Control of dispersion state of silsesquioxane nanofillers for stabilization of polystyrene thin films

The influence of the dispersion states of the nanofillers on the dewetting behavior of the polymer thin film was investigated. Polyhedral oligomeric silsesquioxanes (POSS) with various substituents were added into polystyrene (PS) thin films as the nanofillers. The dewetting rate of the films drastically changed with the surface substituents of POSS additives. Neutron reflectivity measurements indicated that the difference of the dewetting rate was associated with the dispersion state of POSS additives in the films. POSS with phenethyl groups (PhPOSS), which homogeneously dispersed into the films, resulted in the decrease of the glass transition temperature of PS and the enhancement of the dewetting of the films. POSS with a fluoroalkyl group (CpPOSS-R f) segregated to the film surface and showed the retardation of the dewetting by the decrease of the surface energy of the film. POSS with hydroxyl groups (CpPOSS-2OH) segregated to the film surface and film-substrate interface and led to the elimination of the dewetting, suggesting the importance of the interfacial segregation for the inhibition of dewetting. These results revealed the strong relationship between the dispersion state of the nanofillers and the dewetting of the nanofilled films.     

低能量链端对聚苯乙烯薄膜铺展和润湿行为的影响

通过低能量功能端基的表面富集作用,研究了聚苯乙烯（ＰＳ）薄膜在聚甲基丙烯酸甲酯（ＰＭＭＡ）表面上的铺展和润湿动力学．用光学显微镜跟踪了ＰＳ薄膜的润湿行为,并对高分子熔体膜中非连续部分尺寸的增大速率进行了测定．分别用ＸＰＳ和ＡＦＭ对ＰＳ薄膜的表面组成和ＰＳ液滴的平衡接触角进行了测定．发现具有低表面能的氟碳端基在薄膜表面富集使ＰＳ薄膜的表面张力下降,并使ＰＳ液滴在ＰＭＭＡ表面上的平衡接触角减小,从而使高分子熔体膜中非连续部分尺寸的增长速率下降,得到了与液液界面铺展和润湿理论一致的实验结果．     

Dewetting behavior of a block copolymer/homopolymer thin film on an immiscible homopolymer substrate

Numerous previous studies have established that the addition of a microphase-ordered AB diblock copolymer to a thin homopolymer A (hA) film can slow, if not altogether prevent, film rupture and subsequent film dewetting on a hard substrate such as silica. However, only a few reports have examined comparable phenomena when the hA/AB blend resides on a soft B-selective surface, such as homopolymer B (hB). In this work, the dewetting kinetics of thin films composed of polystyrene (PS) and a symmetric poly(styrene-b-methyl methacrylate) (SM) diblock copolymer on a poly(methyl methacrylate) substrate is investigated by hot-stage light microscopy. Without the SM copolymer, the dewetting rate of the PS layer is constant under isothermal conditions and exhibits Arrhenius behavior with an apparent activation energy of approximately 180 kJ/mol. Addition of the copolymer promotes a crossover from early- to late-stage dewetting kinetics, as evidenced by measurably different dewetting rates. Transmission electron microscopy reveals the morphological characteristics of dewetted PS/SM films as functions of film thickness and SM concentration.     

Dewetting of polystyrene thin films on poly(ethylene glycol)-modified surfaces as a simple approach for patterning proteins

A simple technique for patterning proteins utilizing dewetted polystyrene (PS) droplets is demonstrated. A polystyrene thin film was spin coated on a poly(ethylene glycol) (PEG) silane-modified surface. As the PS film dewets from the surface, upon annealing, to form droplets, the PEG-silane-modified surface is exposed, which retains its capability to resist protein adsorption, and the PS droplets allow the selective adsorption of proteins. In contrast to the undewetted flat PS film, the droplet surface had a greater amount of adsorbed proteins. Atomic force microscopy scans reveal that the roughness of the droplet surface is higher, and a multilayer of proteins results on the droplet surface. Moreover, micro- and nanoscale droplet patterns can easily be achieved by tuning the thickness of PS thin films. Because dewetting approaches for generating ordered dewetting droplets have been successfully generated by others, those approaches could be easily combined with this technique to fabricate ordered protein patterns.     

Surface phase separation, dewetting feature size, and crystal morphology in thin films of polystyrene/poly(ε-caprolactone) blend

Thin films of polystyrene (PS)/poly(ε-caprolactone) (PCL) blends were prepared by spin-coating and characterized by tapping mode force microscopy (AFM). Effects of the relative concentration of PS in polymer solution on the surface phase separation and dewetting feature size of the blend films were systematically studied. Due to the coupling of phase separation, dewetting, and crystallization of the blend films with the evaporation of solvent during spin-coating, different size of PS islands decorated with various PCL crystal structures including spherulite-like, flat-on individual lamellae, and flat-on dendritic crystal were obtained in the blend films by changing the film composition. The average distance of PS islands was shown to increase with the relative concentration of PS in casting solution. For a given ratio of PS/PCL, the feature size of PS appeared to increase linearly with the square of PS concentration while the PCL concentration only determined the crystal morphology of the blend films with no influence on the upper PS domain features. This is explained in terms of vertical phase separation and spinodal dewetting of the PS rich layer from the underlying PCL rich layer, leading to the upper PS dewetting process and the underlying PCL crystalline process to be mutually independent.     

Dewetting of thin polystyrene films absorbed on epoxy coated substrates

Various characteristics of dewetting of thin polystyrene (PS) films absorbed on highly cross-linked epoxy-coated and silicon oxide covered substrates are studied as a function of PS film thickness (20h(c1) whereas the spinodal dewetting (SD) occurs through the growth of surface undulations for hh(c2) while the SD mechanism is observed for h相似文献   

Wetting-dewetting transition line in thin polymer films

Thin polymeric films are increasingly being utilized in diverse technological applications, and it is crucial to have a reliable method to characterize the stability of these films against dewetting. The parameter space that influences the dewetting of thin polymer films is wide (molecular mass, temperature, film thickness, substrate interaction) and a combinatorial method of investigation is suitable. We thus construct a combinatorial library of observations for polystyrene (PS) films cast on substrates having orthogonal temperature and surface energy gradients and perform a series of measurements for a range of molecular masses (1800 g/mol < M < 35 000 g/mol) and film thicknesses h (30 nm < h < 40 nm) to explore these primary parameter axes. We were able to obtain a near-universal scaling curve describing a wetting-dewetting transition line for polystyrene films of fixed thickness by introducing reduced temperature and surface energy variables dependent on M. Our observations also indicate that the apparent polymer surface tension gamma(p) becomes appreciably modified in thin polymer films from its bulk counterpart for films thinner than about 100-200 nm, so that bulk gamma(p) measurements cannot be used to estimate the stability of ultrathin films. Both of these observations are potentially fundamental for the control of thin film stability in applications where film dewetting can compromise film function.     

Photoactive additives for cross-linking polymer films: Inhibition of dewetting in thin polymer films

In this report, we describe a versatile photochemical method for cross-linking polymer films and demonstrate that this method can be used to inhibit thin polymer films from dewetting. A bifunctional photoactive molecule featuring two benzophenone chromophores capable of abstracting hydrogen atoms from various donors, including C-H groups, is mixed into PS films. Upon exposure to UV light, the bis-benzophenone molecule cross-links the chains presumably by hydrogen abstraction followed by radical recombination. Photoinduced cross-linking is characterized by infrared spectroscopy and gel permeation chromatography. Optical and atomic force microscopy images show that photocrosslinked polystyrene (PS) thin films resist dewetting when heated above the glass transition temperature or exposed to solvent vapor. PS films are inhibited from dewetting on both solid and liquid substrates. The effectiveness of the method to inhibit dewetting is studied as a function of the ratio of cross-linker to macromolecule, duration of exposure to UV light, film thickness, the driving force for dewetting, and the thermodynamic nature of the substrate.     

Competition between dewetting and cross-linking in poly(N-vinylpyrrolidone)/polystyrene bilayer films

We investigated the dewetting of metastable poly(N-vinylpyrrolidone) (PNVP) thin films (45 nm) on top of polystyrene (PS) thin films (58 nm) as a function of annealing temperature and molecular weight of PS (96 and 6850 kg/mol). We focused on the competition between dewetting, occurring as a result of unfavorable intermolecular interactions at the PNVP/PS interface, and spontaneous cross-linking of PNVP, occurring during thermal annealing, as we recently reported (Telford, A. M.; James, M.; Meagher, L.; Neto, C. ACS Appl. Mater. Interfaces 2010, 2, 2399-2408). Using optical microscopy, we studied how the dewetting morphology and dynamics at different temperatures depended on the relative viscosity of the top PNVP film, which increased with cross-linking time, and of the bottom PS film. In the PNVP/PS96K system, cross-linking dominated over dewetting at temperatures below 180 °C, reducing drastically nucleated hole density and their maximum size, while above 180 °C the two processes reversed, with complete dewetting occurring at 200 °C. On the other hand, the PNVP/PS6850K system never achieved advanced dewetting stages as the dewetting was slower than cross-linking in the investigated temperature range. In both systems, dewetting of the PNVP films could be avoided altogether by thermally annealing the bilayers at temperatures where cross-linking dominated. The cross-linking was characterized quantitatively using neutron reflectometry, which indicated shrinkage and densification of the PNVP film, and qualitatively through selective removal of the bottom PS film. A simple model accounting for progressive cross-linking during the dewetting process predicted well the observed hole growth profiles and produced estimates of the PNVP cross-linking rate coefficients and of the activation energy of the process, in good agreement with literature values for similar systems.     

Dewetting of thin polystyrene films under confinement

The dewetting behavior of thin polystyrene (PS) film has been investigated by placing an upper plate with a ca. 140 nm gap from the underlying substrate with the spin-coated thin polymer films. Three different kinds of dewetting behaviors of thin PS film have been observed after annealing according to the relative position of the PS film to the upper plate. Since the upper plate is smaller than the underlying substrate, a part of the polymer film is not covered by the plate. In this region (I), thin PS film dewetting occurs in a conventional manner, as previously reported. While in the region covered by the upper plate (III), the PS film exhibits unusual dewetted patterns. Meanwhile, in the area right under the edge of the plate (II) (i.e., the area between region I and region III), highly ordered arrays of PS droplets are formed. Formation mechanisms of different dewetted patterns are discussed in detail. This study may offer an effective way to improve the understanding of various dewetting behaviors and facilitate the ongoing exploration of utilizing dewetting as a patterning technique.     

RUPTURING OF POLYMER FILMS WITH RUBBING-INDUCED SURFACE DEFECTS

It has been a long-standing question whether dewetting of polymer film from non-wettable substrate surfaceswherein the bicontinuous morphology never forms in the dewetting film is due to spinodal instability or heterogeneousnucleation. In this experiment, we use a simple method to make the distinction through introduction of topographical defectsof the films by rubbing the sample surface with a rayon cloth. Spinodal dewetting is identified for those films that dewet by acharateristic wavevector, q, independent of the density of rubbing-induced defects. Heterogeneous nucleation, on the otherhand, is identified for those with q increasing with increasing density of defects. Our result shows that PS films on oxidecoated silicon with thickness less than ≈ 13 nm are dominated by spinodal dewetting, but the thicker films are dominated bynucleation dewetting. We also confirm that spinodal dewetting does not necessarily lead to a bicontinuous morphology in thedewetting film, contrary to the classic theory of Cahn.     

Slow Down Dewetting in Polymer Films by Isocyanate-treated Graphite Oxide

Isocyanate-treated graphite oxides(i GOs) were well-dispersed into the polystyrene(PS) thin films and formed a novel network structure. With control in fabrication, an i GOs-web layer was horizontally embedded near the surface of the films and thus formed a composite slightly doped by i GOs. This work demonstrated that the i GOs network can remarkably depress the dewetting process in the polymer matrix of the composite, while dewetting often leads to rupture of polymer films and is considered as a major practical limit in using polymeric materials above their glass transition temperatures(Tg). Via annealing the 50–120 nm thick composite and associated neat PS films at temperatures ranging from 35 °C to 70 °C above Tg, surface morphology evolution of the films was monitored by atomic force microscopy(AFM). The i GOs-doped PS exhibited excellent thermal stability, i.e., the number of dewetting holes was greatly reduced and the long-term hole growth was fairly restricted. In contrast, the neat PS film showed serious surface fluctuation and a final rupture induced by ordinary dewetting. The method developed in this work may pave a road to reinforce thin polymer films and enhance their thermal stability, in order to meet requirements by technological advances.     

Nonsolvent-induced dewetting of thin polymer films

The process of nonsolvent-induced dewetting of thin polystyrene (PS) films on hydrophilic surfaces at room temperature has been studied by using water as a nonsolvent. It is observed that the process of nonsolvent-induced dewetting is greatly different from other previous dewetting processes. The PS film is found in nonviscous state in our study. A mechanism of nonsolvent-induced dewetting is deduced in an order of penetration, replacement, and coalescent, and it is different from other previous dewetting mechanisms. The results of experiments are analyzed from thermodynamics and dynamics to support the hypothetical mechanism.     

Morphological evolution in dewetting polystyrene/polyhedral oligomeric silsesquioxane thin film bilayers

Morphological evolution in dewetting thin film bilayers of polystyrene (PS) and a polyhedral oligomeric silsesquioxane (POSS), trisilanolphenyl-POSS (TPP), was studied as a function of annealing temperature and annealing time. The results demonstrate unique dewetting morphologies in PS/TPP bilayers at elevated temperatures that are significantly different from those typically observed in dewetting polymer/polymer bilayers. During temperature ramp studies by optical microscopy (OM) in the reflection mode, PS/TPP bilayers form cracks with a weak optical contrast at approximately 130 degrees C. The crack formation is attributed to tensile stresses within the upper TPP layer. The weak optical contrast of the cracks observed in the bilayers for annealing temperatures below approximately 160 degrees C is consistent with the cracking and dewetting of only the upper TPP layer from the underlying PS layer. The optical contrast of the morphological features is significantly enhanced at annealing temperatures of >160 degrees C. This observation suggests dewetting of both the upper TPP and the lower PS layers that results in the exposure of the silicon substrate. Upon annealing the PS/TPP bilayers at 200 degrees C in a temperature jump experiment, the upper TPP layer undergoes instantaneous cracking as observed by OM. These cracks in the upper TPP layer serve as nucleation sites for rapid dewetting and aggregation of the TPP layer, as revealed by OM and atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) results indicated that dewetting of the lower PS layer ensued for annealing times >5 min and progressed up to 90 min. For annealing times >90 min, OM, AFM, and XPS results revealed complete dewetting of both the layers with the formation of TPP encapsulated PS droplets.     

Influences of chain heterogeneity on instability of polymeric thin films: dewetting of polystyrenes, polychloromethylstyrenes and its copolymers

This study compares the stability of various polymeric thin films supported on SiO(x)/Si substrate. Dewetting behaviors of polystyrenes (PS), polychloromethylstyrenes, and random poly(styrene-co-chloromethylstyrene)s are investigated by utilizing atomic force microscopy. A systematic addition of the chloromethylstyrene (ClMS) unit into PS chain causes the increase of segment polarity, affecting interfacial and interchain interactions in thin films. It is found that stability of the polymeric films depends on two major parameters, ratio of the ClMS unit and film thickness. For approximately 5 nm thick film, the addition of only 5 mol% ClMS unit causes a drastic increase of its stability, attributed to the enhanced interfacial interactions between ClMS group and SiO(x) layer. Further increasing the ClMS mole ratio to 20, 45, and 100% is accompanied by a systematic increase of the film stability. Thicker films (thicknesses approximately 22 and approximately 45 nm) of the copolymer with 5 mol% ClMS unit exhibit rather different behavior. They are found to be less stable compared to the PS films. However, the films of copolymers with ClMS unit of 20, 45, and 100% are still much more stable than the PS films. These dewetting behaviors of the copolymers are correlated to the interfacial interactions, interchain interactions and segmental segregation in thin films.     

Dewetting behavior of polystyrene film filled with (C6H5C2H4NH3)2PbI4

The dewetting behavior of thin (about 30 nm) polystyrene (PS) films filled with different amount of (C(6)H(5)C(2)H(4)NH(3))(2)PbI(4) (PhE-PbI(4)) on the silicon substrate with a native oxide layer was investigated. For different additive concentrations, PhE-PbI(4) showed different spatial distributions in the PS films, which had a strong influence on the film wettability, dewetting dynamics, and mechanism. With 0.5 wt % additive, PhE-PbI(4) formed a noncontinuous diffusion layer, which caused a continuous hole nucleation in the film. With about 1 wt % additive, a continuous gradient distribution layer of PhE-PbI(4) formed in the film, which inhibited the dewetting. When the concentration is higher (2 wt %), large PhE-PbI(4) aggregates, in addition to the PhE-PbI(4) continuous layer, formed in the film. These large aggregates (larger than radius of gyration of PS) migrated to the interface, resulting in the hole nucleation and eventually the complete dewetting of the film.     

Phase Separation,Wetting and Dewetting in PS/PVME Blend Thin Films: Dependence on Film Thickness and Composition Ratio

The effects of film thickness and composition ratio on the morphology evolution of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blend thin films were investigated. Diverse morphology evolutions including droplet-matrix structure, hole emergence, bicontinuous structure formation, percolation-to-droplet transition could be observed under annealing in two-phase region, depending on film thickness and composition ratio. The mechanism for these morphology variations was related to the complex effects of phase separation, dewetting and preferential wetting. The comparison between the thickness of bottom PVME layer and the twice of gyration radius 2R_g(PVME) played a dominant role in morphology control. Only when the PS/PVME film had specific film thickness and compositional symmetry, phase separation and dewetting could happen in sequence.     

MISCIBILITY AND MORPHOLOGY OF THIN FILMS OF BLENDS OF POLYSTYRENE WITH BROMINATED POLYSTYRENES： EFFECTS OF VARYING THE MOLECULAR WEIGHT, BROMINATION DEGREE AND ANNEALING

Thin films of incompatible polymer blends can form a variety of structures during preparation and subsequent annealing process. For the polymer blend system consisting of polystyrene and poIy(styrene-co-p-bromo-styrene), i.e., PS/PBrxS, its compatibility could be adjusted by varying the degree of bromination and the molecular weight of both components comprised, in this paper, surface chemical compositions of the cast and the annealing films were investigated by X-ray photoelectron spectroscopy (XPS) and contact angle measurement; meanwhile, surface topographical changes are followed by atomic force microscopy (AFM). In addition, substantial attention was paid to the effect of annealing on the morphologic variations induced by phase separation and/or dewetting of the thin film. Moreover, the influences of the molecular weight, Aw, as well as the brominated degree, x%, on the sample surface are explored systematically, and the corresponding observations are explained in virtue of the Flory-Huggins theory, along with the dewetting of the polymer thin film.     

Effect of film thickness on morphological evolution in dewetting and crystallization of polystyrene/poly(ε-caprolactone) blend films

In this Article, the morphological evolution in the blend thin film of polystyrene (PS)/poly(ε-caprolactone) (PCL) was investigated via mainly AFM. It was found that an enriched two-layer structure with PS at the upper layer and PCL at the bottom layer was formed during spinning coating. By changing the solution concentration, different kinds of crystal morphologies, such as finger-like, dendritic, and spherulitic-like, could be obtained at the bottom PCL layer. These different initial states led to the morphological evolution processes to be quite different from each other, so the phase separation, dewetting, and crystalline morphology of PS/PCL blend films as a function of time were studied. It was interesting to find that the morphological evolution of PS at the upper layer was largely dependent on the film thickness. For the ultrathin (15 nm) blend film, a liquid-solid/liquid-liquid dewetting-wetting process was observed, forming ribbons that rupture into discrete circular PS islands on voronoi finger-like PCL crystal. For the thick (30 nm) blend film, the liquid-liquid dewetting of the upper PS layer from the underlying adsorbed PCL layer was found, forming interconnected rim structures that rupture into discrete circular PS islands embedded in the single lamellar PCL dendritic crystal due to Rayleigh instability. For the thicker (60 nm) blend film, a two-step liquid-liquid dewetting process with regular holes decorated with dendritic PCL crystal at early annealing stage and small holes decorated with spherulite-like PCL crystal among the early dewetting holes at later annealing stage was observed. The mechanism of this unusual morphological evolution process was discussed on the basis of the entropy effect and annealing-induced phase separation.     

Ordered droplet formation by thin polymer film dewetting on a stripe-patterned substrate

The dewetting process of thin polystyrene (PS) film on flat and stripe-patterned substrates is presented. Different dewetting processes were observed when the thin PS films annealed at above the glass transition temperature on these different kinds of substrates. The final dewetting on the flat substrate led to formation of polygonal liquid droplets, while on the stripe-patterned substrate, the droplets were observed to align at the centers of the stripes. A possible explanation for the dewetting process on the stripe-patterned substrate is proposed.