Effect of the filler size and content on the thermomechanical properties of particulate aluminum nitride filled epoxy composites

Polymer matrix composites based on brominated epoxy as the matrix and aluminum nitride (AlN) particles as the filler were prepared. The influences of the size, content, and size distribution of AlN on the thermomechanical properties, including the glass‐transition temperature (T_g), coefficient of thermal expansion (CTE), dynamic storage modulus (E′), dynamic loss modulus (E″), and loss factor (tan δ), of the composites were investigated by thermomechanical analysis and dynamic mechanical analysis. There was a total change trend for T_g; that is, T_g of the composites containing nano‐aluminum nitride (nano‐AlN; 50 nm) was lower than that of the micro‐aluminum nitride (micro‐AlN; 2.3 μm) filled composites, especially at high nano‐AlN contents. The T_g depression of the composites containing nano‐AlN was related to the aggregation of nano‐AlN and voids in the composites. On the other hand, the crosslink density of the epoxy matrix decreased for nano‐AlN‐filled composites, which also resulted in a T_g depression. The results also show that E′ and E″ increased, whereas tan δ and CTE of the composites decreased, with increasing the AlN content or increasing nano‐AlN fraction at the same AlN content. These results indicate that increasing the interfacial areas between AlN and the epoxy matrix effectively enhanced the dynamic modulus and decreased CTE. In addition, at a fixed AlN content of 10 wt %, a low E′ of pre‐T_g (before T_g temperature) and high T_g were observed at the smaller weight ratio of nano‐AlN when combinations of nano‐AlN plus micro‐AlN were used as the filler. This may have been related to the best packing efficiency at that weight ratio when the bimodal filler was used. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of the filler material on the thermal stability of one‐component moisture‐curing polyurethane adhesives

Filler materials are part and parcel for the adjustment of adhesives, in particular, their rheological and mechanical properties. Furthermore, the thermal stability of adhesives can be positively influenced by the addition of an expedient filler, with inorganic types common practice in most cases. In this study, one‐component moisture‐curing polyurethane adhesives for engineered wood products based on isocyanate prepolymers with different polymer‐filled polyether polyols were investigated with regard to the filler's potential to increase the thermal stability of bonded wood joints. The property changes due to the addition of fillers were determined by means of mechanical tests on bonded wood joints and on pure adhesive films at different temperatures up to 200°C. Additional analyses by atomic force and environmental scanning electron microscopy advanced the understanding of the effects of the filler. The tested organic fillers, styrene acrylonitrile, a polyurea dispersion, and polyamide, caused increases in the cohesive strength and stiffness over the whole temperature range. However, the selected filler type was hardly important with regard to the tensile shear strength of the bonded wood joints at high temperatures, although the tensile strength and Young's modulus of the adhesive films differed over a wide range. Prepolymers with a lower initial strength and stiffness resulted in worse cohesion, in particular, at high temperatures. This disadvantage, however, could be compensated by means of the filler material. Ultimately, the addition of filler material resulted in optimized adhesive properties only in a well‐balanced combination with the prepolymer used. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of in situ esterification on the performance of carboxyl functionalized rubber‐modified epoxy film adhesives

Epoxy‐based film adhesive formulations were developed with 10 wt % solid carboxyl functional rubber. Due to the high rubber content and resulting viscosity restrictions, the rubber could not be prereacted with the epoxy before hot‐melt filming. Therefore, an esterification catalyst was used to perform this reaction in situ before the epoxy curing reactions. The performance of this adhesive system is compared to that of one without the esterification catalyst. A significant difference in the flow characteristics was observed with incorporation of the esterification catalyst, but only small variations in mechanical performance were found. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 728–734, 2000     

复合填料/聚丙烯酸酯导电压敏胶的制备与性能

针对导电胶黏剂（ECA）在实用中所遇到填料组分单一、易团聚、对基体力学性能影响较大等问题,本文利用不同组分填料间的架桥、插层等“协同”效应,将一定比例的碳黑（CB）、碳纤维（CF）、碳纳米管（CNTs）、纳米石墨微片（NanoG）复合作为导电填料加入到聚丙烯酸酯压敏胶（PSA）中,采用溶液共混法超声分散,得到填料添加量小、导电性能和力学性能良好的导电PSA。运用多种检测手段对导电PSA的电学性质、微观结构、热稳定性和力学性能进行了分析。结果表明,复合填料组成为CF 3%、NanoG 5%、CNTs 5%（均为质量分数）时,导电PSA的电导率达到3.0×10?2S/cm,180°剥离强度为0.38kN/m。     

The sorption and diffusion of water in halogen-containing epoxy resins

The effect of halogen containing substituents on the sorption and transport of water in the epoxy system, tetraglycidyl 4,4′ diaminodiphenyl methane cured with 4,4′ diaminodiphenyl sulphone, has been studied at 40°C, 50°C and 60°C. The introduction of halogen containing groups reduces the sorption over the whole of the activity range, the effect being greatest for the fluorine-containing sample. Sorption-desorption kinetics exhibit many of the features observed for the unsubstituted network including some element of non-Fickian behaviour. Diffusion coefficients are greatest for the fluorine-containing sample and have a relatively weak concentration dependence for all the samples.     

Aging effects on the electrical properties of silver-filled epoxy adhesives

Electrically conductive adhesives, such as silver-filled epoxies, are used in many applications where standard soldering or direct metal-to-metal connections are not feasible. Anomalous behavior at these connections has been observed as the development of increasing resistance over time in the absence of mechanical failure between the adhesive and substrate. The results of aging of electrically conductive adhesive joints to aluminum- and gold-metallized substrates show that little change occurs at low humidity under an ambient flow of nitrogen. With increasing humidity and temperature, there is a measurable increase in resistance over time, particularly in the case of aluminum-metallized substrates. Secondary ion mass spectrometry (SIMS) was used to investigate interfacial phenomena that may be responsible for increasing resistance observed in the aluminum-metallized samples exposed to accelerated aging. Preliminary results from this technique indicate the presence of an oxide layer between the adhesive and the metallization layer that is consistent with increasing resistance measured for samples exposed to accelerated aging. The results also support the conclusion that deterioration at the adhesive-aluminum interface, and not degradation in the bulk adhesive, is the primary cause of increasing resistance.     

Recycling of rigid polyurethane foam: Micro-milled powder used as active filler in polyurethane adhesives

Rigid polyurethane (PUR) foams are widely used as heat insulation material in construction industry or for electronic appliances manufacturing. After finishing their life-time, it is necessary to eliminate foam wastes. The aim of this study was to prepare a pair of industrial PUR adhesives of medium viscosity containing recycled rigid PUR foam. Three methods of milling were tested: knife-milling, two-roll milling, and ball-milling. Only two-roll milling gives the PUR micro-powder usable for following adhesives modification. The micro-powder was used as passive filler in PUR adhesives and potential reactivity for polyol pack replacement was studied. Hydroxyl and amine numbers were determined in mixture with virgin polyol. One-component PUR prepolymer adhesive was prepared using various dosages of the micro powder and the tensile strength of bound wood was measured. As additional parameters, also free film adhesive mechanical parameters were tested and particle size distribution of the micro powder was analyzed. Two adhesive formulations were prepared for independent evaluation of the micro powder reactivity. The results showed growing of the mechanical strength of wood bonding with growing dosage of the micro powder.     

Preparation and properties of heat and ultraviolet‐induced bonding and debonding epoxy/epoxy acrylate adhesives

Heat and ultraviolet (UV)‐induced bonding and debonding (BDB) adhesives were designed and prepared through blending an epoxy resin, diglycidyl ether of bisphenol A (DGEBA) with an epoxy acrylate resin, bisphenol‐A epoxy acrylate resin (BEA). The variation of the chemical structure of DGEBA and BEA in the sequential heat‐ and UV‐curing processes was characterized by Fourier transform infrared spectroscopy (FTIR). The FTIR results indicate that DGEBA and BEA successfully took part in both the heat‐curing and UV‐curing processes. The effects of the mass ratio of BEA to DGEBA, amount of heat‐curing agent, type of diluents, and UV irradiation time on the BDB properties of BDB adhesive were systematically investigated. The results show that the bonding strength increases with the decrease of the mass ratio of BEA to DGEBA and with the increase of the amount of heat‐curing agent in a certain range. The debonding strength decreases with the increase of the mass ratio of BEA to DGEBA. The mass ratio of BEA to DGEBA was set at 10 to ensure the ratio of the bonding strength to debonding strength greater than 10 times. The debonding strength of BDB adhesives also depends on the UV irradiation time, decreasing with the increase of UV irradiation time in a certain range. Based on the FTIR results and the dependence of the bonding and deboning strengths on the reaction conditions, a possible BDB mechanism of BDB adhesive was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46435.     

Electrical properties of conductive adhesives as affected by particle compositions,particle shapes,and oxidizing temperatures of copper powders in a polymer matrix

The effects of particle compositions, particle shapes, and oxidation temperatures on the electrical properties of conductive adhesives have been investigated. Silver‐coated copper powders and uncoated copper powders with spherical and flake‐shaped particles are oxidized at temperatures such as 30, 175, 240, 300°C and 350°C for 2 h and dispersed in an epoxy matrix. The results of this study indicate that the electrical properties of the conductive adhesives are strongly affected by the particle compositions and oxidation temperatures and only slightly affected by the particle shapes. Silver‐coated copper powders show significantly greater oxidation resistance than uncoated copper powders. To understand how silver‐coated copper powders show such oxidation resistance, they are analyzed by the techniques of thermogravimetric analysis (TGA), X‐ray diffraction (XRD), and Auger spectroscopy to observe how metal oxides such as AgO, Cu₂O, and CuO affect the electrical properties of the conductive adhesives. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2045–2053, 2004     

Effect of post-cure on the glass transition temperature and mechanical properties of epoxy adhesives

The effects of post-curing and cure temperature on the glass transition temperature, T _g, and the mechanical properties of epoxy adhesives were studied. T _g was measured by a dynamic mechanical analysis apparatus developed in-house and the mechanical properties of the adhesives (yield strength, Young’s modulus and failure strain) were measured by a tensile machine. The relationships between T _g and mechanical performance under various post-cure conditions were investigated. The curing process was the same for all tests, consisting of an initial stage performed at different temperatures followed by cooling at room temperature. Three sets of specimens were considered, sharing the same initial cure process, but with a different post-curing procedure. In the first set, the specimens were only subjected to a curing process; in the second set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature below the T _g of the fully cured network, T _g∞; and in the third set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature above the T _g∞. When post-cured at a temperature above T _g∞, the mechanical and physical properties tend to have a constant value for any cure temperature.     

Durability of adhesives based on different epoxy/aliphatic amine networks

The mechanical and adhesives properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact tests were used to determine the impact energy. The adhesive properties have been evaluated in terms single lap shear using steel adherends. Its durability in water at ambient temperature (24 °C) and at 80 °C has also been analyzed. The fracture mechanisms were determined by optical microscopy. It was observed a strong participation of the cohesive fracture mechanisms in all epoxy system studied. The 1-(2-aminoethyl)piperazine epoxy adhesive and piperidine epoxy adhesive presents the best adhesive strength and the largest impact energy. The durability in water causes less damage to piperidine epoxy networks. This behavior appears to be associated with the lower water uptake tendency of homopolymerised resins due to its lower hydroxyl group concentration.     

Thermal and dielectric properties of the aluminum particle/epoxy resin composites

Microsized aluminum/epoxy resin composites were prepared, and the thermal and dielectric properties of the composites were investigated in terms of composition, aluminum particle sizes, frequency, and temperature. The results showed that the introduction of aluminum particles to the composites hardly influenced the thermal stability behavior, and decreased T_g of the epoxy resin; moreover, the size, concentration, and surface modification of aluminum particles had an effect on their thermal conductivity and dielectric properties. The dielectric permittivity increased smoothly with a rise of aluminum particle content, as well as with a decrease in frequency at high loading with aluminum particles. While the dissipation factor value increased slightly with an increase in frequency, it still remained at a low level. The dielectric permittivity and loss increased with temperature, owing to the segmental mobility of the polymer molecules. We found that the aluminum/epoxy composite containing 48 vol % aluminum‐particle content possessed a high thermal conductivity and a high dielectric permittivity, but a low loss factor, a low electric conductivity, and a higher breakdown voltage. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

BIMS/filler interactions. II. Effects of filler concentration and BIMS structure

Brominated isobutylene para‐methylstyrene (BIMS) elastomer is a terpolymer of isobutylene, para‐methylstyrene (PMS), and para‐bromomethylstyrene (BrPMS). Viscoelastic measurements have been used to characterize the blends of this BIMS elastomer with different concentrations of a carbon black (CB) filler, N234. Data in the low temperature/high frequency region suggest that N234 at a concentration less than or equal to 15 vol % in BIMS appears not to affect the T_g of BIMS although a slight increase in relaxation time in the transition zone is observed. Also, the effects of BrPMS and PMS contents in BIMS on BIMS/N234 CB interactions have been qualitatively investigated by using the bound rubber measurements. To assess BIMS/CB interactions with reference to diene rubber/CB interactions, mixing of BIMS with various amounts of a polybutadiene rubber in the presence of CB has been performed. Atomic force microscopy and image processing have been employed to quantify filler phase distributions in these blends for a practical ranking of polymer/CB interactions. Preferential partition of CB in the BIMS or BR phase depends on the BrPMS content in BIMS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 659–667, 2006     

Tensile strength of two-part epoxy paste adhesives: Influence of mixing technique and micro-void formation

Two-part epoxy paste adhesives are frequently used to bond metals and composite materials in many structural applications. After mixing two reactive parts (by weight or volume ratio), adhesive paste is applied to the substrate surfaces and cured at elevated temperatures. Air-entrapment during mixing and/or application process often produces micro-voids in the adhesive bondlines and influences the strength of the bonded joints. In this work, void formation was investigated using two adhesive mixing techniques: (a) dual-cartridge and static-mixer with a dispenser and (b) hand-mix. Flat adhesive sheets were cured by mixing a two-part epoxy adhesive, and bulk specimens with notches were cut using CNC-machining. Using X-ray microtomography scans, the micro-voids were detected and material porosity was evaluated. Furthermore, tensile tests were performed on the specimens and two-dimensional digital image correlation (2D DIC) was employed to analyse the surface strain concentrations near the notches. The fracture surfaces were examined using optical and scanning electron microscopy. The results indicated that mixing technique influences the formation of micro-voids and thus the tensile strength of two-part epoxy paste adhesives.     

Effects of matrix moisture on gas diffusion and flow in coal

Gas production from coal is a complex process whereby gas, initially adsorbed in the coal matrix, desorbs and diffuses through the matrix into the cleat and eventually flows through the cleat system into a production well or a drainage borehole. Hence, the gas production rate is mainly controlled by the gas diffusivity in the matrix and gas permeability in the cleat system. Moisture in the coal matrix has significant impact on gas adsorption capacity and would also play a key role in desorption and migration of gas. However, how moisture affects gas desorption and diffusion in the coal matrix is still poorly understood. In this work, experimental study is performed to investigate effects of moisture on gas sorption rate for an Australian coal. Coal seam gases, CH₄ and CO₂, are used in the study. The experimental results show that moisture content in the matrix has significant impact on the gas sorption rate and the impact of moisture content on the diffusion rate is stronger for CH₄ than CO₂. Moreover, the impact of moisture on gas diffusivity in pores with different size is different, suggested from the modelling results using the bidisperse approach. Furthermore, moisture in coal matrix would cause coal swelling/shrinkage and mechanical properties change that could impact on coal permeability under reservoir conditions. Experimental measurements of coal matrix swelling and Young’s modulus on the same coal sample show that matrix moisture content has significant impact on those properties and may have significant implications on coalbed methane recovery and CO₂ storage in coal.     

Determination of water uptake and diffusion of Cl ion in epoxy primer on aluminum alloys in NaCl solution by electrochemical impedance spectroscopy

The electrochemical impedance spectroscopy (EIS) of epoxy-coated aluminum alloy LY12 has been investigated during exposure to 3.5% NaCl solution. Using the continuous simulation of EIS by expanded general electrical model, the time-dependent impedance model of the alloy/coating/solution system was deduced. The results shown that the composite electrode displayed a barrier behavior before water and oxygen penetrated to alloy base. After water and oxygen reached the base, the impedance associated with corrosion of alloy base changed with the immersion time as following: (i) active corrosion period at the beginning (double-layer capacitance, C_dl, in parallel to the charge transfer resistance of electrochemical corrosion R_ct), (ii) impeding of the diffusion of corrosion production at the intermediate period as a result of the presence of coated film (a constant phase element Z_diff was additionally in series with R_ct), and (iii) appearance of the characteristic impedance related to Cl⁻ ion-participating reaction with alloy base at the later stage. From the linear part of ln C_c–t^0.5 curve in the early immersion stage, the apparent diffusion coefficient of water was obtained. The diffusion coefficient of water and Cl⁻ ion through the coating was also calculated by the required time for diffusion of permeation species through the coating to the metal interface obtained from the simulation of EIS data by which the occurrence of characteristic impedance element(s) corresponding to special species arrival can be determined.     

Structure–property relationships in one‐component polyurethane adhesives for wood: Sensitivity to low moisture content

The causes of strength loss of wood joints and their consequent delamination from one‐component polyurethane adhesives used for bonding structural wood when used at a low moisture content was investigated by testing wood joint strength and elongation at rupture at different wood moisture contents and by ¹³C‐NMR spectroscopy and scanning electron microscopy of the hardened bond line. The combination of the relative proportion of the still‐reactive free ? NCO groups on the polyurethane, of the wise choice of degree of polymerization of the resin, and of a slower rate of reaction were the three parameters found to be important in overcoming the problem of poor or no bonding of wood at low to very low moisture contents from one‐component polyurethane adhesives. The results obtained indicated that one‐component polyurethane adhesives that had a combination of a higher proportion of still‐unreacted ? NCO groups, a lower degree of polymerization, and a slower reaction rate were capable of overcoming the problem of the high sensitivity of polyurethane gluing at low to very low wood moisture contents. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4181–4192, 2006     

Influence of radiant exposure on degree of conversion,water sorption and solubility of self-etch adhesives

The purpose of this study was to investigate the influence of the radiant exposure on the degree of C=C conversion (DC), water sorption (WS), and solubility (S) of the Clearfil SE Bond (CSE) and Filtek LS (LS) self-etch adhesive systems. The primer of the LS (LSP), and bond agents of the CSE (CSEB) and LS (LSB) were tested. Specimens were light-cured using a light-emitting diode (LED) at different radiant exposures (6.1, 12.2, 13.9, and 27.8 J/cm²). DC (n=10) was measured using Fourier-transform infrared spectroscopy (FT-IR). WS and S were determined according to ISO 4049. Data were subjected to two-way ANOVA and Tukey's test at pre-set alpha of 0.05. The highest DC was exhibited by LSP, followed by CSEB and LSB, all with statistical difference (p<0.001). The DC was increased with higher radiant exposure and extended light-curing time (p<0.001). LSB and CSEB showed the lower WS followed by LSP, all with statistical difference (p<0.001). CSEB and LSB presented no significance difference on the S values (p>0.05) and were lower than LSP (p≤0.05). The WS and S were not influenced by the different radiant exposures evaluated (p=0.9548 and p>0.05, respectively). The monomer conversion is related to improvement on the mechanical properties of resinous material, but these properties also depend on the polymer network structure formed.     

Mechanical and tribological properties of glass–epoxy composites with and without graphite particulate filler

The objectives of this research article is to evaluate the mechanical and tribological properties of glass‐fiber‐reinforced epoxy (G–E) composites with and without graphite particulate filler. The laminates were fabricated by a dry hand layup technique. The mechanical properties, including tensile strength, tensile modulus, elongation at break, and surface hardness, were investigated in accordance with ASTM standards. From the experimental investigation, we found that the tensile strength and dimensional stability of the G–E composite increased with increasing graphite content. The effect of filler content (0–7.5 wt %) and sliding distance on the friction and wear behavior of the graphite‐filled G–E composite systems were studied. Also, conventional weighing, determination of the coefficient of friction, and examination of the worn surface morphological features by scanning electron microscopy (SEM) were done. A marginal increase in the coefficient of friction with sliding distance for the unfilled composites was noticed, but a slight reduction was noticed for the graphite‐filled composites. The 7.5% graphite‐filled G–E composite showed a lower friction coefficient for the sliding distances used. The wear loss of the composites decreased with increasing weight fraction of graphite filler and increased with increasing sliding distance. Failure mechanisms of the worn surfaces of the filled composites were established with SEM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2472–2480, 2007     

样品制备工艺对石材干挂胶性能测试结果的影响

探讨了石材干挂胶性能测试中样品制备工艺对钢/钢拉剪强度和冲击强度测试结果的影响。结果表明,制备钢/钢拉剪样品时用垫丝控制胶层厚度的方法,控厚更精确,测试结果重复性好;相比于硅胶模具,钢模具制2备的试样冲击强度要高出0.5~0.8 k J/m,样品制备中不同的表面找平方法对冲击强度的影响相对较小。