Interfacial structure and properties of polyurethane/poly(methylacrylate-co-styrene) coating to regenerated cellulose film

A semiinterpenetrating polymer network (IPN) containing 72 wt % polyurethane (PU) and 6 wt % poly(methylacrylate-co-styrene) [P(MA-St)] was coated onto surfaces of regenerated cellulose (RC) film, which was prepared by coagulating a cellulose cuoxam from bagasse pulp. The interfacial structures, bonding manner, and the strength of the coated film were studied by infrared (IR),¹³C nuclear magnetic resonance (NMR), differential thermal analysis (DTA), transmission electron microscopy (TEM), and electron probe microscopy analysis (EPMA). It was shown that the RC film coated with PU/P(MA-St) has strong interfacial interactions, where covalent and hydrogen bonds are formed across the interface between cellulose and the PU/P(MA-St) coating. The interfacial structure of the coated film is regarded as a shared PU network crosslinked simultaneously with P(MA-St) and cellulose film. The tensile strength, water resistivity, and optical transmission of the coated films were considerably higher than that of the uncoated films. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2495–2501, 1997     

Surface Enhanced Raman Scattering Sensing with Nanostructures Fabricated by Soft Nanolithography

The nanospike structures formed with femtosecond laser irradiations have been successfully replicated on the surface of a polyurethane (PU) polymer using a low cost soft nanolithography method. The surface enhanced Raman scattering (SERS) of rhodamine 6G (Rh6G) and dinitrotoluene (DNT) molecules have been measured with silver coated PU nanospike surfaces by a simple portable Raman spectrometer. Compared to a flat silver coated surface, where no Raman Scattering of the molecules can be detected by the simple portable Raman spectrometer, the Raman spectra are enhanced by more than 4 orders of magnitudes. This indicates that the high area/volume ratio and small size of the PU nanospikes can be used for SERS sensing.     

Mucin coating on polymeric material surfaces to suppress bacterial adhesion

Mucin, a group of large glycoproteins, constitutes one of the major components of mucous which covers the lumenal surfaces of epithelial organs and serves as a physical barrier between the extracellular milieu and the plasma membrane. The molecules have a generic structure consisting of a thread-like peptide backbone with densely packed carbohydrate side chains. Protein and carbohydrate contents are about 30 and 50%, respectively. On hydrophobic materials in aqueous environments the naked parts of mucin’s protein backbone will adhere due to their hydrophobicity, while the carbohydrate side chains are thought to orient themselves away from the surface. This gives the mucin molecules their unique properties as surfactants, i.e. they tend to adsorb to hydrophobic surfaces via protein-surface interactions while they hold water molecules via their hydrophilic oligosaccharide clusters. In the present work, bovine submaxillary gland mucin (BSM) is purified by SEC and subsequently characterized with PAGE. Four polymeric materials, PMMA, silicone, Tecoflex® polyurethane and polystyrene, are selected as coating targets. Contact angle measurements show significant changes in these materials after coating with BSM. Surface concentrations of adsorbed BSM are determined by amino acid analysis and found to correlate well with observed reductions in contact angle. Both Staphylococcus aureus and CNS S. epidermidis are used to contaminate uncoated and BSM coated surfaces of all four materials, demonstrating a correlation between suppression of bacterial adhesion and surface concentration of BSM. Thus, bacterial counts on the coated PMMA, PS, PU and silicone specimens amount to ≈3, 10, 8 and 30% of the counts found on their uncoated counterparts. These results suggest that mucin coatings could profitably be employed to reduce the risk of microbial infections on polymeric biomaterials.     

采用层层自组装与光化学修饰法在聚氨酯表面固定生物多糖衍生物

采用层层自组装技术与光化学修饰方法相结合在聚氨酯材料表面固定生物多糖衍生物,首先合成具有光反应活性的叠氮壳聚糖,再在聚氨酯基材表面进行叠氮壳聚糖与香菇多糖硫酸酯的层层自组装,然后通过光化学反应对自组装多层膜修饰层进行交联,制备得到生物多糖衍生物层层自组装与光化学表面修饰的聚氨酯材料.通过红外光谱、X射线光电子能谱、水接触角测量仪、抗菌活性测试、溶血试验和血小板黏附测试等方法对被修饰聚氨酯材料的表面性能和生物性能进行了分析,测试结果表明修饰后的聚氨酯材料表面的亲水性和血液相容性得到改善,并且被修饰材料对大肠杆菌具有良好的抑制效果.     

Mechanical behavior during different weathering tests of the polyurethane elastomers films

Segmented poly(ester-urethane)elastomers (PU) based on poly(ethylene diethylene adipate) diols as a soft segment and aromatic diisocyanates in the hard segment were synthesized by a conventional method. The precipitated and compact polyurethane films have been degraded after a limited exposure to natural weathering. The effects on mechanical properties of precipitated and compact polyurethane films were found to be a measure of the degradation due to weathering. The present study attempts to correlate the physical-mechanical properties of the precipitated polyurethane and compact films with time of weathering. In all cases a certain amount of oxidative change had been initiated. This was probably associated with enzyme adsorption on surfaces. We compared natural weathering of PU films carried out in earth, seawater and exposure to sunlight with untreated samples. In common with other weathering tests, the effect was to decrease the ultimate tensile strain, except seawater. It was found that enzymatic degradation in the earth occurred only after, the ageing process was continuous and practically linear with a relatively short initial period of increase in degradation rate.     

Hot press transferring of graphene nanoplatelets on polyurethane block copolymers film for electroactive shape memory devices

We report a transferring method of graphene nanoplatelets (GNPs) on polyurethane (PU) block copolymers film. We polymerized PU block copolymer films, and then, a GNP layer, deposited on glossy paper by drop casting, was transferred by hot press from the glossy surface to the synthetized PU substrate. Nanoindentation test showed that GNP coated PU substrate exhibits improved mechanical properties with respect to the neat PU film. When an electric bias was applied to the GNP coating, the heat generated by Joule effect was transferred to the PU substrate showing an electroactive shape recovery effect. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1100–1106     

Effects of molecular weight of nitrocellulose on structure and properties of polyurethane/nitrocellulose IPNs

Semi‐interpenetrating polymer network (semi‐IPN) coatings were prepared by using castor oil‐based polyurethane (PU) and nitrocellulose (NC) with various viscosity‐average molecular weights (M_η) from 6 × 10⁴ to 42 × 10⁴, and coated on a regenerated cellulose (RC) film to obtain water‐resistant film. The PU/NC coatings and coated films, which were cured at 80°C for 5 min and 2 min, respectively, were investigated by infrared (IR) and ultraviolet (UV) spectroscopy, X‐ray diffraction, swelling test, strength test, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The results show that the crosslink densities of the PU/NC semi‐IPNs were smaller than that of pure PU, and decreased with the decrease of M_η of nitrocellulose (NC M_η), indicating NC molecules cohered intimately with PU, and hindered the PU network formation. The physical and mechanical properties of the films coated with PU/NC coatings were significantly improved. With the increase of NC M_η, the strength and thermal stability of the coated films increased, but the pliability, water resistivity, and optical transmission decreased slowly. The PU/NC coating with low NC M_η more readily penetrated into the RC film, and reacted with cellulose, resulting in a strong interfacial bonding and dense surface caused by intimate blend of PU/NC in the coated films. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1623–1631, 1999     

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.     

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。     

Antibacterial HPL-DOSS surface coating for commercial plastics

Bacterial colonization and biofilm formation on the surface of materials can lead to serious bacterial infections and are highly detrimental to our health. Here, we prepared a water-insoluble HPL-DOSS complex by compounding hyperbranched polylysine (HPL) with docusate sodium salt (DOSS) and coated HPL-DOSS onto the surfaces of the commercial polypropylene (PP) and thermoplastic polyurethane (TPU) plastics to afford antibacterial PP-HD and TPU-HD plastics. PP-HD and TPU-HD showed excellent antibacterial activities against both Escherichia coli and MRSA. In addition, the bacterial residues on the PP-HD and TPU-HD surfaces were significantly reduced compared with the pristine PP and TPU surfaces, indicating that the HPL-DOSS surface coating had good anti-adhesive property against bacteria and helped to reduce the formation of biofilms. Meanwhile, both PP-HD and TPU-HD exhibited excellent biocompatibility, indicating that the HPL-DOSS complex could be used as a safe antimicrobial coating material to reduce bacterial infections on plastic surfaces.     

Properties of poly(lactic acid-co-glycolic acid) film modified by blending with polyurethane

A number of poly(lactic acid-co-glycolic acid)/polyurethane (PLGA/PU) blend films with various PU mole contents were prepared by casting the polymer blend solution in chloroform. The surface morphologies of the PLGA/PU blend films were studied by scanning electron microscopy (SEM). The thermal, mechanical and chemical properties of the PLGA/PU blend films were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile tests and surface contact angle tests. The results revealed that the introduction of PU could markedly modify the properties of PLGA films.     

Characterization of gas-expanded liquid-deposited gold nanoparticle films on substrates of varying surface energy

Dodecanethiol-stabilized gold nanoparticles (AuNPs) were deposited via a gas-expanded liquid (GXL) technique utilizing CO(2)-expanded hexane onto substrates of different surface energy. The different surface energies were achieved by coating silicon (100) substrates with various organic self-assembled monolayers (SAMs). Following the deposition of AuNP films, the films were characterized to determine the effect of substrate surface energy on nanoparticle film deposition and growth. Interestingly, the critical surface tension of a given substrate does not directly describe nanoparticle film morphology. However, the results in this study indicate a shift between layer-by-layer and island film growth based on the critical surface tension of the capping ligand. Additionally, the fraction of surface area covered by the AuNP film decreases as the oleophobic nature of the surfaces increases. On the basis of this information, the potential exists to engineer nanoparticle films with desired morphologies and characteristics.     

Preparation and characterization of waterborne polyurethanes modified with bis(3-(1-methoxy-2-hydroxypropoxy) propyl) terminated polysiloxanes

Polyurethanes(PU) were prepared using toluene diisocyanate,polypropylene glycol,ethylene glycol, dimethylolpropionic acid and triethylamine,and a siloxane modified PU(PSU) was obtained through reaction of the PU prepolymers with bis(3-(1-methoxy-2-hydroxypropoxy)propyl) terminated polysiloxanes(PMTS) of different molecular weight,specifically designed for this purpose.Results showed that,with increases in molecular weight of PMTS and its content,viscosity of the final PSU latexes decreased;phase separation of the incorporated PMTS in PSU films increased;the average particle sizes of the latexes varied between 110 nm and 330 nm,and the surface tension in the final latexes was relatively constant regardless of PMTS amount and its molecular weight.It was likely that copolymerized polysiloxanes had trend to enrich on top of the film when PMTS molecular weight was around 2000 and its content above 5 wt%.In general, PMTS modified polyurethane films showed higher performance than those from unmodified waterborne polyurethane latexes.     

仿生表面液固界面摩擦力的动态调控

仿生超疏水材料在自清洁、防雾抗冰、油水分离、集水等领域有着重要应用;而在不同疏水状态之间的转换将大大促进仿生超疏水材料在智能技术领域的应用.利用软印刷技术将玫瑰花表面微观结构转印到聚氨酯弹性体PU膜表面,利用机械应力实现表面微结构的动态实时调控,实现了表面微观结构在各向同性与各向异性之间的可逆转换;利用毛细管投影传感技...     

Characterization of nanostructure and cell compatibility of polyaniline films with different dopant acids

Polyaniline (PANi) films were prepared by direct polymerizing deposition with four different kinds of acids as dopants or were prepared by a casting method on the surface of a polytetrafluoroethylene substrate. The properties of PANi films were characterized using atomic force microscopy, electrical conductivity measurements, and water contact angle measurements. Unlike the casting PANi film, experimental results indicated that the synthesized PANi films had a similar nanostructure as that of average nanoparticles (approximate diameter of 30-50 nm). To investigate the potential usefulness of PANi films in biomedical applications, we also studied their biocompatibility through the adhesion and proliferation properties of PC-12 pheochromocytoma cells. All the films were found to be biocompatible and allowed cell attachment and proliferation. However, the synthesized films have a much higher ability for cell adhesion than the casting film. After 4 days of culture on different PANi films, the cells formed more confluent monolayers on the synthesized PANi films than on the casting films. These results demonstrate that the PANi films could be used to culture neurotic cells and that their surface architecture on the nanoscale may affect cell function such as attachment and proliferation.     

热致相分离技术制备聚氨酯多孔膜的条件控制

采用自制的模具 ,利用热致相分离 (TIPS)的原理制备了聚氨酯 (PU)多孔膜 ,并重点研究了聚合物浓度对多孔膜的表面形貌、孔度大小、孔隙率和透湿率的影响 .在不同的聚合物浓度条件下制备的PU多孔膜的共同特征是底面 (与成膜平台接触面 )光滑平整 ,孔洞尺寸较小 ,为纳米级 ;而表面 (与空气接触的自由面 )的形貌结构较为复杂 ,但都有明显的孔洞出现 ,且孔洞的尺度大于底面 ,在微米级以上 .聚氨酯 1,4 二氧六环 (DO)形成的是上临界共溶温度 (UCST)体系 ,在发生相分离后底面与表面粗化时间的不同是导致形貌结构差异的主要原因 .改变冷台温度或调整DO H2 O的比例也会对PU多孔膜的孔度大小和形貌结构产生明显的影响     

CaCO_3颗粒模板法制备聚合物超亲水/超疏水表面

以碳酸钙(CaCO3)颗粒层为模板,运用简单的热压和酸蚀刻相结合的方法制备聚合物超亲水/超疏水表面.首先在玻璃基底上均匀铺撒一层CaCO3颗粒,以此作为模板,通过热压线性低密度聚乙烯(LLDPE)使CaCO3颗粒均匀镶嵌在聚合物表面,获得了超亲水性质;进一步经酸蚀得到了具有微米和亚微米多孔结构的表面,其水滴静态接触角(WCA)可达(152.7±0.8)°,滚动角小于3°,具备超疏水性质.表面浸润性能和耐水压冲击性能研究表明该超疏水表面具有良好的稳定性和持久性.用同样工艺微模塑/酸蚀刻其它疏水性聚合物,得到类似结果.     

Homogeneously aligned liquid crystal molecules on unidirectional buckle pattern of polyurethane films

We present the fabrication of an anisotropic structure on a polyurethane (PU) film for aligning liquid crystal (LC) molecules with ion beam (IB) irradiation at an incident angle. The obtained anisotropic structure assembles the LC cells in a layer that aligns LC molecules uniformly. Polarised optical microscopy images of an LC cell fabricated with IB-irradiated PU were captured to confirm the LC alignment state and compared with those fabricated with non-treated PU. To analyse the effects of the IB irradiation, X-ray photoelectron spectroscopy and field-emission scanning electron microscopy were used to investigate the chemical and morphological modifications, respectively. IB irradiation modifies the chemical structure of PU, which indicates that a new skin layer is formed on the PU films. This skin layer generates an in-plane compressive strain, thereby creating buckles on the PU films. Simultaneously, the physical collision of the reactive Ar⁺ ions during IB irradiation induces a directional strain on the surface, thereby forming a unidirectional structure of buckles along the direction of IB irradiation. The PU film annealed at 200°C showed the high average transmittance of 88.9%, which is appropriate as an alignment layer.     

Efficient One-Step Passivation of Polyurethane Using Transurethanization

The uncontrolled accumulation of biological materials on the surface of medical devices through protein adsorption or cell adhesion causes adverse biological reactions in the living host system, leading to complications. In this study, poly(ethylene glycol) (PEG) is successfully grafted onto polyurethane (PU) surfaces by using a new strategy through a simple and efficient transurethanization reaction. The PEG hydroxyl group is deprotonated and then reacted with the PU surface to provide antiadhesive hydrophilic surfaces in a single step. Surface analysis techniques proved the grafting to be efficient and the formation of a hydrophilic polymeric layer at the surface of PU. Biological assays showed that the surface modification induced lower protein adsorption, cell, platelet, and bacterial adhesion than untreated surfaces, showing a potential for biomedical applications.     

Platelet adhesive resistance of polyurethane surface grafted with zwitterions of sulfobetaine

A possible approach to improve the blood compatibility of poly(etherurethane)s (PU) involves the covalent attachment of key molecular on its surface. Recently, polymer tailed with zwitterions was found having good blood compatibility. The purpose of present study was to design and synthesis a novel nonthrombogenic biomaterial by modifying the surface of poly(etherurethane) with zwitterions of sulfobetaine via HDI spacer. The films of polyurethane were grafted with sulfobetaine by a three-step procedure. In the first step, the film surfaces were treated with hexamethylene diisocyanate (HDI) in toluene at 50 degrees C in the presence of di-n-butyl tin dilaurate(DBTDL) as a catalyst. The extent of the reaction was measured by ATR-IR spectra; a maximum number of free NCO group was obtained after a reaction time of 2.5 h. In the second step, the primary amine group of N,N-diethylethylenediamine (DEA) or N,N-dimethylethylenediamine (DMA) was allowed to react in toluene with isocyanate groups bound on surface. In the third step, two kinds of sulfobetaines were formed in the surface through the ring-opening reaction between tertiary amine of DMA or DEA and 1,3- propanesultone (PS). The reaction process was monitored with ATR-IR spectra and XPS spectra. The wettability of films was investigated by water contact angle measurement. A platelet adhesion experiment was conducted as a preliminary test to confirm the improved blood compatibility of PU. The number of platelets adhering to PU decreased greatly compared to original after 1 h and 3 h of contact with human plate-rich plasma.