一, 聚酰亚胺 (PI) 空心微球采用降解芯轴技术结合双单体气相沉积聚合法 (VDP) 制备. 在PI涂层过程中微球碰撞对表面质量影响较大, 为了减小碰撞提高表面质量, 选用筛网盘做样品盘, 激励方式由压电振动模式改为脉冲敲击模式进行对比. 实验数据表明微球运动过程中碰撞是引起表面质量变差的原因, 通过理论分析确认了筛网盘通过减少接触点可以减少微球与微球间、微球与样品盘间的碰撞, 并且将压电振动改为脉冲敲击模式可以减小微球碰撞次数. 脉冲敲击模式与压电振动模式相比, 其可控性、微球弹跳幅度、消除静电等方面均优于压电振动. 对于微球壁厚均匀性而言, 压电振动略好于脉冲敲击, 但相差较小. 单个微球的壁厚最大偏差前者为0.68 μm, 优于后者的0.73 μm; 单个微球壁厚平均值在同一批次内的最大起伏, 前者为0.26 μm, 优于后者0.57 μm. 白光干涉仪数据显示脉冲敲击起到了提高微球表面质量的作用, 其表面粗糙度Rq值由52–93 nm 减小到28–44 nm. 关键词： 脉冲敲击技术 聚酰亚胺靶丸 表面粗糙度 壁厚均匀性     

Gamma irradiation of cholesteric products: Effect of the presence of organic solvents

The shift δT of the selective reflection temperature due to an exposure to γ-rays is studied for a mixture of cholesteric substances dissolved in various organic solvents. Values of δT such as 0.2°C per krad can be obtained. The influence of the solvent nature (carbon tetrachloride, chloroform, trichloroethylene, …) is also discussed. It is shown that the shift δT is due to the presence of radiolysis products of the solvent; this effect is more specially studied in the case of carbon tetrachloride containing a radical scavenger.     

Structural and optical modifications in gamma-irradiated polyimide/silica nanocomposite

The structural and optical properties of thin films of polyimide composites with nanosilica particle content of 15?wt%, prepared via sol–gel process, were studied as a function of the gamma dose. The resultant effect of gamma irradiation on the properties of polyimide/silica nanocomposite has been investigated using X-ray diffraction and UV spectroscopy. Absorption and reflectance spectra were collected by a spectrophotometer giving UV-radiation of wavelength range 200–800?nm. The optical data obtained were analyzed and the calculated values of the optical energy gap exhibited gamma dose dependence. The direct optical energy gap for the nonirradiated polyimide/silica nanocomposite is about 2.41?eV, and increases to a value of 2.65?eV when irradiated with gamma doses up to 300?kGy. It was found that the calculated refractive index of the polyamide/silica increases with the gamma dose in the range 50–300?kGy.     

Molecular Packing in Crystalline Domains of Unsymmetrical Poly(benzoxazole-imide): Investigation using Modeling of a Model Compound

To probe the molecular packing in crystalline domains of an unsymmetrical poly(benzoxazole-imide) (BPDA-BOA) introduced alternating phenylbenzoxazole and bisphthalimide units via the two-step polymerization of 5-amino-2-(4- aminophenyl)benzoxazole (BOA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), the crystal structure of its model compound, 5-phthalimido-2-(4-phthalimidophenyl)benzoxazole (PA-BOA), was investigated using powder wide-angle X-ray diffraction (WAXD) combined with molecular modeling using a Materials Studio program. Powder WAXD pattern of the model compound can be well indexed in terms of amonoclinic unit cell with parameters of a = 12.005 Å, b = 3.837 Å, c = 23.562 Å, β = 96.711°. There are two molecules in the unit cell with the space group of P2 (3). Based on the crystal structure of the model compound powders and the WAXD analysis of poly(benzoxazole-imide) film, it can be concluded that the projection of the monomer repeat length of the poly(benzoxazole-imide) chains in the chain directionis around 19.0 Å, and the interchain side-by-side distance and face-to-face distance between the centroids of two neighboring BPDA-BOA chains are around 6.10 and 4.01 Å, respectively. The difference of molecular packing between the poly(benzoxazole-imide) chains in their crystalline domains and the model compounds in their crystals are also presented. Both the side-by-side and face-to-face π-π stacking distances between two neighboring polymer chains in the poly(benzoxazole-imide) crystalline domains are significantly larger than the corresponding values between two neighboring molecules in the model compound crystals due to a more kinked and twisted conformation.     

Thermal cross-link between 2,5-furandicarboxylic acid-based polyimides and bismaleimide via Diels–Alder reaction

A series of cross-linked polyimides (PIs) were prepared via two-step solution polycondensation from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and 2,5-furandicarboxylic acid-based diamines, N,N′-bis(4-amino-2-(trifluoromethyl)phenyl)furan-2,5-dicarboxamide (TFFDA) and N,N′-bis(4-aminophenyl)furan-2,5-dicarboxamide (p-FDDA), followed by thermal crosslinking reaction with bismaleimide. The thermal crosslinking reaction and its mechanism were studied by FTIR spectra and model reaction analysis, which showed Diels–Alder reaction between furan group and maleimide group played a main role in the thermal treatment. The properties of cross-linked PIs were characterized using dynamic mechanical thermal analysis, thermogravimetric analyses, tensile testing, ultraviolet-visible spectra, and wide-angle X-ray diffraction. The cross-linked polyimide film showed improved solvent-resistance, thermal and mechanical properties with T_g values of 234–306^oC, tensile strengths of 82–98 MPa and moduli of 2.3–3.0 GPa.     

Molecularly Engineered 6FDA-Based Polyimide Membranes for Sour Natural Gas Separation

Glassy polyimide membranes are attractive for industrial applications in sour natural gas purification. Unfortunately, the lack of fundamental understanding of relationships between polyimide chemical structures and their gas transport properties in the presence of H₂S constrains the design and engineering of advanced membranes for such challenging applications. Herein, 6FDA-based polyimide membranes with engineered structures were synthesized to tune their CO₂/CH₄ and H₂S/CH₄ separation performances and plasticization properties. Under ternary mixed sour gas feeds, controlling polymer chain packing and plasticization tendency of such polyimide membranes via tuning the chemical structures were found to offer better combined H₂S and CO₂ removal efficiency compared to conventional polymers. Fundamental insights into structure–property relationships of 6FDA-based polyimide membranes observed in this study offer guidance for next generation membranes for sour natural gas separation.     

Porphyrin‐containing Polyimide with Enhanced Light Absorption and Photocatalysis Activity

A series of porphyrin‐containing polyimide (PI) photocatalysts were synthesized by a one‐step solvothermal method. Characterization results revealed that porphyrin was uniformly coupled into the PI framework through covalent bonding and the visible‐light absorption was greatly improved. The photodegradation activity of porphyrin‐containing PIs for methyl orange (MO) under visible light was enhanced significantly, with the highest pseudo‐first‐order rate constant 35 times higher than that of neat porphyrin and 10 times higher than that of porphyrin‐free PI. The enhancement is mainly attributed to an increased light harvesting accompanied by a varied HOMO level, which was clarified by control experiments, characterizations and theoretical calculations. This work provides an insight into multiple effects of dye molecules in dye‐containing heterogeneous photocatalysts.