低温等离子体处理聚酯(PET)表面润湿性与表面结构的研究

研究了O₂、N₂、He、Ar、H₂和CH₄气体低温等离子体改性聚酯(PET)的表面润湿性与表面结构的关系.用已知表面张力的液体测定接触角,作Zisman曲线,求得试样的临界表面张力γ_c;并按扩展的Fowkes式计算试样的表面张力γ_s及其三组分值γ_s^a(色散力)、γ_s^c(偶极矩力)和γ(氢键力),发现经O₂、N₂、He和Ar等离子体短时间处理的聚酯表面自由能显著增大,表面润湿性增强,主要是聚酯表面张力的氢键力成分的贡献,X射线光电子能谱分析表明,这是由于聚酯表面含氧或含氮极性基团增加所致.     

聚二甲基硅氧烷-聚苯乙烯复合微流控芯片室温不可逆封合法的研究

研究了一种基于紫外光/臭氧(UV/O₃)表面改性和硅烷化技术的聚二甲基硅氧烷(PDMS)与聚苯乙烯(PS)的不可逆封合的新方法. 首先, 用UV/O₃处理PS使其表面产生羟基、羧基等极性基团; 然后用3-氨丙基三乙氧基硅烷(APTES)对UV/O₃处理后的PS硅烷化, 使其表面形成氨丙基硅分子链; 再将硅烷化后的PS与拟封合的PDMS同时用UV/O₃处理, 使两者表面均产生硅羟基. 最后将处理后的PDMS与PS贴合, 通过硅羟基之间的缩合实现两者的不可逆封合. 以接触角、XPS和ATR-FT-IR对封合过程进行表征. 封合的PDMS-PS复合芯片可承受大于0.5 MPa的压强. 采用该方法制备了PDMS-PS复合微流控芯片用于HeLa细胞的培养. 实验表明, HeLa细胞在PDMS-PS复合芯片通道内的生长状况大大优于在全PS芯片、略好于在全PDMS芯片内的生长状况.     

表面接枝含氟苯乙烯共聚物的聚酯薄膜制备与表征

利用表面引发原子转移自由基聚合(SI-ATRP)在聚对苯二甲酸乙二醇酯(PET)薄膜表面接枝苯乙烯和4-氟苯乙烯的共聚物.研究不同反应时间和不同配比下接枝共聚物对聚酯薄膜表面组成、结构和性能的影响.通过傅利叶变换红外光谱仪(ATR/FTIR),X-射线光电子能谱仪(XPS),凝胶渗透色谱(GPC)和扫描电子显微镜(SEM)对接枝改性前后PET薄膜的表面组成,结构和形貌进行分析;利用接触角测试和表面能计算对比研究接枝改性前后PET薄膜的表面性能.结果表明反应时间和单体百分含量对接枝百分率及接触角有一定的影响,随着反应时间的增长,聚酯薄膜表面接枝百分率增大,接触角增加,表面自由能下降.     

辐射接枝法制备动态超疏水棉织物及其性能研究

以棉织物为基材,利用γ-射线辐射引发甲基丙烯酸十二烷基酯(LMA)接枝聚合,使聚苯乙烯(PS)纳米微球通过接枝链以共价键固定到棉织物上,从而在棉织物表面构筑低表面能的纳米尺度粗糙结构,获得低滚动角的动态超疏水棉织物.傅里叶变换红外光谱(FTIR)分析证明通过辐射接枝,在棉织物上存在PLMA接枝链和PS纳米微球.扫描电子显微镜(SEM)表征证明了PS纳米微球的固定使得棉织物表面呈现纳米尺度的粗糙结构.接触角测试结果证明所获棉织物具有超疏水性能,且相对于仅接枝LMA的改性棉织物,PS纳米微球的固定可以显著降低水滴的滚动角,实现动态超疏水的效果.通过抗弯刚度的测量表征了改性前后棉织物的柔软度,结果表明辐射接枝方法对棉织物的柔软度改变不大,不影响穿着性能.     

碳氟等离子体改性PET表面的反应机制的研究

利用CF₄与cH₄/CF₄等离子体来处理涤沦膜(PET),讨论了不同摩尔比的碳氟等离子体改性PET表面的作用机制.利用变角x光电子能谱(XPS)和接触角测试技术研究了改性后PET表面的结构和性质.结果表明,碳氟等离子体的处理可以显著地改善PET表面的憎水性.不同摩尔比的碳氟混合气体的作用机制不同,其中碳氟混合气体等离子体以聚合为主,在PET表面形成均匀的改性层;而纯CF₄气体则以刻蚀为主,含氟基团主要分布在PET表面.     

具有高离子识别能力的镉离子表面印迹材料的制备及其离子识别机理的研究

采用氨基-过硫酸盐氧化还原引发体系, 先实现了甲基丙烯酸羟乙酯(HEMA)在微米级硅胶微粒表面的引发接枝聚合, 制得高接枝度的接枝微粒PHEMA/SiO₂. 然后使接枝大分子PHEMA的侧羟基与5-氯-8-羟基喹啉(CHQ)发生亲核取代反应, 将8-羟基喹啉(HQ)基团键合在接枝大分子侧链, 使接枝大分子PHEMA实现8-羟基喹啉功能化转变, 制得表面含有高密度HQ基团的功能接枝微粒HQ-PHEMA/SiO₂, 考察研究了功能微粒HQ-PHEMA/SiO₂对Cd²⁺离子的强螯合吸附作用. 在此基础上, 采用本课题组建立的新的分子表面印迹技术, 以Cd²⁺离子为模板离子, 二氯乙醚为交联剂, 对接枝在硅胶表面的功能大分子链HQ-PHEMA进行了离子印迹, 制备了Cd²⁺离子表面印迹材料IIP-HQP/SiO₂, 深入考察研究了其离子识别与结合特性. 实验结果表明, 该离子表面印迹材料对Cd²⁺离子具有特异的识别选择性与优良的结合亲和性, 相对于Cu²⁺和Pb²⁺两种对比离子, 印迹材料IIP-HQP/SiO₂对Cd²⁺离子的识别选择性系数分别高达25.52和22.91, 显示出超高的离子识别能力.     

接枝丙烯酰胺改善聚乙烯膜表面亲水性的研究

利用等离子体技术和紫外照射接枝相结合在聚乙烯膜表面接枝丙烯酰胺(AAm)以改善其亲水性。通过衰减全反射红外光谱(ATR-FTIR)、X射线光电子能谱(XPS)和接触角测定验证了在无光引发剂的条件下,将等离子体预处理和紫外照射接枝结合起来可以有效地提高AAm的接枝效果,很好地改善PE膜表面的亲水性。探讨了等离子体复合参数W/(FM)、等离子体预处理时间、AAm单体浓度以及紫外照射时间对改善PE膜表面亲水性的影响,确定改善PE膜表面亲水性的最佳实验条件。     

聚酯薄膜表面接枝含硅氧烷共聚物及微生物黏附性研究

通过表面引发原子转移自由基聚合(SI-ATRP)在聚对苯二甲酸乙二醇酯(PET)薄膜表面接枝聚苯乙烯-聚二甲基硅氧烷嵌段共聚物(PET-g-PS-b-PDMS),制备具有强疏水性表面的聚酯薄膜.利用X-射线光电子能谱仪(XPS),傅里叶变换红外光谱仪(FTIR/ATR),场发射扫描电镜(FESEM)对改性前后聚酯薄膜的表面组成、结构和形貌进行分析与表征;利用接触角测试仪和微生物黏附实验对比研究接枝改性前后PET薄膜的润湿性和对微生物黏附性的影响.结果表明,随反应时间延长,聚酯薄膜表面接枝量增加,水接触角增大.当接枝聚合反应时间为12 h,接枝密度可达0.72 mg/cm2,接触角达到126°,薄膜表面细菌黏附量也随之降到最低.     

硫酸锰存在下亚硫酸氢钠引发丙烯酰胺水溶液聚合反应的研究

K₂S₂O₈-NaHSO₃是目前工业生产上广泛使用的丙烯酰胺(AM)聚合引发体系。该体系优点很多,但缺点是 O₂ 的存在会明显延长聚合诱导期和使聚合产物分子量下降,而且残存的K₂S₂O₈会导致聚合物降解。单独使用NaHSO₃也能引发AM聚合,但 O₂ 的阻聚作用仍未消除。本文通过加催化剂,组成一个有自己特色的AM聚合引发体系。     

Ag-ZSM-5催化剂上CH4选择催化还原NOx的研究

摘要研究Ag-ZSM-5催化剂上CH₄选择性催化还原NO_x的反应性能,采用TPD和TPSR技术研究NO和O₂共吸附于Ag-ZSM-5催化剂表面形成的吸附物种及其和CH₄之间的反应。结果表明,Ag-ZSM-5催化剂上CH₄选择性还原NO_x活性和选择性较高。NO和O₂共吸附在Ag-ZSM-5催化剂上形成的NO₃(s)吸附物种能被CH₄还原生成N₂.在NO₃(s)和O₂共存的体系中,CH₄能优先并选择性还原NO₃(s)生成N₂.     

颗粒模板法制备大孔Al2O3材料

采用颗粒模板法制备了大孔氧化铝(Al2O3)材料. 扫描电子显微镜(SEM)结果显示, 大孔Al2O3结构中的大孔呈“囊泡状”且孔道的贯通性较差. Zeta电位测量表明, 共沉积条件下聚苯乙烯(PS)和Al2O3两种胶体颗粒带有相反的电荷, 在静电引力作用下先发生了吸附, 再沉积在一起. 吸附在PS微球表面的Al2O3纳米颗粒形成的吸附层是导致大孔呈“囊泡状”和孔道不贯通的主要原因. 采用聚二烯丙基二甲基氯化铵(PD)溶液对PS胶体微球带电性质进行了改性, PS微球的Zeta电位由−44.36 mV变成了+37.41 mV, 进而消除了沉积过程中二元颗粒间的吸附现象. 扫描电子显微镜显示, 大孔样品中“囊泡状”大孔消失, 同时孔道贯通性得到改善.     

Ultralow energy ion beam surface modification of low density polyethylene

Ultralow energy Ar+ and O+ ion beam irradiation of low density polyethylene has been carried out under controlled dose and monoenergetic conditions. XPS of Ar+-treated surfaces exposed to ambient atmosphere show that the bombardment of 50 eV Ar+ ions at a total dose of 10(16) cm(-2) gives rise to very reactive surfaces with oxygen incorporation at about 50% of the species present in the upper surface layer. Using pure O+ beam irradiation, comparatively low O incorporation is achieved without exposure to atmosphere (approximately 13% O in the upper surface). However, if the surface is activated by Ar+ pretreatment, then large oxygen contents can be achieved under subsequent O+ irradiation (up to 48% O). The results show that for very low energy (20 eV) oxygen ions there is a dose threshold of about 5 x 10(15) cm(-2) before surface oxygen incorporation is observed. It appears that, for both Ar+ and O+ ions in this regime, the degree of surface modification is only very weakly dependent on the ion energy. The results suggest that in the nonequilibrium plasma treatment of polymers, where the ion flux is typically 10(18) m(-2) s(-1), low energy ions (<50 eV) may be responsible for surface chemical modification.     

Synthesis of PS and PDMAEMA mixed polymer brushes on the surface of layered silicate and their application in pickering suspension polymerization

An ammonium free radical initiator was ion exchanged onto the surface of clay layers. Polystyrene (PS) and poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) mixed polymer brushes on the surface of clay layers were prepared by in situ free radical polymerization. PS colloid particles armored by clay layers with mixed polymer brushes were prepared by Pickering suspension polymerization. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to characterize the structure and morphology of the colloid particles. Clay layers on the surface of PS colloid particles can be observed. Because of the cationic nature of the PDMAEMA brushes the colloid particles have positive zeta potentials at low pH values. X‐ray photoelectron spectroscopy (XPS) was used to analyze the surface of the colloid particles. N_1s binding energy of PDMAEMA chains on the surface of clay layers was detected by XPS. The two peaks of the N_1s binding energy indicate two different nitrogen environments on the surface of clay layers. The peak with a lower binding energy is characteristic of neutral nitrogen on PDMAEMA chains, and the peak with a higher binding energy is attributed to protonated nitrogen on PDMAEMA chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5759–5769, 2007     

Comparison of protein surface attachment on untreated and plasma immersion ion implantation treated polystyrene: protein islands and carpet

Surface attachment of the enzyme horseradish peroxidase (HRP) was studied on untreated and ion beam implanted polystyrene (PS) films. The PS films of 100 nm thickness on a silicon wafer were treated using the plasma immersion ion implantation (PIII) technique, with argon ions of energy 20 keV and fluences of up to 2 x 10(16) ions/cm2. Differential transmittance Fourier transform infrared (FTIR) spectra confirmed the presence of proteins on the PS surfaces by detection of the amide A, I, and II protein vibrations. Spectroscopic ellipsometry over the UV-vis spectral region provided the optical constants and thickness of the protein layer, while tapping mode atomic force microscopy (AFM) was used to image the protein distribution on the surface. The combination of AFM, ellipsometry, and FTIR analysis showed that, on the untreated PS surface, HRP formed islands 8 nm in height and 30 nm in lateral size, covering approximately 27% of the PS surface. After PIII modification of the PS surface, the protein covered 100% of the surface area.     

XPS研究等离子体处理的聚苯乙烯表面结构

采用不同功率(10、20、60、100、150W)、时间(0.5、1、3、6、15和30分),在Ar、N_2、O_2、H_2和空气中,对聚苯乙烯(PS)片基进行了等离子体处理。 通过XPS技术、谱图的拟合、差谱分析和Ar~+小功率剖面处理,研究了PS表面组成与结构变化,指出处理的聚苯乙烯表面有C—O、C—NH_2、C=O、COOH和基团嵌入,因而改变了材料特性。     

HREELS investigation of the surfaces of nanocrystalline diamond films oxidized by different processes

This article reports on the use of high-resolution electron energy loss spectroscopy (HREELS) for the investigation of as-grown (hydrogen-terminated) and oxidized nanocrystalline diamond films (NCD) using chemical, physical, and electrochemical approaches. The results indicate that the nature and number of oxygen-related chemical groups generated on the NCD surface depend strongly on the oxidation process. A high concentration of C-O functions has been obtained on the NCD surface oxidized by rf (radio frequency) oxygen plasma, whereas the highest C═O/C-O ratio has been achieved by electrochemical oxidation. The NCD surface oxidized by rf plasma was totally free of C═O groups. Traces of surface hydroxyl groups (C-OH) have been detected upon annealing in air or through UV/ozone oxidation.     

Effects of atmospheric plasma treatment on the interfacial characteristics of ethylene-vinyl acetate/polyurethane composites

The surface characteristics of ethylene-vinyl acetate (EVA) were modified by argon, air, and oxygen plasma at atmospheric pressure. The surface energies of the EVA were evaluated by contact angles according to a sessile-drop method and adhesion energy (G(IC)) was estimated by a 180 degrees peel test with polyurethane (PU). After the plasma treatments, the surface free energies (or specific polar component) of the EVA increased about five times compared to that of virgin EVA. The adhesion between the EVA and the PU is significantly improved by the plasma treatment. Especially, Ar/air/O(2) plasma treatment increases G(IC) of EVA/PU up to about 600% compared to that of the sample using virgin EVA.     

Effect of cold atmospheric plasma treatment on hydrophilic properties of fluorosilicone rubber

Vulcanized fluorosilicone rubber for aviation was treated by argon and oxygen cold atmospheric plasma (CAP) in order to modify its hydrophilic properties. The sample's chemical composition was analyzed by X‐ray photoelectron spectroscopy (XPS). The static contact angle, surface free energy, and adhesion strength were used to indicate the hydrophilic properties. Additionally, the surface morphologies of the specimens were observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results showed that the contact angle declined from 101.5° to 22°, and the surface energy rose from 21.3 to 71.2 mJ/m² after they were treated by argon plasma. Alternatively, the water contact angle decreased to 25.5°, and the surface energy increased to 70.6 mJ/m² after they were treated by oxygen plasma. In addition, the SEM and AFM images of the samples illustrate that the treated surface of fluorosilicone rubber becomes rougher than the non‐treated surface. The concentrations of carbon (C) and fluorine (F) elements of the material' surface decreased and the contents of O element greatly enriched after plasma treatment. Additionally, chemical group C―O and C―OH appeared after the treatment. However, the hydrophilic effect of the plasma treatment is aged after the specimens were stored for 8–12 h. Copyright © 2016 John Wiley & Sons, Ltd.     

多孔硅的XPS研究

对两类孔硅样品测量X射线光电子能谱（XPS）：一类为在空气中放置近一年的多孔硅,另一类为HF处理后的具有新鲜表面的多孔硅。通过分析Si2p和O1a芯能级谱可以得到以下结论：新制备的多孔硅表面只有少量的O和F存在,其中氧是以OH^-形式存在,它的形成与清洗过程中F^-被OH^-取代有关。随着放置时间的增加,表面逐渐被氧化,形成正化学计量比的SiO2,而随着从表层向内的深入,逐渐变为次氧化物。结果表明刚制备的多孔硅与大气中放置氧化后的样品表面态的类型是不一致的。     

Surface modification of clay-coated paper by atmospheric-pressure plasma in air

The aim of this work was the wettability improvement of clay-coated paper by ambient air plasma exposure. Industrial corona with a volume dielectric barrier discharge in cylindrical configuration was used as a plasma source; the exposure times varied from 0.25 up to 5 s. Water contact angle (WCA) measurement and surface free energy (SFE) evaluation were carried out for the estimation of wettability changes. Plasma treatment in the duration of 0.25 s was sufficient to decrease the WCA almost to the half of the original value, which was 76°. SFE of paper has increased by 40%–50% after plasma treatment. Long-term ageing effect study of treated samples was carried out up to 3 months after the treatment. WCA did not reach the original value even after 3 months, and it was still 20%–30% lower. O/C ratio increased from 0.7 to 1.8 in case of 5-s plasma treatment, and the new chemical bonds (C=O, O–C=O) were created on the surface.