Modern synthetic adhesives based on epoxy-rubber compositions

Results of investigations of adhesives and compounds based on epoxy resins modified with low-molecular rubbers are presented. A series of epoxy-rubber compositions with improved physicomechanical characteristics and operational properties are developed. Examples of solutions of engineering challenges using high-molecular synthetic adhesive systems are given.     

Low-pressure plasma chlorination of styrene-butadiene block copolymer for improved adhesion to polyurethane adhesives

Studies concerning plasma-surface chlorination of a styrene-butadiene block copolymer (SBS), improving its adhesion to polyurethane adhesives (PU), are presented in this paper. The plasma was generated by an RF discharge (13.56 MHz, plate electrode reactor) in CCl₄ under low pressure. The 180°-peel test, contact angle measurements and XPS spectroscopy were utilized to investigate the SBS surface. A drastic increase in the adhesion (the peel strength 5-7 times higher than that for the non-treated surface) was observed after only a few seconds of the plasma treatment. It was shown that CCl, COH and >CO are the most important functional groups formed as a result of the plasma treatment and they play the crucial role in the chemical bonding between the SBS surface and the adhesive. H₂O molecules strongly attached to the SBS surface were also found. It was determined, however, that they reduce the gluing power. A very good correlation between the concentration of the functional groups and the peel strength was established. On the other hand, no correlation between the peel strength and the surface free energy (estimated from the contact angle measurements) was observed. It indicates that the thermodynamic adhesion is unimportant in this case and confirms the dominant role of the chemical adhesion.     

Mechanism of adhesion of polyurethane/polymethacrylate simultaneous interpenetrating networks adhesives to polymer substrates

Polyether-based polyurethane/poly (methyl methacrylate-co-ethyleneglycol dimethacrylate) interpenetrating polymer networks [PU/P (MMA–co–EGDMA)-IPNs] were synthesized and used as adhesives to adhere vulcanized natural rubber (NR) and soft polyvinyl chloride (PVC). The structure and morphology of the IPN adhesives in bulk and near the adhesive/substrate interfaces were investigated. A new mechanism of adhesion called conjugate interpenetration of networks across interfaces, which is suitable for IPN adhesives and polymer substrates, was put forward. According to this mechanism, while forming simultaneous interpenetrating networks in the adhesive, the monomers in the IPN adhesive can permeate polymer substrates and polymerize in situ to form gradient IPNs, thereby producing conjugate three-component IPNs near the adhesive/substrate interfaces. It is the conjugate interpenetration of the networks across the interfaces that strengthens interfacial combination remarkably and results in high bond strength of IPN adhesives. © 1994 John Wiley & Sons, Inc.     

New polyurethane adhesives for electric and radio components

The article discusses the technological and strength properties of newly developed elastic coldcuring polyurethane adhesives PU-ELBO. Examples are given of applying adhesives in the units and assemblies of electric and radio components that operate under increased humidity, cyclic variations of temperature, and vibration loads. It is noted that, in a cured state, the developed PU-ELBO adhesive is characterized by minimal levels of gas emissions in vacuum and at high temperatures.     

New polyurethane adhesives with improved adhesive effect and heat endurance

Thixotropic polyurethane two-part cold-setting adhesives with an improved adhesive effect and heat endurance developed by OAO Kompozit are presented. These adhesives are based on polyester PU-prepolymer (polybutylene glycol adipate) and toluene diisocyanate and contain NEGP-6 additive developed by OOO Macromer SMC. It follows from the presented comprehensive test results that MTK and MTK-1 adhesives meet the requirements for materials used in spacecraft engineering.     

Properties of solvent based polyurethane adhesives containing fumed silicas

Five hydrophilic and two hydrophobic fumed silicas of different surface area and particle size were added to solvent based polyurethane adhesives. Silica addition produced a noticeable increase in the adhesive viscosity, imparted negative thixotropy, increased the storage modulus (G') and improved the green adhesion of chlorinated rubber/PU adhesive/chlorinated rubber joints. Those modifications were more pronounced in the adhesives which contain hydrophilic silicas.     

Novel tetrapotassium azo diphosphonate (INAZO) as flame retardant for polyurethane adhesives

An inorganic azo diphosphonate (INAZO), (KO)₂(O)P-NN-P(O)(OK)₂·4H₂O, was synthesized and tested as a novel type of flame retardant additive for castor oil and oligomeric methylene diphenyl diisocyanate (PMDI) based two component polyurethane adhesive with or without using dolomite ((CaMg(CO₃)₂) as filler. Flammability according to UL 94 test and performance under forced-flaming conditions (cone calorimeter) were investigated at the additive loadings of 5, 10 and 20 wt %. It was shown that INAZO improves flame retardancy by significantly reducing heat release rate (HRR), maximum average rate of heat emission (MARHE) and total smoke release (TSR) values in comparison to CaMg(CO₃)₂ filled polyurethane adhesives. The macroscopic structure of the sample residues after cone calorimeter measurement was also analysed. The action mechanism of the developed INAZO flame retardant is suggested to be mainly in the condensed phase. UL 94 V-0 rating was achieved in the vertical burning test when 10 wt % loading of INAZO was used, whereas the reference flame retardant ammonium polyphosphate (APP) required a loading of 20 wt % to reach the V-0 classification.     

Recycling of polyurethane wastes using different carboxylic acids via acidolysis to produce wood adhesives

This study aims to provide further understanding on the depolymerization of polyurethanes (PU) via acidolysis. Therefore, polyurethane foams scraps are chemical recycled using different dicarboxylic acids, namely succinic and phthalic dicarboxylic acids, being the reaction products identified using Fourier-transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography. The results obtained show that succinic acid has higher efficiency as cleavage agent, as a result, the succinic acid ensuing recovered polyol (RP) presents higher hydroxyl value and lower viscosity. Additionally, from the oxidative-induction time measurements, it is observed that the RP is considerably more thermally stable, than the petroleum-based polyol, due to the higher content of aromatic moieties. Afterwards, the RP is used as substitute of petroleum-based polyol in the production of polyurethane adhesives (PUA) and compared with conventional polyol based PUA. Due to the higher content of aromatic moieties, higher bonding strength is achieved using the RP. Overall, further understanding on the acidolysis is obtained, proving the suitability of this method for the recycling of PU.     

Investigation of covalently colored polyurethane latexes based on novel anthraquinone polyurethane chain extenders

Novel red and yellow polyurethane (PU) chain extenders with one anthraquinone chromophore and two hydroxyls were synthesized, and then used to fabricate covalently colored PU latexes with pendent chromophores on the PU backbone. The chemical structures of the chain extenders were characterized by ¹H-NMR and FTIR, and the properties of PU latexes and their films were investigated by UV-Vis absorption spectra, particle size analysis, FTIR, Soxhlet's extraction and xenon arc aging testing. Results showed that the covalently colored PUs had the same UV-Vis absorption behavior as the corresponding chain extenders, and amount of the chain extenders had no obvious influence on the latex preparation process and the resulted latex colloidal properties. Compared with the corresponding non-covalently colored PU latex films, both the light fastness and the solvent fastness of the covalently colored PU latex films were significantly enhanced by the covalent incorporation of chromophores with PU matrix.     

MALDI-MS and colorimetric analysis of diisocyanate and polyol migrants from model polyurethane adhesives used in food packaging

The identification of the migrants, into food simulants, from a series of polyurethane adhesives used in the manufacture of plastic film laminates for use in common food packaging is described. Commercial materials, based on four different model adhesive systems, were prepared by an industrial collaborator. The MALDI-MS fingerprint patterns of the three polyether and one polyester polyol components of these adhesives were obtained for reference purposes. The decrease in the level of diisocyanate as a migrant versus time after lamination was confirmed by colorimetric measurements. The migration of the standard polyol samples through polyethylene pouches into water at 70 degrees C has been demonstrated and also the attenuation effect for different polyols. Cured laminates in the form of pouches were used to carry out the migration experiments into distilled water, inside the pouch, at 70 degrees C over a period of 2 h. Comparison of the migration results from the food packaging laminates with those from the polyethylene film confirmed the migration of unreacted polyol components for the polyether-based systems. Cyclic oligomers from the polyol starting materials were identified as the migrants from the polyester-based adhesive.     

Use of calcium carbonate – fumed silica mixtures as filler in polyurethane adhesives

Natural ultramicronized calcium carbonate and mixtures of fumed silica‐natural ultramicronized calcium carbonate are proposed as fillers of solvent based polyurethane (PU) adhesives. PU adhesive containing only calcium carbonate shows similar rheological, thermal, mechanical, surface and adhesion properties than the PU adhesive without filler. Addition of 90 wt% fumed silica +10 wt% calcium carbonate mixture to PU adhesive produced a similar performance than the PU adhesive containing only famed silica. The increase in the amount of natural calcium carbonate in respect to fumed silica in the filler mixture produced detrimental effect on the rheological and mechanical properties of the PU adhesives (in respect to those provided by the PU adhesive only containing fumed silica), although the surface and adhesion properties were not noticeably modified.     

Use of silane coupling agents to improve epoxy-rubber interface

Scrap car tyre particles can be used as filler or toughening agent in rigid epoxy matrices if the resultant interface is adequate. The objective of this work was to investigate the effects of use of different silane coupling agents (SCAs) to improve the interface between the epoxy resin and recycled rubber particles. For this purpose, seven different SCA were used to modify surfaces of the rubber particles. After the preparation of epoxy-rubber specimens, tensile Charpy impact and plane-strain fracture toughness tests were conducted. Mechanical tests and fractographic studies revealed that some of the SCA can improve of the interface between the epoxy matrix and the rubber particles leading to increases in strength while slight decreases in toughness of the samples.     

Chemical nature of adhesion: Plasma modified styrene-butadiene elastomer and polyurethane adhesive joints

A study of the mechanism of gluing between plasma-modified styrene-butadiene elastomer (SBS) surfaces and polyurethane (PU) adhesives is presented in this paper. The plasma treatment was carried out employing low-pressure O₂ plasma generated by an RF discharge (13.56 MHz). FTIR-ATR spectroscopy and peel tests were utilized to characterize the SBS surfaces before and after the plasma treatment. It was found that hydroxyl groups are mainly created on the SBS surface by the plasma treatment and their concentration reveals very good linear correlation with the peel strength of the SBS-PU joints. The grafting of phenyl isocyanate (analog of the PU curing agent) into the plasma-treated SBS surface was also investigated. The process was performed at 353 K, that is at temperature in which the adhesive-bonded joints were made. It was shown that all hydroxyl groups on the SBS surface react with isocyanate groups forming carbamate bonds. The results obtained in this work strongly confirm the conception of the adhesion by chemical bonding between SBS and PU.     

Assessment of adhesion between polyurethane liner and epoxy based substrate: Methodology and experiment

A methodology for assessing interfacial adhesion properties between polyurethane liners and epoxy based substrates was sought to optimize manufacturing procedures for polyurethane lined fibre reinforced epoxy piping. The experimental study showed that the blister test is apposite and expedient for this purpose. The employed methodology allowed for quantification of bond toughness by pressurizing a polyurethane overlayer through a central perforation in an epoxy substrate and measuring the height and pressure of the resulting blister during interfacial fracture. Details of sample fabrication, experimental setup and testing procedures are presented. This study demonstrated that specimens with mechanically bonded polyurethane-epoxy interface underwent interfacial fracture. Samples with a strong chemical bond at the interface, on the other hand, did not exhibit interfacial fracture. A chemically bonded interface is, thus, deemed superior to its mechanically bonded counterpart, and manufacturing protocols for polyurethane lined fibre reinforced epoxy pipe should, therefore, be adjusted to promote chemical bonding at the materials' interface.     

Increased adhesion of Enterococcus faecalis strains with bimodal electrophoretic mobility distributions

Initial adhesion is a determinant in the development of microbial biofilms. It is influenced, amongst others, by the surface hydrophobicity and the electrostatic characteristics of the substratum and adhering organisms. Enterococcus faecalis strains, grown in pure cultures, generally display subpopulations with different electrokinetic features, reflected in a bimodal electrophoretic mobility distribution. Here, the initial adhesion kinetics of five heterogeneous and five homogeneous E. faecalis strains were followed in a parallel-plate flow chamber. After 4h of flow, heterogeneous strains adhered in significantly higher numbers than homogeneous strains (7.3 x 10(6) and 1.9 x 10(6)cm(-2), respectively), but the initial deposition rates were not significantly influenced (740 and 600 cm(-2)s(-1), respectively). Apparently, initial deposition of bacteria is mainly governed by attractive Lifshitz-Van der Waals forces that overwhelm the electrostatic repulsion energy barrier, thus resulting in similar initial deposition rates for the various bacterial populations investigated. In contrast, during later stages of adhesion, bacteria in heterogeneous cultures likely experience a lower electrostatic repulsion from already adhering bacteria than bacteria in homogeneous cultures, thus allowing a closer proximity of the bacteria with respect to each other, which ultimately leads to increased adhesion after 4 h.     

Investigation of shear failure mechanisms of pressure‐sensitive adhesives

We report new experiments investigating the failure mechanisms in shear, of thin layers of acrylic pressure‐sensitive adhesives (PSA). We have developed a novel experimental device able to shear a soft adhesive layer confined between a rigid hemispherical lens and a rigid glass substrate. Using the resources of in situ contact visualization, the nonhomogeneous deformation of the layer and the shear failure processes were observed optically. Depending on the rheological properties of the adhesive, ratios of the contact radius over the layer thickness of 10–30 were achieved, mimicking well the contact conditions encountered in a thin adhesive layer within a joint. When the adhesive was weakly crosslinked, we observed a fluid‐like behavior and could measure a reasonable value for the viscosity of the PSA, implying that flow can occur in the layer and failure will occur by creep. On the other hand, for a more crosslinked adhesive, closer to what is used in applications, a stick‐slip peeling behavior was observed, which involves a coupling between peeling mechanisms at the leading edge of the contact and interfacial slippage. Such a process suggests a failure by fracture rather than by creep. Interestingly, the peeling mechanisms and the associated stress levels change significantly when the layer becomes as thin as 20 μm, implying a fracture process that is controlled by a critical energy release rate in shear G_IIc rather than by a critical shear stress causing failure of the interfacial bonds. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3316–3330, 2005     

Rheological properties of polyurethane adhesives containing silica as filler: influence of the nature and surface chemistry of silica

Four silicas, two fumed silicas (one hydrophilic and one hydrophobic) and two precipitated silicas (one hydrophilic and one hydrophobic), were added as filler to solvent‐based polyurethane (PU) adhesive formulations. In general, the addition of silica increased the viscosity, the storage and loss moduli of the PU adhesives but only the hydrophilic fumed silica exhibited pseudoplasticity and thixotropy. The rheological properties imparted by adding filmed silicas to PU adhesive solutions were more noticeable than that of precipitated silicas. Interactions between the hydrophilic fumed silica, the polyurethane and/or the solvent seemed to be responsible for the improved rheological properties of filled PU adhesives.     

Surface modification of thermoplastic polyurethane in order to enhance reactivity and avoid cell adhesion

Recently, the definition of coating procedures which leads to strong cell repellent surfaces has been an extremely important issue. In the present study, the cell repellency of thermoplastic polyurethane material (Elastollan®1180A50) surfaces was achieved by chemical treatment. Samples of Elastollan®1180A50 processed by injection molding, were oxidized with hydrogen peroxide (H₂O₂) and then impregnated with poly(ethylene glycol). The oxidation time was evaluated as were the effects of the PEG impregnation. Of all the evaluated modifications, a surface oxidation for 2 h, followed by impregnation with poly(ethylene glycol) resulted in the best cell repellent surface.     

New fluorinated oxazoline block copolymer lowers the adhesion of platelets on polyurethane surfaces

We have prepared an amphiphilic oxazoline block copolymer of hydrophilic poly(2-methyl-2-oxazoline) and hydrophobic poly[2-(2-perfluorooctyl)ethyl-2-oxazoline] chains. By controlling the length and composition of polymer chains, we found that this fluorinated block copolymer can be readily dissolved in water. Furthermore, we can achieve a stable surface coating of the fluorinated block copolymer by dissolving the copolymer in water, then coating the aqueous copolymer solution onto surfaces of nonwater-soluble polymers. This is a simple and useful method of modifying the surface character of polymer substrates. We have found that the polyether urethane (PEU) coated by block copolymer has a different surface chemistry and biological reactivity than the uncoated PEU. From XPS analysis, we found the fluorinated copolymer was coated on PEU (atomic % of F: 31.3 on coated PEU, 0.3 on uncoated). The two surfaces have different affinities for biological molecules. Specifically, the fibrinogen adsorption on the fluorinated copolymer-coated PEU was 62 ± 39 ng/cm², compared to a value of 156 ± 99 ng/cm² for uncoated PEU. In an ex vivo evaluation of platelet adhesion, the surface of coated PEU attached a few white cells while uncoated PEU was covered with activated platelets. © 1994 John Wiley & Sons, Inc.