CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

液晶聚合物/柔性链聚合物共混体系相分离形态

利用元胞动力学方法在二维情况下对浓度、取向序参量的含时Ginzberg-Landau方程进行数值求解,研究了液晶聚合物/柔性链聚合物共混体系的相分离动力学,考察了浓度、取向有序过程的耦合对相分离形态的影响.结果表明,此耦合作用对相分离的时间进程以及相分离图样的空间排布都有影响.液晶聚合物的取向有序相当于增加了两组分间的不相容性而促进两相分离;两个序参量在热力学方面的耦合使液晶聚合物趋向于沿着界面方向取向,而动力学方面的耦合使液晶聚合物分子沿着其取向方向扩散,相分离图样的空间排布由这两种效应共同决定通过极化率张量的定义用数值方法模拟得到了相分离体系的小角光散射图样,结果表明,散射强度分布具有方位角依赖性,它是由浓度、取向序参量的空间变化共同决定的.     

A NOVEL APPROACH TO RHEOLOGICAL CHARACTERIZATION FOR THE GELATION IN POLYMER CRYSTALLIZATION

The isothermal crystallizations of three kinds of commercial isotactic polypropylene have been studied by DSC and rheometric experiments, in a range of temperatures where the rate of crystallization is moderate. As the crystallization proceeds, volume contraction induces tensile force upon the parallel plates. The tensile force relaxed quickly in liquid states,but after a critical amount of the relative crystallinity, it starts to accumulate in the static test, that is, with the motionless parallel plates. A new method to determine the liquid-solid transition by the static tensile force is proposed and compared with two dynamic methods of detecting liquid-solid transition, that is, the power-law modulus theory and the yield modulus model. The tensile force method predicted considerably earlier transition than the dynamic methods, and the corresponding DSC data indicate relative crystallinity of larger than 0.2 at the transition times. The limitation of dynamic methods and other possible errors have been analyzed. While the dynamic methods are suitable for slow crystallization, the tensile force method is more appropriate for the crystallization of moderate rates. Moreover, it has the advantage of almost not disturbing the crystallizing materials before the transition.     

Dilatometric study of glass transition kinetics in polyisoprene

From dielectric measurements the thermal dependence and the distribution function of the relaxation times can be determined. In the present contribution we are testing the correspondence between the relaxation times obtained from the dielectric measurement and the dilatometric behavior of the material in the vicinity of the glass transition temperature. The experimental data used for the comparison were obtained for the sample of polyisoprene.     

分子线电子输运特性的第一性原理研究

从第一性原理出发,利用密度泛函理论研究了SH-C8H16-SH分子和金表面的相互作用,并利用分子前线轨道理论和微扰理论定量地确定了该相互作用能常数,然后,利用弹性散射格林函数方法研究了该分子与金表面形成的分子线的伏-安特性.研究结果表明,当含有硫氢官能团的有机分子化学吸附于金表面时,硫原子将与金原子形成以共价键为主的混和键,此时,扩展的分子轨道使分子线的电导呈现出欧姆特性,而对于局域的分子轨道,电子的输运只能通过隧道效应来实现.对分子线伏-安特性的计算结果显示,在零偏压附近,存在一个电流禁区,随着偏压的增加,分子线的电导呈现出平台特征.     

EFFECT OF pH ON THE ADSORPTION OF p-AMINOBENZOIC ACID ON POLYSTYRENE-BASED ADSORBENTS

In the present study the adsorptive properties of p-aminobenzoic acid with hypercrosslinked and multi-functional polymeric adsorbents at different solution pHs were systematically investigated in accordance with the particular physicochemical characteristics of the aromatic amphoteric compound involving both Lewis acid and Lewis base functional groups. It was found that the equilibrium adsorption data of the three polymeric adsorbents fitted well in the Langmuir and Freundlich isotherm equations. Studies at various pH levels indicate that the capacity of the adsorbents for adsorption of the ionic forms of adsorbate is less than that for the corresponding neutral species. At pH 3.78, the adsorption capacities of the three adsorbents are the highest. Whereas the adsorption property of multi-functional polymeric adsorbent NJ-99 is the largest, which may be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of p-aminobenzoic acid. The trend of the adsorption capacities of the three adsorbents towards p-aminobenzoic acid with the solution pH is in accord with the dissociation curve of the neutral molecular p-aminobenzoic acid. The adsorption forces include π-π interaction, hydrogen-bonding interaction and electrostatic attraction or repulsion when there exist the molecular and ionic adsorbing species at different pHs in aqueous solution.     

Thermoelectric Properties of Czochralski GeSi Crystal

In order to discuss the application possibility of SiGe crystal in thermoelectric materials,we investigated the thermoelectric properties of several silicon-germanium alloys with different content,orientation and electric conductive type. As discussed in the experiment result,the absolute value of Seebeck coefficient fluctuates from 300 to 600 μV/K in the whole temperature range. In the present paper,the relationship of Seebeck coefficient against content,orientation and electric conductive type is summarized in detail. The Seebeck coefficient of the sample with <111> orientation is smaller than that in <100> at the same temperature. Absolute value of P-type is larger than that of N-type except pure Ge. But as the temperature increases,the absolute value of pure Ge decreases many times as quickly as that of other specimens. In addition,the specimens of bulk GeSi alloy crystals for experiment were grown by the Czochralski method through varying the pulling rate during the growing process.     

DFT Studies on Non-IPR C68 and Endohedral Fullerene Sc3N@C68

The structures and spectra of 20 possible isomers of C78(CH2)3 have been studied by using AM1,INDO/CIS and DFT methods. The results show that the most stable isomer is 1,2,3,4,5,6-C78(CH2)3 (A) with annulene structures,where three -CH2 groups are added to the 6/6 bonds located at the same hexagon passed by the shortest axis of C78 (C2v). Compared with that of C78 (C2v),the first absorption in the electronic spectrum of C78(CH2)3 (A) is blue-shifted because of its wider LUMO-HOMO energy gap. While the IR frequencies of the C–C bonds on the carbon cage are red-shifted owing to the formation of annulene structures and the extension of the conjugated system. The chemical shifts of the carbon atoms in 13C NMR spectra are moved upfield upon the addition.     

花生酸与铈β-二酮络合物混合单分子膜的成膜特性

将铈β-二酮络合物(Ce(tmhd)4)的氯仿溶液与花生酸(AA)的氯仿溶液以不同摩尔比混合并铺展在纯水亚相上,得到其与AA的混合单分子膜.对混合单分子膜的成膜特性(π-A等温线和体系超额自由能)进行了探讨,发现混合单分子膜的超额自由能为负值,混合过程为热力学自发过程,且在配比为1∶ 2时其绝对值最大,体系最稳定,并进一步讨论了混合单分子膜可能的凝聚态结构.在配比为1∶ 2时,研究了混合单分子膜的静态弹性和动态弹性.     

MISCIBILITY AND MORPHOLOGY OF THIN FILMS OF BLENDS OF POLYSTYRENE WITH BROMINATED POLYSTYRENES： EFFECTS OF VARYING THE MOLECULAR WEIGHT, BROMINATION DEGREE AND ANNEALING

Thin films of incompatible polymer blends can form a variety of structures during preparation and subsequent annealing process. For the polymer blend system consisting of polystyrene and poIy(styrene-co-p-bromo-styrene), i.e., PS/PBrxS, its compatibility could be adjusted by varying the degree of bromination and the molecular weight of both components comprised, in this paper, surface chemical compositions of the cast and the annealing films were investigated by X-ray photoelectron spectroscopy (XPS) and contact angle measurement; meanwhile, surface topographical changes are followed by atomic force microscopy (AFM). In addition, substantial attention was paid to the effect of annealing on the morphologic variations induced by phase separation and/or dewetting of the thin film. Moreover, the influences of the molecular weight, Aw, as well as the brominated degree, x%, on the sample surface are explored systematically, and the corresponding observations are explained in virtue of the Flory-Huggins theory, along with the dewetting of the polymer thin film.     

Theoretical Study on the Catalytic Activity and Sulfur Resistibility of Amorphous Alloy Ni-B-P

In the present paper,one hundred cluster models NinBP (n=1～6) have been designed and studied by density functional theory (DFT) to get an insight into the local structure,catalytic properties and sulfur resistibility of amorphous alloy Ni-B-P. The configurations in triplet state are found more stable than those in the singlet state. It is found that as the content of Ni in the clusters increases,the value of Fermi level in clusters fluctuated,which shows that the content of Ni can influence the Fermi level to a certain extent. Based on the Fermi level and DOS,we consider the activity of catalyst in hydrogenation reaction is the best in cluster Ni3BP. On the basis of the charge of clusters NinBP (n=1～6),we conclude the amorphous alloy Ni-B-P with high Ni content has better sulfur resistibility and the best hydrogenation activity,strong sulfur resistibility appears in clusters Ni3BP,and the amorphous alloy Ni60B20P20 with similar proportion is expected to prepare in the future.     

核因子κB活性抑制剂定量构效关系

The electronic structures, geometric structures and some molecular properties (generalized structural indexes) of quinazoline derivatives were computed by using density functional theory and molecular mechanism methods to investigate the quantitative structure-activity relationship (QSAR) of the inhibitory activity toward the nuclear factor kappa B. Via a stepwise regression analysis, some main factors affecting the activity of the compounds were factored out, and then the QSAR equation was effectively established. It was found that the hydrophobic parameter of the substituent on ring D is the main factor affecting the inhibitory activity of the compound. The analysis indicated, the larger the hydrophobic parameter, the higher the inhibitory activity of the compound. In addition, the net charge of the first atom and the stereoscopic parameter (MR1) of the substituent R1 on A-ring as well as the net charge of C3 are closely correlated with the inhibitory activity of the compound. In order to test the predicted results of the QSAR equation, we adopted the “leave one out” cross-validation , and found that the calculated coefficient q2 was rather high and the predicted results were both accurate and reliable. Such facts show that the obtained equation has great predictive ability. The above results can offer an important theoretical guide in the search for new quinazoline derivatives with higher inhibitory activity, and in an analysis of their action mechanisms. It is noteworthy that this scheme would be very advantageous in factoring out precursors with excellent inhibitory activity via the computer ADDIT molecule-design, since all parameters in the QSAR equation are computable and controllable.     

交流电沉积法制备金属氧化物纳米材料及形貌控制

以不同种类的金属丝为电极,采用交流电沉积的方法在液相水溶液中制备了多种金属氧化物纳米材料,并对其形貌进行了控制.由XRD和TEM分析结果表明,在相同的NaCl电解质水溶液中,不同的金属电极对应的不同金属氧化物纳米产物具有明显不同的形貌.     

Bimodality of molecular mass distribution of polydienes obtained under the action of dilithium initiators in hydrocarbon media: the reasons,mathematical simulations,and their experimental testing

Bimodal molecular mass distribution (MWD) of polymers, obtained upon polymerization of hydrocarbon monomers in the nonpolar media under the action of dilithium initiators, is the consequence of separation of the reaction mixture into two phases. Bifunctional /living/ oligomers produce the insoluble sediment due to tetrameric association of the lithium active sites (the swollen gel-fraction). Part of the active site remains in the solution (the solfraction). Difference in the concentrations of the active sites into the phases leads to difference between the propagation rates of the /living/ chains and, as a result, to Bimodal MWD. The mathematical model of polymerization in the two-phase system is proposed. Satisfactory agreement between the calculations and the experiments is shown for butadiene polymerization in heptane under the action of 1,4-dilithiumpentane. Regulation of MWD up to the complete elimination of bimodality is possible via the programmed dosage of monomer and solvent into the reactor.     

Miscibility of dodecyltrimethylammonium bromide and dodecyltrimethylammonium chloride in surface-adsorbed film and micelle

Surface tension of aqueous solutions of mixtures of dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium chloride (DTAC) has been measured and analyzed by using thermodynamic relations. The adsorbed film has been found to contain more DTAB molecules than the solution. The shape formed by the curves of the total molality at constant surface tension against the solution and surface compositions indicates the ideal mixing of the DTAB and DTAC molecules in the adsorbed film. Micellar composition has been estimated at the critical micelle concentration (CMC). The micelles have been found to be richer in DTAB than the solution, but poorer in DTAB than the adsorbed film at the CMC. The DTAB and DTAC molecules have been shown to mix ideally in the micelles. From the comparison with the results on the system of decylammonium bromide and decylammonium chloride, it has been concluded that, on the mixing of surfactants differing only in counter ions, the adsorbed film is influenced more significantly by the ionic head group of the surfactant than the micelle.     

Small‐angle X‐ray scattering investigation of carbon nanotube‐reinforced polyacrylonitrile fibers during deformation

Structural changes during deformation in solution‐ and gel‐spun polyacrylonitrile (PAN) fibers with multi‐ and single‐wall carbon nanotubes (CNTs), and vapor‐grown carbon nanofibers were investigated using synchrotron X‐ray scattering. Previously published wide‐angle X‐ray scattering (WAXS) results showed that CNTs deform under load, alter the response of the PAN matrix to stress, and thus enhance the performance of the composite. In this article, we find that the elongated scattering entities that give rise to the small‐angle X‐ray scattering (SAXS) in solution‐spun fibers are the diffuse matrix‐void interfaces that follow the Porod's law, and in gel‐spun fibers these are similar to fractals. The observed smaller fraction of voids in the gel‐spun fibers accounts for the significant increase in the strength of this fiber. The degree of orientation of the surfaces of the voids is in complete agreement with those of the crystalline domains observed in WAXS, and increases reversibly upon stretching in the same way as those of the crystalline domains indicating that the voids are integral parts of the polymer matrix and are surrounded by the crystalline domains in the fibrils. The solution‐spun composite fibers have a larger fraction of the smaller (<10 nm) voids than the corresponding control PAN fibers. Furthermore, the size distribution of the voids during elongation changes greatly in the solution spun PAN fiber, but not so in its composites. The scattered intensity, and therefore the volume fraction of the voids, decreases considerably above the glass transition temperature (T_g) of polymer. Implications of these observations on the interactions between the nanotubes and the polymer are discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2394–2409, 2009     

The lamellar phase of the sodium dodecylsulfate/decanol/toluene/formamide system: NMR and phase studies of solubilization

The phase behavior of the system sodium dodecylsulfate/decanol/toluene/ formamide was investigated and pseudo-ternary diagrams established. In particular, the effect of varying the amount of toluene in the system on the stability of the lamellar phase region was studied in detail. Deuterium NMR and low-angle x-ray diffraction measurements showed that more toluene was distributed between the surfactant chains as the amount of decanol in the system is reduced, resulting in a more disordered dynamic structure in the bilayers. Similarly, increased formamide content lead to greater penetration of the toluene into the bilayer and more disorder. Both factors were found to be instrumental in decreasing the stability of the lamellar structure.     

Lipolysis of didecanoyl-lecithin/triolein mixed monolayers by phospholipaseA 2

A study of enzyme lipolysis by pancreatic phospholipaseA ₂ and by vipera berus phospholipaseA ₂ on monomolecular mixed films of didecanoyl-lecithin and triolein on an aqueous subphase of pH 8 has been carried out. The influence of the composition of the mixed film, the surface pressure of the film and the amount and type of the injected enzyme on the lipolysis rate were studied.In order to relate the lipolytic activity with the monolayer state, the compression isotherms of the didecanoyl-lecithin/triolein mixed monolayers have also been obtained.The resuls are compared to observations on lipolytic activity of phospholipaseA ₂ on the didecanoyl-lecithin/cholesterol mixed monolayers. Triolein improves the kinetic conditions of the lipolysis of lecithin films in a higher degree than cholesterol. Probably it increases the enzyme penetration by the fluidifying effect exerted on the lecithin monolayers.