Role of silane crosslinking on the properties of melt blended metallocene polyethylene‐g‐silane/clay nanocomposites at various clay contents

A study to investigate matrix properties and their interaction with loaded nanoclay was designed under controlled clay dispersion. Metallocene polyethylene grafted vinyltriethoxy silane (mPE‐g‐silane) was served as the matrix, with or without silane crosslinking (grafting and post crosslinking with catalyst versus only grafting without catalyst), to assess the strength of commercial organoclay (20A)‐filled nanocomposites prepared via a melt mixing. According to X‐ray diffraction and transmission electron microscopy analyses, all nanocomposites achieved similar dispersion degrees at specific clay contents mainly due to the silane interaction with the dispersed clay via hydrogen bonding and/or chemical bonding. Chemical bonding of grafted silane with clay was inferred based on the slightly higher crosslinking degree with increasing clay content for crosslinked cases. For uncrosslinked cases, the crosslinking degree was virtually zero regardless of clay content. The dynamic mechanical properties revealed enhanced interaction between mPE‐g‐silane and clay with increasing clay content based on the increased glass transition temperatures. Young's modulus of nanocomposites with crosslinked cases showed higher values in comparison with uncrosslinked cases at a specific clay content, indicating the significance of matrix crosslinking effect and the effective interfacial interaction between silane and clay especially at higher clay content. To the authors' best knowledge, this is the first study which generally maintains similar clay dispersions through the effect of uncrosslinking (only grafting) and crosslinking (grafting and post crosslinking), and then probes the effect of matrix properties and interfacial interactions at the large deformation state (tensile test) and small deformation state (cutting test). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Silane grafting and moisture crosslinking of polypropylene

Peroxide initiated vinylsilane grafting of polypropylene in an intensive mixer, and the subsequent water crosslinking process were studied. Different concentrations of vinyl trimethoxysilane and dicumyl peroxide were used. The materials obtained after mixing in the rheocord were hot pressed at 190°C. The melt viscosity of the obtained sheets, the melting enthalpy and melting temperature (DSC, differential scanning calorimetry), the mechanical properties and the thermal decomposition behavior (TG, thermogravimetric analysis) were studied. No evidence of grafting during the rheocord processing was observed. Nevertheless, for the hot pressed sheets with concentrations higher than 4 phr of vinyl silane an important increase in the melt viscosity was observed. This increase agrees with the change observed in the mechanical properties, which show a maximum for the water crosslinked samples containing 4 phr of vinyl silane. The modulus increases by 39% at 90°C and 33% at 130°C, while the tensile strength rises by ～22% at both temperatures. The silane grafted water crosslinked samples show a more stable thermal behavior than both the silane grafted samples and the unmodified polypropylene.     

Effect of Silane Coupling Agents on Adhesion of Polybutadiene to Glass

The chosen silane coupling agents consist of a polybutadiene skeleton with  Si(CH₃)₂OCH₃ or  Si(OCH₃)₃ pendent groups hydrolyzable on the glass surface. Their number, and therefore the amount of potential bonds, can be varied. These modified polybutadiene polymers act as primer compatible with the polybutadiene coating to be deposited. The subsequent cross-linking of the double bonds of the silane primed surface with polybutadiene is initiated by benzoyl peroxide, creating chemical bonds between the solid support and its coating. The strength of the adhesion of polybutadiene to glass is measured by the 180° peel test and the values are compared with a non-modified glass surface.     

Adhesion properties of UV crosslinked polystyrene-block-polybutadiene-block-polystyrene copolymer and tackifier mixture

The peel and tack properties of mixtures of polystyrene-block-polybutadiene-block-polystyrene (SBS) and a tackifier were investigated after these were crosslinked by ultraviolet (UV) irradiation at various amounts of benzophenone (BP) as a photoinitiator and trimethylolpropane mercaptopropionate (TRIS) as a crosslinking agent.The degree of crosslinking of polybutadiene (PB) block in the SBS mixture was qualitatively estimated from the amount of gel fraction as well as the change in the glass transition temperature of the PB block. The crosslinking of the PB block was done within 3 min after UV irradiation and the peel strength of crosslinked specimens was as low as 45[percnt] of specimens without crosslinking. Nano-tack and bulk tack properties as well as the surface tension of mixtures were measured depending upon amounts of BP and TRIS.     

Modification of a nitrile-phenolic bonding agent by addition of an interfacial agent: effect on the practical adhesion between nitrile rubber and metal

—The mechanism of vulcanization bonding of a nitrile rubber (NBR) elastomer to metal with a single-coat nitrile-phenolic bonding agent is discussed. A nitrile-phenolic bonding agent consisting of NBR, phenol formaldehyde (PF) resin, and vulcanizing agents was modified with an interfacial agent (p-cresol formaldehyde resin) and the effect of interfacial agent addition on the practical adhesion between metal and the NBR elastomer after vulcanization was investigated. The adhesion strength was measured in terms of the metal-to-NBR elastomer peel strength using the bonding agent. The addition of p-cresol formaldehyde (PCF) resin to the bonding agent with a proportionate reduction of PF resin initially improved the peel strength; a maximum was reached at about 20% PCF content and then decreased with a further increase in the PCF content. The improvement in peel strength produced by the addition of PCF resin is attributed to the increased chemical bonding between NBR and the phenolic resin. The drop in peel strength above 20% PCF content is explained by the increased diffusion of the bonding agent into the NBR elastomer, away from the bond line, leading to a starved glue line. The mechanism for the optimum performance at about 20% PCF resin content is believed to be due to the balance of diffusion and chemical crosslinking.     

Adhesion and Crosslinking in Epoxy Resin/Steel Assemblies

A novel technique has been employed to investigate the development of interfacial bonding between steel and epoxy resins. Whereas such systems are usually rigid, precluding use of the very informative peel test, we have used spring steel as a flexible adherend and peeled this from the (relatively) rigid crosslinked polymers. Peel energy has been assessed for 180° and 90° tests, using a cylindrical former to limit irreversible deformation of the steel. Cure cycles for the resins DGEBA/DDA and DGEBA/DDS have been studied using DSC, and results exploited in such a way that peel tests could be effected on assemblies for which the total degree of polymer crosslinking was standardised, yet polymer/steel contact time during crosslinking was varied. The degree of potential reactivity of the polymers with respect to the steel was thus controlled. It was found, for both polymers, that measured adhesion energy was an approximately linear function of the fraction of crosslinking agent that reacted whilst epoxy/steel contact was maintained. Master curves for the two systems have been plotted, irrespective of cure conditions, the DGEBA/DDS system presenting better adhesion. Although no direct evidence of type and/or number of interfacial bonds is presently available, a simple argument suggests that chemical reactions occurring at ca. 1% of available surface sites may markedly improve adhesion.     

Dynamic Mechanical and ESCA Studies of Aluminium-Aluminium Bonding by an Epoxidised Natural Rubber-Polyacrylic Acid Blend

A polyacrylic acid (PAA)-epoxidised natural rubber (ENR) blend becomes crosslinked during high temperature moulding and such a blend was found to be a good adhesive for aluminium (Al)-aluminium (Al) bonding. The joint strength can be improved by the incorporation of silica filler into the adhesive up to a loading of 5 phr. However, higher filler loading causes deterioration of the joint strength. Electron Spectroscopy for Chemical Analysis (ESCA) studies of the peeled and then leached Al surface shows that the ENR phase of the blend is primarily responsible for the adhesion with the Al surface. With the increase in filler loading adhesion with Al increases at the cost of crosslinking between the component polymers. This is substantiated by dynamic mechanical analyses of the blends and joints (that is, Al/blend/Al composites). The changes in dynamic mechanical properties of the blends due to Al adhesion could be correlated with the peel strength of the Al/blend/Al joints.     

Influences of liquid elastomer additive on the behavior of short glass fiber reinforced epoxy

In this study, improvements in mechanical and thermal behavior of short glass fiber (GF) reinforced diglycidyl ether of bisphenol-A (DGEBA) based epoxy with hydroxyl terminated polybutadiene (HTPB) modification have been studied. A silane coupling agent (SCA) with a rubber reactive group was also used to improve the interfacial adhesion between glass fibers and an epoxy matrix. 10, 20, and 30 wt% GF reinforced composite specimens were prepared with and without silane coupling agent treatment of fibers and also HTPB modification of epoxy mixture. In the ruber modified specimens, hardener and HTPB were premixed and left at room temperature for 1 hr before epoxy addition. In order to observe the effects of short glass fiber reinforcement of epoxy matrix, silane treatment of fiber surfaces, and also rubber modification of epoxy on the mechanical behavior of specimens, tension and impact tests were performed. The fracture surfaces and thermal behavior of all specimens were examined by scanning electron microscope (SEM), and dynamic mechanical analysis (DMA), respectively. It can be concluded that increasing the short GF content increased the tensile and impact strengths of the specimens. Moreover, the surface treatment of GFs with SCA and HTPB modification of epoxy improved the mechanical properties because of the strong interaction between fibers, epoxy, and rubber. SEM studies showed that use of SCA improved interfacial bonding between the glass fibers and the epoxy matrix. Moreover, it was found that HTPB domains having relatively round shapes formed in the matrix. These rubber domains led to improved strength and toughness, due mainly to the “rubber toughening” effect in the brittle epoxy matrix.     

硅烷接枝温水交联天然橡胶的研究

以多功能乙烯基硅烷为接枝单体,过氧化苯甲酰为引发剂,通过熔融混炼接枝和温水交联分别制备了硅烷接枝天然橡胶和交联硅烷接枝天然橡胶。采用傅里叶红外光谱仪和扫描电子显微镜分别对硅烷接枝天然橡胶和交联硅烷接枝天然橡胶进行了表征,并研究了接枝单体及引发剂的用量、接枝和交联工艺（温度和时间）等对交联硅烷接枝天然橡胶凝胶含量的影响,同时研究了不同凝胶含量对交联硅烷接枝天然橡胶力学性能的影响。结果表明,天然橡胶发生了硅烷接枝和交联反应;随着接枝单体及引发剂用量、混炼时间和温度以及交联温度和时间的增加,交联硅烷接枝天然橡胶的凝胶含量单调增加;交联硅烷接枝天然橡胶的力学性能随着凝胶含量的增加而明显得到改善,凝胶含量为80%的交联硅烷接枝天然橡胶的拉伸强度比纯天然橡胶提高了30%,断裂伸长率提高了8.5倍。     

Profile extrusion and mechanical properties of crosslinked wood–thermoplastic composites

Challenges for wood‐thermoplastic composites to be utilized in structural applications are to lower product weight and to improve the long‐term load performance. Silane crosslinking of the composites is one way to reduce the creep during long‐term loading and to improve the mechanical properties. In this study, silane crosslinked wood‐polyethylene composites were produced by reactive extrusion and subsequently manufactured into rectangular profiles. The silane crosslinked composites were stored in a sauna at 90 °C to increase the degree of crosslinking. The toughness of the silane crosslinked composites was significantly higher than for the non‐crosslinked composites. Improved adhesion between the wood and polyethylene phases is most likely the reason for the improved toughness of the crosslinked composites. There was no significant difference in flexural modulus between the crosslinked and non‐crosslinked composites. In addition, impact testing showed that the impact strength of the crosslinked composites was considerable higher (at least double) than the non‐crosslinked. The effect of temperature on the impact strength of the composites indicated slightly higher impact strength at −30 °C than at 0° and at 25 °C, and then an incrase in impact strength at 60 °C. Crosslinking also reduced the creep response during short‐term loading. Moreover, scanning electron microscopy on the fracture surface of the crosslinked composites revealed good adhesion between the polyethylene and wood phases. POLYM. COMPOS. 27:184–194, 2006. © 2006 Society of Plastics Engineers     

Effect of curing agent on interfacial adhesion in acrylic polymer-based laminates

The effect of crosslinking on interfacial adhesion between an acrylic elastomer and poly(methyl methacrylate) has been studied using a 90° peel test. Elastomers were master-batched with a 1 : 10 sulfur/sodium mixture. The compounded elastomer was then bonded with poly(methyl methacrylate) by in situ curing at various temperatures. Variations in the curing affect both the mechanism of adhesion and separation. The relationship between peel strength and crosslink density is found to be P = kM_c. Crosslinking at relatively low temperatures produced a partially crosslinked elastomer that leads to high peel strengths. When crosslinked at 180°C, the acrylic elastomer was completely cured, and the peel strength decreased by more than 80%. This is consistent with an optimum level of crosslinking required for peel strength. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1277–1284, 1998     

The Effectiveness of Silane Adhesion Promoters in the Performance of Polyurethane Adhesives

A model polyurethane (PUr) adhesive has been modified by the addition of various silane adhesion promoters and used to bond PVC, ABS, a polyblend and glass. Inverse gas chromatography (IGC) data showed that epoxy silane substantially increased the surface reactivity of the adhesive while maintaining its amphoteric character. An aminosilane shifted the PUr surface to basicity, while vinyl, mercapto and chlorosilanes promoted surface acidity. Lap-shear data identified the amphoteric epoxy silane as the most successful adhesion promoter in all polymer and glass assemblies, increasing their initial bond strengths and also their residual bond strengths following accelerated aging. Elsewhere, the success of silane additives reflected the strength of interfacial acid/base interactions, the aminosilane being favored for bonding PVC, the others being preferred for the basic ABS and polyblend substrates. Correlations were developed between residual bond strength and initial bond properties of the assemblies and also between these system characteristics and an acid/base interaction parameter. The correlations may be useful as guidelines to the formulation of superior adhesives for bonding with substrates of known acid/base interaction potential.     

Influence of the degree of crosslinking on the stringiness of crosslinked polyacrylic pressure‐sensitive adhesives

The stringiness of crosslinked polyacrylic pressure‐sensitive adhesive (PSA) was observed during 90° peeling under the constant peel load. The random copolymer of butyl acrylate with 5 wt % acrylic acid crosslinked by N,N,N′,N′‐tetraglycidyl‐m‐xylenediamine was used as PSA. All observed stringiness upon peeling was sawtooth‐shaped, but it could be classified into three types dependent on the degree of crosslinking. The typical sawtooth‐shaped stringiness with interfacial failure was observed at the relatively higher crosslinker content ranging from 0.008 to 0.016 chemical equivalents (Eq.), where the PSA has high cohesive strength and low interfacial adhesion. The frame formed at the front end of stringiness at the content ranging from 0.002 to 0.004 Eq. Sufficient interfacial adhesion and deformability generate large internal deformation of the PSA layer. Internal deformation occurred preferentially over peeling as a result of front frame formation. The mode of peeling was changed from cohesive failure to interfacial failure in this range of crosslinker content. The sawtooth‐shaped with cohesive failure was observed at the lower content ranging from 0 to 0.001 Eq. The PSA has high interfacial adhesion and low cohesive strength, and thus exhibited cohesive failure. The PSA after peeling remained in the shape of belts. It was found that the shape of stringiness is strongly dependent on the balance between the interfacial adhesion and the cohesive strength of PSA. When the sawtooth‐shaped stringiness with frame formed, the peeling rate was lowest. This means the peel strength should be the maximum in this shape of stringiness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40336.     

The use of UNIFAC for the estimation of adhesion enhancement between polymers and mineral surfaces treated with silane coupling agents

The group contribution method of UNIFAC is used to investigate the influence on adhesion of thermodynamic compatibility between the filler surface and the polymeric matrix in filled polymeric composites. Compatibility is enhanced between polymers and mineral surfaces through the use of silane coupling agents of varying chemistry. In this study, glass beads were treated with ten different organofunctional silanes intended to induce differences in interfacial strength. Interfacial strength measurements were obtained from tests in which single, silane-treated glass beads were embedded in rectangular poly(vinyl butyral) specimens subjected to uni-axial stress until interfacial failure occurred at one of the poles of the sphere. The UNIFAC method was used to estimate the Gibbs free energies of mixing using the chemical structure of the polymer repeat unit and each of the silane organofunctional groups, and these values were correlated with the measured interfacial strengths. The results indicate that enhanced interfacial strength corresponds to systems with more favorable thermodynamic mixing.     

Mechanical properties of particulate composites

The mechanical properties of glass bead (30 micron diameter glass spheres) filled epoxy and polyester resins have been studied as a function of volume fraction of filler and the strength of the interfacial bond. The bonding between glass and resin was varied by chemically surface treating the glass using a silicone mold release to prevent chemical bonding at one extreme and a silane coupling agent to maximize bonding at the other extreme. Theoretical predictions of the elastic modulus and tensile strength have been made utilizing a finite element method. Excellent agreement is obtained with the experimental results. Izod impact energies have been measured for these composites as a function of filler content and interface treatment.     

Reactive bonding of natural rubber to metal by a nitrile–phenolic adhesive

The mechanism of adhesive bonding of rubber to metal using an interlayer of bonding agent (adhesive) is discussed with respect to various physical and chemical events such as adsorption at the metal surface, chemical crosslinking within the adhesive, interdiffusion, and formation of interpenetrating networks at the rubber–adhesive interface. An investigation on the peel strength of a natural rubber (NR)–adhesive–metal joint, made by vulcanization bonding using nitrile–phenolic adhesive containing various concentrations of toluene diisocyanate–nitrosophenol (TDI–NOP) adduct, is presented. A single‐coat adhesive, consisting of a p‐cresol phenol formaldehyde resin, nitrile rubber (NBR), and vulcanizing agents in methyl ethyl ketone solvent, was selected for the study. Considerable improvement in the peel strength was obtained by the incorporation of TDI–NOP adduct into the nitrile–phenolic adhesive. The peel strength increases as the concentration of TDI–NOP adduct in the adhesive composition increases, then levels off with a transition from interfacial failure to cohesive tearing of rubber. The peel strength improvement is believed to be attributed to the interfacial reactions between the bonding agent and natural rubber, when TDI–NOP adduct is incorporated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2597–2608, 2001     

The adhesion promotion mechanism of organofunctional silanes

The adhesion promotion mechanism of organofunctional silanes has historically been attributed to the formation of an “interpenetrating polymer network” between a polymerized silane film and the polymer. This notion was investigated by formulating and testing two hypotheses. First, if the adhesion promotion is due to the formation of an interpenetrating polymer network, variation in the time-temperature profile of the bonding conditions should alter the extent of interdiffusion and thus interfacial strength. Second, if the adhesion promotion is due to compatibility and penetration of the silane organofunctional group, not the bulk silane film, variation in the structure of that group should change interfacial strength. Direct interfacial strength measurements using single-particle composites show that variation in the time-temperature profile of bond formation does not significantly affect interfacial strength. However, use of a series of aminofunctional silanes (with constant C : N ratio and identical surface energetics) revealed a relationship between length of the aminofunctional group and interfacial strength. These results suggest that the adhesion promotion for the system studied is controlled by compatibility and penetration of the silane organofunctional group. Whereas all of the interfaces studied here featured poly(vinyl butyral), the conclusions should apply to all amorphous polymeric materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1025–1033, 1998     

Methods for improving the performance of silane coupling agents

The use of silane coupling agents in mineral- and glass-reinforced composites is well known. They impart improved initial mechanical properties, but, more importantly, they cause mechanical properties to be retained during the use of the composite. The main cause of loss of mechanical properties is attack of water at the interface. Recent research has focused on imparting more durable bonding of the silane coupling agent to both the polymer and the reinforcement. Improved silane coupling agent systems have been developed by utilizing several techniques: blends of hydrophobic silanes with hydrophilic silanes to give greater hydrophobic character; use of 1,2-bis-(trimethoxysilyl)ethane as an additive to give increased siloxane crosslinking; use of more thermally stable silanes such as phenyltrimethoxysilane and N-[2-(vinylbenzylamino)-ethyl]-3-aminopropyltrimethoxysilane to give increased thermal stability; and the use of a carboxy-functional silane with a carboxy-functional polymer and zinc salt to give ionomer bonds at the interface. The effectiveness of these new coupling agent systems was tested by measuring the flexural strength of composites and the adhesion strength of coatings on inorganic substrates. The results show that composites have increased flexural strength and better strength retention during thermal aging; coatings have greater adhesion strength; there is greater resistance of interfacial bonding to degradation by moisture; and thermoplastic composites have better properties after high shear processing.     

Mechanical and thermal properties of blends of low‐density polyethylene and ethylene vinyl acetate crosslinked by both dicumyl peroxide and ionizing radiation for wire and cable applications

Formulations of chemically crosslinked and radiation‐crosslinked low‐density polyethylene (LDPE) containing an intumescent flame retardant such as ammonium polyphosphate were prepared. The influence of blending LDPE with a poly(ethylene vinyl acetate) copolymer (EVA) and the effects of various coadditives, including polyethylene grafted with maleic anhydride (PEgMA), vinyl silane with boric acid, and talc, on the mechanical and thermal properties were investigated. Chemical crosslinking by dicumyl peroxide and crosslinking by ionizing radiation from an electron‐beam accelerator were both used and compared. Improved mechanical properties were observed by the partial replacement of LDPE with EVA. Similar mechanical or thermal properties were observed with coadditives such as PEgMA and vinyl silane with boric acid. The addition of a small amount of talc improved the tensile strength of the formulations. All crosslinked formulations showed good thermal stability on the basis of the retention of mechanical properties after thermal aging for 168 h at 135°C and a hot‐set test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical Properties of Benzoylated Oil Palm Empty Fruit Bunch Short Fiber Reinforced Poly(vinyl chloride) Composites

The influence of untreated and benzoylated oil palm empty fruit bunch (OPEFB) short fiber loading on the mechanical properties of the poly(vinyl chloride) (PVC) composite was studied. Benzoylated OPEFB was produced by mixing OPEFB with NaOH solution and agitating vigorously with benzoyl chloride. The PVC resin, various additives, and OPEFB were first dry blended using a laboratory mixer before being milled into sheets on a two-roll mill at 165°C and then hot pressed into composite samples at 180°C. The tensile and impact strength of untreated and benzoylated OPEFB composites decreased whereas the tensile modulus increased with increasing fiber loading from 0 to 40 phr. However, the benzoylated OPEFB was able to improve the tensile properties and impact strength of composites when compared to the untreated fiber. The enhancement of mechanical properties showed that the treatment improved the OPEFB fiber-PVC matrix interfacial adhesion. The improvement of adhesion was clarified by SEM micrographs, the increase of water resistance, and the reduction of glass transition temperature of the composites.