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.     

耐酸碱聚氨酯弹性体胶辊的研制

以端羟基聚丁二烯(HTPB)和聚四亚甲基醚二醇(PTMEG)为软段,2,4-甲苯二异氰酸酯(TDI-100)和3,3′-二氯-4,4′-二氨基二苯基甲烷(MOCA)为硬段,采用预聚体法制备了聚氨酯弹性体,讨论了不同软段比例对弹性体力学性能、耐酸碱性能及加工性能的影响。结果表明,软段中HTPB与PTMEG质量比为50∶50时,弹性体的综合性能较好,适合做耐酸碱胶辊的包覆胶。     

EFFECT OF A REACTIVE INTERFACIAL AGENT ON THE PROPERTIES OF A NITRILE-RUBBER-MODIFIED EPOXY FILM ADHESIVE

Reactive interfacial agents are often used to homogenise the morphology of immiscible polymer blends and to improve the level of adhesion between the phases to achieve enhanced properties. This paper demonstrates the ability of hydroxyl methyl bisphenol A (HMBPA) to function as a reactive interfacial agent (compartibilizer) in a nitrile-epoxy film adhesive made from nitrile rubber (NBR) and solid epoxy resin blend. The curing of the adhesive film was achieved at 170° C by adding dicyandiamide, a latent curing agent for epoxy resin, and rubber vulcanising agents. Hydroxyl methyl bisphenol A resins with different hydroxyl methyl content, synthesised by the base-catalysed reaction of bisphenol A and formaldehyde in various mole ratios, were used to compatibilize a blend of nitrile rubber (NBR) and epoxy resin 50/50wt/wt. The effect of addition of HMBPA on the morphology, adhesive, thermal, and mechanical properties of the adhesive film was investigated. The nitrile-epoxy adhesive films were characterised by measurements of adhesive joint strength, stress-strain properties, DSC, TGA, TMA, DMA, and SEM. Results revealed that significant improvement in joint strength occurred at low levels of HMBPA, and the optimum strength was obtained at about 15 wt% of HMBPA in the blend. The hydroxyl methyl content in HMBPA was found to influence the properties of the adhesive film. The concept of strengthening the interphase between NBR and epoxy through the coupling reactions of HMBPA was used for interpreting the results. The effect of addition of silica, alumina, and aluminium fillers on the properties of the nitrile-epoxy adhesive film was also studied, and a comparison of properties with and without HMBPA is presented.     

Effect of a reactive interfacial agent on the properties of a nitrile-rubber-modified epoxy film adhesive

Reactive interfacial agents are often used to homogenise the morphology of immiscible polymer blends and to improve the level of adhesion between the phases to achieve enhanced properties. This paper demonstrates the ability of hydroxyl methyl bisphenol A (HMBPA) to function as a reactive interfacial agent (compartibilizer) in a nitrile-epoxy film adhesive made from nitrile rubber (NBR) and solid epoxy resin blend. The curing of the adhesive film was achieved at 170° C by adding dicyandiamide, a latent curing agent for epoxy resin, and rubber vulcanising agents. Hydroxyl methyl bisphenol A resins with different hydroxyl methyl content, synthesised by the base-catalysed reaction of bisphenol A and formaldehyde in various mole ratios, were used to compatibilize a blend of nitrile rubber (NBR) and epoxy resin 50/50wt/wt. The effect of addition of HMBPA on the morphology, adhesive, thermal, and mechanical properties of the adhesive film was investigated. The nitrile-epoxy adhesive films were characterised by measurements of adhesive joint strength, stress-strain properties, DSC, TGA, TMA, DMA, and SEM. Results revealed that significant improvement in joint strength occurred at low levels of HMBPA, and the optimum strength was obtained at about 15 wt% of HMBPA in the blend. The hydroxyl methyl content in HMBPA was found to influence the properties of the adhesive film. The concept of strengthening the interphase between NBR and epoxy through the coupling reactions of HMBPA was used for interpreting the results. The effect of addition of silica, alumina, and aluminium fillers on the properties of the nitrile-epoxy adhesive film was also studied, and a comparison of properties with and without HMBPA is presented.     

氯丁橡胶与金属热硫化型胶膜的研究

采用机械共混法和胶料成膜技术制备出一种酚醛树脂(PF)-橡胶型膜状胶粘剂(胶膜)。结果表明:当n(37%甲醛)∶n(苯酚)∶n(氢氧化钠)=1.8∶1∶0.1、反应温度为70℃和反应时间为2.5 h时,合成的甲阶PF具有较高的羟甲基含量(28.3%),满足PF-橡胶型胶膜的制备要求;当m(氯丁橡胶)∶m(氯化天然橡胶)∶m(PF)∶m(炭黑)=100∶(5～10)∶(70～80)∶40、m(PF)∶m(硼酚醛树脂)=4∶1时,胶膜的剪切强度超过5.0 MPa、180°剥离强度超过4.0 kN/m且胶接件的破坏形式多为橡胶内聚破坏;该胶膜具有较好的热稳定性(热失重温度为300℃左右),满足氯化橡胶生胶片与金属之间的热硫化胶接要求;该胶膜与适宜底胶配合而成的双涂型胶接体系,可实现氯化橡胶生胶片与树脂基复合材料之间的热硫化胶接。     

Comparison of fracture behavior between acrylic and epoxy adhesives

An experimental study was conducted on the strength of adhesively bonded steel joints, prepared epoxy and acrylic adhesives. At first, to obtain strength characteristics of these adhesives under uniform stress distributions in the adhesive layer, tensile tests for butt, scarf and torsional test for butt joints with thin-wall tube were conducted. Based on the above strength data, the fracture envelope in the normal stress-shear stress plane for the acrylic adhesive was compared with that for the epoxy adhesive. Furthermore, for the epoxy and acrylic adhesives, the effect of stress triaxiality parameter on the failure stress was also investigated. From those comparison, it was found that the effect of stress tri-axiality in the adhesive layer on the joint strength with the epoxy adhesive differed from that with the acrylic adhesive. Fracture toughness tests were then conducted under mode l loading using double cantilever beam (DCB) specimens with the epoxy and acrylic adhesives. The results of the fracture toughness tests revealed continuous crack propagation for the acrylic adhesive, whereas stick-slip type propagation for the epoxy one. Finally, lap shear tests were conducted using lap joints bonded by the epoxy and acrylic adhesives with several lap lengths. The results of the lap shear tests indicated that the shear strength with the epoxy adhesive rapidly decreases with increasing lap length, whereas the shear strength with the acrylic adhesive decreases gently with increasing the lap length.     

Durability of Adhesive Bonds to Zinc-Coated Steels: Effects of Corrosive Environments on Lap Shear Strength

The effects of corrosive environments on adhesive bonds to electro-galvanized, zinc/aluminum alloy coated, coated electro-galvanized, and cold-rolled steels have been investigated. Bonds prepared using a rubber-modified dicyandiamide-cured epoxy adhesive, an epoxy-modified poly(vinyl chloride)-based adhesive, an acrylic-modified poly(vinyl chloride)-based adhesive a one-part urethane adhesive, and a two-component epoxy-modified acrylic adhesive were exposed under no-load conditions to constant high humidity or cyclic corrosion exposure for 50 days or 50 cycles (10 weeks) respectively.

Over the course of this study, exposure to constant high humidity had little effect on lap shear strength for any of the systems studied. Bond failures were initially cohesive, and with few exceptions remained so.

Bond strength retention under the cyclic corrosion exposure conditions employed was strongly dependent on adhesive composition and on substrate type. On galvanized substrates, lap shear strengths for the poly(vinyl chloride)-based adhesives were reduced by 90–100% during the course of the corrosion exposure, and a change in the mode of bond failure (from cohesive to interfacial) was observed. On the coated electro-galvanized steel substrate, the poly(vinyl chloride)-based adhesives showed about 50% retention in lap shear strength and a cohesive failure throughout most of the corrosion test. The dicyandiamide-cured epoxy adhesive used in this study generally showed the best lap shear strength retention to zinc-coated substrates; bonds to cold-rolled steel were severely degraded by corrosion exposure. The performance of the acrylic and urethane adhesives were intermediate to the dicyandiamide-cured epoxy and poly(vinyl chloride)-based adhesives in strength retention.     

Durability of Adhesive Bonds to Zinc-Coated Steels: Effects of Corrosive Environments on Lap Shear Strength

The effects of corrosive environments on adhesive bonds to electro-galvanized, zinc/aluminum alloy coated, coated electro-galvanized, and cold-rolled steels have been investigated. Bonds prepared using a rubber-modified dicyandiamide-cured epoxy adhesive, an epoxy-modified poly(vinyl chloride)-based adhesive, an acrylic-modified poly(vinyl chloride)-based adhesive a one-part urethane adhesive, and a two-component epoxy-modified acrylic adhesive were exposed under no-load conditions to constant high humidity or cyclic corrosion exposure for 50 days or 50 cycles (10 weeks) respectively.

Over the course of this study, exposure to constant high humidity had little effect on lap shear strength for any of the systems studied. Bond failures were initially cohesive, and with few exceptions remained so.

Bond strength retention under the cyclic corrosion exposure conditions employed was strongly dependent on adhesive composition and on substrate type. On galvanized substrates, lap shear strengths for the poly(vinyl chloride)-based adhesives were reduced by 90-100% during the course of the corrosion exposure, and a change in the mode of bond failure (from cohesive to interfacial) was observed. On the coated electro-galvanized steel substrate, the poly(vinyl chloride)-based adhesives showed about 50% retention in lap shear strength and a cohesive failure throughout most of the corrosion test. The dicyandiamide-cured epoxy adhesive used in this study generally showed the best lap shear strength retention to zinc-coated substrates; bonds to cold-rolled steel were severely degraded by corrosion exposure. The performance of the acrylic and urethane adhesives were intermediate to the dicyandiamide-cured epoxy and poly(vinyl chloride)-based adhesives in strength retention.     

Effect of trifunctional cross-linker triallyl isocyanurate (TAIC) on the surface morphology and viscoelasticity of the acrylic emulsion pressure-sensitive adhesives

Acrylic pressure sensitive adhesive (PSA) latexes were synthesized via a starved monomer-seeded semi-continuous emulsion polymerization process with butyl acrylate (BA), methyl methacrylate, acrylic acid (AA), 2-hydroxyethyl acrylate and trifunctional cross-linker, triallyl isocyanurate (TAIC). Influences of TAIC on the resultant latex and PSA properties were comprehensively investigated. The results indicated that latex particle size was independent of the amount of TAIC in the pre-emulsion feed, while the viscosity of the latex increased remarkably with TAIC content increased. Thermal gravimetric analysis result showed that the thermal stability of the polymers was improved significantly with the addition of TAIC. Besides, with the increase in TAIC content, gel content of the polymer increased significantly, while molecular weight between cross link points (M_c) and sol molecular weight (M_w, M_n) of the polymer decreased remarkably. Moreover, for the cross-linked adhesive film, the shear strength was improved greatly while at the sacrifice of loop tack and peel strength, when compared with the uncrosslinked counterparts. Finally, dynamic mechanical analysis and atomic force microscopy were also used to evaluate the viscoelastic properties and surface morphology of the acrylic emulsion PSA film, respectively.     

Study on bonding properties of PVC-based WPC bonded with acrylic adhesive☆

In this paper, the bonding properties of polyvinylchloride (PVC)-based wood–plastic composite (WPC) materials bonded with acrylic adhesive have been studied. The results showed that dry compression shear strength of bonded specimens glued with acrylic adhesive was 6.12?MPa, and reached 58.8% of the strength of the PVC-based WPCs. The results also showed that wet compression shear strength in accordance with Chinese standard GB/T17657 was 0.9 times the dry compression shear strength of 5.48?MPa. In addition, the retention rate of the compression shear strength of the bonded specimens gluing with acrylic adhesive after UV aging for 7?days and 14?days was 69.1 and 66.8%, respectively. The aging was done in accordance with UV-aging test process as given in this paper. The scanning electron microscopy (SEM) analysis of the bonded specimens of PVC-based WPCs showed that the J-39 acrylic adhesive penetrated into the adjacent porous regions of the PVC-based WPC which had resulted from foaming. This penetration enhanced the mechanical interlocking between the substrate and the acrylic adhesive.     

Modification of aqueous polyurethane dispersions by polybutadiene

Aqueous polyurethane (PU) adhesives are nontoxic and nonflammable and do not pollute the air. However, they have low adhesive strengths compared to solvent‐based PU adhesives because of a low affinity with rubber substrates. In this study, PU adhesives were synthesized from isophorone diisocyanate with dimethylol propionic acid as the ionic center in the main chain, triethylamine as the neutralization agent, and hydrazine as the chain extender. The polyol was modified with hydroxyl‐terminated polybutadiene (HTPB) and hydroxyl‐terminated acrylonitrile–butadiene copolymer (HTBN). The effect of the HTPB and HTBN content on the adhesive strength was investigated. The effect of the prepolymer molecular weight was also investigated. Increases in the HTPB and HTBN contents led to an increase in the adhesive strength because of the increase of chemical affinity between the adhesive and the substrate. The adhesive strength increased as the prepolymer molecular weight increased. This was due to an increase in the tensile strength and modulus. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1062–1068, 2005     

A Method of Predicting the Stresses in Adhesive Joints after Cyclic Moisture Conditioning

The durability of adhesive joints is of special concern in structural applications and moisture has been identified as one of the major factors affecting joint durability. This is especially important in applications where joints are exposed to varying environmental conditions throughout their life. This paper presents a methodology to predict the stresses in adhesive joints under cyclic moisture conditioning. The single lap joints were manufactured from aluminium alloy 2024 T3 and the FM73®-BR127® adhesive-primer system. Experimental determination of the mechanical properties of the adhesive was carried out to measure the effect of moisture uptake on the strength of the adhesive. The experimental results revealed that the tensile strength of the adhesive decreased with increasing moisture content. The failure strength of the single lap joints also progressively degraded with time when conditioned at 50°C, immersed in water; however, most of the joint strength recovered after drying the joints. A novel finite element based methodology, which incorporated moisture history effects, was adopted to determine the stresses in the single lap joints after curing, conditioning, and tensile testing. A significant amount of thermal residual stress was present in the adhesive layer after curing the joints; however, hygroscopic expansion after the absorption of moisture provided some relief from the curing stresses. The finite element model used moisture history dependent mechanical properties to predict the stresses after application of tensile load on the joints. The maximum stresses were observed in the fillet areas in both the conditioned and the dried joints. Study of the stresses revealed that degradation in the strength of the adhesive was the major contributor in the strength loss of the adhesive joints and adhesive strength recovery also resulted in recovered joint strength. The presented methodology is generic in nature and may be used for various joint configurations as well as for other polymers and polymer matrix composites.     

Synthesis and characterization of lignin-polyurethane based wood adhesive

The present work aims to evaluate the influence of addition of kraft lignin in moisture curing polyurethane (PU) based wood adhesives. The mechanical, thermal properties and chemical structure of the adhesive were studied. The lignin-PU adhesives were obtained by replacing 1%, 3% and 5% of polypropylene glycol (PPG) by Kraft lignin and further reacted with monomeric diphenylmethanediisocyanate (MDI). The aliphatic hydroxyl level of lignin was not taken into consideration in the stoichiometry, in order to find out effect on % free NCO of the final product. The chemical structure of the synthesized lignin-PU adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR). The lap shear strength of the adhesives was tested by bonding canarium wood substrates. The results illustrated that by increasing the weight % of lignin in such lignin-PU adhesives, a decrease in the free isocyanate content, leading to slower setting time but higher shear strength values, were observed. Similarly, the thermal properties of lignin-PU adhesive were also studied, showing an increase in glass transition temperature (Tg) with increase in lignin content.     

Mechanical and dielectric properties of epoxy resin modified using reactive liquid rubber (HTPB)

In the present study, hydroxyl‐terminated polybutadiene (HTPB) liquid rubber was employed to modify epoxy resin using 2,4,6‐tri (dimethylaminomethyl) phenol as a catalyst, and methyl hexahydrophthalic anhydride as a curing agent. The reactions between HTPB and epoxy were monitored by Fourier transform infrared (FTIR); the mechanical and dielectric properties of HTPB modified epoxies were evaluated and the morphology was investigated through scanning electronic microscopy (SEM). The FTIR analysis evidenced the occurrence of a chemical reaction between the two components. The mechanical results indicated that the impact strength of HTPB‐modified epoxy was superior to that of the pure epoxy. As the HTPB content increased up to 10 phr the best mechanical performances in terms of tensile and flexural properties were achieved when compared to the unmodified epoxy. Higher concentration of HTPB resulted in larger particles and gave lower mechanical strength values. The incorporation of HTPB into epoxy decreased the dielectric constant and dissipation factor over a wide frequency range from 1 to 10⁶ Hz, and improved the electrical resistivity. SEM micrographs showed that the modified epoxy exhibited a two‐phase morphology where the spherical rubber domains were dispersed in the epoxy matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of primers on adhesive properties and strength of adhesive joints made with polyurethane adhesives

The paper presents selected aspects of the effect of primers on adhesive properties and strength of aluminium sheet adhesive joints, made using polyurethane adhesives. The strength of adhesive joints was determined based on two cure time variants: 15 and 64 h. It was found that the longer cure time at a humidity of 33% is more desired, as it leads to a substantial increase in strength of the tested adhesive joints. In addition, two variants of surface preparation were applied: degreasing and degreasing followed by the application of a primer (a pro-adhesive agent). It was observed that the primer application prior to the application of an adhesive leads to a significant increase in strength compared to the variant where the adhesive application is preceded only by degreasing. Moreover, the aluminium sheet surface that was subjected to cataphoretic painting and priming exhibits better adhesive properties. It has a higher value of both surface free energy and its dispersion and polar components compared to the surface that was only subjected to degreasing.     

Adhesive properties of epoxy resin modified by end‐functionalized liquid polybutadiene

Adhesive properties of epoxy resin networks modified with different functionalized liquid polybutadiene were evaluated by using aluminum adherent. The end‐functionalized polybutadiene rubbers were hydroxyl‐ (HTPB), carboxyl‐ (CTPB), and isocyanate‐terminated polybutadiene (NCOTPB). The adhesive properties depend upon the morphology and the degree of interaction between the rubber–epoxy system. The most effective adhesive for Al–Al joint in both butt and single‐lap shear testing was epoxy resin–NCOTPB system. This system presents stronger rubber–epoxy interactions and a higher degree of rubber particle dispersion with particle size diameter in the nanoscale range. These characteristics were not important for improving the toughness of the bulk network but are fundamental for the improvement of adhesive strength. The effect of the pretreatment of the aluminum surface on the roughness was also evaluated by using profilometry analysis. The type of failure was also investigated by analyzing the adhered surfaces after fracture by scanning electron microscopy and profilometry. A proportion of cohesion failure higher than 90% was observed in all systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2370–2378, 2004     

Synthesis and properties of polyurethane wood adhesives derived from crude glycerol-based polyols

Crude glycerol, a waste stream of the biodiesel production process, is low-cost renewable feedstock for the production of chemicals and polymers. In this study, polyurethane (PU) adhesives were synthesized from crude glycerol-based polyols (CG-based polyols) for wood bonding applications. Effects of different variables, including hydroxyl values of CG-based polyols, chain extenders, and the molar ratio of NCO/OH on the properties of PU adhesives were investigated. The chemical structures of PU adhesives were characterized, and their thermal, mechanical, and chemical resistance properties were evaluated. The experimental results indicated that an increase of the NCO/OH molar ratio (1.3) substantially improved bonding strength by up to 38 MPa. Higher thermal stability and stronger chemical resistance to hot and cold water and to alkali and acid solutions were observed comparing to vegetable oil-based adhesives. However, the effect of the hydroxyl value of polyols on bonding strength was not significant. Additionally, bond strength of crude glycerol-based PU adhesives was comparable to that of some commercial PU wood adhesives. All these properties demonstrated the potential of CG for PU wood adhesive applications, particularly for fast-curing uses.     

一种耐高温发泡胶的性能研究

对FP发泡胶进行了热分析和力学性能测试。通过热分析，研究了该发泡胶的固化特性。研究结果表明，发泡胶的力学性能与填充密度、固化温度等有关。增大填充密度，可提高管剪强度；提高固化温度，可增加剪切强度。FP发泡胶中温固化，具有优异的耐高温性能。     

Failure behavior of adhesively bonded joints with a rubber modified epoxy adhesive under tensile-shear combined cyclic loading

Rubber-modified epoxy adhesives are used widely as structural adhesive owing to their properties of high fracture toughness. In many cases, these adhesively bonded joints are exposed to cyclic loading. Generally, the rubber modification decreases the static and fatigue strength of bulk adhesive without flaw. Hence, it is necessary to investigate the effect of rubber-modification on the fatigue strength of adhesively bonded joints, where industrial adhesively bonded joints usually have combined stress condition of normal and shear stresses in the adhesive layer. Therefore, it is necessary to investigate the effect of rubber-modification on the fatigue strength under combined cyclic stress conditions. Adhesively bonded butt and scarf joints provide considerably uniform normal and shear stresses in the adhesive layer except in the vicinity of the free end, where normal to shear stress ratio of these joints can cover the stress combination ratio in the adhesive layers of most adhesively bonded joints in industrial applications.

In this study, to investigate the effect of rubber modification on fatigue strength with various combined stress conditions in the adhesive layers, fatigue tests were conducted for adhesively bonded butt and scarf joints bonded with rubber modified and unmodified epoxy adhesives, wherein damage evolution in the adhesive layer was evaluated by monitoring strain the adhesive layer and the stress triaxiality parameter was used for evaluating combined stress conditions in the adhesive layer. The main experimental results are as follows: S–N characteristics of these joints showed that the maximum principal stress at the endurance limit indicated nearly constant values independent of combined stress conditions, furthermore the maximum principal stress at the endurance limit for the unmodified adhesive were nearly equal to that for the rubber modified adhesive. From the damage evolution behavior, it was observed that the initiation of the damage evolution shifted to early stage of the fatigue life with decreasing stress triaxiality in the adhesive layer, and the rubber modification accelerated the damage evolution under low stress triaxiality conditions in the adhesive layer.     

Comparative role of Interface in reinforcing mechanisms of Nano silica modified by Silanes and liquid rubber in SBR composites

The objective of the present study is to discuss the role of silica-rubber interfacial interactions on vulcanization kinetics, morphology, mechanical and viscoelastic behavior of silica filled styrene butadiene rubber (SBR) composites. Three types of modifiers, namely mono- and bi-functional silanes as well as hydroxyl-terminated poly butadiene (HTPB) liquid rubber were grafted to silica surface, and composites prepared by these fillers were characterized. Results showed that modified silica, especially grafted by bi-functional silane and liquid rubber, accelerated vulcanization reactions, while pristine silica slowed down vulcanization kinetics of SBR. Morphological studies indicated that all modifications improved dispersion of silica, but HTPB-grafted silica was dispersed to a greater extent in SBR. The observed differences in mechanical and dynamic-mechanical properties of vulcanizates were correlated to the significant differences in silica-rubber and silica-silica interactions. Type of interfacial interactions, i.e. rigid covalent bonds in the bi-functional silane, flexible polymeric bonds in the liquid rubber, and weak energetic bonds in the mono-functional silane, could explain the observed differences. Although all modifications reduced filler networking, rigid covalent bonding by bi-functional silane significantly improved mechanical properties and stabilized the filler network. The mono-functional silane lacks these mechanisms. The soft and flexible interphase of HTPB could create bonds and transfer stresses between the rubber matrix and silica to some extent, however it could not improve the mechanical properties and reduce the Payne effect as much as the bi-functional silane did.