Interface morphology snapshots of vertically segregated thin films of semiconducting polymer/polystyrene blends

We present atomic force microscopic images of the interphase morphology of vertically segregated thin films spin coated from two-component mixtures of poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene-vinylene] (MEH-PPV) and polystyrene (PS). We investigate the mechanism leading to the formation of wetting layers and lateral structures during spin coating using different PS molecular weights, solvents and blend compositions. Spinodal decomposition competes with the formation of surface enrichment layers. The spinodal wavelength as a function of PS molecular weight follows a power-law similar to bulk-like spinodal decomposition. Our experimental results indicate that length scales of interface topographical features can be adjusted from the nanometer to micrometer range. The importance of controlled arrangement of semiconducting polymers in thin film geometries for organic optoelectronic device applications is discussed.     

Comparison of the phase behaviour of the liquid-crystalline polymer/poly(methyl methacrylate) and poly(vinyl acetate)/poly(methyl methacrylate) blends

The phase behaviour of blends of a liquid-crystalline polymer (LCP) and poly(methyl methacrylate) (PMMA), as well as the phase state of blends of PMMA and poly(vinyl acetate) (PVA) has been investigated using light scattering and phase-contrast optical microscopy. The blends of LCP and PMMA have been obtained by coagulation from ternary solutions. The cloud point curves were determined. It was established that both pairs demix upon heating, ie have an LCST. In the region of intermediate composition, the phase separation proceeds according to a spinodal mechanism; however for LCP/PMMA blends, the decomposition proceeds according to a non-linear regime from the very onset. In the region of small amounts of LCP, the phase separation follows a mechanism of nucleation and growth. For PMMA/PVA blends, the spinodal decomposition proceeds according to a linear regime, in spite of the molecular mobility that PVA chains develop at lower temperatures. Only after prolonged heat treatment does the process transit to a non-linear regime. The data show a similarity between the phase behaviour of blends of liquid-crystalline and of flexible amorphous polymers. The distinction consists of the absence of a linear regime of decomposition for LCP-PMMA blends. © 1999 Society of Chemical Industry     

Photocrosslinking kinetics of polymer blends undergoing spinodal decomposition process

Photocrosslinking reaction kinetics of poly(2-chlorostyrene) performed inside the spinodal region of poly(2-chlorostyrene)/poly(vinyl methyl ether) (P2CS/PVME) blends was investigated by means of ultraviolet (UV)-visible absorption spectroscopy. The reaction was performed via photodimerization of anthracene moieties chemically labeled on the P2CS chains. The crosslinking kinetics of (P2CS/PVME) blends submitted to a temperature jump from the one-phase into the spinodal regions was observed by monitoring the irradiation time dependence of the absorbances of anthracene as well as of the blend in two regions of wavelengths. One is inside and the other is outside the absorption range of anthracene. The contribution of the sample cloudiness to the absorbance of anthracene was subtracted from the absorption data by using an empirical power law experimentally established between the incident wavelengths and the absorption of the blends. It was found that the reaction kinetics approximately follows the mean-field kinetics inside the spinodal region, resembling the behavior of the crosslinking reaction performed in the miscible region at relatively low crosslinking densities. On the other hand, the method described here fails to estimate the crosslinking densities when the phase separation proceeds rapidly, overcoming the reaction. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:885–893, 1998     

Orientational phase-separated domains in a polyolefin blend under a temperature gradient field

We investigate the effect of a temperature gradient on the orientation of phase-separated structures in a polyolefin blend system. Phase contrast optical microscopy (PCOM) has been used to measure the morphology of phase separation via spinodal decomposition as a function of phase separation time and temperature gradient. The bicontinuous and interconnected tubelike structure, the characteristic morphology of the spinodal decomposition process, exhibits a preferential alignment along the direction of temperature gradient after phase separation. The orientation of the bicontinuous and interconnected tubelike structures gradually increases with phase separation time and temperature gradients. Also the orientation of phase-separated domains can respond really quickly to the change in the direction of external temperature gradient field. The results suggest that “thermal force” induced by the temperature inhomogeneity might play an important role in aligning phase-separated domains preferentially along the temperature gradient direction.     

Polymer blends with spatially graded structures prepared by phase separation under a temperature gradient

Phase separation of poly(2-chlorostyrene)/poly(vinyl methyl ether) (P2CS/PVME) blends driven by a temperature gradient was investigated by phase-contrast optical microscopy combined with digital image analysis. The samples were set in a temperature gradient in such a way that the two ends of the gradient cover both sides of the critical point. When the high-temperature side of the gradient is increased with a constant rate, the interface that divides the miscible and the phase separated regions of the blend moves toward the low temperature side, leaving the phase separating region behind. It was found that in the vicinity of this interface, the phase separation takes place slowly via the spinodal decomposition process, giving interconnecting structures. In the region far from the newly growing interface, the droplet morphology appears as a result of the late stage of the spinodal decomposition. These droplets grow with time according to the power law ξ ∝ tβ, with β increasing from 0.30 to 0.44 along the temperature gradient. The phase separated blends with these graded morphologies show the broadened mechanical tanδ due to the graded structures distributed along the temperature gradient.     

Effects of shear flow and annealing on the morphology of rapidly precipitated immiscible blends of polystyrene and polyisoprene

Binary blends of polystyrene (PS) and polyisoprene (PI) were prepared by rapidly precipitating a homogeneous solution, consisting of PS, PI and toluene, into methanol under vigorous agitation. In this study, a series of PSs and PIs were synthesized via anionic polymerization in our laboratory. Portions of the as-precipitated blend were annealed at 110°C for different periods up to 12 h and the rest was extruded at 160 or 180°C using a capillary die. The extrudates were also annealed for different periods up to 12 h. Then, the morphology of the as-precipitated blend with and without annealing, and the extrudate with and without annealing, was investigated using transmission or scanning electron microscopy. We found that: (1) the asprecipitated blend had a co-continuous (or quasi co-continuous) morphology, often observed in two-phase polymer mixtures which have undergone spinodal decomposition; (2) annealing or extrusion transformed the initially co-continuous (or quasi co-continuous) morphology of the as-precipitated blend into a well-defined dispersed two-phase morphology; (3) during annealing, the elongated droplets in an extrudate specimen recoiled considerably, the extent of which depended upon the duration of annealing. The effects of blend composition and the viscosity ratio of the constituent components on two-phase blend morphology are discussed.     

Mesoscopic simulation of asymmetric-copolymer/homopolymer blends: Microphase morphological modification by homopolymer chains solubilization

In this work we present the results of a mesoscopic dynamic simulation study of ordered microphases modification in asymmetric-copolymer/homopolymer binary blends, where we explore the influence of the composition, packing density and solubilization of homopolymer chains into the compatible microdomains of the asymmetric copolymer. The poly(styrene)-poly(isoprene) (PS-PI) and homopoly(styrene) (HPS) molecules were built and represented by Gaussian chain models. The pure asymmetric copolymer generates spherical microdomains of poly(styrene) (PS) in the matrix of majority component, poly(isoprene) (PI), and is taken as the base for the binary blends. The mesoscopic dynamic evolution of asymmetric-PS-PI/HPS blends display a coarse-grained system sufficiently large to determine the separation of the microphase and the formation of ordered structures. The HPS chains tend to be selectively solubilized in the PS microdomains of the asymmetric copolymer, the repulsive interaction forces between homopoly(styrene) and poly(isoprene) chains assure that essentially all the HPS homopolymer exists in the PS microdomains. As the asymmetric-PS-PI/HPS composition is varied the mesoscale simulations predict ordered structures with defined morphologies of body-centred-cubic (BCC), hexagonal packed cylinders (HPC), hexagonal perforated layers (HPL) and lamellar phases (LAM). Ordered microphases appear in reverse order when the homopoly(styrene) composition is increased in the binary blend. The agreement between our mesoscopic simulation results and available experimental outcome open a new strategy to modify the microphase morphology of asymmetric copolymers.     

Preparation and Phase Separation Behavior of (Co,Fe)3O4 Films

(Co,Fe)₃O₄ films were synthesized by the sol–gel method through metalorganic compounds. The (Co,Fe)₃O₄ films (Co:Fe = 2:1) showed the characteristic behavior of the spinodal decomposition by heat treatments within the miscibility gap. The coercive force of the spinodally decomposed films increased from 0.9 kOe for a solid solution to 2.0 kOe for films that underwent the spinodal decomposition. The nonmagnetic phase (rich in Co) formed by the spinodal decomposition contributes to the pinning of the movement of magnetic domain walls. On the other hand, the (Co,Fe)₃O₄ films (Co:Fe = 1:1) showed the typical feature of binodal decomposition during heat treatment within the miscibility gap. The binodally decomposed films showed a slight increase in the coercive force depending upon the evolution of the magnetic region.     

Morphology and properties control on rubber-epoxy alloy systems

Morphology and properties of polymer alloys can be controlled by thermody-namlcally reversible (structure freeze-in) or irreversible (structure lock-in) processes by simultaneously manipulating miscibility, mechanisms of phase separation, glass transition temperature (structural relaxation), and cure kinetics of polymer systems. Using phase diagrams consisting of binodal and spinodal curves, the morphology of epoxy/CTBN (carboxyl-terminated butadiene acryloni-trile copolymer) systems can be controlled by the mechanism of nucleation and growth or by spinodal decomposition via simultaneously manipulating the kinetic processes of phase separation and curing reactions. We have found that the particle size of the rubber reinforcement in epoxies is affected by the mechanisms of phase separation. Phase separation by nucleation and growth gives larger rubber particles than the corresponding phase separation by spinodal decomposition. This contrast in the morphology development is the consequence of controlling phase separation through chemorheological behavior. Medication of the phase separation kinetics in epoxy/CTBN systems was extremely effective at altering both morphology and properties of these alloys. This technique offers a means to shift the glass transition temperature of the rubber-rich phase drastically without reducing the glass transition temperature of the epoxy-rich phase significantly. Such control over morphology is the key to ultimately controlling material properties. This morphology manipulation allows us to tailor the mechanical properties of alloy systems.     

Shear field in the mold cavity of multimelt multi‐injection molding revealed by the morphology distribution of a model polymer blend

The morphology distribution of a model polymer blend, polystyrene (PS)/polyethylene (PE), molded by multimelt multi‐injection molding (MMMIM) process was studied by scanning electronic microscopy and polarizing light microscopy. An unusual double skin/core morphology was observed. The minor phase, PS, showed highly deformed morphology in both the skin layer near the mold wall and the core layer near the skin/core layer's interface. Meanwhile, in the regions that highly deformed PS phase showed, highly ordered cylindritic crystal structures of PE are also formed. As we all know the driving force and the basic prerequisite to deform the dispersed droplet and form the oriented crystal structure is the shear field. So an attempt was made to correlate the dispersed phase morphology, crystalline morphologies, and shear rate. The shear rate, estimated via the capillary number, across the thickness of the parts molded by MMMIM was bimodal. Even if the coalescence and relaxation of the dispersed phase during and after mold filling cannot be ignored, both the highly dispersed PS domains and the highly ordered crystal structure of PE showed in the regions with the maximum calculated shear rate, which is consistent with the generally accepted theories that strong shear flow is favorable to the formation of the oriented structures. POLYM. ENG. SCI., 54:2345–2353, 2014. © 2013 Society of Plastics Engineers     

Morphology development and characterization of the phase-separated structure resulting from the thermal-induced phase separation phenomenon in polymer solutions under a temperature gradient

This paper studied the morphological development during the fabrication of anisotropic polymeric materials using the thermal-induced phase separation phenomenon (spinodal decomposition) in a model binary polymer solution under a linear spatial temperature gradient using mathematical modeling and computer simulation. The model incorporated the non-linear Cahn-Hilliard theory for spinodal decomposition and the Flory-Huggins theory for polymer solution thermodynamics. Moreover, the slow mode theory and Rouse law were used to account for polymer diffusion. The two-dimensional numerical results showed that an anisotropic morphology was developed when a temperature gradient was imposed along the polymer solution sample. The droplet size and droplet density decrease as temperature increases during the intermediate stage of spinodal decomposition. The spatial temperature gradient, however, had insignificant effect on the droplet shape.     

Analysis of unsaturated polyester-polyurethane interpenetrating polymer networks II: Phase separation behavior

The phase separation behavior of unsaturated polyester (UPE)-polyurethane (PU) interpenetrating polymer networks (IPNs) was investigated by light scattering measurements during simultaneous polymerization. The scattered light intensity change with time showed the formation of the dispersed domains, and the average domain correlation length could be calculated from the angle of maximum scattering intensify. It was noted that the dominant phase separation process was spinodal decomposition due to fast reaction. The morphology observed by the transmission electron micrographs for various process conditions showed similar results as obtained from the light scattering experiment.     

Solvent annealing assisted self-assembly of hydrogen-bonded interpolymer complexes of AB block copolymer/C homopolymer in thin film

A simple process of solvent annealing has been shown to produce ordered self-assembly structures of poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP)/poly(4,4′-oxydiphenylenepyromellitamic acid) (POAA) block copolymer/homopolymer blends in thin film, where POAA chains selectively interact with P4VP blocks by strong interpolymer hydrogen-bonding. By simply exposing the thin film to benzene/NMP (0.97/0.03, in volume) vapor mixture, ordered microphase-separated structures with PS spherical microdomains distributed within P4VP/POAA complexes matrix were obtained. The formation of the microphase-separated structures could be attributed to the substantial mobility of PS blocks and P4VP/POAA complexes and enhanced repulsion between them under the benzene/NMP mixture vapor. When the volume ratio of benzene to NMP increased to 0.98/0.02, the increasing benzene in the mixture vapor induced the adhesive collision of spherical microphase-separated structures to form long “pearl necklaces”. With increasing volume ratio of benzene to NMP to 0.99/0.01, an ordered “pearl necklace” array oriented parallel to the film surface formed. The self-assembly structures were studied by FTIR spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM). Finally, possible mechanism of self-assembly and formation of microphase morphology was proposed.     

New insights into the thermal aging mechanism of yttria stabilized zirconia: A phase field study

In this paper, a novel phase-field (PF) model is proposed to study the thermal aging mechanism of single crystalline t'-YSZ. The influences of the initial compositional content of yttria and the initial twin structure of the t' phase on the aging process are systematically discussed. The PF model can recover the modulated structure and nano/micro hybrid structure observed in experiments. The PF simulation results indicate that the initial compositional content of yttria is the most important influential factor of the thermal aging process. Besides that, the transformation strain, the initial twin structure and the anti-phase boundaries (APBs) of the t' phase can also have significant influences on the thermal aging kinetics. The typical spinodal region is more suitable to predict the thermal aging behavior of single domain YSZ. For multi-domain YSZ with initial twin structures and APBs, the spinodal region should be further divided into the kernel region and marginal region. In the kernel region, the thermal aging occurs by spinodal decomposition with the formation of a modulated structure, which is followed by merging and coarsening. In the marginal region and outside the spinodal region, the phase decomposition leads to a hybrid structure with coarse grained cubic phase and fine grained tetragonal phase, which exhibits the characteristics of nucleation and growth. The hybrid structure is consistent with previous experimental observations. It is revealed that the boundaries of the nano sized tetragonal grains evolve from the twin boundaries and APBs. The nucleation-growth mechanism should be properly understood when it is applied to illustrate the evolution process of the hybrid structure. The PF model and the new insights obtained in this study are helpful to understand the thermal aging mechanisms of t'-YSZ.     

Multilayer formation via spinodal decomposition in TiO2-VO2 epitaxial films on sapphire substrates

We present multilayer formation via spinodal decomposition in rutile TiO₂-VO₂ (TVO) epitaxial films on sapphire substrates. (001)- and (101)-oriented TVO solid-solution films are grown epitaxially on TiO₂/Al₂O₃ using a pulsed laser deposition technique and annealed inside the spinodal region. X-ray diffraction measurements and scanning transmission electron microscopy (STEM) observations show that the films are phase-separated along the [001] direction and lamellar structures are formed in a parallel or slanted direction to the sapphire substrates depending on the film orientation. The results indicate the multilayer formation via spinodal decomposition in the TVO films. STEM investigations also reveal a relatively high Ti concentration in the decomposed phases, reflecting the influence of lattice deformation on the phase decomposition in the films. Our work shows that spinodal decomposition is a promising approach for the formation of a multilayer structure in TVO films and helps deepen understanding the spinodal decomposition in TVO system.     

Effect of selective localization of cellulose nanowhiskers on viscoelastic phase separation

Viscoelastic phase separation (VPS) is a fundamental physical phenomenon that creates percolated network structure in dynamically asymmetric mixtures. The object of this study was to investigate the effect of rod shape nanoparticles with different surface chemistries on VPS in the polystyrene/poly(vinyl methyl ether), PS/PVME, blend. For this purpose, hydrophilic (CNWs) and hydrophobic (M‐CNWs) cellulose nanowhiskers (CNWs) were prepared to be used as nanorods. Rheological measurments were employed to investigate the effect of nanowhiskers on phase separation temperature, kinetics of phase separation, and dynamic asymmetry. The evolution of morphology during the phase separation at a fixed quench depth was assessed using polarized optical microscopy. The nanowhiskers were effective in decreasing the correlation length, which slowed down the phase separation. CNWs self‐assembled into the PVME‐rich phase during the phase separation, which led to a decrease in the dynamic asymmetry and beyond a critical volume fraction of CNWs, the VPS mechanism changed to spinodal decomposition (SD). However, in the presence of M‐CNW, the localization of M‐CNWs into the PS‐rich phase enhanced the dynamic asymmetry and at 2 vol% M‐CNWs, the induced PS‐rich network by VPS was arrested. The linear and non‐linear viscoelastic behavior of the samples were studied as well. POLYM. ENG. SCI., 58:928–942, 2018. © 2017 Society of Plastics Engineers     

Crystallization of polycarbonate induced by spinodal decomposition in polymer blends

We found that amorphous polycarbonate (PC) can be crystallized in several minutes by blending poly(ethylene oxide) (PEO). When the blends were annealed in the two-phase region below the upper critical solution temperature, highly interconnected two-phase structure characteristic of the spinodal decomposition was developed and then the crystallization occurred in the PC-rich phase during the spinodal decomposition. As the molecular weight of PEO decreased, the crystallization rate decreased and the crystallizable temperature became narrower in spite of the acceleration of the polymeric segmental motion. These results suggest that the crystallization of the PC is not induced by the acceleration of the polymeric segmental motion, but by the up-hill diffusion of the liquid-liquid phase separation via spinodal decomposition. Owing to the competitive progress of the crystallization and the spinodal decomposition, the melting peak of the PC crystallites shifted to lower temperature with increasing annealing temperature.     

三聚磷酸二氢铝Ⅰ型二水物一步合成法及热分解动力学

研究三聚磷酸二氢铝Ⅰ型二水物的微波合成工艺及其热分解动力学。以氢氧化铝和磷酸为原料,用XRD、Ram an、SEM等手段对产物进行表征,运用TG-DTG技术、4种积分法和3种微分法、选用43种机理方程研究产物的热分解动力学模型。结果表明:在微波750 W、15 m in下一步合成的化合物是A lH2P3O10.2H2O(I),该化合物在393—533 K区间脱去2分子结晶水,属于二维扩散控制,活化能E为61.375 kJ/mol,指前因子A为1.78×107s-1;在703—843 K区间脱去1分子结构水,属于成核生长控制,活化能198.890 kJ/mol,指前因子A为2.458 5×1013s-1。     

Synthesis of graft copolymers. III. Polystyrene‐g‐poly(butyl acrylate)

Polystyrene (PS) chains functionalized with pendant 1,2‐bis(trimethylsilyloxy)tetraphenylethane (TPSE) groups are used as macroinitiators to initiate the polymerization of n‐butyl acrylate (BuA) to synthesize PS‐g‐poly(BuA) (PS‐g‐PBuA) copolymers at 130°C. The TPSE groups are known to function as initers in the polymerization of several vinyl monomers. The homolytic decomposition of TPSE results in a diphenylmethyl (DPM) radical attached to the main chain and a free DPM radical. The former is responsible for the polymerization initiation and the latter momentarily stops the growth of the growing grafts by the formation of a dormant species. Unfortunately, side reactions like the combination between growing grafts take place and the polymerization can only be controlled in a limited range of conversion. The most appropriate conditions for the synthesis of PS‐g‐PBuA are reported to present their potential use as thermoplastic elastomers with relatively controlled structures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 19–26, 2002     

Phase morphology and stability of co-continuous (PPE/PS)/PA6 and PS/PA6 blends: effect of rheology and reactive compatibilization

(PPE/PS)/PA6 and PS/PA6 blends were prepared by means of melt-extrusion. They were compatibilized using the reactive styrene-maleic anhydride copolymer with 2 wt% maleic anhydride (SMA2). The effect of compatibilization on the phase inversion and the stability of the resulting co-continuous blend structures were investigated using scanning electron microscopy, dissolution and extraction experiments. The onset of co-continuity shifted towards lower PA6 concentrations according to the change in blend viscosity ratio. The melting order of the components inside the extruder could result in a change in the observed co-continuity interval in slowly developing phase morphologies. The unmodified co-continuous blends were not stable and did break-up into a droplet/matrix type of morphology upon annealing in the melt depending on the blend composition. Although the stability of the threads during annealing improved upon compatibilization because of the lower resulting interfacial tension, the decreased possibility for recombination and coalescence during flow reduced the co-continuous region for the compatibilized blends. It is proposed that a dynamic equilibrium between break-up and recombination phenomena after the initial network formation is necessary to maintain the network structure.