Synthesis and characterization of a series of star-branched poly(ε-caprolactone)s with the variation in arm numbers and lengths

A series of star-branched poly(ε-caprolactone)s (SPCLs) was synthesized with structural variation of the arm numbers and lengths through ring-opening polymerization under bulk condition. Arm numbers were varied to be 3, 4, and 6 by using multifunctional initiating cores such as trimethylol propane, pentaerythritol, and dipentaerythritol, respectively. The lengths of the poly(ε-caprolactone) arms were varied by controlling the molar ratio of monomer-to-initiating hydroxyl group molar ratio ([CL]₀/[-OH]₀=5, 10, 15). Molecular weights were determined by both ¹H NMR end-group analysis and MALDI-TOF mass spectrometry, which gave reasonably consistent values. On the contrary, the GPC method failed to give accurate values of molecular weight of SPCLs due to the discrepancy with the linear standard. The branching architecture of SPCLs was evaluated by the branching ratio, g, which is the ratio of the mean-square radius of SPCL to that of liner counterpart, linear poly(ε-caprolactone) (LPCL), which is of the same chemistry and having the same molecular weight. The radii of gyration of SPCLs and LPCLs were determined using small-angle X-ray scattering (SAXS) from the initial slopes of Zimm plots, represented as 1/I(q) vs q² with I(q) and q being the scattered intensity and scattering vector, respectively. The g values were observed to decrease with increasing arm numbers, indicating more compact molecular structure for SPCLs with higher arm numbers, while no such effect was observed for arm length variation. Thermal properties as well as the degree of crystallinity of SPCLs were found to be also dependent on structural variations. The melting points and the degradation temperatures were observed to increase with increasing arm lengths but with constant arm number. On the other hand, arm number variation with constant arm length gave no such changes to the thermal transitions of SPCLs. However, for the SPCLs with equivalent molecular weights, the degree of crystallinity was found to decrease with increasing arm numbers.     

Potential tissue implants from the networks based on 1,5-dioxepan-2-one and ε-caprolactone

The synthesis and characterization of degradable polymeric networks for biomedical applications was performed. Cross-linked films of poly(ε-caprolactone) (PCL) and poly(1,5-dioxepan-2-one) (PDXO) having various mole fractions of monomers and different cross-link densities were successfully prepared using 2,2′-bis-(ε-caprolactone-4-yl) propane (BCP) as cross-linking agent. Reaction parameters were carefully examined to optimise the film-forming conditions. Networks obtained were elastomeric materials, easy to cast and remove from the mould. Effect of CL content and cross-link density on the final properties of the polymer network was evaluated. High CL content or degree of cross-linking led to increase in Young's modulus and decrease in elongation at break. An increase in crystalline domains in films having a higher CL content was observed by optical microscopy. A greater thermal stability was observed in films having a high CL content. The hydrophilicity of the materials could be tailored by changing the CL content. The surface of the films became rougher with higher CL content.     

Corrosion Behavior of 316LN and 316 Stainless Steels During Long-term Exposure to Aerated 0.5 M NaCl Using Electrochemical Noise Technique

In the present work 316LN as well as 316 stainless steel (SS) coupons each of dimensions (0.025 × 0.018 × 0.006 m³) in well-polished condition were used as two nominal electrodes which were immersed in the aerated solution of 0.5 M NaCl. Correlated current and potential electrochemical noise (EN) signals were collected at 1 Hz sampling frequency for 1 h daily over a period of 30 days. The detrended EN data were used to calculate the noise resistance (R _N) as well as the spectral noise resistance at zero frequency (R _SN^o) values and other statistical parameters. To study the nature of pits and distribution of their diameters as well as depths, extensive observations of the pitted and the blank specimens were carried out using Confocal Laser Scanning Microscopy (CLSM). The current and the potential records of the two alloys showed distinct differences in their corrosion behavior. It was observed that within less than 4 h of immersion, 316SS showed signals indicative of unstable pitting and onset of stable pitting was noticed after 48 h of exposure. However, until about 24 h, 316LN showed just the random signals and unstable pitting was observed after 28 h. The signals clearly indicated continuous growth of the stable pits in 316SS as against the repassivation of the unstable pits in 316LN after 7 days exposure. It was observed that R _N values showed a continuous decrease in the case of 316SS, but were quite stable in the case of 316LN over the exposure period. Concurrent to these observations it was observed that 316SS specimen was extensively pitted. The frequency distributions of pit diameters as well pit depths were observed to be highest at 10-20 μm and 5-10 μm, respectively. However, pits with as large as 70-80 μm diameter and as deep as 20-25 μm too were observed. No pits were observed in case of 316LN even after 30 days of exposure, an observation that corroborates well with the stable R _N values. Thus, in the present investigation, the long-term tests using EN technique coupled with CLSM studies conclusively prove that many unstable pits initiated in 316SS turn into stable ones resulting in insidious localized corrosion attack whereas the unstable pits initiated in 316LN get passivated in the simulated coastal environment.     

Crystallization and thermoelectric behavior of conductive-filler-filled poly(ε-caprolactone)/poly(vinyl butyral)/montmorillonite nanocomposites

Crystallization and thermoelectric properties of poly(ε-caprolactone) (PCL)/poly(vinyl butyral) (PVB)/montmorillonite (MMT) nanocomposites containing carbon black (CB) have been studied as a functions of a small amount of amorphous PVB content and a wide range of molecular weight of PVB. X-ray diffraction data of PCL/PVB/MMT nanocomposites indicates most of the swellable silicate layers are exfoliated and randomly dispersed into PCL/PVB system. The band spacings of PCL spherulites in PCL/PVB/MMT nanocomposites decrease with increasing PVB content, and this indicates that increasing the PVB content greatly shortens the period of lamellar twisting. The presence of 1 wt% MMT and higher molecular weight of PVB also shorten the period of PCL lamellar twisting. Nucleation and crystallization parameters, such as growth rate G and Avrami exponent n, can be determined by using POM and DSC isothermally crystallized at 41 °C. For samples with the same CB content, the intensity of positive temperature coefficient (PTC) (I_PTC, defined as the ratio of peak resistivity to resistivity at room temperature) of the nanocomposites was increased as the content and the molecular weight of PVB increases. The change of the PTC property related to the morphological difference (i.e. period of lamellar twisting) in the nanocomposites can be discussed.     

A Facile Approach toward Thermoplastic Triple-Shape Memory Polymers

In this work, a ternary blend of polyolefin elastomer (POE), lauric acid (LA), and poly(ε-caprolactone) (PCL) with triple-shape memory effect (triple-SME) is reported. LA and PCL exhibit distinct thermal transitions and construct two reversible switching networks capable of fixing and releasing different temporary shapes under a mild condition. The ternary blend shows excellent triple-shape memory properties and good toughness. Besides, the permanent shape can be reconfigured by a simple thermal treatment. These particular features make the novel blend a competitive candidate for diverse applications. And the creative combination of crystalline small molecule and semicrystalline polymer expands the freedom for producing triple-shape memory polymers (triple-SMPs).     

Crystallization behavior of polymer/montmorillonite nanocomposites. Part II. Intercalated poly(ε-caprolactone)/montmorillonite nanocomposites

The combination of surfactant modified montmorillonite (MMT) silicate layers, poly(ε-caprolactone) (PCL) and the adopted melt processing procedure results in intercalated nanocomposites in which the silicate layers act as nucleating agents for the crystallization of the PCL matrix and by which in turn the overall crystallization rate increases. At a sufficiently high MMT concentration and degree of supercooling the polymer-swollen silicate layer stacks disturb crystal growth, resulting in a decrease in the overall crystallization rate. Simultaneous, time resolved, synchrotron small and wide angle X-ray scattering experiments reveal that—when the retarding effect is absent at a sufficiently high temperature—the final semicrystalline structures of pure PCL and its nanocomposites are identical. The poorer nucleation in the case of pure PCL, however, results in a time wise smearing of primary and secondary crystallization whereas in the nanocomposites these events are well separated due to a nucleation induced, efficient and rapid primary crystallization. Secondary crystallization involves the insertion of new lamellar crystals in between the already existing ones.     

THREE-DIMENSIONAL NUMERICAL SIMULATION OF AERATED FLOWS DOWNSTREAM SUDDEN FALL AERATOR EXPANSION-IN A TUNNEL

Air entrainment is known to be one of efficient and inexpensive methods to prevent cavitation damages in hydropower projects.The shape of sudden expansion-fall is used as a common device for mitigating cavitation erosions.The complex flow patterns with cavitation are numerically simulated by using the realizable k-εturbulence model and the air-water mixture model.The calculated results are compared well with the experimental results as well as those obtained with the k-εturbulence model with the Volume Of Fluid(VOF)Model.The calculated results agree well with the experimental data for the aeration cavity and wall pressure.Moreover,the air concentration near sidewall is simulated by a mixture model.It is found that the mixture turbulence model is superior to the VOF turbulence model.     

Composites of Nano-hydroxyapatite and Poly（ε-caprolactone） Composite Fibers by Electrospinning

用水热法合成的棒状纳米羟基磷灰石（nHA）,引发ε-己内酯（ε-CL）开环聚合得到nHA-PCL复合材料。用静电纺丝法分别制备了聚己内酯（PCL）、nHA/PCL共混材料和nHA-PCL复合材料的3种电纺纤维膜。通过FT-IR、DSC、SEM、TGA和拉伸试验机表征了样品的结构、热性能和力学性能。结果表明：nHA-PCL电纺膜的结晶性能优于nHA/PCL材料,且热稳定性和力学性能都优于其他两种膜,nHA-PCL电纺膜的完全分解温度为420°C,拉伸强度和断裂伸长率分别达到28.2MPa和55.6%。3种膜的纤维直径均小于500 nm,nHA-PCL电纺膜的纤维表面比较粗糙。在人体仿生液中诱导矿化4 d后,nHA-PCL电纺膜纤维表面出现磷灰石沉积,而纯PCL和共混nHA/PCL电纺膜的纤维表面沉积的磷灰石很少,nHA-PCL复合电纺膜具有较好的诱导成骨性能。     

Approximate optimal control with εerror bound

近似动态规划方法求解非线性系统最优控制,需要迭代无限步才能得到最优控制律．本文提出了一种ε-近似最优控制算法,选择ε误差限,通过自适应迭代不断逼近哈密顿-雅可比-贝尔曼（HJB）方程的解,应用神经网络实现在有限步迭代后得到带ε误差限的近似最优控制律．计算机仿真结果表明了该算法的有效性．