火焰喷涂制备纳米陶瓷超润滑涂层及其防污性能

仿猪笼草结构的灌注液体型超润滑涂层(SLIPS)因具有优异的自清洁防污性能备受关注,但目前存在制备工艺复杂、成本较高、不适宜大规模制备等问题,影响了该技术的实际应用。针对这一问题,利用火焰喷涂技术制备SLIPS表面的技术工艺,成功在不锈钢表面制备了基于纳米二氧化钛的SLIPS涂层,并研究了涂层结构及性能。利用SEM分析了涂层的表面形貌和微观结构;利用接触角测量仪研究了涂层的浸润性能;通过藻类贴附试验评价了涂层的防污性能。结果表明：所制备涂层表面接触角达到118.01°,滚动角达到4.54°,呈超润滑性能,对海洋小球藻附着率降低了98.56%。文中研究为制备低成本、大规模SLIPS涂层提供了一种可行的思路。     

基于超疏水和卤代过氧化物酶活性协同防污的氧化铈纳米涂层研究

目的 将特定防污功能的纳米粒子引入到环氧复合涂料中,制备具有超疏水和卤代过氧化物酶活性协同防污的氧化铈纳米涂层。方法 以环氧树脂和羟基封端的聚二甲基硅氧烷为基质,球形氧化铈（CeO₂）纳米颗粒为填料,采用溶液共混的制备方式,通过空气喷涂法构建氧化铈超疏水纳米涂层。借助X射线衍射仪、扫描电子显微镜、接触角测试仪等设备对涂层进行表征,并以典型海洋污损生物芽孢杆菌和三角褐指藻为研究对象分析涂层的防污性能。结果 当涂层中纳米氧化铈的质量分数为55%时,氧化铈纳米涂层具有超疏水特性,接触角达到153°,接触角滞后低至3°。在防污性能方面,相比于环氧复合涂层,超疏水氧化铈纳米涂层对三角褐指藻和芽孢杆菌的防污率分别为97.5%和97.3%。在存在过氧化氢和溴化铵的条件下,失去疏水性能的氧化铈涂层通过卤代过氧化物酶的活性减少了96.2%的三角褐指藻和96.8%的芽孢杆菌贴附。结论 该体系所构建的纳米涂层在初期可以利用其超疏水性能防污,后期利用其卤代过氧化物酶的活性防污,实现防污的长效性。     

NH2-ZIF-7 MOFs负载羧基化苯并异噻唑啉酮防污剂的制备和抗菌防污性能研究

目的 开发长效缓释且具有生物相容的绿色环保防污剂,消除防污剂在涂层中初期“爆释”、后期无法释放的弊端,实现新型缓释剂长效防污的功效。方法 通过简单的浸渍法负载防污剂分子,实现有效且缓慢释放;通过SEM、TEM观察负载前后纳米粒子的形貌;通过FT-IR、XRD、TGA、XPS、BET探究客体分子与纳米容器间的耦合作用,利用UV-Vis测试其释放性能;通过抑菌圈、平板菌落计数法、浊度法测试其抑菌性能;通过激光共聚焦观察涂层表面防细菌/藻类贴附性能。结果 氨基ZIF-7(NH2-ZIF-7)成功负载羧基化1,2-苯并异噻唑啉-3-酮(BIT-COOH),实现了有效封装和稳定释放,并且金属有机框架材料负载后(NH2-ZIF-7@BIT-COOH),革兰氏阴性菌(E.coli)和革兰氏阳性菌(S.aureus)的抑菌圈直径分别提高至(21.7±0.2)和(21.7±0.3)mm。进一步利用激光共聚焦观察涂层表面的细菌/藻类贴附情况,表明添加质量分数4%NH2-ZIF-7@BIT-COOH的混合树脂涂层具有优异的防细菌/藻类贴附性能。结论 利用NH2-ZIF-7封装BIT-COOH防污剂,可有效捕获、稳定释放并具有优异的抗菌性能,另外在丙烯酸树脂涂层中加入NH2-ZIF-7@BIT-COOH新型缓释防污剂能够有效抑制细菌/海藻的贴附,为新型缓释长效广谱低毒的防污剂开发提供了新的思路。     

Nano-TiO2/FEVE氟碳涂层的水云藻附着性能

为了研发新型无毒舰船防污涂料,以FEVE氟碳树脂为成膜物、纳米TiO2粉末为功能添加剂,试制了系列Nano–TiO2/FEVE氟碳涂层,研究了纳米TiO2含量对大型藻(水云藻)附着行为的影响。结果表明,水云藻的附着量随着涂层中纳米TiO2含量的增加而减少,当纳米TiO2含量达到0.8%时,水云藻附着量降至最少,纳米TiO2含量由0.8%增大至2%,水云藻的附着量增大,纳米TiO2含量继续增大至4%,涂层上水云藻的附着量反而减小。纳米TiO2对水云藻的附着具有明显的阻止作用,可以成为一种安全环保的防污功能添加剂。     

仿甲鱼壳织构化有机硅改性丙烯酸酯涂层的制备及其防污行为

借鉴海洋生物表皮具有天然的防污特性,通过"生物原样-PDMS模板-目标涂层"的制备过程,实现了表面具有甲鱼壳仿生织构正负形貌的有机硅改性丙烯酸酯涂层的制备。系统考察了仿甲鱼壳正负形貌织构涂层的表面形貌、润湿性、对蛋白质的抗吸附能力、对舟形藻和新月藻的防污性能。结果表明:仿甲鱼壳正负形貌织构化涂层表面存在类似颗粒状的突起,表面疏水性增强,与空白涂层相比,可使蛋白质、舟形藻和新月藻的附着量分别降低58%、69%、50%和46%、52%、53%,由此可以看出,正负形貌涂层对蛋白质和2种藻类的防污效果略有差异。仿甲鱼壳涂层具有较好的防污效果,究其原因,与其表面存在的微观形貌有着很大的关系。     

改性纳米TiO_2粒子改善PP-R性能的研究

文章以锐钛型纳米二氧化钛为添加剂来提高PP-R树脂的各项性能,并系统研究了纳米TiO_2粒子的包膜改性,以及改性后的纳米二氧化钛对PP-R树脂耐热性、力学性能以及抗菌性等的影响;通过扫描电镜观察了材料的断面以及晶须在基体中的分散性。研究表明,使用6%的硅铝复合包膜改性后的纳米TiO_2粒子具有较好的分散性;与纯PP-R相比,纳米TiO_2粒子添加量为3%～5%的改性PP-R材料的性能有较大的提高,其热变形温度由72℃提高到96℃,断裂伸长率由45%提高到91%。锐钛型纳米二氧化钛不仅可改善PP-R材料的热学和力学性能,而且可提高材料的抗菌性,其适用添加量为4%。     

Ag/TiO_2/PA自洁净涂料的原位聚合制备及其抗菌性能（英文）

使用钛酸丁酯,乙酸,乙醇等材料,制备了含TiO_2纳米粒子浓缩液,其中TiO_2尺寸约250 nm,分配系数0.631。采用上述浓缩液,获得了纳米二氧化钛改性聚丙烯酸树脂(TiO_2/PA),并将其涂在铝箔上。通过紫外可见光谱和漫反射光谱(DRS),发现纳米二氧化钛有强烈的紫外线吸收效果。将改性添加剂加入浓缩液,并采用原位聚合方法,生成银纳米粒子,最后获香Ag/TiO_2/PA涂层。根据国标准GBT 1741-2007防霉测试,该Ag/TiO_2/PA外墙涂料没有观察到霉菌的明显生长。测试了Ag/TiO_2/PA对大肠杆菌和金黄色葡萄球菌的抗菌活性,质最低抑菌浓度(MIC)为7.285×10~(-5)mg/mL,银的抗菌效果显著,但是它不能消除细菌死亡后释放的有毒物质。对3种薄膜的光催化性能进行了测试,在464 nm的可见光下,Ag/TiO_2/PA外墙涂料存在时,甲基橙(MO)2.5 h后的脱色率接近50%,研究认为,该涂层的光催化能力来自于表面上的二氧化钛。     

压力烧结制备二氧化钛包覆的石墨烯增强铝基复合材料（英文）

使用压力烧结方法制备了石墨烯纳米片(GNP)增强的7075铝基纳米复合材料,提出了一种通过在GNP的表面涂覆二氧化钛(TiO_2)来优化界面结合的新工艺,并比对了原石墨烯及具有包覆层石墨烯对铝基纳米复合材料的力学性能和微观结构的影响。结果表明,与添加纯GNP相比,添加具有TiO_2涂层的GNP的纳米复合材料的力学性能提高。相比于基体,TiO_2包覆GNP增强的纳米复合材料的屈服强度、抗拉强度和显微硬度分别增加了38.9%、34.4%和20.1%。性能的进一步改善是由于TiO_2涂层优化了增强相与基体之间的界面结合,从而提高了载荷传递的有效性。     

纳米二氧化钛浓缩浆对硼酚醛环氧涂料性能的影响

目的提高硼酚醛环氧涂料的耐腐蚀性、表面接触角、粘结强度及耐磨性等。方法用纳米二氧化钛浓缩浆改性硼酚醛环氧涂料,制备耐温耐蚀型纳米复合涂料。通过高温高硫原油浸泡试验评价纳米复合涂层的耐腐蚀性能,通过扫描电镜观察、表面接触角测试、粘结强度测试和耐磨性测试等手段分析纳米二氧化钛浓缩浆对涂层性能的影响。结果硼酚醛环氧纳米复合涂层在100℃高硫原油腐蚀浸泡后,微观上没有出现腐蚀坑和裂纹。添加2%纳米二氧化钛浓缩浆的硼酚醛环氧纳米复合涂层与未添加纳米粒子的硼酚醛环氧涂层相比,抗渗性与耐磨性有所提高。720 h腐蚀试验后,纳米复合涂料的粘结强度由试验前的7.7 MPa降低至6.9 MPa。腐蚀过程中,其表面接触角比非纳米涂层高4°~7°。结论高温高硫原油没有破坏硼酚醛环氧纳米复合涂层的形貌结构、粘结强度和耐磨性。添加2%纳米二氧化钛提高了涂层的抗渗透性和表面接触角。     

Si掺杂对溶液等离子喷涂TiO2涂层结构及光催化性能的影响

目的采用溶液前驱体等离子喷涂制备TiO_2以及Si掺杂TiO_2涂层,并分别研究H2流量和Si掺杂对TiO_2涂层光催化性能的影响。方法通过X射线衍射、扫描电子显微镜、拉曼光谱和傅里叶变换近红外光谱表征样品的晶相、表面形貌以及化学结构,然后以甲基橙为目标物,借此模拟有机污染物,利用光化学反应仪测试TiO_2以及Si掺杂TiO_2涂层的光催化性能。结果适量Si掺杂可以细化晶粒,提升TiO_2涂层中锐钛相含量(从7.4%提高到49%),同时形成Ti—O—Si键,Si掺TiO_2涂层甲基橙的降解率达到95%左右,高于纯TiO_2涂层80%的降解率。随着H2流量增加,TiO_2涂层中的晶粒明显粗化,主要以金红石相的形式存在,H2流量为8 L/min的TiO_2涂层甲基橙降解率达到82%,要远高于H2流量为4、10 L/min的52%和33%。结论 Si掺杂TiO_2涂层比纯TiO_2涂层的光催化性能更优,当H2流量为8 L/min时,光催化性能最好。     

Antifouling properties of micro arc oxidation coatings containing Cu2O/ZnO nanoparticles on Ti6Al4V

Micro arc oxidation (MAO), as a new special surface treatment method, has been introduced to the marine antifouling field for titanium alloys because of the anatase and rutile TiO₂ with antibacterial effects obtained during the oxidation process. Despite this, metallic oxide antifouling additives have been added into MAO coatings to improve the antibacterial and antifouling abilities of titanium alloy. In this study, MAO coatings containing nanometer particles were obtained by adding nano Cu₂O and nano ZnO into the electrolyte. Structure, morphology, phase constitution and chemical composition of the MAO coating film were studied by SEM, XRD and EDS. The antibacterial properties of the film were evaluated by exposing the specimens to Escherichia coli and comparing the Ti-MAO and Ti-bared controls. The results showed that the MAO process on Ti6Al4V has an outstanding antibacterial property which can be further enhanced by nano Cu₂O and nano ZnO. The Ti-MAO–Cu₂O group had the best antibacterial ability. These findings indicate that by means of this process adding nanometer metallic oxide into an MAO coating film via an electrolyte is useful for enhancing the antibacterial and antifouling abilities of titanium.     

Effects of TiO2 particles size and heat treatment on friction coefficient and corrosion performance of electroless Ni-P/TiO2 composite coatings

The effects of the titanium dioxide (TiO₂) particles size on the friction coefficient and corrosion performance of the Ni-P/TiO₂ composite coatings before and after heat treatment at 400°C for 1h have been investigated. Pin-on-disc analysis results have revealed that the highest and the lowest friction coefficients belonged, respectively, to the simple Ni-P coating and the Ni-P/TiO₂ composite coating containing TiO₂ particles of the average size of 0.1 μm (μ ～ 0.62 against 0.52). Eventually, a relative reduction in the corrosion resistance and the friction coefficient (as low as μ ～ 0.38) have been observed after heat treatment of Ni-P and Ni-P/TiO₂ composite coatings.     

Effect of different structured TiO2 particle on anticorrosion properties of waterborne epoxy coatings

Anticorrosion properties of waterborne epoxy coatings with three structured nano-particles of TiO₂ were investigated and compared. The surface morphology and structure of TiO₂ have been analysed by XRD, SEM and N₂ adsorption–desorption. Corrosion performance of the nano-composite coating was investigated employing electrochemical impedance spectroscopy and salt spray test. Coatings with mesoporous TiO₂ (meso-TiO₂) possessed the best corrosion performance among the coating specimens. The EIS results show that the resistance value of coating with meso-TiO₂ was above 5.4?×?10⁸?Ω?cm² which was higher than the other nano-composite coatings. Possible strong interactions between polymeric matrix and meso-TiO₂ caused high barrier properties.     

Characterization of plasma-sprayed hydroxyapatite/TiO2 composite coatings

To enhance the bonding between hydroxyapatite (HA) coating and titanium alloy substrate, HA/TiO₂ composite coatings have been fabricatedvia plasma spraying. Bonding strength evaluation, simulated body fluid tests, and cell culturein vitro were carried out to characterize the composite coatings. The results obtained showed that the addition of TiO₂ to HA coating improved the bonding strength of the coating significantly. After being immersed in simulated body fluid (SBF) for a period, the surfaces of HA/TiO₂ composite coatings were completely covered by carbonate-containing apatite, which indicated that the coatings possess good bioactivity. Thein vitro cell culture indicated good cytocompatibility for HA/TiO₂ composite coatings.     

钛基表面TiO_2-HA生物陶瓷膜层的血液相容性研究

采用微弧氧化法及微弧氧化-水热法对纯钛进行改性,制备了TiO_2与TiO_2-HA生物陶瓷膜层,通过溶血率实验、动态凝血时间实验和血小板黏附实验等方面评价其血液相容性。结果表明:各试样的溶血率都远小于5%,均符合医用材料的溶血率要求,不会产生溶血作用。与钛基TiO_2生物陶瓷膜层和钛基材相比,钛基TiO_2-HA生物陶瓷膜层的溶血率更低,动态凝血时间曲线变化更为缓慢,黏附的血小板更少,且变形程度更轻,具有更好的抑制血小板的聚集与变形的性能,血液相容性更优。     

Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO_2?x ) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO₂ particles fragmented when impacting onto the hard surface of the APS TiO_2?x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO₂ coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25^® photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.     

Electrodeposition of sol-enhanced nanostructured Ni-TiO2 composite coatings

A novel electroplating method has been developed to produce nanocrystalline metal-matrix nano-structured composite coatings. A small amount of transparent TiO₂ sol was added into the traditional electroplating Ni solution, leading to the formation of nanocrystalline Ni-TiO₂ composite coatings. These coatings have a smooth surface. The Ni nodules changed from traditional pyramid-like shape to spherical shape. The grain size of Ni was also significantly reduced to the level of 50 nm. It was found that the amorphous anatase TiO₂ nano-particles (∼ 10 nm) were highly dispersed in the coating matrix. The microhardness was significantly increased from 320 HV₁₀₀ of the traditional Ni coating to 430 HV₁₀₀ of the novel composite coating with 3.26 wt.% TiO₂. Correspondingly, the wear resistance of the composite coating was improved by ∼ 50%.     

A novel electroless plating of Ni-P-TiO2 nano-composite coatings

A new processing concept has been developed to produce nano-structured metal-matrix composite coatings. This method combines sol-gel and electroless plating techniques to prepare highly dispersive oxide nano-particle reinforced composite coatings. Transparent TiO₂ sol was added into the standard electroless plated Ni-P solution at a controlled rate to produce Ni-P-TiO₂ nano-composite coatings on Mg alloys. The coating was found to have a crystalline structure. The nano-sized TiO₂ particles (∼ 15 nm) were well dispersed into the Ni-P coating matrix during the co-deposition process. This technique can effectively avoid the agglomeration of nano-particles in the coating matrix. As a result, the microhardness of the composite coatings were significantly increased to ∼ 1025 HV₂₀₀ compared to ∼ 710 HV₂₀₀ of the conventional composite coatings produced with solid particle mixing methods. Correspondingly, the wear resistance of the new composite coatings was also greatly improved.     

pH响应性聚合物抗菌涂层的制备及性能研究

目的 制备一种具有pH响应性的智能聚合物抗菌涂层,能按需实现涂层从防污到杀菌功能的转换.方法 以季铵盐甲基丙烯酰氧乙基二甲基辛烷基溴化铵(DMAEMA-8C)、对-(2-甲基丙烯氧乙氧基)苯甲醛(MAEBA)和甲基丙烯酸异辛酯(EHA)作为共聚单体,通过自由基聚合制备了一种季铵盐聚合物PMQE-CHO,并将其利用浸涂技术在不锈钢316L(SS)表面制备季铵盐聚合物涂层SS-PMQE-CHO.随后,使用PEG-NH2对季铵盐涂层SS-PMQE-CHO表面进行接枝改性,得到pH响应性聚合物涂层SS-PMQE-PEG.对涂层的基本性能进行了表征.通过大肠杆菌和荧光素偶联的牛血清白蛋白(FITC-BSA)的附着力测试,评估涂层的防污和抗菌性能.利用抗菌实验表征涂层在不同pH条件下的抗菌效果.进行体外细胞毒性分析和溶血试验,评估涂层的生物相容性.结果 涂层结构致密规整、机械性能优异,具有良好的生物相容性和低溶血率,并且可以有效地防止BSA和大肠杆菌的粘附.在菌液里培养10 h后,涂层SS-PMQE-PEG-30和SS-PMQE-PEG-40表面的细菌与SS表面的细菌相比,分别减少了94％和96％.此时,PEG显示出有效的防污作用.在菌液里培养24 h后,菌液的pH值降低.涂层SS-PMQE-PEG-30和SS-PMQE-PEG-40的功能从防污转化为杀菌,杀菌效率分别为93％和92％.即使是在PBS中浸泡两周后,涂层仍呈现出良好的功能转化性能.结论 在正常条件下,涂层SS-PMQE-PEG中的PEG可以有效抵抗蛋白质和细菌的粘附.当涂层附近的微环境变为弱酸性时,席夫碱键发生断裂,此时涂层底部的杀菌层暴露出来,以杀死细菌并抑制感染的发生.