Effect of organically modified layered silicates on the morphology of symmetrical blends of polystyrene and poly(methyl methacrylate)

The changes in morphology caused by the addition of organically modified layered silicate on equal volume fraction blends of polystyrene and poly(methyl methacrylate) are investigated. In thin films supported on silicon, without layered silicates, the PMMA forms a layer on the silicon, while the PS tend to minimize contact with both the hydrophilic silicon substrate and the PMMA phase, and tend to form discrete domains on top of the PMMA layer. With the introduction of layered silicates, the characteristic length scale of the structure decreases. On the other hand, in bulk samples, without the layered silicates, the equal volume fraction blend has the PS domains in a PMMA matrix. At 0.6 wt% of added silicate, in both thin film and bulk, the blend morphology converts from discrete to co-continuous. Electron micrographs reveal well dispersed silicate sheets locating at the interface between small PS domains in the PMMA phase. The change in morphology is conjectured to be the result of the interfacial location of the layered silicates rather than the change in viscosity ratio between the two phases.     

Morphological evolution of thin PS/PMMA films: Effects of surface energy and blend composition

We systematically compare the morphological evolution of thin PS/PMMA films, with varying compositions, during thermal annealing on preferential and non-preferential surfaces. On native silicon oxide surfaces, the phase evolution in the films was dictated by the preferential substrate-wetting of PMMA. However, the resulting PS relief structures on the PMMA wetting layer varied with the blend composition, and transitioned from capillary-fluctuation-mediated breakup to random nucleation with increased PS concentration. In contrast, the morphological evolution of the PS/PMMA films on non-preferential surfaces was also dictated by the coarsening of PMMA domain, but proceeded without the formation of a PMMA wetting layer. Both the PS and PMMA domains maintain direct contact with both the substrate and free surfaces throughout the evolution of the morphology. The morphologies at the interfaces were highly correlated, but with distinctive length scales. A variety of dispersed and continuous phase-separated structures can thus be obtained.     

拉曼Mapping成像研究聚苯乙烯/聚甲基丙烯酸甲酯共混体系的相态结构

利用拉曼光谱成像技术研究了聚苯乙烯/聚甲基丙烯酸甲酯（PS/PMMA）共混薄膜体系及其增容体系（增容剂为PS-b-PMMA嵌段共聚物）的相态结构及化学成分分布。实验结果表明,拉曼Mapping成像技术不仅可以得到PS/PMMA共混体系化学成分的精确分布图,同时也可以获取共混体系中分散相、界面相和连续相的分子指纹光谱。研究发现,共混体系中分散相和连续相组分分布与体系的组成紧密相关,当PS/PMMA质量比30/70时,分散相为PS,连续相为PMMA;当PS/PMMA质量比为50/50时,分散相为PS,但PS分子链仍存在于PMMA连续相中;当PS/PMMA质量比为70/30时,分散相为PMMA,连续相为PS。当增容剂PS-b-PMMA加入到PS/PMMA共混体系中后,分散相粒径减小、分布更加均匀、共混体系相容性指数（N_c）增大,说明PS/PMMA共混体系由完全不相容体系趋向变成半相容性体系,这是因为增容剂能增加PS和PMMA之间的相互作用,降低了体系的相分离程度,改善了共混体系的相容性。     

Surface morphology control of immiscible polymer-blend thin films

The effects of the molecular weights (molecular weight of polystyrene, M_w,PS, varying from 2.9 to 129 k) on the surface morphologies of spin-coated and annealed polystyrene/poly (methyl methacrylate) (PS/PMMA=50/50, w/w) blend films were investigated by atomic force microscopy and X-ray photoelectron spectroscopy. For the spin-coated films, when the M_w,PS varied from 2.9 to 129 k, three different kinds of surface morphologies (a nanophase-separated morphology, a PMMA cellular or network-like morphology whose meshes filled with PS, a sea-island like morphology) were observed and their formation mechanisms are discussed, respectively. Upon annealing, two different morphology-evolution processes were observed. It is found that a upper PS-rich phase layer is formed when M_w,PS<4 k, and this behavior is mainly attributed to the low interfacial tension between PS and PMMA component. When M_w,PS>4 k, the PS-rich phase forms droplets on top of the PMMA-rich phase layer which wets the SiO_x substrate. These results indicate that the surface morphology of the polymer blend films can be controlled by the polymer molecular weight and annealing conditions.     

CO2 foaming based on polystyrene/poly(methyl methacrylate) blend and nanoclay

A poly(methyl methacrylate) (PMMA) and nanoclay composite was dispersed into polystyrene (PS) using a twin‐screw extruder. The mixture was then batch foamed with supercritical CO₂. It was found that the cell density of foams based on the blend is higher than that based on the weight average of the two pure polymer components at the same foaming conditions. The cell size decreases and the cell density increases with the increase of the PMMA domain size. One explanation is that the large PMMA domains serve as a CO₂ reservoir and the nucleation in the PS phase is enhanced by the diffusion of CO₂ from the PMMA phase to the PS phase. Very small PMMA domains cannot function as a CO₂ reservoir, and so they are not able to facilitate the nucleation. A much higher cell density and smaller cell size were observed when nanoclay was located at the interface of the PMMA and the PS domains, serving as the heterogeneous nucleating agents. POLYM. ENG. SCI., 47:103–111, 2007. © 2007 Society of Plastics Engineers     

A study on weld line morphology and mechanical strength of injection molded polystyrene/poly(methyl methacrylate) blends

In this work, the mechanical strength and weld line morphology of injection molded polystyrene/poly(methyl methacrylate) (PS/PMMA) blends were investigated by scanning electron microscopy (SEM) and mechanical property test. The experimental results show that the tensile strength of PS/PMMA blends get greatly decreased due to the presence of the weld line. Although the tensile strength without the weld line of PS/PMMA (70/30) is much higher than that of the PS/PMMA (30/70) blend, their tensile strength with weld line shows reversed change. The viscosity ratio of dispersed phase over matrix is a very important parameter for control of weld‐line morphology of the immiscible polymer blend. In PS/PMMA (70/30) blend, the PMMA dispersed domains at the core of the weld line are spherically shaped, which is the same as bulk. While in the PS/PMMA (30/70) blend, the viscosity of the dispersed PS phase is lower than that of the PMMA matrix, the PS phase is absent at the weld line, and PS particles are highly oriented parallel to the weld line, which is a stress concentrator. This is why weld line strength of PS/PMMA (30/70) is lower than that of PS/PMMA (70/30) blend. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1856–1865, 2002; DOI 10.1002/app.10450     

Relation between the viscoelastic and flammability properties of polymer nanocomposites

Previous work has shown that the formation of a network structure of nanoparticles within a polymer matrix can significantly reduce nanocomposite flammability and that viscoelastic properties could be utilized to predict their flammability reduction. The present work extends this type of investigation to the study of clay and carbon nanotube nanocomposites. In particular, we study PS/clay, PS/MWNT, PMMA/clay, and PMMA/SWNT nanocomposites. At a clay level of about 10% by mass, the network structure is formed for the PS and the PMMA clay nanocomposites; it requires a level of about 0.5% with the SWNT and 2% with the MWNT. These samples showed significantly reduced mass loss rates of PS and PMMA. However, the solid residues collected from radiative gasification tests of PS/clay and PMMA/clay showed many small cracks, despite the network formation within the initial sample. This is in contrast to the smooth, continuous residues (no cracks or openings) for PS/MWNT and PMMA/SWNT nanocomposites. The cracks in the clay samples are probably formed due to weaker network at elevated temperatures due to weaker bridging interaction between clay platelets as compared to stronger network resulting from dense entanglement and bridging of carbon nanotubes.     

New applications in studies of waterborne coatings by atomic force microscopy

Atomic force microscopy (AFM) is rapidly emerging as an important tool for coatings characterization. We report several new applications of AFM of particular value to the development of improved waterborne coatings systems. First, an AFM method was developed to quantitatively assess the extent of coalescence and film formation for latex films by measurement of particle number density of protruding (uncoalesced) particles in dried coatings. Second, the use of topographic imaging to evaluate environmental (temperature) effects on film formation was investigated for a waterborne latex system. Finally, specular gloss of waterborne epoxy coatings was studied by AFM and optical measurements, and topographic features analyzed using power spectral density calculations were found to correlate with optical gloss measurements. Mechanisms for gloss reduction over time (particularly in early pot life coatings) were elucidated in the studies. Further applications in coatings studies will be driven by the development of new modes of AFM (friction force, force modulation, and phase contrast) that can be used to map mechanical properties (friction, stiffness, and adhesion) while simultaneously imaging topography. Examples of the use of the phase contrast mode to identify chemically different domains in early pot life waterborne epoxy coatings are presented.     

Structured latex particles based on natural rubber for high-impact polymer blends

Natural latex (NR) particles, modified with a hard shell of poly(methyl methacrylate) (PMMA) and with a substructure of PMMA (type "NR-M") or polystyrene (type "NR-SM"), were tested as compatibilizers in blends of polycarbonate (of bisphenol A, PC) and PMMA or PS. During melt blending, the modified NR particles were torn apart, from an original size of >0.5 μm down to ≅0.1 μm in diameter. Two different types of particle distribution were observed in the blends: in PC/PMMA/NR-M blends, the NR-M particles were dispersed in the PMMA phase, whereas, in PC/PS/NR-SM blends, the NR-SM particles formed interface layers between PC and PS phase domains. The latter blend morphology, distinguished by continuous rubbery interface layers of NR-SM, turned out to be mechanically excellent in injection-moulded parts. The poor impact strength of PC/PS was raised by an order of magnitude. The effect depends on the orientation in the injection-moulded test bars.     

Comparison of morphologies and mechanical properties of crosslinked epoxies modified by polystyrene and poly(methyl methacrylate)) or by the corresponding block copolymer polystyrene-b-poly(methyl methacrylate)

Polystyrene (PS, M_n=28,400, PI=1.07), poly(methyl methacrylate) (PMMA, M_n=88,600, PI=1.03), and PS (50,000)-b-PMMA (54,000) (PI=1.04), were used as modifiers of an epoxy formulation based on diglycidyl ether of bisphenol A (DGEBA) and m-xylylene diamine (MXDA). Both PS and PMMA were initially miscible in the stoichiometric mixture of DGEBA and MXDA at 80 °C, but were phase separated in the course of polymerization. Solutions containing 5 wt% of each one of both linear polymers exhibited a double phase separation. A PS-rich phase was segregated at a conversion close to 0.02 and a PMMA rich phase was phase separated at a conversion close to 0.2. Final morphologies, observed by scanning electron microscopy (SEM), consisted on a separate dispersion of PS and PMMA domains. A completely different morphology was observed when employing 10 wt% of PS-b-PMMA as modifier. PS blocks with M_n=50,000 were not soluble in the initial formulation. However, they were dispersed as micelles stabilized by the miscible PMMA blocks, leading to a transparent solution up to the conversion where PMMA blocks began to phase separate. A coalescence of the micellar structure into a continuous thermoplastic phase percolating the epoxy matrix was observed. The elastic modulus and yield stress of the cured blend modified by both PS and PMMA were 2.64 GPa and 97.2 MPa, respectively. For the blend modified by an equivalent amount of block copolymer these values were reduced to 2.14 GPa and 90.0 MPa. Therefore, using a block copolymer instead of the mixture of individual homopolymers and selecting an appropriate epoxy-amine formulation to provoke phase separation of the miscible block well before gelation, enables to transform a micellar structure into a bicontinuous thermoplastic/thermoset structure that exhibits the desired decrease in yield stress necessary for toughening purposes.     

On the presence of a critical shell volume fraction leading to pseudo-pure droplet behavior in composite droplet polymer blends

During melt mixing a ternary blend system comprised of a high density polyethylene matrix containing dispersed polystyrene and poly(methyl-methacrylate) spontaneously forms a composite droplet structure where the PS encapsulates the PMMA. This study demonstrates that the PS/PMMA composite droplet exhibits pure PS droplet behavior at a critical volume fraction of encapsulating phase (PS:PMMA∼0.6:0.4). This critical volume fraction is shown to be independent of the overall dispersed phase concentration, shell thickness or dispersed phase size. Furthermore, the effect is observed even though the PMMA is significantly more viscous than the encapsulating PS phase. Interfacial slip as well as the maintenance of a complete PS shell during deformation are proposed as being important factors related to this behavior. The blends were prepared via melt mixing using an internal mixer and the morphology was examined by electron microscopy.     

Ultraporous poly(l-lactide) scaffolds prepared with quaternary immiscible polymer blends modified by copolymer brushes at the interface

The activity of polystyrene-block-poly(l-lactide) (PS-b-PLLA) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer brushes located at a PS/PLLA interface were employed as a route to control the final microstructure of 95% void volume, ultraporous PLLA scaffolds. The latter were initially prepared from melt-processed quaternary blends of ethylene propylene diene rubber/poly(?-caprolactone)/polystyrene/poly(l-lactide) (EPDM/PCL/PS/PLLA) 45/45/5/5%vol. modified with the diblock copolymers. The blends display a layer comprised of the PS and PLLA phases located at the interface of the co-continuous EPDM and PCL phases. When the PS-b-PLLA copolymer is added, sub-micrometric PLLA droplets are encapsulated within the PS continuous layer phase. In comparison, both the PS and PLLA phases compete for the encapsulation process when the PS-b-PMMA is used, indicating that the microstructure of the PLLA phase can be fine-tuned with an adequate choice of interfacial modifier. These effects were investigated by analyzing the microstructure of ternary high-density polyethylene (HDPE)/PS/PMMA 80/10/10%vol. blends displaying PS/PMMA shell/core composite droplets in a HDPE matrix. An inversion of the shell/core structure is observed when the PS-b-PLLA copolymer is used to compatibilize the PS/PMMA interface, whereas no such restructuring occurs with the PS-b-PMMA. These effects are explained by the activity and swelling powers of the copolymer brushes. For the EPDM/PCL/PS/PLLA quaternary systems modified with the PS-b-PMMA, the PLLA homopolymer phase significantly penetrates and swells the PMMA blocks due to their mutual high affinity, as compared to the classical like-prefers-like compatibilization approach. The swelling of the blocks will tend to bend the interface toward the PS phase in order to minimize the lateral compression of the PMMA blocks. A similar effect explains the reversal of the PS/PMMA shell/core structure in the HDPE/PS/PMMA ternary system. This level of control ultimately leads to quite significant differences in microstructures and surface textures for the PLLA scaffolds.     

Effect of composition on the linear viscoelastic behavior and morphology of PMMA/PS and PMMA/PP blends

Here, the effect of concentration on the morphology and dynamic behavior of polymethylmethacrylate/polystyrene (PMMA/PS), for PS with two different molecular weight, and polymethylmethacrylate/polypropylene (PMMA/PP) blends was studied. The blends concentrations ranged from 5% to 30% of the dispersed phase (PS or PP). The dynamic data were analyzed to study the possibility of inferring the interfacial tension between the components of the blend from their rheological behavior using Palierne [Palierne JF. Rheol Acta 1990;29:204-14] [1] and Bousmina [Bousmina M. Acta 1999;38:73-83] [2] emulsion models. The relaxation spectrum of the blends was also studied. The dynamic behavior of 85/15 PS/PMMA blend were studied as a function of temperature. It was possible to fit both Palierne and Bousmina's emulsion models to the dynamic data of PMMA/PS blends, to obtain the interfacial tension of the blend. This was not the case for PMMA/PP. The relaxation spectrum of both blends was used to obtain the interfacial tension between the components of the blends. The values of interfacial tension calculated were shown to decrease when the concentration of the blends increased. It was shown using morphological analysis that this phenomenon can be attributed to the coalescence of the dispersed phase during dynamic measurements that occurs for large dispersed phase concentration. When the ‘coalesced’ morphology is taken into account in the calculations the interfacial tension inferred from rheological measurement did not depend on the concentration of the blend used. The values of interfacial tension found analyzing the dynamic behavior of one of the PMMA/PS blend were shown to decrease with temperature.     

High-throughput preparation of complex multi-scale patterns from block copolymer/homopolymer blend films

A simple, straightforward process for fabricating multi-scale micro- and nanostructured patterns from polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP)/poly(methyl methacrylate) (PMMA) homopolymer in a preferential solvent for PS and PMMA is demonstrated. When the PS-b-P2VP/PMMA blend films were spin-coated onto a silicon wafer, PS-b-P2VP micellar arrays consisting of a PS corona and a P2VP core were formed, while the PMMA macrodomains were isolated, due to the macrophase separation caused by the incompatibility between block copolymer micelles and PMMA homopolymer during the spin-coating process. With an increase of PMMA composition, the size of PMMA macrodomains increased. Moreover, the P2VP blocks have a strong interaction with a native oxide of the surface of the silicon wafer, so that the P2VP wetting layer was first formed during spin-coating, and PS nanoclusters were observed on the PMMA macrodomains beneath. Whereas when a silicon surface was modified with a PS brush layer, the PS nanoclusters underlying PMMA domains were not formed. The multi-scale patterns prepared from copolymer micelle/homopolymer blend films are used as templates for the fabrication of gold nanoparticle arrays by incorporating the gold precursor into the P2VP chains. The combination of nanostructures prepared from block copolymer micellar arrays and macrostructures induced by incompatibility between the copolymer and the homopolymer leads to the formation of complex, multi-scale surface patterns by a simple casting process.     

影响HDPE/PS/PMMA三元体系核壳形态的因素

通过密炼得到高密度聚乙烯(HDPE)、聚苯乙烯(PS)和聚甲基丙烯酸甲酯(PMMA)三元体系核壳结构。用扫描电镜(SEM)考察了组分配比、增容剂氢化苯乙烯-丁二烯-苯乙烯弹性体(SEBS)和退火对体系核壳形态的影响。结果表明,组分用量最大的HDPE总是形成基体相,而PS形成壳,PMMA形成核;核壳粒子的尺寸和内部结构随组分用量而变化,随着分散相用量(PS+PMMA)增加,核壳粒子间碰撞融合机会增多,因此核壳粒子尺寸变大,同时核壳粒子由一核一壳逐渐转变为多核一壳结构;而随着核壳粒子中PS用量增加,PMMA核的尺寸显著减小;增容剂SEBS的加入,抑制了共混中核壳粒子间的融合,导致核和壳的尺寸减小;200℃下退火处理使分散相向体系自由能更小的一核一壳结构转变。     

Preparation and tribological properties of poly(methyl methacrylate)/styrene/MWNTs copolymer nanocomposites

Poly(methyl methacrylate)/styrene/multi‐walled carbon nanotubes (PMMA/PS/MWNTs) copolymer nanocomposites with different contents have been prepared successfully by means of in situ polymerization method. The structure and the microhardness of PMMA/PS/MWNTs copolymer nanocomposites were characterized. The tribological behaviors of the copolymer nanocomposites were investigated by a friction and wear tester under dry conditions. The relative humidity of the air was about 50% ± 10%. Comparing with pure PMMA/PS copolymer, the copolymer nanocomposites showed not only better wear resistance but also smaller friction coefficient. MWNTs could help the nanocomposites dramatically improve the wear resistance property. The mechanisms of the improvements on the tribological properties of the PMMA/PS/MWNTs copolymer nanocomposites were also discussed in detail. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology of polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) composite particles

Polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) (PS/PS-b-PMMA/PMMA) composite particles were prepared by releasing toluene from PS/PS-b-PMMA/PMMA/toluene droplets dispersed in a sodium dodecyl sulfate aqueous solution. The morphology of the composite particles was affected by release rate of toluene, the molecular weight of PS-b-PMMA, droplet size, and polymer composition. ‘Onion-like’ multilayered composite particles were prepared from toluene droplets of PS-b-PMMA and of PS/PS-b-PMMA/PMMA, in which the weights of PS and PMMA were the same. The layer thicknesses of the latter multilayered composite particles increased with an increase in the amount of the homopolymers. PS-b-PMMA/PS composite particles had a sea-islands structure, in which PMMA domains were dispersed in a PS matrix. On the other hand, PS-b-PMMA/PMMA composite particles had a cylinder-like structure consisting of a PMMA matrix and PS domains.     

Effect of ultrasonic oscillations on weld line strength of PS,PMMA, and their blends

The effect of ultrasonic oscillations on the weld line strength of amorphous polystyrene (PS), polymethyl methacrylate (PMMA), and PS/PMMA (20/80, 50/50, 80/20) blends at various temperatures was investigated. By facilitating the molecular diffusion across the weld line, the introduction of ultrasonic oscillations could evidently improve the weld line strength of PS, PMMA, and their blends. The different effects on the weld line strength of PS/PMMA (20/80, 50/50, 80/20) blends were investigated. The ultrasonic oscillations could greatly increase the weld line strength of PS/PMMA (80/20) by ～ 70%, but was less efficient to PS/PMMA (50/50, 20/80) blends, due to the great difference of weld line morphologies of these blends. The dispersed phase of PS/PMMA (80/20) in the weld line was spherical while two different morphologies in the weld line of PS/PMMA (50/50) were observed. And the stripe‐like morphology of PS perpendicular to the flow direction in the weld line of PS/PMMA (20/80) is responsible for the little effect of ultrasonic oscillations. The fractured surfaces of PS, PMMA, and PS/PMMA (80/20) with weld line became much rougher due to the introduction of ultrasonic oscillations. The morphology study of PS/PMMA (80/20) showed that the spherical dispersed phase of PS/PMMA at the skin turned smaller under ultrasonic oscillations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2990–2997, 2006     

Nanostructured polymer blends based on polystyrene‐b‐polybutadiene‐b‐poly(methyl methacrylate) triblock copolymers modified with polystyrene and/or poly(methyl methacrylate) homopolymers

Morphologies of polymer blends based on polystyrene‐b‐ polybutadiene‐b ‐poly(methyl methacrylate) (SBM) triblock copolymer were predicted, adopting the phase diagram proposed by Stadler and co‐workers for neat SBM block copolymer, and were experimentally proved using atomic force microscopy. All investigated polymer blends based on SBM triblock copolymer modified with polystyrene (PS) and/or poly(methyl methacrylate) (PMMA) homopolymers showed the expected nanostructures. For polymer blends of symmetric SBM‐1 triblock copolymer with PS homopolymer, the cylinders in cylinders core?shell morphology and the perforated lamellae morphology were obtained. Moreover, modifying the same SBM‐1 triblock copolymer with both PS and PMMA homopolymers the cylinders at cylinders morphology was reached. The predictions for morphologies of blends based on asymmetric SBM‐2 triblock copolymer were also confirmed experimentally, visualizing a spheres over spheres structure. This work presents an easy way of using PS and/or PMMA homopolymers for preparing nanostructured polymer blends based on SBM triblock copolymers with desired morphologies, similar to those of neat SBM block copolymers. © 2017 Society of Chemical Industry     

Surface feature size of spin cast PS/PMMA blends

Thin films of polystyrene (PS)/polymethylmethacrylate (PMMA) blends have been spin cast on mica from chloroform solutions. When the concentration of PMMA in the casting solution is less than that of PS a pitted morphology is formed. The average sizes of the pits are shown to increase with both the total concentration of the casting solution and the relative concentration of PMMA. The change in pit size is explained in terms of incomplete dewetting of a PMMA solution from an underlying PS solution. For a given ratio of PMMA/PS the average pit diameters appear to increase linearly with the square of the film thickness, the gradient of which is dependent on the film composition.