Annealing effect on surface segregation behavior of hydroxypropylcellulose/polyethylenimine blend films

The surface properties of hydroxypropylcellulose (HPC) and polyethylenimine (PEI) blend films prepared by solution casting method before and after annealing were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and contact angle measurements. SEM and AFM analysis of the blends revealed that the PEI component segregated on the surface of the air-surface side of the blend films with increasing annealing temperature. The band intensity of PEI component at 1630 cm⁻¹ also increased depending on annealing temperature. The water contact angle decreased abruptly with increasing annealing temperature and reached almost 31° on the surface of the air-surface side of the blends at 150 °C. The results of these studies showed that the PEI chains with low surface energy segregated or enriched mainly on the surface of the air-surface side, and that, on the other hand, HPC chains with high surface energy oriented to the surface of the glass-surface side and inside of the films with increasing annealing temperature.     

End group effect on surface and interfacial segregation in PS-PMMA blend thin films

Thin films of polystyrene (PS)/poly (methyl methacrylate) (PMMA) blends with different end groups were investigated using ToF-SIMS and AFM. PS with -OH and -NH₂ end groups were blended in toluene solvent with pure PMMA homopolymer, and PMMA having anhydride end group. The ToF-SIMS spectra of PS-OH/PMMA resembled that of pure PS-PMMA blends showing an increase of PMMA intensity after annealing. On the contrary, the PS-NH₂ blended with PMMA showed an increase in PS intensity on the surface after annealing. The ToF-SIMS spectra were similar to that of a pure PS-PMMA di-block copolymer. These results indicate copolymer formation at the surface. The PS-NH₂ with PMMA-anhydride blend spectra showed very slight changes in spectra before and after annealing and the AFM images revealed spinodal bi-continuous structures on the surface before and after annealing. The copolymer formation is found to occur in the as-cast film itself and not after thermal treatment.     

Annealing effects on the surface morphologies of thin PS/PMMA blend films with different film thickness

The surface morphology evolution of three thin polystyrene (PS)/polymethyl methacrylate (PMMA) blend films (<70 nm) on SiO_x substrates upon annealing were investigated by atomic force microscopy (AFM) and some interesting phenomena were observed. All the spin-coated PS/PMMA blend films were not in thermodynamic equilibrium. For the 67.1 and the 27.2 nm PS/PMMA blend films, owing to the low mobility of the PMMA-rich phase layer at substrate surfaces and interfacial stabilization caused by long-range van der Waals forces of the substrates, the long-lived metastable surface morphologies (the foam-like and the bicontinuous morphologies) were first observed. For the two-dimensional ultrathin PS/PMMA blend film (16.3 nm), the discrete domains of the PS-rich phases upon the PMMA-rich phase layer formed and the secondary phase separation occurred after a longer annealing time.     

Dynamic mechanical and morphological studies of homopolymer/block copolymer blends

A triblock copolymer of styrene-butadiene-styrene (SBS) was blended with a high and a low molecular weight polybutadiene [designated as PB(H) and PB(L), respectively]. Electron micrographs of these blends show that PB(L) was solubilized into the butadiene domains of the SBS, while PB(H) was present in a separate phase. Dynamic mechanical data of the SBS&PB(L) blends indicate the presence of an intermediate loss peak between those of the glass transitions of the styrene and butadiene blocks in SBS, which can be attributed to the slippage of untrapped entanglements of PB(L) chains. Similar data for blends containing PB(H) also show an intermediate loss peak, which is, however, due to crystallization and melting of the polycisbutadiene chains. The peak due to the primary glass transition of the butadiene phase was shifted to lower temperatures upon incorporation of PB(L) as a result of plasticization effect of PB(L). The same transition for PB(H) blends is split into a doublet because of the presence of the homopolymer in a separate phase. Dynamic mechanical data for cross-linked blends were also taken for comparison.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

The influence of UV irradiation on surface composition of collagen/PVP blended films

The surface chemical composition and surface properties of collagen/poly(vinyl pyrrolidone) (PVP) blended films before and after UV irradiation (λ = 254 nm) were investigated using X-ray Photoelectron Spectroscopy (XPS), FTIR-ATR spectroscopy and Atomic Force Microscopy (AFM).The XPS results showed that collagen is enriched on the surface of the collagen/PVP blend. The surface composition of the collagen film was changed more by UV irradiation than the surface composition of the collagen/PVP blend.FTIR-ATR spectra showed that the positions of the amide bands in collagen are more altered after UV irradiation than those for the collagen/PVP blends.AFM images showed that the collagen surface is ordered contrary to PVP. The blend surface was similar to the pure collagen surface and confirms that there is more collagen present at the surface (higher concentration of collagen at the surface compared to PVP). UV irradiation caused only the small changes in the surface morphology of the collagen/PVP films. All of the results confirm that the surface of the collagen/PVP blend is more photoresistant than collagen.     

芴-咔唑新型共聚物/PVK掺杂体系的电致发光特性研究

研究了新型的芴-咔唑共聚物(PFC)与聚乙烯咔唑(PVK)掺杂体系的光致发光和电致发光特性.制备了结构分别为indium-tin-oxide(ITO)/PVK:PFC/bathocuproine(BCP)/tris-(8-hydroxylquinoline)-aluminum (Alq₃) /Mg:Ag，ITO/PFC/BCP/Alq₃/Mg∶Ag和ITO/PVK/BCP/Alq₃/Mg∶Ag的三种有机电致发光器件.对器件的光电特性进行了测试.结果表明，掺杂体系中的PVK有效地抑制了固态膜中PFC激基缔合物的形成.掺杂器件在不同的外加电场作用下发生发光层位置的移动，通过调节外加电场，可以获得从绿光到蓝光的可见光发射.当外加电压大于7V时，掺杂器件的蓝色发光亮度达到1650cd/m²，推测其中可能存在从PVK到PFC的能量传递过程.     

Nano- and microstructured polymer LB layers: A combined AFM/SIMS study

Ultra thin structured polymer films have been prepared by horizontal precipitation Langmuir-Blodgett (HP-LB) method of polymer blends. In particular we used mixtures of two incompatible polymers, poly-2-vinylpyridine and polystyrene, the former giving the necessary surface activity for LB film formation. Upon spreading at the air-water interface, the blend forms different surface structures depending on the relative amount of the two components. By adjusting the experimental parameters it is possible to obtain relatively regular structures in the submicron size range, which can be transferred on a solid substrate. These systems have been investigated by means of SIMS and atomic force microscopy.     

Adhesion enhancement in polystyrene/polyethylene blends by corona treatment and triblock copolymer addition

A comparative study of interfacial effects due to styrene-butadiene-based triblock copolymer (SEBS) addition and to corona treatment has been investigated for blends of polyethylene (PE) and polystyrene (PS). Blends of PS/PE covering a wide range of weight composition have been prepared in the molten state. Scanning electron microscopy demonstrated that moderate amounts of SEBS copolymer addition (2-5%) resulted in finer particle dispersion and in better interfacial adhesion between PE and PS phases. Tensile strength and elongation at break were also significantly improved. In the case of corona treatment of both polyethylene and polystyrene, the tensile strength of the blends increased while their elongation at break remained almost unchanged. The same trend was found when small amounts of corona-treated blend (5%) were added to the non-modified PS/PE blends. Rheological measurements revealed that corona treatment resulted in a decrease of dynamic shear viscosity of both PE and PS. From a view-point of morphological and mechanical properties, the triblock copolymer was found to be the more efficient modifier. Nevertheless, much higher tensile strengths, but lower elongations at break were obtained when the blends were modified by corona-treated SEBS copolymer. The results suggest that a combination of the two modification methods may be a promising route to enhance performance properties in the immiscible PS/PE system.     

Surface segregational behaviour studied as an effect of thickness by SIMS and AFM in annealed PS-PMMA blend and block copolymer thin films

The surface behaviour of a two-phase polymer mixture depends on the chemical structure of the polymer components, the interaction between the two polymers and the processing conditions. The microscopic morphology and the surface composition need to be known in order to fully utilize the thin film properties. The technique of static time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to obtain the molecular surface composition of thin films of blends and block copolymers. The depth profiling tool of Nano-SIMS, a dynamic SIMS technique, helps to provide the chemical mapping of the surface in 2D and 3D. The surface morphology is investigated using AFM. Thin films of PS and PMMA diblock copolymers with molecular weight of 12K-12K and 10K-10K and blends of PS/PMMA (10K/10K) for thicknesses ranging from 5 nm to 50 nm are examined. For the blends, the ToF-SIMS spectra for all the thicknesses show the same behaviour of a high increase of PMMA on the surface after annealing. Nano-SIMS images reveal the formation of nanostructures on the annealed surfaces and AFM studies show these nanostructures to be droplets having distinct phase shift from the surrounding matrix. The droplet dimensions increase with the increase of the thickness of the film but the absolute intensity from the ToF-SIMS spectra for all the annealed films remains almost the same. For the copolymers, the ToF-SIMS spectra show that there is a decrease of PMMA on the surface for the annealed films when compared to the as-cast ones. AFM morphology reveals that, for different thicknesses, annealing induces different topographical features like droplets, holes, spinodal patterns, etc. but with no distinct phase shift between the patterns and the surrounding matrix. The two different copolymers of comparable molecular weight are found to exhibit very different topography even when the thickness of the films remained the same. The surface composition from the ToF-SIMS data, however, was not found to vary even when the topography was completely different.     

AB/CD嵌段共聚物共混体系多尺度结构的自洽场模拟

本文采用自洽场理论模拟了AB/CD嵌段共聚物共混体系的自组装. 改变组分B与D间的相互作用, 得到了不同空间尺度上的两种层状结构和只能在非对称组成情况才能得到的核壳结构. 结果表明, 这种多尺度结构的形成是因为BD间排斥作用的减弱或者吸引 作用的增强导致二者间相互融合程度的增加. 当BD间的相互融合程度与AB和CD间的相互融合程度相当时, 体系会发生宏观层状与微观层状结构间的转变. 此外, 本文还从能量角度揭示了体系发生这种结构转变的深层次原因. 关键词： 嵌段共聚物 共混 多尺度结构 自洽场     

A study of AFM-based scratch process on polycarbonate surface and grating application

We report on the possibility of applying atomic force microscope (AFM) lithography to draw micro/nano-structures on the surface of a polycarbonate (PC) substrate. We also fabricated a grating structure on the PC surface using the scratch method. An AFM silicon tip coated with a diamond layer was utilized as a cutting tool to scratch the surface of the sample. In order to obtain pattern depth deeper than the control method of interaction force, we used a scanner movement method which the sample scanner moves along the Z-axis. A grating of 100 μm × 150 μm was fabricated by the step and repeat method wherein the sample stage is moved in the direction of the XY-axis. The period and the depth of the grating are 500 and 50 nm, respectively. Light of 632.8 nm wavelength was diffracted on the surface of the PC substrate.     

fcc金属表面能的各向异性分析及表面偏析的预测

本文将元素变量(φ^*和n_WS)和MAEAM相结合,从原子尺度上对10种fcc金属Cu,Ag,Au,Ni,Pd,Pt,Rh,Al,Ir和Pb的38个不同晶面的表面能进行模拟计算及各向异性分析. 结果表明,fcc金属的密排面(111)的表面能最小,则该晶粒取向优先生长,与实验结果和第一原理的LMTO-ASA计算结果一致;各个晶面的表面能均随着其他晶面与(111)晶面的夹角cosθ_(hkl)的增长而呈线性 关键词： FCC金属 MAEAM 表面能 表面偏析     

SMMA/SMA共聚物共混物的自由体积的热动态特性与相分离行为的PALS研究

基于自由体积理论，利用正电子湮灭寿命谱仪(PALS)分别研究在不同升温速率条件下，聚苯乙烯-甲基丙烯酸甲酯共聚物(SMMA)和聚苯乙烯-马来酸酐共聚物(SMA)混合物(30/70)的自由体积参数的温度依赖性，探索相容共混物相行为的热动态特性.在PALS实验中，在玻璃化转变温度T_g以上，当结构松弛的弛豫时间与等温停留时间相当，发现在某一段温度范围内，共混物的自由体积参数随着温度的变化明显地偏离线性关系.从自由体积孔的浓度I₃值在该段的变化趋势，初步推断共混物在该温 关键词： 正电子湮没 正电子素 聚合物共混物 相分离     

Surface energetics of poly(N-vinyl-2-pyrrolidone)/chitosan blend films

Poly(N-vinyl-2-pyrrolidone) (PVP) and chitosan (CTS) with three different molecular weights (MW: 150,000, 400,000 and 600,000 g/mol) blends were prepared as films having 13, 20, 33, 43 and 50% (w/w) CTS by solution casting method. Surface properties of the films were analyzed by contact-angle measurements and scanning electron microscopy (SEM). The contact angles of water, glycerol, ethylene glycol, formamide and paraffin oil drop were measured on these films. The contact-angle results were evaluated in terms of surface free energy components by using Van Oss-Good methodology. It was found that all PVP/CTS blend surfaces are enriched in low surface free energy component, i.e. CTS. This conclusion was further confirmed by the cross-sectional SEM images observation of these blends.     

Crystalline morphologies of P(VDF-TrFE) (70/30) copolymer films above melting point

To further understand the crystallization behavior from melts of P(VDF-TrFE) (70/30) copolymer, the morphologies of P(VDF-TrFE) copolymer thin and ultra-thin films are studied by AFM. It is found that P(VDF-TrFE) (70/30) copolymer films exhibit morphologic transition from big grains to fiber-like rods above melting point. And this may be on account of the molecule chains plastic flow and self-organization, corresponding to polymer homoepitaxy.     

Equilibrium and kinetic surface segregation in binary alloy thin films

A general theoretical analysis of the effect of film thickness on equilibrium and kinetic surface segregation in binary alloy thin films is presented. In this analysis, a constrained condition that represents the finite size of thin film system has been introduced to the modified Darken model, which has been used to describe both equilibrium and kinetic surface segregation in bulk materials. Simulation of surface segregation for alloy thin films can be carried out for all composition ranges and all film thicknesses if only knowing the surface segregation parameters for bulk materials. Simulations of equilibrium and kinetic surface segregation in Cu(1 1 1)Ag binary alloy thin film are presented.     

Effect of the surface-modifying macromolecules on the duration of the surface functionalization

Functionalization of polystyrene films by the preferential surface enrichment of surface-modifying macromolecules (SMM) to achieve a hydrophilic surface with long effective duration is described. The comb-like amphiphilic copolymers (PKG-g-PS) based on styrene-maleic anhydride copolynier (SMA) backbone was synthesized by esterification of SMA with poly(ethylene glycol) (PEG). When PEG-g-PS was melt blended with polystyrene, the preferential surface enrichment of PEG-g-PS was much evident resulting in the large increase of the surface polarity. The effective duration of the surface functionalizatoin was also hugely extended as SMMs were added into the blends. Furthermore, more polyether chain segments on PEG-g-PS could selectively migrate to the surface by the inducement of polar solvent. Compared with the PEG-g-PS/PS and PEG/PEG-g-PS/PS blends, the surface polarity and the effective duration of surface modification both increased greatly when PEG-g-PS was used as the compatibilizer of PEG/PS blends. It was an effective solution to balance the conflict between the duration and efficiency of the surface-modifying additives.     

Effect of different solid matrixes on surface free energy of EGDMA and TRIM polymers

Advancing and receding contact angles of water, formamide, glycerol and diiodometane were measured on the two polymers; EGDMA (dimethacrylate of ethylene glycol) and TRIM (trimethacrylate-1,1,1-trihydroksymethylopropane) which were polymerized next to glass, silanized glass, stainless steel, mica and silicon surfaces as the matrices. Then from the contact angle hystereses (CAH) and van Oss, Good, Chaudhury (LWAB) approaches the apparent surface free energies were evaluated. The measured contact angles not only depend solely on the polymer chemical structure but also, to some extent, on the solid matrix next to whose surface the sample has polymerized. Surface free energy of the polymer samples calculated from the LWAB approach shows that they interact mainly by dispersive forces. The apparent surface free energy of the polymers calculated from the diiodomethane contact angles hysteresis is practically the same irrespective of the kind of the matrix used. Therefore it can be concluded that the observed weak polar interactions in the surface free energy of the samples depend on the polymer surface preparation. The AFM images show that the obtained surfaces are of different roughness. The RMS values of roughness range between 3.7-90.2 nm for EDGMA, and 5.3-124.5 nm for TRIM. However, as reported in literature, rather protrusions bigger than 1 μm may significantly affect the contact angles, especially the receding ones.     

Preparation, characterization and surface pKa values of poly(N-vinyl-2-pyrrolidone)/chitosan blend films

Blend films of poly(N-vinyl-2-pyrrolidone) (PVP) and chitosan (CTS) were prepared by casting method from acetic acid solutions. All blend films obtained are optically clear to the naked eye. The structure and physical properties of the blend films were analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), mechanical testing (Instron) and contact-angle measurements. The ATR-FTIR results indicated that there is no detectable band shifts at 1650 cm⁻¹. From TGA studies, it was found that the onset degradation temperature of the blends almost unchanged due to the presence of a weak interaction between PVP and CTS chains. The DSC analysis showed a single glass transition temperature for all the blends, indicating that these polymers are miscible over the entire composition range. The mechanical properties of the blends, such as breaking stress and elongation at break and Young modulus were greatly affected with increase of CTS content. In addition, we found that the blends exhibit well defined contact angle titration curves from which the surface pK_a values were determined. In conclusion, these experimental findings provide fundamental knowledge for the preparation of bioreactive surfaces of controlled reactivity on CTS based blends.