Simultaneous imaging for surface and internal structure of polymer blend thin films

A novel experimental technique for three-dimensional (3D) visualization of phase-separated structure of polymer blend thin film was proposed. Polystyrene/poly(methyl methacrylate) (PS/PMMA) blend thin films with the thickness of approximately 100 nm were cut at extremely low angle by utilizing surface and interface cutting analysis system (SAICAS), and the cross-section was exposed as gradient surface with the width of approximately 2.5 μm. SFM investigation for the grazing cross-section imaged the detailed internal and surface phase separated structure of the (PS/PMMA) blend thin films on one image.     

Effect of Polymer-Substrate Interactions on the Surface Morphology of Polymer Blend Thin Films

Surface structures and compositions of poly(Styrene-block-Ethylene/Butylene-block-Styrene) (SEBS)/Poly(Methyl Methacrylate) (PMMA) blend films have been studied by Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS). Substrates with different hydrophobicity and SEBS with and without Maleic Anhydride (MA) grafting were used to study the effect of polymer-substrate interactions. It is indicated that the surface energy of the substrate (substrate/air) plays a crucial role on the surface composition of the polymer component. For a fixed surface, the adsorption of polymer on the substrate is also important. The hydrophilic sites of SEBS-g-MA can prevent the dewetting of the SEBS-g-MA from the substrate. The dewetting of PMMA from the SEBS-g-MA will make the PMMA protrusions more pronounced, and the SEBS-g-MA phase domains are enlarged after annealing treatment. An adsorption scheme is suggested to explain the phase inversion and height difference observed in the various polymers used. In addition, SEBS triblock copolymers form wormlike and meshlike microphase separation morphologies on the hydrophilic and hydrophobic substrates, respectively.     

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.     

Effect of Polymer-Substrate Interactions on the Surface Morphology of Polymer Blend Thin Films: Comparison between Simulation and Experiment

Microphase and macrophase separation phenomena can simultaneously appear in ABA/C copolymer blend systems due to the immiscibility among monomers A, B, and C. In this work, the surface morphologies and compositions of ABA/C blend thin films confined between two walls, which were used to mimic SEBS/PMMA films, have been simulated by a lattice Monte Carlo (MC) method. The effect of the polymer-wall interaction on the surface morphologies and compositions of thin films was investigated as a function of blend composition and film thickness. It is shown that the simulated surface morphologies of thin films resulting from the macrophase separation between copolymer ABA and homopolymer C and the microphase separation between block A and block B in ABA copolymer are similar to the experimental surface morphology of SEBS/PMMA polymer blend films observed by atomic force microscope (AFM). The effect of substrate on the surface morphologies by MC simulation is qualitatively consistent with the experimental results. The composition profiles of thin films are given to characterize the micro- and macrophase separation in thin films. It is indicated that the surface energy of the substrate (substrate/air) plays a crucial role on the surface composition. For a fixed surface, the adsorptions of polymer on the substrate and film thickness are also important.     

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.     

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.     

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     

表面增强拉曼光谱研究高分子共混物薄膜相结构

采用拉曼光谱法研究了由聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)的四氢呋喃(THF)溶液在玻璃基板上旋转涂膜得到的共混物薄膜。应用显微共焦拉曼光谱,根据PS在1604,1585cm-1处苯环的伸缩振动峰和PMMA在1728cm-1处羰基的伸缩振动峰,可以确定薄膜(厚度约为800nm)表面海岛状相结构的组分分布信息。另外,还对210℃下PS/PMMA(30/70)共混物薄膜退火过程中表面的变化进行了分析。采用表面增强拉曼散射效应对高聚物的增强作用得到了薄膜(厚度约为400nm)的Raman光谱,并且成功地对其组成进行了分析。     

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.     

Photoluminescence of ZnO films prepared by r.f. sputtering on different substrates

Polycrystalline ZnO films with good orientation were deposited on sapphire, quartz, Si and 7059 glass substrates by r.f. magnetron sputtering. A strong UV photoluminescence (PL) peak (located at 356 nm) and a weak blue emission peak (located at 446 nm) were observed at room temperature (RT) for the films deposited on sapphire, quartz and Si substrates when excited with 270 nm light. For the films prepared on Corning 7059 glass, only a strong 446 nm blue emission peak was found, and the PL intensity decreased with increasing oxygen pressure during films deposition. The intensity of the UV emission increased 7 and 14 times, respectively, for the films on sapphire and quartz substrates after high temperature annealing in vacuum. The UV emission originates from the inter-band transition of electrons and the blue emission is due to transition of electrons from the shallow donor level of the oxygen vacancies to the valence band.     

Retardation of enzymatic degradation of microbial polyesters using surface chemistry: effect of addition of non-degradable polymers

The effects of addition of non-degradable polymers on the rate of enzymatic erosion for the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] have been studied at 37 °C and pH 7.4 in the aqueous solution of an extracellular PHB depolymerase from Alcaligenes facalis. Polystyrene (PS) or poly(methyl methacrylate) (PMMA) was selected as a minor component (5 wt%) in a blend because of their non-enzymatic activity. Enzymatic degradation behaviors of the “as-cast” and “annealed” blend films were investigated using atomic force microscopy and weight loss measurements. Although the spherulites of P(3HB-co-3HV) cover all blend film surfaces throughout, the retardation of biodegradation in the P(3HB-co-3HV)/PS blend films was detected from morphological observation and weight loss measurement for both as-cast and annealed blend films while there was little difference between the P(3HB-co-3HV)/PMMA blend and pure P(3HB-co-3HV). Since the enzymatic degradation of P(3HB-co-3HV) initially occurs by a surface erosion process, these degradation behaviors were explained by the surface structure of blend films measured by X-ray photoelectron spectroscopy. The surface of P(3HB-co-3HV)/PS blend films revealed an excess of PS, whereas the surface of P(3HB-co-3HV)/PMMA blend films was nearly covered by P(3HB-co-3HV). It was concluded, therefore, that the PS, which exists within P(3HB-co-3HV) spherulites at surface acts as a retardant of enzymatic attack to the surface of the blend film.     

Structure and photoluminescence properties of ZnS films grown on porous Si substrates

ZnS films were deposited on porous silicon (PS) substrates with different porosities. With the increase of PS substrate porosity, the XRD diffraction peak intensity decreases and the surface morphology of the ZnS films becomes rougher. Voids appear in the films, due to the increased roughness of PS structure. The photoluminescence (PL) spectra of the samples before and after deposition of ZnS were measured to study the effect of substrate porosity on the luminescence properties of ZnS/PS composites. As-prepared PS substrates emit strong red light. The red PL peak of PS after deposition of ZnS shows an obvious blueshift. As PS substrate porosity increases, the trend of blueshift increases. A green emission at about 550 nm was also observed when the porosity of PS increased, which is ascribed to the defect-center luminescence of ZnS. The effect of annealing time on the structural and luminescence properties of ZnS/PS composites were also studied. With the increase of annealing time, the XRD diffraction peak intensity and the self-activated luminescence intensity of ZnS increase, and, the surface morphology of the ZnS films becomes smooth and compact. However, the red emission intensity of PS decreases, which was associated with a redshift. White light emission was obtained by combining the luminescence of ZnS with the luminescence of PS.     

The effect of annealing on structural,optical and electrical properties of ZnS/porous silicon composites

ZnS films were prepared by pulsed laser deposition (PLD) on porous silicon (PS) substrates. This paper investigates the effect of annealing temperature on the structural, morphological, optical and electrical properties of ZnS/PS composites by x-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) and I–V characteristics. It is found that the ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction, and the intensity of diflraction peak increases with increasing annealing temperature, which is attributed to the grain growth and the enhancement of crystallinity of ZnS films. The smooth and uniform surface of the as-prepared ZnS/PS composite becomes rougher through annealing treatment, which is related to grain growth at the higher annealing temperature. With the increase of annealing temperature,the intensity of self-activated luminescence of ZnS increases, while the luminescence intensity of PS decreases, and a new green emission located around 550 nm appeared in the PL spectra of ZnS/PS composites which is ascribed to the defect-center luminescence of ZnS. The I-V characteristics of ZnS/PS heterojunctions exhibited rectifying behavior, and the forward current increases with increasing annealing temperature.     

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.     

Interaction of Domains in Ternary Polymer Melt Blends with Separate Dispersions of the Inner Phases

The morphology evolution in three immiscible ternary polymer systems characterized by separate dispersions of the dispersed phases (i.e., no encapsulation phenomena takes place) was characterized. The components used were three of the following: commercial atactic poly(methyl methacrylate) (PMMA) and polystyrene (PS), crystallizable poly(butylene terephthalate) (PBT) and isotactic polypropylene (PP) and glass microspheres (GMS). In System I PMMA/PS/PP (primary dispersed phase/matrix/secondary, or minor, dispersed phase), all of the components were liquid on blending at 190°C. In System II PP/PS/PBT and System III PP/PSyGMS, at 190°C, the minor PBT and GMS dispersed phases were nondeformable. It was shown that small portions (0.5–1.0 wt%) of the PP minor dispersed phase added to the binary PMMA/PS blend produced a dual action: (a) transition of the PMMA dispersed phase to a cocontinuous one and (b) simultaneous substantial (up to a 6-fold) growth of the degree of dispersion of the blend. Moreover, these effects were accompanied by about a three-fold reduction of the threshold PMMA concentration (C*) at which it formed its own co-continuous phase in the ternary blend compared to that in the PMMA/PS binary mixture. The observed phenomena took place regardless of whether the domains of the minor dispersed phase were liquid (System I) or solid (Systems II and III), and was strongly related to the domain sizes of this phase and blend composition. A mechanism underlying the outlined behavior is proposed.     

The effect of PS porosity on the structure,optical and electrical properties of ZnS/PS

ZnS films were deposited on porous silicon (PS) substrates with different porosities by pulsed laser deposition (PLD). The crystalline structure, surface morphology of ZnS films on PS substrates and optical, electrical properties of ZnS/PS composites were studied. The results show that, ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction corresponding to crystalline structure of cubic phase. With the increase of PS porosity, the XRD diffraction peak intensity of ZnS films decreases. Some voids and cracks appear in the films. Compared with as-prepared PS, the PL peak of PS for ZnS/PS has a blueshift. The larger the porosity of PS, the greater the blueshift is. A new green light emission located around 550 nm is observed with increasing PS porosity, which is ascribed to defect-center luminescence of ZnS. The blue, green emission of ZnS combined with the red emission of PS, a broad photoluminescence band (450–750 nm) is formed. ZnS/PS composites exhibited intense white light emission. The I–V characteristics of ZnS/PS heterojunctions showed rectifying behavior. Under forward bias conditions, the current density is large. Under reverse bias conditions, the current density nearly to be zero. The forward current increases with increasing PS porosity. This work lay a foundation for the realization of electroluminescence of ZnS/PS and solid white light emission devices.     

Luminescence properties of Er in SiN/PS : Er

The decrease in luminescence from host porous silicon (PS) by thermal annealing prevents the optical activation of Er ions. We prepared a SiN layer on erbium-doped porous silicon (PS : Er) as the capping layer by photo-chemical vapor deposition (photo-CVD). After deposition of SiN, the sample was annealed in pure Ar atmosphere for optical activation. We observed an Er-related emission at 1532 nm with a full-width at half-maximum (FWHM) of 10 nm at 18 K from the sample with the SiN layer. In contrast, no emission was observed from the sample without the SiN layer. At 300 K, the peak intensity of Er³⁺-related photoluminescence (PL) for the sample annealed at 1100°C decreased to 40.0% of that observed at 18 K. From these results, it was found that the SiN layer on PS:Er is useful for both host PS and Er-related 1.5 μm luminescences.     

Phase Ordering and Crystallization Kinetics in Ultrathin Poly(ethylene oxide)/Poly(methyl methacrylate) Blend Films

Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane.     

Calorimetric study of blend miscibility of polymers confined in ultra-thin films

Miscibility in blends of polystyrene and poly(phenylene oxide) (PS/PPO) confined in thin films (down to 6 nm) was investigated using a recently developed sensitive differential alternating current (AC) chip calorimeter. Comparison of composition dependence of glass transition in thin films with common models should provide information on miscibility. This study focuses on the blend system polystyrene and poly(phenylene oxide) (PS/PPO) because it is thought as a miscible model system in the whole composition range. Furthermore, its local dynamic heterogeneity is already identified by dynamic mechanic thermal analysis (DMTA) and solid state NMR techniques. For this blend, we find that even for the thinnest films (6 nm, corresponding to about half of PPO’s radius of gyration R _g) only one glass transition is observed. The composition dependence of T _g is well described by the Fox, Couchman or Gordon-Taylor mixing law that are used for the miscible bulk blends. Although there is a contradicting result on whether T _g decreases with decreasing film thickness between our calorimetric measurements and Kim’s elipsometric measurements on the same blend (Kim et al. Macromolecules 2002, 35, 311–313), the conclusion that the good miscibility between PS and PPO remains in ultrathin films holds for both studies. Finally, we show that our chip calorimeter is also sensitive enough to study the inter-layer diffusion in ultrathin films. PS chain in a thin PS/PPO double layer that is prepared by spin coating PPO and PS thin film in tandem will gradually diffuse into the PPO layer when heated above T _g of PS, forming a PS_xPPO_100−x blend. However, above the PS_xPPO_100−x blend, there exists an intractable pure PS like layer (∼30  nm in our case) that does not diffuse into the blend beneath even staying at its liquid state over 10 hours.     

CVD两步法生长ZnO薄膜及其光致发光特性

用CVD两步法在常压下于p型Si(100)衬底上沉积出具有较好择优取向的多晶ZnO薄膜。在325nm波长的光激发下,室温下可观察到显著的紫外光发射(峰值波长381nm)。高温退火后氧空位缺陷浓度增加,出现了一个450~600nm的绿光发光带,发光峰值在510nm。作为比较,用一步法生长的ZnO薄膜结晶质量稍差。在其PL谱中不仅有峰值波长389nm的紫外发射而且还出现了一个很强的蓝光发光中心(峰值波长437nm),退火后同样产生绿光发光带。对这两种绿光发光带的发光机制进行了研究,认为前者源于VO,而后者与O_Zn有密切的关系。