T-peel Strength Tests Research Articles

Robotised atmospheric plasma treatment to improve the adhesion of vulcanised and thermoplastic rubber materials for a more sustainable footwear

Surface treatment is essential to ensure the resistance and durability of adhesive upper-to-sole joints for footwear. This study investigates robotised atmospheric pressure plasma technology to increase adhesion on styrene-butadiene vulcanised (SBR) and styrene-butadiene-styrene thermoplastic (SBS) rubbers, which constitutes a more sustainable surface treatment as an alternative to solvent-based chemical treatments (i.e., halogenation). In this work, the different parameters such as application speed and distance of the nozzle of the atmospheric plasma system have been optimised and the effects of the plasma treatment on the physicochemical properties in the materials’ surface, roughness, wettability, as well as the adhesion properties have been evaluated by means of different experimental techniques: Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Photoelectron Spectroscopy (XPS), Field Emission Scanning Electron (FESEM), Contact Angles (CA) and Surface Free Energy (SFE) measurements and T-peel strength tests. The results show that the values obtained for the T-peel strength of the reactive hot melt polyurethane adhesive (HMPUR) joints studied exceed the minimum quality requirements for footwear according to standardised tests. In consequence, the optimisation and validation of operating plasma conditions and adhesion properties of rubbers could consolidate atmospheric plasma as a solvent-free alternative for the preparation of footwear soling materials. The great advantage of this technology is its introduction into the production line by fully automating the bonding process with the use of robots.

Influence of biobased polyol type on the properties of polyurethane hotmelt adhesives for footwear joints

Polyurethanes, one of the most used polymers worldwide, are strongly dependent of non-renewable fossil resources. Thus, boosting the production of new polyurethanes based on more sustainable raw materials is crucial to move towards the footwear industry decarbonisation. The aim of this study is to synthesise and characterise reactive hotmelt polyurethanes from biomass and CO2-based polyols as bioadhesives for the footwear industry. The influence of biobased polyols on the polyurethane structure, and therefore, on their final properties was analysed by different experimental techniques such us Fourier transform infrared spectroscopy (FTIR), Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), Melting viscosity, Softening temperature and T-peel strength test, in order to assess their viability for the upper to sole bonding process. The results obtained indicated that the incorporation of different amounts of the biobased polyols produces changes in the structure and final performance of the polyurethanes. Therefore, adhesion test carried out by the T-peel test 72 h after the upper -to- sole bonding of the sustainable adhesives show high final adhesion values. These sustainable raw materials provide polyurethane adhesives with additional beneficial non-toxicity and sustainable characteristics, without harming their properties during their useful life.

Adhesion enhancement between aluminum and butyl rubber by (3-mercaptopropyl) trimethoxy silane for vibration damping plate

A silane coupling agent for an aluminum-based vibrational damping plate with a butyl rubber damper, which shows excellent viscoelasticity and thermal stability, was studied to enhance the adhesion strength between aluminum and butyl rubber. Considering the chemical structure of the butyl rubber, we introduced (3-mercaptopropyl) trimethoxysilane (MPTMS) as the silane coupling agent because it has a thiol functional group that can bind to the carbon chain of butyl rubber via thiol-ene reaction under heating. Based on the results of various surface analyses and the T-peel strength test, the MPTMS treatment condition was optimized, and a 180% enhancement of peel strength was obtained. Finally, a central supporting vibration test was conducted to prove the damping performance of aluminum damping plated with MPTMS. As a result, a 7-fold enhancement in the damping loss factor was seen in the damping with MPTMS compared to without.

CO2 derived amino-alcohol compounds for preparation of polyurethane adhesives

A series of novel amino-alcohol curing agents for PU adhesives were synthesized from CO2, glycidyl ether and diamine through carbonation and amination reactions. By physically evaluating the compounds through FT-IR and 1H NMR spectroscopy and mechanically analyzing the adhesives through T-peel strength tests, the raw materials have successfully been transformed into curing agents and the curing agents were found to endow the adhesives with specific structures and unique properties. For PVC bonding, compared to the traditional curing agents HDA and HDO, the T-peel strength and medium resistance from the novel amino-alcohol compounds improved. Further analysis revealed distinction in mechanical properties for different curing agents, the trifunctional curing agent exhibited the largest tensile strength and hardness. Moreover, thermal analysis of the adhesives demonstrated the considerable thermal stability to those prepared from HDA and HDO.

Studies on adhesive properties of polypropylene (PP) and polycarbonate (PC) film surfaces using DC glow discharge plasma

Direct current (DC) glow discharge plasma has been used to increase the adhesive properties of polypropylene (PP) and polycarbonate (PC) film surfaces and make them suitable for technical applications. The modified surfaces were characterized by contact angle, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) analysis. Also, improved adhesion properties were analyzed using T-Peel strength test. The results show that the surface wettability has been increased due to decrease in contact angle and increase in surface energy. After plasma treatment the root mean square (RMS), roughness of PP and PC films were gradually increased with different exposure time. XPS results detected polar functional groups on plasma treated PP and PC film surfaces. T-Peel strength test for adhesion strength measurement showed that the surface modified PP and PC films were increased with adhesive properties. Key words: Glow discharge, polypropylene (PP), polycarbonate (PC), contact angle, surface energy.

Influence of environmental humidity on plasma etching polyamide 6 films

The environmental humidity (EH) may have potential influence on atmospheric pressure plasma treatment. In order to investigate how the environmental humidity affects atmospheric pressure plasma treatment, polyamide 6 (PA 6) films were treated by helium/oxygen (He/O2) plasmas using atmospheric pressure plasma jet (APPJ) at different environmental humidity. The plasma treated samples had lower contact angles than the control. Atomic force microscopy (AFM) showed increased surface roughness, while X-ray photoelectron spectroscopy (XPS) revealed increased oxygen contents after the plasma treatments. The plasma treated films had higher T-peel strength than that of the control as revealed by T-peel strength tests. It was shown that the addition of environmental humidity increased effectiveness of the plasma in polymer surface modification after the treatment.

Influence of the Treatment with Sulfuric Acid on Adhesion of Natural Rubber and Cast Polyurethane Elastomers

In this study, natural rubber (NR) was treated with sulfuric acid to improve its adhesion properties to polar polymer. T-peel strength tests, scanning electron microscopy, contact-angle measurement (water), Energy Dispersive X-ray Detector were used to analyze the nature of the NR surface modifications which were carried out with sulfuric acid. A noticeable decrease in contact angle was observed on the rubber surface by contact-angle measurements which can be ascribed to the increase of oxidized moieties on the rubber surface. EDX revealed that oxidized moieties were created through treatment with sulfuric acid. The surface modification and mode of bond failure were studied by scanning electron microscopy (SEM). Immersion in sulfuric acid for 15min produced the maximum adhesion strength (10kN/m) and produced a mixed failure mode (interface & rubber failure in the rubber). Treatment with sulfuric acid produced improved wettability as well as chemical (surface oxidation) and morphological modifications (roughness) of the rubber surface.

Influence of the Treatment with Sulfuric Acid on Adhesion of Natural Rubber and Cast Polyurethane Elastomers

In this study, natural rubber (NR) was treated with sulfuric acid to improve its adhesion properties to polar polymer. T-peel strength tests, scanning electron microscopy, contact-angle measurement (water), Energy Dispersive X-ray Detector were used to analyze the nature of the NR surface modifications which were carried out with sulfuric acid. A noticeable decrease in contact angle was observed on the rubber surface by contact-angle measurements which can be ascribed to the increase of oxidized moieties on the rubber surface. EDX revealed that oxidized moieties were created through treatment with sulfuric acid. The surface modification and mode of bond failure were studied by scanning electron microscopy (SEM). Immersion in sulfuric acid for 15min produced the maximum adhesion strength (10kN/m) and produced a mixed failure mode (interface & rubber failure in the rubber). Treatment with sulfuric acid produced improved wettability as well as chemical (surface oxidation) and morphological modifications (roughness) of the rubber surface.

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.

A New Organofunctional Ethoxysilane Self-Assembly Monolayer for Promoting Adhesion of Rubber to Aluminum

Practical adhesion of rubber to aluminum is measured for various aluminum silanization treatments. In this study, 6-(3-triethoxysilylpropylamino)-1,3,5-triazine-2,4- dithiol (TES) was used as the coupling agent for preparing self-assembly monolayers (SAMs) on an aluminum surface. The structure and chemical composition of the SAMs were analyzed using Fourier transform infra-red spectroscopy (FT-IR) and X-ray photo-electron spectroscopy (XPS). The changes in the surface features of the aluminum surface due to TES treatment were investigated by atomic force microscopy (AFM). The adhesive properties of the silanized aluminum surface and EPDM rubber have been evaluated by a T-peel strength test. The results suggested that the Si-O-Al bonding at aluminum TES interface existed and a TES self-assembly monolayer was formed on the aluminum surface. More than 6.0 KN/m adhesion strength is obtained when the aluminum is silanized with 2.5 mmol/dm3 TES, cured at 160 °C and vulcanized with EPDM rubber at 160 °C for 30 min. It is suggested that the TES self-assembly monolayer is bound to aluminum through its ethoxysilyl functional group, and the thiol function group is strongly cross-linked to EPDM rubber, respectively.

Adhesive properties of polypropylene (PP) and polyethylene terephthalate (PET) film surfaces treated by DC glow discharge plasma

In this study, the adhesive properties of the plasma modified polypropylene (PP) and polyethylene terephthalate (PET) film surfaces have been investigated. Hydrophilicity of these polymer film surfaces was studied by contact angle measurements. The surface energy of the polymer films was calculated from contact angle data using Fowkes method. The chemical composition of the polymer films was analyzed by X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) was used to study the changes in surface feature of the polymer surfaces due to plasma treatment. The adhesion strength of the plasma modified film was studied by T-peel strength test. The results showed a considerable improvement in surface wettability even for short exposure times. The AFM and XPS analyses showed changes in surface topography and formation of polar groups on the plasma modified PP and PET surfaces. These changes enhanced the adhesive properties of polymer film surfaces.

UV-Ozone Surface Treatment of SBS Rubbers Containing Fillers: Influence of the Filler Nature on the Extent of Surface Modification and Adhesion

SBS rubbers containing different loadings of calcium carbonate and/or silica fillers were surface treated with UV-ozone to improve their adhesion to polyurethane adhesive. The surface modifications produced on the treated filled SBS rubbers have been analyzed by contact angle measurements, ATR-IR spectroscopy, XPS and SEM. The adhesion properties have been evaluated by T-peel strength tests on treated filled SBS rubber/polyurethane adhesive/leather joints. The UV-ozone treatment improved the wettability of all rubber surfaces, and chemical (oxidation) and morphological modifications (roughness, ablation, surface melting) were produced. The increase in the time of UV-ozone treatment to 30 min led to surface cleaning (removal of silicon-based moieties) due to ablation and/or melting of rubber layers and also incorporation of more oxidized moieties was produced. Although chemical modifications were produced earlier in an unfilled rubber for short time of treatment with UV-ozone, they were more noticeable in filled rubbers for extended length of treatment, mainly for S6S and S6T rubbers containing silica filler. The oxidation process seemed to be inhibited for S6C and S6T rubbers (containing calcium carbonate filler). On the other hand, the S6S rubber containing silica filler and the lowest filler loading showed the higher extent of modification as a consequence of the UV-ozone treatment. The UV-ozone increased the joint strength in all joints, more noticeably in the rubbers containing silica filler, in agreement with the greater extents of chemical and morphological modifications produced by the treatment in these rubbers. Finally, the nature and content of fillers determined the extent of surface modification and adhesion of SBS rubber treated with UV-ozone.

Water-based chlorination treatment of SBS rubber soles to improve their adhesion to waterborne polyurethane adhesives in the footwear industry

Solutions of trichloroisocyanuric acid (TCI) in different organic solvents are commonly employed in the footwear industry to improve the adhesion of SBS (styrene-butadiene-styrene) rubber soles to polyurethane adhesive. To avoid the use of organic solvents in the chlorinating solutions, several water-based chlorinating treatments were investigated in this study: (i) inorganic chlorine compounds (HCl-acidified sodium hypochlorite solution; free active chlorine (FAC) = 47.8 g/l); (ii) organic chlorine donors (aqueous solution of 3 wt% TCI/H2O, and ethanol solutions of 3 wt% HD (1,3-dichloro-5,5-dimethylhydantoine), or NCS (N-chlorosuccinimide); (iii) organic chlorine donor salts (aqueous solutions containing 3 wt% DCI (sodium dichloro isocyanurate), CB (chloramine B, N-chloro-sodium-phenylsulphenamide), or CT (chloramine T, N-chloro-sodium-p-toluenesulphenamide). The surface modifications produced by treatment of SBS rubber with the aqueous chlorinating agents were compared with those obtained by using the current solvent-based chlorinating treatment (3 wt% TCI/MEK). The FAC concentration and the chlorine stability in the solutions were determined by iodine titration, and the SBS rubber surface pH was determined with a flat pH probe. The surface modifications on the SBS rubber were analyzed by ATR-IR spectroscopy, XPS, contact-angle measurements and SEM. The adhesion properties were evaluated by T-peel strength tests on treated SBS rubber/waterborne polyurethane adhesive/roughened leather joints. The failed surfaces obtained after peel tests were analyzed by ATR-IR spectroscopy to precisely assess the locus of failure of the adhesive joints. The nature of the modifications produced on the SBS rubber surface depended on the chlorinating system used, the SBS rubber surface pH value, and the free active chlorine concentration of the chlorinating solution. The most effective chlorinating agents were TCI/H2O and HD/EtOH, but they were not stable over time due to quick chlorine evolution. Treatment with NaClO/HCl and DCI/H2O provided acceptable adhesive strength values although there was fast chlorine evolution in the NaClO/HCl solution; the free active chlorine concentration in the DCI/H2O solution was stable for at least 4 days after preparation. Finally, the treatment with NCS/EtOH, CB/H2O and CT/H2O did not chemically modify the SBS rubber surface, so the adhesion to polyurethane adhesive was not improved.

CFRP/알루미늄 복합재에서 이온도움반응법을 적용한 CFRP의 표면처리가 T-peel 강도에 미치는 영향에 대한 연구

It is well-known that the bond strength between CFRP(Carbon Fiber Reinforced Plastic) and aluminum is significantly affected by the surface treatment of the CFRP and the aluminum. This study investigates the surface treatment of CFRP to improve the T-peel strength of CFRP/aluminum composites. The surface of was treated by the ion assisted reaction method under oxygen environment. T-peel strength tests were performed based on the procedure of ASTM D1876-95. The T-peel strength of surface-treated CFRP/aluminum composites was compared with that of untreated CFRP/aluminum composites. The results showed that the T-peel strength of surface-treated CFRP/aluminum composites was about 5.5 times higher than that of untreated CFRP/aluminum composites. SEM examination showed that the improvement of T-peel strength was attributed to the uniform spread and fracture of epoxy adhesive.

A new water-based chemical treatment based on sodium dichloroisocyanurate (DCI) for rubber soles in the footwear industry

A new water-based chemical treatment based on sodium dichloroisocyanurate (DCI) solutions for rubber soles of different natures is reported in this study. Different concentrations (1-5 wt%) of DCI and two rubber formulations (vulcanized styrene-butadiene rubber, R2; thermoplastic rubber, TR) were considered. The effects produced by treatment of the rubber soles with DCI were compared with the standard halogenation method using trichloroisocyanuric acid (TCI) solutions in an organic solvent (ethyl acetate). The effects of chlorination on the rubber surfaces were studied using contact angle measurements, ATR-IR spectroscopy, and scanning electron microscopy. The adhesion strength was obtained from T-peel strength tests on canvas/PUD adhesive/treated rubber joints. The adhesive used throughout this study was a water-based polyurethane dispersion (PUD). The surface treatment with aqueous DCI solutions modified the surface chemistry of both the TR and R2 rubbers, creating C—Cl moieties on the surface and removing the zinc stearate from the R2 rubber surface. The use of a low DCI concentration in water was less effective in modifying the TR rubber, but was sufficient to obtain good T-peel strength values for the R2 rubber joints. On the other hand, heterogeneities and cracks were created on the rubber surface (mainly on the R2 rubber surface), which may contribute to an increase in the mechanical interlocking with the adhesive. A noticeable increase in the T-peel strength and a cohesive failure in the rubber for the joints produced with TR rubber were obtained when the rubber was treated with aqueous DCI solutions. For the canvas/PUD adhesive/chlorinated R2 rubber joint, the failure was located in a thin surface layer on the canvas. Finally, the surface treatment with TCI in ethyl acetate produced a more significant surface modification on both the TR and the R2 rubber, creating deeper roughness on the R2 rubber surface. Consequently, higher peel strength values were obtained using TCI solutions in ethyl acetate. Furthermore, the T-peel strength values were high in all joints produced with TR rubber treated with either TCI solution in ethyl acetate or aqueous DCI solution.

Surface Graft Copolymerization Enhanced Lamination of Poly(tetrafluoroethylene) Film to Copper and Epoxy-Based Print Circuit Board (PCB)

Lamination of poly(tetrafluoroethylene) (PTFE) film to a copper foil or to an epoxy-based print circuit board (PCB) Substrate (FR4®) was carried out. Lamination was achieved during surface graft copolymerization of glycidyl methacrylate (GMA) on an Ar plasma pretreated PTFE film at elevated temperature and in the presence of an epoxy resin adhesive. The plasma pretreatment introduces peroxides which are thermally degraded into free radicals to initiate the graft polymerization of GMA on the PTFE surface. The graft copolymerization with concurrent lamination is carried out in the complete absence of a polymerization initiator or system degassing. The modified surfaces and interfaces are characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The adhesion strength between the PTFE film and copper or the FR4® substrate was assessed by the T-peel strength test method. The adhesion strength was affected by plasma pretreatment time, as well as the grafting and curing temperature. The PTFE/GMA-epoxy resin/Cu and PTFE/GMA-epoxy resin/FR4 assemblies exhibit significant higher interfacial adhesion strengths compared to those assemblies in which only epoxy resin or GMA was used. They also exhibit better interfacial adhesion reliability. The PTFE/GMA-epoxy resin/Cu and PTFE/GMA-epoxy resin/FR4® joints delaminated by cohesive failure inside the bulk of PTFE film. The results suggest that the enhanced adhesion between the graft-modified PTFE film and copper or FR4® surfaces is attributable to the formation of covalent bonds between the tethered GMA graft chains on PTFE and the network of epoxy resin.

Properties of elastomeric polyurethanes obtained with ϵ-caprolactone macroglycol

Three elastomeric polyurethanes were obtained by reacting MDI (diphenylmethane-4,4′-diisocyanate) with ϵ-caprolactone macroglycols of different molecular weight (1000–3000 daltons); the chain extender used was 1,4-butane diol. The increase in the molecular weight of the macroglycol modified the degree of phase separation and the interactions between the hard and soft domains in the polyurethane structure. The properties of elastomeric polyurethanes were studied by using Gas Permeation Chromatography, FTIR spectroscopy, DSC, DMTA, rheology (stress-controlled rheometer), contact angle measurements, and T-peel strength tests. The use of low molecular weight macroglycol produced polyurethane with small crystallinity, relatively higher T g and reduced softening enthalpy. Therefore a poor degree of phase separation was produced and reduced mechanical and viscoelastic properties were obtained. On the other hand, a high molecular weight macroglycol improved the degree of phase separation producing better mechanical, viscoelastic and thermal properties in the polyurethanes. Furthermore, the increase in molecular weight of macroglycol increased the adhesion of PVC/polyurethane adhesive joints and further changed the locus of failure.