Ar plasma treated and Al metallised polycarbonate: a XPS, mass spectroscopy and SFM study

Ar plasma etched and Al metallised bisphenol A carbonate was analysed by mass spectroscopy, photoelectron spectroscopy (XPS), and scanning force microscopy (SFM). We mainly used a technical polymer (Makrolon 2808, Bayer) made by injection-moulding, as well as spin coated bisphenol A carbonate (n=1) and polycarbonate (PC) (n=115). The mass spectroscopy during the etching process shows the degradation of the PC in the form of carbon monoxide, carbon dioxide and methyl groups. The photoelectron spectroscopy shows in detail the surface modification after Ar plasma treatment and metallisation. The plasma induces a reduction of the carboxylic carbon (C 1s), a strong reduction of singly bonded oxygen (O 1s) and also a slight reduction of doubly bonded oxygen. After Al metallisation, a reaction of Al with the oxygen groups and an interaction with the aromatic system is documented. Ar plasma etching increases the chemical interaction of Al mainly with the aromatic carbon. The X-ray photoelectron spectroscopy of metallised PC under different initial conditions shows a strong influence of incorporated water in the PC bulk that cannot be seen by XPS on uncoated PC. The O 1s signal increases during metallisation and results in an oxidation of Al probably caused by the fact that the hydrophobic surfaces becomes hydrophillic. Temperature-dependent XPS was done on technical PC samples and on spin coated samples (n=1, n=115) and supports the influence of the bulk state for the Al–PC interface. For n=1 carbonate, a diffusion of Al into the PC volume was observed. The SFM measurements showed a roughening effect on the nanometer scale even after short treatment times. Al can be seen as a weakly bound cluster on the virgin PC, and if a pre-etching is done, Al seems to grow as a good wetting film. The adhesion force of Al films on PC without any influence of the volume can be explained by the chemical bonding of Al to the carboxylic and aromatic systems. The adhesion can be increased by plasma pre-treatment. A breakdown of the adhesion on technical PC is probably induced by a reaction of Al with mobile intercalated gas, that is enriched near the surface after Al coating.     

聚甲基丙烯酸甲酯和聚碳酸酯各向异性光学性质理论研究

作为重要的光学薄膜材料,聚甲基丙烯酸甲酯(PMMA)和聚碳酸酯(PC)在诸多工业领域已得到广泛应用.本文利用密度泛函理论结合分子动力学方法深入系统地研究了这两种聚合物的各向异性光学性质,并对比分析了不同分子链长度和微观结构对其各向异性光学性质的影响.计算结果表明PMMA和PC都具有较高的本征双折射率,且分子链长度对本征折射率的影响显著.在可见光范围内,单体单元PMMA本征双折射率在10%以上,而三单元结构本征折射率则不到4%.对于体相结构多聚体,从立方结构拉伸到厚度仅有6?的过程中,PC不同方向折射率最大差异高达6%,而同样情况下PMMA不同方向折射率差异仅有1.3%.此项研究有助于理解PMMA和PC聚合物各向异性光学特征产生的原因和影响因素,从而进一步指导和促进其在更多领域的发展与应用.     

Influence of molecular weight and chemical structure of soft segment in reaction kinetics of polycarbonate diols with 4,4′-diphenylmethane diisocyanate

This third paper in this series regarding the mechanism and kinetics of urethane systems presents the results obtained in the study of the influence of molecular weight and chemical structure of several polycarbonate diols on the polycondensation reaction with 4,4′-diphenylmethane diisocyanate (MDI), comparing them with those obtained previously for condensation reaction with p-tolyl isocyanate (p-TI). The substitution effect induced in the second isocyanate group by the reaction of the first isocyanate group of a symmetric diisocyanate likes MDI has been studied by size exclusion chromatography (SEC) using a model monoalcohol. The condensation reaction kinetics is adequately described by an autocatalyzed third order rate equation. The values obtained for rate constants, using a Runge-Kutta mathematical model, suggest association phenomena by hydrogen bonding implying hydroxyl groups but also urethane groups. In bulk and in stoichiometric conditions, the association phenomena observed increase proportionally on one hand, to the decrease of molecular weight of macrodiol and on the other hand, to the tendency to form intramolecular hydrogen bonds. The activation energies were obtained from the evaluation of kinetic data at different temperatures in the range 45-65 °C. As association phenomena increase, activation energies decrease. The slightly higher activation energies obtained for polycondensation compared to condensation are explained because of the rapid increase of viscosity of the medium.     

Metal-free synthesis of amphiphilic functional polycarbonates

Amphiphilic block copolymers of poly(5-benzyloxy trimethylene carbonate)(PBTMC) and poly(ethylene glycol)(PEG) were synthesized through enzymatic polymerization using immobilized porcine pancreas lipase(IPPL).The obtained copolymers with different compositions were characterized by GPC and ~1H NMR.The copolymer composition was in agreement with the feed ratio. The molecular weight of the copolymers showed an increasing trend with the decrease of PEG contents.Micelles of the copolymers were formed by dialysis procedure,and characterized by transmission electron microscopy (TEM).     

X射线衍射分析的微量粉末制样法

在X射线衍射法中,一般制备粉末样品比较简单。但对微量样品,如还需经过研磨和制样等操作手续,会使样品进一步损失,这就给制样带来了困难。为了达到以最少粉末获得足够衍射强度的要求,为此,对微量粉末的制样法进行了试验,并取得了良好的效果。     

用扫描电镜研究工程塑料的断裂行为

本文研究了工程塑料——聚碳酸酯及聚对苯二甲酸丁二醇酯的微观断裂行为。研究中采用了静载和动载破断实验,用扫描电镜观察断裂形态特征,并结合宏观力学试验过程分析其断裂行为。实验结果表明,热塑性工程塑料,在加载速率及环境温度固定条件下,其微观断裂行为受材料损伤体积空间分布的影响,材料损伤体积宏观空间分布范围宽,则大分子相互协同动作强,应变均匀,微观塑性形变差别小,断口表面趋于平坦;反之,大分子相互协同动作差,应变易于集中,微观塑性形变差异大,断口表面高低起伏大。     

Fracture toughness of gamma irradiated polycarbonate sheet using the essential work of fracture

Polycarbonate (PC), a ductile polymer, has been found by both linear elastic fracture mechanics and impact tests to present a ductile-brittle transition, which depends on notched specimen thickness, test speed and gamma irradiation. Owing to large amounts of plastic deformation, fracture toughness measurements by these test methods are not precise. In the present communication, a better method, the Essential Work of Fracture (EWF), to assess the fracture characteristics in plane state of stress was for the first time used to evaluate the fracture toughness of PC sheets subjected to gamma irradiation dose. Three-points bend tests of sharp pre-cracked specimens with different ligament lengths were 340 kGy gamma irradiated. EWF results showed that the total fracture work increased linearly with length for both non-irradiated and gamma irradiated conditions. A significant decrease in EWF fracture toughness was associated with brittleness promoted by gamma irradiation. This brittleness was also confirmed by macro and microscopy (SEM) evidence.     

生物相容性聚碳酸酯聚氨酯微纤维人工血管的研究

以分子量为2000的聚碳酸酯(PCDL)、1,4-丁二醇(BD)和4,4-二环己基甲烷二异氰酸酯(H12MDI)为原料合成出了一系列聚碳酸酯聚氨酯(PCU)。通过NMR、红外(FT-IR)、拉力实验、差示扫描量热仪(DSC)表征了该聚氨酯的化学结构、机械性能和热性能。在25度时,PCU的杨氏模量随硬段含量增加而略有升高。在有酶催化和没有酶的条件下,考察了材料的降解性能,发现吸水率和重量损失分别低于4%和1%。细胞毒性和血液相容性检测表明材料是生物相容、无毒的。经过喷纺技术制备的人工血管具有微孔结构,初步进行体内植入研究,PCU血管具有超细纤维交联的结构,并提供开放孔。研究结果表明聚碳酸酯聚氨酯具有优异的物理性能、高生物稳定性和良好的生物相容性,因此聚碳酸酯聚氨酯是人工血管合适材料。     

Solid-state NMR on thermal and fire residues of bisphenol A polycarbonate/silicone acrylate rubber/bisphenol A Bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) — Part II: The influence of SiR

Solid residues of bisphenol A polycarbonate (containing 0.45 wt% poly(tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) after thermal treatment were investigated by solid-state and liquid-state NMR, focusing on the role and interaction of SiR with the other components of the polymer blend.In PC/SiR/BDP, part of the SiR reacts to an amorphous silicate network rather than being completely released in the gas phase. The silicate network consists of Q₄ and Q₃ groups formed via intermediate D and T groups. The D groups are formed by a reaction of SiR with bisphenol-A units as well as phenyl groups of PC and BDP. In addition a small amount of silicon diphosphate was observed after thermal treatment at temperatures higher than 810 K. The same decomposition products (without SiP₂O₇) occur in the solid residues of PC/SiR/BDP/ZnB samples. The formation of intermediate D and T groups occurs earlier, at slightly lower temperatures. Any formation of a borosilicate network was excluded.The results also apply for the fire residues of PC/SiR/BDP and PC/SiR/BDP/ZnB and are thus valuable for understanding the impact of SiR on pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of PC/SiR/BDP blends. SiR was found to influence the pyrolysis and the char formed. Beyond the replacement of highly combustible mechanical modifiers, SiR harbours the potential to enhance flame retardancy.     

Mechanical and thermal properties and flame retardancy of phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS)/polycarbonate composites

A novel polyhedral oligomeric silsesquioxane containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-POSS) has been incorporated into polycarbonate (PC) composites in order to study its effect on mechanical and thermal properties and flame retardancy. The mechanical and thermal properties of the DOPO-POSS/PC composites have been investigated by tensile and flexural testing, DSC, and DMA. Slight enhancements of yield stress, and flexural strength and modulus, and obvious decreases of fracture strength and strain of the DOPO-POSS/PC composites were observed with an increase in DOPO-POSS loading. The glass transition temperatures (T_g) of the composites were reduced with increasing DOPO-POSS loading. The morphology of the PC composites was evaluated by SEM, which indicated that the DOPO-POSS was dispersed with a particle size of 100-250 nm in the PC matrix. The thermal degradation behaviour and flame retardancies of PC composites with different DOPO-POSS loadings were investigated by TGA, LOI, UL-94 standard, and cone calorimetry. The composite had an LOI value of 30.5 and a UL-94 rating V-0 when the content of DOPO-POSS was 4%.