Plasma-induced grafting of polydimethylsiloxane onto polyurethane surface: Characterization and in vitro assay

Plasma-induced grafting of polydimethylsiloxane (PDMS) onto the surface of polyurethane (PU) film. The virgin, plasma treated, and PDMS grafted PU films were characterized by means of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, water drop contact angle measurements, and scanning electron microscopy (SEM). The ATR-FTIR spectrogram of the grafted film showed the new characteristic peaks of PDMS. These grafted surfaces exhibited higher hydrophobicity and homogenous morphology. In vitro cell culture study showed that modified surfaces as well as virgin film were compatible with fibroblast cells. The formation of graft polymers combines the biostability of silicone with excellent physical and mechanical properties of PU.     

New biocompatible polypyrrole-based films with good blood compatibility and high electrical conductivity

A novel O-butyryl chitosan (OBCS)-grafted polypyrrole (PPy) film was described. The immobilization was accomplished by photocrosslinking the OBCS onto PPy films under ultraviolet light irradiation. The surfaces of OBCS-grafted PPy film were characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and electron spectroscopy for chemical analysis (ESCA). The blood compatibility of the OBCS-grafted PPy film was evaluated by platelet-rich plasma (PRP) contacting experiments and protein adsorption experiments in vitro. These results have demonstrated that the surface with immobilized OBCS shows much less platelet adhesive and fibrinogen adsorption compared to the control surface. The bulk conductivity values of PPy films were measured by a modified four-probe method. The composite films have both good blood compatibility and high electrical conductivity that make them suitable for using as potential biomaterials, such as electrically conducting blood vessel and functionally haemocompatible substrate of biosensor used directly in whole blood.     

Average orientation of a molecular rotor embedded in a Langmuir-Blodgett monolayer

A molecular rotor in which a naphthalene rotator is attached through a silicon atom to three fatty acid chains has been synthesized, and Langmuir-Blodgett techniques were used to deposit on silica surfaces monolayers of its calcium salt, both neat and diluted with stearic acid salts. The monolayer films have been characterized by ellipsometry and Fourier transform infrared (FT-IR) grazing-incidence attenuated total internal reflection (GATR) spectroscopy on Si-SiO(2) and by UV-vis absorption spectroscopy on SiO(2). The measurements were combined with calculations of the electronic (INDO/S) and vibrational (DFT) transition moment directions to deduce the average orientation of the rotor molecules, including the naphthalene ring, relative to the surface. In both neat and mixed films, the naphthalene ring is found to preferentially tilt toward the surface, enough that its rotation is most likely hindered. A comparable picture was obtained from molecular mechanics calculations on a mixed film of the naphthalene rotor and stearic acid.     

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.     

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

In situ photoelastic‐modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the cross‐linked film. This high water activity at the interface leads to a reversible wet de‐adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S–Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross‐linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

Oxidation of polyethylene surface by corona discharge and the subsequent graft polymerization

Oxidation of a polyethylene (PE) surface by corona discharge and the subsequent graft polymerization of acrylamide (AAm) were studied. The maximum amount of peroxides introduced by corona treatment at a voltage of 15 kV was about 2.3 × 10^?9 mol cm^?2. The decomposition rate of peroxide and the dependence of graft amount on the storage period of the corona-treated PE films showed that there were several kinds of peroxides, the labile one being mainly responsible for the initiation of graft polymerization. When the corona-treated film was brought into contact with a deaerated aqueous solution of AAm, graft polymerization took place more strongly with the treatment time, but was reduced after passing a maximum. Although the x-ray photoelectron spectroscopic analyses of the corona-treated PE films showed homogeneous oxidation of the outer polymer surface by corona discharge, optical microscopy on the cross section of the grafted film revealed the graft polymerization to be limited to a very thin surface region.     

不饱和糖功能单体接枝聚氨酯膜的制备及其血液相容性

通过葡萄糖、丙烯酸羟乙酯和丁二胺反应,制备了含不饱和双键的糖基功能单体。 采用傅里叶红外光谱和核磁共振氢谱对合成的产物进行结构表征确定。 采用紫外光引发接枝聚合技术,将制备的不饱和糖单体接枝聚合到聚氨酯膜的表面,以衰减全反射模式下傅里叶红外光谱对表面接枝反应进行了确认。 通过静态水接触角实验和血小板黏附实验,分别对改性聚氨酯膜表面的亲水性和血液相容性进行了研究,结果表明,改性聚氨酯膜表面的接触角从86°降低到45°,血小板的粘附量由14.36×10³ cells/mm²减少到2.57×10³ cells/mm²,亲水性明显增强,血液相容性显著改善。     

壳聚糖/聚乙烯醇共混膜在织物化学镀中的应用

天然高分子壳聚糖(CS)与聚乙烯醇(PVA)共混后存在强烈的氢键作用能够促进二者相容,形成互穿网络(IPN)结构的CS/PVA二元共混膜。 通过傅里叶红外(FT-IR)和强力测试对共混膜结构及拉伸强力性能进行了表征。 利用掺杂少量氯化钯的CS与PVA共混液的成膜性能,在涤纶织物表面预制一层具有自催化活性的薄膜,并对经过处理后的涤纶织物进行化学镀镍研究。 采用扫描电子显微镜(SEM)、热重分析(TG)、电磁屏蔽效能测试和水洗牢度测试,分别对织物表面形貌、热稳定性、电磁屏蔽性能和结合牢度进行测试。 结果表明,CS与PVA共混液处理后的涤纶织物,经化学镀镍能获得表面均匀致密、导电性优良、与织物结合力良好的镀层。     

Effect of Corona Discharge Treatment on the Dyeability of Low-Density Polyethylene Film

The effect of corona discharge on low-density polyethylene (LDPE) film was studied in terms of surface functionality and surface energetics of the film surfaces, improving the dyeability. The introduction of a polar group (O=C-O, C=O, and C-O) to a corona-treated LDPE film with acrylic acid could be confirmed by ESCA. The Owens-Wendt and Wu models using geometric means were studied to analyze the surface free energy of corona-treated film. It was found that the corona-treated LDPE film did lead to an increase in surface free energy, mainly due to the increase of its specific (or polar) component as the corona discharge power increased. Also, the K/S values were increased as the concentrations of dye increased. From the acid-base interaction point of view, it was found that the graft polymerization of acrylic acid onto the corona-treated LDPE film plays an important role in growing the acidic character which is one of the specific components of surface free energy, resulting in improving the dyeability with basic dyeing agent. A direct linear relationship is shown between the O(1s)/C(1s) ratio and the resulting K/S value or the specific component for this work. Copyright 2001 Academic Press.     

Characterisation of the aluminium–electropolymerised poly(3,4-ethylenedioxythiophene) system

Poly(3,4-ethylenedioxythiophene) (PEDOT) was electropolymerised on aluminium substrates. The Al/Al oxide/PEDOT junction was studied by electrochemical impedance spectroscopy, comparing the impedance response of the polymer film in oxidised, neutral and reduced form. The p- and n-doping behaviour of the PEDOT films was studied by in situ external reflection Fourier transform infrared spectroscopy during stepwise potential cycling of the films. The Al surface underneath the polymer was analysed with X-ray photoelectron spectroscopy. The impedance spectra indicate that an insulating layer between the metal and the polymer grows thicker during doping of the polymer film. The other techniques used suggest that this interfacial layer consists mainly of Al oxides and fluorides. Neither the conductivity nor the dopability of the polymer is notably affected by the growing of this insulating interfacial layer, which makes the concept of PEDOT electropolymerised on Al promising from an organic electronics applications point of view.     

Deposition of polyacrylic acid films on PDMS substrate in dielectric barrier corona discharge at atmospheric pressure

This paper reports on deposition of acrylic acid films polymerized by an efficient and cost‐effective technique of dielectric barrier corona discharge at atmospheric pressure. The liquid acrylic acid was vaporized and carried by argon gas into plasma to deposit polyacrylic acid films on polydimethylsiloxane substrate. A nonthermal corona discharge was generated in a pyrex flask using a steel tube‐to‐plate asymmetric electrode configuration. The plasma was excited using an in‐house developed power supply operating with continuous wave signals of 10‐kHz frequency. The emission spectra of plasma species were recorded to know their contribution during deposition process. The deposited surfaces were characterized using contact angle measurements, atomic force microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy and film thickness measurements. A maximum film growth rate of 363 nm/min was achieved under optimal condition of discharge. The results suggest that this plasma technique is capable of depositing organic coatings with a high concentration of carboxylic functional groups that could be potentially used for biomedical and microfluidic applications.     

Structure Studies on Ion Coordination in 2,4-Dihydroxy-N-Octadecybenzylideneamine LB Films by UV-Vis Absorption and FTIR Spectroscopy

The coordination reaction of Cu(2+) ions with the Schiff base amphiphile 2,4-dihydroxy-N-octadecylbenzylideneamine in ultrathin organic LB films was probed by Fourier transform infrared (FTIR) transmission spectroscopy and UV-Vis electronic absorption spectroscopy. FTIR spectral changes owing to LB films of 2,4-dihydroxy-N-octadecylbenzylideneamine contacting aqueous Cu(OAC)(2) solution suggest the formation of ion-coordination films, which is corroborated by UV-Vis absorption spectra. The coordination reaction of the annealing film at different temperatures suggests that the microstructure of LB films had an important effect on the reaction rate. Detailed analysis shows that ion-coordination films take an isotropic unaxial orientation and exhibit phase transition behavior, which is determined by the different complex structures of headgroups and of subphase and surface film. Copyright 2000 Academic Press.     

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization of glycidyl methacrylate and its relevance to the electroless deposition of copper

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization and deposition of glycidyl methacrylate (GMA) was carried out. The effects of glow‐discharge conditions on the chemical structure and composition of the deposited GMA polymer were analyzed by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. XPS and FTIR results revealed that the epoxide groups in the plasma‐polymerized GMA (pp‐GMA) layer had been preserved to various extents, depending on the plasma deposition conditions. The morphology of the modified PTFE surface was investigated by atomic force microscopy (AFM). The pp‐GMA film with well‐preserved epoxide groups was used as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper on the PTFE film. The T‐peel adhesion test results showed that the adhesion strength between the electrolessly deposited copper and the pp‐GMA‐modified PTFE (pp‐GMA‐PTFE) film was much higher than that between the electrolessly deposited copper and the pristine or the Ar plasma‐treated PTFE film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3498–3509, 2000     

Multi-dimensional spectroscopy of polymer films; surface and interfacial interactions

Behavior of macromolecules near surfaces and interfaces of polymeric thin films and coatings may play a vital role in numerous applications. Therefore, understanding of molecular level processes responsible for durability, adhesion, and many other macroscopic processes is of a particular importance. This presentation will focus on stratification processes in multi-component polymeric films, with particular emphasis to polymer-surfactant interactions in latexes, responsiveness of individual components during coalescence of water-borne polyurethanes, and behavior of thermoplastic olefins (TPO). The presence of macromolecular arrangements and interactions among various components near the film-air (F-A) and the film-substrate (F-S) interfaces can be effectively monitored using attenuated total reflectance (ATR) and step-scan photoacoustic (SS-PA) Fourier transform infrared (FT-IR) spectroscopy. Both approaches are capable of obtaining information from various surface depths and complement each other if one seeks molecular level information from 0 – 150 μm into the film. If one combines ATR and PA information with IR and/or Raman surface imaging, it is possible to obtain a 3-dimensional representation of polymeric films.     

Surface modification of LDPE film by CO2 pulsed laser irradiation

The influence of the pulsed CO₂ laser irradiation on the surface structure of the LDPE film was investigated. Significant changes were observed on the surface of laser treated films as it was verified by the attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy and contact angle-measurement. Formation of polar functional groups onto the LDPE surfaces exhibited by the ATR-FTIR spectra was shown to be strongly dependent on the number of the CO₂ laser pulses. The intensity of the polar groups increased with increasing the number of pulses up to two and then slightly decreased at three laser pulses. This was also confirmed with the contact angle measurements in which the sample subjected to two laser pulses showed the highest wettability i.e. the lowest water drop contact angle. The concentration of peroxide groups formed on the surface of the laser treated films was determined quantitatively by UV spectroscopic method using iodide procedure. The latter results showed a similar trend with the results obtained using FTIR spectroscopy.     

Mechanisms and energetics of hydride dissociation reactions on surfaces of plasma-deposited silicon thin films

We report results from a detailed analysis of the fundamental silicon hydride dissociation processes on silicon surfaces and discuss their implications for the surface chemical composition of plasma-deposited hydrogenated amorphous silicon (a-Si:H) thin films. The analysis is based on a synergistic combination of first-principles density functional theory (DFT) calculations of hydride dissociation on the hydrogen-terminated Si(001)-(2x1) surface and molecular-dynamics (MD) simulations of adsorbed SiH(3) radical precursor dissociation on surfaces of MD-grown a-Si:H films. Our DFT calculations reveal that, in the presence of fivefold coordinated surface Si atoms, surface trihydride species dissociate sequentially to form surface dihydrides and surface monohydrides via thermally activated pathways with reaction barriers of 0.40-0.55 eV. The presence of dangling bonds (DBs) results in lowering the activation barrier for hydride dissociation to 0.15-0.20 eV, but such DB-mediated reactions are infrequent. Our MD simulations on a-Si:H film growth surfaces indicate that surface hydride dissociation reactions are predominantly mediated by fivefold coordinated surface Si atoms, with resulting activation barriers of 0.35-0.50 eV. The results are consistent with experimental measurements of a-Si:H film surface composition using in situ attenuated total reflection Fourier transform infrared spectroscopy, which indicate that the a-Si:H surface is predominantly covered with the higher hydrides at low temperatures, while the surface monohydride, SiH((s)), becomes increasingly more dominant as the temperature is increased.     

Introduction of O-butyrylchitosan with a photosensitive hetero-bifunctional crosslinking reagent to silicone rubber film by radiation grafting and its blood compatibility

Based on an in vitro test for an improvement of the blood compatibility of silicone rubber (SR) films by grafting O-butyrylchitosan (OBCS), OBCS was covalently immobilized onto SR film surface using the photosensitive hetero-bifunctional crosslinking reagent, 4-azidobenzoic acid, which was previously bonded to OBCS by reaction between an acid group of the crosslinking reagent and a free amino group of OBCS. Surface properties of SR film were investigated by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), electron spectroscopy for chemical analysis (ESCA) and the water contact angle measurements. The blood compatibility of SR film was evaluated by platelet rich plasma (PRP) contacting experiments and the results were observed by scanning electron microscopy (SEM). The state of platelet adhesion was described. The suitable modifications could be carried out to tailor SR films biomaterial to meet the specific needs of different biomedical applications. These results suggest that the blood compatible of SR films/OBCS films show their suitability as potential biomaterials.     

Preparation and characterization of ultrathin dual-layer ionic liquid lubrication film assembled on silica surfaces

A novel ultrathin dual-layer film, which contained both bonded and mobile phases in ionic liquids (ILs) layer, was fabricated successfully on a silicon substrate modified by a self-assembled monolayer (SAM). The formation and surface properties of the films were analyzed using ellipsometer, water contact angle meter, attenuated total reflectance Fourier transform infrared spectroscopy, multi-functional X-ray photoelectron spectroscopy, and atomic force microscope. Meanwhile, the adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball-on-plate tribometer was used to evaluate the microtribological performances of the films. Compared with the single-layer ILs film deposited directly on the silicon surface, the as-prepared dual-layer film shows the improved tribological properties, which is attributed to the special chemical structure and outstanding physical properties of the dual-layer film, i.e., the strong adhesion between bonded phase of ILs and silicon substrate via the chemical bonding with SAM, the interlinked hydrogen bonds among the molecules, and two-phase structure composed of steady bonded phase with load-carrying capacity and flowable mobile phase with self-replenishment property.     

Surface characterization, modification chemistry, and separation performance of polyimide and polyamidoamine dendrimer composite films

6FDA-polyimide films modified by polyamidoamine (PAMAM) dendrimers with generations of 0, 1, and 2 are reported in this article. The actual molecular conformation and bulk size of these three generation dendrimers immobilized on polyimide surface were characterized by atomic force microscopy. After comparing with the results of dynamic simulation, we believe that the disk-shape cluster structure of dendrimers has been developed on the polymer surfaces. The amidation and cross-linking reaction between dendrimers and polyimide were examined and quantified by X-ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, and gel content measurements. Modification time and the generations of PAMAM dendrimer have been verified as two important factors in determining the properties of modified polyimide films. These modified polyimide films exhibit excellent gas separation performance. The ideal selectivity of He/N(2) increases tremendously to about 200% as compared to that of the original polyimide film. Particularly, the separation performance of CO(2)/CH(4) gas pair can be improved beyond the upper bond limit possibly due to the strong interactions of dendrimer molecules with CO(2), which was verified by sorption tests.     

Synthesis and characterization of highly ordered mesoporous thin films with -COOH terminated pore surfaces

Highly ordered mesoporous inorganic-organic hybrid thin films with covalently bonded carboxylic acid (-COOH) terminal groups on the pore surfaces were synthesized by evaporation induced self-assembly of tetraethoxysilane, organosilanes, and a nonionic surfactant followed by acid hydrolysis and characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, surface acoustic wave (SAW) based N2 sorption, and thermogravimetric analysis (TGA) techniques.