Comparative characterization of oligomeric precursors intended for injectable implants

The use of injectable materials is a simple approach for drug delivery and tissue repair, in, e.g. minimally invasive surgery applications. If these materials are used past their glass transition temperature and have a low viscosity, they will be able to flow while delivered in situ. Whether these materials are to be used as low viscosity drug carriers or further crosslinked for tissue repair, there is a need for a better understanding of their handling properties. In this study, oligo(trimethylene carbonate) (oTMC) and oligo[D,L‐lactide‐co‐(ε‐caprolactone)] (oDLLA‐co‐CL) of various molecular weights within a relevant injectability range were synthesized via ring‐opening polymerization. The materials were comparatively characterized by ¹H NMR spectroscopy, differential scanning calorimetry, gel permeation chromatography, and rheological measurements. After comparing the viscosities and molecular weights of the materials, it was concluded that oDLLA‐co‐CLs were, generally, better suited as an injectable in situ crosslinking network, whereas oTMCs were found to be better candidates as injectable drug carriers. This study provides useful data and guidelines on the use of these and other similar oligomers intended for injectable implants. Copyright © 2012 John Wiley & Sons, Ltd.     

Nanosurface Mechanical Properties of Polymers Based on Continuous Stiffness Indentation

A systematic experimental study of the large strain surface mechanical properties of a number of polymers {polymethylmethacrylate (PMMA), polyetheretherketone (PEEK), polystyrene (PS), polycarbonate (PC), polypropylene (PP), and ultra-high molecular weight polyethylene (UHMWPE)} at the nanometer scale is described. The polymeric surfaces were indented and the data were analyzed using a contact compliance method in conjunction with a nano-indenter system. The indentation experiments were performed using a Berkovich Tip indenter with a continuous contact compliance indentation mode. The indentations were performed using a constant loading rate (300 μN/sec) to a maximum penetration depth of 5 μm. The experimental results showed a considerable strain-rate hardening effect for the polymers and a peculiarly harder response of these surfaces at the near-to-surface (submicron) layers. PMMA was the hardest polymer of the selection, whereas UHMWPE and PP were observed to be the softest polymers. The paper includes practical consideration of a creeping effect and appropriateness of tip calibration using harder surfaces for nanoindentation experimentation of polymers.     

Gold polycarbonate microchannels for electrochemical applications

In this paper, we present gold-plating polycarbonate (PC) microchannels. The fabrication of the gold microfluidic channels is achieved by tuning the sequence of reagent insertion into milled and closed submillimeter PC system channels. The resulting gold surface can be utilized in many applications where the benefits of microfluidics, (bio)chemistry of surfaces, and electrochemistry can be combined. Here, we combine the advantages of electrochemistry with microfluidics by mixing the gold sensor with microfluidics. This approach differs from the classic one – the sensor will undergo modifications (e. g., shape and size) depending on the specific scientific problem and will be designed individually; hence its characteristics will be changed. Our goal in this work is to indicate new possibilities for combining two methodologies – electrochemistry and microfluidics. In our work, we emphasize that it confirms the validity of our chosen concept (proof-of-concept). In this work, we present one such application, the use of a gold microfluidic channel as a working electrode (WE). We describe the microchip‘s construction and electrochemical characterization, including the gold flow-through WE, the Ag/AgCl wire pseudo-reference, and the Pt auxiliary electrode. The measured current is the result of the flow through a rectangular duct of the gold microchannel electrode embedded in the four walls of the chip.     

Effect of novel compatibilizers on the properties and morphology of PP/PC blends

A series of compatibilizers, including polypropylene (PP) grafted with 2‐tertbutyl‐6‐(3‐tertbutyl‐ 2‐hydroxy‐5‐methylbenzyl)‐4‐methylphenyl acrylic ester (BPA), glycidyl methacrylate (GMA), GMA/styrene (GMA‐st), and 2‐allyl bisphenol A (2A) were investigated for the purpose of improving the compatibility of PP/polycarbonate (PC) blends. PP‐g‐BPA shows a remarkable compatibilizing effect on PP/PC blends since it has similar group‐benzene ring with PC, and it is a sort of heat‐resistant antioxidant in the meantime, which can reduce the molecular degradation of PP during grafting and blending under high temperatures. Its compatibilizing effect was examined in terms of the mechanical, thermal properties, and morphologies. PP/PC blends show a decreasing and much more homogeneous size of dispersed PC particles through addition of a small amount of PP‐g‐BPA, and dynamic mechanical analysis (DMA) reveals a noticeable approach of T_g between PP and PC, indicating the improvement of the compatibility of PP/PC blends. Furthermore, styrene‐ethylene‐butylene‐styrene (SEBS) as a toughening rubber and a compatibilizer was applied to PP/PC blends. Around 25 wt% SEBS and 20 wt% PC lead to high toughness and strength of PP. Copyright © 2008 John Wiley & Sons, Ltd.     

Fire protection of polypropylene and polycarbonate by intumescent coatings

An innovative way to improve fire‐retardant properties of different polymers by applying intumescent coatings on their surface has been studied. Two polymers have been investigated: polypropylene and polycarbonate. The surfaces were first subjected to a flaming treatment in order to clean them and to increase their wettability and thus improve the adhesion of the coatings. Two different formulations were then applied: a transparent intumescent varnish, based on an acrylic resin, and an intumescent coating based on polyvinylacetate resin. Different parameters have been obtained using several fire tests. The cone calorimeter, the limiting oxygen index and UL94 tests have been carried out to evaluate the fire‐retardant properties obtained for both the intumescent coating and the intumescent varnish. Results clearly evidence an outstanding improvement of the fire‐retardant properties using intumescent coatings without any incorporation of flame retardants in the bulk. Copyright © 2010 John Wiley & Sons, Ltd.     

不同链结构的双酚A聚碳酸酯对脂肪族聚碳酸酯结晶行为的影响

脂肪族聚碳酸酯(APC)是一类可降解的高分子材料,因其生产工艺可固定温室气体的主要成分二氧化碳,这种可降解塑料得到了越来越多的关注.作为半结晶高分子材料,脂肪族聚碳酸酯的结晶性能和结晶结构对成型加工、力学性能和降解性能具有重要的影响.借助热分析(示差扫描量热仪DSC)和形态学观察(偏光显微镜POM)两种方法研究了不同链结构的双酚A型聚碳酸酯对半结晶脂肪族聚碳酸酯——聚碳酸1,4-丁二醇酯结晶动力学行为的影响.实验发现质量分数1%的双酚A聚碳酸酯的加入促进了聚碳酸1,4-丁二醇酯的成核,但不同链结构的双酚A聚碳酸酯对其晶体生长具有相反的作用,线形双酚A聚碳酸酯(PC-L)能够促进晶体生长,而支化双酚A聚碳酸酯(PC-B)则抑制晶体生长.用原子力显微镜在轻敲模式下研究了两种双酚A聚碳酸酯与APC共混物熔融状态下的相结构,发现熔体结构的不同是导致两种共混物与纯的APC相比,结晶速率呈现相反变化趋势的主要原因.     

食品级聚碳酸酯的热释放成分和热分解机理研究

利用程序控温式热裂解-气相色谱/质谱联用技术研究了4种聚碳酸酯(PC)样品在加热情况下的释放物化学成分.分别考察了4个解吸温度和5个裂解温度下PC的降解产物.结果发现在200℃时PC粒料中就有小分子化学物质释放出来,随温度升高,释放和分解出的小分子化学成分的种类和数量都愈加增多,主要成分为酚端基化合物;由不同聚合工艺合成的聚碳酸酯中释放的化学成分有很大的差别.同时通过分析PC的裂解产物成分,阐述了其热分解机理.升温过程中PC分子链发生断裂和重排生成多种以酚类为主的小分子化合物.     

硬脂酸改性纳米羟基磷灰石表面性能的研究

采用硬脂酸(C₁₇H₃₅COOH)对纳米羟基磷灰石(n-HA)表面进行处理,并研究了n-HA与C₁₇H₃₅COOH的界面作用。透射电子显微镜(TEM)、傅立叶红外光谱(FTIR)以及X光电子能谱(XPS)分析表明,C₁₇H₃₅COOH在n-HA表面黏附,其中羧酸根离子(-COO^-)与钙离子(Ca^2＋)之间形成了稳定的离子键,以羧酸钙形式存在。C₁₇H₃₅COOH改性后的n-HA与聚碳酸酯(PC)复合后,复合材料的力学性能与未改性n-HA相比有明显提高。扫描电子显微镜(SEM)结果显示,经处理后的HA微粒在PC中分散均匀,两者间结合紧密,无明显界面,复合材料的断裂呈明显的韧性断裂,随着n-HA无机粒子含量增加,复合材料的断裂也逐渐向韧性与脆性断裂共存转变。     

Rheology of polycarbonate reinforcedwith functionalized and unfunctionalized single-walled carbon nanotubes

Nanocomposites of polycarbonate (PC) containing low concentrations of pristine and COOH and OH functionalized single-walled carbon nanotubes (SWNTs, COOH-SWNTs and OH-SWNTs) were prepared by melt-mixing and analyzed using rheology and scanning electron microscopy (SEM). The steady state and linear viscoelastic behavior of each nanocomposite material is presented and compared to that of the neat PC. SEM analysis revealed that samples containing functionalized SWNTs were more dispersible than samples containing the pristine SWNTs.     

新型含磷双酚A型共聚碳酸酯的合成与表征

新型含磷双酚A型共聚碳酸酯的合成与表征;聚碳酸酯;三光气;合成;阻燃