Anti-scratch and transparency properties of transparent conductive carbon nanotube films improved by incorporating polyethoxysiloxane

Transparent conductive films of single-walled carbon nanotubes (SWCNTs) were fabricated by a simple method to significantly enhance anti-scratch and transparency properties by the incorporation of polyethoxysiloxane (PES). The reasons for changes in the mechanical properties and transmittance were investigated through the reflection property and morphology of thin films. With the incorporation of PES, the sheet resistance of the SWCNT thin film remained unchanged after the anti-scratch test. It was found that the transmittance of the thin films suddenly increased when the thickness of the PES layer was ca 100 nm. Although the PES incorporation resulted in a slight increase in the sheet resistance, the experimental results revealed that the sheet resistance of the SWCNT thin films with PES was lower than that of films without PES for the same transmittance due to the increase of the transmittance caused by the PES incorporation. We have demonstrated that the sheet resistance was halved at a transmittance of ～86% due to PES incorporation. SWCNT thin films with PES showed better electrical properties than those without PES after a bend test.     

聚醚砜溶液流变性的研究

研究了聚醚砜（PES）/二甲基亚砜（DMSO）体系中PES的质量分数、原液温度对流变性的影响和原液中PES的质量分数对粘流活化能的影响,从而得出PES/DMSO体系属于切力变稀流体,非牛顿指数随着PES质量分数的增加而不断减小,随着溶液温度的升高而不断增大.     

Enhanced antifouling and anticoagulant properties of grafted biomolecule polyethersulfone membranes

Polyethersulfone (PES) has been widely used in membrane technology and used to purify water in water treatments application or as a dialyzer to purify blood in hemodialysis. In this work, PES was chemically modified by separately grafting two biomolecules, 4‐aminobenzenesulfonamide (ABS), and 4‐amino‐N‐(5‐methylisoxazol‐3‐yl)benzenesulfonamide (AMBS), on PES backbone, and these modified membranes were blended to unmodified PES, in 1:1 ratio, in order to obtain PES‐b‐PES‐ABS and PES‐b‐PES‐AMBS membranes. The first aim of this study is to measure the anticoagulant properties of the modified membrane by measuring the activated partial thromboplastin time (APTT) and prothrombin time (PT). The second aim of the study is to evaluate the antifouling properties of the modified PES membranes by examining its antimicrobial activity against two Gram‐negative bacteria, which are Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli (E. coli); two Gram‐positive bacteria, which are Bacillus subtilis (B. subtilis) and Staphylococcus aureus (S. aureus); and a fungus, which is Candida albicans (C. albicans). The results showed that grafting of ABS and AMBS improved overall the hydrophilicity properties of the modified PES membranes. PES‐b‐PES‐ABS membranes showed better anticoagulant properties with 13 seconds for PT and 38 seconds for APPT, in comparison with the control sample (pure plasma), which showed 12 seconds for PT and 30 seconds for APPT. For antimicrobial tests, both PES‐b‐PES‐ABS and PES‐b‐PES‐AMBS membranes did not show any antibacterial activity, but when zinc oxide (ZnO) nanoparticles were added to the modified PES membranes in concentrations between 3% to 5% w/w, PES‐b‐PES‐ABS‐ZnO (M‐4 and M‐5), and PES‐b‐PES‐AMBS‐ZnO (M‐8 and M‐9) nanocomposite membranes showed antibacterial activity against P. aeruginosa and S. aureus.     

Vibrational energy levels for CH4 from an ab initio potential

Many areas of astronomy and astrophysics require an accurate high temperature spectrum of methane (CH4). The goal of the present research is to determine an accurate ab initio potential energy surface (PES) for CH4. As a first step towards this goal, we have determined a PES including up to octic terms. We compare our results with experiment and to a PES based on a quartic expansion. Our octic PES gives good agreement with experiment for all levels, while the quartic PES only for the lower levels.     

Kinetics of model energy landscapes: an approach to complex systems

An idealized potential energy surface (PES), simply a PES-like network of stationary points, is demonstrated to be a useful tool to study kinetic relaxation of complex energy landscapes. Combined with a master equation, we show that if constructed with proper regularity, the kinetics of the PES is easy to predict and understand by carefully examining the eigenmodes of the master equation. By modifying the idealized PES model to make it more and more complicated, we demonstrate a systematic method to study the complex kinetics on large PES. The idealized PES model is used to explore the feasibility and the robustness of statistical sampling of large PES. We develop several sampling strategies, such as the "rough topography sampling" and the "low barrier saddle sampling" in the idealized PES model and find they are also applicable to a realistic PES of the 13-atom Morse cluster with range parameter rho= 6. To measure the robustness of the sampling methods, we compare the eigenvalue spectra, the eigenvector similarity and the relaxation times of the total energy of the full and sample PESs.     

用神经网络方法拟合的反应体系H＋CH4←→H2＋CH3的一个全域势能面

利用神经网络力法,基于47783个高精度从头算能量点构建了反应体系H＋CH4←→H2＋CH3的一个全域势能面．通过大最的准经典轨线以及量子散射计算测试了势能面的收敛性质．这个势能面对于拟合过程以及从头算点的数目都已经完全收敛,拟合误差很小县比Shepard插值的势能面计算速度更快,代表了此标志性多原子反应体系最好的势能面．     

Modification of polyethersulfone ultrafiltration membranes with phosphorylcholine copolymer can remarkably improve the antifouling and permeation properties

The synthesized phosphorylcholine copolymer composed of 2-methacryloyloxyethylphosphorylcholine (MPC) and n-butyl methacrylate (BMA), blended with polyethersulfone (PES), was used to fabricate antifouling ultrafiltration membranes. Water contact angle measurements confirmed that the hydrophilicity of the MPC-modified PES membranes was enhanced to certain extent. X-ray photoelectron spectroscopy (XPS) analysis verified the substantial enrichment of MPC at the surface of the MPC-modified PES membranes. The adsorption experiments indicated that the adsorption amounts of bovine serum albumin (BSA) on the MPC-modified PES membranes were dramatically decreased in comparison with the control PES membrane. Ultrafiltration experiments were carried out to investigate the effect of MPC modification on the antifouling and permeation properties of the PES membranes, it was found that the rejection ratio of BSA was decreased, the flux recovery ratio was remarkably increased, and the degree of irreversible fouling decreased from 0.46 to 0.09. In addition, the MPC-modified PES membranes could run several cycles without substantial flux loss.     

The preparation,compatibility and structure of PEEK–PES blends

Blends of polyetheretherketone and polyethersulfone (PEEK–PES blends) were prepared either by mechanically mixing fine PEEK and PES powders or by mixing PEEK and PES solutions in H₂SO₄ (98%). Partially compatible blends were obtained in the latter method. The sulfurization of PEEK or PES in concentrated sulphuric acid did not occur provided that the experiment was performed within 30 min. The T_g of the PEEK component increased and that of PES component decreased with the increase of PES weight fraction; the melting exothermic peak of the PEEK component did not appear in the DSC curves of the quenched blends, suggesting that PES can effectively reduce the crystallization of PEEK component. The major absorbances of the bands were characterized by IR spectroscopy; the frequency difference between PEEK or PES and their blends were observed. A linear correlation of absorbance ratios with PEEK weight fraction was found.     

Improved protein-adsorption-resistant property of PES/SPC blend membrane by adjustment of coagulation bath composition

To improve surface protein-adsorption-resistant property of polyethersulfone (PES) membranes, soybean phosphatidylcholine (SPC) was added to PES casting solution. The blend membranes were prepared by a phase inversion method in a wet process. The surface of PES/SPC blend membranes was characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). XPS data revealed that the phosphorylcholine (PC) groups were concentrated at the surface by changing the composition of coagulation bath. Addition of N,N-dimethylformamide (DMF) in coagulation bath could prolong coagulation time and facilitate the migration of SPC from polymer bulk to membrane surface. The PES/SPC blend membranes dramatically reduced BSA and fibrinogen adsorption compared to PES control membrane due to effective immobilization of PC groups at the surface of PES/SPC blend membranes.     

A new "spectroscopic" potential energy surface for formaldehyde in its ground electronic state

We report a new "spectroscopic" potential energy surface (PES) of formaldehyde (H(2)(12)C(16)O) in its ground electronic state, obtained by refining an ab initio PES in a least-squares fitting to the experimental spectroscopic data for formaldehyde currently available in the literature. The ab initio PES was computed using the CCSD(T)/aug-cc-pVQZ method at 30 840 geometries that cover the energy range up to 44 000 cm(-1) above equilibrium. Ro-vibrational energies of formaldehyde were determined variationally for this ab initio PES by means of the program TROVE [Theoretical ROtation-Vibration Energies; S. N. Yurchenko, W. Thiel, and P. Jensen, J. Mol. Spectrosc. 245, 126 (2007)]. The parameter values in the analytical representation of the PES were optimized in fittings to 319 ro-vibrational energies with J = 0, 1, 2, and 5. The initial parameter values in the fittings were those of the ab initio PES, the ro-vibrational eigenfunctions obtained from this PES served as a basis set during the fitting process, and constraints were imposed to ensure that the refined PES does not deviate unphysically from the ab initio one in regions of configuration space not sampled by the experimental data. The resulting refined PES, referred to as H(2)CO-2011, reproduces the available experimental J ≤ 5 data with a root-mean-square error of 0.04 cm(-1).     

聚乙二醇对聚醚砜微孔膜致孔作用的研究

以聚醚砜聚乙二醇溶剂为铸膜液体系、采用干湿相转化法制备微孔滤膜,研究了各种制膜条件对膜孔径结构的影响.实验发现聚乙二醇在体系中起到分散稳定的作用,只有到浓度大于70%时,才会对铸膜液的粘度产生明显影响,聚合物在铸膜液中的溶解状态也随之改变,进而影响膜的结构.不同溶剂NMP、DMF、DMAc、DMSO等极性溶剂或固体溶剂己内酰胺均可制得开孔率较高的微孔膜,但对膜的结构和性能影响差别不大.在本研究体系中,膜的结构取决于聚乙二醇、溶剂的浓度比例关系.     

Thermal and dynamic mechanical properties of PES/PPS blends

Blends of poly(ether-sulfone) (PES) and poly(phenylene sulfide) (PPS) with various compositions were prepared using an internal mixer at 290°C and 50 rpm for 10 min. The thermal and dynamic mechanical properties of PES/PPS blends have been investigated by means of DSC and DMA. The blends showed two glass transition temperatures corresponding to PPS-rich and PES-rich phases. Both of them decreased obviously for the blends with PES matrix. On the other hand, T_g of PPS and PES phase decreased a little when PPS is the continuous phase. In the blends quenched from molten state the cold crystallization temperature of PPS was detected in the blends of PES/PPS with mass ratio 50/50 and 60/40. The melting point, crystallization temperature and the crystallinity of blended PPS were nearly unaffected when the mass ratio of PES was less than 60%, however, when the amount of PES is over 60% in the blends, the crystallization of PPS chains was hindered. The thermal and the dynamic mechanical properties of the PPS/PES blends were mainly controlled by the continued phase. This revised version was published online in August 2006 with corrections to the Cover Date.     

链段刚性对非溶剂致相分离成膜过程影响的耗散粒子动力学模拟

通过分子动力学(MD)模拟映射方法构建了符合聚醚砜(PES)刚性结构的耗散粒子动力学(DPD)简谐力场, 并研究了PES链段刚性对PES/N-甲基-2-吡咯烷酮(NMP)/水体系非溶剂致相分离(NIPS)过程的影响. 结果表明, 由于非溶剂和溶剂在两相界面上发生的质量交换, 导致在相界面处PES链段发生堆积, 形成了薄而致密的聚合物表层, 在PES溶液内部, 由于非溶剂的侵入导致体系发生了旋节相分离, 从而在整体上得到了明显的非对称结构; 同时, PES链段刚性的提升能够明显加快体系的相分离速度, 导致相界面处的PES薄层形成得更加快速, 薄层更加致密、 孔径更小, 而对内部的疏松结构影响较小; 此外, 结合不同力场下聚合物浓度对相分离过程的影响可以发现, 不同PES浓度下, 链段刚性的提升对相分离过程的特征和演变趋势没有造成根本性的影响, 与经典的弹簧力场的模拟结果在整体趋势上有相似性. 研究结果表明, 简谐力场能提升PES链段的刚性, 从而能更真实地模拟实际体系的非溶剂相分离法成膜过程.     

A sensitivity analysis of a diatomics-in-molecules model of the 1A′ states of H2O

A method for computing the sensitivity of diatomics-in-molecules (DIM) potential energy surfaces (PES) to variations in the parameters characterizing the diatomic fragment matrices is applied to the ¹A′ states of H₂O. The analysis, presented explicitly for 2 × 2 and 3 × 3 fragment matrices, identifies those parameters having the largest influence on local features of the PES. Estimates of the parameter alterations necessary to effect specific changes in the PES are easily provided, allowing manipulation of the DIM model so as to obtain a good overall representation of the PES. Local regions of the PES turn out to be sensitive to only a few parameters and are largely unaffected by the rest. This supports the notion, customary in reaction dynamics, that processes may be discussed qualitatively in terms of the local properties of a PES such as the position of a barrier or the type of energy release.     

Crystal growth rates and master curves of poly(ethylene succinate) and its copolyesters using a nonisothermal method

The spherulitic growth of poly(ethylene succinate) (PES) and two PES‐rich copolyesters at constant cooling rate was monitored and recorded using a system of polarized light microscope. Individual experiment of these polyesters lasted 40, 60, and 120 min, respectively. A continuous curve of isothermal growth rates between the melting and glass transition temperatures can be obtained after curve fitting procedures. These curves fit very well with those data points determined in the isothermal experiments, which are time consuming. The continuous data of PES was analyzed with the Hoffman (Lauritzen equation. A transition of regime II → III was found at 70.7 °C, which is very close to the literature values. The maximum growth rate was formulated in the Arrhenius and WLF expressions for the molecular transport term. A master curve of crystal growth rate for PES was constructed based on the continuous data of PES. When the reduced growth rates after normalization were plotted against the reduced temperatures, a universal master curve was observed for PES and two PES‐rich copolyesters. This nonisothermal method provides an efficient and reliable way for studying the crystallization kinetics of polymer and for constructing a universal master curve of crystal growth rate of PES. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 932–939, 2010     

A global potential energy surface and time‐dependent quantum wave packet calculation of Au + H2 reaction

A global potential energy surface (PES) corresponding to the ground state of AuH₂ system has been constructed based on 22 853 ab initio energies calculated by the multireference configuration interaction method with a Davidson correction. The neural network method is used to fit the PES, and the root mean square error is only 1.87 meV. The topographical features of the novel global PES are compared with previous PES which is constructed by Zanchet et al. (Zanchet PES). The global minimum energy reaction paths on the two PESs both have a well and a barrier. Relative to the Au + H₂ reactants, the energy of well is 0.316 eV on the new PES, which is 0.421 eV deeper than Zanchet PES. The calculation of Au(²S) + H₂(X¹Σ_g⁺) → AuH(X¹Σ⁺) + H(²S) dynamical reaction is carried out on new PES, by the time‐dependent quantum wave packet method (TDWP) with second order split operator. The reaction probabilities, integral cross‐sections (ICSs) and differential cross‐sections are obtained from the dynamics calculation. The threshold in the reaction is about 1.46 eV, which is 0.07 eV smaller than Zanchet PES due to the different endothermic energies on the two PESs. At low collision energy (<2.3 eV), the total ICS is larger than the result obtained on Zanchet PES, which can be attributed to the difference of the wells and endothermic energies.     

Surface characterization and barrier properties of plasma‐modified polyethersulfone/layered silicate nanocomposites

This study describes the preparation of polyethersulfone (PES)/layered silicate nanocomposites (PLSNs) by mixing PES polymer chain into organically‐modified layered silicate in 1‐methyl‐2‐pyrrolidinone (NMP) solution. Both X‐ray diffraction data and transmission electron microscopy images of PLSNs indicate that the silicate layers were almost exfoliated and randomly distributed into the PES matrix. The mechanical and barrier properties of PLSNs show remarkable enhancement in the storage modulus and water/oxygen permeability when compared with that of neat PES matrix. Surfaces modification of PES and PLSN films with various treated times, system pressures, and radio frequency (RF) powers were performed using a mixture of oxygen (O₂) and nitrogen (N₂) plasmas. The topographical and physical properties of plasma‐modified PES and PLSN surfaces were investigated using scanning probe microscopy (SPM), contact‐angle measurements, and X‐ray photoelectron spectroscopy (XPS). These results indicate that the surface roughness of PLSNs with the same condition of plasma modification is lower than that of neat PES matrix and is probably due to the increase of stiffness with the presence of inorganic layered silicates in PES matrix. The surface properties of the PES and PLSNs are also changed from hydrophobic to hydrophilic. The XPS spectra suggest that the exposure of the PES and PLSNs to the plasmas led to the combination of etching reactions of polymer surface initiated by plasma and the following addition reactions of new oxygen‐ and nitrogen‐containing functional groups onto polymer surfaces to change their surface properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3185–3194, 2006     

聚苯硫醚及其聚醚砜共混物结晶形态的研究

本文借用偏光显微镜(PLM)、扫描电子显微镜(SEM)、小角激光光散射仪(SALS)及蚀刻的方法,研完了聚苯硫醚及其与聚醚砜共混物的结晶形态和织构,讨论了共混方法及其共混组成对其共混物的结晶形态的影响。结果表明,聚苯硫醚在应力作用下能生成横晶;溶液共混物和粉末机械共混物呈现不同的共混结晶形态;随着聚醚砜组分的增加,共混物的织构从聚苯硫醚为连续相逐渐转变为聚醚砜为连续相,同时,聚醚砜的聚集区域从分散在聚苯硫醚的球晶之间转变为聚集在聚苯硫醚的球晶内,使聚苯硫醚的球晶形态逐渐变得不规整。     

Synergistic effects of functionalized graphene and functionalized multi-walled carbon nanotubes on the electrical and mechanical properties of poly(ether sulfone) composites

Mixed fillers composed of functionalized graphene (f-G) and functionalized multi-walled carbon nanotubes (f-CNTs) (f-G-f-CNTs) were prepared and their synergistic effects in terms of enhancing the electrical conductivity and tensile modulus of poly(ether sulfone) (PES) composites were investigated. The results indicate that the electrical conductivity of the 5 wt% f-G-f-CNTs(W_f-G/W_f-CNTs = 1:1)/PES composite was 2.2 times higher than that of the 5 wt% f-G/PES composite and 8.9 times higher than that of the 5 wt% f-CNTs/PES composite. Moreover, the tensile modulus of the 5 wt% f-G-f-CNTs(W_f-G/W_f-CNTs = 1:1)/PES composite relative to that of the 5 wt% f-G/PES composite and 5 wt% f-CNTs/PES composite increased by 16.5% and 50.6%, respectively. Additionally, enhancements in the electrical conductivity and tensile modulus of the PES composite depended on the weight ratio of f-G and f-CNTs in the mixed fillers. The electrical conductivity and tensile modulus exhibited maximum values when the weight ratios of f-G and f-CNTs were 1:3 and 1:1, respectively. When the weight ratio of f-G and f-CNTs was fixed at 1:1, the f-G-f-CNTs(W_f-G/W_f-CNTs = 1:1)/PES composite showed a percolation threshold of 0.22 vol%, much lower than that of the f-G/PES composite.