离子束辅助沉积氧化钛对改善热解碳抗凝血性能作用的初步研究

用离子束辅助沉积的方法在人工心脏瓣膜热解碳材料表面制备氧化钛薄膜，研究其对抗凝血性能的改善情况，以探索新型的人工瓣膜材料．对样本分别进行体外血小板黏附试验和动物体内试验以观察血栓形成的情况．结果表明，相比较传统的热解碳材料而言，氧化钛薄膜处理过的材料上黏附的血小板数目和聚集的血小板团数均明显减少，且血小板伪足数目亦明显减少．动物体内试验亦表明有氧化钛薄膜的样本表面形成的血栓较传统的热解碳材料要少，且没有热解碳材料表面有大量的血小板聚集和纤维蛋白形成．研究结果显示用离子束辅助沉积技术制备的氧化钛薄膜，其抗凝血性能优于目前临床应用的热解碳材料，很可能成为新一代的人工瓣膜材料。     

三种生物碳素材料表面的血小板粘附研究

介绍了生物碳素材料的血液相容性的研究概况 ,研究了血小板在石墨、金刚石膜和类金刚石膜材料表面的粘附行为 ,结果表明 ,血小板粘附后的形态指数大小为 :石墨 >金刚石膜 >类金刚石膜。从一定角度定性地得出 :类金刚石膜的血液相容性优于金刚石膜 ,金刚石膜的血液相容性优于石墨     

稀土铈掺杂的非晶碳薄膜的微结构及其抗凝血性能的影响

采用射频磁控溅射方法制备了稀土元素铈掺杂的非晶碳薄膜．通过改变稀土铈的掺杂量，利用拉曼光谱，紫外可见光谱等方法，研究了稀土元素铈掺杂的非晶碳薄膜的微结构、成分、形貌及亲水性的影响。结果表明：在非晶碳薄膜中掺入稀土元素铈后，薄膜中sp^3／sp^2的比率显著发生变化，薄膜的疏水性明显提高。血小板粘附实验表明掺杂稀土铈有利于改变非晶碳薄膜的抗凝血性能，适当的掺杂量能使薄膜的血液相容性得到优化。分析了稀土元素铈对材料的血容性能的影响机制．     

新型液晶对其与聚硅氧烷复合膜抗凝血性能的影响

本研究合成出三种胆甾型液晶化合物,并用IR和DSC进行了表征.将三种液晶化合物与聚硅氧烷制成复合膜,测定其抗凝血性能,结果表明,亲水性愈高的复合膜血液相容性愈好.     

生物驻极体材料

驻极习性是天然生物材料的基本属性,驻极态存在于生物体生命的整个过程中,人工合成生物驻极体材料已逐渐步入医学临床应用阶段,造福于人类。     

316L不锈钢表面聚氨酯多孔涂层的制备及其生物性能研究

利用湿法相转化原理在316L不锈钢表面制备聚氨酯涂层时，空气湿度和溶液浓度是影响涂层形貌的两个主要因素．涂层表面形貌的观察结果表明：空气湿度增大或者溶液浓度减少，都有增大涂层表面孔径的趋势，而且可以加深孔的深度．通过控制空气湿度和溶液浓度，孔径可以在几个微米到30多个微米的范围内变化．通过亲疏水性测量、血小板粘附试验和动态凝血试验考察了涂层的血液相容性．以316L不锈钢作为参照组进行对比分析，结果可知：PU多孔涂层表面为超疏水性，明显降低了血小板在材料表面的粘附，延长了动态凝血时间，表现出良好的血液相容性．     

316L不锈钢表面聚氨酯多孔涂层的制备及其生物性能的研究

利用湿法相转化原理在316L不锈钢表面制备聚氨酯涂层时，空气湿度和溶液浓度是影响涂层形貌的两个主要因素。涂层表面形貌的观察结果表明：空气湿度增大或者溶液浓度减少，都有增大涂层表面孔径的趋势，而且可以加深孔的深度。通过控制空气湿度和溶液浓度，孔径可以在几个微米到三十多个微米的范围内变化。通过亲疏水性测量、血小板粘附试验和动态凝血试验考察了涂层的血液相容性。以516L不锈钢作为参照组进行对比分析，结果可知：PU多孔涂层表面为超疏水性，明显降低了血小板在材料表面的粘附，延长了动态凝血时间，表现出良好的血液相容性。     

钕掺杂ZnO薄膜的制备及抗凝血性能研究

采用射频磁控溅射方法在硅(100)衬底上制备了不同含量元素钕(Nd)掺杂的氧化锌薄膜.XRD分析表明,所有ZnO薄膜都具有c轴择优取向.随着Nd掺杂量的增加,(002)衍射峰的强度减弱,颗粒的尺寸变小.紫外-可见光谱分析表明,所有薄膜在可见光区的透过率超过85%,随着Nd掺杂量的增加,光学带隙从3.30 eV增加到3.40 eV.用XPS对薄膜的表面化学态进行表征,Nd元素在ZnO薄膜表面以Nd3+离子态存在.用接触角测试薄膜表面的浸润性,并计算其表面能.用血小板粘附实验研究不同含量Nd掺杂ZnO薄膜的血液相容性,其结果表明稀土钕掺杂后血小板的粘附数量和形变都较少,稀土掺杂和疏水性的提高是改善氧化锌薄膜抗凝血性能的主要原因.     

用于体外循环装置的材料涂层技术综述与展望

近几十年来,血液透析、心肺分流术、骨科、血管和重建手术等医学技术的不断进步促进了直接与生物组织接触的人工材料的迅速发展。由于任何外物与血液接触都会导致血液产生各种应急反应,最终引发凝血,导致医疗器械的闭塞和栓塞,这极大限制了材料在医学领域的应用。因此,提高体外循环中材料的生物相容性,特别是血液相容性,是解决问题的关键。目前,表面涂层技术是改善材料表面生物相容性最有效、应用最广泛的技术。本文主要综述了提高材料血液相容性的三种主要途径:构建生物材料惰性表面、材料表面仿生化、负载生物活性物质。同时介绍了诸如白蛋白、聚氧化乙烯、聚己酸内酯-聚二甲硅氧烷-聚己酸内酯、聚2-丙烯酸-2-甲氧基乙酯、磷酰胆碱、糖胺多糖、肝素、水蛭素、双嘧达莫等多种表面涂层技术及其临床应用,并对未来提高体外循环系统血液相容性的新方向提出展望。     

新型抗凝血纳米复合材料的制备及其性能研究

利用溶液插层法合成了新型的硅橡胶/氧化石墨-十六烷基三甲基溴化铵-肝素抗凝血纳米复合材料.通过FT-IR、XRD、SEM和机械性能测试了解改性氧化石墨微观纳米结构对材料宏观性能的影响;溶血试验和血小板粘附试验测定表明硅橡胶/改性氧化石墨抗凝血纳米复合材料的血液相容性得到极大的改善;这种新型的、兼具优良血液相容性和良好力学性能的复合材料可望在生物医学工程方面得到应用.     

Blood compatibility of gas plasma-treated diamond-like carbon surface—Effect of physicochemical properties of DLC surface on blood compatibility

From the knowledge that zwitterion-type polymers show good blood compatibility, the introduction of both cationic and anionic functional groups onto diamond-like carbon (DLC) surface is expected to improve blood compatibility. Thus, DLC films were treated with oxygen and ammonia gas plasmas. The surfaces were characterized in terms of chemical composition by XPS, contact angle, and zeta potential. XPS analysis showed the introductions of a carboxyl group by oxygen plasma treatment and nitrogen atoms by ammonia plasma treatment. The evaluation of blood compatibility for the DLC surfaces was carried out in terms of platelets and the coagulation system. Excellent improvement of platelet compatibility was observed by the treatment with the gas plasmas, regardless of the plasma species. As for the compatibility with the coagulation system, DLC surfaces with a high concentration of carboxyl groups (COOH) markedly activated the system via the intrinsic pathway. However, the surfaces treated with ammonia plasma did not activate the system even though they had high COOH concentration. Measurement of the zeta potential revealed that the ammonia plasma treatment raised the potential from a negative value to a positive one. Though the introduction of amino groups to the surface was not detected directly, the treatment of ammonia plasma changed the electrical state of the DLC surface having COOH group, causing a difference in blood compatibility among the DLCs obtained by various plasma conditions.     

MMA/MPEOMA copolymers as coating materials for improved blood compatibility: protein adsorption study

Surface-induced thrombosis remains one of the main problems in the development of blood-contacting devices. When a foreign surface comes in contact with blood, the initial blood response is adsorption of blood proteins, followed by platelet adhesion and activation, leading to thrombus formation. A particularly effective polymer for the prevention of protein adsorption and platelet adhesion appears to be polyethylene oxide (PEO). In this study, water-insoluble copolymers of methyl methacrylate (MMA) and methoxy PEO monomethacrylates (MPEOMA) with different PEO molecular weights (200, 400, and 1000) and monomer composition were synthesized and characterized by gel permeation chromatography and ¹H-nuclear magnetic resonance spectroscopy. The synthesized copolymers were coated on glass slides by a spin coating method to prepare PEO-rich surfaces as blood-compatible surfaces. The surface properties of the copolymers and their interaction with blood proteins (albumin, γ-globulin, fibrinogen, and plasma proteins) were investigated by the measurement of water contact angles and by electron spectroscopy for chemical analysis, respectively. It was observed that the protein adsorption on the copolymer surfaces decreased with increasing PEO molecular weight and MPEOMA content in the copolymers. The copolymers with long PEO chains in MPEOMA (MMA/MPEO₀₀₀MA copolymers) were effective in preventing protein adsorption, even though their MPEOMA content was less than the copolymers with shorter PEO chains. © 1999 Kluwer Academic Publishers     

Physical properties of nano-HAs/ZrO2 coating on surface of titanium materials used in dental-implants and its biological compatibility

A gradient composite coating on the surface of titanium materials, which are used in dental implants, is prepared using an electric-chemical method. The physical properties of the composite coating and its strength of combining with titanium material are studied by the scanning electron microscope, energy dispersive spectrum and X-ray diffraction analysis, etc. The results show that the nanohydroxyapatite/ZrO2 composite coating is uniformly deposited and formed on the surface of titanium materials, its strength of combining with titanium surface reaches 16.3 MPa, which is determined by the tensile test. The immersion experiment shows that a new matter of carbonate-apatite is distributed uniformly on the surface of the composite coating of nanohydroxyapatite/ZrO2. The cell experiment of cultivate exhibits that the osteoblasts MG-63 is also grown well on the surface of the composite coating. These results indicate that the nanohydroxyapatite/ZrO2 composite coating on the surface of titanium materials has a good biological activity and compatibility and could be used in the dental-implants.     

Spectroscopic ellipsometry characterization of amorphous carbon and amorphous, graphitic and fullerene-like carbon nitride thin films

Carbon nitride (CN_x) and amorphous carbon (a-C) thin films are deposited by reactive magnetron sputtering onto silicon (001) wafers under controlled conditions to achieve amorphous, graphitic and fullerene-like microstructures. As-deposited films are analyzed by Spectroscopic Ellipsometry in the UV-VIS-NIR and IR spectral ranges in order to get further insight into the bonding structure of the material. Additional characterization is performed by High Resolution Transmission Electron Microscopy, X-ray Photoelectron Spectroscopy, and Atomic Force Microscopy. Between eight and eleven resonances are observed and modeled in the ellipsometrically determined optical spectra of the films. The largest or the second largest resonance for all films is a feature associated with C-N or C-C modes. This feature is generally associated with sp³ C-N or sp³ C-C bonds, which for the nitrogen-containing films instead should be identified as a three-fold or two-fold sp² hybridization of N, either substituted in a graphite site or in a pyridine-like configuration, respectively. The π→π? electronic transition associated with sp² C bonds in carbon films and with sp² N bonds (as N bonded in pyridine-like manner) in CN_x films is also present, but not as strong. Another feature present in all CN_x films is a resonance associated with nitrile often observed in carbon nitrides. Additional resonances are identified and discussed and moreover, several new, unidentified resonances are observed in the ellipsometric spectra.     

低碳钢热浸Zn-0.15%Ni合金镀层组织及第二相粒子

采用热浸Zn-Ni合金镀锌方法，在含0.03%-0.36%Si的低碳钢上获得Zn-Ni合金镀层，研究了镀浴中Ni含量和钢中Si含量对镀层中δ相和ζ相生长速率的影响，以及Zn-Ni合金镀层η相中的第二相粒子即Zn-Fe-Ni三元化合物Γ2相粒子的形成和长大过程，结果表明，在Zn-0.15%Ni镀浴中，含硅0.03%-0.215%钢镀层的ζ相明显受到抑制，δ相厚度略有增加，Γ2相粒子的形成和长大过程包括ζ相的溶解，Γ2相的形核和成比例吸收铁，镍而长大。     

Microstructure of amorphous tantalum nitride thin films

The main purpose of the present microstructural analysis by transmission electron microscopy (TEM) and X-ray diffraction was to investigate whether amorphous TaN films are a potential candidate as diffusion barrier for Cu wiring used in Si devices. The TaN thin films were prepared by a sputter-deposition technique using Ar and N₂ mixed gas, and the film structure was found to be sensitive to the gas flow ratio of N₂ vs. Ar during sputtering. Polycrystalline TaN films were obtained when the N₂/(Ar+N₂) ratio was smaller than 0.10 and amorphous TaN films were obtained when the ratio was larger than 0.15. Cross-sectional TEM observations revealed that the amorphous films had columnar structure with fine grains and that nano-scaled voids segregated at the boundaries. In addition, two-layered structures were observed in the amorphous TaN films and high density of the grain boundaries was formed close to the substrate. The present results suggested that the amorphous TaN films would not have high resistance against interdiffusion between two different materials because the density of grain boundaries with small voids was extremely high.     

Blood compatibility and tissue responsiveness on simple and durable methylsiloxane coating

This study was conducted to evaluate the blood compatibility and tissue responsiveness of methylsiloxane (MS)-coated inorganic (glass and metal) substrates both in vitro and in vivo. MS was prepared from methyltriethoxysilane (MTES) through hydrolysis of a sol–gel solution at 80 °C. The adhesive strength of the MS coating was evaluated by using a tear-off test, revealing that the MS strongly adhered to the surface of the inorganic substrates. Blood compatibility was evaluated by assessing platelet adhesion and blood plasma coagulation time. The platelet aggregation ratio of the MS-coated glass tube was reduced to 10%, which was much smaller than that of the coating-free glass tubes (99%) and conventional blood-compatible polystyrene (PS) tubes (18%). Coagulation time was measured by active partial thromboplastin time (APTT) test, which showed that MS coating is as inert as PS in activating blood coagulation factor XII. Tissue responsiveness to the bulk MS sample, evaluated by animal test, showed a desirable compatibility comparable to that of the control titanium sample. This study indicated that MS coating is readily available to convert inorganic materials to useful biomaterials that have suitable mechanical strength and are compatible with blood and tissue.     

High-temperature compatibility of carbon fibres with nickel

A study has been made of the elevated temperature degradation of a number of carbon fibre types coated with nickel by a variety of methods (electroless, electrolytic, carbonyl and physical vapour deposition). At high temperatures, Ni-coated fibres undergo a transformation of structure to crystalline graphite with a consequent loss of strength and elastic modulus. Resistance to this recrystallization is related to the fibre type and structure and increases in the order HTS PAN-based, HM PAN-based, HM rayon-based. For PAN-based fibres the resistance increases with the degree of structural order and orientation. The recrystallization of HTS fibres is consistent with a simple model of dissolution and reprecipitation controlled by diffusion of carbon in nickel. To explain the higher stability of HM fibres an additional factor must be introduced. For example, their behaviour can be explained in terms of a highly stable surface layer between about 0.1 and 0.5m thick. Rapid recrystallization occurs when the nickel breaks through this layer e.g. by dissolution. The recrystallization was not greatly affected by the type of nickel coating but the recrystallization temperature of HM fibres was considerably reduced by a small proportion of air in the heat-treatment atmosphere. HTS fibres were not affected in this way but the fibres were severely weakened through surface attack by both air and hydrogen at temperatures well below the recrystallization temperature.     

Ex-vivo blood compatibility of silicone-containing biomaterials

The acute blood-contacting properties of five silicone-containing elastomers and a poly(vinyl alcohol) coated silicone elastomer were assessed using a canine ex vivo shunt model. The silicone-containing elastomers studied included two thermoset amorphous silica reinforced dimethyl methylvinyl siloxane-based polymers which were extruded as Silastic^® RX-50 Medical Grade Tubing (RX-50) and Silastic^® Medical Grade Tubing H.P. (HP). They also included three experimental thermoplastic silicone-urea urethane copolymers received as X7-4074 (SP-1), X7-4037 (SP-2), and X7-4943 (SP-3). The RX-50 tubing material showed less thrombus deposition compared to the silicone-urea urethane copolymers. This suggests that the blood-contacting response of a silicone elastomer is strongly affected by the incorporation of the urea urethane segments. Among the silicone-urea urethane copolymers, the SP-3 material showed higher levels of platelet and fibrinogen deposition than the SP-1 and SP-2 materials, whereas the SP-1 and SP-2 samples had similar levels of deposition. These results indicate that the blood-contacting properties of the silicone-urea urethane copolymers were influenced more by the molecular weight of the polydimethylsiloxane than by the type of diol used in the urea urethane segments. The maximal platelet deposition on the poly vinyl alcohol-coated silicone was approximately an order of magnitude greater than those on the silicone-containing elastomers indicating that the PVA coating was more thrombogenic.