再生纤维素基底上FC膜的制备及其结构与性能研究

采用磁控溅射法,以聚四氟乙烯(PTFE)为靶,氩气为栽气,在再生纤雏素膜表面沉积氟碳(FC)膜.用扫描电镜(SEM)、原子力显微镜(AFM)、红外光谱仪(FT-IR)和静态接触角测试仪对氟碳膜的表面形貌、表面结构和表面性能进行了研究,结果表明:随着溅射压力的增加,沉积的FC粒子数量增多,粒径变小,覆盖度增加;随着沉积时间的增加,FC膜逐渐变厚,FC膜由-CF3、-CF2-、-CF-和-C-4种组分组成.沉积FC膜后,再生纤维素膜实现了由亲水性向疏水性的转变.     

溅射气氛对氟碳疏水薄膜表面结构及性能的影响

以聚四氟乙烯(PTFE)为靶材,用射频磁控溅射方法在玻璃衬底上制备了氟碳高分子薄膜,并对其结构和表面性能进行了研究.由XPS的结果可知,构成薄膜的大分子由-CF-、-CF2-和-CF3等组分组成.随着氩气压强的增加,缺氟基团-C-增加,而-CF2-、-CF3等富氟基团以及F/C均减少;随着氮气偏压的增加,-CF-、-CF2-和-CF3以及F/C和N/C增加.同时探讨了溅射气氛对薄膜表面形貌、疏水性能及表面能的影响.     

FC／ZnO杂化材料的制备及结构与性能

采用射频磁控溅射法,分别以聚四氟乙烯(PTFE)和锌为靶,在聚对苯二甲酸乙二醇酯(PET)基底上沉积氟碳(FC)膜以及FC/ZnO的有机-无机纳米杂化材料。用SEM、UV、XPS对氟碳膜和杂化材料进行了表征。结果表明,氟碳膜形成了一种由纳米粒子-纳米孔洞组成的双纳米结构,随着ZnO沉积时间的不同,FC/ZnO杂化膜呈现出不同的表面形貌,杂化膜的生长模式是一种依附于有机核的沉积-扩张生长模式;杂化材料的F/C较低,随着氧化锌沉积时间的增加,F/C出现逐渐增大的趋势;杂化膜是一种多重抗紫外线辐射的功能膜。     

氟代聚丙烯酸酯乳液的合成及其用于氟碳涂料的防水性能

为了制备一种廉价且具有优异防水性的水性涂料,用氟碳乳液,以阴/非离子复合表面活性剂为乳化剂,过硫酸铵为引发剂,通过乳液聚合法制得了全氟烷基乙基丙烯酸酯(FA)-甲基丙烯酸十八醇酯(SMA)-丙烯酸羟丙酯(HPA)-对氯甲基苯乙烯(CMS)四元无规共聚氟代聚丙烯酸酯乳液(FSHC),采用红外光谱仪(IR),核磁共振氢谱(1H-NMR),纳米粒度仪及Zeta电位分析仪,光电子能谱仪(XPS)和接触角测定仪分别对FSHC乳液的结构、粒径分布和Zeta电位及膜表面的化学元素组成和疏水性进行了表征。结果表明:FSHC具有预期的结构,其平均粒径为146.2 nm,Zeta电位为-21.2 mV;FSHC膜表面存在较多的F元素,含氟基团迁移至表面,发挥优异的防水性能;以FSHC乳液为成膜物质所制备的氟碳涂料,表现出良好的拒水效果,水在氟碳涂料涂层表面的静态接触角达128.6°。     

改性纳米TiO2/PTFE复合氟碳防污闪涂层的制备及其性能

为防止输电线路上污闪事故的发生,以氟碳树脂(FEVE)为成膜剂,以改性纳米TiO2和聚四氟乙烯(PTFE)微粉为复合填料,制备了一种新型的有自清洁效应的纳米TiO2/PTFE复合氟碳防污闪涂料.采用傅里叶变换红外光谱仪(FTIR)表征纳米TiO2改性前后的结构,通过扫描电镜(SEM)、X射线光电子能谱仪(XPS)、接触角测量仪对复合氟碳防污闪涂层表面的微观结构及疏水性进行了分析,对涂层表面的光催化自清洁性和疏水性保持机制进行了深入探讨.结果表明:改性纳米TiO2和PTFE通过化学键合作用在复合氟碳防污闪涂层表面构建了微纳复合粗糙结构,与水静态接触角达134°,涂层不仅具有优良的理化、电气绝缘性能,而且还具有有效的自清洁功能和疏水性保持性能.     

用AFM研究硅基上沉积铜膜生长过程

室温下,利用磁控溅射在P型Si(111)衬底上沉积了铜(Cu)膜.用原子力显微镜(AFM)对不同沉积时间制备的Cu膜形貌进行了观测,研究了磁控溅射沉积Cu膜时膜在硅衬底上成核和生长方式.Cu膜在Si衬底生长时,Cu的临界核以Volmer-Weber模式生长.溅射时,核长大增高为岛状,岛与岛相互连接构成岛的通道,最后形成连续膜.随着沉积的进行,Cu膜表面粗糙度由于晶粒凝聚和合并而增大.当形成连续致密的、具有一定晶向的Cu膜时,粗糙度反而减小.     

非对称表面氟化聚乙烯醇膜的制备及性能研究

以水溶性聚乙烯醇(PVA)为基膜,全氟-2,5—二甲基-3,6—二氧杂壬酰氟为氟化剂,通过表面控制氟化,制备了PVA非对称膜.PVA膜在单一表面上接枝一层全氟烷基醚链段,氟化面水接触角高达126°.由于氟元素在表面富集,接枝层氟含量最高达49.1％,且自表面开始由外至内,氟元素含量逐渐减少,膜呈现出由疏水全氟烷基醚相到亲水PVA基体相的特殊过渡结构.在表面氟化过程中,氟醚链段通过自组装聚集在膜的表面形成有序的岛状结构,有利于表面疏水性的提高.非对称膜结合了两表面完全不同的亲/疏水性,对水流方向具有独特的响应性,在微型反应器或化学阀等精密仪器中有很大潜在应用价值.     

射频溅射法制备氟碳高分子膜的表征EI北大核心

为研制高性能防水透湿织物 ,在涤纶薄膜基底上沉积了氟碳高分子膜。利用光电子能谱 (XPS) ,表面衰减全反射红外光谱 (ATR- FT- IR) ,掠角红外光谱 (GAIR)对膜进行了表征。构成该膜的大分子由 - C- ,- CF- ,CF2 -和 CF3- 4个组分组成 ,随着施加能量的增加 ,缺氟基团 - C-和富氟基团 CF3-同时增加 ,这可由分子内分支。     

纯钛基体长效超疏水表面的低成本制备

为降低钛基上超疏水表面的制备成本,提高超疏水表面的耐久性能,以喷砂-阳极氧化法在纯钛基体上构造微纳复合粗糙结构,并使用商用氟碳罩光漆直接对其进行修饰获得超疏水性表面。利用傅里叶变换红外光谱(FTIR),场发射扫描电子显微镜(FE-SEM)和接触角测试等技术对超疏水性表面的化学组成、表面形貌、润湿性和表面耐久性进行了研究。结果表明:喷砂处理在钛基表面构筑微米级凹坑,阳极氧化通过形成网状氧化膜在钛基表面构造纳米级结构,氟碳罩光漆修饰该微纳复合粗糙表面后,为表面引入大量含氟基团,使其获得超疏水性能。超疏水性表面与纯水的静态接触角达162°±2.3°,滚动角为2.1°±0.2°,具有优异的环境耐久性。     

壳聚糖膜表面的氦等离子体改性研究

采用溶液浇铸法制备了壳聚糖膜,通过氮等离子体对壳聚糖膜进行表面改性以提高其表面亲水性.采缮用扫描电子显微镜(SEM)、表面接触角分析仪和X射线光电子能谱(XPS)对改性前后壳聚糖膜的表面结构和性能进行分析和表征,研究了不同等离子体处理时间和不同放电功率对壳聚糖膜表面结构和性能的影响.结果表明:经氮等离子体处理后,壳聚糖膜的表面接触角可由103.0°降为48.8°,表面亲水性得到明显改善.由XPS分析得知,膜表面的氧、氮含量及氧碳比增加,表面的C-C键发生了断裂而生成新的>C=O(COOR、COOH或CONH)等极性基团,从而使其亲水性增强.     

Durability of nitrided fluorocarbon polymer films for nanoimprint lithography

Hydrophobic fluorocarbon polymer films have been used as anti-sticking and releasing coatings for templates in nano-imprint lithography, but have poor durability against repeated high pressure pressing processes. The addition of nitrogen into fluorocarbon-based gas plasma can provide nitrided fluorocarbon polymer films, as confirmed by Fourier-transform infrared spectroscopy. Fluorocarbon and nitrided fluorocarbon films have almost the same 110.0° contact angle with water drops. The nitrided fluorocarbon films are harder and significantly enhance durability as anti-sticking layers. Durability enhancement has been confirmed by fabricating replicas with silicon templates using nitrided fluorocarbon anti-sticking layers.     

Composite SiOx/fluorocarbon plasma polymer films prepared by r.f. magnetron sputtering of SiO2 and PTFE

Composite films SiO_x/fluorocarbon plasma polymers were prepared by r.f. sputtering from two balanced magnetrons equipped with polytetrafluoroethylene (PTFE) and silica (SiO₂) targets. Argon was used as the working gas. The obtained films were characterised by means of XPS, RBS, FTIR, AFM, TEM, microhardness and static contact angle measurements. The obtained SiO_x/fluorocarbon plasma polymer films reveal different wettability (static contact angle of water ranges from 68° to 40°) and hardness (ranges from 720 to 3200 N/mm²) when the volume fraction ratio (filling factor) of SiO₂ changes from 0.01 to 0.7. The concentration of elements determined by RBS/ERDA varies strongly over this range of filling factors. The heterogeneous structure of the composite films is indicated by TEM at high SiO_x contents.     

Surface characterization and platelet adhesion studies of aliphatic polyurethanes grafted by fluorocarbon oligomers: effect of fluorocarbon chain length and carboxylic acid group

The surfaces of aliphatic polyurethane films, which were synthesized by 1,6 hexamethylene diisocyanate, poly(tetramethylene glycol) and 1,4 butanediol, were modified by grafting different chain length of fluorocarbon oligomers. The fluorocarbon oligomers on polyurethane surfaces were terminated with trifluorocarbon or carboxylic acid functionality. The alkyl groups were also grafted onto polyurethane surfaces for comparison. The surface characterization and platelet-contacting property were studied using electron spectroscopy for chemical analysis (ESCA), static contact angle analysis and in vitro platelet adhesion experiments. The effects of fluorocarbon oligomers and their terminal functionalities are discussed. The ESCA results demonstrate the fluorocarbon enrichment at the outmost layer in fluorocarbon oligomer grafted polyurethanes. The fluorocarbon content at the surface increases with increasing the chain length of fluorocarbon oligomers. The fluorocarbon oligomer grafted polyurethanes exhibit highly hydrophobic surfaces, while alkyl groups grafted polyurethanes show relatively hydrophobic surfaces compared with the untreated polyurethane. The in vitro platelet adhesion experiments indicated that the fluorocarbon oligomer and carboxylic acid functionality significantly reduced the number and the degree of activation of the adherent platelets.     

Plasma polymer films rf sputtered from PTFE under various argon pressures

Fluorocarbon plasma polymer films were prepared by radio-frequency (rf) sputtering of polytetrafluoroethylene (PTFE). Their wettability decreased with the increase in pressure of argon working gas. The films deposited at 70 Pa were found to be superhydrophobic plasma polymers with a static contact angle 146° for water. Sputtered fluorocarbon plasma polymer films were characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. The paper shows that the surface composition and chemical structure of the films vary with altering the argon gas pressure.     

FC/ZnO杂化材料的制备及耐水洗牢度

采用射频磁控溅射法,首先以聚四氟乙烯(PTFE)为靶,氩气为载气,在聚对苯二甲酸乙二醇酯(PET)基底上沉积氟碳(FC)膜,然后以金属锌为靶,氩气为载气,氧气为反应气体,在FC膜上再沉积一层ZnO膜而形成FC/ZnO有机-无机纳米杂化材料。用原子力显微镜(AFM)、X射线光电子能谱仪(XPS)以及静态接触角测定仪对FC膜以及FC/ZnO杂化膜的耐水洗牢度性质进行了研究。结果表明,该法制得的沉积膜接触角都大于90°,呈现出良好的疏水性。FC/ZnO杂化膜由于沉积了无机ZnO膜,其耐水洗牢度较氟碳膜好。     

溅射-氟碳高分子膜在空气中的结构和表面自由能变化

通过磁控溅射在PET织物上沉积用于新型防水透湿织物的氟碳高分子膜。为了解其在空气中的氧化机理和控制其结构及憎水性的变化，利用光电子能谱（XPS）和接触角测定仪对溅射氟碳膜的时间效应进行了研究。发现由于不饱和键及自由基的存在，随着放置时间的增加及氧化作用的进行，氧／碳比值逐渐增大。部分双键及自由基被氧化导致原－CF－，－C－CF，－C－和带有悬垂键的组分中产生－C＝O，－C－D－并产生断键，从而使其氟含量减少，碳的相对比例增加。上述结构变化导致随放置时间增加膜表面自由能极性分量增加而膜的憎水性降低。     

自交联含氟丙烯酸酯共聚物的乳液合成与表征

以十二烷基硫酸钠（SDS）和OP-10为乳化剂,甲基丙烯酸十二氟庚酯（DFHM）为含氟单体,双丙酮丙烯酰胺（DAAM）和已二酰肼（ADH）为交联单体,采用饥饿态半连续种子乳液聚合方法,合成了一系列自交联含氟丙烯酸酯共聚物乳液。研究了氟单体对酮肼交联的影响以及交联反应对乳胶膜的表面性能以及力学性能的影响,采用FTIR、TEM、接触角测量仪对乳液及乳胶膜性能进行了表征。研究表明,酮羰基和酰肼的交联反应在室温下可以顺利进行;氟碳基团的引入,使一部分酮羰基被屏蔽,在一定程度上阻碍了交联反应的进行;通过引入氟碳基团可以极大地提高涂膜表面的疏水性,降低涂膜的吸水率,提高涂膜接触角;通过交联反应可以有效地提高氟碳乳液的综合性能,当DFHM为7．5％,DAAM为4％时,交联膜的接触角和吸水率分别达到96．8°和8．5％,拉伸强度为24．8MPa。     

Surface modification of materials by dielectric barrier discharge deposition of fluorocarbon films

Dielectric barrier discharges have been used to deposit fluorocarbon (FC) films on various materials, such as paper, glass, and silicon substrates. The primary monomers used for plasma polymerization were difluoromethane (CH₂F₂), octafluoropropane (C₃F₈), and octafluorocyclobutane (C₄F₈). FC films were characterized using Fourier transform infrared spectroscopy, atomic force microscopy, static contact angle measurements, and scanning electron microscopy. Surface and structural properties of deposited films are strongly dependent on the plasma compositions and plasma parameters. FC films deposited on paper are to enhance its barrier properties and to achieve hydrophobic surfaces. Contact angle studies reveal that a minimum FC film thickness of about 200 nm on paper is required to completely cover surface and near-surface fibers, thereby providing the paper with long term hydrophobic character. In the C₃F₈ and C₄F₈ systems, the contact angles of the deposited films do not change appreciably with plasma parameters and are strongly dependent on the substrate roughness. Hydrogenated FC films deposited with CH₂F₂ plasmas show the relatively low contact angles due to the existence of CH_X (x = 1-3) groups.     

Plasma-deposited fluorocarbon films on silicon studied by ellipsometry

The refractive index (at 632.8 nm, He-Ne laser light) of fluorocarbon films on silicon, deposited either inadvertently in the course of SiO₂ contact hole reactive ion etching with CF₄Xvol.%H₂ (X⩽40) or deliberately in a CF₄50vol.%H₂ glow discharge, was determined by ellipsometry. The best fit of the data gives a complex refractive index of 1.48-i0.003. The calculated refractive index was used to measure film thicknesses of fluorocarbon films deposited under a great variety of experimental conditions. Complementary results were provided by helium ion backscattering measurements. The results obtained by the two methods compared favorably. Ellipsometry therefore represents a probe which can be used to determine rapidly the fluorocarbon contamination state of a silicon wafer after reactive ion etching in CF₄-H₂. The extension of the present method to characterize films deposited by reactive ion etching processes utilizing other etching gas combinations is discussed.     

Surface oxidation of cellulose by ozone-gas in a vacuum cylinder to improve the functionality of fluoromonomer

The influence of the ozone-gas treatment on the performance of the fluorocarbon monomer on cotton fiber was investigated employing Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), water contact angle (WCA) and bending length (BL). FTIR results indicated that the ozone-gas pre-treatment oxidized the surface of the fibers increasing reactivity of the substrate toward the fluoromonomer. The contact angle and microscopic tests showed that the combination of ozone and fluorocarbon treatments on cotton can increase the contact angle due to higher efficiency of the water repellent polymer on the surface of the ozone-gas treated fibers. The results obtained from the weight of the samples verified the successful grafting of the fluoromonomer on the cotton fabrics.