Nanocomposite adhesives: Mechanical behavior with nanoclay

The major objective for this research was to examine the role of epoxy-clay nanocomposites in the area of epoxy bonding to porous stone (granite) substrates. Two bisphenol A epoxy systems were selected based on the prior work that determined optimal adhesive properties from a larger set of epoxy systems to determine the role of viscosity on the intercalation and exfoliation of the clay tactiods in the epoxy resin. The systems were characterized and mechanically tested at varying levels of intercalated and exfoliated organic clay tactiods. In the first stage of the work, epoxy-clay systems were characterized by wide-angle X-ray diffraction (WAXD) to detect inter-laminar distances of clay layers and to determine if the mixing procedures had indeed dispersed and exfoliated the clay layers sufficiently. The second stage of the work involved examining mechanical properties of the epoxy-nanoclay systems. Fracture behavior was studied using granite stone substrates in notched double lap configuration. Compressing a wedge between the cover plates induced the fracture. Fracture toughness was approximated by the load at fracture. Tensile properties were measured using cast dog bone tensile samples. The better layered silicate nanocomposite performance was seen with the lower viscosity resin. The most noticeable improvements in mechanical properties for the lower viscosity resin system were found to be maximum stress, elastic modulus, and yield stress. Increased toughness and stress whitening at 1% by weight nanoclay loading revealed that the clay can act as a shear-yielding toughening agent in this epoxy system.     

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.     

Structural Carbon/Epoxy Prepregs Properties Comparison by Thermal and Rheological Analyses

Two different carbon/epoxy prepreg materials were characterized and compared using thermal (DSC, TGA, and DMA) and rheological analyses. A prepreg system (carbon fiber preimpregnated with epoxy resin F584) that is currently used in the commercial airplane industry was compared with a prepreg system that is a prospective candidate for the same applications (carbon fiber prepreg/epoxy resin 8552). The differences in the curing kinetics mechanisms of both prepreg systems were identified through the DSC, TGA, DMA, and rheological analyses. Based on these thermal analysis techniques, it was verified that the curing of both epoxy resin systems follow a cure kinetic of n order. Even though their reaction heats were found to be slightly different, the kinetics of these systems were nevertheless very similar. The activation energies for both prepreg systems were determined by DSC analysis, using Arrhenius's method, and were found to be quite similar. DMA measurements of the cured prepregs demonstrated that they exhibited similar degrees of cure and different glass transition temperatures. Furthermore, the use of the rheological analysis revealed small differences in the gel temperatures of the two prepreg systems that were examined.     

Analysis of the nonlinear behavior of adhesives in bonded assemblies—Comparison of TAST and Arcan tests

This paper describes a study in which the shear behavior of a structural epoxy adhesive has been measured using the standard thick adherend shear test (TAST) specimen and a modified Arcan test. A numerical study of the TAST test taking into account the nonlinear behavior of the adhesive and the finite deformations of the adhesive joint, shows that there is a localization of plastic zones close to the adhesive–substrate interface near the free edge of the adhesive. Experimental tests carried out with steel and aluminum substrates and with various adhesives also show that failure initiates in this region. These edge effects in the TAST fixture can lead to an incorrect analysis of the behavior of the adhesive (for instance, underestimation of the shear stress in the joint at failure), particularly when an adhesive failure mode is dominating. The modified Arcan fixture provides a more homogeneous stress state. A similar improvement of the TAST fixture is proposed.     

Thermal Properties,Fracture Toughness and Water Absorption of Epoxy-Palm Oil Blends

Epoxidized palm oil (EPO) was blended with cycloaliphatic epoxide, epoxy novolac and diglycidyl ethers of bisphenol-A. The fracture toughness and thermal properties of epoxy/EPO blends were characterized using single-edge notched bending tests and differential scanning calorimetry. Increased EPO loading improved the fracture toughness (K _IC ) of the epoxy blends. The epoxy blends with higher EPO loading exhibited higher degree of conversion. The glass transition temperature (T _g ) of the epoxy blends shifted to higher temperature as the increasing of DSC heating rate. Water absorption caused T _g reduction of epoxy blends but it was determined that the water molecules absorbed were totally reversible.     

Influence of Nanogels on Mechanical, Dynamic Mechanical, and Thermal Properties of Elastomers

Use of sulfur crosslinked nanogels to improve various properties of virgin elastomers was investigated for the first time. Natural rubber (NR) and styrene butadiene rubber (SBR) nanogels were prepared by prevulcanization of the respective rubber lattices. These nanogels were characterized by dynamic light scattering, atomic force microscopy (AFM), solvent swelling, mechanical, and dynamic mechanical property measurements. Intermixing of gel and matrix at various ratios was carried out. Addition of NR gels greatly improved the green strength of SBR, whereas presence of SBR nanogels induced greater thermal stability in NR. For example, addition of 16 phr of NR gel increased the maximum tensile stress value of neat SBR by more than 48%. Noticeable increase in glass transition temperature of the gel filled systems was also observed. Morphology of these gel filled elastomers was studied by a combination of energy dispersive X-ray mapping, transmission electron microscopy, and AFM techniques. Particulate filler composite reinforcement models were used to understand the reinforcement mechanism of these nanogels. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Effect of Environmental Exposure on the Fracture Properties of an Epoxy Adhesive

An experimental study was carried out about the effect of warm moisture on the fracture energy of an adhesive system formed by steel adherends joined by an epoxy adhesive. The specimens were double cantilever beams, manufactured with the open-face technique. The halves of the specimens (single beams covered by the “primary” adhesive layer) were degraded in a climatic cell at 50°C and 100% RH, for time periods in the range of 1–5 weeks. At the end of each desired period, the half-specimens were dried, to account for irreversible effects only, and the bonds were completed with the second halves.

Static fracture tests were carried out on an Instron 100 kN machine, monitoring crack propagation with a charge-coupled device microscope. The data were processed by means of the Simple Beam Theory to calculate the strain energy release rate and the R-curves were obtained. Similar trends were found for initial and steady critical strain energy release rates: compared to unexposed specimens, great part of the reduction (about ?50%, ?40%, respectively) occurred in the first week, stabilized values (about ?80%, ?60%) were observed after 3 weeks. The load-displacement curves decreased likewise. The fracture, mostly interfacial, followed a stepped crack path between the adherends.     

Mechanical and Damping Properties of Glass Fiber and Mica-Reinforced Epoxy Composites

Mica/glass fiber-reinforced epoxy with 0° and 45° ply angle were prepared by hand lay-up and the mechanical and damping properties were studied. Results show that the addition of mica resulted in decrease of tensile strength and modulus for both composites. Althogh flexural strength and modulus of composites with 45° appeared a maximum at 5 phr mica loading, that of composites with 0° reached a maximum at 10 phr mica loading. For composites with 0°, damping ratio reaches maximum at 5 phr mica. Although for composites with 45°, damping ratio decrease with increasing mica loading.     

聚碳酸酯改性环氧树脂的固化动力学与热性能研究

用动态DSC法研究了聚碳酸酯(PC)改性环氧树脂(EP)体系的固化行为,采用Flynn-Wall-Ozawa法分析了EP/PC体系固化活化能与转化率的关系,利用Kissinger和Crane方程研究了EP/PC体系固化动力学参数,并用TG和DSC研究了复合体系的热性能。结果表明:PC的加入没有改变EP的固化机理,反应级数基本不变,但是降低了EP固化物的热分解温度和玻璃化转变温度。     

PC／Epoxy／LCP共混体的相容性与力学性能

研究了ＰＣ／Ｅｐｏｘｙ／ＬＣＰ三元混体的相容性与力学性能,将少量的小分子环氧树脂加入到ＰＣ／ＬＣＰ二元共混体中来改善共混体的相容性,进而改进ＬＣＰ的成纤维力,从而提高共混体的力学性能。     

New T-Shape Polyurethanes: Synthesis,Thermal and Mechanical Properties

A series of new T-shaped polyurethanes were prepared from various diisocyanates and 2,5-dihydroxybenzelidene aniline (azomethine bisphenol). The latter compound was synthesized by the reaction of 2,5-dihydroxy-benzaldehyde with aniline. The structures of azomethine bisphenol and T-shaped polyurethane were confirmed by FT-IR, ¹H-NMR, ¹³C-NMR Spectroscopy and elemental analysis (CHN). The mechanical properties were characterized by tensile strength, tear strength and shore hardness. Thermal properties were also studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Mechanical and thermal studies showed that the synthesized polyurethanes possess good mechanical and thermal properties.     

The chemical,kinetic and mechanical characterization of tannin-based adhesives with different crosslinking systems

Network formation, cure characteristics and bonding performance of tannin-based resins were investigated in order to establish structure–property relationships between the stage B and stage C. Tannin–aldehyde and base-catalyzed autocondensed tannin resins were synthesized and characterized for molecular weight distribution, cure kinetics and cure chemistry by means of GPC, DMA and ¹³C CP/MAS NMR spectroscopy and solvent stability tests. The resins performance as wood adhesives was further established from lap-shear tests and microscopic observation of the bondline. Resins prepared with highly reactive aldehydes, such as formaldehyde or glyoxal, exhibited a significant extent of hetero-condensation reactions, fast cure kinetics, a high storage modulus and good solvent stability of the stage C-resin. In contrast, resins prepared with bulky aldehydes of low reactivity, such as citral, were dominated by autocondensation reactions, and exhibited slower cure kinetics, a lower storage modulus and solvent-stability of the stage C-resin, alike those neat autocondensed tannin resins. However, all resin systems fulfilled the standard requirements for wood adhesive bonding for interior applications. Additionally, storage modulus increase during cure was found to be a good predictor of the stiffness of the wood-bonded assembly, useful to discriminate between the autocondensation and heterocondensation cure chemistries.     

A New Methodology to Evaluate the Cure of Resin-Impregnated Paper for HPL

This paper presents a study on the curing conditions of several resin-impregnated papers and its impact on the performance of HPL (high-pressure decorative laminate). A new methodology for evaluating the bond strength development between the different layers of a HPL(overlay, decorative, and kraft papers) was developed using ABES (Automated Bonding Evaluation System) equipment. The proposed method can be applied to the study of the curing step of the different impregnated paper and the development of bonds between them (overlay paper on decorative paper, decorative paper on kraft paper, and kraft paper on kraft paper) trying to simulate the hot-pressing of an industrial HPL. This will permit to establish a more adapted temperature gradient in hot-press in order to achieve the same curing rate for all layers and provide a good final overall product quality.     

Simultaneously Increasing Impact Resistance and Thermal Properties of Epoxy Resins Modified by Polyether-Grafted-Epoxide Polysiloxane

In this paper, polyether-grafted-epoxide polysiloxane (FEPMS) was synthesized via hydrosilylation among poly(methylhydrosiloxane) (PMHS), allyl polyoxyethylene polyoxypropylene ether (F6) and allyl glycidyl ether to modify Diglycidyl Ether of Bisphenol A (DGEBA). The morphology, thermal properties, and toughness of all cured samples were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and impact testing. Results indicated that grafted polysiloxane can be well dispersed in epoxy matrix, and the epoxy resin modified with FEPMS at relatively low addition levels exhibited higher thermal properties and improved toughness than the neat epoxy resin.     

The Effect of Moisture Content in Epoxy Film Adhesives on their Performance. III: Bulk Properties

Humidity absorbed by epoxy film adhesives during low temperature storage or exposure to atmosphere may result in reversible changes and irreversible modifications. Vacuum treatment may partially remedy the reversible changes. The consequences of vacuum drying are manifested in enhancement of both the peel and shear properties of bonded joints (Part I and Part II of this series of papers) and the thermal, physical and mechanical properties of the bulk adhesive, characterized in the present study.

Experimental results have shown that the bulk properties of structural epoxy based adhesives are highly correlated with the aging processes caused by water absorption in the prepolymerized adhesive. Applying the vacuum process is harmful to fresh unaged adhesive due to devolatization of low molecular species of the film adhesive.

The characterization of bulk properties for the purpose of following the aging and recovery processes is advantageous, since the bulk is independent of geometrical and interfacial effects which dominate in the case of property evaluation of the adhesive in a bonded joint.     

The Effect of Moisture Content in Epoxy Film Adhesives on their Performance. III: Bulk Properties

Humidity absorbed by epoxy film adhesives during low temperature storage or exposure to atmosphere may result in reversible changes and irreversible modifications. Vacuum treatment may partially remedy the reversible changes. The consequences of vacuum drying are manifested in enhancement of both the peel and shear properties of bonded joints (Part I and Part II of this series of papers) and the thermal, physical and mechanical properties of the bulk adhesive, characterized in the present study.

Experimental results have shown that the bulk properties of structural epoxy based adhesives are highly correlated with the aging processes caused by water absorption in the prepolymerized adhesive. Applying the vacuum process is harmful to fresh unaged adhesive due to devolatization of low molecular species of the film adhesive.

The characterization of bulk properties for the purpose of following the aging and recovery processes is advantageous, since the bulk is independent of geometrical and interfacial effects which dominate in the case of property evaluation of the adhesive in a bonded joint.     

Characterization and material model definition of toughened adhesives for finite element analysis

Some toughened adhesives used for structural joints are characterised by non-linear behaviour prior to failure that may significantly influence the entire joint response. The determination of appropriate and accurate material models for use in analysis and design phases covering both nonlinearities and final material rupture constitutes one of the main challenges for the utilisation of adhesives and for offering designers the same confidence level as that offered by other joining techniques.The present research proposes the utilisation of both elasto-plastic and continuum damage models as a combination that can fully reproduce the mechanical response of toughened adhesives in finite element (FE) analysis. In this context, the Drucker-Prager exponential model has demonstrated to provide accurate fits with the nonlinearities of these materials, allowing the real plastic behaviour of the adhesives to be adjusted in the computational models with a high degree of correlation. On the other hand, a continuum damage model has been proposed to simulate the final material failure process introducing a displacement-based damage parameter into the constitutive equation of the damaged material. The definition of the parameters associated with the mentioned models has been carried out through the execution of an experimental programme combining traction and torsion tests, described in the present paper as part of the study developed. The research is finally completed with an experimental and FE analysis of a specific bonded joint that allows the operation of the material model to be checked in a real application.     

The Effect of Surface Modification of TiO2 with Diblock Copolymers on the Properties of Epoxy Nanocomposites

The TiO₂ nanoparticles were modified by diblock copolymers, poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS), via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the epoxy nanocomposites containing different TiO₂ and with different contents were prepared. Subsequently, the effects of TiO₂ content on the mechanical and thermal properties of nanocomposites were investigated. The results indicated that after grafting copolymers onto TiO₂, the dispersion of TiO₂ and interaction with epoxy matrix could be significantly increased, therefore, the mechanical properties of the nanocomposites were improved greatly. When the TiO₂-PMMA-b-PS content was 1 wt%, the impact strength and flexural strength reached their the best, and increased up to 96% and 43%, respectively. Furthermore, the thermal stability of the nanocomposites was also distinctly improved.     

环氧树脂/有机蒙脱土复合材料的制备与力学性能研究

利用插层聚合法制备了环氧树脂/有机蒙脱土(EP/OMMT)复合材料.采用XRD对复合材料进行了表征,并研究了复合材料力学性能.实验表明:环氧树脂/有机蒙脱土形成了剥离型的纳米复合材料结构;环氧树脂中加入适量的有机蒙脱土,可以提高环氧树脂的拉伸强度和冲击强度.当经过改性的OMMT质量分数为5%时,EP/钛酸酯偶联剂(Coupler)-OMMT复合材料的拉伸强度达到51.21 MPa,提高了40.26%;当OMMT质量分数为3%时,EP/Coupler-OMMT复合材料冲击强度达25.31 kJ/m2,提高了34.56%.     

Effect of Nano-CaCO3 on Mechanical and Thermal Properties of Polyamide Nanocomposites

Polyamide-CaCO₃ nanocomposites were prepared by melt intercalation on twin-screw extruder. Various particle sizes (23, 17 and 11 nm) of CaCO₃ were synthesized by in-situ deposition technique. The shape and sizes of nano-CaCO₃ particles were confirmed by transmission electron microscopy (TEM). Nano-CaCO₃ was added from 1 to 4 wt% in the polyamide. Properties such as Tensile strength, Elongation at break, Hardness, and Flame retardency were studied. These results were compared with commercial CaCO₃ filled composites. Nano-CaCO₃ filled in polyamide shows, 3 fold improvement in Young's modulus in comparison to commercial CaCO₃ and 4–7 folds to virgin polyamide. Besides that, a polyamide nanocomposite shows 2 times improvements in flame retarding and vicat softening properties compared to commercial CaCO₃. Moreover, thermal degradation was studied on TGA and found to be improved compared to commercial CaCO₃. This was due to uniform dispersion of nano-CaCO₃ with greater surface area in comparison to commercial CaCO₃ in the polyamide matrix. Extent of dispersion of nano-CaCO₃ was studied along with microcracks generated during tensile testing using scanning electron microscope (SEM).