Influence of processing window and weight ratio on the morphology of the extruded and drawn PET/PP blends

To obtain polyethylene terephthalate (PET)/polypropylene (PP) microfibrillar composite (MFC) with good mechanical properties, a high content of PET fibrils in the drawn strand (i.e. PET droplets in the extrudate) is preferred. However, a phase inversion (from PP matrix to PET matrix) takes place when the concentration of the PET reaches 40 wt% at the screw speed of 40 rpm (rounds per minute). This “PP domains in PET matrix” phase structure is the undesired phase structure for preparing MFC. However, the desired phase structure of “PET droplets in PP matrix” can be regained by adopting a low screw speed (20 rpm) during extrusion of the PET/PP (40/60); if a higher screw speed is adopted (80 rpm), then a suitable amount of PP grafted maleic anhydride (PP‐g‐MA) should be incorporated. The PET/PP blends which demonstrate the desired “PET droplets in PP matrix” phase structure were stretched into strands, and PET/PP MFC was prepared. The MFC with high content of PET microfibrils as the reinforcement exhibits superior tensile properties than the neat PP. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Solubility behavior and thermodynamic modeling of sodium monosulfoaluminate (“U-phase”) in cementitious systems

The “U-phase,” a sodium-containing (alumino-ferrite-monosubstituent) AFm phase, has been observed to form in sodium-enriched highly alkaline cementitious systems, for example, of relevance to nuclear waste, and saline industrial brine management. But, minimal information is available of the U-phase's (e.g., solubility or thermodynamic properties) due to its limited stability and its tendency to transform into ettringite or monosulfoaluminate. Herein, the U-phase was systematically synthesized at four temperatures (5, 15, 25, and 50°C) and fully characterized in terms of its thermochemical properties. The average composition of the synthesized U-phase (4CaO·Al₂O₃·1.85SO₃·0.85Na₂O·12H₂O) deviates slightly from typical disclosures in the literature. The solubility product of the U-phase formation was measured from conditions of oversaturation. The measured thermodynamic data accurately predicted experimental observations of U-phase formation in cementitious environments. In general, it was noted that the U-phase forms and persists (i.e., remains stable) at pH > 13.7 and [Na⁺] concentrations superior to 1 mol/L.     

Facile preparation of homogenous waterborne poly(urethane/acrylate) composites and the correlation between microstructure and improved properties

Homogenous waterborne polyurethane/polyacrylate emulsions were synthesized based on the prepared polyurethane and polyacrylate through a facile process. The attention was attracted to the miscibility and performance of waterborne polyurethane and polyacrylate. The structures and properties of waterborne polyurethane and waterborne polyurethane/polyacrylate samples were characterized by using Fourier transform infrared spectroscopy, transmission electron microscope, X-ray photoelectron spectroscopy, X-ray diffractometer, thermogravimetric, and so forth, as well as solid content and tensile testing. The results showed that the micro morphology of waterborne polyurethane/polyacrylate emulsion presented single-phase structure with the stoichiometric polyacrylate content increasing from 33% to 80% to waterborne polyurethane. The waterborne polyurethane/polyacrylate films surface is rich in polyacrylate phase. Meanwhile, waterborne polyurethane/polyacrylate composites showed significant improvement in thermal stability and elongation at break, smaller particle size and narrower particle size distribution comparing with waterborne polyurethane.     

Micromechanical processes and failure phenomena in reactively compatibilized blends of polyamide 6 and styrenic polymers. I. Polyamide 6/acrylonitrile– butadiene–styrene copolymer blends

In this work, in situ investigations of the micromechanical properties of reactively compatibilized blends of polyamide 6 (PA6) and an acrylonitrile–butadiene–styrene copolymer (ABS) were performed with transmission electron microscopy. Three PA6/ABS blends were prepared with a disperse morphology (inclusions of PA6 or ABS) and with a cocontinuous structure. The objective of this work was to study the deformation of the inclusions and the interface between the PA6 phase and the ABS phase. Our transmission electron microscopy investigations revealed that the morphology of the blends was strongly influenced by the asymmetric nature of the interface between PA6 and ABS. In the blends with a PA6 matrix, the interface between PA6 and the ABS inclusions was deformed in tensile deformation under uniaxial loading. A strong influence of the PA6 water content on the (micro)mechanical behavior was observed. Although the “dry” blends behaved in a brittle fashion, the “wet” blends behaved in a ductile fashion with the formation of deformation bands in the matrix (PA6 or ABS), which were initiated by stress concentration at the particles (ABS or PA6, respectively). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Physical properties and dielectric behavior of the poly(urethane-urea) based on o-dianisidine and renewable cross-linkers

The novelty of the poly(urethane-urea) series consists in inclusion of o-dianisidine units in the main chain and cross-linking with renewable biomaterials, unused compounds so far in the synthesis of the poly(urethane-urea) (Tween 20, Span 20, Phloroglucinol). The effects of these components on the structure, surface, thermo-mechanical properties and dielectric behavior of the obtained poly(urethane-urea) were investigated by Fourier transform infrared (FTIR) spectroscopy, thermo-gravimetric analysis, static contact angles, broadband dielectric spectroscopy, and mechanical testing. The FTIR spectra showed that the urethane hydrogen bonds decreased with the increase of o-dianisidine content. Such that, at the increase of the o-dianisidine content, decreased the thermo-mechanical properties, and increased strongly the water contact angle from 83 to 108°. By dielectric relaxation spectroscopy was studied the molecular dynamics within the polymeric matrices with identical soft segments but different structure of the hard domains. These poly(urethane-urea) materials exhibit two secondary relaxations (β and γ) and a relaxation process α, corresponding to the segmental movements in the soft phase, which occurs around the temperature of −50°C independent of the measurement frequency. o-Dianisidine prevents the formation of all the urethane hydrogen bonds and so increases the chains mobility and dipoles polarization of polymer matrix, thus increasing the dielectric constants.     

The roles of polyacrylate in poly(vinyl chloride)‐lignin composites

A novel method was adopted to improve the adhesion between lignin particles and poly(vinyl chloride) (PVC) matrix in PVC‐lignin composites. Lignin was treated with a polyacrylate, poly(ethyl acrylate‐co‐acrylic acid), and the composites was prepared with PVC and the treated lignin. The mechanical properties and morphology of the composites were investigated, and the roles of polyacrylate in the composites were discussed. The results show that both the tensile and impact strengths of the composites are improved when both the content of carboxyl in polyacrylate and its dosage are low, and the optimum is: yield strength, 24.17 MPa, higher than that of PVC control (21.88 MPa); breaking strength, 33.59 MPa, close to that of PVC control (35.62 MPa); and impact strength, 8.0 kJ m⁻², 31% higher than that of PVC control (6.1 kJ m⁻²). Microscopic morphology analysis suggests that polyacrylate improved the adhesion between lignin particles and PVC matrix. The roles of polyacrylate are as the following: polyacrylate is combined with lignin by hydrogen bond and ester bond, and most of its chains spread into PVC matrix due to its good compatibility with PVC, thereby lignin particles can be well bound with PVC matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Discontinuous carbon fiber/polyamide composites with microencapsulated paraffin for thermal energy storage

This work focuses on the development of multifunctional thermoplastic composites with thermal energy storage capability. A polyamide 12 (PA12) matrix was filled with a phase change material (PCM), constituted by paraffin microcapsules (T_melt = 43 °C), and reinforced with carbon fibers (CFs) of two different lengths (chopped/CF “long”[CFL] and milled/CF “short” [CFS]). DSC tests showed that the melting/crystallization enthalpy values increase with the PCM weight fraction up to 60 J/g. The enthalpy was 41–94% of the expected value and decreased with an increase in the fiber content, because the capsules were damaged by the increasing viscosity and shear stresses during compounding. Long CFs increased the elastic modulus (+316%), tensile strength (+26%), and thermal conductivity (+54%) with respect to neat PA12. Thermal imaging tests evidenced a slower cooling for the samples containing PCM, and once again the CFS-containing samples outperformed those with CFL, due to the higher effective PCM content. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47408.     

Dispersion of "guava-like" silica/polyacrylate nanocomposite particles in polyacrylate matrix

A series of “guava-like” silica/polyacrylate nanocomposite particles with close silica content and different grafting degrees were prepared via mini-emulsion polymerization using 3-(trimethoxysilyl)propyl methacrylate (TSPM) modified silica/acrylate dispersion. The silica/polyacrylate composite particles were melt-mixed with unfilled polyacrylate (PA) resin to prepare corresponding silica/polyacrylate molded composites and the dispersion mechanism of these silica particles from the “guava-like” composite particles into polyacrylate matrix was studied. It was calculated that about 110 silica particles were accumulated in the bulk of every silica/polyacrylate composite latex particle. Both the solubility tests of silica/polyacrylate composite latex particles in tetrahydrofuran (THF) and the section transmission electron microscope (TEM) micrographs of silica/polyacrylate molded composites indicated that the grafting degree of silica particles played a crucial role in the dispersion of silica/polyacrylate composite particles into the polyacrylate matrix. When the grafting degree of polyacrylate onto silica was in a moderate range (ca. 20%–70%), almost all of silica particles in these “guava-like” composite particles were dispersed into the polyacrylate matrix in a primaryparticle-level. However, at a lower grafting degree, massive silica aggregations were found in molded composites because of the lack of steric protection. At a greater grafting degree (i.e., 200%), a cross-linked network was formed in the silica/polyacrylate composite particles, which prevented the dispersion of composite particles in THF and polyacrylate matrix as primary particles.     

Dispersion of “guava-like” silica/polyacrylate nanocomposite particles in polyacrylate matrix

A series of “guava-like” silica/polyacrylate nanocomposite particles with close silica content and different grafting degrees were prepared via mini-emulsion polymerization using 3-(trimethoxysilyl)propyl methacrylate (TSPM) modified silica/acrylate dispersion. The silica/polyacrylate composite particles were melt-mixed with unfilled polyacrylate (PA) resin to prepare corresponding silica/polyacrylate molded composites and the dispersion mechanism of these silica particles from the “guava-like” composite particles into polyacrylate matrix was studied. It was calculated that about 110 silica particles were accumulated in the bulk of every silica/polyacrylate composite latex particle. Both the solubility tests of silica/polyacrylate composite latex particles in tetrahydrofuran (THF) and the section transmission electron microscope (TEM) micrographs of silica/polyacrylate molded composites indicated that the grafting degree of silica particles played a crucial role in the dispersion of silica/polyacrylate composite particles into the polyacrylate matrix. When the grafting degree of polyacrylate onto silica was in a moderate range (ca. 20%–70%), almost all of silica particles in these “guava-like” composite particles were dispersed into the polyacrylate matrix in a primary-particle-level. However, at a lower grafting degree, massive silica aggregations were found in molded composites because of the lack of steric protection. At a greater grafting degree (i.e., 200%), a cross-linked network was formed in the silica/polyacrylate composite particles, which prevented the dispersion of composite particles in THF and polyacrylate matrix as primary particles.     

A crosslinked waterborne poly(urethane-urea) oligomer enables mechanically strong waterborne polyacrylate–poly(urethane-urea) hybrid films with superior film-forming ability

In this article, a crosslinked waterborne poly(urethane-urea) (WPUU) is synthesized based on the terminal aromatic amine polyether (DP-1000) and aliphatic isophorone diisocyanate. Then WPUU is compound with acrylate monomer by emulsion polymerization to produce waterborne polyacrylate–poly(urethane-urea) (WPUUA) hybrid emulsions. Compared with waterborne polyacrylate (WPA) film, the film-forming ability of WPUUA film is improved and the surface roughness R_a and R_q of WPUUA film decreases from 47.5 and 36.4 nm to 35.2 and 18.8 nm, respectively. Meanwhile, the mechanical properties of WPUUA films are significantly improved compared to WPA film. In addition, the performances of WPUUA hybrid films can be modified according to requirements by adjusting the molar ratio between DP-1000 and polyisocyanate. As a result, these WPUUA hybrid emulsions have great application potential in waterborne coatings and other fields.     

Mechanically strong waterborne poly(urethane-urea) films and nanocomposite films

A series of transparent waterborne poly(urethane-urea) (PUU) films and nanocomposite films were prepared using isocyanate excess (5–50 mol% excess relative to the hydroxyl groups) and omitting the common chain-extension step in the acetone method of the preparation. The surplus isocyanate groups were converted into urea and eventually biuret linkages via the reaction with water during the last phase inversion step. Nanocomposites were prepared by the direct mixing of the PUU nanoparticles in water with aqueous nanosilica or montmorillonite powder followed by slow water evaporation. Variable urea/biuret content is responsible for substantially different tensile properties; the neat organic films show elongation-at-break values of 100%–1120%, tensile strength values of 0.07–22.1 MPa, and energy-to-break of 0.1–85 mJ × mm⁻³. All of the materials can be potentially used as soft-to-hard topcoats, depending on the specific demands. The most promising materials are films prepared at 30 and particularly 40 mol% isocyanate excess.     

Effect of chain extender on microphase structure and performance of self-healing polyurethane and poly(urethane-urea)

In this work, four aliphatic chain extenders, hexanediol (HDO), hexane diamine (HDA), cystamine (CY), and cystine dimethyl ester (CDE), were chosen to synthesize four kinds of polyurethane and poly(urethane-urea)s (PUs), respectively. HDO extended polyurethanes, HDA extended poly(urethane-urea), CY extended poly(urethane-urea), and CDE extended poly(urethane-urea) were denoted as OPU, APU, CPU, and SPU, respectively. The effect of chain extender type on microphase structure and performance of four PUs was investigated. Our research showed that mechanical strength increased in the following order: OPU < SPU < CPU < APU, and self-healing performance increased in the opposite direction. This result is attributed to the increasing degree of microphase separation: OPU < SPU < CPU < APU. The optimal sample SPU has not only excellent mechanical properties (tensile strength of 27.1 MPa and elongation at break of 397.7%), but also exhibits superior self-healing performance (self-healing efficiencies of 95.3% and 93.5% based on tensile strength and elongation at break). The moderate degree of microphase separation between the soft segments and the hard segments, the introduction of disulfide bonds and low degree of hydrogen bonding are responsible for preparing a polyurethane or poly(urethane-urea) system with high mechanical strength and excellent self-healing performance simultaneously. This work provides useful information for us to develop self-healing polyurethane or poly(urethane-urea) materials in the future.     

Tensile behavior of polyolefin composites: the effect of matrix parameters

Polyolefin composites were prepared from 14 PE matrices and three different mineral fillers (montmorillonite, palygorskite and glass microspheres) via melt compounding in an extruder. Mechanical properties of the obtained systems were analyzed with emphasis on elongation at break and conditions for ductile/brittle failure were determined. When filler content is raised beyond a certain “critical” value, tensile properties are dramatically altered and transition occurs from ductile behavior to brittle fracture. This transition is displayed by a well‐defined “step” on the plot of strain at break versus concentration of particles. The value of “critical filler content” was found to depend mainly on level of crystallinity of a matrix while other parameters (chemical nature of filler particles, their size, shape and surface treatment) are less significant. “Critical filler content” will decrease with growth of crystallinity of a polymer and with highly crystalline HDPEs it is as low as 2–8 vol %. Otherwise, with noncrystallizing and low‐crystalline polymers elongation at break decreases gradually with concentration of mineral particles and ductile type deformation is maintained at fairly large filler fractions. The results presented here will be useful for a proper selection of a matrix polymer in composites with mineral fillers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43819.     

Molecular recognition within a poly(amide urethane) system

The heterodimer recognition within a poly(amide urethane) (PAU) has been achieved through the incorporation of the amphiphilic alkylated nucleobase, 1-hexadecyluracil (U16). The heterodimer recognition led the poly(amide urethane) to exhibit the “plug and play” behavior even the heterodimer recognition coincided with several other hydrogen bonding motifs. In addition, the PAU/U16 blends possess nano-scale lamellar structure of U16 phase within lamellar structure of PAU phase. The nano-scale lamellar structure of the packed U16 gradually transforms from one to the other with the change in the U16 content in the blends.     

Plasma preparation of carbon black used in conductive coatings

A conductive coatings was prepared using a kind of spherical carbon black (CB) as conductive pigment and polyacrylate (PA) as polymer matrix. The conductive pigment CB nanoparticles were prepared by AC plasma arc method, and then treated with concentrated nitric acid. The pristine and oxidized CB nanoparticles were characterized by scanning and transmission electron microscopy. Afterwards, CB powders were dispersed in PA to produce conductive coatings. The effects of CB content and titanium coupling agent on the volume resistivity were investigated. Furthermore, the rheological and mechanical properties of PA/CB coatings were also investigated. The results showed that the volume resistivity of the PA/CB films was decreased with the increasing of CB content and the electrical percolation threshold was about 2.0 wt%. An interesting result could be observed that the rheological threshold value was close to electrical percolation threshold. In addition, the tensile properties were improved with the addition of CB nanoparticles. POLYM. COMPOS. 37:1078–1084, 2016. © 2014 Society of Plastics Engineers     

Application of thermal methods in the characterisation of poly(urethane-urea)s formed by reaction injection moulding

Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) have been used in conjunction with tensile testing and transmission electron microscopy (TEM) to characterise novel segmented poly(urethane-urea) (PUU) network materials formed by reaction injection moulding (RIM). Materials were based on a modified liquid 4,4′-diphenylmethane diisocyanate and a polyether triol in admixture with one of three hindered aromatic diamines: 3,5-diethyltoluene diamine (DETDA); methylene-bis-2,6-diisopropylaniline (MMIPA); methylene-bis-(2-methyl-6-isopropylaniline) (MMIPA). The materials ranged from tough translucent elastomers to opaque brittle plastics depending on the chemical nature and weight fraction of the hard segments (HS). DSC and DMTA studies showed the PUU materials to be phase-separated; this was confirmed by TEM and tensile testing. The soft-segment glass transition temperatures (DSC and DMTA) were independent of composition but varied with diamine structure. Hard-segment glass transition temperatures could only be evaluated by DMTA and no evidence of crystallinity was found by thermal methods or by wide angle x-ray diffraction. Heat capacity measurements and DMTA suggested that some degree of phase mixing had occurred, to a greater extent in the DETDA and MDIPA systems. Phase inversion was observed by DMTA and confirmed at ～55% hard-segment content for DETDA systems by tensile testing.     

Mechanical properties and microstructure of acrylonitrile–butadiene rubber vulcanizates reinforced by in situ polymerized phenolic resin

The phenolic resin (PF) was incorporated into acrylonitrile–butadiene rubber (NBR) vulcanizates by in situ polymerization during the vulcanization process. It was found that the tensile strength, tearing strength, and tensile strength (300% elongation) could be considerably enhanced 59.4, 80.2, and 126.4%, respectively, at an optimum PF content of only 15 phr, but the elongation at break and shore A hardness were only slightly affected on the basis of silica‐reinforced NBR vulcanizates. A systematic study of the PF structure formed within the NBR matrix using various experimental schemes and procedures has revealed that the PF resin would form the localized discontinuous three‐dimensional interconnected network structures in the NBR matrix. The substantial reinforcement of PF on the mechanical properties of vulcanized NBR were attributed to the morphology, high flexibility, and moderate stiffness of the PF phases and their excellent bonding with rubbers through “rubber to rubber” and interface layer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

水下搅拌摩擦加工制备碳纳米管增强PE-HD结构与拉伸性能研究

通过水下搅拌摩擦加工技术制备多壁碳纳米管（MWCNTs）增强高密度聚乙烯（PE-HD）复合材料,并研究了旋转速度和MWCNTs含量对复合材料结构和性能的影响。结果表明,MWCNTs在基体中以云状形式分布,组织相对均匀;MWCNTs含量为从1 %（质量分数,下同）增加到2 %时,复合材料拉伸强度随着旋转速度的增加先增大后减小;MWCNTs含量为4 %时,复合材料拉伸强度随着旋转速度的增加而减小;PE-HD的结晶度随着MWCNTs含量的增加而下降。     

Reactive extrusion of polystyrene/polyethylene blends

The feasibility of inducing beneficial changes to polystyrene/polyethylene (PS/PE) blends via reactive extrusion processes is considered. Experiments have been conducted on 50:50 wt.% PS/PE blends that were treated with different levels of dicumyl peroxide and triallyl isocyanurate coupling agent. Both a low molecular weight and a high molecular weight blend series have been investigated. A “more reactive” polystyrene was synthesized by incorporation of a minor amount of ortho-vinylbenzaldehyde. Blends containing this modified polystyrene were subjected to identical processing' conditions on a counter-rotating twin screw extruder. Examination of the tensile properties of the extrusion products suggested that a judicious level of peroxide and coupling agent additives would be beneficial to the ultimate physical properties. The quantity of styrenic phase becoming chemically grafted to the polyethylene matrix was influenced most strongly by the level of the chosen coupling agent. As determined by scanning electron microscopy, the phase morphologies of the tensile test fracture surfaces were strongly dependent upon the reaction extrusion process; those extruded blends that had been exposed to the additive pre-treatment displayed substantially finer microstructure. The enthalpy of fusion of the polyethylene melting endotherm was likewise influenced by both the presence or absence of the additives as well as the molecular weight nature of the blend series.     

Mechanical and thermal properties of environment-friendly “green” composites made from pineapple leaf fibers and poly(hydroxybutyrate-co-valerate) resin

This paper presents the mechanical and thermal properties of unidirectional, degradable, environment-friendly “green” composites made from pineapple fibers and poly(hydroxybutyrate-co-valerate) (PHBV) resin. Tensile and flexural properties of the “green” composites with different fiber contents were measured in both longitudinal and transverse directions. Compared to those of virgin resin, the tensile and flexural strengths of “green” composites are significantly higher in the longitudinal direction while they are lower in the transverse direction. However, the mechanical properties are lower than those predicted by simple models. Scanning electron microscope (SEM) photomicrographs of the tensile fracture surfaces demonstrate fibers being pulled out from the matrix, the interfacial failure, fiber fibrillation, and the nonunidirectional nature of the “green” composites. The thermal behavior of the “green” composites, studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), showed that the presence of pineapple fibers does not affect the nonisothermal crystallization kinetics, crystallinity, and thermal decomposition of PHBV resin.