Enhancement of composite‐metal interfacial adhesion strength by dendrimer

The interface between carbon fiber reinforced polymer composites and metal plays a critical role in determining the strength of epoxy/metal laminated composites. We propose to introduce one dendrimer layer into the epoxy/metal interface, aiming to enhance the interfacial adhesion strength so that the interface could more effectively transfer the load from epoxy to metal. In this paper, the preparation and adsorption of dendrimer layer onto the alumina surface were systematically investigated. The results show that a highly stable and nanopatterned dendrimers layer was dip‐coated onto alumina substrates by adsorbing poly (amidoamine) dendrimers. It was confirmed that the dendrimers were adsorbed onto the alumina via acid‐base chemical interactions. The adsorption depends on the reaction time. The adhesion property between dendrimers and alumina was examined by sonication method. Copyright © 2010 John Wiley & Sons, Ltd.     

CaSO_4晶须补强增韧聚氨酯弹性体机理的研究

提高聚氨酯弹性体的力学性能是聚氨酯研究领域里普遍关心的课题之一,一般采用刚性粒子和纤维类无机填料增强聚氨酯弹性体,但上述填料在提高强度的同时,会导致韧性降低,空易造成脆性断裂,因此填料能否同时补强增韧聚氨酯弹性体具有重要的实际应用价值,晶须是一种单晶纤维状材料,其直径极小,几乎不存在任何缺陷,由于内在的完整性,高度有序的原子排列,使其强度接近晶体理论－－原子间价键的强度,晶须凭借微细的直径、较短的长度、极高的强度,成为一种新型补强增韧剂,目前晶须的复合基体多为陶瓷基、金属基和树脂基,有关复合基体多为陶瓷基、金属基和树脂基,有关复合聚氨酯弹性体的理论及应用研究报道很少,本文制备了具有较高强度和韧性的CaSO4晶须／聚氨酯弹性体复合材料,通过微观分析揭示了CaSO4晶须对聚氨酯弹性体补强增韧的机理,并对其影响因素进行了讨论。     

Nanostructure-driven analyte-interface electron transduction: a general approach to sensor and microreactor design

A concept describing the nanostructure-directed dynamics of acid/base interaction and the balance between physisorption and chemisorption on an extrinsic semiconductor interface is evaluated and compared for n- and p-type semiconductors. The inverse hard/soft acid/base (IHSAB) concept, as it complements the HSAB concept, defines the nature of a dominant physisorption behavior and enables the creation of a matrix of controllable interactions. The technology results in the coupling of Lewis acid/base chemistry with the extrinsic semiconductor majority carriers. Nanoporous silicon layers facilitate the application of nanostructured metal/metal oxides, which provide sensitivity and selectivity for the modified interface. Applied fractional depositions can produce a dominant reversible physisorptive (sensors) or chemisorptive (microreactors) interaction at the semiconductor interface as the nanostructures act as antennas to focus the interaction. The dynamic natures of n- and p-type silicon are evaluated and compared, by focusing on the controlled manipulation of these semiconductors as they are modified with nanostructures and interact with the gas-phase analytes. The observed semiconductor responses correlate well with the temperature dependence of the extrinsic semiconductor, the population of the donor or acceptor levels, and the inherent mobilities of electrons. The response of the modified n-type semiconductors is found to exceed that of comparable p-type systems. The IHSAB concept can be extended to assess the properties of several additional semiconductor interfaces including nanowires. The results obtained not only pertain to sensor and microreactor array design, but also suggest the importance of the dynamic changes created, as the majority charge-carrier concentrations are manipulated and the Fermi energies are modified through chemical interaction.     

鞋用水性聚氨酯胶黏剂的制备及表征

通过预聚体分散法,以二羟甲基丙酸(DMPA)、蔗糖(sucrose)为亲水扩链剂和交联剂制备了一种鞋用水性聚氨酯胶黏剂.通过FTIR、DSC、力学性能、固化速度等研究了蔗糖用量对聚氨酯结构与性能的影响.结果表明蔗糖己引入聚氨酯主链.随着蔗糖用量的增加,相同处理温度下聚氨酯胶液的固化速度提高,胶膜的吸水率降低,拉伸强度增大,断裂伸长率减小,粘接试样的T-剥离强度逐渐增大.当蔗糖用量超过5.52 wt%时,合成及乳化过程中体系容易凝聚,且所制得的胶黏剂粘接强度有所下降.总之,通过改变蔗糖用量可以显著改变水性聚氨酯结构与性能.     

Elucidating the hard/soft acid/base principle: a perspective based on half-reactions

A comprehensive analysis is presented for the acid-base double-exchange reaction as well as the associated acid-displacement and base-displacement "half-reactions" with the goal of elucidating the meaning of the hard/soft acid/base (HSAB) principle and the conditions for its validity. When electron-transfer effects are important and other effects are negligible, the HSAB principle is driven by the surpassing stability of the soft acid/soft base product. When electrostatic effects dominate the reactivity, the HSAB principle is driven by the surpassing stability of the hard acid/hard base product. Because electron-transfer effects favor soft/soft interactions, while electrostatic effects favor hard/hard interactions, acid-base exchange reactions may be used to determine whether a reagent's reactivity is dominated by electron-transfer or by electrostatic effects. Because electron-transfer and electrostatic considerations separately favor the HSAB principle whenever the electronic chemical potentials of the acids and bases involved in the reaction are similar, our analysis provides strong support for the HSAB principle. The electronic chemical potential measures the intrinsic strength of acids and bases.     

聚氨酯与乙酰丙酮铽复合物的相互作用

合成了聚氨酯、乙酰丙酮铽及其复合物. 红外光谱研究结果表明, 铽离子与聚氨酯分子链中的羰基发生了配位作用. 力学性能测试结果表明, 稀土配合物的加入提高了聚氨酯的拉伸强度和断裂伸长等力学性能. 流变性能测试结果显示, 乙酰丙酮铽的加入使聚氨酯溶液的粘度增大, 表明溶液中两者之间存在明显的相互作用.     

Intermolecular interactions in substituted phenols. Investigation of model compounds

The results of heats of mixing experiments on a series of ortho-substituted phenols with an amide or an ester are described. Substituents were chosen to span a wide range of electronic and steric character. Enthalpy of mixing results do not correlate solely with the acid strength of the phenol, or with a Hammett linear free-energy analysis. Rather, interactions are favored by the presence of groups with the ability to weaken the base strength of the proton donor while simultaneously increasing its acid strength. Such groups share a combination of electron-withdrawing ability and/or steric bulk that causes an effective decrease in the electron density about the phenolic oxygen. Trifluoromethyl and tert-butyl, and to a lesser extent halogen and hydroxy substituents ortho to the phenolic OH, give the highest exothermic enthalpies of mixing and are thus the most effective at promoting intermolecular interactions with weak bases such as amides and esters. These results should be useful in designing miscible or compatible polymer blends in which specific interactions such as hydrogen bonding are important. © 1995 John Wiley & Sons, Inc.     

Strength and toughness of carbon fibers reinforced rigid polyurethane composites by adsorbing tannic acid and refining Ni grains on carbon fibers surface

In this article, short carbon fibers (CFs) reinforced rigid polyurethane (RPU) composites were prepared with the aim of improving both strength and toughness. A tannic acid (TA)‐nickel (Ni) composite coating was spontaneously co‐deposited onto CFs surface by a one‐step electrodeposition method to strengthen the interface bonding of the composites. The satisfactory mechanical properties of the composites were mainly attributed to the superior interfacial adhesion. On the one hand, TA could play a role in refining Ni grain during electrodeposition. On the other hand, the hydroxyl groups attached to composite coating, which were introduced by TA, could react with the RPU matrix to form chemical bonds. When the composites were under stress, the chemical bonds could effectively transfer the stress from matrix to the interface, while the refined Ni crystals could greatly increase the stress transfer path, and thus improve the strength and toughness of the material. Compared with pure RPU, the tensile strength, bending strength,interlaminar shear strength, and impact strength of TA‐Ni‐coated CFs/RPU composites were improved by 14.8%, 83.1%, 28.7%, and 121.4%, respectively.     

一种反应型染料的合成及其在聚氨酯革染色中的应用

针对传统聚氨酯色浆中色基与聚氨酯结合力弱(分子间力),导致成品革色牢度差、色迁移严重等技术难题,本文设计合成了一种反应型彩色二元醇:在四氢呋喃介质中,控制n(对苯二胺)∶n(乙酸酐)=1.00∶0.95,0~5℃下,用乙酸酐将对苯二胺单酰化反应15 h,得到对氨基乙酰苯胺(产率85%),经重氮化,与过量摩尔分数为5%N-苯基二乙醇胺偶合制得了一种含两个端羟甲基的偶氮化合物4-乙酰基胺基-4'-N,N-二羟乙氨基偶氮苯(产率82%);将其与聚酯二元醇、聚醚二元醇以不同比例混合,与双异氰酸酯预聚、扩链后形成红色聚氨酯树脂色浆,在离型纸上铺展成膜,其断裂增长率443.0%,断裂相对强度125.5 g,色迁移量21.4μg,进口同类产品形成膜后的断裂增长率、断裂相对强度与色迁移量分别为442.2%、125.3 g和29.2μg.合成产品优于同类进口产品。     

一锅法合成含磺酸基超支化聚氨酯

N-三羟甲基甲基氨基乙磺酸(TES)的胺基与异佛尔酮二异氰酸酯(IPDI)环上活性较高的NCO在低温15℃下发生选择性反应,生成AB3型单体.随后提高反应温度(70～90℃),使AB3型单体原位聚合,一锅法合成出含磺酸基超支化聚氨酯.随着聚合温度的提高,超支化聚氨酯的支化度、分子量及分子量分布系数变大.90℃时,聚合产物的Mn为22410,支化度达到0.87.以此含磺酸基超支化聚氨酯为基础制得的聚合物电解质膜具有良好的耐热性、机械强度,其锂盐室温(约25℃)的离子电导率为3.1×10-5S/cm,100℃达到1.4×10-3 S/cm.     

Halogen Bonding in Two-Dimensional Crystal Engineering

Halogen bonds, which provide an intermolecular interaction with moderate strength and high directionality, have emerged as a promising tool in the repertoire of non-covalent interactions. In this review, we provide a survey of the literature where halogen bonding was used for the fabrication of supramolecular networks on solid surfaces. The definitions of, and the distinction between halogen bonding and halogen-halogen interactions are provided. Self-assembled networks formed at the solution/solid interface and at the vacuum-solid interface, stabilized in part by halogen bonding, are discussed. Besides the broad classification based on the interface at which the systems are studied, the systems are categorized further as those sustained by halogen-halogen and halogen-heteroatom contacts.     

催化剂酸碱性对异丙醇脱水活性的影响

研究了具有不同酸碱中心的催化剂对异丙醇脱水反应活性及选择性的影响,结果表明:催化剂表面有合适的酸碱强度和H_0,max值,能引起高的脱水活性和选择性。红外吸附态证实:在接近反应状态下,催化剂表面出现了-CH₂结构吸附,这表明反应物的碱基(OH基)与催化剂表面酸中心作用的同时,酸基(反应物的β-H)与催化剂表面碱作用,催化剂上这种酸碱活性中心协同作用结果使异丙醇脱水生成丙烯的过程很可能以协同机理方式进行。     

Electro-conductive resins filled with graphite for casting applications

Electro-conductive resins, convenient for casting and coating applications were investigated in this paper.Electrical conductivity of epoxy and polyurethane resins, filled with two different grades of synthetic graphite (different average size) was studied. It was found that all the investigated composites became electro-conductive when filled with 22-vol% of the filler.The impact strength of epoxy and polyurethane resins filled with graphite was also investigated. A decrease in impact strength with an increase in filler content was observed in all cases. The highest values of impact strength were found for polyurethane/graphite KS 6 composites.The strength of adhesion of the filled resins to aluminum was also determined. A decrease in the strength of adhesive joints to aluminum foils with an increase in filler content was observed in all cases. The strongest adhesive joints were found for the epoxy/graphite KS 6 composites.     

Acid–Base Interactions in the Dichloroacetic Acid–Ethyl Acetate System according to IR Spectroscopic Data

The method of multiple total internal reflection infrared spectroscopy (MTIRIRS) is used to study ion–molecular interactions in the system dichloroacetic acid–ethyl acetate in the range of concentrations from pure acid to pure base at 30°C. Depending on the ratio of components in the solution, molecular complexes with acid : base ratios of 1 : 1 or 2 : 1 are formed in the solutions. In the case of excess acid, base is not protonated and species with a strong symmetric hydrogen bond are not formed. It is shown that the absorption coefficient near 2000 cm^–1 can be used to judge the type of the complex formed and the strength of a hydrogen bond in molecular complexes.     

Rheological properties and the interface in polycarbonate/impact modifier blends: Effect of modifier shell molecular weight

Core-shell impact modifiers are used to enhance the impact strength of thermoplastics such as polycarbonate. The shell of the modifier is designed specifically to interact with the matrix polymer because interfacial adhesion between the modifier and matrix is important in improving the impact strength. Several methods have been proposed to study the interactions at the modifier/matrix interface. One measure of this interaction is the strength of lap joints. The degree of interactions at the interface can be characterized as the thickness of the interfacial region where the chains of the two polymers mix. Yet another aspect is related to the effect of interfacial interactions on the dynamic mechanical properties of the blend. Previous studies have shown that the viscoelastic properties of these blends deviate from the emulsion models that have been proposed for such blends. The deviation of the measured viscoelastic behavior of these blends compared to that predicted by the models has been attributed to the formation of network structure of particles in the blend. The formation of the network structure is a consequence of larger effective volumes of the particles due to interactions at the interface with the matrix. This study provides a means of using rheological properties and the emulsion models to estimate the extent of interaction at the modifier/matrix interface. In blends used in this study it can be shown that the interactions between the modifier and matrix extend far beyond the boundary between the two and the estimated effective volume fraction of modifier is much larger than the actual modifier content in the blend. The effective volume fraction is frequency dependent and decreases with increasing frequency. The data suggest that beyond certain frequencies the modifier no longer interacts with the matrix and the system has properties similar to the matrix with holes. The data are presented which indicate that, within the range studied, lower modifier shell molecular weight results in a higher level of interaction with polycarbonate. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1095–1105, 1998     

Adsorption mechanisms of glucose in aqueous goethite suspensions

The adsorption of glucose and polysaccharides onto solid surfaces is important in several areas of science and engineering including soil chemistry and mineral processing. In this work we have studied the adsorption of D-glucose at the water-goethite (α-FeOOH) interface as a function of pH using batch adsorption measurements and a simultaneous infrared and potentiometric technique. Molecular orbital calculations were also performed in order to support interpretations of the infrared spectroscopic data. Infrared spectroscopy has shown that glucose adsorbs at the water-goethite interface with an intact ring structure and that the β-form is favored relative to the α isomer. The collective spectroscopic and macroscopic results were fully consistent with an adsorption mechanism where glucose interacts with goethite surface sites via hydrogen bonding interactions. Specific infrared peak shifts indicated that glucose primarily acts as a hydrogen bond donor and that it interacts with acceptor sites that become increasingly more prevalent as the surface is deprotonated. These results are in general agreement with the acid/base model for mono- and polysaccharide interactions at metal oxide surfaces, but contradict the inner sphere hypothesis that was proposed based on ex situ spectroscopic measurements.     

Non-Watson-Crick base pairing in RNA. quantum chemical analysis of the cis Watson-Crick/sugar edge base pair family

Large RNA molecules exhibit an astonishing variability of base-pairing patterns, while many of the RNA base-pairing families have no counterparts in DNA. The cis Watson-Crick/sugar edge (cis WC/SE) RNA base pairing is investigated by ab initio quantum chemical calculations. A detailed structural and energetic characterization of all 13 crystallographically detected members of this family is provided by means of B3LYP/6-31G and RIMP2/aug-cc-pVDZ calculations. Further, a prediction is made for the remaining 3 cis WC/SE base pairs which are yet to be seen in the experiments. The interaction energy calculations point at the key role of the 2'-OH group in stabilizing the sugar-base contact and predict all 16 cis WC/SE base-pairing patterns to be nearly isoenergetic. The perfect correlation of the main geometrical parameters in the gas-phase optimized and X-ray structures shows that the principle of isosteric substitutions in RNA is rooted from the intrinsic structural similarity of the isolated base pairs. The present quantum chemical calculations for the first time analyze base pairs involving the ribose 2'-OH group and unambiguously correlate the structural information known from experiments with the energetics of interactions. The calculations further show that the relative importance and absolute value of the dispersion energy in the cis WC/SE base pairs are enhanced compared to the standard base pairs. This may by an important factor contributing to the strength of such interactions when RNA folds in its polar environment. The calculations further demonstrate that the Cornell et al. force field commonly used in molecular modeling and simulations provides satisfactory performance for this type of RNA interactions.     

Immersion of charged nanoparticles in a salt solution/air interface

Electrostatic interactions strongly affect the immersion depth of nanoparticles into an interface. We prove this statement by measuring the diffusion constant of charged nanoparticles at a sodium chloride solution/air interface. Interfacial diffusion of nanoparticles slows down with increasing ionic strength of the sodium chloride solution. Hydrodynamic calculations are used to estimate the immersion depth from the diffusion constant, suggesting that nanoparticles with a carboxylate surface are only slightly immersed into a bare air/water interface. With increasing molarities of sodium chloride, the immersion depth increases to complete immersion for a 10(-2) molar solution. Our experiments show that the location of nanoparticles at interfaces is determined by an intricate interplay between the electrostatic properties of the solution/air interface, the solution/solid interface, and the classical contact angle.     

Nanostructure‐Directed Physisorption vs Chemisorption at Semiconductor Interfaces: The Inverse of the HSAB Concept

A concept, complementary to that of hard and soft acid–base interactions (HSAB‐dominant chemisorption) and consistent with dominant physisorption to a semiconductor interface, is presented. We create a matrix of sensitivities and interactions with several basic gases. The concept, based on the reversible interaction of hard‐acid surfaces with soft bases, hard‐base surfaces with soft acids, or vice versa, corresponds 1) to the inverse of the HSAB concept and 2) to the selection of a combination of semiconductor interface and analyte materials, which can be used to direct a physisorbed vs chemisorbed interaction. The technology, implemented on nanopore coated porous silicon micropores, results in the coupling of acid–base chemistry with the depletion or enhancement of majority carriers in an extrinsic semiconductor. Using the inverse‐HSAB (IHSAB) concept, significant and predictable changes in interface sensitivity for a variety of gases can be implemented. Nanostructured metal oxide particle depositions provide selectivity and complement a highly efficient electrical contact to a porous silicon nanopore covered microporous interface. The application of small quantities (much less than a monolayer) of nanostructured metals, metal oxides, and catalysts which focus the physisorbtive and chemisorbtive interactions of the interface, can be made to create a range of notably higher sensitivities for reversible physisorption. This is exemplified by an approach to reversible, sensitive, and selective interface responses. Nanostructured metal oxides developed from electroless gold (Au_xO), tin (SnO₂), copper (Cu_xO), and nickel (NiO) depositions, nanoalumina, and nanotitania are used to demonstrate the IHSAB concept and provide for the detection of gases, including NH₃, PH₃, CO, NO, and H₂S, in an array‐based format to the sub‐ppm level.     

The correspondence of detachment characteristics and acid-base interaction measures

A quantitative estimate for the intensity of interphase acid-base interactions is proposed based on the acid and base parameters of the free surface energy of polymer adhesives and substrates of a different nature. An interaction between acid-base and strength characteristics of adhesive compounds is established. An increase in the adhesive strength with an increase in the difference between the surface acid and base properties of connected materials is revealed for a number of compounds (polyolefine-metal, rubber mixtures-brass, and Thiokol compounds-glass).