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1.
Adhesion of a polystyrene coating to solvent cleaned steel is increased two-fold by addition of 0.5% wt/wt of aminosilane (A1120). A study has been carried out on the coating-substrate interfacial chemistry to gain an understanding of the mechanism of adhesion promotion. It is shown that in peel experiments the coating fails adhesively between the polystyrene and an adsorbed layer of aminosilane on the steel surface. The improvement in adhesion results from displacement by the silane of the 1.4 nm thick layer of residual carbonaceous contamination on the steel surface. It is proposed that this leads to a stronger substrate-coating interaction either through improved intermolecular contact between the segregated silane and the polymer or through secondary bonding between the amine groups of the silane and the polarisable aromatic rings of the polystyrene.  相似文献   

2.
We show that the pH of the aminosilane solution has a significant effect on its efficacy as an adhesion promoter. Furthermore, the maximum adhesion is observed to be in the pH range close to the natural pH of the dilute silane solution. It would be interesting to extend this kind of study to other silanes as well as to various coating materials.  相似文献   

3.
The Cr2O3 nanoparticles were modified with 3-amino propyl trimethoxy silane in order to obtain proper dispersion and increment compatibility with the polyurethane coating matrix. The nanocomposites prepared were applied on the St-37 steel substrates. The existence of 3-amino propyl trimethoxy silane on the surface of the nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA). Dispersion of the surface modified particles in the polyurethane coating matrix was studied by a field emission-scanning electron microscope (FE-SEM). The electrochemical impedance spectroscopy (EIS) and salt spray tests were employed in order to evaluate the corrosion resistance of the polyurethane coatings. Polarization test was done in order to investigate the corrosion inhibition properties of the Cr2O3 nanoparticle on the steel surface in 3.5 wt.% NaCl solution. The adhesion strengths of the coatings were evaluated by pull-off adhesion tester before and after 120 days immersion in 3.5 wt.% NaCl solution. FT-IR and TGA analyses revealed that surface modification of the nanoparticles with 0.43 silane/5 g pigment resulted in the greatest amount of silane grafting on the surface of particles. Results obtained from FE-SEM analysis showed that the surface modified nanoparticles dispersed in the coating matrix properly. Results obtained from EIS and salt spray analyses revealed that the surface modified particles enhanced the corrosion protection performance of the polyurethane coating considerably. The improvement was more pronounced for the coating reinforced with 0.43 g silane/5 g pigment. Moreover, the adhesion loss decreased in the presence of surface modified nanoparticles with 0.43 silane/5 g pigment.  相似文献   

4.
Sugar cane bagasse fibers were modified by surface treatments using either physical or chemical methods in order to improve their adhesion to polystyrene matrices. The surface treatment methods used were alkaline treatment, treatment with silane coupling agents, physical coating with polystyrene and grafting of polystyrene with and without crosslinker. Fiber modifications were monitored by Fourier Transform Infrared Spectroscopy (FTIR), Differential Thermal Analysis coupled with Thermogravimetric Analysis (DTA-TGA) and Scanning Electron Microscopy (SEM). On the other hand, the improvement of the adhesion between sugar cane modified fibers and polystyrene was assessed by micromechanical pull-out and by macromechanical Iosipescu tests. It was found, from Interfacial Shear Strength values (IFSS), that substantial improvements in fiber-matrix compatibility were achieved. According to micro- and macromechanical test results, the IFSS increased for all treated fibers as compared to non-treated fibers. Particularly, both the coating the fibers or grafting with polystyrene using crosslinker resulted in substantial adhesion improvement to the polystyrene matrix in comparison with the non-treated fibers and fibers treated by alkaline and silane methods only. Polym. Compos. 25:134–145, 2004. © 2004 Society of Plastics Engineers.  相似文献   

5.
Interactions occurring at the interface between injection-molded poly (vinyl chloride) (PVC) and steel substrates that were coated with thin films of aminosilanes were investigated by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). The silane films were formed by adsorption of γ-aminopropyltriethoxysilane (γ-APS) or N-(2-aminoethyl-3-aminopropyl)trimethoxysilane (γ-AEAPS) from 2% aqueous solutions onto polished steel substrates. PVC was injection molded onto the silane-primed steel substrates and annealed at temperatures up to 170°C for times as long as 30 min. PVC was peeled off of the primed steel substrates using a 90° peel test and the substrate failure surfaces were thoroughly rinsed with tetrahydrofuran (THF) and distilled water to remove PVC and other compounds that were not strongly bonded to the substrates. The PVC failure surfaces were characterized by attenuated total reflection infrared spectroscopy (ATR) and PVC rinsed off of the substrate failure surfaces was characterized by transmission infrared spectroscopy. The resulting transmission and ATR spectra showed an absorption band near 1650 cm-1 that was attributed to unsaturation in PVC. The substrate failure surfaces were characterized by XPS; curve-fitting of N(1s) and Cl(2p) high-resolution spectra showed the formation of amine hydrochloride complexes by protonation of amino groups of the silanes with HCl that was liberated from PVC during the onset of thermal dehydrochlorination. Furthermore, quaternization or nucleophilic substitution of labile pendent allylic chloride groups by amino groups on the silanes took place, thus grafting PVC onto the aminosilanes. It was determined that PVC that had β-chloroallyl groupings along its chains showed better adhesion with steel primed with aminosilanes and that generation of allylic chloride groups in PVC chains was the rate-limiting step in the reaction between PVC and aminosilane. Moreover, the effect of crosslinking of silane films on adhesion between PVC and aminosilane primed steel was investigated and it was concluded that interdiffusion of the polymer phase and the silane phase was also critical in obtaining good adhesion.  相似文献   

6.
Interactions occurring at the interface between injection-molded poly (vinyl chloride) (PVC) and steel substrates that were coated with thin films of aminosilanes were investigated by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). The silane films were formed by adsorption of γ-aminopropyltriethoxysilane (γ-APS) or N-(2-aminoethyl-3-aminopropyl)trimethoxysilane (γ-AEAPS) from 2% aqueous solutions onto polished steel substrates. PVC was injection molded onto the silane-primed steel substrates and annealed at temperatures up to 170°C for times as long as 30 min. PVC was peeled off of the primed steel substrates using a 90° peel test and the substrate failure surfaces were thoroughly rinsed with tetrahydrofuran (THF) and distilled water to remove PVC and other compounds that were not strongly bonded to the substrates. The PVC failure surfaces were characterized by attenuated total reflection infrared spectroscopy (ATR) and PVC rinsed off of the substrate failure surfaces was characterized by transmission infrared spectroscopy. The resulting transmission and ATR spectra showed an absorption band near 1650 cm?1 that was attributed to unsaturation in PVC. The substrate failure surfaces were characterized by XPS; curve-fitting of N(1s) and Cl(2p) high-resolution spectra showed the formation of amine hydrochloride complexes by protonation of amino groups of the silanes with HCl that was liberated from PVC during the onset of thermal dehydrochlorination. Furthermore, quaternization or nucleophilic substitution of labile pendent allylic chloride groups by amino groups on the silanes took place, thus grafting PVC onto the aminosilanes. It was determined that PVC that had β-chloroallyl groupings along its chains showed better adhesion with steel primed with aminosilanes and that generation of allylic chloride groups in PVC chains was the rate-limiting step in the reaction between PVC and aminosilane. Moreover, the effect of crosslinking of silane films on adhesion between PVC and aminosilane primed steel was investigated and it was concluded that interdiffusion of the polymer phase and the silane phase was also critical in obtaining good adhesion.  相似文献   

7.
《Progress in Organic Coatings》2013,76(12):1765-1772
Three layers polyolefin coatings are widely used in Europe to protect pipelines against corrosion. Loss of adhesion at a fusion bonded epoxy (FBE)/steel interface has occasionally been observed even on pipelines without external defects. Silane-based surface pre-treatments are developed to improve adhesion with limited impact on the environment unlike usual chromate conversion pre-treatments; however the mechanisms involved in silane action need to be more deeply understood. The application process of silane surface treatment implies a series of key parameters of which optimization is imperative to form a silane layer with good properties at the interface. This paper studies the influence of the cure temperature and the pH of an aminosilane based pre-treatment on adhesion strength and durability via single lap shear tests. SEM/EDX, FT-IR and XPS analyses are used to characterize the silane and silane/epoxy structures. Silane pretreatment improved the FBE joints durability and appears as a relevant solution to replace the usual chromate conversion pretreatments. The joints pretreated at pH 10.6 had better durability than at pH 4.6. This was related to the formation of a bridge across the silane/epoxy interface at pH 10.6, whereas, at pH 4.6, formic acid reacts with amino groups of silanes, limiting the reaction between amino groups and epoxy.  相似文献   

8.
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.  相似文献   

9.
Filled polymer composites have been prepared in which the energetics of the filler surfaces was systematically varied in order to investigate the dependence of the mechanical properties of the composite on the interfacial strength as predicted by the thermodynamic work of adhesion at the filler-matrix interface. A high-purity silica filler was used, treated with three different organofunctional silane coupling agents (two alkylsilanes and an aminosilane) to varying degrees from zero to complete coverage. The surface energetics of the modified fillers was characterized using both inverse gas chromatography (IGC) and dynamic contact angle analysis (DCA). While the surface energy assessments from IGC were higher than those obtained with wetting measurements, as expected, the trends with fractional coverage of silane were the same for each method, and were used to evaluate the thermodynamic work of adhesion. Highly filled polymer composites were prepared by dispersing the variously treated silica fillers into the amorphous thermoplastic matrix polymers: poly(methyl methacrylate) and poly(vinyl butyral). Specimens of the composites were tested mechanically to give the yield stress. The poly(methyl methacrylate) composites all failed cohesively in the matrix, unaffected by any of the filler surface treatments. The poly(vinyl butyral) composites, however, all displayed purely interfacial failure, with the yield stress strongly dependent on the type and extent of the filler surface treatment. While all three silanes were found to decrease the filler surface energy, and consequently the thermodynamic work of adhesion, with higher surface coverage, corresponding decreases in the yield stress were found only for the alkylsilanes. For the aminosilane, the measured yield stress was found to increase with surface coverage and therefore to decrease with the work of adhesion. The difference in behavior between the two types of coupling agent is explained in terms of acid-base effects.  相似文献   

10.
Single crystals of ferromagnetic Ni–Mn–Ga shape memory alloys show magnetic-field and stress induced twinning, leading to shape memory. Adaptive composites can thus be produced by embedding single crystalline particles or bamboo-structured Ni–Mn–Ga fibres into a polymer matrix. To guarantee a durable performance of these composites, adhesion between reinforcement phase and matrix should be quantified and optimised. The influence of annealing and surface treatment with an aminosilane of melt-spun Ni–Mn–Ga fibres on their strength and adhesion to an epoxy matrix was investigated using single fibre tension and fragmentation tests. Annealing of the melt-spun Ni–Mn–Ga fibres changed the surface from a “pimpled” to a smooth microstructure. This resulted in a reduced adhesion of the annealed fibres in comparison to the as-spun fibres embedded in an epoxy matrix. As-spun fibres exhibited an interfacial shear strength (IFSS) comparable to the shear strength of the epoxy matrix so that the silylation did not change the adhesion significantly. For the annealed fibres, the silane treatment improved the IFSS by 67%. Furthermore, the silylation increased the fracture strength of the Ni–Mn–Ga fibres due to surface flaw healing or forming of a protective surface coating.  相似文献   

11.
The practical adhesion of maleic anhydride grafted polyethylene (MAH-PE) to galvanised steel was studied using 3-point flexure tests, before and after hydrothermal ageing. Before bonding, the electro-galvanised steel was treated with γ-aminopropyltriethoxysilane (γ-APS). The influence of the silane coating thickness and deposition pH on the practical adhesion of MAH-PE to steel was investigated. FT-IR spectroscopy and microscopy enabled to gain understanding of the interphase formation between the silane and the metal substrate. It was found that, at the natural pH of the γ-APS, Zn ions dissolved in the silane coating with subsequent formation of crystals. This interphase could be held responsible for the better durability of the bonds than for silane coatings applied at quasi-neutral pH, for which dissolution of Zn ions was not observed.  相似文献   

12.
The effect of aminosilane on the properties of rice straw fiber (RSF) reinforced poly(butylene succinate) (PBS) composites was studied. RSF was pretreated with four different aminosilane coupling agents, 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMES), 3-(2-aminoethylaminopropyl)triethoxysilane (AEAPTES), and 3-(2-aminoethylaminopropyl)-trimethoxysilane (AEAPTMES). The results of Fourier transform infrared spectroscopy (FTIR) and ζ potential measurements confirmed that amino groups were introduced to the silane-treated RSF (TRSF) for all four silane coupling agents. The results also indicated a higher degree of hydroxyl ion adsorption by the fiber surface, which was chemically grafted by silane hydroxyl, was obtained with ethoxy silane than with methoxy silane. This difference might be because the relative rates of hydrolysis and ensuing silanol self-condensation of methoxy silane were too fast to reduce the number of silanol groups grafted on the fiber surface. The TRSF composite produced clearly enhanced tensile properties for the aminosilane coupling agents having ethoxy groups. The AEAPTES-RSF-PBS composite showed the highest tensile strength. It might be because of the higher amino content of AEAPTES than APTES; the amino groups on the surface of TRSF were confirmed by FT-IR to react with the carbonyl groups of PBS to form a blue-shifted hydrogen bond. The water absorption process of composites was found to follow the kinetics and mechanisms described by Fick's theory. The aminosilane treatment significantly reduced the moisture diffusion coefficient but did not change the mechanism of water adsorption. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

13.
Polymer–metal hybrids are replacing steel structures in many applications. Combining metals and plastics is, however, complicated because they have very different physical and chemical characteristics. This study characterizes plastic–metal adhesion in insert-injection-molded hybrids. Diaminofunctional silane was used as a coupling agent between thermoplastic urethane and stainless steel. Before silane treatment, various surface treatments, including electrolytic polishing and different oxidation treatments, were applied to the steel inserts to understand better the bonding between silane and steel. The effects of the surface treatments and silane application on plastic–metal adhesion were studied by means of contact angle measurements, adhesion tests, and microscopic characterizations. Electrolytic polishing and oxidation of the steel inserts significantly improved the silane bonding to the steel insert, and consequently the plastic adhesion to steel.  相似文献   

14.
New experimental results are described from Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and Atomic Force Microscopy (AFM) on the molecular orientation, chemical composition, and topography of PMDA/ODA Polyimide (PI) deposited by the Langmuir-Blodgett (LB) technique onto Si (100) surfaces covered with a native oxide (SiOx) and onto SiOx substrates pre-treated with a variety of alkylsilanes. The alkylsilane monolayers used as adhesion promoters were found to be chemically and structurally stable during temperature treatments used to imidize the polymer precursor films. On both the oxidized silicon surface and on the silane-treated surfaces, we find a thickness-dependent, preferential orientation of the pyromellitimide unit in PI, but randomly-oriented oxydianiline fragments. We can not identify any specific chemical bonds between the polymer and the aminosilane film or, in the case of the untreated surface, the SiOx substrate. However, a quantitative analysis of the NEXAFS data reveals a pronounced deficit in oxydianiline in the monolayer (ML) films, which decreases with film thickness, and a higher degree of imidization on the 3-aminopropyltrimethoxysilane (APS) surface indicating that imide linkages are formed between the polymer and the aminosilane. The AFM images show a heterogeneous surface topography with nucleation of PI polycondensates on both the SiOx and aminosilane-treated surfaces. On the aminosilane surface additional nuclei are detected, believed to be polycondensates of aminosilane formed during imidization of the PI precursor. Nucleation of aminosilane polycondensates is not observed in the absence of polyamic acid. As suggested by a comparison of Lateral Force Microscopy (LFM) and Atomic Force Microscopy measurements, these aminosilane nuclei are covered by PI with increasing film thickness and, hence, provide mechanical connections between the polymer and substrate on a mesoscopic scale. Delamination experiments of 2 μm thick PI films spun onto ω-amino and methyl terminated alkylsilanes indicate that bond fracture always occurs in the aminosilane/PI and alkylsilane/PI and interphase. We conclude that the adhesion promotion effect of LB-deposited polyimide films by aminosilanes can be explained by chemical stabilization of the interface against decomposition and mechanical interlinking surface via polycondensates of aminosilane on a mesoscopic length scale. Our study is not conclusive as to whether covalent bonding of the polymer to the substrate via the silane is important for macroscopic adhesion.  相似文献   

15.
As an alternative process to phosphate and chromate conversion coatings, silane pretreatment was used to improve the performance of cathodic electrophoretic coating (E-coat) on AZ31 Mg alloy in this study. The galvanic corrosion behavior of AZ31 Mg alloy with E-coat coupled with Q235 steel was investigated. Compared to bare Mg alloy and Mg alloy with conventional painting, the corrosion properties of the AZ31 Mg alloy pretreated with silane and subsequently E-coated were studied during salt solution immersion and salt spray testing. The surface morphologies of the Mg alloy were examined in detail after immersion in NaCl solution for different times using digital photography and scanning electron microscopy (SEM). The corrosion current density of the specimens was characterized by DC polarization tests. It was found that silane pretreatment of AZ31 Mg alloy followed by subsequent E-coat led to much better corrosion protection than that without silane treatment. The silane pretreatment and E-coat delayed the galvanic corrosion of Mg alloy coupled with 235 steel bolts.  相似文献   

16.
In the recent years, silane materials, because of their environmental friendly nature and ease of application have been attended as an alternative for chromate conversion coatings. Different materials were searched for improvement of the efficiency of silane formulation. In this research, pretreatment of carbon steel substrates was carried out using γ-glycidoxypropyl-trimethoxysilane (γ-GPS) as functionalized silane. Cerium nitrate as a corrosion inhibitor material was introduced into the silane material and epoxy resin was applied on the pretreated steel substrates. Effects of the pretreatment on electrochemical properties, cathodic disbondment, dry and wet adhesion strength, and surface morphology of resultant epoxy coating were investigated. Results showed that pretreatment of steel substrate with γ-glycidoxypropyl-trimethoxysilane (γ-GPS) doped with cerium nitrate leads to improvement of cathodic disbondment and also dry and wet adhesion of epoxy coating. Furthermore, this type of pretreatment reduced the disruption of interfacial bonds at the binder/substrate interface. Addition of 2?wt% cerium nitrate into the silane formulation led to the maximum efficiency of resultant coating.  相似文献   

17.
One of the most important factors in corrosion prevention by protective coatings is the coating adhesion loss under environmental influence. Thus, adhesion strength is often used when characterizing protective properties of organic coatings on a metal substrate. In order to improve the adhesion of organic coating the metal substrate is often pretreated in some way. In this work, the adhesion of polyester coatings on differently pretreated aluminium surface (by anodizing, with and without sealing, by phosphating and by silane film deposition) was examined. The dry and wet adhesion of polyester coatings were measured by a direct pull-off standardized procedure, as well as indirectly by NMP test. It was shown that under dry test conditions all polyester coatings showed very good adhesion, but that aluminium surface pretreated by silane film showed superior adhesion. The overall increase of wet adhesion for polyester coating on aluminium pretreated by silane film was maintained throughout the whole investigated time period. The different trends in the change of adhesion of polyester coatings were observed for different aluminium pretreatments during exposure to the corrosive agent (3% NaCl solution). The highest adhesion reduction was obtained for polyester coating on aluminium pretreated with phosphate coating. The corrosion stability of polyester coated aluminium was investigated by electrochemical impedance spectroscopy in 3% NaCl solution. The results confirmed good protective properties of polyester coating on aluminium pretreated with silane film, i.e. greater values of pore resistance and smaller values of coating capacitance were obtained in respect to other protective systems, whereas charge-transfer resistance and double-layer capacitance were not measurable during 2 months of exposure to a corrosive agent.  相似文献   

18.
When a thermoplastic polyurethane elastomer (TPU) is co-molded with galvanized steel, the subsequent adhesion and its durability are very sensitive to the chemical bonds created at the interface. Silane coupling primers are known for enhancing adhesion between inorganic substrates and several polymers and this study addresses their efficiency at the TPU–metal interface. γ-APS aminosilane was deposited with different parameters, including pH and solvents. Several other surface treatments were studied for comparison: degreasing, corona discharge, acidic etching, gas flame, and a zinc phosphate conversion coating. The adhesion was characterized with a single wire pull-out test derived from the microbond test geometry, after different aging conditions. Results confirmed that γ-APS worked as a coupling agent in between TPU and the inorganic substrate, outperforming all other surface treatments tested in term of strength and durability, but the silane required the appropriate deposition parameters to be really efficient.In parallel, a finite element approach was proposed for the modeling of fiber reinforced thermoplastic elastomer composites accounting for the non-linear viscoelastic material properties and its results compared to an analytical elastic shear-lag interpretation of the single filament pull-out test. The analytic interpretation was found to be sufficiently accurate for stress analysis but not for fracture mechanics. The FEM analysis offered an evaluation of the internal stresses developed within the entire system, which helped the interpretation of results. The model, compared to experimental results, also revealed that it is important to account for internal stresses, mostly for treatments leading to low intrinsic interfacial shear strength values.  相似文献   

19.
硅烷偶联剂在环氧涂料中的应用   总被引:2,自引:0,他引:2  
本文对硅烷偶联剂的水解特性,以及对硅烷偶联剂直接添加到环氧涂料中形成的涂层与钢铁基材的附着力进行了研究。研究发现硅烷偶联剂水解能力很强且容易在涂层与基材之间形成化学键作用;将硅烷偶联剂直接添加到环氧涂料中能够显著地提高涂层对钢铁基材的附着力。  相似文献   

20.
An underfill is used to fill the gap between the integrated circuit chip and substrate to improve the solder joint fatigue life in flip-chip packaging. The influence of aging in an environment with a high temperature and a high humidity on the adhesion performance of an underfill material (epoxy cured with acid anhydride) to the passivation layer in flip-chip packaging is discussed. Adhesion of the underfill to all passivation materials investigated degrades after aging in a high temperature and high humidity environment. The extent of this degradation is dependent on the hydrophilicity of the passivation layer surface. Hydrophilic passivation layer surfaces, such as silicon dioxide (SiO2) and silicon nitride (Si3N4), show much more severe adhesion degradation than hydrophobic passivation layer surfaces, such as benzocyclobutene (BCB) and polyimide (PI). The mobility of both the absorbed water and polymer chains is studied with solid state nuclear magnetic resonance (NMR) spectroscopy. Higher mobility of both the absorbed water and polymer chains in the rubbery state of polymers contributes to faster adhesion degradation during high temperature and high humidity aging. The adhesion stability of hydrophilic passivation layers can be successfully improved by use of a silane coupling agent that introduces a stable chemical bond at the interface. A flow micro-calorimeter is used to study the adsorption of silane coupling agents onto glass surface. The difference in adhesion retention improvement between aminosilane and epoxysilane is discussed.  相似文献   

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