Interaction between wood and polyvinyl acetate glue studied with dynamic mechanical analysis and scanning electron microscopy

The long‐term properties of bonds are those that are of special interest. To achieve good bonds, the wood polymers and the adhering polymers must be compatible. This paper describes studies of the interaction of wood (Pinus sylvestris) with commercial polyvinyl acetate (PVAc) glue, polymethylmethacrylate (PMMA), and a more hydrophilic acrylate. Interaction was studied with a dynamic mechanical thermal analyzer (DMTA) operating in tensile mode in the tangential direction of wood. DMTA results were correlated with scanning electron microscopy (SEM) fractography studies of adhesion between polymers and wood on a cell wall level. The hypothesis put forward is that a good adhesion on the cell wall level results in a decrease in the glass transition temperature (T_g) measured with DMTA. A decrease in T_g for the hydrophilic acrylate was shown when it was impregnated in wood. The decrease of T_g was correlated with good adhesion to wood on the cell wall level. For PVAc and PMMA no decrease in T_g was measured when glued or impregnated in wood. SEM study also showed that the adhesion on a cell wall level was poor. The results show that DMTA can be a useful technique to study adhesion between wood and glue on a molecular level. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3009–3015, 2004     

Challenges in forming successful mixed matrix membranes with rigid polymeric materials

Mixed matrix materials comprised of molecular sieve domains embedded in processable polymer matrices have the potential to provide membranes with higher permselectivity and equivalent productivity compared to existing membrane materials. It has been shown that successful mixed matrix materials can be formed using relatively low glass transition (T_g) polymers that have a favorable interaction with the sieves. This article extends this earlier work to include the use of more practical rigid matrix polymers with high T_gs that can ultimately be used in forming high‐performance mixed matrix layers for composite membranes. Initial attempts to form mixed matrix materials based on high T_g polymers with a type 4A zeolite resulted in poor adhesion between the polymer and sieve. Correcting this problem was pursued in this study by forming the composite material close to the T_g of the polymer by addition of a plasticizer to match the matrix T_g with the solvent volatility. Forming the films at elevated temperatures presented substantial challenges, and this work discusses overcoming these challenges in detail. With some modifications in the film casting procedure, successful materials were achieved. Promising oxygen/nitrogen transport results are presented for these zeolite 4A–Matrimid®/plasticizer membranes, and this data compares favorably with predictions of the well‐known Maxwell model for composite systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 881–890, 2002     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Ionic interphase of glass fiber/polyamide 6,6 composites

Interfacial polymerization to polyamide 6, 6 followed by introduction of ionic groups was performed on the surface of short glass fibers. The ionic interphase-modified fibers were used with poly(ethylene-co-methacrylic acid) (DuPont Surlyn) to prepare composites with specific fiber-matrix interactions. Fiber treatment increased composite tensile and bending properties. An increase in the average fiber length was observed, which was attributed to a decrease in the fiber attrition during mixing. The effect of increasing temperature on the composite mechanical properties was studied. Different behavior was observed before and after the glass transition temperature, T_g, of the matrix. The dynamic mechanical measurements showed an increase in the T_g of the matrix after the treatments, which is attributed to a decrease in chain mobility at the interface resulting from increased interactions of the treated fiber surface with the polymer. Scanning electron microscopy of fractured composites after tensile tests revealed a smooth fiber surface with no polymer at the surface for the untreated composites. Adhered polymer was clearly observed on the surface of treated fibers, indicating better fiber wetting by the matrix. This improved adhesion was attributed to the grafted nylon molecules at the glass fiber surface.     

Thermal and dynamic mechanical behavior of poly(vinyl chloride)/wood flour composites

Thermal and dynamic mechanical behaviors of wood plastic composites made of poly vinyl chloride (PVC) and surface treated, untreated wood flour were characterized by using differential scanning calorimetry and dynamic mechanical analysis. Glass transition temperature (T_g) of PVC was slightly increased by the addition of wood flour and by wood flour surface treatments. Heat capacity differences (ΔC_p) of composites before and after glass transition were markedly reduced. PVC/wood composites exhibited smaller tan δ peaks than PVC alone, suggesting that less energy was dissipated for coordinated movements and disentanglements of PVC polymer chains in the composites. The rubbery plateaus of storage modulus (E′) curves almost disappeared for PVC/wood composites in contrast to a well defined plateau range for pure PVC. It is proposed that wood flour particles act as “physical crosslinking points” or “pinning centers” inside the PVC matrix, resulting in the absence of the rubbery plateau and high E′ above T_g. The mobility of PVC chain segments were further retarded by the presence of surface modified wood flour. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dynamic mechanical study of epoxy,epoxy/glass,and glass/epoxy/wood hybrid composites aged in various media

It was proposed and subsequently established that wrapping of red oak wood crossties with epoxy impregnated glass fiber composites will impart longer service life and better stiffness and strength characteristics to these hybrid ties than conventional ones and will help them better withstand environmental extremes. The objective was to understand the degrading effects of aqueous (distilled water), saline (NaCl), acidic (HCl), and alkaline (NaOH) solutions, as well as accelerated aging and freeze/thaw cycling environments on the dynamic and static mechanical properties of these hybrid materials (i.e., wood, wrapped with fiber reinforced resin) and their components. Also micrographs of composite samples, obtained through scanning electron microscopy (SEM), were studied to determine the failure mechanism of composite specimens aged in different environments. Results showed that immersion in aging media lowered the glass transition temperature (T_g) and enhanced apparent phase separation in the samples because of polymer plasticization. In water immersion, the T_g and the stiffness increased with time owing to continued resin curing. At ambient temperature, sustained load had little effect on the mechanical behavior of the aged samples. The extent of degradation was the least for samples aged in salt solution. Soaking in room‐temperature acid solution was most damaging to pure red oak wood samples. Six‐cycle aging did not damage the neat resin or the hybrid samples, whereas it damaged pure wood specimens. Therefore, the composite wrapping around the wood core of the hybrid sample protected it sufficiently, thereby preventing damage to the hybrid specimen during the aging process. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Dynamic mechanical properties of extruded nylon–wood composites

Dynamic mechanical properties determine the potential end use of a newly developed extruded nylon–wood composite in under‐the‐hood automobile applications. In this article, the dynamic mechanical properties of extruded nylon–wood composites were characterized using a dynamic mechanical thermal analyzer (DMTA) to determine storage modulus, glass transition temperature (T_g), physical aging effects, long‐term performance prediction, and comparisons to similar products. The storage modulus of the nylon–wood composite was found to be more temperature stable than pure nylon 66. The T_g range of the nylon–wood composite was found to be between 23 and 56°C, based on the decrease in storage modulus. A master curve was constructed based on the creep curves at various temperatures from 30 to 80°C. The results show that the relationship between shift factors and temperature follows Arrhenius behavior. Nylon–wood composites have good temperature‐dependent properties. Wood fillers reduced the physical aging effects on nylon in the wood composites. The comparison of the nylon–wood composite with other similar products shows that nylon–wood composites are a promising low cost material for industrial applications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Mechanical properties of films prepared from model high‐glass‐transition‐temperature/low‐glass‐transition‐temperature latex blends

The mechanical properties of films prepared from model high‐glass‐transition‐temperature (T_g)/low‐T_g latex blends were investigated with tensile testing and dynamic mechanical analysis. Polystyrene (PS; carboxylated and noncarboxylated) and poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) [P(BMA/BA); noncarboxylated] were used as the model high‐T_g and low‐T_g latexes, respectively. Carboxyl groups were incorporated into the PS latex particles to alter their surface properties. It was found that the presence of carboxyl groups on the high‐T_g latex particles enhanced the Young's moduli and the yield strength of the PS/P(BMA/BA) latex blend films but did not influence ultimate properties, such as the stress at break and maximum elongation. These phenomena could be explained by the maximum packing density of the PS latex particles, the particle–particle interfacial adhesion, and the formation of a “glassy” interphase. The dynamic mechanical properties of the latex blend films were also investigated in terms of the carboxyl group coverage on the PS latex particles; these results confirmed that the carboxyl groups significantly influenced the modulus through the mechanism of a glassy interphase formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2788–2801, 2002     

Rigid thermosetting liquid molding resins from renewable resources. II. Copolymers of soybean oil monoglyceride maleates with neopentyl glycol and bisphenol A maleates

Soybean oil monoglycerides (SOMG), obtained by the glycerolysis of soybean oil, were reacted with maleic anhydride to produce SOMG maleate half esters. The copolymers of the SOMG maleates with styrene produced rigid thermosetting polymers. The dynamic mechanical analysis (DMA) of this polymer showed a glass‐transition temperature (T_g) around 133°C and a storage modulus (E′) value around 0.94 GPa at 35°C. The tensile tests performed on this polymer showed a tensile strength of 29.36 MPa and a tensile modulus of 0.84 GPa. Mixtures of SOMG with neopentyl glycol (NPG) and SOMG with bisphenol A (BPA) were also maleinized under the same reaction conditions and the resulting maleates were then copolymerized with styrene. The resulting polymers were analyzed for their mechanical properties. The T_g of the copolymers of the SOMG/NPG maleates with styrene was 145°C and the E′ value at 35°C was 2 GPa. The tensile strength of this polymer as calculated from the stress–strain data was 15.65 MPa and the tensile modulus was 1.49 GPa. The T_g of the copolymers of SOMG/BPA maleates, on the other hand, was found to be around 131°C and the E′ value was 1.34 GPa at 35°C. The changes observed in the mechanical properties of the resulting polymers with the introduction of NPG maleates and BPA maleates to the SOMG maleates can be explained by the structural changes on the polymer backbone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 972–980, 2002     

Ideality of pressure‐sensitive paint. I. Platinum tetra(pentafluorophenyl)porphine in fluoroacrylic polymer

The pressure sensitive paint (PSP) properties of a fluoroacrylic polymer, FIB, with the luminophor platinum tetra(pentafluorophenyl)porphine (PtTFPP) are presented. This paint forms a hard coating that displays Stern–Volmer plots with a high dynamic range (∼ 0.9) [defined as (I_vac − I_atm)/I_vac], good photostability, a response time of less than 1 s and a relatively low temperature dependence (∼ 0.6% per degree). The temperature dependence is low because FIB has a unusually low activation energy for the diffusion of oxygen. Pressure and temperature affect intensity independently making this PSP “ideal.” The basecoat affects the functionality of the PSP it underlies, and the optimal basecoat used to date also includes the FIB polymer. The synthesis of the FIB polymer is a copolymerization that occurs in one step with a peroxide initiator. Annealing the painted model above T_g = 70°C procures adhesion and ideality. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2795–2804, 2000     

Use of an epoxidized oil‐based resin as matrix in vegetable fibers‐reinforced composites

Hemp fibers were used as natural reinforcement in composites of thermosetting vegetal oil based resin. Boards with fibers content from 0 to 65 vol % were produced by hot pressing. The mechanical properties were investigated with flexural testing. The effect of effect has been observed on both modulus and strength, indicating a good fiber–matrix interfacial adhesion, which was confirmed by means of scanning electron microscopy observations. Dynamic mechanical analysis also showed an important reinforcement effect in the polymer rubbery region, where at 180°C the storage modulus increased from 17 MPa for the neat resin to 850 MPa for 65 vol % fiber content composites. It also revealed an glass transition temperature decrease when fiber amount in the composite increased. Additional experiments based on differential scanning calorimetry show a weakly accelerated cure when fibers content increases, which usually lead to a lower T_g. But, this phenomenon alone cannot explain the observed T_g change. Contact angle on hemp evolution with time for the resin components show that anhydride is totally absorbed after a few seconds, whereas contact angle of epoxydized oil decreases slowly. This indicates probably a preferential anhydride absorption that leads to a lower amount of anhydride in the matrix and as a consequence to a reduced T_g. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4037–4043, 2006     

Influence of polymer type on adhesion performance of a blended cement mortar

The purpose of this study was to examine the influence of various polymeric materials on the adhesion characteristics of a rapid setting, minimum defect mortar based upon a blend of calcium sulfoaluminate (CSA) cement and ordinary Portland cement (OPC). Four different polymer powders were added to the base mortar at a polymer/cement ratio (p/c) of 0.15. The water/cement (w/c) ratio remained constant for all mortars at 0.42. The polymeric materials consisted of an acrylic polymer powder with T_g=−10 °C, a styrene butadiene rubber (SBR) polymer powder with T_g=15 °C and two vinyl acetate/ethylene (VAE) polymer powders, one with T_g=−7 °C and the other with T_g=20 °C. Mortars were tested for direct tensile strength following ASTM C307 and pull-off strength following a variant of ASTM C1583 after curing for either 24 h or 13 days at ambient laboratory temperature of 23 °C. Mortars were cast over concrete, wood, metal and glass substrates. Pull-off tests over concrete substrate resulted in substrate failure for all polymer modified mortars. Pull-off tests cast over wood, glass and metal substrate materials highlighted the SBR polymer for demonstrating the poorest adhesion performance. Statistical analysis was performed with Minitab software.     

Analysis of the dielectric spectra of composite sealing coatings in a wide frequency range

Polymer coatings on the basis of the biphenol-Novolac potting epoxy compound with a 65% content of spherical particles of fused quartz as a filler were studied by the method of dielectric spectroscopy in a wide frequency range. Dielectric measurements were performed in frequency and temperature ranges of (10⁻² to 5 × 10⁹) Hz and 20 to 200°C, respectively, on film samples of composite coatings formed on different substrates. It was shown that the application of dielectric spectroscopy allows one to study the effect of the degree of the adhesion interaction with the substrate on the processes of structuring in the epoxy polymer matrix and to investigate the degradation processes in the coatings under the effect of high temperature and relative humidity. It was also shown that the values of the glass transition temperature (T _g ) of the composite determined by applying the method of low-frequency dielectric spectroscopy agree well with the T _g values obtained by applying the method of dynamic mechanical analysis (DMA).     

Thermal and mechanical properties of wood flour–polystyrene blends from postconsumer plastic waste

Polystyrene (PS) from packing materials and plastic cups was reinforced with 30 and 50% wood flour through a blending process with and without a commercial compatibilizing agent. The processability of the pure recycled polystyrene (rPS) and wood–rPS composites was studied in terms of the torque of the mixing process; this was then compared with that of a commercial virgin multipurpose PS. The physical and mechanical properties were compared with those of the virgin PS reinforced with 30 and 50% wood flour. The results show that the mechanical properties of the pure and reinforced rPS did not decrease with respect to the virgin PS, and in terms of the impact strength, the rPS was superior to the virgin plastic. The mechanical properties were not affected by the commercial compatibilizing agent, but the torque of the blends was significantly lower with the compatibilizer. Differential scanning calorimetry (DSC) and dynamic mechanical analysis were used to study the glass‐transition temperature (T_g) of both the pure virgin PS and pure rPS and the wood flour–PS composites. The T_g values of the rPS and wood–rPS composites were higher than those of the virgin PS and wood–virgin PS composites. The use of rPS increased the stiffness and flexural modulus of the composites. Thermogravimetric analysis revealed that the thermal stability of rPS and its composites was slightly greater than that of the virgin PS and its composites. These results suggest that postconsumer PS can be used to obtain composite materials with good mechanical and thermal properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Properties of polycarbonate/acrylonitrile-butadiene-styrene blends

To help make a good polymer blend by melt blending, the properties of polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) systems with various compositions have been investigated. As ABS is blended into PC to form a binary system, Brabender torque is reduced, a phenomenon that results in Improved processability of PC. With increasing ABS content, the mechanical properties of the blends such as tensile strength, modulus, hardness, and shrinkage decrease. However, with the variation of composition, Izod impact strength shows a maximum, while elongation at break exhibits a minimum. These phenomena are discussed with dynamic viscoelasticities and scanning electron microscopic morphological results. The value of ΔT_g(T_gβPC ? T_gβABS) is at its smallest when the ratio of PC to ABS is 90:10, However, the value rises with an increase in ABS because the butadiene content of the ABS hinders compatibility in the binary system. At the 90:10 composition, the damping height is optimal. In addition, the dispersed phase of the ABS is most ideal, absorbing the impact force and showing high impact strength. Composition ratios other than 90:10 present high damping as well as undesirable phase separation because of poor adhesion between two phases. As a result, the mechanical properties are reduced.     

Effects of aging and moisture on the dynamic viscoelastic properties of oriental lacquer (urushi) film

The effects of aging and moisture on the dynamic viscoelastic properties of three oriental lacquer films were investigated. With aging over 1000 days at room temperature, the glass‐transition temperature of the lacquer films (T_α) shifted to higher temperatures, the maximum loss tangent (tanδ_α) decreased, and the storage modulus at 20°C (E) increased. These changes were analogous irrespective of lacquers. With increasing moisture content, E decreased and tanδ increased at room temperature. Although the equilibrium moisture content of the virgin lacquer (sap) film was higher than that of the clear lacquer film, its E and tanδ were more stable with an increase of moisture content. It was speculated that the polysaccharides aggregated in the sap film did not effectively contribute to the mechanical properties of the film, while their hygroscopicity resulted in higher moisture content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2288–2294, 2002     

Comparison of viscoelastic properties of polydimethylsiloxane/poly(2‐hydroxyethyl methacrylate) IPNs with their physical blends

Interpenetrating polymer networks (IPNs) of polydimethylsiloxane (PDMS) and poly(2‐hydroxyethyl methacrylate) (PHEMA) were prepared by sequential method. The dynamic mechanical parameters of obtained IPNs and their variations with the structural composition were evaluated. The results for the IPNs were compared with corresponding physically blended systems. The tensile properties and damping factor (tan δ) were assessed by stress–strain measurement and dynamic mechanical thermal analysis (DMTA), respectively. The glass–rubber transition temperature (T_g) was assessed by DMTA and differential scanning calorimetry (DSC). The results showed higher tensile strength and elongation at break for IPNs than those for physical blends. The shifts of T_g for that two components that make up the IPNs were greater than those for corresponding blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3480–3485, 2002     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

Limiting surface tension by gas chromatography

The change in retention mechanism at the glass transition temperature (T_g) of a polymer stationary phase from surface adsorption below T_g to bulk sorption above T_g allows for a separate determination of the magnitude of the solute interaction with both the bulk and the surface of the polymer. As a result, the limiting surface tension of the polymer-probe solution can be obtained from the corresponding partition coefficients. Examples of such determinations are given for several polymer-solute systems.     

Electrical and mechanical characteristics of composites consisting of fractionated poly(3‐hexylthiophene) and conducting particles

The dynamic viscoelasticity of fractionated poly(3‐ hexylthiophene)titanium carbide (P3HT/TiC) composites was examined with regard to their electrical characteristics. The elastic modulus (E′) at 0°C [i.e., near the glass‐transition temperature (T_g) of P3HT] increased with increasing TiC content of the composite. In particular, composites whose TiC content exceeded the threshold concentration showed a high E′. This was caused by the high E′ of TiC and the strong interaction between TiC and P3HT. When the sample was heated above the T_g, E′ decreased rapidly and an increase in the loss tangent appeared near the T_g of P3HT. Mechanical loss was caused by friction between TiC and P3HT. The change in mechanical characteristics affected the electrical conductivity. When the TiC content of the composite approximated to the threshold concentration, a significant change in mechanical characteristics took place, so that a large positive temperature coefficient (PTC) effect was observed near the T_g. To explain the PTC phenomenon, we propose a model of conductive pathway for P3HT/TiC. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1429– 1433, 2002