Material characterization of blended epoxy resins related to fracture toughness

The present study describes the effect of the macromolecular modifications on the fracture toughness of an epoxy system. We synthesized epoxy networks by the reaction of diglycidyl ether of bisphenol A (DGEBA) with methyl-tetrahydro-phthalic anhydride (MTHPA), initiated by a tertiary amine. Several materials were obtained by adding a high molecular weight monomer to one with low molecular weight (both based on DGEBA) at different concentrations. In every case, a stoichiometric amount of MTHPA was employed. The glass transition temperature and the Angell’s fragility index, derived from thermo-viscoelastic properties, were used to characterize the materials. Relationship between these two parameters and the fracture properties, including the fracture toughness and the microscopic roughness of the fracture surfaces observed by atomic force microscope (AFM), was then investigated. We found that there were direct correlations among the glass transition temperature, the fragility, the fracture toughness, and the roughness. This study revealed that both the glass transition temperature and the fragility are effective for characterizing material in relation to the fracture toughness of the blended epoxy resins.     

Cryogenic mechanical behaviors of carbon nanotube reinforced composites based on modified epoxy by poly(ethersulfone)

Cryogenic mechanical properties are important parameters for epoxy resins used in cryogenic engineering areas. In this study, multi-walled carbon nanotubes (MWCNTs) were employed to reinforce diglycidyl ether of bisphenol F (DGBEF)/diethyl toluene diamine (DETD) epoxy system modified by poly(ethersulfone) (PES) for enhancing the cryogenic mechanical properties. The epoxy system was properly modified by PES in our previous work and the optimized formulation of the epoxy system was reinforced by MWCNTs in the present work. The results show that the tensile strength and Young’s modulus at 77 K were enhanced by 57.9% and 10.1%, respectively. The reported decrease in the previous work of the Young’s modulus of the modified epoxy system due to the introduction of flexible PES is offset by the increase of the modulus due to the introduction of MWCNTs. Meanwhile, the fracture toughness (K_IC) at 77 K was improved by about 13.5% compared to that of the PES modified epoxy matrix when the 0.5 wt.% MWCNT content was introduced. These interesting results imply that the simultaneous usage of PES and MWCNTs in a brittle epoxy resin is a promising approach for efficiently modifying and reinforcing epoxy resins for cryogenic engineering applications.     

Fracture toughness and mechanical behaviour of an epoxy resin

The variation of fracture and mechanical properties of epoxy resin Epikote 828, cured with diaminodiphenyl-methane by variation of the resin/amine ratio has been determined. Observations of the crack tip have shown that fracture toughness variations can be attributed to the different blunting characteristics of the various resin/amine compositions. A systematic variation in the thermal transitions of the resins also occurs as a function of composition. Investigations by chemical etching and small angle X-ray scattering have failed to reveal a structural entity which can be invoked to explain the trends in fracture and mechanical properties. It has been found that care must be taken when choosing the method of evaluation of fracture parameters in order that meaningful comparisons can be made between different resin compositions.     

Mechanical properties of epoxy composites reinforced with a low volume fraction of nanosilica fillers

In this paper we focus on the preparation and mechanical properties of the nanosilica-reinforced, epoxy resin Epikote 828LVEL. Epoxy composites containing two sizes of spherical silica nanoparticles, 130 nm and 30 nm, were prepared at a fixed volume fraction (V_P = 0.5%). To prevent agglomeration, the silica fillers were initially pre-treated with diglycidyl ether of bisphenol A (BADGE). Due to the low content of silica fillers, their inclusion in the matrix was confirmed by the increased roughness of a fracture surface compared to the smooth surface of the neat epoxy. Raman spectroscopy was employed to obtain additional information about the crack-propagation path. The mechanical properties, characterized by a three-point bending test, revealed a 10–20% increase in the composite's modulus of elasticity with 30-nm and 130-nm silica-filler inclusions. Elongation at break, on the other hand, decreased for 5–10% in both composites compared to neat epoxy, suggesting brittle fracture behavior in silica/epoxy composites. The fracture toughness results showed a 25–30% improved toughening for both composites compared to the pure epoxy. The composite's resistance to failure in terms of the impact energy was, however, strongly dependent on the size of the silica: we observed a 30% increase for the 130-nm, and a 60% increase for the 30-nm, silica/epoxy composites, compared to the pure epoxy.     

反应性聚碳酸酯/环氧树脂体系的反应活性与性能研究

采用DSC和TGA等方法研究了反应性聚碳酸酯/环氧树脂体系的固化特性，热性能和力学性能。结果表明，α-PC的加入，增加了体系的反应活性，固化体系的相容性也良好，形成一个均相网络结构。固化体系在350℃无任何分解，具有较好的耐热性，且体系的韧性也有所提高。     

Effects of testing temperature and thermal treatments on some mechanical properties of a Si3N4–TiN composite

Strength and fracture toughness of an electroconductive hot-pressed Si₃N₄–35vol.% TiN ceramic composite were evaluated in air as a function of testing temperature up to 1200 °C. The toughness already shows a clear decrease at 800 °C and then remains almost constant, and the flexural strength steadily decreases with increasing testing temperature. At 1200 °C, the strength value is about 40% of that measured at room temperature. After thermal treatments in air (800, 1000 and 1200 °C) and argon (1200 °C) for 100 h, the Young's modulus, hardness, fracture toughness and flexural strength were measured at room temperature and compared to the baseline material. Young's modulus and hardness remain unchanged. The fracture toughness does not show any clear trend with the treatment temperature, while the strength, which is unaffected by the thermal treatment in argon, decreases with increasing treatment temperature in air. The long-term oxidation involves microstructural changes at the surface and in the bulk, such as the formation of a surface oxide layer and a porous sub-layer. In the bulk, the main modification is the partial crystallization of the grain boundary phase.     

混合型固化剂对环氧树脂室温和低温力学性能的影响

研究了一种刚性和柔性胺混合型固化剂（芳香胺DETD和聚醚胺D-400）固化环氧树脂浇铸体的力学性能、材料断裂表面的微观形貌和玻璃化转变温度等性能。结果表明:当D-400加入量占固化剂总量的40%时,其室温拉伸强度呈现最大值,为82.52 MPa,弹性模量为2.30 GPa,与未加D-400的体系相比分别提高了6.3%和14.4%,其低温冲击强度提高了14%。对冲击断面形貌进行扫描电子显微分析表明:D-400的加入致使断口形貌变得粗糙,抗开裂能力得到提高。热分析实验结果显示,体系的玻璃化转变温度随着D-400含量的增加而降低。此外,还探讨了环氧树脂体系低温增韧机制。      

Influence of electroless nickel-plating on fracture toughness of pitch-based carbon fibre reinforced composites

Nickel-Pitch-based carbon fibres (Ni-PFs) were prepared by electroless nickel-plating to enhance fracture toughness of Ni-PFs reinforced epoxy matrix composites (Ni-PFs/epoxy). The surface properties of Ni-PFs were determined by scanning electron microscopy (SEM), X-ray photoelectron spectrometry (XPS), and X-ray diffraction (XRD). The fracture toughness of the Ni-PFs/epoxy was assessed by critical stress intensity factor (K_IC) and critical strain energy release rate (G_IC). The fracture toughness of Ni-PFs/epoxy was enhanced compared to those of PFs/epoxy. These results were attributed to the increase of the degree of adhesion at interfaces between Ni-PFs and matrix resins in the composites.     

Prestressed double network thermoset: preparation and characterization

An innovative scheme to prepare Prestressed double network (PDN) epoxies is presented using a judicious combination of tetrafunctional curatives that have similar molecular weights but different reaction kinetics. A diglycidyl ether of bisphenol A epoxy monomer was reacted stoichiometrically and sequentially with various molar ratios of an aliphatic polyetheramine curing agent and an aromatic curing agent. Deformation was imposed on the partially cured resins after the formation of the first network, and postcuring was conducted at 50% compressive strain. Physical properties of the resulting PDN epoxies were examined using thermomechanical analysis, dynamic mechanical analysis, uniaxial tensile test, and plane-strain fracture toughness test. The application of prestress resulted in no changes in glass transition temperature, coefficient of linear thermal expansion, and Young’s modulus. However, a marked increase in fracture toughness is observed, accompanied by strong birefringence and visible roughness on the fracture surface.     

Non-stoichiometric curing effect on fracture toughness of nanosilica particulate-reinforced epoxy composites

Non-stoichiometric curing effects on the fracture toughness behaviors of nanosilica particulate-reinforced epoxy composites were experimentally investigated in this study by comparing them with bending strengths to take into consideration the effect of interaction between nanoparticles and network structures in matrix resins. The matrixes were prepared by curing them with an excess mixture of diglycidyl ether of bisphenol A-type epoxy resin as the curing agent for the stoichiometric condition. The volume fractions of the silica particles with a median diameter of 240 nm were constantly 0.2 for all composites. The neat epoxy resins and the composites were cured non-stoichiometrically to change the crosslinking densities of the neat epoxy resins and the matrix resins of the composites within 2740–490 mol/m³. The fracture toughnesses and bending strengths of the composites and the neat epoxy resins strongly depended on the crosslinking densities in the resins. Although the fracture toughness decreased monotonously from that of the stoichiometrically cured resins as the crosslinking density decreased, the fracture toughnesses of composites were largest at a slightly lower crosslinking density of approximately 2490 mol/m³ from the stoichiometric condition of 2740 mol/m³. The fracture toughness and the bending strength were improved for crosslinking densities higher than 2000 mol/m³ by adding particles. At crosslinking density lower than 2000 mol/m³, the particles worked against the mechanical properties as defects in matrix resins.     

Temperature dependence of fracture toughness of epoxy resins cured with diamines

The fracture toughness (critical stress intensity factor, K _Ic) of epoxy resins cured with four diamines has been measured as a function of temperature over the range from –35° C to above T _g. It was found that K _Ic for each epoxy-diamine system did not vary below room temperature, and in the higher temperature range K _Ic increased with increasing temperature to a maximum and then decreased. The temperature which maximized K _Ic, agreed with the temperature at which the flexural modulus of the epoxy resins abruptly dropped. This temperature was therefore considered as T _g. This temperature was found to be about 20° C lower than the heat deflection temperature under load (1.82 M Pa) of the resins.     

Epoxy composites with 200 nm thick alumina platelets as reinforcements

Composites were prepared by dispersing Alumina platelets of polygonal shape having a thickness of 200 nm and size of 5–10 μm in epoxy (LY 556) matrix using sonication. Good dispersion of the platelets was observed through scanning electron microscopy (SEM). The quasi-static plane-strain fracture toughness and tensile properties of the composites were determined for platelet volume fraction varying from 0% to 10%. The results indicated that addition of the platelets give considerable improvement in fracture toughness and good improvement in the elastic modulus of epoxy. For 10% volume fraction of the platelets, the fracture toughness improved by 110% where as the improvement in elastic modulus was 78%. However there was an associated reduction of 53% in tensile strength and 73% in failure strain. SEM of fractured surface was carried out to understand the various mechanisms responsible for the improvement in fracture toughness. By appropriately accounting for the orientation and stacking effects of the platelets, the applicability of predictive models, such as the Halpin-Tsai and Mori-Tanaka, for estimating the composite modulus is demonstrated.     

Mode I interlaminar fracture behavior and mechanical properties of CFRPs with nanoclay-filled epoxy matrix

The mechanical properties and fracture behavior of nanocomposites and carbon fiber composites (CFRPs) containing organoclay in the epoxy matrix have been investigated. Morphological studies using TEM and XRD revealed that the clay particles within the epoxy resin were intercalated or orderly exfoliated. The organoclay brought about a significant improvement in flexural modulus, especially in the first few wt% of loading, and the improvement of flexural modulus was at the expense of a reduction in flexural strength. The quasi-static fracture toughness increased, whereas the impact fracture toughness dropped sharply with increasing the clay content.Flexural properties of CFRPs containing organoclay modified epoxy matrix generally followed the trend similar to the epoxy nanocomposite although the variation was much smaller for the CFRPs. Both the initiation and propagation values of mode I interlaminar fracture toughness of CFRP composites increased with increasing clay concentration. In particular, the propagation fracture toughness almost doubled with 7 wt% clay loading. A strong correlation was established between the fracture toughness of organoclay-modified epoxy matrix and the CFRP composite interlaminar fracture toughness.     

Fracture toughness of the nano-particle reinforced epoxy composite

Although thermoset polymers have been widely used for engineering components, adhesives and matrix for fiber-reinforced composites due to their good mechanical properties compared to those of thermoplastic polymers, they are usually brittle and vulnerable to crack. Therefore, ductile materials such as micro-sized rubber or nylon particles are added to thermoset polymers are used to increase their fracture toughness, which might decrease their strength if micro-sized particles act like defects.In this work, in order to improve the fracture toughness of epoxy adhesive, nano-particle additives such as carbon black and nanoclay were mixed with epoxy resin. The fracture toughness was measured using the single edge notched bend specimen at the room (25 °C) and cryogenic temperature (−150 °C). From the experimental results, it was found that reinforcement with nano-particles improved the fracture toughness at the room temperature, but decreased the fracture toughness at the cryogenic temperature in spite of their toughening effect.     

Fiber-reinforced composites based on epoxy resins modified with elastomers and surface-modified silica nanoparticles

The properties of fiber-reinforced composites made using epoxy resin formulations can be improved using modified epoxy resins. As epoxies are inherently brittle, they are toughened with reactive liquid rubbers or core–shell elastomers. Surface-modified silica nanoparticles, 20 nm in diameter and with a very narrow particle size distribution, are available as concentrates in epoxy resins in industrial quantities for the past 10 years. Some of the drawbacks of toughening like lower modulus or a loss in strength can be compensated when using nanosilica together with these tougheners. Apparently, there exists a synergy as toughness and fatigue performance are increased significantly. Some of these improvements in bulk resin properties can be found for fiber-reinforced composites as well. In this article, the literature published in the last decade is studied with a focus on mechanical properties. Results are compared, and the mechanisms responsible for the property improvements are discussed. A relationship between the improvements of the fracture energy of the cured bulk epoxy resins and the fracture energy of the fiber-reinforced composites could be established.     

Simultaneously enhanced cryogenic tensile strength and fracture toughness of epoxy resins by carboxylic nitrile-butadiene nano-rubber

Epoxy resins are important matrices for composites. Carboxylic nitrile-butadiene nano-rubber (NR) particles are employed to improve the tensile strength and fracture toughness at 77 K of diglycidyl ether of bisphenol-F epoxy using diethyl toluene diamine as curing agent. It is shown that the cryogenic tensile strength and fracture toughness are simultaneously enhanced by the addition of NR. Also, the fracture toughness at room temperature (RT) is enhanced by the addition of NR. On the other hand, the tensile strength at RT first increases and then decreases with further increasing the NR content up to 5 phr. 5 phr NR is the proper content, which corresponds to the simultaneous enhancements in the tensile strength and fracture toughness at RT. Moreover, the comparison of mechanical properties between 77 K and room temperature indicates that the tensile strength, Young’s modulus and fracture toughness at 77 K are higher than those at RT but the failure strain shows the opposite results. The results are properly explained by the SEM observation.     

CF/EP composite laminates with carbon black and copper chloride for improved electrical conductivity and interlaminar fracture toughness

An experimental study was conducted to improve the electrical conductivity of continuous carbon fibre/epoxy (CF/EP) composite laminate, with simultaneous improvement in mechanical performance, by incorporating nano-scale carbon black (CB) particles and copper chloride (CC) electrolyte into the epoxy matrix. CF/EP laminates of 65 vol.% of carbon fibres were manufactured using a vacuum-assisted resin infusion (VARI) technique. The effects of CB and the synergy of CB/CC on electrical resistivity, tensile strength and elastic modulus and fracture toughness (K_IC) of the epoxy matrix were experimentally characterised, as well as the transverse tensile modulus and strength, Mode I and Mode II interlaminar fracture toughness of the CF/EP laminates. The results showed that the addition of up to 3.0 wt.% CB in the epoxy matrix, with the assistance of CC, noticeably improved the electrical conductivity of the epoxy and the CF/EP laminates, with mechanical performance also enhanced to a certain extent.     

Effect of microfibrillated cellulose on mechanical properties of plain-woven CFRP reinforced epoxy

This investigation concerns about study the effect of natural fiber on high performance composite. Effect of addition microfibrillated cellulose (MFC) as natural fiber to plain woven carbon fiber reinforced plastic (CF) reinforced epoxy on mechanical and thermal properties has been investigated. CF/epoxy composites with addition 0.5, 1 and 2 wt.% of MFC were characterized by different techniques, namely tensile, DMA, fracture toughness (mode I) test and SEM. The results reveal that at 2 wt.% of MFC, initiation and propagation interlaminar fracture toughness in mode I improved significantly by 80% and 44% respectively. Although there is slight tendency to increase tensile strength and Young’s modulus with addition MFC up to 2%, it is still not significant with those low contents of MFC. With addition 2 wt.% MFC, the glass transition temperature increased by about 12 °C compared to neat CF/epoxy composite indicating better heat resistance with addition of MFC.     

Thermo-mechanical properties of randomly oriented carbon/epoxy nanocomposites

The thermo-mechanical properties of epoxy-based nanocomposites based on low weight fractions (from 0.01 to 0.5 wt%) of randomly oriented single- and multi-walled carbon nanotubes were examined. Preparation methods for the nanocomposites, using two types of epoxy resins, were developed and good dispersion was generally achieved. The mechanical properties examined were the tensile Young's modulus by Dynamic Mechanical Thermal Analysis and the toughness under tensile impact using notched specimens. Moderate Young's modulus improvements of nanocomposites were observed with respect to the pure matrix material. A particularly significant enhancement of the tensile impact toughness was obtained for specific nanocomposites, using only minute nanotube weight fractions. No significant change in the glass transition temperature of SWCNT/epoxy nanocomposites was observed, compared to that of the epoxy matrix. The elastic modulus of the SWNT-based nanocomposites was found to be slightly higher than the value predicted by the Krenchel model for short-fiber composites with random orientation.     

The effects of alumina nanofillers on mechanical properties of high-performance epoxy resin

In the past decade extensive studies have been focused on mechanical properties of inorganic nanofiller/epoxy matrices. In this work we systematically investigated the mechanical properties of nano-alumina-filled E-54/4, 4-diaminodiphenylsulphone (DDS) epoxy resins, which were prepared via combining high-speed mixing with three-roll milling. Homogeneous dispersion of nano-alumina with small agglomerates was obtained in epoxy resin, which was confirmed using transmission electron microscopy (TEM). The static/dynamic modulus, tensile strength and fracture toughness of the nanocomposites were found to be simultaneously enhanced with addition of nano-alumina fillers. About 50% and 80% increases of K(IC) and G(IC) were achieved in nanocomposite filled with 18.4 wt% alumina nanofillers, as compared to that of the unfilled epoxy resin. Furthermore, the corresponding fracture surfaces of tensile and compact tension samples were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques in order to identify the relevant fracture mechanisms involved. Various fracture features including cavities/debonding of nanofiller, local plastic deformation as well as crack pinning/deflection were found to be operative in the presence of nano-alumina fillers.