Amelioration of mechanical brittleness in hyperbranched polymer. 1. Macroscopic evaluation by dynamic viscoelastic relaxation

Hyperbranched poly(ether ketone)-b-linear poly(ether ketone)-b-hyperbranched poly(ether ketone) (HLHPEK) triblock copolymers with two different block compositions were prepared as an approach to improve the mechanical brittleness of hyperbranched poly(ether ketone) (HPEK). From the time-temperature superposition of dynamic shear moduli, G′(ω) and G″(ω), of HPEK and two HLHPEKs, it was investigated that the junction points between G′(ω) and G″(ω) shifted to the higher frequencies and the rubbery plateau region spread wider over the reduced frequency axis as the linear blocks were introduced and their compositions were increased. Such changes in viscoelastic response were consequences of increase in the amount of chain entanglements additionally formed by the linear blocks. In order to verify the effect of the linear block incorporation on amelioration of the mechanical brittleness, the degree of brittleness and its improvement were evaluated from the temperature dependence of the shift factors, a_Ts, experimentally obtained during the superposition of the dynamic moduli and of the average viscoelastic relaxation times, τ_HNs, determined with empirical Havriliak-Negami distribution function. From the nonlinear curve fittings of the a_Ts and the τ_HNs by the Vogel-Tamman-Fulcher equation, the degree of brittleness for HPEK and HLHPEK triblock copolymers were quantified as values of the material parameter D, an indicative of deviation from the linear Arrhenius behavior and a measure of fragility of the given material. The tendency of increasing D values with the linear block compositions confirmed substantial improvement of the mechanical brittleness in the HLHPEK triblock copolymers compared to HPEK. Therefore, the approach to copolymerize HPEK with its chemically analogous linear counterpart was verified to be an effective strategy to impart molecular entanglements and hence ameliorate the mechanical brittleness on the basis of macroscopic rheological evaluation.     

Adsorption properties of polyacrylonitrile‐based activated carbon hollow fiber

In this work, polyacrylonitrile (PAN) hollow fibers are pretreated with ammonium dibasic phosphate and then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The adsorption properties of the resultant activated carbon hollow fibers (ACHF) prepared in different conditions were studied. The results show that the adsorption properties of ACHF change regularly with preparing conditions of ACHF. The different adsorption ratios to three adsorbates reflect the number of micropores and mesopores in PAN‐based ACHF. Pretreatment with phosphate can increase the number of mesopores. Proper oxidation temperature and time can increase the number of micropores and mesopores. When carbonization temperature is more than 900°C and carbonization time ranges from 50 to 90 min, the number of micropores and mesopores, especially mesopores, greatly increases. Compared with other treatments, activation treatment greatly increases the number of micropores and mesopores, and the dominant pore sizes of mesopores in PAN‐based ACHF are from 2 to 10 nm. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 602–607, 2004     

m-LLDPE／纳米SiO2的力学性能和光学性能研究

采用熔融共混法制备了m-LLDPE／纳米SiO2复合材料，并对该体系的力学性能和光学性能进行了系统研究。结果表明，纳米SiO2对m-LLDPE具有一定的增强、增韧作用。复合材料的红外吸收能力较m-LLDPE明显提高，此外，m-LLDPE／纳米SiO2复合材料的可见光透光度有所降低，雾度却有明显的上升。通过SEM电镜得出，表面处理方法对纳米SiO2在基体中的分散性能有显著影响。     

EFFECTS OF NONIONIC SURFACTANTS ON PERFORMANCE OF COPPER CHEMICAL MECHANICAL POLISHING

During copper chemical mechanical polishing (Cu-CMP), the physical properties of slurry, such as the dispersion and suspension stability of abrasives, the interaction between particles and the polished surface, and the rheological characteristics, greatly affect the planarization efficiency. In this study, several nonionic surfactants were added to change the aforementioned physical characteristics of slurry and Cu-CMP performance. Their effects were investigated. The experimental results showed that Al₂O₃ slurry with 300 ppm Triton DF-16 could enhance the wettability of the Cu surface and stabilize the dispersion of abrasives in the slurry. Therefore, the passivation reaction on the Cu surface during CMP would occur uniformly, and the removal of particles during post cleaning could be improved. Cu CMP using the slurry with an adequate amount of nonionic surfactants, Triton DF-16, is proposed to reduce the surface roughness, enhancing the planarity.     

Mechanism of paper wet strength development by polycarboxylic acids with different molecular weight and glutaraldehyde/poly(vinyl alcohol)

In our previous research, we found that crosslinking paper using poly(carboxylic acid)s with different molecular weight or using the combination of glutaraldehyde and poly(vinyl alcohol) (PVA) significantly improved the wet strength of the paper. In this research, we studied the mechanism of paper wet strength development using crosslinking systems with different molecular weight by measuring scanning electron microscopic (SEM) images, wet strength, folding endurance, wet thickness, water retention, and Z‐direction tensile strength of the treated paper. The paper crosslinked by a high‐molecular weight (MW) poly(carboxylic acid) shows more swelling by water than that crosslinked by a low‐MW polycarboxylic acid in the SEM micrographs even though both treated paper samples have similar wet strength. Thus, the data suggest that high‐MW poly(carboxylic acid)s promote the formation of interfiber crosslinking. Crosslinking paper by glutaraldehyde, a crosslinking agent of small molecular size, improves wet strength and reduces flexibility and swellability of paper because of the formation of intrafiber crosslinking. Combining glutaraldehyde with PVA as a coreactant increases wet strength and also retains flexibility and swellability of the treated paper because of the formation of interfiber crosslinking. The hypothesis that PVA reacts with glutaraldehyde to form a polymeric pentanedialated‐PVA crosslinking system and promotes the formation of interfiber crosslinking on the paper is supported by the data of wet strength, folding endurance, wet thickness, water retention, and Z‐direction tensile strength of the treated paper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 277–284, 2006     

Synthesis and electrochemical performance of LiNi0.5Mn1.5O4 spinel compound

Spinel compound LiNi_0.5Mn_1.5O₄ was synthesized by a chemical wet method. Mn(NO₃)₂, Ni(NO₃)₂·6H₂O, NH₄HCO₃ and LiOH·H₂O were used as the starting materials. At first, Mn(NO₃)₂ and Ni(NO₃)₂·6H₂O reacted with NH₄HCO₃ to produce a precursor, then the precursor reacted with LiOH·H₂O to synthesize product LiNi_0.5Mn_1.5O₄. The product showed a single spinel phase under appropriate calcination conditions, and exhibited a high voltage plateau at about 4.6-4.8 V in the charge/discharge process. The LiNi_0.5Mn_1.5O₄ had a discharge specific capacity of 118 mAh/g at about 4.6 V and 126 mAh/g in total in the first cycle at a discharge current density of 2 mA/cm². After 50 cycles, the total discharge capacity was above 118 mAh/g.     

甲基丙烯酸锌在NBR／木质素中的应用

研究了α－甲基丙烯酸锌（ＭＡＡ－Ｚｎ）对ＮＢＲ／木质素（１００／１００，质量比）硫化胶性能的影响。结果表明，加入１．５～５．０份ＭＡＡ－Ｚｎ，可提高硫化胺的１００％的定伸应力，硬度和抗压缩永久变形能力，但对其他力学性能影响甚微，经分析可知，ＭＡＡ－Ｚｎ还可以降低硫化反应活化能，提高硫化胶的交联密度和耐热老化性能。     

Dynamic Mechanical Properties and Adhesive Strengths of Emulsion Polymer by Power Feed Technique, I

Dynamic mechanical properties and adhesive strengths of power feed copolymer and random copolymer synthesized using styrene or methyl methacrylate and n-butyl acrylate were investigated. Although the two systems were synthesized from the same raw materials, power feed copolymer had a very broad transition compared with random copolymer. This fact was explained by the fact that the system synthesized through power feed method was an alloy of copolymers which are a continuous series from monomer A rich copolymers to monomer B rich copolymers. The dynamic mechanical behavior of film cast from solution was almost the same as that of emulsion film, which indicated more extensive application of power feed copolymer. In the P(nBA/St) system, power feed copolymer maintained its adhesive strengths over a wide temperature range compared with random copolymer. The absolute value, however, was not so high. This was due to the low cohesive strengths of the films.     

Effect of hydrocarbons precursors on the formation of carbon nanotubes in chemical vapor deposition

High-temperature decomposition of hydrocarbons may lead to the formation of carbon deposits. However in our present studies, we found that the morphology of carbon deposits over MgO supported Fe catalyst during chemical vapor deposition (CVD) process was closely related to the thermodynamic properties and chemical structures of hydrocarbon precursors. Six kinds of hydrocarbons (methane, hexane, cyclohexane, benzene, naphthalene and anthracene) were used as carbon precursors in this study. Methane which has a pretty simple composition and is more chemically stable was favorable for the formation of high-purity single walled carbon nanotubes (SWNTs). For high-molecular weight hydrocarbons, it was found that the chemical structures rather than thermodynamic properties of carbon precursors would play an important role in nanotube formation. Specifically, the CVD processes of aromatic molecules such as benzene, naphthalene and anthracene inclined to the growth of SWNTs. While the cases of aliphatic and cyclic hydrocarbon molecules seemed a little more complicated. Based on different pyrolytic behaviors of carbon precursors and formation mechanism of SWNTs and multi-walled carbon nanotubes (MWNTs), a possible explanation of the difference in CVD products was also proposed.     

Mechanical properties of high-strength concrete after fire

With compressive strength grade of C40, C60, and C70, respectively, normal-strength concrete (NSC) and high-strength concrete (HSC) were used to investigate compressive strength, splitting tensile strength, and bending strength after high temperature. The oil furnace is used in this study. Its temperature-time curve is close to standard curve, which conforms to Chinese standard GB/T 9978-1999. After being heated to temperatures of 200, 400, 600, 800, and 1000 °C, respectively, the mechanical properties of HSC were tested. The influence of temperature, water content, specimen size, strength grade, and temperature profiles on mechanical properties of HSC are discussed.