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.     

Instability of nanostructures patterned in polystyrene under high electric field gradients

A nanolithography technique based on the lateral displacement of electrically biased AFM tip was developed for nanostructures formation of 30-100 nm in width and 1-10 nm in height in the polystyrene (PS) films. It was demonstrated that the nanostructures patterned in annealed PS films (90K Mw) show slow exponential relaxation between 55 and 265 h depending on their size. Relaxation of the nanostructures in non-annealed films usually occurred in minutes. It was observed that in the annealed samples a negative electric charge accumulated in the areas where the nanostructures formed while in the non-annealed samples only the positive charge in exposed areas was detected using the electric force microscopy. After 320 h of monitoring under the humidity maintained between 25 and 27% it was suggested that slow dynamical changes of the nanostructures can be attributed to the negative electric charge dissipation in the annealed samples.     

PLA-PMMA blends: A study by XPS and ToF-SIMS

This paper reports which are the possibilities of quantification by time of flight secondary ion mass spectrometry (ToF-SIMS) for some polymer blends. In order to assess the composition of the mixtures, we studied first different poly(l-lactide)/polymethylmethacrylate (PLA/PMMA) blends by X-ray photoelectron spectroscopy (XPS), this technique being quantitative. By XPS fitting of the C 1s level, we found a very good agreement of the measured concentrations with the initial compositions. Concerning ToF-SIMS data treatment, we used principal component analysis (PCA) on negative spectra allowing to discriminate one polymer from the other one. By partial least square regression (PLS), we found also a good agreement between the ToF-SIMS predicted and initial compositions. This shows that ToF-SIMS, in a similar way to XPS, can lead to quantitative results. In addition, the observed agreement between XPS (60-100 Å depth analyzed) and ToF-SIMS (10 Å depth analyzed) measurements show that there is no segregation of one of the two polymers onto the surface.     

Preferential surface segregation of homopolymer and copolymer blend films

Surface film properties of the homopolymers polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(butyl methacrylate) (PBMA) and the copolymer poly(methyl methacrylate)-co-poly(butyl methacrylate) (PMMA-co-PBMA) and their blends with PS have been examined by atomic force microscopy (AFM) and contact angle measurements. The total and the Lifshitz-van der Waals, acid and base components of the surface free energy together with the work of adhesion and its components, the cohesive energy density and the solubility parameters of the homopolymer, copolymer and blend films were determined. Films of about 3 μm were considered. The results are discussed in terms of surface migration mechanisms based on surface free energy and solubilities of the polymers in the solvent, toluene in this paper. AFM imaging and contact angles revealed surface enrichment at the air polymer interface of PBMA for both the PS/PBMA blend and the copolymer PMMA-co-PBMA, whereas the PS/PMMA and PS/PMMA-co-PBMA blend film surfaces show island-like phase-separated structure of typical size 27.4-86.5 nm in diameter and 6.9-15.6 nm in height for PS/PMMA, while for PS/ PMMA-co-PBMA film surface the typical size is 49.6-153.3 nm in diameter and 1.6-14.2 nm in height.     

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.     

热处理对MgO基片的表面形貌以及对CeO_2和Tl-2212薄膜生长的影响

研究了MgO基片在高温退火时表面形貌和表面结构的变化,以及它对CeO2缓冲层和Tl-2212超导薄膜生长的影响。原子力显微镜(AFM)研究表明,在流动氧环境中1100℃温度下退火,MgO的表面首先由未退火时的皱褶形貌,演化为光滑表面,随着退火时间的延长,表面形貌最终演化为具有光滑基底的独立生长峰结构。XRD测试表明,通过高温热处理可以大幅度提高MgO基片表面结晶的完整性。在1100℃温度下热处理8小时的MgO基片上可以生长出具有高度c轴取向的CeO2(001)缓冲层。然后在此缓冲层上制备了厚度为500nm的外延Tl-2212超导薄膜,其临界转变温度(Tc)达到108.6K,液氮温度下临界电流密度(Jc)为2.8mA/cm2,微波表面电阻Rs(77K,10GHz)约为360.9μΩ。     

Fabrication of segmented nanofibers by template wetting of multilayered alternating polymer thin films

Segmented polystyrene (PS) and poly-methyl methacrylate (PMMA) nanofibers were fabricated by wetting nanoporous alumina templates with multilayered polymer thin films. The order and thickness of the polymers within the thin films affected the resulting nanofiber morphology, PS and PMMA segment properties, and created unique core-shell structure in the PMMA segments. The core-shell structure suggests a complex wetting phenomenon. Fabrication of polymer nanostructures by wetting of layered thin films opens the arena of multifunctional, one-dimensional, polymer nanostructures with segments having individual and specific functionalities.     

Microhardness Studies of the Interphase Boundary in Rubber‐Softened Glassy Polymer Blends Prepared with/without Compatibilizer

Abstract

The interphase boundary of incompatible polymer blends such as poly(methyl methacrylate) (PMMA)/natural rubber (NR) and polystyrene (PS)/NR, and of compatible blends such as PMMA/NR/epoxidized NR (ENR) and PS/NR/styrene–butadiene–styrene (SBS) block copolymer, where ENR and SBS were used as compatibilizers, was studied by means of microindentation hardness (H) and microscopy. Cast films of neat PMMA and PS, and blended films of PMMA/NR, PS/NR, PMMA/NR/ENR, and PS/NR/SBS were prepared by the solution method using a common solvent (toluene). Hardness values of 178 and 173 MPa were obtained on the surfaces of the neat PMMA and PS, respectively. After the inclusion of soft phases, the binary (incompatible) and the ternary (compatible) blend surfaces show markedly lower H‐values. Scanning electron and optical microscopy reveal a clear difference at the phase boundary of the surface of compatible (smooth boundary) and incompatible (sharp boundary) blends. The compatibilized blends were characterized by using microhardness measurements, as having the thinnest phase boundary (～30 µm), while incompatible blends were shown to present a boundary of about 60 µm. The hardness values indicate that the compatibilizer is smoothly distributed across the interface between the two blend components. Results highlight that the microindentation technique, in combination with microscopic observations, is a sensitive tool for studying the breadth and quality of the interphase boundary in non‐ or compatibilized polymer blends and other inhomogeneous materials.     

Characterization of WO3:Ag films: ToF-SIMS studies of ammonia adsorption

In this work, the composition and morphology of WO₃ films loaded with different levels of Ag, prepared by screen-printing onto Si substrates and annealed in air were investigated. The TEM micrography showed that the films are grain-like; the grain size increases with the increase of the Ag loading level. The Raman spectroscopy showed the formation of a AgWO₃ bronze structure. XPS and ToF-SIMS results showed that while undergoing annealing, the Ag atoms migrate to the surface forming clusters. The molecular images obtained by ToF-SIMS showed that the NH₃ binds preferentially at the surface of the Ag clusters. No preferential binding site was found for hydrocarbon contamination.     

衰减全反射傅里叶红外光谱在聚丙烯的表面改性的应用

应用衰减全反射傅里叶变换红外光谱法(ATR-FTIR)对聚丙烯共混薄膜的表面组成进行了测试.通过比尔定律的验证,确认1 103和1 733 cm-1可以分别用于含聚乙二醇和含羰基结构单元的改性剂共混体系的定量计算.利用ATR校正程序,以相应的特征峰峰面积比作为定量测定的基准,可以减少测试误差.通过工作曲线法,定量地分析了聚丙烯共混物薄膜表层中改性剂的含量.此外,利用变角全反射,通过改变入射光线的角度,可以测定不同深度的改性剂含量,剖析改性剂在PP共混薄膜的表层分布.     

Influence of drying conditions on the optical and structural properties of sol–gel-derived ZnO nanocrystalline films

Zinc oxide nanothin films were prepared on glass substrate by sol–gel dip-coating method using zinc acetate dihydrate, methanol, and monoethanolamine as precursor, solvent, and stabilizer, respectively. The relationship between drying conditions and the characteristics of ZnO nanocrystalline films (c-axis orientation, grain size, roughness and optical properties) was studied. The films were dried in an oven at different temperatures and by IR radiation. Then, the films were annealed at 500°C in a furnace. The chemical composition, transmission spectra, structure, and morphology of the samples were studied using infrared (IR) and UV–visible spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM), respectively. The XRD results show that the drying conditions affect the orientation of crystallization along the (0 0 2) plane. AFM images show that the thicknesses of the films decrease from 128 to 93 nm by changing the drying conditions. The photoluminescence (PL) of ZnO nanothin films shows the UV emission at near band edge and broad green radiation at about 465 nm wavelength.     

高温退火对蓝宝石基片的表面形貌和对CeO2缓冲层以及Tl-2212超导薄膜生长的影响

研究了蓝宝石(1102)基片在不同温度和时间下退火时表面形貌和表面相结构的变化,以及它对CeO₂缓冲层和Tl-2212超导薄膜生长的影响.原子力显微镜(AFM)研究表明,在流动氧环境中1000℃温度下退火,蓝宝石(1102)的表面首先局部区域形成台阶结构,然后表面形成叠层台阶结构,随着退火时间的延长,表面发生了台阶合并现象,表面形貌最终演化为稳定的具有光滑平台的宽台阶结构.XRD测试表明,通过高温热处理可以大幅度提高蓝宝石基片表面结构的完整性.在1000℃温度下热处理20 h的蓝宝石 关键词： Tl-2212超导薄膜 蓝宝石 缓冲层     

Characterization of fluoroalkylsilane monolayer on polystyrene sphere arrays after plasma treatment

Polystyrene (PS) colloidal crystal films with well-ordered arrays of PS spheres treated with argon plasma and coated with fluoroalkylsilane (FAS) were characterized by means of spectroscopy ellipsometry, X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF-SIMS). The XPS analysis indicated that the FAS film on the plasma treated PS surface was a monolayer with an orderly packed CF₃ group pointing outwards from the surface. The chemical composition of the PS surface changed immediately after a very short period of argon plasma treatment, while the subsequent coating of FAS on the plasma treated PS surface further modified the surface chemistry. The untreated PS surface exhibited poor interaction with FAS molecules. XPS and ToF-SIMS analyses showed the plasma treatment involved the oxidation of PS surface, where oxygen functional groups -O and O were generated, promoting FAS deposition on the plasma treated surface with strong secondary ion fragments originating from the FAS. The overall results indicated that plasma treatment was beneficial to the deposition of the FAS monolayer.     

Annealing effects on the optical and structural properties of Al2O3/SiO2 films as UV antireflection coatings on 4H-SiC substrates

Al₂O₃/SiO₂ films have been prepared by electron-beam evaporation as ultraviolet (UV) antireflection coatings on 4H-SiC substrates and annealed at different temperatures. The films were characterized by reflection spectra, ellipsometer system, atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. As the annealing temperature increased, the minimum reflectance of the films moved to the shorter wavelength for the variation of refractive indices and the reduction of film thicknesses. The surface grains appeared to get larger in size and the root mean square (RMS) roughness of the annealed films increased with the annealing temperature but was less than that of the as-deposited. The Al₂O₃/SiO₂ films maintained amorphous in microstructure with the increase of the temperature. Meanwhile, the transition and diffusion in film component were found in XPS measurement. These results provided the important references for Al₂O₃/SiO₂ films annealed at reasonable temperatures and prepared as fine antireflection coatings on 4H-SiC-based UV optoelectronic devices.     

Effects of the embedding kinetics on the surface nano-morphology of nano-grained Au and Ag films on PS and PMMA layers annealed above the glass transition temperature

The morphology evolution of nano-grained Ag and Au films deposited on polystyrene (PS) and poly(methyl methacrylate) (PMMA) polymeric layers were studied, using the atomic force microscopy technique, when annealed above the polymers glass transition temperature. The main effects on the morphology changes were identified with those concerning the embedding kinetics of the Ag and Au nanoparticles in the PS or PMMA layers. The embedding process of the nanoparticles follows as a consequence of the long-range mobility of the polymeric chains above the glass transition temperature. In particular, the dependence of the nanoparticles mean height and surface density on the annealing time at various temperatures was quantified. The analyses of these behaviors allowed us: (1) to distinguish the overall embedding process in a first stage in which a thin wetting layer of the polymer coats the nanoparticles followed by a true embedding process of the nanoparticles into the polymer layer; (2) to evaluate the characteristic coating time for the Ag and Au nanoparticles in the PS and PMMA in the first stage; (3) to evaluate the characteristic embedding velocity for the Ag and Au nanoparticles in the PS and PMMA in the second stage; (4) to derive the activation energies for the embedding process of the Ag and Au nanoparticles in PS and PMMA; (5) to identify the embedding statistics of the Ag and Au nanoparticles in PS and PMMA with a “failure” Weibull statistics.     

Glass transition temperature of freely-standing films of atactic poly(methyl methacrylate)

We have used ellipsometry to measure the glass transition temperature T(g) of high molecular weight (M(w)=790 x 10(3)), freely-standing films of atactic poly(methyl methacrylate) (a-PMMA), as well as films of the same polymer supported on two different substrates: the native oxide layer of silicon (Si) and gold-covered Si. We observe linear reductions in T(g) with decreasing film thickness h for the freely-standing PMMA films with 30 nm < h<100 nm, which is qualitatively similar to previous results obtained for freely-standing polystyrene (PS) films. However the magnitude of the T(g) reductions for PMMA is much less than for freely-standing films of PS of comparable molecular weight and thickness. We also find that for films supported on either substrate, with thicknesses as small as 30 nm, the T(g) values do not deviate substantially from the value measured for thick films.     

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.     

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.     

用显微红外光谱法研究高分子共混物溶液自组织形成的相组成分布

本文制备了ＰＳ／ＰＣ（７／３）和ＰＳ／ＰＭＭＡ（５／５）的四氢呋喃（ＴＨＦ）溶液,通过缓慢蒸发溶剂制得ＰＳ／ＰＣ和ＰＳ／ＰＭＭＡ的共混物薄膜。利用不同的ＦＴＩＲ测试方法检测了制得薄膜中的组成分布。将ＰＳ／ＰＣ薄膜超薄切片,通过显微投射红外方法检测了其纵剖面的组成分布（测试步长为１６μｍ）。结果表明：ＰＳ含量从膜底面到表面缓慢增大呈梯度分布,在膜表面附近急剧增大,即ＰＳ组分在成膜过程中向表面（与空气     

Effect of nano-metric changes on morphology and optical constants of TiO2 thin films

Titanium dioxide films of different thicknesses, ranging from 10 to 110 nm were deposited on glass substrate, at room temperature by physical vapor deposition method. Topography, roughness and crystallography of produced layers were determined by AFM and XRD methods respectively. Optical properties were measured by transmission spectroscopy in the spectral range of 300–1100 nm wave length range. The optical constants were obtained using Kramers-Kronig analysis of the reflectivity curves. It was found that film thickness plays an important role on the nanostructures as well as optical properties of layers and cause significant variations in behavior of thin titanium oxide films.