Flame retardant high density polyethylene optimized by on-line ultrasound extrusion

The effect of on-line ultrasound application by a special static mixer die which promotes extensional flow simultaneously during the single screw extrusion process was thoroughly studied. The proportion of aluminum trihydroxide (ATH) used as flame retardant on high density polyethylene (HDPE) was optimized. The morphological, thermal, flammability, combustion, mechanical and rheological properties of the materials were investigated. The morphological study pointed out that this process is able to strongly reduce the size of ATH particles and improve their dispersion and distribution within the polymer matrix. The addition of zinc borate (ZB) at low concentration (namely 3 phr) showed its well-known synergistic effect in the thermal, oxygen index and fire combustion behavior. According to the UL94 standard, the rating for all materials tested changed from HB to V2, with respect to materials prepared without ultrasound; furthermore a rating V0 was achieved only with the addition of 2 phr organo-clay. Rheological results under simple and small amplitude oscillatory shear flow confirmed the enhanced particle dispersion and finer particle morphology evidenced by larger values of the moduli and by deviations from the semicircular shape observed in the Cole–Cole diagram. Mechanical properties such as Izod impact resistance, tensile strength, strain at break and tenacity were also improved by the on-line ultrasound process. In this work, the appropriate on-line ultrasound extrusion conditions to use the lowest ATH content (30 phr or 21.5 in wt%) were found, rendering HDPE optimized flame retardant materials with improved processability and mechanical properties.     

Nuclear quantum effect and temperature dependency on the hydrogen‐bonded structure of base pairs

The structure of Watson–Crick‐type adenine‐thymine and guanine‐cytosine pairs has been studied by hybrid Monte Carlo (HMC) and path integral hybrid Monte Carlo (PIHMC) simulations with the use of semiempirical PM6‐DH+ method in the gas phase. We elucidated the nuclear quantum effect and temperature dependency on the hydrogen‐bonded moiety of base pairs. It was shown that the contribution of nuclear quantum effect on the hydrogen‐bonded structure is significant not only at low temperature 150 K but also at temperature as high as 450 K. The relative position of hydrogen‐bonded proton between two heavy atoms and the nuclear quantum nature of the proton are also shown. Furthermore, we have applied principal component analysis to HMC and PIHMC simulations to analyze the nuclear quantum effect on intermolecular motions. We found that the ratio of Buckle mode (lowest vibrational mode from normal mode analysis) decreases due to the nuclear quantum effect, whereas that of Propeller mode (second lowest vibrational mode) increases. In addition, nonplanar structures of base pairs were found to become stable due to the nuclear quantum effect from two‐dimensional free energy landscape along Buckle and Propeller modes. © 2013 Wiley Periodicals, Inc.     

Explanation of Theoretical Mechanism of Isomerization of L-Alanine Conformation for Experimental Results

B3LYP/6-31＋＋G＊＊ method was applied to investigate the mechanism of alanine isomerization.12 minima and 22 transition states were obtained after optimization and several paths of isomerization were found.It is found that intramolecular single-bond rotation and proton transfer might lead to isomerization.The energy barrier of C–N bond rotation was lower than 2.52 kcal·mol 1,while the energy barrier ranges of the rotation of C–C and C–O were separately 0.43~ 7.01 and 4.69~12.19 kcal·mol 1,and the minimum energy barrier of proton transfer was 30.76 kcal·mol 1.The most probable isomerization path and mechanism for the two most stable conformations was discussed to find that the highest energy barrier to be crossed in this path was 11.87 kcal·mol 1.In order to understand the microscopic nature why only 4 conformations were detected in the experiment,thermodynamic properties of all conformations at the experimental temperature of 391 K was calculated.It is found that conformations XII,XI,X and IX can only unidirectionally convert into conformations rapidly with low energy and vanish immediately.The other conformations were distributed according to Maxwell-Boltzman＇s law,and the distribution probabilities of conformations I,II,III,IV,V,VI,VII and VIII were respectively 27.2%,26.5%,25.8%,6.4%,5.2%,4.8%,2.5% and 1.6%.Conformations I,II and III with bigger probability and stronger absorption peak were easy to detect in the experiment.Conformation IV had a relatively smaller probability（6.4%） and weak absorption peak which,however,could also be identified.The other conformations had too small probability to identify in the spectrum.     

室内环境中脑控轮椅的路径跟踪控制

为了实现室内环境中脑控轮椅的自主导航,提出了一种简单有效的路径跟踪控制方法。给定的路径通常被表示为一系列离散点,根据这一特点,提出了分段直线路径跟踪方法,即依次跟踪由前后两个路径点构成的直线路径到达目标点。基于预瞄点技术并结合模糊算法和传统的PID控制方法设计控制器,完成各分段直线路径的跟踪,并给出了有效的切换条件。实验结果表明,本文提出的路径跟踪控制方法能够使脑控轮椅在室内环境中精确地跟踪给定路径。     

采用反应挤出三次加料法合成苯乙烯/异戊二烯/苯乙烯

以同向啮合双螺杆挤出机为反应器,采用苯乙烯和异戊二烯为聚合单体,以正丁基锂为引发剂,采用三次加料法合成苯乙烯/异戊二烯/苯乙烯(SIS)三嵌段热塑性弹性体.氢核磁共振(1H NMR)谱分析结果表明,共聚物中聚异戊二烯嵌段以1,4-结构为主.采用四氧化锇催化双氧水氧化降解聚合物分子链,利用凝胶渗透色谱对氧化降解后的聚苯乙烯碎片进行分析,证明共聚物分子为(聚苯乙烯-聚异戊二烯-聚苯乙烯)(PS-PI-PS)三嵌段结构.动态力学分析(DMA)及透射电子显微镜(TEM)分析结果表明,SIS具有两相分离结构.拉伸试验结果表明,共聚物拉伸强度与苯乙烯含量有关.     

计算化学在正丁醚制备实验教学中的应用*

正丁醚的制备是重要的大学有机化学实验,为提高学生对该实验所涉及的反应机理和关键操作要点的深入了解,采用Gaussian计算软件对正丁醇在酸催化下和无催化剂下的反应体系进行了研究,重点考察了酸催化下反应的主、副反应方向的反应机理。结果表明无催化剂下,正丁醇在常压液相下几乎不能发生反应;在酸催化下,正丁醇发生取代反应生成醚的反应路径是优势反应通道;酸催化下正丁醇的取代和消除反应速率常数均随温度增加而迅速增大,但消除反应的反应速率随温度增加更快,温度超过420 K消除反应将变得很明显,综合考虑,制备正丁醚的反应温度应控制在130~140 ℃之间较为合适。利用计算化学以图、表和动图等形式直观、动态、量化地解释了正丁醇成醚和成烯反应的竞争,该结果有助于更好地控制该反应体系,可用作实验教材的补充内容。     

Optical constants of organic insulators in the UV range extracted from reflection electron energy loss spectra

Reflection electron energy loss spectroscopy (REELS) spectra were measured for seven insulating organic compounds (DNA, Irganox 1010, Kapton, polyethylene [PE], poly(methyl methacrylate) [PMMA], polystyrene [PS] and polytetrafluoroethylene [PTFE]). Optical constants and energy band gaps were extracted from the measured REELS spectra after elimination of multiple electron scattering via a deconvolution and fitting the normalised single scattering energy loss spectra to Drude and Drude–Lindhard model dielectric functions, constrained by the Kramers–Kronig sum and f-sum rules. Satisfactory agreement is found for those optical constants for which literature data exists. For PTFE, the observed features in the optical data correspond to its electronic structure.     

浅析高分子树脂无溶剂生产技术中的高分子凝聚态相关化学问题

在没有溶剂介质参与的高分子聚合反应中,高分子凝聚态的变化与化学反应之间的作用关系变得更加直接。以熔融聚合、反应挤出、固相聚合为代表的高分子树脂无溶剂生产技术是集高分子树脂合成、材料加工制备及工程一体化的新兴科学与技术,是当代材料科学领域发展的前沿领域,代表着高分子树脂生产技术发展的必然趋势。本文将上述这三种典型的树脂工业合成技术及相应机理进行了简要的介绍,并分别以聚对苯二甲酸乙二醇酯(PET)和聚乳酸(PLA)的实际生产研究情况为例,展示三种生产技术之间的相互联系,揭示这三种无溶剂型高分子制备技术过程中出现的高分子凝聚态变化与化学反应之间的基本问题,为广大科研工作提供一些有价值的参考。     

Adding Value in Production of Multifunctional Polylactide (PLA)–ZnO Nanocomposite Films through Alternative Manufacturing Methods

Due to the added value conferred by zinc oxide (ZnO) nanofiller, e.g., UV protection, antibacterial action, gas-barrier properties, poly(lactic acid) (PLA)–ZnO nanocomposites show increased interest for utilization as films, textile fibers, and injection molding items. The study highlights the beneficial effects of premixing ZnO in PLA under given conditions and its use as masterbatch (MB), a very promising alternative manufacturing technique. This approach allows reducing the residence time at high processing temperature of the thermo-sensitive PLA matrix in contact of ZnO nanoparticles known for their aptitude to promote degradation effects onto the polyester chains. Various PLA–ZnO MBs containing high contents of silane-treated ZnO nanoparticles (up to 40 wt.% nanofiller specifically treated with triethoxycaprylylsilane) were produced by melt-compounding using twin-screw extruders. Subsequently, the selected MBs were melt blended with pristine PLA to produce nanocomposite films containing 1–3 wt.% ZnO. By comparison to the more traditional multi-step process, the MB approach allowed the production of nanocomposites (films) having improved processing and enhanced properties: PLA chains displaying higher molecular weights, improved thermal stability, fine nanofiller distribution, and thermo-mechanical characteristic features, while the UV protection was confirmed by UV-vis spectroscopy measurements. The MB alternative is viewed as a promising flexible technique able to open new perspectives to produce more competitive multifunctional PLA–ZnO nanocomposites.