Hydrophobic or Hydrophilic Fumed Silica as Filler of Polyurethane Adhesives

Two hydrophilic and two hydrophobic fumed silicas of different characteristics were added to solvent-based polyurethane adhesives (PU). IR spectroscopy, contact angle measurements and rheology (viscosity measurements, determination of viscoelastic properties) were used to monitor the variation of properties of PU adhesives produced by addition of silica. Immediate (green) adhesion was determined by T-peel testing of halogenated synthetic rubber/PU adhesive/halogenated synthetic rubber joints. Silica addition produced a noticeable increase in the PU adhesive viscosity which can be related to the variation of viscoelastic properties. Viscosity of PU adhesives containing hydrophilic silica slightly increased with time after preparation; the increase was less significant in PU adhesives with hydrophilic silica. In the rheological studies, silica imparted shear thinning and negative thixotropy to PU adhesives due to a better dispersion of the silica in the polyurethane during shearing. The addition of silica produces an increase in the storage modulus (G') of PU adhesives, the values obtained being independent of the hydrophilic or hydrophobic nature of the fumed silica. The increase of G' and the changes in tan δ of PU adhesives containing silica corresponded to an improvement in the green adhesion properties of chlorinated rubber/PU adhesive/chlorinated rubber joints. In general, in disagreement with previous results,¹ the presence of silica did affect the properties of solvent-based PU adhesives, but these properties were not dependent on the type of silica (hydrophobic or hydrophilic) used in this study.     

硅溶胶改性紫外光固化环氧丙烯酸酯胶黏剂的研究

以正硅酸乙酯（TEOS）为无机前驱体,γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）为偶联剂,HCl为催化剂,采用溶胶-凝胶（Sol-Gel）法制得了硅溶胶,并以此硅溶胶对自制的紫外光固化环氧丙烯酸酯（EA）胶黏剂进行改性。通过傅立叶红外光谱（FT-IR）表征了EA的结构,通过热分析以及力学性能测试表征了此复合胶黏剂的热性能以及力学性能。结果表明：硅溶胶的加入显著地提高了环氧丙烯酸酯胶黏剂的耐高低温性能以及热稳定性,当硅溶胶的固体质量为体系总质量的40%时,复合胶黏剂在-196℃、室温、100℃的拉伸剪切强度分别提高了600%、320%、400%;热分解温度提高了50℃。     

F-992抗蠕变光学结构胶

以改性环氧树脂为主粘料,用反应性端羧基丁腈橡胶（CTBN）为增韧剂,与改性多元胺端氨基聚醚固化剂配制成具有较高交联密度的光学结构胶。因较高的交联密度和使用耐热改性剂,提高了耐热性;CTBN与环氧树脂进行预反应,并加入气相法白炭黑,提高了胶液的贮存稳定性和粘接强度。制备的光学结构胶拉伸剪切强度15．7MPa,压缩剪切强度25．4MPa,常温条件下蠕变值小于2英寸,表现出良好的粘接强度和耐热、耐冲击振动及抗蠕变性。     

Comparison of the Properties of Polyurethane Adhesives Containing Fumed Silica or Sepiolite as Filler

Fumed silica is a well-known mineral filler of epoxy and polyurethane adhesives. Although effective, the small particle size and the relative high cost of fumed silicas suggest the need for an alternative filler. In this study, the usefulness of adding a natural hydrated magnesium silicate (sepiolite) as a new filler in solvent-based polyurethane (PU) adhesive formulations has been demonstrated. The rheological and adhesion performance of the sepiolite-filled PU adhesive was compared with that in PU adhesives containing fumed silicas. The addition of a filler to PU adhesives provided an increase in viscosity, imparted thixotropy and pseudoplasticity to the adhesive solution, produced an increase in storage and loss moduli, and improved the rheology of the PU. The mechanical properties of adhesive films were increased by adding filler, mainly with fumed silica. On the other hand, the immediate T-peel strength of roughened or (roughened + chlorinated) styrene-butadiene rubber/PU adhesive joints was greatly improved in filled PU adhesives. The effects produced by adding sepiolite or fumed silica to the adhesives were very similar, although in general more noticeable in fumed silica filled PU due to the formation of hydrogen bonds between the filler and the solvent and/or the polyurethane (in sepiolite-filled adhesives, van der Waals forces seemed to be responsible for the interactions between the filler and the solvent and/or polyurethane).     

缩合型RTV有机硅胶粘剂的补强及老化研究

烟气道用胶粘剂对耐酸性、耐热性和阻燃性有严格的要求。考查了经酸和热老化后,无机阻燃剂Al(OH)3、气相SiO2和沉淀法SiO2对室温固化(RTV)有机硅胶粘剂力学性能的影响。结果表明,加入这3种填料的胶粘剂的力学性能均有大幅度提高;经10%的硫酸老化5d后,胶粘剂的强度有明显下降,而经180℃老化24h后,胶粘剂的强度有所增大;胶粘剂老化后的断裂伸长率均大幅降低。     

Studies on the adhesion behavior of water-based adhesives blended with asan gum

The influence of asan gum, a locally available waste material obtained from the Terminalia alata tree, in blends with waterborne natural rubber adhesive and poly(vinyl acetate), on the lap shear strength and the peel strength has been investigated. Both the strength values increase, even with a small quantity of the gum. At a higher gum content, both these parameters, however, decrease. Fourier Transform Infrared studies reveal that there is no covalent bonding between the gum and the adhesives, although some hydrogen bonding exists in the poly(vinyl acetate) blend. Morphological studies reveal mechanical interlocking of the adhesive in the substrates. The pseudoplastic nature of the gum-modified waterborne adhesives has been confirmed from rheological studies using a Brookfield viscometer. The higher lap shear and peel strength values of the gum-modified adhesives compared to the control adhesives are attributed to the higher shear modulus of the former. The 100% modulus and tensile strength of the adhesives blended with the gum are also higher, compared to their controls.     

Effect of using sepiolite silicate + fumed silica mixtures as fillers on the characteristics of solvent-based polyurethane adhesives

Abstract —Both fumed silica and sepiolite have been used as a filler of polyurethane (PU) adhesives. Although effective, the small particle size and the relative high cost of fumed silica are limitations in some applications. Sepiolite is cheaper than fumed silica, but its relatively large particle size facilitates its settling from the adhesive solutions. In this study, the usefulness of using sepiolite + fumed silica mixtures as a filler in solvent-based PU adhesives is demonstrated. The rheological and adhesion properties of the PU adhesive solutions and the rheological and mechanical properties of the PU films (without solvent) were studied. SEM micrographs of PU films showed the morphology and compatibility of the fillers with the PU matrix. The use of sepiolite + fumed silica mixtures inhibited the settlement of the filler from the PU adhesive solutions, increased both the storage and the loss moduli, and improved the rheological and mechanical properties of the PU. On the other hand, the green (immediate) T-peel strengths of roughened styrene-butadiene rubber/PU adhesive joints and plasticized PVC/PU adhesive joints were greatly improved in filled PU adhesives. The effects produced by using fumed silica alone or sepiolite + fumed silica mixtures were very similar, although in general, somewhat more marked in fumed silica-filled PU.     

Synthesis of Kenyaite, Magadiite and Octosilicate Using Poly(ethylene glycol) as a Template

Three types of layered silicates, namely octosilicate, magadiite and kenyaite, were synthesized using poly(ethylene glycol) (PEG). The influence of reaction parameters, including alkali source, silica source, PEG molecular weight, reaction time and temperature, on the formation of these three phases was investigated. The results indicate that magadiite is preferred when (i) using NaOH as the alkali source and at a lower temperature (150°C), with fumed silica, tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), Ludox-AS 40 or colloidal sol acting as the silica source in the presence of PEG 200; (ii) using fumed silica as the silica source and PEG 300 as the template at 150°C; (iii) at a higher temperature (180°C), using PEG 200 as template and TEOS as the silica source; and (iv) at 180°C with a combination of PEG 300 and fumed silica. Compared to magadiite, kenyaite was favored at a higher temperature (180°C) with PEG 200 and NaOH, KOH or RbOH, while using fumed silica, silica gel, or colloidal sol as silica source; or at the lower temperature (150°C) using NaOH as alkali source, PEG 200 as template, and silica gel or silicic acid as the silica source. Octosilicate was obtained at 90°C with the combination of NaOH, PEG 200 and fumed silica.     

Viscosity and shear strength of natural‐rubber‐based adhesives in the presence of gum rosin and petroresin

The viscosity and shear strength of pressure‐sensitive adhesives based on natural rubber (standard Malaysian rubber grade L) were studied with gum rosin and petroresin as the tackifying resins. Effects of the concentration of the tackifying resin and the molecular weight of rubber on the two properties were systematically investigated. Toluene was used as the solvent throughout the study to prepare the adhesives. The viscosity and shear strength of the adhesives were determined with a rotary viscometer and a texture analyzer, respectively. For the shear test, a hand coater was used to coat the adhesives on the release paper substrate to provide coating thicknesses of 60 and 120 μm. The results indicated that the viscosity increased with the resin loading and molecular weight of rubber increasing. The viscosity of the adhesive prepared from petroresin had a higher value than that of the gum‐rosin‐based adhesive. The shear strength of the adhesives decreased gradually with increasing resin content for both tackifying resins and coating thicknesses, and this observation was attributed to the decrease in the cohesive strength due to the dilution effect of the resins. However, the shear strength passed through a maximum at a molecular weight of rubber of 8.5 × 10⁴ for both resins. The gum‐rosin‐based adhesive consistently showed higher shear strength than that of the petroresin/natural rubber adhesive because of the better cohesiveness and compatibility of the former system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparative Properties of Hydrophilic and Hydrophobic Fumed Silica Filled Two-Component Polyurethane Adhesives

Two fumed silicas, one hydrophilic and another hydrophobic, were added to a two-component polyurethane (PU) adhesive and their properties compared. The filled polyurethanes were characterized by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and water and diiodomethane contact angle measurements. The adhesive strength was evaluated from single lap-shear tests of solvent wiped stainless steel/polyurethane adhesive joints. The fumed silicas were well-dispersed in the polyurethane matrix as bundles of nanometric spherical silica particles. However, some micron size agglomerates of fumed silica appeared in the filled polyurethane. The addition of fumed silica favoured the degree of phase separation between the hard and the soft segments in the polyurethane. The polyurethanes were not fully cured under the conditions used in this study and the addition of fumed silica inhibited the curing reaction; the extent of the curing reaction was not affected by the hydrophilic or hydrophobic nature of the fumed silica. The filled polyurethanes were further cured during DSC experiments and this was noticed by the appearance of the melting of the hard segments and the displacement of the second glass transition to a higher temperature. On the other hand, the addition of fumed silica increased the wettability and the surface energy of the polyurethane; this increase was mainly due to an increase in the polar component of the surface energy. The increase in surface energy is somewhat more marked in the case of the hydrophilic silica filled polyurethane, indicating that the polarity of the fumed silica affected the surface properties of the polyurethane. Finally, the addition of the hydrophilic fumed silica increased the adhesion of the filled polyurethane adhesive to stainless steel which was in agreement with the higher surface energy of the hydrophilic fumed silica filled polyurethane.     

木材加工用水性聚氨酯胶粘剂的研究

为了获得稳定性较好的水性聚氨酯(WPU)胶粘剂,以丙酮为溶剂、聚醚(N210)为软段、二苯基甲烷-4,4′-二异氰酸酯(MDI)为硬段、二羟甲基丙酸(DMPA)为亲水性扩链剂、三乙胺(TEA)为成盐剂和聚乙烯醇(PVA)为增稠剂等,制备了环保型木材粘接用WPU胶粘剂。研究了MDI、N210、DMPA、TEA和PVA用量等对乳液稳定性、胶粘剂剪切强度及黏度的影响。结果表明:当n(MDI)∶n(N210)∶n(DMPA)∶n(TEA)=2.4∶1∶0.8∶0.64、w(PVA)=2.0%～3.0%时,可制得常温(20～30℃)存放90 d以上、剪切强度超过4.2 MPa的稳定WPU胶粘剂。     

Anionomeric waterborne poly(urethane semicarbazide) dispersions and their adhesive properties

Aqueous polyurethane dispersions were prepared from isocyanate‐terminated ionic polyurethane prepolymers by chain extension with dihydrazides. These water‐borne dispersions had excellent adhesive properties and were used to bond leather and canvas. The base polymers were varied with respect to (1) the ionic content with the same chain extender and (2) the nature of the chain extender with the ionic content kept constant. Studies on the particle size and viscosity revealed that the ionic content had an influence on the aforementioned properties: the particle size decreased and the viscosity increased with increasing ionic content. The polarity of the films cast from the dispersions were determined with contact‐angle measurements: hydrophilic character was exhibited by all the compositions. X‐ray studies revealed that the increase in the ionic content led to increasing intensities of the diffraction peaks due to increased secondary forces of bonding. The tensile strength measurements showed that the films were highly elastomeric and had good mechanical strength, which varied with the composition. A shear strength and peel strength analysis of specimens obtained through the bonding of leather to leather, leather to canvas, and canvas to canvas revealed that the waterborne dispersions were excellent adhesives for bonding leather surfaces. Thus, a very efficient, ecofriendly waterborne dispersion of polyurethane that could find applications in bonding leather in the footwear industry was prepared successfully. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheology and curing kinetics of fumed silica/cyanate ester nanocomposites

A low‐viscosity bisphenol E cyanate ester (BECy) monomer was combined with fumed silica with average primary particle diameters of 12 and 40 nm to form high‐temperature adhesives with processability at ambient temperatures. Rheological evaluation revealed that for silica loadings below 15 vol%, suspensions of both particle sizes exhibited shear thinning and thixotropic behavior. Samples with high silica loadings (>15 vol%) of 40‐nm silica also showed intense shear thickening at shear rates above 10 s^?1. Thixotropy was most pronounced for the 12‐nm silica, but the formation of a gel was slow, indicating that the polar nature of the BECy monomer was responsible for disrupting hydrogen bonds between silica particles. Rheokinetic evaluation of catalyzed samples showed that increasing silica content reduced gel time and increased gel viscosity, and this effect was most pronounced for the 12‐nm silica. Differential scanning calorimetry confirmed that the silica's hydroxyl groups have a minor catalytic effect on the polymerization kinetics, such that the activation energies of the catalyzed suspensions were decreased with increased nanoparticle loading and decreased particle size. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

水性环氧树脂包覆有机蒙脱土制备木材胶粘剂

摘要：水性环氧树脂通常含有水溶性分子或分子链，导致在高温和潮湿条件下作为木材胶粘剂时耐水性及力学性能较差。采用有机改性的纳米蒙脱土改性水性环氧树脂增强水性环氧树脂胶粘剂的耐水性及力学性能。并通过乳液包覆蒙脱土的方法与直接共混的方法对比，研究了不同添加量有机蒙脱土（0%，3%，6%，9%）对胶粘剂性能的影响。胶粘剂的耐水性及力学性能通过测量胶粘剂在干燥及潮湿条件下的剪切强度来表示。通过TGA、SEM、TEM、DSC研究了复合胶粘剂的热稳定性和结构。结果表明，在水性环氧树脂中添加有机改性的纳米蒙脱土，可以有效地提高胶粘剂的粘结强度，此外，采用乳液包有机覆蒙脱土的方法比直接共混的方法制备得到胶粘剂，有机蒙脱土在胶粘剂中分布更均匀，具有更优异的力学性能，说明有机蒙脱土在复合材料中的分散质量是影响复合胶粘剂性能的主要原因。     

Fabrication and Pore Size Control of Large-Pore Mesoporous Silica Particles through a Solvent Evaporation Process

Large-pore mesoporous silica particles were synthesized through a solvent evaporation process using hydrophobic fumed silica particles and tetraethyl orthosilicate (TEOS) as silica sources. The solvent evaporation of an ethanol solution of fumed silica particles, TEOS, HCl and triblock copolymer (F127) resulted in mesoporous silica particles with pores with sizes of about 7 nm. In addition, the interplanar spacing of the mesoporous silica particles can be controlled by changing the solvent evaporation temperatures.     

水性聚氨酯压敏胶的合成及其性能表征

以异佛尔酮二异氰酸酯(IPDI)、聚醚多元醇(N220、N210)、二羟甲基丙酸(DMPA)和三羟甲基丙烷(TMP)为主要原料制得了环保交联型水性聚氨酯(WPU)压敏胶,讨论了n(-NCO)/n(-OH)比值、交联剂用量以及聚醚相对分子质量大小对该压敏胶性能的影响。研究结果表明,由N220合成的WPU压敏胶的初粘力优于由N210合成的WPU压敏胶;随着n(-NCO)/n(聚醚中-OH)比值的减小,压敏胶的初粘力提高,持粘力呈先降后增再降的趋势;适度的交联可以提高压敏胶的粘接强度;当n(-NCO)∶n(聚醚中-OH)为2.5∶1、n(TMP中-OH)∶n(聚醚中-OH)为1∶3.0时,压敏胶的综合性能优异,初粘力达到13号钢球,持粘力达到23.1h,180°剥离强度达到20.14N/(20mm)。     

Effect of loading chemically and mechanically pre-treated fumed silica as filler on an etch & rinse model dental adhesive

Fumed silica is one of the most commonly used fillers for dental resin adhesives. However, fumed silica produced by flame hydrolysis of chlorosilanes are typically agglomerated aggregates instead of isolated primary particles. The fumed silica aggregates may affect the dispersion of fillers in the resin matrix, thus affect the bonding performance of the dental adhesives. In this study, fumed silica fillers chemically treated with methacrylsilane were loaded into an etch & rinse model dental adhesive. Filler 1 was only chemically pre-treated, while Filler 2 was combined chemically and mechanically pre-treated to break the agglomerated aggregates. The experiment result indicated that Filler 1 has faster rheology control effect than Filler 2 on the handling property of the filled resin adhesive showing as the rapid increased viscosity, which may due to the fast inorganic phase growing in the Filler 1 filled resin matrix. As for the mechanical properties, neither Filler 1 nor Filler 2 has an positive effect on the micro-tensile bond strength in short term and long term, despite of the fact that lower weight percent of Filler 2 loading is favourable to the penetration of the experimental adhesive into dentin substrate. In conclusion, mechanically pre-treatment to break the agglomerated fumed silica is helpful to increase the limit of filler loading percent while maintaining appropriate handling property, but the chemically and mechanically pre-treatment cannot provide positive effect on bonding performance within the range of this study.     

Mechanical properties of adhesively single lap-bonded joints reinforced with multi-‌‌‌walled carbon nanotubes and silica nanoparticles

This paper aims to investigate the effect of adding nanoparticles to the adhesive layer on the shear strength and elongation at failure of adhesively bonded single lap joints (SLJs). Two different toughening particles including the silica nanoparticles (SNPs) and the multi-walled carbon nanotubes (MWCNTs) were considered for reinforcing the adhesive joints. The experimental results showed that the highest improvements in the SLJ shear strength and elongation at failure were obtained for 0.2 and 0.8 wt% of MWCNTs and SNPs, respectively. The fractography results indicated that adding nanoparticles improved the failure mode from adhesive to dominant cohesive representing improved adhesion between the adhesive and adherends. Moreover, different damage mechanisms were observed for the adhesives reinforced with different toughening particles. Several mechanisms including crack growth deviation, shear yielding, plastic deformation, and pull out phenomena were observed from scanning electron microscope (SEM) fractography of the fracture surfaces of the joints reinforced by MWCNTs. While in the case of reinforcing by SNPs, the shear yielding, the particle debonding, and subsequent void growth were found as the effective energy absorbing mechanisms.     

聚氨酯胶粘剂的研究进展

综述了聚氨酯胶粘剂的合成、特性和种类。概述了近年来国内外聚氨酯胶粘剂的研究和应用进展,重点介绍了聚氨酯胶粘剂的发展动态和几类主要的聚氨酯胶粘剂,并对其进行了分析,结合实际情况对今后聚氨酯胶粘剂的发展方向作出了展望。     

Preparation and Properties of a Waterborne Contact Adhesive Based on Polychloroprene Latex and Styrene-Acrylate Emulsion Blend

Environmental protection and legislative pressure to eliminate the use of solvents in the adhesive industry have inspired the search for safer alternatives. In the area of contact adhesives, the waterborne route has proved to be of particular interest. Based on the synergistic effect of polychloroprene latex and styreneacrylate emulsion, a waterborne contact adhesive consisting of polychloroprene latex (PCL) and styreneacrylate emulsion (SAE) blend has been developed. In order to blend PCL with SAE easily and to accelerate the drying rate of the adhesive, boric acid was chosen for use in the PCL/SAE blend system. Effects of boric acid and SAE content on the properties of PCL/SAE blends, such as pH value, storage stability and set time, were investigated. At the same time, the effect of SAE content on the mechanical properties of PCL/SAE blend films was studied. The morphology of blend films was characterized by Atomic Force Microscopy. The adhesive performance of the waterborne contact adhesive was evaluated by peel and shear tests. The results showed that when the waterborne contact adhesive formulation contained 40 wt% styrene-acrylate emulsion (dry weight) and 1.25 wt% boric acid, it had a good shelf-stability, its set time was 5 min, and the blend film with this formulation was ductile and flexible with reasonably good tensile strength and very high elongation at break. And the blend films showed structure with a sea–island morphology. The waterborne contact adhesives derived from PCL/SAE blends were found to be comparable to the commercially available solvent-based contact adhesives. The synergistic effect of polychloroprene latex and styrene-acrylate copolymer emulsion was also discussed.