Hybrid resins from polyisocyanate,vinyl ester,melamine formaldehyde and water glass: structure and properties

Abstract

Hybrid thermosets were produced from polymeric methylene diphenyl isocyanate (PMDI), styrene cross-linkable vinyl ester (VE) and water glass (WG) using melamine formaldehyde (MF) resin as additional reactive emulsifier. Vinyl ester (VE) was added to the PMDI/MF mixture in which the WG was dispersed next. The content of MF in the resin formulation was varied between 0·5 and 15 wt-%. The resulting water in oil type (W/O) emulsion (water=WG, oil=organic phase composed of PMDI+VE+MF) was cured at room temperature for 24 h followed by post-curing at T=100°C for 4 h. The chemorheology of the hybrid resins was assessed by plate/plate rheometry. Information on the morphology of the cured hybrid resins was received from scanning electron microscope (SEM), atomic force microscopic (AFM) and dynamic mechanical thermal analysis (DMTA) studies. The mechanical and fracture mechanical properties as well as the resistance to thermal degradation of the hybrid thermosets were determined and discussed.     

Dynamic mechanical properties of high density polyethylene and teak wood flour composites

The dynamic mechanical properties of high density polyethylene (HDPE) and teak wood flour (TWF) composites at varying volume fraction (Φ _f) of TWF from 0.00 to 0.32 have been studied. In HDPE/TWF composites, storage modulus (E′) decreased at Φ _f = 0.05, then increases with Φ _f; however, values were lower than HDPE up to Φ _f = 0.16, due to a pseudolubricating effect of filler. Loss modulus (E″) values were higher than HDPE in β and α relaxation regions while in γ relaxation region values were marginally equal to HDPE. Tan δ value decreases with Φ _f which may be due to enhanced amorphization and decreased crystallinity of HDPE. In presence of maleic anhydride grafted HDPE (HDPE-g-MAH), E′ values were lower than HDPE/TWF composites. In HDPE/TWF/HDPE-g-MAH, E″ were slightly higher than HDPE/TWF due to slippage of HDPE chains facilitated by the extent of degradation of coupling agent. Tan δ were higher for both systems than the rule of mixture.     

Glass fiber/wood flour modified high density polyethylene composites

Composites of high density polyethylene (HDPE) with the reinforcements of glass fiber (GF) and wood flour (WF) have been studied in this work. High‐density polyethylene‐grafted maleic hydride (HDPE‐g‐MAH) was used as a compatibilizer. In particular, the effect of GF, WF, and HDPE‐g‐MAH on the overall properties of GF/WF/HDPE composites (GWPCs in short form) was systematically studied. The results indicate that HDPE‐g‐MAH as a compatibilizer can effectively promote the interfacial adhesion between GF/WF and HDPE. By the incorporations of GF/WF, the heat deflection temperature can reach above 120°C, and the water absorption can be below 0.7%, also the tensile strength, flexural strength, and impact strength of GWPCs can surpass 55.2 Mpa, 69.4 Mpa, and 11.1 KJ/m², respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and mechanical characterization of linear low‐density polyethylene/wood flour composites

A linear low‐density polyethylene (LLDPE) matrix was modified with an organic peroxide and by a reaction with maleic anhydride (MAn) and was simultaneously compounded with untreated wood flour in a twin‐screw extruder. The thermal and mechanical properties of the modified LLDPE and the resulting composites were evaluated. The degree of crystallinity was reduced in the modified LLDPE, but it increased with the addition of wood flour for the formation of the composites. Significant improvements in the tensile strength, ductility, and creep resistance were obtained for the MAn‐modified composites. This enhancement in the mechanical behavior could be attributed to an improvement in the compatibility between the filler and the matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2775–2784, 2003     

Studies on thermal,mechanical, morphological,and viscoelastic properties of polybenzimidazole fiber reinforced high density polyethylene composites

High density polyethylene (HDPE) and polybenzimidazole fiber (PBI) composites were prepared by melt blending in a twin screw extruder. The thermomechanical properties of PBI fiber reinforced HDPE composite samples (1%, 4%, and 8%) of fiber lengths 3 mm and 6 mm were investigated using differential scanning calorimeter (DSC), universal testing machine, rheometer, and scanning electron microscopy (SEM). The effects of fiber content and fiber lengths on the thermomechanical properties of the HDPE‐PBI composites were studied. The DSC analysis showed a decrease in crystallinity of HDPE‐PBI composites with an increase of fiber loading. SEM images revealed homogeneous distribution of the fibers in the polymer matrix. The thermal behavior of the composites was evaluated from thermogravimetric analysis and the thermal stability was found to increase with the addition of fibers. The evidence of homogeneous distribution was verified by the considerably high values of tensile strength and flexural strength. In the rheology study, the complex viscosities of HDPE‐PBI composites were higher than the HDPE matrix and increased with the increasing of PBI fiber loading. POLYM. COMPOS., 5–13, 2016. © 2014 Society of Plastics Engineers     

HDPE/竹粉复合材料的界面演变及流变特性

采用扫描电子显微镜-X射线能谱仪跟踪硅烷偶联剂中Si元素在高密度聚乙烯(HDPE)基竹塑共混体系界面处的分布,并结合旋转流变仪研究了共混体系加工过程中的界面演变过程。发现随着加工时间的延长,界面处Si元素的含量相对增加,体系的动态模量、黏度升高。表明偶联剂连接的竹粉与HDPE分子链间的相互作用增强,界面层厚度增加。共混体系的动态流变测试结果表明,竹粉填充体系在低频末端区的线性黏弹行为显著不同于HDPE基体,表现出"类固体"特性,动态流变测试对偶联剂的加入所引起的体系的黏弹行为及结构变化响应较敏感。Cole-Cole曲线可反映竹粉粒子网络结构及竹粉与HDPE基体界面相关的松弛信息,体现体系界面性质及竹粉与分子链间网络结构的变化。     

Rheological behavior and mechanical properties of wood flour/high density polyethylene blends: Effects of esterification of wood with citric acid

This study explored the modifying effects of wood flour (WF) with citric acid (CA) on the rheological and mechanical properties of WF/high density polypropylene (HDPE) composites. WF was treated with CA, which acts a cross‐linking agent and melt‐blended with HDPE with a twin‐screw extruder. Injection molding was used to make tensile and impact tests samples. The rheological properties of the blends were characterized using a Haake microcompounder, torque‐, capillary‐, and rotational‐rheometer, respectively. Results show that the thermal stability of WF decreased after treatment. Compared with those of untreated composites, the tensile strength, elongation‐at‐break, and impact strength of the composites treated with 5% CA were reduced by 6%, 14%, and 16%, respectively. This reduction was attributed to embrittlement of WF, which may negatively influence the mechanical properties of the resulting composites. Scanning electron microscopy revealed better dispersion of CA‐treated WF in the composites than the untreated WF. For composites treated with 5% CA, the melt torque, viscosity, moduli, and shear stress decreased significantly, indicating an improvement in processibility. This improvement is attributed to uniform dispersion of the modified WF, as well as to better interfacial adhesion between WF and the matrix. Results suggest that treating WF with CA shows promise for improving the processibility of highly filled thermoplastic composites via extrusion/injection molding processing. POLYM. COMPOS., 37:553–560, 2016. © 2014 Society of Plastics Engineers     

Preparation of highly filled wood flour/recycled high density polyethylene composites by in situ reactive extrusion

Highly filled wood flour/recycled high density polyethylene (WF/RHDPE) composites were directly prepared by in situ reactive extrusion using a twin‐screw/single‐screw extruder system. The effects of dicumyl peroxide (DCP) content on extrusion pressure, rheological behavior, mechanical properties, fractured surface morphology of the composites, and melting temperature of RHDPE in the composites were investigated. The extrusion pressure and torque of WF/RHDPE composite melt increased with DCP content. Mechanical property tests and scanning electron microscopy analysis results confirmed that the interfacial interaction of the composites was improved by in situ reaction. The composites show lower melting peak temperature (T_m) than RHDPE. The cooling in profile extrusion shortened the crystallization time, resulting in decrease of crystalline order of RHDPE in the composites. There are no noticeable changes of T_m values with increasing DCP content. Comparative study on composites with maleic anhydride grafted polyethylene as compatibilizer demonstrated that mechanochemical treatment with DCP and maleic anhydride was an effective method to improve interfacial adhesion for WF/RHDPE composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological properties of teak wood flour reinforced HDPE and maize starch composites

Teak wood flour reinforced high density polyethylene and maize starch composites were prepared by using maleic anhydride grafted polyethylene as a compatibilizer. The mechanical properties (tensile and flexural) of all the composites increased after addition of 10%–40% teak wood flour into HDPE matrix. The complex viscosity (η*) was higher for all the composites at the low frequency, but decreased with increasing frequencies indicating a shear thinning behavior of the composites. The storage modulus and loss modulus increased for the composites compared to the HDPE at low frequencies. Damping factor peak of HDPE and composites showed high below 1 Hz, but the peak start decreasing with increasing above 1 Hz. The relaxation behavior of HDPE and the composites after incorporating teak wood flour, maize starch, and compatibilizer was obtained by Han plot. Biodegradability was enhanced with the incorporation of teak wood flour, maize starch into the composites. Appreciable water uptake and the thickness swelling for the composites indicating it's potential for interior, automobile and packaging applications.     

Comparative mechanical,fire‐retarding,and morphological properties of high‐density polyethylene/(wood flour) composites with different flame retardants

Aluminum hydroxide, magnesium hydroxide, and 1,2‐bis(pentabromophenyl) ethane were incorporated into high‐density polyethylene (HDPE) and wood flour composites, and their mechanical properties, morphology, and fire‐retardancy performance were characterized. The addition of flame retardants slightly reduced the modulus of elasticity and modulus of rupture of composites. Morphology characterization showed reduced interfacial adhesion among wood flour, HDPE, and flame retardants in the composites compared with control composites (HDPE and wood flour composites without the addition of flame retardants). The flame retardancy of composites was improved with the addition of the flame retardants, magnesium hydroxide and 1,2‐bis(pentabromophenyl) ethane, especially 1,2‐bis(pentabromophenyl) ethane, with a significant decrease in the heat release rate and total heat release. Char residue composition and morphology, analyzed by attenuated total reflectance, Fourier‐transform infrared spectroscopy, and scanning electron microscopy, showed that the char layer was formed on the composite surface with the addition of flame retardants, which promoted the fire performance of composites. The composites with 10 wt% 1,2‐bis(pentabromophenyl) ethane had good fire performance with a continuous and compact char layer on the composite surface. J. VINYL ADDIT. TECHNOL., 24:3–12, 2018. © 2015 Society of Plastics Engineers     

Low density polyethylene composites reinforced with Australian King Palm fibers: mechanical and thermal properties

The aim of this work is to obtain and evaluate the mechanical and thermal properties of low Density Polyethylene (LDPE) composites reinforced with fibers from Australian King Palm fibers. Raw fibers were characterized by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) Spectroscopy. The chemical composition of the fibers was also evaluated. After characterizing the fibers were mixed into the LDPE, in proportions of 5, 10, 15 and 20% (wt/wt) using a thermokinetic mixer model MH-50H. Furthermore tensile, flexural and impact specimens were prepared for evaluation of mechanical properties. The composites were analyzed through SEM micrographs of fractured surfaces and thermal analysis. The results indicate that the reinforcement decreases the thermal stability of the composites, but caused an increase the mechanical properties of the composites. The composites reinforced with of raw fibers 20% (wt/wt) showed significant increase in the tensile strength, flexural and impact.     

Wood‐thermoplastic composites from wood flour and high‐density polyethylene

High‐density polyethylene/wood flour (HDPE/WF) composites were prepared by a twin‐screw extruder. The effects of WF, silane coupling agents, polymer compatibilizers, and their content on the comprehensive properties of the WF/HDPE composites have been studied in detail, including the mechanical, thermal, and rheological properties and microstructure. The results showed that both silane coupling agents and polymer compatibilizers could improve the interfacial adhesion between WF and HDPE, and further improve the properties of WF/HDPE composites, especially with AX8900 as a compatibilizer giving higher impact strength, and with HDPE‐g‐MAH as a compatibilizer giving the best tensile and flexural properties. The resultant composite has higher strength (tensile strength = 51.03 MPa) and better heat deflection temperature (63.1°C). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on recyclable composites: nylon fibre reinforced high density polyethylene composites

Abstract

A commercial grade of high density polyethylene (HDPE) matrix reinforced with nylon fibre up to 30 wt-% of HDPE was studied as a potential candidate for recyclable composites. These composite materials show improvement in mechanical properties such as tensile strength and flexural strength. Modification using styrene maleic anhydride – grafted HDPE significantly improved the mechanical and thermal properties. The HDPE/nylon composites/blends obtained by recycling of the composites also show good mechanical properties.     

Incorporation effect of enzymatic hydrolysis lignin on the mechanical and rheological properties of the resulting wood flour/high‐density polyethylene composites

Enzymatic hydrolysis lignin (EHL) from ethanol production was used as an additive to incorporate in the wood flour/high‐density polyethylene (HDPE) composite during the melt extrusion, and the incorporating effects on the mechanical and rheological properties of the resulting composites were investigated. The addition of EHL caused an improvement in both the tensile strength and impact strength, and a reduction in the complex viscosity of the composites as evidenced by the rotational rheometry, which suggests an increased flowability of the composite melt due to incorporation of EHL. The water absorption and swelling of the composites decreased with increasing EHL content during water immersion test. The scanning electron microscopy micrographs of EHL incorporated wood flour/high‐density polyethylene composites showed a homogeneous dispersion of wood flour and EHL in the HDPE matrix. POLYM. COMPOS., 37:379–384, 2016. © 2014 Society of Plastics Engineers     

Modified polypropylene wood flour composites. II. Fracture,deformation, and mechanical properties

The effect of grafting level of maleic anhydride (MA) in the maleated polypropylene (PPMA) on the fracture, deformation mechanisms, and mechanical properties of polypropylene (PP) wood flour composites was studied. Tensile strength, elongation at break, and impact strength are noticeably improved with addition of interfacial modifiers as maximum values of the examined mechanical properties were detected when concentration of MA in the compatibilizer was 1 wt %. To explore the microstructure and deformation mechanisms, scanning electron microscopy was employed. It was found that low concentrations of MA up to 1 wt % led to the creation of a thin and irregular polymer layer assisted formation of fibrillated plastic deformation zone around the wood particles, while the bulk PP matrix experienced voiding and brittle fracture. Higher concentrations of MA fetch to stronger interaction between PP and wood flour, the reason for brittle fracture and reduced ductility of the matrix. The impact fracture behavior of the composites during Instrumented impact tests is also discussed with respect to the interfacial bond strength. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1286–1292, 2004     

Mechanical properties and morphology of impact modified polypropylene–wood flour composites

The mechanical properties and morphology of polypropylene/wood flour (PP/WF) composites with different impact modifiers and maleated polypropylene (MAPP) as a compatibilizer have been studied. Two different ethylene/propylene/diene terpolymers (EPDM) and one maleated styrene–ethylene/butylene–styrene triblock copolymer (SEBS–MA) have been used as impact modifiers in the PP/WF systems. All three elastomers increased the impact strength of the PP/WF composites but the addition of maleated EPDM and SEBS gave the greatest improvements in impact strength. Addition of MAPP did not affect the impact properties of the composites but had a positive effect on the composite unnotched impact strength when used together with elastomers. Tensile tests showed that MAPP had a negative effect on the elongation at break and a positive effect on tensile strength. The impact modifiers were found to decrease the stiffness of the composites. Scanning electron microscopy showed that maleated EPDM and SEBS had a stronger affinity for the wood surfaces than did the unmodified EPDM. The maleated elastomers are, therefore, expected to form a flexible interphase around the wood particles giving the composites better impact strength. MAPP further enhanced adhesion between WF and impact-modified PP systems. EPDM and EPDM–MA rubber domains were homogeneously dispersed in the PP matrix, the diameter of domains being between 0.1–1 μm. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1503–1513, 1998     

Comparative study on the effect of manchurian ash and larch wood flour on mechanical property,morphology, and rheology of HDPE/wood flour composites

Effects of wood flour species and polyethylene grafted with maleic anhydride (MA‐PE) on mechanical properties and morphology and torque rheology of high density polyethylene (HDPE)/wood flour composites have been comparatively investigated. The results demonstrated that without compatbilizer, wood flour species exhibited little influence on mechanical properties. In the presence of MA‐PE, the mechanical properties were obviously increased. On the basis of the mechanical property data obtained from wood flour extracted by different methods, the extractant was an important factor affecting the mechanical properties. Manchurian ash and larch wood flours extracted by hot water presented almost the same mechanical properties, and larch wood flour was the most beneficial to enhance the mechanical properties. The scanning electron microscopy (SEM) and the atomic force microscopy (AFM) further confirmed that interfacial adhesion and dispersion of manchurian ash wood flour in composites were effectively improved by MA‐PE. The torque results demonstrated that the chemical reactions of maleic anhydride groups on MA‐PE with hydroxyl on cellulose in wood flour probably took place due to the increase of the equilibrium torque and the appearance of the torque peak, and larch wood flour was more beneficial to prepare the composites containing the higher wood flour content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphological,mechanical, tribological,and thermal expansion properties of organoclay reinforced polyethylene composites

The morphological, mechanical, thermal, and tribological properties of high‐density polyethylene (HDPE) composites reinforced with organo‐modified nanoclay (3 and 6 wt%) were studied. A commercial maleic anhydride‐based polymeric compatibilizer (PEgMA) was used to improve the adhesion between the polyethylene and clay. Transmission electron microscopy (TEM) characterization of composites revealed that nanoclay exists mainly in a multilayered structure in the HDPE matrix. Mechanical testing of composites showed that Young's modulus and tensile strength increased with nanoclay content. Coefficients of the linear thermal expansion (CLTE) of HDPE–PEgMA–clay composites were slightly lower in the flow direction than those of HDPE–PEgMA. The tribological properties were measured in dry conditions against a steel counterface. The friction coefficient of the matrix was decreased by the addition of clay. Electron microscopic results suggested that the wear mechanism for HDPE and HDPE composites was mainly adhesive. Clay agglomerates were observed on the worn surfaces of the composites, which may partly explain decreased friction. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Functionalization of high density polyethylene in melt state through ultrasonic initiation and its effect on mechanical properties of glass fiber reinforced composites

Summary Functionalization reaction of high density polyethylene (HDPE) with γ-methacryloxy-propyltrimethoxysilane (MAS) or with MAS and MAH performed in melt state through ultrasonic initiation by a laboratory-scale ultrasonic extruding reactor was studied in this paper. The effect of ultrasonic intensity on the percentage of grafting and melt flow rate of the functionalized products was investigated. The results show that by imposing ultrasonic vibration during melt-extruding process, the scission of HDPE chain bonds can be caused to form macroradicals, the functionalization reaction of HDPE with MAS or with MAS and MAH can be realized. The percentage of grafting and the melt flow rate of the functionalized products depend upon the ultrasonic intensity and reaction temperature. The fuctionalization reaction of HDPE with MAS can be promoted by adding a second grafting monomer MAH. The ultrasonic-induced products have a higher reactivity with the coupling agents coated on the surface of glass fibers, the mechanical properties of the composite improved by the ultrasonic induced product are higher than that of by peroxide initiated product and the mechanical properties of HDPE/GF composite modified by HDPE-g-MAH-MAS are higher than that of by HDPE-g-MAH. The SEM experimental results indicate that an oriented crystal layer exists between the interface of glass fiber and the HDPE matrix, the interfacial bonding strength is the determining factor of the formation of the oriented crystal layer.