Effects of crystallization on dispersion of carbon nanofibers and electrical properties of polymer nanocomposites

Polymer nanocomposites filled with low volume fractions of carbon nanofibers (CNFs) were prepared by melt‐compounding. Three types of polymers with different crystallization behavior, i.e., weakly‐crystallized low density polyethylene (LDPE), strongly crystallized high density polyethylene (HDPE) and amorphous polystyrene (PS), were selected as matrices for the nanocomposites. The effects of polymer crystallization on the dispersion of CNFs were examined. Optical and electron microscopic examinations revealed that the dispersion of CNFs in the nanocomposite matrices was strongly depended on the crystallization behavior of polymer matrices. The CNFs were found to disperse uniformly in weakly crystallized LDPE and amorphous PS matrices, but agglomerated in HDPE due to its strong crystallization tendency. Such a distinct dispersion behavior of CNFs in polymers had a profound effect on the electrical properties of the nanocomposites investigated. The PS/CNF nanocomposites exhibited the lowest percolation threshold. The HDPE/CNF nanocomposites showed the largest percolation threshold due to the CNF agglomeration within the amorphous phase of HDPE. POLYM. ENG. SCI., 48:177–183, 2008. © 2007 Society of Plastics Engineers     

Preparation of polystyrene–clay nanocomposites via dispersion polymerization using oligomeric styrene‐montmorillonite as stabilizer

This study describes the preparation of polystyrene–clay nanocomposite (PS‐nanocomposite) colloidal particles via free‐radical polymerization in dispersion. Montmorillonite clay (MMT) was pre‐modified using different concentrations of cationic styrene oligomeric (‘PS‐cationic’), and the subsequent modified PS‐MMT was used as stabilizer in the dispersion polymerization of styrene. The main objective of this study was to use the clay platelets as fillers to improve the thermal and mechanical properties of the final PS‐nanocomposites and as steric stabilizers in dispersion polymerization after modification with PS‐cationic. The correlation between the degree of clay modification and the morphology of the colloidal PS particles was investigated. The clay platelets were found to be encapsulated inside PS latex only when the clay surface was rendered highly hydrophobic, and stable polymer latex was obtained. The morphology of PS‐nanocomposite material (after film formation) was found to range from partially exfoliated to intercalated structure depending on the percentage of PS‐MMT loading. The impact of the modified clay loading on the monomer conversion, the polymer molecular weight, the thermal stability and the thermomechanical properties of the final PS‐nanocomposites was determined. Copyright © 2012 Society of Chemical Industry     

Surface modification of CNFs via plasma polymerization of styrene monomer and its effect on the properties of PS/CNF nanocomposites

Carbon nanofibers (CNF) were modified via plasma assisted polymerization in a specially designed reactor. The effect of the plasma reactor conditions, such as power and time, on the extent of the CNFs modification was examined. Polystyrene (PS) coated nanofibers plus PS polymer were then processed in a Brabender torque rheometer mixing chamber to obtain PS/CNF nanocomposites, with 0.5, 1.0, 3.0, and 5.0 wt % of CNF. The effect of the plasma treatment on the dispersion of the nanofibers and on the compatibility between the nanofibers and the polymer matrix was also examined. Modification of the CNFs was assessed by measuring the contact angle of water in a “bed” of nanofibers and by examining its dispersion in several solvents. The morphology of PS/CNF nanocomposites was studied through scanning electron microscopy (SEM). Contact angles decreased in all cases, indicating a change in hydrophobicity of the modified CNFs. This change was confirmed in the CNF dispersion tests in several solvents. SEM micrographs show the difference between the original and the PS coated CNF. In addition, fractured samples show the effect of this treatment, in the sense that the CNF seem to be completely embedded in the polymer matrix, which clearly indicates the high compatibility between the PS and the modified (PS coated) CNF. As a consequence, a much better dispersion of the treated CNF was observed. Finally, the tensile modulus of PS/CNF composites increased slightly with respect to PS when using untreated CNFs, but more than doubled when using plasma treated CNFs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrically conductive polystyrene nanocomposites incorporated with aspect ratio-controlled silver nanowires

Polymer nanocomposites consisting of electrically conductive nanofillers with high aspect ratios are widely utilized for high-performance applications such as sensors and electronics. Silver nanowires (AgNWs) synthesized through polyol reduction have been reported to show excellent electrical conductivity, hydrophilicity, and high aspect ratios. In this study, the influence of the aspect ratios of the AgNWs on the rheological and electrical properties of the fabricated polystyrene (PS)/AgNW nanocomposites was chiefly investigated. The nanocomposites were made by combining a dispersion of AgNWs with a suspension of PS particles, followed by freeze-drying the PS/AgNW mixture harnessing the latex technology. Scanning electron microscopy, UV–Vis spectroscopy, and thermogravimetric analysis were performed on the nanocomposites to investigate the morphological, optical, and thermal properties, respectively; in addition, X-ray photoelectron spectroscopy was performed to examine the hydrophilic polymer poly(vinylpyrrolidone)-capped AgNW surfaces. The rheological behavior of the nanocomposites changed from liquid-like to solid-like after the addition of AgNWs with high aspect ratios. The electrical percolation threshold of the AgNWs in the nanocomposites was determined by the aspect ratio of the nanofiller rather than by its length. Thus, the various properties of the PS/AgNW nanocomposites could be tuned by tailoring the aspect ratios of the AgNWs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47927.     

Preparation of transparent polystyrene nano-latexes by an UV-induced routine emulsion polymerization

Transparent polystyrene (PS) latexes were prepared by photo-polymerization of a routine styrene (St) emulsion with a surfactant concentration of 0.4 wt% and a monomer concentration of 10 wt%, by using UV light as well as a hydrophilic photo-initiator. The entire polymerization could be performed within 1-2 h and display a conversion higher than 90%. The particle sizes could be tuned in the range of 20-40 nm. The formation mechanism for these of nano-sized latex particles was attributed to an in situ formation of PS chains with terminal hydroxyl groups. The presence of the hydroxyl-functionalized polymer chains seemed to promote a colloidal stability of the small latex particles and prevent coagulation even at low surfactant concentrations.     

Effect of the cationic starch on removal of Ni and V from crude oils under microwave irradiation

The effect of cationic starches on removal of nickel and vanadium from crude oils in the presence of microwaves was investigated. A series of cationic starches with different degrees of substitution synthesized by a microwave-dry process were used to remove nickel and vanadium from crude oils. The effects of a number of factors, such as the degree of substitution of cationic starches, microwave time and cationic starches dose on nickel and vanadium removal efficiencies from the crude oils were investigated. The results indicate that the higher the degree of cation substitution on the cationic starch, the greater the effect of electrostatic adsorption of the heavy metal positive ions. Sample CS4 (CS is the abbreviation of the cationic starch) had the best effect on nickel and vanadium removal efficiencies in cationic starch series. The optimum conditions for nickel and vanadium removal from crude oils were as follows: (a) amount of CS4 200 mg/L, (b) microwave power 300 W and (c) microwave time 5 min. Under these conditions, the removal efficiencies of nickel from Iranian and Shengli crude oils were 55% and 60%, respectively, and the removal efficiencies of vanadium were 76% and 79%, respectively.     

One-step fabrication of multihollow polystyrene particles from miniemulsion system with nonionic surfactant

This paper presented a new facile approach to fabricate polystyrene (PS) multihollow particles from miniemulsion polymerization. The surfactant used in this miniemulsion system was OP-10, a nonionic surfactant of nonyl phenyl polyoxyethylene with an average of 10 ethylene oxide units per molecule (hydrophilic-lipophilic balance, HLB = 13.9). Due to the partition characteristic of OP-10 in miniemulsion, W/O/W structured monomer droplets could be formed after ultrasonic dispersion. Under irradiation by γ-ray, styrene polymerized through a droplet nucleation mechanism, which was the feature of miniemulsion polymerization. The formation of multihollow structure was affected by the content of OP-10 (W_OP) and pre-added PS (W_PS). It was found that when W_OP was above 2 wt% and W_PS was in the region of 2-10 wt% based on the monomer, multihollow PS particles could be obtained. The molecular weight of the PS latex particles synthesized was determined to be 10⁵ g/mol by GPC.     

Self-organized Multilayer Films and Porous Nanocomposites of Gold Nanoparticles with Octa(3-aminopropyl)octasilsesquioxane

Successive deposition of octa(3-aminopropyl)octasilsesquioxane octahydrochloride and gold nanoparticles coated with carboxylate groups (Au–COO⁻) on glass substrates alternately under mild basic conditions led to systematic buildup of a gold colloidal multilayer. The driving force of the self-assembly was electrostatic interaction between ammonium cations of octa(3-aminopropyl)octasilsesquioxane octahydrochloride and carboxylate anions on Au–COO⁻. A linear increase of surface plasmon resonance of Au–COO⁻ with the deposited bilayers indicated the multilayer manipulation was reproducible. Porous nanocomposites were accomplished by precipitation of octa(3-aminopropyl)octasilsesquioxane octahydrochloride modified polystyrene (PS) latex particles and Au–COO⁻ followed by removal of the PS particles via tetrahydrofuran (THF) extraction. Porous nanocomposite films were obtained by layer-by-layer (LBL) self-assembly of the octa(3-aminopropyl)octasilsesquioxane octahydrochloride modified PS latex particles and Au–COO⁻ followed by removal of the PS particles via THF extraction. Dedicated to Professor Christopher W. Allen for his advances in inorganic ring and polymer chemistry.     

Natural rubber-based nanocomposites by latex compounding with layered silicates

Natural rubber (NR) based nanocomposites with 10 wt% natural and synthetic layered silicates were produced via the latex compounding method. As layered silicates, sodium bentonite (natural) and sodium fluorohectorite (synthetic) were selected in addition to a non-layered inert filler (English India clay or commercial clay) as reference material. The nanocomposites were prepared by compounding the dispersions of clays and other latex chemicals necessary for vulcanization. The vulcanized nanocomposites were subjected to mechanical, thermal and swelling tests. The silicate dispersion was studied by transmission electron microscopy. Layered silicates outperformed the reference material (commercial clay) in all aspects. This was attributed to the intercalation/exfoliation of the silicates and to the formation of a skeleton ‘(house of cards)’ silicate network in the NR matrix.     

The synthesis and characterization of polystyrene/magnetic polyhedral oligomeric silsesquioxane (POSS) nanocomposites

Fc-CHCH-C₆H₆-(C₅H₉)₇Si₈O₁₂ (POSS1, Fc: ferrocene) which contain both metal and CC double bond was firstly synthesized by Wittig reaction. The chemical structure of POSS1 was characterized by FTIR, ¹H, ¹³C and ²⁹Si NMR, mass spectrometry and elemental analysis, and the magnetic property of POSS1 have also been studied. Polystyrene composites containing inorganic-organic hybrid polyhedral oligomeric silsesquioxane (POSS1) were prepared by bulk free radical polymerization. XRD and TEM studies indicate that POSS1 is completely dispersed at molecular level in PS matrix when 1 wt% POSS1 is introduced, while some POSS1-rich nanoparticals are present when content of POSS1 is beyond 3 wt%. GPC results show that molecular weight of the PS/POSS1 nanocomposites are increased with addition of POSS1. TGA and TMA data show the thermal stabilities of PS/POSS1 nanocomposites have been improved compared to neat PS. The PS/POSS1 nanocomposites also display higher glass transition temperatures (T_g) in comparison with neat PS. Viscoelastic properties of PS/POSS1 nanocomposites were investigated by DMTA. The results show the storage modulus (E′) values (temperature>T_g) and the loss factor peak values of the PS/POSS1 nanocomposites are higher than that of neat PS. Mechanical properties of the PS/POSS1 nanocomposites are improved compared to the neat PS.     

Effect of Carbon Nanofiber Functionalization on the Dispersion and Physical and Mechanical Properties of Polystyrene Nanocomposites

Summary: The effect of peroxide functionalization of carbon nanofibers (CNF) on the physical and mechanical properties of polystyrene (PS)–CNF nanocomposites prepared via melt mixing was studied. The CNF functionalization was evidenced by Raman spectroscopy, comparing the ratio of peaks at 1 371 and at 1 590 cm^?1 (peaks related to the disordered sp³‐hybridized carbon atom and to the graphitic structure of the sp²‐hybridized carbon atoms, respectively). The variation of the storage (E′) and tensile modulus (E) of the PS–CNF composites as a function of the untreated and peroxide treated CNF concentration were evaluated. Three different peroxide concentrations were used for treating the CNF. It was found that both E′ and E increase with CNF concentration and, in addition, increase further with the peroxide treated CNFs. Nonetheless, it was found that the greater the peroxide concentration used in treating the CNF, the greater the PS degradation via free radical attack on the polymer chain, with the corresponding negative effect on the storage and tensile modulus. Dispersion of the CNF was assessed using scanning and optical microscopy, and the positive effect of the peroxide treatment on the dispersion of the CNF is evidenced.

Tensile stress‐strain behavior of PS/CNF nanocomposites.     

Catalytic decomposition of methane for the simultaneous co-production of CO2-free hydrogen and carbon nanofibre based polymers

Through the catalytic decomposition of methane (CDM) it is possible to obtain in a single step both CO₂-free hydrogen and carbon nanostructures with a wide range of applications such as nanocomposite reinforcements. In this work, a Ni-based catalyst has been used to carry out the catalytic decomposition, obtaining an hydrogen concentration up to 47% (vol.) in the flue gas and carbon nanofibres (CNF). These structures have been inserted into two epoxy resins with different viscosity in order to study the influence of the CNF load in the electrical resistivity of the new materials prepared. As a result, the resistivity of these materials decreases up to 10⁶ Ω cm, values which avoid the electrostatic discharge and allow the electrostatic painting.     

Temperature dependence of electrical resistivity in carbon nanofiber/unsaturated polyester nanocomposites

This article described the temperature dependence of electrical resistivity for carbon nanofiber (CNF)/unsaturated polyester resin (UPR) nanocomposites prepared by a solvent evaporation method. It was found that the CNF/UPR nanocomposites had quite low electrical percolation threshold due to CNFs having a large aspect ratio and being well dispersed into the UPR matrix. A sharp decrease in the electrical resistivity was observed at about 1 wt% CNF content. The influence of CNF content on the electrical resistivity was investigated as a function of temperature in detail. The nanocomposites showed a positive temperature coefficient effect for the resistivity, and had a strong temperature dependence near the percolation threshold. When the number of thermal cycles was increased, the electrical resistivity decreased and had a weak temperature dependence, especially in the case of melting temperature. Moreover, the size influences of CNFs on the electrical properties of nanocomposites were analyzed and discussed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Synthesis of cationic binder through surfactant-free emulsion polymerization for textile pigment applications

The cationic P(DMDAAC-BA-MMA-HEA) copolymer latex was prepared with diallyldimethylammonium chloride, butyl acrylate, methylmethacrylate and hydroxyethyl acrylate as monomers via surfactant-free emulsion polymerization. The structures and morphologies of the latex were confirmed by Fourier transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM). The utilization performance of the cationic latex as a binder for pigment dyeing of cotton fabrics was investigated. FT-IR showed that the polymer was prepared successfully. TEM micrograph revealed that the hybrid latex particles were uniform spheres with the diameter ranged from 500 to 600 nm. Cotton fabric dyed with the cationic binder demonstrated 3–4 grade dry and wet rubbing fastness and 4 grade soaping fastness, which were comparable with commercial binders. Moreover, the binder can be used safely in pigment dyeing to give the dyed fabric improved hand feel and excellent elongation at break. It could be said that an efficient way to produce a binder with good performance was developed by the use of cationic emulsifier-free emulsion polymerization.     

Niobium-doped titanium oxide for fuel cell application

High surface area niobium-doped titanium oxide catalyst supports were synthesized through a chemical method using nano-sized polystyrene (PS) latex as a template. By varying the concentration of template with respect to titania and niobium precursors, we were able to produce niobium-doped titanium oxides with surface areas of 75-115 m²/g and sufficient electrical conductance to function as fuel cell catalyst supports. The oxides were subsequently platinized and evaluated as oxygen reduction catalysts using a rotating disk electrode. One of the samples showed a mass activity of 0.16 A/mg_Pt and a specific activity of 170 μA/cm²_Pt at 900 mV, which are comparable to our benchmark Pt/C electrocatalyst.     

Studies on thermal properties of PS nanocomposites for the effect of intercalated agent with side groups

Polystyrene-layered silicate nanocomposites were prepared from three new organically modified clays by emulsion polymerization method. These nanocomposites were exfoliated up to 3 wt% content of pristine clay relative to the amount of polystyrene (PS). The intercalated agents C₂₀, C₂₀-4VB, and C₂₀-POSS intercalated into the galleries result in improved compatibility between hydrophobic polymer and hydrophilic clay and facilitate the well dispersion of exfoliated clay in the polymer matrix. Results from X-ray diffraction, TEM and Fourier transform infrared spectroscopy indicate that these intercalated agents are indeed intercalated into the clay galleries successfully and these clay platelets are exfoliated in resultant nanocomposites. Thermal analyses of polystyrene-layered silicate nanocomposites compared with virgin PS indicate that the onset degradation temperature ca. 25 °C increased and the maximum reduction in coefficient of thermal expansion (CTE) is ca. 40% for the C₂₀-POSS/clay nanocomposite. In addition, the glass transition temperatures of all these nanocomposites are higher than the virgin PS.     

Synthesis of carboxylic acid functionalized nanoparticles by reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization of styrene

In this study, an addition-fragmentation chain transfer agent bearing carboxylic acid, 4-toluic acid dithiobenzoate (TADB), was used to synthesize carboxylic acid functionalized PS nanospheres via the miniemulsion polymerization. In addition, non-functionalized RAFT agent, benzyl dithiobenzoate (BDB), was also used to compare the surface properties of the PS nanoparticles. For the TADB system, the rate of polymerization was approximately two-fold faster than the BDB system, while the molecular weights and PDI of PS remain intact.With increasing the molar ratio of [TADB]/[AIBN] from 0 to 3.0, the average particle diameter is substantially increased from 90 to 126 nm. The absolute value of zeta potential and conductivity also correspondingly increase from 49.1 mV and 3.47 mS/cm to 53.9 mV and 4.21 mS/cm, respectively. The results indicate that the surface of PS nanospheres could be functionalized by means of a carboxylic acid group on the RAFT agent and the stability of the PS miniemulsion latex could be significantly improved.     

Thermotropic LCP/CNF nanocomposites prepared with aid of ultrasonic waves

Ultrasound assisted twin screw extrusion process was developed to disperse carbon nanofibers (CNFs) in a polymer matrix. CNFs were separately added into the melt stage to reduce the breakage of CNFs and to avoid intense stresses in the feed zone. The effect of ultrasound and CNFs loading on die pressure, rheological, mechanical, electrical and morphological properties of liquid crystalline polymer (LCP) filled with 0-20 wt% CNFs was studied. Ultrasonic treatment caused a reduction in die pressure and a decrease in electrical percolation threshold value of treated samples. It was also found that mechanical properties of ultrasonically treated LCP/CNF nanocomposite moldings were preserved, improved or slightly decreased in comparison with those of LCP. This is in contrast to available literature typically showing a deterioration of mechanical properties with addition of CNFs. SEM studies have indicated an improved dispersion of CNFs and a reduction of LCP rich area in nanocomposites upon ultrasonic treatment.     

Fabrication of hybrid nanocomposites with polystyrene and multiwalled carbon nanotubes with well-defined polystyrene via multiple atom transfer radical polymerization

The PS-grafted multiwalled carbon nanotubes (MWNTs) were produced by the bromo-ended PS (PS-Br) and pristine MWNTs in 1,2-dichlorobenzene at 110 °C for 72 h via atom transfer radical polymerization (ATRP). Bromo-ended PS (PS-Br) used as an initiator for the functionalization of MWNTs was synthesized with styrene by ATRP conditions using CuBr and N,N,N′,N′,N″-pentamethyldiethylenetriamine as catalyst. The PS-grafted MWNTs were fully characterized by ¹H-NMR, FT-IR, DSC, TGA, and SEM. The PS-grafted MWNTs were found to be highly soluble in a variety of organic solvents. The PS was chemically attached to the surfaces of MWNTs via ATRP approach, and the grafting amount of PS was 40–90%. From TGA and DSC measurements, the PS-grafted MWNTs were decomposed at lower temperature compared to that of PS-Br, and the functionalization of MWNTs increased the glass-transition temperature (T_g) of the grafted PS. The PS/PS-grafted MWNTs nanocomposites were prepared with PS and PS-grafted MWNTs by solution mixing in dimethylformamide (DMF). The resulting nanocomposites were found to be the homogeneous dispersion of PS-grafted MWNTs in PS matrix via aromatic (π–π) interactions between PS and PS-grafted MWNTs as determined by SEM and TEM.     

Synthesis of cationic poly(methyl methacrylate)-poly(N-isopropyl acrylamide) core-shell latexes via two-stage emulsion copolymerization

Thermally sensitive poly(methyl methacrylate (MMA))-poly(N-isopropylacrylamide (NIPAM)) core-shell particles were prepared via a two-stage emulsion copolymerization process. Methylene bisacrylamide (MBA), 2,2′-azobis (2-amidinopropane) dihydrochloride (V50) and dodecylethyl dimethyl ammonium bromide (DEDAB) were used as crosslinker, cationic initiator and surfactant, respectively. Functional core-shell particles were prepared using aminoethyl methacrylate hydrochloride (AEMH) as cationic co-monomer to increase the surface charge density. The influences of the crosslinker and co-monomer concentrations on the thickness and swelling capacity of the PNIPAM-based shell layer were studied. The latex particle size and particle size distribution were determined both by dynamic light scattering (DLS) and scanning electron microscopy (SEM). Monodisperse particles were produced with diameters between 150-250 nm (at 25 °C) and 140-190 nm (at 50 °C). The surface charge density was determined by chemical titration and higher values (∼10 μmol/g) were obtained for the functional core-shell particles. The electrokinetic properties of the dispersions at several pH and temperature values confirm the presence of the shell layer and cationic surface charges.