Enhanced anti-graffiti or adhesion properties of polymers using versatile combination of fluorination and polymer grafting

Commonly used polymers and polymer articles have some advantages, e.g. low. But very often they have not very good adhesion, barrier properties, low conductivity, etc. Specialty polymers possessing necessary properties, e.g. fluoropolymers, can be used to fabricate polymer articles. However, practical use of specially synthesized polymers is restricted due to their high cost and complexity of synthesis. It is possible to coat a polymer with another polymer layer with necessary properties but this co-extrusion method is difficult to apply due to a complexity of applied equipment. Also the problems of adhesion between two polymers and polymers compatibility are to be solved. Very often application properties of polymer goods (adhesion, barrier properties, conductivity, etc.) are defined mainly by their surface properties. Hence, it is not necessary to fabricate articles from specialty polymers but simpler, cheaper, and more convenient to apply a surface treatment of articles made from commonly used relatively cheap polymers. In this case, only thin surface layer several nm to several μm in thickness is to be modified and direct fluorination (treatment with mixture of F₂ and other gases) can be effectively used. For our research we have chosen common widely used polymers. We targeted to improve hydrophobicity/hydrophylicity, adhesion properties and surface conductivity of polymers. For the first time modification of the surface of high density (HDPE), low density (LDPE) and ultrahigh molecular weight polyethylene (UHMWPE), polypropylene (PP), polyethylene terephthalate (PET) and polyvinylchloride (PVC) was performed by direct fluorination followed by a grafting of acrylic acid, styrene, acrylonitrile, vinylidene chloride, aniline and thiophene from the gas phase. Aniline grafting was studied to improve surface conductivity of polymers. Grafting of polymers was confirmed by ATR and MATR FTIR spectroscopy and energy-dispersive X-ray microprobe spectroscopy (cartography). AFM was used to study polymers surface. Influence of the nature of grafted monomers on the surface energy was studied. It was shown that depending on the nature of a grafted monomer hydrophobicity or hydrophilicity can be markedly improved. The hydrophobicity of modified polymers is not changed and is even improved with time contrary to virgin polymers. For the case of PP and UHMWPE grafting of styrene and acrylonitrile improved anti-graffiti properties (graffiti and pollutions from the polymer surface can be easier removed). For the case of HDPE and LDPE grafting of styrene and acrylonitrile improved printability. Grafting of aniline did not improved electrical conductivity. The uniformity of grafted polymers distribution was investigated by energy-dispersive X-ray microprobe spectroscopy (cartography) for the first time.     

Design and optimization of zirconia functional surfaces for dental implants applications

Zirconia is becoming a promising solution for biomedical applications, namely for dental implants, due to its biocompatibility, and mechanical and aesthetical properties. Despite the constant developments in the dentistry field, strategies to promote an effective vascularization at the implant's surface and consequently improved osseointegration are still not enough.In this sense, with the aim of promoting the vascularization at the implant's surface, zirconia surfaces with micro-channels were designed and evaluated regarding their hydrophilicity and capillarity. A CAD/CAM system was used to design and produce the specimens and different techniques were used to characterize the surfaces. The obtained average surface roughnesses are in accordance with the literature for similar materials. Results revealed that the produced materials present high levels of hydrophilicity, whether in contact with water or FBS - Fetal Bovine Serum. Additionally, micro-channels with 200 μm of width and 100 μm of depth were the ones that presented higher capillarity, thus being promising solutions for the promotion of implants vascularization, and consequently improved osseointegration.     

Improving the hydrophilicity of polyethersulfone membrane by the combination of grafting technology and reverse thermally induced phase separation method

In this work, surface grafting modification technology was combined with reverse thermally induced phase separation (RTIPS) method in order to improve the structure and permanent hydrophilicity of polyethersulfone (PES) membranes. Acrylic solution with different concentrations was grafted on the surface of PES membranes while grafting temperature and grafting time were also varied. The modified PES membranes were characterized in all aspects. Attenuated total reflectance Fourier transform-infrared confirmed successful modification of the PES membrane by grafting acrylic acid. Scanning electron microscopy revealed that homogeneous porous top surface as well as spongy-like cross-section structure appeared in the membrane by RTIPS procedure. Moreover, porosity was affected by changes of acrylic acid concentration, grafting temperature, and grafting time. Atomic force microscopy showed that grafting acrylic acid gave a reduction in roughness of PES membrane. Combined with the decreased values of contact angle, the hydrophilicity and antifouling performance of the PES membrane were improved. The pure water flux and BSA rejection rate of the grafted PES membranes were remarkably improved for pure PES membrane and attained a maximum, which was 1,646.24 L/(m²h) and 94.5%, respectively. The long-term test demonstrated that grafting membranes exhibited outstanding elevated water flux recovery ratio (>85%).     

季铵化改性氨基聚硅氧烷的合成及应用性能

采用氯乙酸乙酯对N,N-二甲基-γ-氨丙基-γ-氨丙基聚二甲基硅氧烷(ASO-121)进行季铵化改性,合成了一种季铵化改性氨基聚硅氧烷(QASO-121)。利用红外光谱(IR)、核磁共振氢谱(1HNMR)、扫描电镜(SEM)、纳米粒度仪等仪器对QASO-121及其乳液进行了表征和纤维表面的成膜性分析,并讨论了氨值、黏度及硅乳用量对所整理织物应用性能的影响。结果表明,QASO-121乳液平均粒径为75.3 nm,电位为+21.2mV,且其在织物纤维表面具有良好的成膜性。经氨值为0.6 mmol/g、黏度为2.600 Pa·s、硅乳用量为4 g/L的QASO-121整理的布样,织物柔软性提高,亲水性增强,白度基本不变。将QASO-121与未季铵化ASO-121进行应用性能对比,发现两者整理织物的柔软性相近,但经QASO-121所整理织物具有良好的亲水性且富有弹性,其抗黄变性能也得到了改善。     

N-乙烯基吡咯烷酮接枝改性聚乳酸组织工程支架的制备与性能

利用热致相分离技术制备了N-乙烯基吡咯烷酮接枝改性聚乳酸(M-PLA)组织工程支架。在接枝率36%条件下,讨论了聚合物浓度、水/二氧六环比例和粗化温度对支架孔隙度和微孔结构的影响;并进一步探讨了在相同制备工艺条件下,不同接枝率对支架结构的影响,并对M-PLA支架的亲水性和蛋白粘附性能进行测试。结果显示,在一定接枝率下,支架孔隙度随聚合物浓度增大而降低;水的添加有利于规则孔径的形成;粗化温度降低,支架孔径和孔隙度提高。与PLA支架相比,随着接枝率提高,共聚物支架孔隙度变化不大,孔径略减小,但孔隙规整性和连通性较好,亲水性和蛋白粘附率明显增大,生物相容性提高。     

丙三醇对PBST共聚酯结构和性能的影响

基于生物可降解性聚酯——聚丁二酸-共-对苯二甲酸丁二醇酯(PBST),通过原位添加不同含量的丙三醇作为第四单体,制备出共聚改性的PBST共聚酯。通过核磁共振仪(NMR)、差示扫描量热仪(DSC)、广角X射线衍射仪(WAXD)及接触角测试,分别对PBST共聚酯的结构和性能进行了研究。结果表明:丙三醇的加入并没有改变PBST共聚酯的化学组成和结构;随着丙三醇含量的增加,共聚酯的玻璃化转变温度先上升后下降,而熔点是逐步降低的;改性前后和拉伸前后PBST的晶型均未发生变化,但分子结构的规整性受到破坏,且发生拉伸诱导取向;改性PBST共聚酯的亲水性能较纯PBST有明显提高。     

热处理对TiO2薄膜制备及亲水性的影响

采用廉价的TiCl_4为前驱体水解合成TiO_2水溶胶,利用辊涂装置镀膜并通过热处理制得了一系列TiO_2薄膜。运用X射线粉末衍射(XRD)、扫描电镜(SEM)、紫外-可见光谱(UV-Vis)、光致发光谱(PL)对TiO_2薄膜进行了表征,并采用接触角测量仪考察了热处理温度、避光保存时间、UV光照时间对各薄膜亲水性的影响。结果表明,制得的薄膜不影响玻璃基材的可见光透过率;通过热处理,能有效增强薄膜对可见光的吸收能力,显著抑制光生电子和空穴的复合;当热处理温度为450℃时,TiO_2薄膜表现出了最好的亲水性,其薄膜与水的接触角达到0°。     

Effect of hydroxyl groups on hydrophilic and photocatalytic activities of rare earth doped titanium dioxide thin films

Rare earth(Y, La and Nd) doped TiO2 thin films were prepared on glass slides by sol-gel method. The photocatalytic decomposition of methylene blue in aqueous solution was used as a probe reaction to evaluate their photocatalytic activities. The effects of hydroxyl groups on hydrophilic and photocatalytic activities were investigated by means of techniques such as X-ray diffraction(XRD), atomic force microscopy(AFM), Fourier transform infrared(FTIR), optical contact angle, UV-Visible spectroscopy and VIS spectroscopy. The results showed that an appropriate doping of rare earth could cause the TiO2 lattice distortion, inhibited phase transition from anatase to rutile, accelerated surface hydroxylation and produced more hydroxyl groups, which resulted in a denser surface and smaller grains(40–60 nm), and a significant improvement in the hydrophilicity and photoreactivity of TiO2 thin films. The optimal content of rare earth was between 0.1 wt.% and 0.3 wt.%. Moreover, the modification mechanism of rare earth doping was also discussed.