Morphology and rheology of immiscible polymer blends filled with silica nanoparticles

The effect of silica nanoparticles on the morphology and the rheological properties of an immiscible polymer blend (polypropylene/polystyrene, PP/PS 70/30) was investigated. Two types of pyrogenic nanosilica were used: a hydrophilic silica with a specific surface area of 200 m²/g and a hydrophobic silica having a specific surface area of 150 m²/g. First, a significant reduction in the PS droplet volume radius, from 3.25 to nearly 1 μm for filled blends with 3 wt% silica, was observed. More interestingly, image analysis of the micrographs proved that the hydrophilic silica tends to confine in the PS phase whereas hydrophobic one was located in the PP phase and at the PP/PS interface (interphase thickness ≈ 100-200 nm). Furthermore, a migration of hydrophilic silica from PP phase toward PS domains was observed.An analysis of the rheological experimental data was based on the framework of the Palierne model, extended to filled immiscible blends. Due to the partition of silica particles in the two phases and its influence on the viscosity ratio, limited cases have been investigated. The rheological data obtained with the hydrophobic silica were more difficult to model since the existence of a thick interphase cannot be taken into account by the model. Finally, the hypothesis that hydrophilic silica is homogeneously dispersed in PS droplets and that hydrophobic silica is dispersed in PP matrix was much closer to the actual situation. It can be then concluded that stabilization mechanism of PP/PS blend by hydrophilic silica is the reduction in the interfacial tension whereas hydrophobic silica acts as a rigid layer preventing the coalescence of PS droplets.     

Viscoelastic properties and morphological characterization of silica/polystyrene nanocomposites synthesized by nitroxide-mediated polymerization

Polystyrene (PS) chains with molecular weights comprised between 15,000 and 60,000 g/mol and narrow polydispersities were successfully grown from the surface of silica nanoparticles by nitroxide-mediated polymerization (NMP). Small angle X-ray scattering was used to characterize the structure of the interface layer formed around the silica particles, and at a larger scale, dynamic light scattering was used to determine the hydrodynamic diameter of the functionalized silica suspension. In a second part, blends of PS-grafted silica particles and pure polystyrene were prepared to evaluate the influence of the length of the grafted PS segments on the viscoelastic behavior of the so-produced nanocomposites in the linear viscoelasticity domain.Combination of all these techniques shows that the morphology of the nanocomposite materials is controlled by grafting. The steric hindrance generated by the grafted polymer chains enables partial destruction of the agglomerates that compose the original silica particles when the latter are dispersed either in a solvent or in a polymeric matrix.     

Hydrophobic coating of mica by piranha solution activation,silanization grafting,and copolymerization with acrylate monomers

Hydrophobic mica particles were prepared by piranha solution activation, silanization, and copolymerization with acrylate monomers. Its surface morphology, hydrophilic properties, and thermogravimetric analysis changed differently in comparison with those of pristine mica. Scanning electron microscopy (SEM) showed that the modified (001) mica surface changed from flat to coarse. Thermogravimetric curves demonstrated that silane coupling agents and the grafted polymer were anchored on the modified‐mica surface. The alternating surface polarity state was verified by different dispersion performances in the solvents. SEM images showed that the polypropylene (PP)/modified‐mica composites had a better quality compatibility than the PP/untreated‐mica composites. The PP/polymer‐grafted‐mica composites had improved mechanical properties, including stretching, tension, and impact properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44985.     

Surface‐initiated atom transfer radical polymerization (ATRP) of styrene from silica nanoparticles under UV irradiation

Diethyldithiocarbamyl‐modified silica nanoparticles were prepared and used as macroinitiator for the surface‐initiated atom transfer radical polymerization (SI‐ATRP) of styrene under UV irradiation. Well‐defined polymer chains were grown from the nanoparticle surfaces to yield particles composed of a silica core and a well‐defined, densely grafted outer PS layer with a mass ratio of styrene to silica, or percentage grafting, of 276.3% after an UV irradiation time of 5 h. Copyright © 2004 Society of Chemical Industry     

Dependence of thin polystyrene films stability on the thickness of grafted polystyrene brushes

We investigate the stability of thin polystyrene (PS) films on chemically identical grafted brushes of various thickness and grafting density. We observe an essential influence of the brush thickness on the stability of the PS films. For brushes with a thickness of 20-35 nm no de-wetting of the PS film occurs, while considerably thicker or thinner PS brushes lead to de-wetting of the PS top layer. We suggest that in the thin brush-like layers, the unfavorable interactions with underlying silica favor de-wetting. The tendency to de-wet is reduced once the brush is sufficiently thick to insulate the free PS layer from the surface. Beyond that point, the de-wetting process speeds up as the brush becomes thicker and has a higher grafting density with a substantial increase of the interfacial tension between the brush and the free polymer.     

Grafting of polystyrene chains on surfaces of nanosilica particles via peroxide bulk polymerization

This article describes an in situ bulk polymerization process of styrene in the presence of silica nanoparticles. In this peroxide bulk polymerization process, two polystyrene fractions are formed: A polystyrene (PS) fraction attached to the particle's surface, which cannot be detached by hot xylene extraction, and an unattached PS fraction which dissolves in xylene. Solvent extraction and TGA measurements have confirmed the existence of grafted PS chains to the silica surfaces. FTIR measurements have indicated the existence of Si O C bonds connecting the PS grafts to the silica surface. Polypropylene (PP) was blended with the extracted PS‐g‐silica particles to produce concentrations of 1–3% nanoparticles in the PP composites. A remarkably improved dispersability of the nanoparticles was achieved, thus grafting reduces re‐agglomeration and increases the affinity of the grafted surface to the polymer matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Rheological behavior of a polymerically stabilized latex for use in water‐borne coatings

A unique urethane linkage that permits chemical grafting of poly(ethylene oxide) (PEO) linear chains to the surfaces of polystyrene (PS) latex particles has been developed. Chemically grafting the functionalized hydrophilic PEO macromers to the PS particle surface allows the latex to be polymerically stabilized in a water‐based medium. Advantages of the urethane linkage include the high yield of the macromer synthesis and the hydrolytic stability of the final latex. Rheological experiments are used to examine both processing behavior and interparticle interactions for latex systems with different amounts of grafted PEO. Dynamic rheological experiments reveal that, at high macromer concentrations, the grafted PEO layer is effective in shielding the attractive interactions of the core PS particles that lead to flocculation. However, at low macromer concentrations, strong interactions are seen even at low particle weight fractions, indicating the presence of a flocculated system. Steady shear rheological evaluations show that the latex systems possessed suitable flow behavior for coating applications, even at relatively high particle weight fractions. Experimental steady shear data is utilized in conjunction with the Krieger‐Dougherty equation to determine the size of the PEO stabilizing layer. The stabilizing layer thickness decreases as particle concentration increases, indicating a compressible system. Finally, the relationship between the strength of interparticle interactions and PEO graft density is gauged from the dependence of the power‐law exponent of the elastic modulus on particle concentration.     

Synthesis and properties of amphiphilic nonspherical SPS/PS composite particles by multi-step seeded swelling polymerization

Amphiphilic nonspherical particles have asymmetric surface physical and chemical properties. Such a unique structure makes them suitable for applications in many areas, such as chemical and biological sensors, colloidal surfactants, self-assembly, building blocks of complex superstructures, and materials engineering. In this study, amphiphilic sulfonated polystyrene/polystyrene (SPS/PS) composite particles with controllable morphologies are synthesized by combining modified treatment and multistage seeded swelling polymerization. Core-shell SPS particles were first obtained by modifying cross-linked PS particles with concentrated sulfuric acid, and the surface of SPS particles was a hydrophilic sulfonated polystyrene layer. With further twice seeded swelling polymerization, new hydrophobic PS oil phase sprouted on the strong hydrophilic surface even without any surfactant assistance in aqueous media. The morphologies of these SPS/PS composite particles could be adjusted by changing the crosslinking density of the seed microspheres, the sulfonation temperature and the swelling ratio of monomer/seed. These polymer composite particles can be used as solid surfactants.     

Grafting of branched polymers onto nano-sized silica surface: Postgrafting of polymers with pendant isocyanate groups of polymer chain grafted onto nano-sized silica surface

To control the surface wettability of nano-sized silica surface, the postgrafting of hydrophilic and hydrophobic polymers to grafted polymer chains on the surface was investigated. Polymers having blocked isocyanate groups were successfully grafted onto nano-sized silica surface by the graft copolymerization of methyl methacrylate (MMA) with 2-(O-[1′-methylpropylideneamino]caboxyamino)ethyl methacrylate (MOIB) initiated by azo groups previously introduced onto the surface. The blocked isocyanate groups of poly(MMA-co-MOIB)-grafted silica were stable in a desiccator, but isocyanate groups were readily regenerated by heating at 150 °C. The hydrophilic polymers, such as poly(ethylene glycol) (PEG) and poly(ethyleneimine) (PEI), were postgrafted onto the poly(MMA-co-MOIB)-grafted silica by the reaction of functional groups of PEG and PEI with pendant isocyanate groups of poly(MMA-co-MOI)-grafted silica to give branched polymer-grafted silica. The percentage of grafting increased with increasing molecular weight of PEG, but the number of postgrafted chain decreased, because of steric hindrance. The hydrophobic polymers, such as poly(dimethylsiloxane) were also postgrafted onto poly(MMA-co-MOI)-grafted silica. It was found that the grafting of hydrophobic polymer and the postgrafting of hydrophilic polymer branches readily controls the wettability of silica surface to water.     

Morphology and rheological properties of silica‐filled poly(carbonate)/poly(methyl methacrylate) blends

The effect of silica nanoparticles on the morphology and the rheological properties was investigated in the immiscible polymer blend poly(carbonate)/poly(methyl methacrylate) (PC/PMMA). In the melt state, the linear viscoelastic properties of the nanocomposite showed a reduction effect of the silica nanoparticles on the mobility of one of the polymer which is related to the state of distribution of the silica nanoparticles. Hydrophilic and hydrophobic silica particles were used to study particle migration and their effects on the morphology and it was shown that the distribution of the nanoparticles depends on the balance of interactions between the surface of the particles and the polymer components. The effect on the coarsening kinetics was investigated in both hydrophilic and hydrophobic silica‐filled blends. Compared to the hydrophilic silica, a better compatibilization can be obtained by introducing the hydrophobic silica particles at the PC/PMMA interface as the solid barrier. POLYM. ENG. SCI., 55:1951–1959, 2015. © 2014 Society of Plastics Engineers     

The nature of polymer grafts and substrate shape on the surface degradation of poly(l‐lactide)

Surface grafting of functional polymers is an effective method to alter material properties and degradation behavior. Two different substrate shapes of poly(l ‐lactide) (PLLA), i.e., films and microparticles, were surface‐grafted with hydrophilic monomers, and their surface degradation was monitored. Surface grafting with a hydrophilic and acidic polymer graft [acrylic acid (AA)] induced large alterations in the surface morphology and topography of the films. In contrast, hydrophilic and neutral polymer grafts [acrylamide (AAm)] had no significant effect on the surface degradation behavior, while the PLLA reference and co‐monomeric (AA/AAm) polymer‐grafted samples exhibited intermediate surface degradation rates. The grafted PAA chains induced a local acidic environment on the surface of the substrates, which in turn catalyzed the surface degradation process. This effect was more pronounced in the films than in the microparticles. Thus, the nature of the grafted chains and substrate geometry were shown to affect the surface degradation behavior of PLLA substrates. © 2015 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42736.     

Functional polymers supported on porous silica. II.Radical polymerization of vinylbenzyl chloride from grafted precursors

Vinylbenzyl chloride was chosen as a model monomer for grafting a functional polymer onto silica carrying radical active precursors, such as monomer, transfer agent or initiator, previously grafted onto silica via a suitable coupling agent. The grafting efficiency was studied as a function of the texture of the initial silica, the nature of the active precursor and the polymerization conditions. Evidence for grafting was obtained from FTIR and ²⁹Si CP-MAS NMR spectra, and the thickness of the grafted layer was estimated from surface area and porosimetry measurements. From molecular weight measurements of nongrafted polymer it can be deduced that there is a trend toward the elongated conformation of the grafted polymer. Attempts to separate the grafted polymer through digestion of the silica with HF, failed to give a soluble linear polymer except when the active precursor was a transfer agent; in the two other cases a crosslinked polymer with a low crosslink density was obtained, which kept the morphology of the initial silica.     

Polymerization compounding of polyurethane‐fumed silica composites

Polymerization Compounding (PC) offers the possibility to design composite materials by controlling the architecture of a grafted polymer on the surface of solid substrates to be incorporated in a polymer matrix. The approach consists in involving the surface of a reinforcement in a polymerization process of a polymer to be used either as a matrix in the final composite or else as a special surface treatment to enhance solid/polymer interface properties in the composite. The PC process is illustrated here with fumed silica as a solid substrate and polyurethane as a matrix. The hydroxyl sites on silica particles were reacted consecutively with a toluene diisocyanate (TDI) compound and then with either bis‐phenol‐A (BA) or hydroxy‐terminated polybutadiene (HTPB) in order to obtain the desired coating. Soxhlet extractions were conducted to confirm grafting of the polymer on the solid surface. The amount of grafted polymer was evaluated by thermogravimetric analysis. Modified particles were incorporated into HTPB/TDI compounds at concentrations as high as 25% w/w. Water absorption, thermorheological as well as mechanical properties all show clear contribution of the improved bonding between the solid phase and the binder. POLYM. ENG. SCI. 46:360–371, 2006. © 2006 Society of Plastics Engineers     

Adhesion interaction in water/n-alcohol mixtures between silanized silica and polymer particles

The adhesion of polyethylene and nylon particles to silanized silica plates was investigated in water/n-alcohol (methanol, ethanol, 1-propanol, and 1-butanol) mixtures. Silica plates were treated with γ-aminopropyltriethoxysilane, methyltriethoxysilane, and perfluoroethyltrimethoxysilane. The number of particles adhering to the plate at 60 min as an apparent equilibrium adhesion value increased as a result of the silanization of silica and decreased with increasing volume ratio of n-alcohol in the water/n-alcohol mixtures. The acid-base components of the surface free energies of the substrates and liquids were decreased by the silanization of silica and by the addition of cthanol to water. The apparent equilibrium particle adhesion is discussed in terms of the total potential energies of interaction which were calculated as the sum of the electrical double layer, Lifshitz-van der Waals, and acid-base interactions, using the electrokinetic potentials and the surface free energy components. In addition, the relationship between the extent of particle adhesion and the work of adhesion was investigated. The particle adhesion in the present systems was found to be dominated by the acid-base interaction between the particle and the substrate.     

紫外光引发PNIPAAm及其共聚物改性PS表面研究

采用紫外光引发聚合将聚N-异丙基丙烯酰胺(PNIPAAm)接枝在聚苯乙烯(PS)表面或在PS表面形成与之相容性较好的NIPAAm与苯乙烯(St)共聚物即P(NIPAAm/St)共聚物层,以改性PS的表面性质。红外光谱分析(FTIR)和表面接触角测试结果表明,PNIPAAm或P(NIPAAm/St)共聚物可以在PS表面稳定存在,使PS表面由疏水性变为亲水性,且具有一定的温敏性。单纯PNIPAAm接枝PS改性层的温敏性更为明显,当温度由23℃增加到40℃时,PNIPAAm改性PS表面与水的接触角由44°左右增加到68°左右。P(NIPAAm/St)共聚物中的St有利于提高改性层与PS的相容性、透明性及稳定性,但其温敏性下降。     

Magnetic solid phase extraction for chromatographic separation of carbamates

Magnetic solid phase extraction particles (MSPE) were produced using magnetite nanoparticles with diameters between 9 and 13 nm as nucleating agent. The produced particles with magnetite cores were smaller, and more irregular and poly‐dispersed, than those produced in the absence of the magnetite particles. The average diameters of the particles were 377 and 521 nm, respectively, for silica particles with and without magnetic core, whereas the diameters of the different grafted particles were of the same order of magnitude than the silica particles with magnetic cores. BET results indicated surface areas ranging between 9 and 37 m² g^?1 The TGA results showed that the particles contained about 10% water and other solvents, and between 5 to 6% grafted groups. The thermal decomposition of the particles (presented under Supplementary Information ) was autocatalytic with activation energies of 367, 546, and 616 kJ mol^?1 for particles grafted with cyanopropyl (cyano), octyl, and trimethyl (TMS), respectively. The order of dispersity of the particles in water followed the sequence cyano > PMA > TMS ? octyl, whereas the pesticides removing efficiency followed the reverse order.     

Fabrication of oriented electrospun cellulose nanocrystals–polystyrene composite fibers on a rotating drum

Nitrobenzene (CNC-1), trifluoromethyl benzene (CNC-2) modified and polystyrene-grafted (CNC-g) cellulose nanocrystals in polystyrene (PS)-N,N dimethylformamide (DMF) solutions were electrospun and collected as stretched and aligned fibers on a rotating drum. Scanning electron microscope pictures showed significant alignment in the case of unmodified and nitrobenzene-modified CNC-1/PS nanocomposite fibers once the linear speed of rotor reached to 15 m s⁻¹. Fiber diameter decrease was more strong with rotor speed increase in the case of trifluoromethyl benzene modified (CNC-2) and polystyrene-grafted (CNC-g) cellulose nanocrystals/PS systems. Dynamic mechanical analysis including storage and elastic modulus of electrospun-oriented fibers were performed on surface-modified and polymer-grafted CNC/PS samples. According to α transition peak, the increase in the glass-transition temperature with filler concentration was the highest in polymer-grafted CNC-g/PS composite fibers. It was due to the interpenetration of grafted polymer brushes and free polymer chains in continuous phase and resulted in restrictions of motions of polymer chains in the PS matrix. The elastic moduli of nitrobenzene (CNC-1) and trifluoromethyl benzene (CNC-2)-modified CNC-filled PS composite fibers agreed well with percolation model, which indicates the CNC–CNC interactions and network formation with an increase in concentration. Magnitude of the elastic modulus of polymer grafted CNC-g at 0.33 vol % in PS was significantly higher than the prediction from percolation theory. It was due the immobilized polymer chains around CNC-g particles. However, grafted polymer chains, at higher CNC concentrations acted like stickers among CNC particles and caused CNC agglomerates with entrapped free polystyrene from the matrix, thus caused a decrease in the elastic modulus. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48942.     

Effect of nano‐silica filler on the rheological and morphological properties of polypropylene/liquid‐crystalline polymer blends

A fumed hydrophilic nano‐silica‐filled polypropylene (PP) composite was blended with a liquid‐crystalline polymer (LCP; Rodrun LC5000). The preblended polymer blend was extruded through a capillary die; this was followed by a series of rheological and morphological characterizations. The viscosity of the PP matrix increased with the addition of the hydrophilic nano‐silica. At shear rates between 50 and 200 s^?1, the composite displays marked shear‐thinning characteristics. However, the incorporation of LC5000 in the PP composite eliminated the shear‐thinning characteristic, which suggests that LC5000 destroyed the agglomerated nano‐silica network in the PP matrix. Although the viscosity ratio of LCP/PP was reduced after the addition of nano‐silica fillers, the LCP phases existed as droplets and ellipsoids. The nano‐silicas were concentrated in the LC5000 phase, which hindered the formation of LCP fibers when processed at high shear deformation. We carried out surface modification of the hydrophilic nano‐silica to investigate the effect of modified nano‐silica (M‐silica) on the morphology of the PP/LC5000 blend system. Ethanol was successfully grafted onto the nano‐silica surface with a controlled grafting ratio. The viscosity was reduced for PP filled with ethanol‐M‐silica when compared to the system filled with untreated hydrophilic nano‐silica. The LC5000 in the (PP/M‐silica)/LC5000 blend existed mainly in the form of fibrils. At high shear rates (e.g., 3000 s^?1), the LC5000 fibril network was formed at the skin region of the extrudates. The exclusion of nano‐silica in the LC5000 phase and the increased viscosity of the matrix were responsible for the morphological changes of the LCP phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1484–1492, 2003     

Graft polymerization of vinyl monomers initiated by peroxycarbonate groups introduced onto silica surface by Michael addition

The introduction of peroxycarbonate groups onto a silica surface and the graft polymerization of vinyl monomers initiated by peroxycarbonate groups introduced onto a silica surface were investigated. The introduction of peroxycarbonate groups onto a silica surface was achieved by Michael addition of amino groups introduced onto the silica surface to t‐butylperoxy‐2‐methacryloyloxyethylcarbonate (HEPO). The amount of peroxycarbonate groups was determined to be 0.17 mmol/g. The graft polymerization of various vinyl monomers such as styrene (St), N‐vinyl‐2‐pyrrolidinone (NVPD), and 2‐hydroxyethyl methacrylate (HEMA) was initiated by peroxycarbonate groups introduced onto the silica surface to give the corresponding polymer‐grafted silicas. The percentage of poly(St)‐grafting reached about 120% after 5 h. This means that 1.20 g of poly(St) is grafted onto 1.0 g of silica. The surface of poly(St)‐grafted silica shows a hydrophobic nature, but the surfaces of poly(NVPD) and poly(HEMA)‐grafted silica show a hydrophilic nature. Furthermore, the poly(St)‐grafted silica was found to give a stable colloidal dispersion in a good solvent for the grafted polymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1491–1497, 1999     

Preparation of core–shell poly(acrylic acid)/polystyrene/SiO2 hybrid microspheres

Core–shell poly(acrylic acid)/polystyrene/SiO₂ (PAA/PS/SiO₂) hybrid microspheres were prepared by dispersion polymerization with three stages in ethanol and ethyl acetate mixture medium. Using vinyltriethoxysilane (VTEOS) as silane agent, functional silica particles structured vinyl groups on surfaces were prepared by hydrolysis and polycondensation of tetraethoxysilane and VTEOS in core stage. Then, the silica particles were used as seeds to copolymerize with styrene and acrylic acid sequentially in shell stage I and stage II to form PAA/PS/SiO₂ hybrid microspheres. Transmission electron microscope results show that most PAA/PS/SiO₂ hybrid microspheres are about 40 nm in diameter, and the silica cores are about 15 nm in diameter, which covered with a layer of PS about 7.5‐nm thick and a layer of PAA about 5‐nm thick. This core–shell structure is also conformed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and differential scanning calorimetry. FTIR results show that silica core, PS shell, and PAA outermost shell are bonded by covalents. In the core–shell PAA/PS/SiO₂ hybrid microsphere, the silica core is rigidity, and the PAA outermost shell is polarity, while the PS layer may work as lubricant owning to its superior processing rheological property in polymer blending. These core–shell PAA/PS/SiO₂ hybrid microspheres have potential as new materials for polar polymer modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1729–1733, 2006