Acrylic pressure‐sensitive adhesives with nanodiamonds and acid–base dependence of the pressure‐sensitive adhesive properties

A high performance and functional properties in pressure‐sensitive adhesives (PSAs) are attractive in fundamental and industrial fields. To control the performance of PSAs, nanofillers have been loaded into them. In this study, we focused on composites of acrylic PSAs and nanodiamonds (NDs). The loaded NDs reinforced the mechanical properties and increased the performance of the PSAs. NDs in a PSA formed a network structure. In this study, we revealed that the acidic–basic state was a key factor in the control of the dispersion of the NDs. When a PSA emulsions and ND aqueous dispersion was mixed under basic conditions, the composites demonstrated higher PSA properties (tack, holding, and peeling strength). We investigated the effect of the ND loading on the PSA properties from the viewpoints of the nanostructure and acid–base interactions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46349.     

Effect of different skin permeation enhancers on tack of a pressure sensitive adhesive

Solutions of an acrylic copolymer pressure sensitive adhesive with different concentrations of propylene glycol (PG) and oleic acid (OA) were cast on a PET film. A rolling ball tack test was carried out on the adhesive coated tapes with different thicknesses. The results were explained on the basis of the surface (energy and roughness) and viscoelastic properties of the copolymer, which were related to the glass‐transition temperature. The 60‐μm PG samples with an approximately equal glass‐transition temperature and surface energy did not have a significantly different tack value. The tack value of the 30‐μm tapes decreased with PG concentrations above 15% (w/w), which was related to an increase in the surface roughness with a more prominent effect at the lower thickness. OA, which improved both the surface and viscoelastic properties, increased the tack value up to 15% (w/w). However, the tack value decreased above 15% (w/w). This was explained on the basis of OA large crystals, which can decrease viscoelastic energy dissipations and form a mechanically weak surface layer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1287–1291, 2005     

Elastic properties of adhesive polymers. II. Polymer films and bond lines by means of nanoindentation

Seven different polymers used frequently as adhesives and/or matrix polymers in wood, wood composites, and natural fiber‐reinforced composites were studied by uniaxial tensile tests and nanoindentation. It was shown that the elastic modulus, the hardness, the creep factor, and the elastic‐, plastic‐, and viscoelastic work of indentation of the seven different polymers is essentially the same regardless whether the polymers were tested in the form of pure films or in situ, i.e., in an adhesive bond line with spruce wood. An excellent correlation was found between the elastic modulus measured by tensile tests and the elastic modulus measured by nanoindentation. In spite of the good correlation, the elastic modulus measured by nanoindentation is significantly higher than the elastic modulus measured by tensile tests. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1234–1239, 2006     

Effects of the degree of crosslinking and test rate on the tensile properties of a crosslinked polyacrylic pressure-sensitive adhesive and vulcanized rubber

The effects of the tensile test rate on the properties of a pressure-sensitive adhesive (PSA) and of vulcanized rubber were ascertained and compared, using a poly(n-butyl acrylate-acrylic acid) random copolymer with varying degrees of crosslinking as the PSA. The 100% modulus of the PSA was found to increase along with the crosslinking degree and with faster tensile test rates. In contrast, the 100% modulus of the vulcanized rubber did not exhibit any test rate dependence. To assess this effect, the molecular weights between chemical and physical crosslinking points were determined via equilibrium swelling, dynamic mechanical analysis, and tensile tests. The proportion of physical crosslinking points was found to be far larger in the crosslinked PSA. Because these entanglement points can readily disentangle in response to slow deformation, variations in the test rate only affected the PSA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47272.     

Thermal and mechanical properties of woodflour/tannin adhesive composites

Composite materials formulated with a natural polyphenolic matrix (commercial tannin adhesive made from quebracho tannin extract), pine woodflour as reinforcing material, and hexamethylenetetramine as hardener were prepared and tested. Scanning electron microscopy of fractured samples was used to analyze the efficiency of the wetting and adhesion of the filler to the surrounding matrix. Thermogravimetric analysis was used in the thermal characterization of the woodflour and the tannin extract. Flexural, compression, and dynamic‐mechanical tests were performed on composites to study the relationship of the filler content and particle size with the composite final properties. Moreover, the influence of the moisture content on the physical and mechanical properties of the different composites was analyzed. Results indicated that the mechanical properties were severely affected by the absorbed moisture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3074–3082, 2004     

Atomic force microscopy investigation of phase morphology correlated with adhesive properties for modified telechelic natural rubber based-pressure sensitive adhesive

Atomic force microscopy (AFM) is a powerful technique to determine phase morphology and surface mechanical properties of materials. In this research natural rubber was degraded and grafted by malelic anhydride before modification with 3-amino-1,2,4-triazole to obtain modified telechelic natural rubber or modified TNR. It was then blended with cumarone-indene resin at 10, 30, and 50 phr, acting as tackifier. Phase morphology and surface topography were investigated by intermitted AFM. The results showed that tackifier enriched domains were clearly observed in modified TNR matrix after added 30 and 50 phr and the domain sizes were approximately to be the order of micrometer (5–10 µm) which it increased with increasing tackifier content. The intermolecular hydrogen bonding interaction between tackifier and modified TNR was observed by attenuated total reflectance Fourier transform infrared spectroscopy. The adhesive properties (loop tack, peel, and shear strength) were governed by the size of tackifier enriched domains, surface mean roughness and compatibility or interaction between modified TNR rubber and cumarone-indene tackifier resin.     

Effects of aging on the adhesive properties of poly(lactic acid) by atmospheric air plasma treatment

The aim of this study was to analyze the durability of a plasma treatment on the surface of poly(lactic acid) (PLA). We used atmospheric‐plasma treatment with air to improve the wettability of PLA by evaluating the aging effect under controlled conditions of relative humidity (RH) and temperature (25% RH and 25°C). We studied the durability of the atmospheric‐plasma treatment by measuring the contact angle, calculating the surface energy, and observing changes in the resistance of the PLA–PLA adhesive bonds. These techniques allowed us to evaluate the hydrophobic recovery phenomenon that the PLA surface suffered as a consequence of the aging process. The results provide the maximum storage time of PLA treated with atmospheric plasma at which the sample retained its good adhesion properties; this time was lower than 3 days under normal atmospheric conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43040.     

Effects of radio frequency and heat on wood bonding with a poly(vinyl acetate) dispersion adhesive

Water‐based poly(vinyl acetate) dispersions are widely used as wood adhesives with dielectric heating systems. However, little is known about the effects of radio frequency (RF) exposure or heat on the adhesive characteristics and on the performances of bonded joints. In this study, the properties of bonded joints exposed to RF were compared with hot pressing and with standard drying, and the observed behavior was explained. Joint characteristics were evaluated by means of both conventional (e.g., shear strength in both dry and wet conditions, etc.) and unconventional (e.g., bondline temperature, moisture content at interface, etc.) procedures, and also selected properties of polymeric film were measured (e.g., water absorption, analysis of the fraction dissolved in water, glass transition temperature [T_g], etc.) to explicate the observed differences. Results evidenced that the effect of both RF and heating was to appreciably speed up the drying process. However, when high values of energetic impulse (owing to both hot pressing and RF) were given to the assemblies, permanent changes were induced into the polymeric glueline. This occurrence was a time‐driven process and reflected mainly on the mechanical performance in wet conditions, which improved appreciably in comparison to the standard reference series. The reason of such behavior was connected to the poly(vinyl alcohol) phase present inside the polymer, and a role was also assigned to AlCl₃, used as complexing agent of the polymeric protective colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication of a model cellulose surface from straw with an aqueous sodium hydroxide/thiourea solution

Model cellulose surfaces were prepared with both microcrystalline cellulose and cellulose isolated from wheat straw with different molecular weights. A sodium hydroxide/thiourea aqueous solution, instead of any organic solvents, worked as the solvent for dissolving cellulose, and model cellulose films were prepared by a two‐step method: first, the cellulose solution was deposited onto the surface of the substrate with the spin‐coating method, and second, the as‐prepared film was washed with deionized water to remove the impurities and was formed with a flattened surface. Atomic force microscopy was used to measure the morphology, surface roughness, and thickness of the cellulose thin films. X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray spectrometry were used to characterize the surface chemical information of the films. The results revealed that model cellulose surfaces could form from both kinds of cellulose. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dynamic mechanical properties of very thin adhesive joints

The effective mechanical properties of a polyurethane adhesive (oligoetherdiol, ‐triol, MDI) in gold joints (bond line thickness, d_P = 35–550 µm) are studied in the linear deformation range by dynamic mechanical analysis in shear mode. These properties depend on d_P: thin ones possess a higher dynamic glass transition temperature and show a narrower glass transition than the thick ones. The storage modulus rises with decreasing d_P for the rubbery plateau. The results attest mechanical interphases in the polyurethane with increased crosslink density and reduced cooperative mobility than in bulk. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42058.     

Formulation of a novel soybean protein‐based wood adhesive with desired water resistance and technological applicability

A novel soybean protein‐based wood adhesive with good bond strength, excellent water resistance, and the desired technological applicability was formulated by combining thermal alkali degradation, thermal acid treatment, and crosslinking. The characterization results indicated that thermal alkali degradation could effectively improve the technological applicability, thermal acid treatment could positively improve the water resistance, and appropriate crosslinking modification could significantly enhance the bond strength and water resistance of the soybean protein adhesive. The crosslinker species, crosslinker level, and ratio of thermal alkali‐degraded soybean protein (DSP) to thermal acid‐treated soybean protein (TSP) had important effects on the primary properties of the soybean protein adhesives. The modified polyamide aqueous solution was the most preferable crosslinker because of its low viscosity, good crosslinking efficiency, and excellent miscibility with soybean protein solution. The optimal soybean protein adhesive that was formulated from 20 wt % modified polyamide as the crosslinker and a DSP/TSP ratio of 1:3 had a solid content of more than 35 wt %, suitable viscosity (～2180 mPa s), a long work life (>16 h), good dry bond strength (2.94 MPa), and 28 h of boiling–dry–boiling cycled wet strength (1.29 MPa) that met the required values for structural use according to JIS K6806‐2003 commercial standards. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43586.     

Blending poly(2-ethyl-2-oxazoline) with hydrophobic polymers as a hybrid adhesive with enhanced water-resistant properties

The use of poly(2-ethyl-2-oxazoline) (PEOX) in a wet environment is limited because of its high hydrophilicity. In this study, PEOX based blends were prepared via blending PEOX with hydrophobic polymers, such as poly(styrene-co-acrylonitrile) (SAN), poly(4-vinylphenol) (PVPh), and poly(vinylidene fluoride) (PVDF), in order to improve the water-resistance of PEOX. The blends' water resistance properties are evaluated by the contact angle, solubility, moisture absorption, and mechanical strength in a wet environment. The results show that the water resistance and the adhesion strength of PEOX in a wet environment are dramatically enhanced by polymer blending. The blend with 30 wt% PVPh demonstrates excellent performances in transparency and water-resistant abilities. It is found that the stable hydrogen bonding within the blend plays an important role in hydrophobic modification. The PVPh/PEOX blend can be applied as a new type of transparent coating or adhesive with enhanced water-resistant properties in a wet environment.     

Studying the effects of chain extenders chemical structures on the adhesion and mechanical properties of a polyurethane adhesive

Chain extenders including diethanol amine (DEA) and 2-cyano-N,N-bis-hydroxyethyl acetamide (CNBA) were utilized to enhance the adhesion and mechanical properties of a polyurethane (PU) adhesive. The adhesion and mechanical properties of the adhesives were studied by peel test, tensile test and dynamic thermal analysis (DMTA) respectively. Results revealed that both chain extenders (DEA and CNBA) increased peel test modulus. The cross-linking density and toughness of the adhesive were significantly increased using chain extenders. Results showed that chain extender without side chain (DEA) could improve the adhesion and mechanical properties of the adhesive greater than chain extender with aliphatic side group (CNBA).     

Effect of adhesive thickness on the stringiness of crosslinked polyacrylic pressure‐sensitive adhesives

The effect of adhesive thickness on stringiness behavior during 90° peel testing was investigated for crosslinked poly(n‐butyl acrylate‐acrylic acid) (A) and poly(2‐ethylhexyl acrylate‐acrylic acid) (B) with a constant crosslinker content. The adhesive thickness was varied over the range from 15 to 60 μm. All adhesive thicknesses exhibited sawtooth‐type peeling with a front frame for B, but only the 30‐μm thickness generated a front frame‐type for A. The peel rate decreased from 15 to 45 μm and plateaued above 45 μm under a constant load test. These results indicate that the adhesion strength increases with adhesive thickness, but reaches a constant value at high thicknesses. The stringiness was also analysed for B and the sawtooth interval observed to increase with increasing thickness. This means the sawtooth number decreased. As a result, the concentrated stress per sawtooth induces easier peeling and so this factor tend to increase the peel rate. Conversely, the stringiness width increased with increasing thickness. The stress load over the stringiness region decreased with an increase in thickness, meaning that a decrease in the concentrated stress decreases the peel rate. The actual peel rate is influenced by the contributions of these two factors. The strain rates during constant peel rate tests decreased slightly with increasing thickness, due to a reduction in the apparent modulus. The molecular mobilities near the adherend and the backing surfaces were evidently restrained by these surfaces, and the relative rates of motion of such restrained molecules decrease with increased thickness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42210.     

Viscoelastic and adhesive properties of single‐component thermo‐resistant acrylic pressure sensitive adhesives

Poly(butyl acrylate‐vinyl acetate‐acrylic acid) based acrylic pressure sensitive adhesives (PSAs) were synthesized by solution polymerization for the fabrication of high performance pressure sensitive adhesive tapes. The synthesized PSAs have high shear strength and can be peeled off substrate without residues on the substrate at temperature up to 150°C. The PSAs synthesized in the present work are single‐component crosslinked and they can be used directly once synthesized, which is convenient for real applications compared to commercial multi‐component adhesives. The results demonstrated that the viscosity of the PSAs remained stable during prolonged storage. The effects of the preparation conditions such as initiator concentration, cross‐linker amount, organosiloxane monomer amount and tackifier resin on the polymer properties, such as glass transition temperature (T_g), molecular weight (M_w), surface energy and shear modulus, were studied, and the dependence of the adhesive properties on the polymer properties were also investigated. Crosslinking reactions showed a great improvement in the shear strength at high temperature. The addition of tackifier resin made peel strength increase compared to original PSAs because of the improvement of the adhesion strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40086.     

Shear properties of isotropic conductive adhesive joints under different loading rates

Epoxy-based conductive adhesives have been widely used in the electronic field given the lead-free development of electronic packaging. The conductive adhesive joints must be subjected to shear loads during the service of electronic products considering the mismatch in mechanical properties between packaged chip and substrate. In this study, INSTRON 5544 universal material testing machine was used for tensile–shear tests of isotropic conductive adhesive joint specimens, which were prepared using pure copper plate adherend in the form of single-lap joints. Four loading rates, that is, 0.05, 0.5, 5, and 10 mm/min, were adopted. The relationship between shear load and displacement of two overlapping copper plates is deduced from a mechanical perspective. A mechanical model of the conductive adhesive shear specimen was developed by introducing dimensionless parameters, which are obtained from interfacial fracture energy and shear strength, to interpret the effect of loading rate on the shear properties of the conductive adhesive specimen considering the loading rate. Results show that this model can effectively reflect the relationship between shear load and displacement in the range of 0.05–10 mm/min.     

The viscoelastic properties of natural rubber pressure‐sensitive adhesive using acrylic resin as a tackifier

Acrylic tackifier resins were prepared by free radical polymerization. A natural rubber base was prepared from Standard Malaysian Rubber through mechanical milling. The acrylic tackifier was blended with the rubber base in various ratios. The blends were coated onto strips of paper and tested for shear and peel strengths. Circular samples of the blends were cast onto release paper and their viscoelastic properties studied using DMTA. On plotting storage modulus G′ against frequency, differences between the low frequencies and high frequencies explain the change in pressure‐sensitive adhesive (psa) properties as the percentage of tackifier resin was varied. Blends with good psa have higher loss tangent at higher frequencies. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2118–2123, 2003     

Polymeric nanocapsules containing methylcyclohexane for improving thermally induced debonding of thin adhesive films

The thin adhesive film with tunable interfacial adhesion can be applied in a broad range of display applications, from optically clear films to flexible devices. We have fabricated adhesive films including evaporable polymeric nanocapsules which can form thermally induced bubble gaps at the interface. These nanocapsules consisted of a poly(methyl methacrylate) core and a polyethyleneimine shell, and were impregnated with methylcyclohexane as a vaporization material. The evaporated core materials facilitated the desorption of thin adhesive film through bubble formation on the adhesive interface after thermal treatment, resulting in improved detachment of the adhesive layer. The optimization of the bubble gaps was performed to adjust the adhesive strength by varying the duration and temperature of thermal treatment, as well as the quenching temperature. The evaporable adhesive film with nanocapsule concentration of 1.0 wt % resulted in high transmittance of 94.9%, with the best adhesive strength reduction of 57.6% obtained after thermal treatment. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46586.     

Elastic properties of adhesive polymers. I. Polymer films by means of electronic speckle pattern interferometry

The elastic modulus and Poisson's ratio of seven different polymers frequently used as wood adhesives and/or matrix polymers in wood‐ and natural‐fibre‐reinforced composites, respectively, were determined by means of tensile tests. Specimen deformation during testing was measured by means of a mechanical extensometer and an electronic speckle pattern interferometry system, respectively. The results from both methods show an excellent correlation for the elastic modulus. The elastic moduli of the studied polymers cover a wide range from 0.47 GPa for polyurethane to 6.3 GPa for melamine–urea–formaldehyde, whereas Poisson's ratios show less variability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3936–3939, 2007     

Improving the properties of water-borne pressure sensitive adhesives by using non-migratory surfactants

The adhesive performance of high solids content water-borne acrylic pressure sensitive adhesives synthesized using polymerizable surfactants (Latemul^®PD-104 and Sipomer^®Pam-200) or a polymerizable stabilizer (Sipomer^®Cops-1) has been studied. The use of a high pH during the polymerization process has a deleterious effect on the final adhesive properties because gel polymer is not formed. Interestingly, at low pH it is found that the surfactant concentration used during the polymerization process has also an effect on the polymer microstructure; the higher the surfactant concentration, the higher the final gel content of the latex. When polymerizable surfactants or a stabilizer are used the peel strength of the final films is considerably improved due to the surfactant incorporation into the polymer backbone and hence reduced surfactant migration to the air-film interface. Work of adhesion and shear adhesion failure temperature (SAFT) are not noticeably affected by surfactant migration but their performance is affected by the surfactant employed.