Effects of polymer-filler adhesion on the properties of polychloroprene elastomers filled with surface-treated fillers

A new analytical method has been employed to determine values for the surface-energy properties, such as the solid/vapor surface energy and the equilibrium work of adhesion, of several polychloroprene compositions filled with organosilane-treated wollastonite fillers. The equilibrium work of adhesion, which represents the amount of energy stored in the interface formed between polymer and filler, has been used as a key material parameter to correlate changes in the mechanical and rheological properties of wollastonite-filled polychloroprene compositions. Experimental results show that some properties such as tear strength, tensile modulus, shear viscosity, and compression set, which depend on polymer-filler adhesion to varying degrees, increase as the equilibrium work of adhesion increases. On the other hand, properties such as tensile strength and ultimate elongation, which largely depend on the degree of mixing of filler particles and such defect structures as microvoids, decrease with the increase of the equilibrium work of adhesion. A power-law relationship between the tensile modulus and the equilibrium work of adhesion has also been established. This relationship can be used for selecting organosilane-treated fillers in order to achieve optimum properties.     

Effects of hydrocarbon tackifiers on the adhesive properties of contact adhesives based on polychloroprene - III. The effect of the molecular weight of the tackifier

Aromatic hydrocarbon resins with different molecular weights (M_w = 1300-50400 daltons) were added to a solvent-based polychloroprene adhesive. The hydrocarbon resins were characterized using infra-red (IR) and differential scanning calorimetry (DSC) measurements. The properties and compatibility of the polychloroprene/resin blends were studied using mechanical tests, DSC measurements, scanning electron microscopy (SEM), and stress-controlled rheology. Tack measurements were also carried out and the adhesion strength was obtained from T-peel tests on roughened styrene-butadiene rubber/polychloroprene adhesive joints. The addition of low-molecular-weight tackifiers produced a compatible polychloroprene/tackifier system (only one T_g was found in DSC measurements), while the addition of a high-molecular-weight (and broad molecular weight distribution) tackifier produced a partially incompatible system (two Tg's were found in DSC measurements). The compatibility of polychloroprene/tackifier blends was also assessed with stress-controlled rheology and SEM. An increase in the T-peel strength and tack were produced when the molecular weight of the tackifier increased, although the addition of a hydrocarbon resin with a M_w higher than about 50 000 reduced the tack. A broad molecular weight distribution in the tackifier favoured incompatibility with the polychloroprene, resulting in a reduction in the tack and rheological properties.     

Behavior of adhesion forces of the aqueous-based polychloroprene adhesive magnetically conditioned

This research is an innovation proposal for magnetic conditioning of the aqueous-based polychloroprene contact adhesive with the purpose of increasing the adherence capacity between the adhesive and the substrate. Today, the aqueous-based polychloroprene contact adhesive presents an adhesion capacity variation between 1.15 and up to 2.75 kgf/cm². On the other hand, the solvent-based polychloroprene adhesives support average tensions of shearing of 3.8 kgf/cm². To promote an increase in adhesion to the aqueous-based polychloroprene contact adhesive, we formulated one adhesive using a nano-additive, carbon dioxide as catalyst, and a magnetic conditioning process before the phase of application on the substrates. The results obtained show an average increase of 292% in the shearing tension of the adhesive magnetically conditioned when compared with an adhesive of same formulation without the magnetic conditioning and when compared to the commercial aqueous-based polichloroprene adhesive, the increase reaches 122%.     

Improved adhesion of EVAs with different vinyl acetate contents treated with sulphuric acid

Four ethylene vinyl acetate copolymers (EVAs) containing 9, 12, 18 and 20 wt% vinyl acetate (VA) were treated with concentrated sulphuric acid to improve their adhesion to polychloroprene (PCP) adhesive. The tensile strength and Young's modulus of EVAs decreased as the VA content increased, due to the reduction in crystallinity of the polyethylene blocks in the copolymer. The modifications produced in the EVAs by treatment with sulphuric acid were followed using contact angle measurements (water, 25 °C), ATR-IR spectroscopy and scanning electron microscopy (SEM). Adhesive-bond strength was obtained by T-peel tests on treated EVA/polychloroprene adhesive joints. The vinyl acetate content in the EVA affected the extent, but not the nature, of the surface modification produced by treatment with sulphuric acid. The treatment produced both sulfonation and oxidation on the EVA surfaces. The higher the vinyl acetate content in the EVA, the more significant the modifications produced. Increased T-peel strengths of EVA/polychloroprene adhesive + 5 wt% polyisocyanate joints were obtained and a mixed failure (adhesion failure + cohesive failure in the adhesive) was produced. It was found that, to be effective, the treatment of EVAs must be carried out with 96 wt% sulphuric acid.     

The influence of the polymerization on properties of an ethylacrylate/2-ethyl hexylacrylate pressure-sensitive adhesive suspension

In this paper, the batch suspension copolymerization process for production of microsphere acrylic pressure-sensitive adhesives (PSA) is presented. The effects of different process and chemical parameters on adhesion properties are discussed. The reaction was monitored in-line by using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Properties of the adhesive suspension (particle size), adhesive (gel phase, molecular weight, glass transition temperature (T_g)) and adhesion properties (tack, peel strength and shear) were determined. The results have shown that reaction kinetics strongly depends on polymerization temperature and initiator concentration. On the other hand, adhesion properties depend mainly on the T_g of the polymer and on the amount of insoluble gel fraction in the adhesive.     

Corona discharge treatment of EVAs with different vinyl acetate contents

Four ethylene vinyl acetate (EVA) co-polymers with different vinyl acetate (VA) contents (9–20 wt%) were treated with corona discharge to improve their adhesion to polychloroprene (PCP) adhesive. The thermal properties of the EVAs decreased as their VA content increased, caused by a decrease in crystallinity. The elastic and viscous moduli of the EVAs decreased and the temperature and modulus at the cross-over between these moduli decreased with increasing VA content. Contact-angle measurements (water), infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to analyse the surface modifications produced in the corona-discharge-treated EVAs. The corona discharge treatment produced improved wettability and created roughness and oxygen moieties on the EVA surfaces. The higher the VA content and the higher the corona energy, the more significant modifications were produced on the EVA surface. The VA content also affected the T-peel strength values of treated EVA/polychloroprene + isocyanate adhesive joints, as the values increased with increasing VA content. Mixed failure modes (interfacial + cohesive failure in the EVA) were obtained in the adhesive joints produced with corona discharge treated EVAs containing more than 9 wt% VA. The accelerated ageing of the joints did not affect the T-peel strength values, but the locus of failure in most cases became fully cohesive in the EVA, likely due to the higher extent of curing of the adhesive.     

Fiber-Matrix Interfacial Adhesion Improvement in Carbon Fiber-Bisphenol-A Polycarbonate Composites by Polymer Grafting

Fiber-matrix interfacial adhesion in thermoplastic composites is generally poor due to the lack of formation of strong covalent and/or ionic bonds between the generally inert thermoplastic resins and the surface of the reinforcing fiber. Adhesion can be improved by forming covalent linkages between the fiber and the matrix by grafting a polymer of appropriate compatibility, molecular weight, and sufficient density onto the surface of the fiber. We have grafted low molecular weight polycarbonate and polymethyl methacrylates onto the surface of carbon fibers and measured an improvement in the level of adhesion ranging from 25% to100% over the ungrafted composites. It was also observed that the level of improvement in adhesion appears to be independent of the molecular weight of the grafted polymer. Examination of the fracture surface of these composites reveals that the failure is cohesive in the matrix for the polymer grafted fiber composites, while it is adhesive for the ungrafted composites.     

Influence of Processing Additives on Adhesive Properties of Surface‐Modified Low‐Density Polyethylene

Summary: The paper deals with the surface and adhesive properties of low‐density polyethylene modified by corona discharge, which appear during the long‐term hydrophobic recovery of the modified polymer. The study was aimed at the change in polarity during aging of low‐density polyethylene modified by corona discharge reducing the surface free energy, its polar component and the mechanical work of adhesion. During the long‐term hydrophobization of low‐density polyethylene the main decrease of the surface properties appeared within the first 30 d after modification. In the course of further aging the hydrophobic recovery of the polymer proceeded more slowly. It has been found that the value of the surface and adhesive properties of low‐density polyethylene after modification with corona discharge as well as the dynamics of their decrease during the aging is to a great extent dependent on the presence of the processing additives in the polymer.

Mechanical work of adhesion of LDPE modified by corona discharge to poly(vinyl acetate) during hydrophobic recovery: a) additive‐free LDPE, b) LDPE with additives.     

SURFACE MODIFICATIONS ON EVA TREATED WITH SULPHURIC ACID

In this study, treatment with sulphuric acid was used to increase the adhesion of an ethylene-vinyl acetate copolymer containing 20 wt% vinyl acetate (EVA20). The treatment with sulphuric acid improved the wettability of EVA20 due to thecreation of different oxygen and sulphonic acid moieties on the surface. The treatment also created cracks and heterogeneities on the EVA20 surface, and enhanced T-peel strength values of EVA20/polychloroprene adhesive+5 wt% isocyanate joints were obtained. The loci of failure of the joints were mixed, i.e. , adhesional and cohesive in the adhesive. Peel strength values of both as-received and sulphuric acid-treated EVA20/polychloroprene adhesive joints increased after ageing at 50°C and 95 wt% relative humidity for 72 because the complete cure of the adhesive was thereby was produced. The durability of the EVA20 treated with sulphuric acid was monitored between 15 min and 5 years. High peel strength values were obtained for times up to 61 days; the joints produced with the treated EVA20 five years after treatment showed lower peel strength value due to the creation of a weak boundary layer produced by reaction of the residual sulphuric acid on the surface with EVA20. On the other hand, different experimental variables in the treatment of EVA20 with sulphuric acid were considered. The optimum treatment conditions for EVA20 were obtained by immersion in highly concentrated sulphuric acid (96 wt%) for one minute followed by neutralisation with ammonium hydroxide.     

Surface modifications on eva treated with sulphuric acid

In this study, treatment with sulphuric acid was used to increase the adhesion of an ethylene-vinyl acetate copolymer containing 20 wt% vinyl acetate (EVA20). The treatment with sulphuric acid improved the wettability of EVA20 due to thecreation of different oxygen and sulphonic acid moieties on the surface. The treatment also created cracks and heterogeneities on the EVA20 surface, and enhanced T-peel strength values of EVA20/polychloroprene adhesive+5 wt% isocyanate joints were obtained. The loci of failure of the joints were mixed, i.e. , adhesional and cohesive in the adhesive. Peel strength values of both as-received and sulphuric acid-treated EVA20/polychloroprene adhesive joints increased after ageing at 50°C and 95 wt% relative humidity for 72 because the complete cure of the adhesive was thereby was produced. The durability of the EVA20 treated with sulphuric acid was monitored between 15 min and 5 years. High peel strength values were obtained for times up to 61 days; the joints produced with the treated EVA20 five years after treatment showed lower peel strength value due to the creation of a weak boundary layer produced by reaction of the residual sulphuric acid on the surface with EVA20. On the other hand, different experimental variables in the treatment of EVA20 with sulphuric acid were considered. The optimum treatment conditions for EVA20 were obtained by immersion in highly concentrated sulphuric acid (96 wt%) for one minute followed by neutralisation with ammonium hydroxide.     

Fiber-Matrix Interfacial Adhesion Improvement in Carbon Fiber-Bisphenol-A Polycarbonate Composites by Polymer Grafting

Fiber-matrix interfacial adhesion in thermoplastic composites is generally poor due to the lack of formation of strong covalent and/or ionic bonds between the generally inert thermoplastic resins and the surface of the reinforcing fiber. Adhesion can be improved by forming covalent linkages between the fiber and the matrix by grafting a polymer of appropriate compatibility, molecular weight, and sufficient density onto the surface of the fiber. We have grafted low molecular weight polycarbonate and polymethyl methacrylates onto the surface of carbon fibers and measured an improvement in the level of adhesion ranging from 25% to100% over the ungrafted composites. It was also observed that the level of improvement in adhesion appears to be independent of the molecular weight of the grafted polymer. Examination of the fracture surface of these composites reveals that the failure is cohesive in the matrix for the polymer grafted fiber composites, while it is adhesive for the ungrafted composites.     

Effect of nanowhisker-modified zeolites on mechanical and thermal properties of poly(vinyl acetate) composites with pure-silica MFI

The effect of nanoscale surface morphology of pure-silica MFI zeolite on the interfacial, mechanical, and thermal properties of pure-silica MFI zeolite/poly(vinyl acetate) (PVAc) composites was investigated under different annealing conditions. Mg(OH)₂ inorganic whisker- or asperity-like nanostructures were achieved on MFI nano- and micro-particle surfaces via Grignard or solvothermal treatment. The creation of nano-roughness on the MFI surface promoted compatibility between the zeolite and the polymer matrix, resulting in void-free interfaces. PVAc composites containing surface-modified particles showed increased tensile strength and elongation at break as compared with composites containing unmodified zeolite. Surface modification of the microparticles exhibited interfacial and mechanical enhancement over a wider range of annealing temperatures than nanoparticles. Differential scanning calorimetry revealed that surface treatment of MFI resulted in broader glass transitions compared to composites containing unmodified MFI. This is explained by improved interfacial adhesion and associated slower chain relaxation dynamics. Furthermore, X-ray diffraction demonstrated that enhanced adhesive interactions between the PVAc and the MFI surface are associated with surface-induced orientation of the MFI particles within the polymer matrix. The optimal surface morphology, associated with the most enhanced mechanical and thermal properties of composites, was produced with the solvothermal method.     

Water-based adhesive formulations for rubber to metal bonding developed by statistical design of experiments

Waterborne adhesives for rubber to metal bonding have been available since 1990. However, published information about their formulation has been limited, as proprietary restrictions are exercised by companies. As a consequence, the way these adhesives interact with substrates has not been studied extensively. With the aim of investigating the effect the components of a waterborne adhesive have on rubber to metal bonding, fractional factorial and surface response methodologies of design of experiments were employed in this study. Twenty six formulations were prepared with a polychloroprene latex as the adhesive polymer. Viscosity, wettability and non-volatile solids content were measured with each liquid adhesive, while the mechanical strength was evaluated by applying a tensile mechanical stress over cured solid adhesive films. Adhesion properties were evaluated by using a single lap-shear test on metal to metal joints and a pull-out test on rubber to metal joints. The results showed that the components with the largest relative influence on cohesive and adhesives forces were tackifier resin, silicon dioxide and polychloroprene latex type. In order to better understand the contributions of these variables, mathematical models correlating them with the response variables were obtained. This study is valuable in explaining how, through statistical methods, a waterborne adhesive for rubber to metal bonding can be formulated with a reasonably low number of experiments.     

Temperature dependence of tack and pulse NMR analysis of polystyrene block copolymer/tackifier system

The influence of tackifier structure on the temperature dependence of tack for a polystyrene block copolymer/tackifier system was investigated. A blend of polystyrene-block-polyisoprene-block- polystyrene triblock and polystyrene-block-polyisoprene diblock copolymers was used as the base polymer. Four different tackifiers were used: special rosin ester resin (RE), rosin phenolic resin (RP), hydrogenated cyclo-aliphatic resin (HC), and aliphatic petroleum resin (C5). Tack at 20?°C increased with the tackifier content for both RE and HC tackifier systems. Tack is affected by two factors: the work of adhesion at the adherend interface and the viscoelastic properties of the adhesive. The good balance of these two factors brought high tack. The adhesive with 10 wt.% tackifier exhibited the highest tack at 20?°C, whereas those with 30 and 50 wt.% tackifier were lower than those systems with 10 wt.% of the RP or C5 tackifiers. The adhesive with overly high hardness lowered the work of adhesion and the tack was not improved with more than 30 wt.%. A compatibility test in toluene solution and in solid state showed that tackifier RE has good compatibility with both polyisoprene and polystyrene, whereas tackifier RP has lower compatibility. Tackifiers HC and C5 had good compatibility with polyisoprene, but poor compatibility with polystyrene, and that of C5 was poorer. Pulse nuclear magnetic resonance (NMR) analyses indicated that tackifiers RE and HC effectively restrict the molecular mobility of polyisoprene phase.     

Adhesion of polymer coils to a solid surface: influence of the depletion effect

The specific properties of polymer coils are often disregarded in theories of adhesion, but polymer properties are essential for the strength of the adhesive bond. Polymer coils are repelled entropically from impenetrable surfaces. This causes the depletion effect and creates a layer of reduced concentration right at the interface. To bond a polymer coil to a substrate, it must be forced actively towards the interface, driven by the gaining of adsorption energy. The adsorption of specific groups in the (co)polymer, which interact with 'polar' sites on the substrate, must be used to suppress the depletion. Adsorption diminishes the effective distance between the surface and the adhesive polymer. The balance between adsorption and depletion (rather than the effect of polar groups or pretreatments on the work of adhesion as such) is the most important chemical possibility of affecting adhesion. The strength of the bond between polymeric materials and solid surfaces varies as H^-3, with the effective distance H between the polymer and substrate. Therefore, it changes by an order of magnitude when the polymer adhesive is pulled towards the substrate by adsorption.     

Über den Einfluß der Grenzflächenspannung auf die Haftfestigkeit

The values of adhesion between four diffrent adhesive,and (i) steel substrates whose surface energy had been altered by adsorption, and (ii) several polymer having different surface energies, had been measured. The results show that the adhesion has a maximum value when the surface energy of the hardened adhesive is equals to that of the substrate, i.e. when the interfacial energy adhesive/substrate is a minimum. The adhesion of the adhesives to the polymer was much smaller than to the steel sprcimens and the dependence of the adhesion onm the interfacial energy was sharper in the case of the polymers. The decrease of the adhesion with increasing interfacial energy was fiund to be greater if the liquid adhesive wets the substrate badly than the steel speciman.     

Chemical modification of styrene–butadiene–styrene co-polymer by grafting of N-carbamyl maleamic acid

A styrene–butadiene–styrene (SBS) block co-polymer was functionalized using different amounts of N-carbamyl maleamic acid (NCMA) and benzoyl peroxide as initiator. NCMA, which is a bifunctional monomer, was synthesized in our laboratories. The concentration of NCMA used in the functionalization of SBS ranged from 0.5 to 3% (w/w) based on the co-polymer mass. Benzoyloxy radicals generated from the thermal decomposition of benzoyl peroxide initiated the grafting reaction. The concentration of the initiator was kept constant at 0.076% (w/w). FT-IR spectroscopy was used to determine the amount of NCMA effectively grafted onto the SBS. The maximum amount of monomer grafted was about 0.3% (w/w) when the SBS was modified with 1% (w/w) NCMA. The effect of grafting on the surface properties and the adhesion to polyurethane adhesive of the modified SBS were evaluated. Contact angle values were obtained using liquid droplets. When the concentration of the NCMA used in the grafting reaction was 1% (w/w), the contact angles with water on original and modified SBS were 95° and 77°, respectively. Adhesion properties were evaluated by standard peel tests employing a commercial polyurethane adhesive. The modified SBS having the largest amount of NCMA displayed a T-peel strength value 5-times higher than the corresponding value measured with the original SBS.     

Contribution of physico-chemical properties of interfaces on dispersibility, adhesion and flocculation of filler particles in rubber

Reinforcing fillers are added to elastomeric compounds to improve and adjust several mechanical, dynamical, tribological, etc. properties with respect to different applications, i.e. for automotive tires, or technical rubber goods. Carbon black and precipitated silica are widely used as rubber reinforcing fillers; however, some new classes of nanosized substances like organophilic modified clay or carbon nanotubes are presently intensive studied as possible future filler systems in combination with carbon black or silica.An important parameter for the dispersibility and compatibility of the filler in the polymer matrix of rubber compounds is the surface energy and surface polarity of the solid filler particles. Therefore, we systematically measured and compared the dynamic contact angles of a collection of different filler types (carbon blacks, silica, carbon nanotubes and organoclays) using the Wilhelmy method, whereby the particles were fixed as a thin layer at a double-sided adhesive tape. From the contact angle values the polar and disperse part of the surface energies of the filler particles were calculated by fitting Fowkes formula. For an estimation of the compatibility of the fillers with different types of rubber polymers we additionally analyzed the surface energy and polarity of the gum (unfilled) elastomers. From the evaluated surface energies and polarities, thermodynamic predictors for the dispersibility (enthalpy of immersion), the adhesion between filler particles and polymer matrix in the nanocomposite, and for the flocculation behaviour of the particles in a rubber matrix (difference in the works of adhesion) were derived. These thermodynamic predictors improve considerably the compounding process of novel rubber nanocomposites with respect to target-oriented adjustment of rubber properties.