单分散氟烷基改性双疏SiO2球的制备

本文通过化学嫁接法引入氟烷基,对溶胶-凝胶法制得的单分散二氧化硅进行改性,得到了油水双疏的纳米二氧化硅小球,并考察了水和氟烷基硅烷对颗粒形貌及双疏性的影响。采用傅立叶红外光谱仪(FTIR)、扫描电子显微镜(SEM)、接触角测量仪(CA)及热重分析(TG)对产物进行了表征。结果表明,一定范围内延迟氟烷基硅烷的加入时间和增加水含量,可得到分散性、均匀性和双疏性都较好的表面改性SiO2球。增加氟烷基硅烷量,改性SiO2球的双疏性增强,但是分散性和均匀性变差,并出现了不规则形貌颗粒。     

聚偏氟乙烯接枝3-苯基丙烯酸的改性研究

以过氧化对苯二甲酰(BPO)为引发剂,3-苯基丙烯酸为单体,在N,N-二甲基甲酰胺溶液中引发接枝聚合,制得接枝3-苯基丙烯酸的聚偏氟乙烯.通过红外测试、差示扫描量热仪以及热失重分析表明3-苯基丙烯酸(CA)接枝到PVDF骨架上.通过接触角测试,发现改性后的聚偏氟乙烯(PVDF-g-P(CA))的接触角由88°降低到54...     

改性硅藻土/聚偏氟乙烯-六氟丙烯共聚物插层结构多孔聚合物电解质的制备及电化学性能EI北大核心CSCD

采用聚偏氟乙烯-六氟丙烯共聚物[P(VDF-HFP)]为基体,掺杂不同质量分数的表面改性硅藻土,通过浇铸-热压法制膜。利用扫描电镜、X射线衍射、热重-差示扫描量热法、交流阻抗法等测试手段对电解质膜的物理和电化学性能进行了表征与测试。实验表明,添加2%改性硅藻土的聚合物电解质膜相比于纯聚合物电解质膜的孔隙率、吸液率和热稳定性都有所提高,结晶度降低,界面稳定性极大改善,电导率(30℃)和电化学稳定窗口分别达2.90 mS/cm和5.5V。表明在聚合物基体中嵌入高开孔结构的硅藻土构成插层结构的方案具有取代造孔剂制膜方法的可能性。     

臭氧引发接枝制备聚偏氟乙烯亲水膜

利用臭氧的强氧化性,对溶解在N-甲基吡咯烷酮中的聚偏氟乙烯进行处理引入过氧基团,然后通过热引发接枝聚合亲水性聚乙二醇甲基丙烯酸酯(PEGMA),通过相转变法(phase inversion)制备具备亲水特性的PVDF分离膜.通过红外光谱、热重分析和接触角测试对接枝改性后的聚偏氟乙烯的结构和性能进行表征.红外光谱显示在1 734 cm-1处出现PEGMA的特征吸收峰,表明已成功接枝上PEGMA.接枝后的PVDF膜接触角降低到42°,表现出很好的亲水性;同时研究了接枝条件对改性膜亲水性的影响,随接枝单体浓度增加其亲水性增大;改性前后的聚偏氟乙烯膜的表面形貌通过扫描电子显微镜(SEM)分析表明,在相同成膜条件下改性后分离膜表面形貌发生很大变化,改性后制备的分离膜有较大的膜孔出现;水通量测试和牛血清蛋白吸附实验进一步表明,接枝改性可以明显改善PVDF分离膜的亲水性和抗污染性能.     

含有不饱和键氟聚合物的合成与表征

用商业化的偏氟乙烯-三氟氯乙烯共聚物(P(VDF-co-CTFE))为起始原料,以叔胺为催化剂制备了含有不饱和键的氟聚合物。分别用核磁共振(NMR)、热重分析(TGA)、力学性能测试等表征了所得到的聚合物。结果表明,在N-甲基吡咯烷酮(NMP)中,以三乙胺(TEA)为催化剂,消去反应可以很好地被控制;催化剂的浓度、碱性和位阻效应,溶剂的极性及其吸收HCl的能力,反应时间和反应温度影响着P(VDF-co-CTFE)的脱氯化氢反应;含不饱和键的氟聚合物可以用过氧化物固化,得到的交联氟聚合物热稳定性和抗溶剂性有所提高,同时,交联聚合物薄膜的断裂强度从原始聚合物的2.7 MPa增加到8.6 MPa,断裂伸长率则从305%增加到1131%。     

辐照剂量对偏氟乙烯-六氟丙烯共聚物结构和性能的影响

采用凝胶含量、凝胶渗透色谱、核磁共振波谱、差示扫描量热分析、热重分析、拉伸性能等表征手段,研究不同辐照剂量(60 kGy, 90 kGy, 120 kGy, 160 kGy和200 kGy)对辐照交联的偏氟乙烯-六氟丙烯共聚物(P(VDF-HFP))的结构、热性能和力学性能的影响。结果表明,在60～200 kGy辐照范围内,随着辐照剂量的增大,P(VDF-HFP)中凝胶含量增加、交联度增加,而可溶解的未交联部分相对分子质量及其分布均减小;P(VDF-HFP)的熔融温度和热分解温度均降低,600℃残炭量增加;P(VDF-HFP)的力学性能在辐照剂量60 kGy时显著改善,且断裂伸长率随辐照剂量的增加而降低。本研究对P(VDF-HFP)形状记忆材料的性能提升和应用提供了有力的理论支持。     

纳米二氧化硅补强可生物降解聚酯弹性体的制备与性能

通过原位聚合和界面改性,制备出SiO2含量0phr～20phr(质量份数)的纳米SiO2/聚(癸二酸-丙三醇-柠檬酸)酯复合材料,并研究了其结构与性能。力学性能测试结果表明,改性纳米SiO2对弹性体表现出了优异的补强效果,拉伸强度可从0.9MPa提高到5.3MPa;扫描电镜(SEM)和透射电镜(TEM)表明,SiO2以纳米网络状态分散于基体中,与基体间界面结合良好;X射线衍射(XRD)谱图从分子短程相互作用的角度反映出SiO2的存在不利于有序结构的生成;差示扫描量热(DSC)曲线显示,随SiO2含量增加,材料的Tg向低温方向移动;降解性能测试表明,SiO2的加入有助于调节材料的降解速度。     

KH570改性SiO2复合耐腐蚀涂层结构及性能

采用溶胶-凝胶法,以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH570)改性正硅酸乙酯(TEOS)水解聚合物,在钢片上制备有机-无机复合防腐薄膜。通过傅里叶红外光谱(FTIR)、扫描电镜(SEM)等测试手段研究薄膜材料的结构,并通过盐雾腐蚀试验和电化学阻抗谱测试对复合薄膜的防腐蚀性能进行检测,并探讨了最适加水量(R)。结果表明:随R从1增加至5,涂层防腐性能先提高后降低。R=3时,薄膜结构致密,抗腐蚀性能最好;FTIR结果表明,样品经180℃热处理后,KH570的结构无明显变化。     

丙烯腈含量对PVDF/SAN共混物性能的影响

采用乳液聚合方法制备了一系列不同丙烯腈(AN)含量的苯乙烯-丙烯腈共聚物(SAN),将其与聚偏氟乙烯(PVDF)共混,考察了AN含量对PVDF/SAN共混物性能的影响。动态力学热分析结果表明,随着AN含量增加,PVDF的Tg向高温移动,PVDF与SAN的相容性提高。X射线衍射仪测试得出PVDF结晶为α晶型,不同AN含量的SAN对PVDF的晶型没有影响。差示扫描量热分析发现PVDF及其共混物中,PVDF具有双重熔融行为。随着AN含量增加,PVDF结晶温度向低温方向有所移动,结晶能力降低。扭矩测试发现,PVDF具有较高的黏度,SAN的引入降低了PVDF的黏度。接触角结果表明SAN提高了PVDF的表面亲水性,AN含量越高,共混物极性越大,材料表面亲水性越强。     

生物可降解PLA/PHBV共混包装薄膜的热行为和力学性能研究

采用溶液铸涂法,以3-羟基丁酸酯-3-羟基戊酸酯共聚物(PHBV)对生物可降解聚乳酸(PLA)进行增韧改性,制备出不同配比的PLA/PHBV生物可降解共混包装薄膜,研究了PHBV的添加对共混包装薄膜的热行为和力学性能的影响规律。通过差示扫描量热法(DSC)测试发现,随着PHBV含量的增加,共混包装薄膜的玻璃化温度(Tg)、结晶温度(Tc)和熔点(Tm)都呈现下降趋势;热重分析法(TG)测试表明,PHBV的加入使共混包装薄膜的热稳定性变差;通过力学性能测试发现,当PHBV加入后,共混包装薄膜的拉伸强度和拉伸模量降低,而断裂伸长率明显增加,薄膜的韧性得到了改善。     

阴极真空弧源沉积氟化类金刚石薄膜的结构与性能研究

采用脉冲磁过滤阴极真空弧源沉积系统(FCVA)在单晶硅基片上制备了含氟量不同的一系列氟化类金刚石膜(a-C:F).重点研究了氟掺杂对非晶态碳基薄膜结构、机械性能和疏水性能的影响.薄膜的成分和结构采用X射线光电子能谱仪(XPS)和激光拉曼光谱(Raman)进行了表征,薄膜表面形貌和粗糙度采用原子力显微镜(AFM)进行了分析.使用纳米压痕仪测量了薄膜硬度,纳米划痕仪测量了膜基结合力.采用躺滴法测量薄膜与双蒸水之间的接触角来评价其疏水性能.结果表明,随着CF4流量的逐渐增加,薄膜的氟化程度逐渐增强,膜中最大氟含量达45.6 at%;薄膜呈典型的类金刚石状结构,但薄膜的无序化程度增强;由于-CFn+的刻蚀,薄膜表面更加致密化、粗糙度逐渐减小.薄膜的机械性能良好,硬度在12GPa以上.薄膜的疏水性能得到增强,与双蒸水之间的最大接触角达106°,接近于聚四氟乙烯(PTFE,110°).     

氟化PVA-SiO2薄膜单面疏水性的研究与表征

目的 研究开发一种具有单面疏水性能的聚乙烯醇薄膜材料作为包装材料。方法 将质量分数为12%、醇解度为88%的PVA溶液与质量分数为5%的纳米SiO2溶液按体积比为1∶1混合并加热搅拌,通过流延干燥的方式制备PVA-SiO2薄膜。然后分别用体积分数为2.5%,5%,7.5%的十七氟癸基三甲氧基硅烷（FAS）-乙醇溶液以浸泡方式修饰薄膜的其中一面,并通过溶解性测试、接触角测试、场发射扫描电子显微镜（FE-SEM）、傅里叶变换衰减全反射红外光谱测试（ATR-FTIR）等方法表征改性结果。结果 结果表明薄膜单面疏水性得到改善,改性后的薄膜在水中的溶解时间增加,且接触角均在120°以上,表明FAS起到了降低表面能的作用;FE-SEM结果显示,Si元素含量对薄膜的疏水性能有着重要影响;ATR-FTIR显示,FAS改性成功将氟原子引入到薄膜表面,且增加了硅原子的数量。其中用质量分数为5%的FAS-乙醇溶液修饰后的薄膜疏水性最好,接触角达到了126.21°。结论 与未改性薄膜相比,经FAS单面疏水改性的PVA-SiO2薄膜疏水性能得到大大提高,拓宽了PVA薄膜材料的应用领域。     

Influence of fibre treatment and glass fibre hybridisation on thermal degradation and surface energy characteristics of hemp/unsaturated polyester composites

The effect of fibre treatment on the thermal degradation and surface energy characteristics of hemp fibre reinforced unsaturated polyester (HFRUP) composites was investigated by means of a thermogravimetric analyser (TGA) in a nitrogen atmosphere and contact angle measurement. In order to modify the fibre/matrix interface, NaOH treatment and glass fibre hybridisation were employed. HFRUP composites were compared to the unreinforced UP, NaOH treated hemp and glass fibre hybridised hemp/UP composites. TGA test results show that the weight loss for all samples occurred between 200 and 415 °C. The unreinforced UP had a maximum weight loss of 1.011%/°C. For the HFRUP composites, the maximum rate of weight loss was 0.81%/°C. For the NaOH treated and glass fibre hybridised hemp/UP composites, the maximum rate of weight loss was 0.78%/°C and 0.79%/°C, respectively. The effect of fibre treatment on the surface energy of studied samples and their dispersive and polar components were also investigated. Surface energy characteristics obtained from contact angle measurement revealed that for unreinforced UP, the contact angle measured with glycerol is 49.37°. For hemp/UP composites, the contact angle is 76.05°. For NaOH treated hemp/UP composites sample, the contact angle was recorded 78.89°, higher than untreated one. For hemp/CSM/UP specimen, the contact angle was recorded 69.80°. Both TGA and contact angle results indicated that surface treatment and glass fibre hybridisation led to better thermal stability and the wetting behaviour of hemp/UP composites.     

Tailoring Surface Properties via Functionalized Hydrofluorinated Graphene Compounds

A new compound material of 2D hydrofluorinated graphene (HFG) is demonstrated whose relative hydrogen/fluorine concentrations can be tailored between the extremes of either hydrogenated graphene (HG) and fluorinated graphene (FG). The material is fabricated through subsequent exposures to indirect hydrogen plasma and xenon difluoride (XeF₂). Controlling the relative concentration in the HFG compound enables tailoring of material properties between the extremes offered by the constituent materials and in‐plane patterning produces micrometer‐scale regions with different surface properties. The utility of the technique to tailor the surface wettability, surface friction, and electrical conductivity is demonstrated. HFG compounds display wettability between the extremes of pure FG with contact angle of 95° ± 5° and pure HG with contact angle of 42° ± 2°. Similarly, the HFG surface friction may be tailored between the two extremes. Finally, the HFG electrical conductivity tunes through five orders of magnitude when transitioning from FG to HG. When combined with simulation, the electrical measurements reveal the mechanism producing the compound to be a dynamic process of adatom desorption and replacement. This study opens a new class of 2D compound materials and innovative chemical patterning with applications for atomically thin 2D circuits consisting of chemically/electrically modulated regions.     

PVDF/SiO2/PDMS涂层超疏水纺织品性能

目的 针对普通纺织品材料防水性和防污性较差的问题,制备具有自清洁功能的超疏水涂层纺织品,并研究其性能.方法 以涤纶织物为基材,通过非溶剂诱导相分离法,使用聚偏氟乙烯和疏水纳米二氧化硅复合液在纺织品表面构筑微纳粗糙结构,采用聚二甲基硅氧烷对其进行疏水化处理,获得自清洁超疏水涂层纺织品.采用扫描电子显微镜、X射线能量散射光谱和视频光学接触角测量仪等对其结构和性能进行表征,并通过机械摩擦、洗涤、酸/碱/盐溶液浸渍和紫外光照等方法对其表面超疏水稳定性进行考察.结果 当聚偏氟乙烯质量分数为2％,疏水纳米二氧化硅质量分数为0.4％,聚二甲基硅氧烷质量分数为1％时,制备的纺织品的表面接触角可达(162.2°±0.8°),滚动角达(2.0°±0.4°),具有优异的超疏水自清洁效应;经72 h酸/碱/盐溶液浸渍、196 h紫外光照、2500次摩擦和120次家庭水洗后,其表面接触角仍大于150°,表现出优异的超疏水稳定性.结论 采用简便的非溶剂相分离法制备的涂层纺织品具有优异的自清洁性能,并且其超疏水性能具有机械耐久性和化学稳定性,有望应用于纺织材料包装领域.     

Preparation and characterization of self-cleaning stable superhydrophobic linear low-density polyethylene

Abstract

Porous superhydrophobic linear low-density polyethylene (LLDPE) surface was prepared by a simple method. Its water contact angle and sliding angle were 153±2° and 10°, respectively. After contamination, 99% of the contaminant particles were removed from the superhydrophobic LLDPE surface using artificial rain. The superhydrophobic LLDPE surface showed high stability in the pH range from 2 to 13. When LLDPE samples were stored in ambient environment for one month, their water contact angle and sliding angle remained constant. Their superhydrophobic property was also maintained after annealing in the temperature range 10–90 °C.     

Surface functionalization of silk fabric by PTFE sputter coating

This paper describes the surface functionalization of woven silk fabric by magnetron sputter coating of PTFE (polytetrafluoroethylene). The PTFE sputter coating was applied to improve the hydrophobic property of silk fabric. The effects of PTFE sputter coating on surface morphology and surface chemical properties were characterized using atomic force microscopy (AFM) and ATR-FTIR (attenuated total reflection-Fourier transform infrared spectroscopy). The wettability of the fabric was characterized through measuring the surface contact angle by a dynamic sessile analysis (DSA) technique. The contact angle of the PTFE coated fabric showed a significant increase from 68° to about 138°. The experimental results also revealed that larger sputtering pressures brought less contact angle hysteresis.     

动态毛吸法测定纤维及粉末料的接触角研究

本文用动态毛吸法研究了表面处理对纤维浸润性的影响,结果表明碳纤维及聚酯纤维表面经冷等离子体氧处理,浸润性有很大的改善,碳纤维约提高四倍,这是因为等离子氧表面处理过程,将含氧基团羧基,羟基及羰基等引入到表面所致。同时从测得的浸润过程表面自由能改变值△γ,计算出水对纤维的接触角,它与采用接触角测定仪倾斜法所测得的结果基本上一致。从所测得的接触角值也可以看出表面经处理之后,浸润性得以改善。如碳纤维由77°降为63°,聚酯纤维由77°降为52°。此外我们还研究了煤粉和玻璃粉体系对水的浸润性,发现水对玻璃粉的浸润性优于煤粉,前者的浸润接触角为47°、后者则为90°,此接触角值也与采用接触角测定仪由静滴法测得水对片材的接触角相一致。由此可见动态毛吸法可以用于研究纤维及粉末体系的浸润性,而且操作简单易行,测试周期短。      

Grafting of cellulose by fluorine-bearing silane coupling agents

The surface of model cellulose fibres, Avicell (AV), as well as that of Whatman paper (WP) was chemically modified with two fluorine-bearing alkoxysilane coupling agents, namely: 3,3,3-trifluoropropyl trimethoxysilane (TFPS) and 1H,1H,2H,2H,perfluorooctyl trimethoxysilane (PFOS). The occurrence of the grafting of soxhlet extracted modified cellulose was confirmed by the presence of silicon and fluorine atoms detected by elemental analysis, X-ray photoelectron spectroscopy and Electron Dispersion Energy/Scanning Electron Microscopy (EDS/SEM). The contact angle measurements showed that, after grafting, the surface of AV and WP samples became totally highly hydrophobic with a contact angle of 140°. Thus, the polar contribution to the surface energy of the modified substrates was found to be close to zero. These modified substrate could be interesting for application such as self-cleaning surface, wipes paper, grease barrier paper or for biocomposite with a polar matrix.     

MAP-POSS/不饱和环氧树脂混杂光固化膜制备与性能

由KH-570水解缩合制备甲基丙烯酰氧基丙基笼型倍半硅氧烷(MAP-POSS),并将其与不饱和环氧树脂组成自由基-阳离子混杂光固化体系。用红外光谱(FT-IR)表征固化过程特征吸收峰的变化;测试MAP-POSS含量对固化膜表面水接触角、硅元素分布以及涂膜力学性能、热性能的影响。结果表明:MAP-POSS的加入增加了体系的交联度,提高了涂膜的疏水性、热稳定性和玻璃化温度(Tg)。当MAP-POSS含量为12%(质量分数,下同)时,Tg增加了16.9℃。当MAP-POSS含量为15%时,涂膜对水的接触角由58.0°增大到94.2°。MAP-POSS的加入使涂膜的冲击强度先增加后减小。