Adhesion Mechanisms of Polyurethanes to Glass Surfaces. III. Investigation of Possible Physico-Chemical Interactions at the Interphase

Surface free energies of polyurethanes made from toluene diisocyanate and 1, 4 butanediol-based hard segments and caprolactone polyol-based soft segments were calculated using additive functions. Good agreement was found between the calculated values based on additive functions and the calculated values based on contact angle measurements. The phase-separated polyurethanes were found to have a higher polar surface free energy component (γ^P). This was linked to the preferential segregation of butanediol/butanediol-derived moieties to the polyurethane surfaces due to phase separation. The adhesion values of these polyurethanes to soda-lime glass were correlated with their respective γ^P values and a linear relationship was found. It was also shown that the adhesion values of the low γ^P polyurethanes improved substantially when the glass surfaces were coated with a thin layer of butanediol prior to the bonding. The modulus of the interphase region rich in butanediol was evaluated. Although a modulus increase was found at the interface, this increase was found to play a secondary role in the adhesion. The chemical interactions at the polyurethane/glass interphase were investigated by pre-treating the glass surfaces with methyl-trimethoxysilane and trimethylchlorosilane prior to adhesion testing. The adhesion data showed no significant difference between the uncoated and the silane-treated glass substrates. Based on this experimental evidence, the possibility of any covalent or ionic bonding at the polyurethane/glass interphase was assumed negligible. It was determined that the mechanism of adhesion between the polyurethanes and the glass surface could be through the formation of an interphase region in which hydrogen bonding between the butanediol-rich interphase region and the hydroxylated glass surface plays a key role.     

Properties of crosslinked blends of pellethene and multiblock polyurethane containing poly(ethylene oxide) for biomaterials

A series of multiblock polyurethanes, containing various poly(ethylene oxide) (PEO; number‐average molecular weight = 400–3400) contents (0–80 wt %) and prepared from hexamethylene diisocyanate/PEO/poly(dimethylsiloxane) diol/polybutadiene diol/1,4‐butanediol, were used as modifying additives (30 wt %) to improve the properties of biomedical‐grade Pellethene. Different molecular weights of PEO were used to keep poly(ethylene glycol) at a fixed molar content, if possible, although the PEO content, related to the PEO block length in the multiblock polyurethanes, was varied from 0 to 80 wt %. The hydrophilic PEO component was introduced through the addition of PEO‐containing polyurethanes and dicumyl peroxide as a crosslinking agent in a Pellethene matrix. As the PEO content (PEO block length) increased, the hydrogen‐bonding fraction of the crosslinked Pellethene/multiblock polyurethane blends increased, and this indicated an increase in the phase separation with an increase in the PEO content in the crosslinked Pellethene/multiblock polyurethane blends. According to electron spectroscopy for chemical analysis, the ratio of ether carbon to alkyl carbon in the crosslinked Pellethene/multiblock polyurethane blends increased remarkably with increasing PEO content. The water contact angle of the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased with increasing PEO content. The water absorption and mechanical properties (tensile modulus, strength, and elongation at break) of the crosslinked Pellethene/multiblock polyurethane blend films increased with increasing PEO content. The platelet adhesion on the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased significantly with increasing PEO content. These results suggest that crosslinked Pellethene/multiblock polyurethane blends containing the hydrophilic component PEO may have potential for biomaterials that come into direct contact with blood. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2348–2357, 2004     

An efficient nanoscale representative volume element simulation including graded interphase for tensile behavior of epoxy/silica nanocomposites

The behavior of interphase-particle adhesion and interphase region around the nanoparticles can significantly affect the stress distribution and mechanical properties of polymeric nanocomposites. In this study, the elastic modulus of epoxy/silica nanocomposites is analyzed using the finite element method and different mathematical models. A nanoscale representative volume element including graded interphase, homogenous interphase, and no interphase model is implemented. Furthermore, the effect of interfacial adhesion is also considered. The final elastic modulus was clearly affected by the interphase modulus, especially at higher nanoparticle content. Under imperfect interfacial bonding, the existence of an interphase region leads to a slight increase in modulus, and in the absence of that area, the elastic modulus decreases to 3.28 GPa. In perfect bonding models, stress transferred from the matrix to interphase and, then, to nanoparticle, which led to a significant increase in elastic modulus. Unlike the imperfect bonding, the maximum stress was located in the elements along to the loading direction. A maximum 26% increase in elastic modulus for perfect bonding/graded interphase model with 6.54 vol% of nanosilica particles compared to bulk epoxy was achieved. Finally, on comparing the FEM analysis and theoretical results with the experimental data, good agreement between obtained results was found.     

Peel Adhesion: Influence of Surface Energies and Adhesive Rheology

The adhesion properties of polymers are known to be influenced by both intermolecular forces operative at the interface and the rheological history of both bonding and unbonding. Recent adsorption and viscoelastic theories of adhesion and cohesion are implemented in a comprehensive examination of these phenomena. Eight peel force “master curves” extending over 14 decades of reduced rate and representing glassy state to flow region rheology are superimposed to provide a composite response envelope. Each master curve represents rate-temperature reduced adhesion of an alkyl acrylate adhesive (γ_c = 26 dyne/cm) to substrates ranging from low adhesion fluorinated polymers (γ_c = 15 to 17 dyne/cm) to polar poly-amide surfaces (γ_c = 45 dyne/cm) and glass. The rate dependent transition from interfacial to cohesive failure, a subject not treated by adsorption theory, is shown to be coincident with the onset of entanglement slippage within the polymeric adhesive. Thermodynamic criteria of polymer adhesion are shown to be applicable only to the flow region of polymeric response. This study indicates that measured surface tensions or calculated surface energies of polymeric solids do not properly account for the contributions of three dimensional network structure of the polymeric bulk phase to its total work of cohesion. Evidence of true interfacial failure of a polymer-polymer bond is supported by critical surface tension measurements.     

Prospect of nanoscale interphase evaluation to predict composite properties

For meeting the requirements of lightweight and improved mechanical properties, composites could be tailor-made for specific applications if the adhesion strength which plays a key role for improved properties can be predicted. The relationship between wettability and adhesion strength has been discussed. The microstructure of interphases and adhesion strength can be significantly altered by different surface modifications of the reinforcing fibers, since the specific properties of the interphase result from nucleation, thermal and/or intrinsic stresses, sizing used, interdiffusion, and roughness. The experimental results could not confirm a simple and direct correlation between wettability and adhesion strength for different model systems. The main objective of the work was to identify the interphases for different fiber/polymer matrix systems. By using phase imaging and nanoindentation tests based on atomic force microscopy (AFM), a comparative study of the local mechanical property variation in the interphase of glass fiber reinforced epoxy resin (EP) and glass fiber reinforced polypropylene matrix (PP) composites was conducted. As model sizings for PP composites, γ-aminopropyltriethoxysilane (APS) and either polyurethane (PU) or polypropylene (PP) film former on glass fibers were investigated. The EP-matrix was combined with either unsized glass fibers or glass fibers treated with APS/PU sizing. It was found that phase imaging AFM was a highly useful tool for probing the interphase with much detailed information. Nanoindentation with sufficiently small indentation force was found to be sufficient for measuring actual interphase properties within a 100-nm region close to the fiber surface. Subsequently, it also indicated a different gradient in the modulus across the interphase region due to different sizings. The possibilities of controlling bond strength between fiber surface and polymer matrix are discussed in terms of elastic moduli of the interphases compared with surface stiffness of sized glass fibers, micromechanical results, and the mechanical properties of real composites.     

Waterborne polyurethane dispersions obtained with polycarbonate of hexanediol intended for use as coatings

Three waterborne polyurethane dispersions derived from polycarbonate of hexanediol (PCD) with molecular weight of 1000 Da were synthesized by the acetone method and used as coatings for stainless steel plates. Different hard segments content in the polyurethanes were obtained by varying the isocyanate/macroglycol (NCO/OH) molar ratio. A decrease in the NCO/OH ratio produced an increase in the mean particle size as well as a decrease in the Brookfield viscosity of the dispersions. Furthermore, the greater the NCO/OH ratio the higher the urea and urethane hard segment content, the higher the glass transition temperature value and the higher the elastic modulus of the polyurethane was. On the other hand, the NCO/OH ratio affected the adhesion of the polyurethanes. The adhesion was evaluated by using three different procedures: T-peel strength tests of flexible PVC/waterborne polyurethane dispersion/flexible PVC joints; single lap-shear tests of aluminium/waterborne polyurethane dispersion/aluminium joints and cross-cutter adhesion test of polyurethane coatings on stainless steel pieces. Finally, several properties of the polyurethane coatings on stainless steel pieces were tested including Persoz hardness, gloss, chemical resistance and yellowness index.     

Dispersion-Polar Surface Tension Properties of Organic Solids

A new definition for work of adhesion W_a is applied to computationally define the dispersion γ_s^d and polar γ_s^d components of the solid surface tension γ_s = γ_s^d + γ_s^d for twenty-five low energy substrates. These calculated surface properties are correlated with surface composition and structure. Surface dipole orientation and electron induction effects are respectively distinguished for chlorinated and partially fluorinated hydrocarbons. Published values for critical surface tension of wetting γ_c are correlated with both γ_s^d and γ_s.     

Improvement of polyurethane adhesion to glass using novolac primer

The adhesion of polyurethane (PU) coatings based on toluene diisocyanate, poly(propylene glycol) (PPG) 2000, polyethylene adipate (PEA) 2000 and castor oil (CO) was studied. The coatings were applied to glass slides with and without novolac primer (due to the high functionality of castor oil, the resultant PU coatings have limited shelf life). Our studies showed that satisfactory adhesion strengths were achievable for immediate bonding. Furthermore, our study also found that the adhesion of polyurethane to glass surfaces was increased by using a thin layer of novolac primer.     

Formation of epoxy-diamine/metal interphases

Epoxy-diamine networks are extensively used as adhesives or paints in many industrial applications. When the precursors are applied onto metallic substrates and cured, an interphase, having chemical, physical and mechanical properties quite different from that of bulk polymer, is created between the substrate and the polymer. Moreover, chemical reactions between diamine and metallic surfaces induce an increase in the practical adhesion (adherence). When the same epoxy-diamine mixtures are applied onto gold coated or polyethylene substrates, the interphase properties are the same as bulk ones. When epoxy-diamine mixtures are applied onto aluminum or titanium alloy surfaces, the glass transition temperature, amine and epoxy reaction extent, the interphase thickness, residual stresses within the interphase, Young's modulus of the interphase all depend on the amine nature (aromatic, aliphatic or cycloaliphatic), the stoichiometric ratio, the processing conditions (time and temperature), the organic layer thickness and the metallic surface treatment. Coating analyses (FTIR, FTNIR, DSC, DMTA, H⁺ and C¹³ NMR, SEC, ICP and POM) suggest that diamine monomers chemically react with and dissolve the metallic hydrated oxide layer. Then, metallic ions diffuse through the organic layer to form a complex by coordination with diamine monomers (chelate or ligand). Metal–diamine complexes are insoluble, at room temperature, both in diamine as well as in DGEBA monomers and they induce a phase separation during the curing cycle of the epoxy-diamine precursors. Furthermore, the chemical bonding of diamine monomers to the metallic surfaces and the diamine–metal crystal orientation parallel to the metallic surface within the interphase lead to chemical, physical and mechanical properties to the epoxy-diamine network which are different from those of the bulk.     

Poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol based polyurethane elastomers. I. Synthesis and properties

The compatibilizing effect of poly(hexamethylene oxide) (PHMO) on the synthesis of polyurethanes based on α,ω‐bis(6‐hydroxyethoxypropyl) poly(dimethylsiloxane) (PDMS) was investigated. The hard segments of the polyurethanes were based on 4,4′‐methylenediphenyl diisocyanate (MDI) and 1,4‐butanediol. The effects of the PDMS/PHMO composition, method of polyurethane synthesis, hard segment weight percentage, catalyst, and molecular weight of the PDMS on polyurethane synthesis, properties, and morphology were investigated using size exclusion chromatography, tensile testing, and differential scanning calorimetry (DSC). The large difference in the solubility parameters between PDMS and conventional reagents used in polyurethane synthesis was found to be the main problem associated with preparing PDMS‐based polyurethanes with good mechanical properties. Incorporation of a polyether macrodiol such as PHMO improved the compatibility and yielded polyurethanes with significantly improved mechanical properties and processability. The optimum PDMS/PHMO composition was 80 : 20 (w/w), which yielded a polyurethane with properties comparable to those of the commercial material Pellethane™ 2363‐80A. The one‐step polymerization was sensitive to the hard segment weight percentage of the polyurethane and was limited to materials with about a 40 wt % hard segment; higher concentrations yielded materials with poor mechanical properties. A catalyst was essential for the one‐step process and tetracoordinated tin catalysts (e.g., dibutyltin dilaurate) were the most effective. Two‐step bulk polymerization overcame most of the problems associated with reactant immiscibility by the end capping of the macrodiol and required no catalysts. The DSC results demonstrated that in cases where poor properties were observed, the corresponding polyurethanes were highly phase separated and the hard segments formed were generally longer than the average expected length based on the reactant stoichiometry. Based on these results, we postulated that at low levels (∼ 20 wt %) the soft segment component derived from PHMO macrodiol was concentrated mainly in the interfacial regions, strengthening the adhesion between hard and soft domains of PDMS‐based polyurethanes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2026–2040, 2000     

The role of the terminal functional group of self‐assembled monolayers on fiber matrix adhesion

Adhesion at the fiber‐matrix interface of a composite is often influenced by a combination of factors such as mechanical interlocking, physicochemical interactions, and chemical bonding in the fiber‐matrix interphase region. We demonstrate the use of an approach using self‐assembled monolayers (SAMs) for studying the impact of one of the factors, chemical bonding, on the overall adhesion of the glass‐fiber/matrix interface. Transformation of these monolayer surfaces using conventional chemistry with a focus on the creation of a terminal functional group that interacts with epoxy resin is reported. The modified surfaces were characterized by ellipsometry, X‐ray photoelectron spectroscopy, and contact angle techniques for chlorosilane coverage, and in situ conversion. The adhesion of diglycidyl ether of bisphenol‐A resin to modified SAMs on E‐glass fibers was measured by performing single‐fiber fragmentation test. The extent of adhesion between the fiber and matrix was found to be dependent on the type of functional group at the terminal end of the SAM in contact with the epoxy matrix. Methyl terminal group resulted in the least adhesion, while amine terminal groups resulted in the most adhesion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

XPS and AFM Study of Interaction of Organosilane and Sizing with E-Glass Fibre Surface

Organosilanes are often used in commercial sizings for glass fibres to provide wettability with the resin and promote strong interfacial adhesion to the matrix in a fibre reinforced polymer composite. The silane treatment is introduced as part of a complex deposition from an aqueous emulsion immediately at the spinaret and determines the optimum properties of the cured composite. To understand the interaction of organosilanes contained in sizings for glass surfaces, XPS was used to investigate the adsorption of γ-aminopropyltriethoxysilane (APS) from a simple sizing system containing a polyurethane (PU) film former. It has been found that both APS and the sizing (containing APS and PU) deposits on E-glass fibre surfaces contained components of differing hydrolytic stability. The differences observed in the AFM images of APS coated E-glass fibres before and after water extraction also confirmed that the APS deposit contained components with different water solubility.     

Wettability and Adhesion Characteristics of Plasma-Treated Carbon Fibers

The surface free energy (γ_s) of modified carbon fibers was determined by tensiometry and effects of CF₄-O₂ plasma treatment were evaluated. The treatment with the gas mixture in which oxygen was above 40% accelerated preferentially the oxidation of fiber surfaces and the nondispersive component of the surface free energy, γ^P_S, increased to about three times that of the untreated fiber. On the other hand, the treatment with the gas containing CF₄ above 80% induced fluorination and surface species such as - CF, - CF₂, or - CF₃ were formed. The γ^P_S values decreased to almost zero and the dispersive component became about 18 mJ/m². The calculated work of adhesion between various fibers and the epoxy resin was well correlated with the interfacial shear strength of the composites formed with these materials.     

Experimental Investigation of the Interphase in an Epoxy-Aluminum System

The interphase in an epoxy-aluminum system has been revealed and characterized using scanning electron microscopy, ion etching, energy-dispersive x-ray analysis, and nano-indentation. The interphase was of irregular thickness, nominally between 2 and 6 μ, and corresponds to a region of greater resistance to ion etching and a marked absence of the silica particles used in the epoxy adhesive. Nano-indentation tests, traversing various sections of the interphase from the aluminum to the bulk resin, showed that the interphase region had, on average, an effective elastic modulus (E/(1-v²)) that was 13% greater than that of the bulk resin, far from the aluminum. The interphase was also approximately 4% harder than the bulk adhesive.     

High molecular weight polyurethanes and a polyurethane urea based on 1,4-butanediisocyanate

Summary New biomedical polyurethanes and a polyurethane urea based on Ε-caprolactone and 1,4-butanediisocyanate have been developed. On degradation, only non-toxic products are produced. The polyurethane urea with poly(Ε-caprolactone) soft segments and butanediisocyanate/butanediamine hard segments shows a high tensile strength, a high modulus and a high resistance to tearing but as a result of the strong interactions between the solvent and the polymer processing is difficult. When butanediamine is replaced by butanediol in the chain extension step, a processible polyurethane is obtained but the polymer lacks the desired mechanical properties for biomedical applications. By chain extending with a longer urethane diol block, a processible polymer was obtained with mechanical properties comparable to the polyurethane urea. This polyurethane has been made porous and can be used as a meniscal prosthesis. Received: 12 March 1998/Accepted: 27 March 1998     

Synthesis and antifouling activities of fluorinated polyurethanes

A series of fluorinated polyurethanes (FPUs) with various contents of fluorinated chain extender (EF) and the same amount of poly(oxytetramethylene glycol) and diphenylmethanediisocyanate were synthesized to explore the relationship between the surface physicochemical properties and bulk microphase separation structures of these FPUs and their antifouling activities against model bacteria and platelets. The bulk microphase separation of FPUs increased with the amount of incorporated EF. It was found that the surfaces of all FPUs were saturated by a layer of fluorocarbon chains which resulted in similar chemical composition and wetting activities for the three kinds of FPUs. The FPUs with lower or similar microphase separation compared with non‐fluorinated polyurethane chain‐extended with 1,4‐butanediol showed similar or even increased adhesion of bacteria and platelets. Notably, FPU with a higher degree of microphase separation than non‐fluorinated polyurethane displayed excellent antifouling activities against both model bacteria and blood platelets. It is therefore concluded that the increased microphase separation of the FPUs results in enhanced antifouling properties. © 2019 Society of Chemical Industry     

Interfacial Bonding and Environmental Stability of Polymer Matrix Composites

Recently developed adsorption-interdiffusion (A-I) theory of adhesion is employed to isolate the (London) dispersion γ_i,j^d and (Keesom) polar γ_i,j^p components of the excess interfacial free energy γ_i,j=γ_i,j^d+γ_i,j^p at the fiber-matrix interface in polymer matrix composites. For adsorption bonded interfaces the theory defines a new method of mapping the surface energy effects of an immersion phase upon the Griffith fracture energy γ_G. The stability of interfacial bonding between graphite fiber-epoxy matrix is defined in terms of the theoretical model and experimentally evaluated by accelerated aging studies which monitor changes in fracture energy for crack propagation perpendicular to the fiber axis. Applications of the model to control fiber surface treatments and select matrix components for optimized bond strength and environmental resistance is discussed.     

New composites based on short melamine fiber reinforced epdm rubber

Melamine fibre is a new category of advanced synthetic fiber having superior heat and flame resistance with decomposition temperature above 350°C. It suitability as a reinforcing fiber for ethylene propylene diene terpolymer, abbreviated as EPDM rubber, where ‘M’ stands for polymethylene chain, was investigated. It has been observed that tensile strength and stress at 100% strain of EPDM‐melamine fiber composites increase with the addition of a three‐component dry bonding system, comprising hexamethylene tetramine (hexa), resorcinol, and hydrate silica, abbreviated HRH system. Moreover, the fiber‐filled composites anisotropy in stress‐strain properties due to preferential of the short fibers along the milling direction (longitudinal), which is substantiated by the results of swelling and fractography studies. Aging causes an increase in the modulus, tensile strength and hardness of the composites. The fractographs show an increase in interfacial adhesion between the fibers and the matrix during aging, which is further confirmed by the reduction in tan δ peak height of the aged composites during dynamic mechanical studies. Atomic Force Microscopy (AFM) studies reveal the formation of an interphase with the addition of bonding agents and a better fiber‐matrix adhesion due to aging. AFM images also confirm the role of dry bonding systems in improving the fiber‐matrix adhesion of the aged vulcanizates. The composite modulus has been theoretically calculated using the well‐known Halpin‐Tsai equation. It is found that in the transverse direction, observed modulus values are greater than the calculated values, while in the longitudinal direction, the experimental modulus values are found to be lower than the calculated values for both unaged and aged composites owing to some degree of anisotropy in fiber orientation.     

Effect of Interphase Structure on the Debonding of Polycarbonate from S-2 Glass Fibers

The effect of interphase structure on the debonding of polycarbonate from S-2 glass fibers has been studied. The shear strength, fracture toughness and hydrolyic stability of the interphases were measured in a single fiber composite of a continuous S-2 glass fiber embedded in a polycarbonate matrix. Polycarbonate oligomers were chemically grafted onto the glass fiber surfaces through use of a silicon tetrachloride intermediary and the properties of the resulting interphases were compared with those of two commercial sizings and ozone-cleaned surfaces. Evaluation was accomplished by measuring the stress transmission across the interphase, τ, by carrying the embedded single fiber fragmentation test to saturation and by using computer simulations and a finite element analysis to calculate the strain energy release rate, G, of the observed fiber-matrix debonding accompanying the first fiber fracture. The oligomer-grafted interphase exhibited improved stress transmissibility and toughness, after 24 hours in boiling water. The tenacity of the tightly bound oligomers was confirmed via DRIFT, TGA and GC/MS experiments on Soxhlet-extracted fibers.

The grafting reaction was modeled on a high surface area silica and studied using solid state NMR to determine reasons for the greater stability of the oligomer-treated surfaces. Measurements of chemical shifts and spin-lattice relaxation times indicate that the oligomers are chemically attached to the surfaces, providing for a well bonded, water resistant interphase. Parallel experiments on a monomeric Bisphenol A-primed silica surface provided evidence that chemical bonding was primarily responsible for the greater hydrolytic stability.     

Influence of the solids content on the properties of waterborne polyurethane dispersions obtained with polycarbonate of hexanediol

Waterborne polyurethane adhesives are an interesting alternative to the current solvent-borne polyurethane adhesives used in the industry. Different aliphatic waterborne polyurethane dispersions (PUDs) with different solids content were synthesised by reacting isophorone diisocyanate (IPDI) with a polycarbonate derived from hexanediol via the acetone method. The PUDs were characterised by Brookfield viscosity, pH, particle size, transmission electron microscopy (TEM) and solids content measurement. The dry polyurethane films were characterised by ATR-IR spectroscopy, plate–plate rheology, differential scanning calorimetry (DSC) and thermal gravimetry (TGA). Their adhesion was evaluated from T-peel tests of flexible PVC/waterborne polyurethane dispersion/flexible PVC joints and single lap-shear tests of aluminium/waterborne polyurethane dispersion/aluminium joints.The PUDs showed bimodal particle size distribution. The mean particle size of the PUDs decreased by increasing their solids content but the particle size distribution of the PUDs increased by decreasing their solids content. As the solids content increased the Brookfield viscosity of the PUDs increased due to lower mean particle size where particle crowding was favoured, the PUD having 44 wt% solids content was an exception (higher particle size but lower polydispersity). On the other hand, the increase in the solids content increased the hard segments content and the degree of phase separation of the polyurethanes. The greater the solids content of the polyurethanes, the lower their glass transition temperatures values and the lower the elastic moduli. Adhesive strength under peel stresses were not affected by the solids content in the polyurethanes but the single lap-shear strength values decreased by increasing the solid contents in the polyurethanes due to lower hard segments content.