Effect of silica nanoparticle size on toughening mechanisms of filled epoxy

The addition of silica nanoparticles (23 nm, 74 nm, and 170 nm) to a lightly crosslinked, model epoxy resin, was studied. The effect of silica nanoparticle content and particle size on glass transition temperature (T_g), coefficient of thermal expansion (CTE), Young's modulus (E), yield stress (σ), fracture energy (G_IC) and fracture toughness (K_IC), were investigated. The toughening mechanisms were determined using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and transmission optical microscopy (TOM). The experimental results revealed that the addition of silica nanoparticles did not have a significant effect on T_g or the yield stress of epoxy resin, i.e. the yield stress and T_g remained constant regardless of silica nanoparticle size. As expected, the addition of silica nanoparticles had a significant impact on CTE, modulus and fracture toughness. The CTE values of nanosilica-filled epoxies were found to decrease with increasing silica nanoparticle content, which can be attributed to the much lower CTE of the silica nanoparticles. Interestingly, the decreases in CTE showed strong particle size dependence. The Young's modulus was also found to significantly improve with addition of silica nanoparticles and increase with increasing filler content. However, the particle size did not exhibit any effect on the Young's modulus. Finally, the fracture toughness and fracture energy showed significant improvements with the addition of silica nanoparticles, and increased with increasing filler content. The effect of particle size on fracture toughness was negligible. Observation of the fracture surfaces using SEM and TOM showed evidence of debonding of silica nanoparticles, matrix void growth, and matrix shear banding, which are credited for the increases in toughness for nanosilica-filled epoxy systems. Shear banding mechanism was the dominant mechanism while the particle debonding and plastic void growth were the minor mechanisms.     

Mechanical characterization of porous Ba0.5Sr0.5Co0.8Fe0.2O3−d

The mechanical stability of porous Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−d (BSCF) material was investigated using depth-sensitive microindentation and ring-on-ring biaxial bending tests. The porous BSCF was characterized as potential substrate material for the deposition of a dense membrane layer. Indentation tests yielded values for hardness and fracture toughness up to a temperature of 400 °C, while bending tests permitted an assessment of elastic modulus and fracture stress up to 800 °C. In addition the fracture toughness was evaluated up to 800 °C measuring in bending tests the fracture stress of pre-indented specimens. The results proof that the indentation-strength method can be applied for the determination of the fracture toughness of this porous material. In comparison to dense material the values of the mechanical parameters were as expected lower but the temperature dependences of elastic modulus, fracture strength and toughness were similar to those reported for dense BSCF.     

Hydrothermal effects on the thermomechanical properties of high performance epoxy/clay nanocomposites

The effects of hydrothermal ageing on the thermomechanical properties of high performance epoxy and its nanocomposite were studied. The epoxy–clay nanocomposite was prepared through a recently developed “slurry‐compounding” approach. The cured samples were immersed in distilled water at 60°C for different periods of time before subjecting to characterization. The storage modulus, relaxation behavior, fracture toughness, and tensile properties were investigated. It was found that the storage modulus and α‐relaxation were strongly affected by water uptake, while the fracture toughness and Young's modulus were less influenced. Dependence of tensile strength and strain at break on water uptake was found to be different in neat epoxy and epoxy–clay systems. POLYM. ENG. SCI., 46:215–221, 2006. © 2005 Society of Plastics Engineers     

Deformation and fracture behaviour of a rubber-toughened epoxy: 2. Failure criteria

In part 1 the microstructure and fracture characteristics of a rubber-modified epoxy, and for comparison that of the unmodified epoxy, were examined in detail. Based on this analysis a qualitative mechanism involving cavitation, shear yielding and plastic flow was proposed. As an extension of this work, the present paper considers the yield behaviour of the epoxy material and uses the data determined, together with the previously reported fracture results, to calculate values of the crack opening displacement. The rate/temperature dependence of the crack opening displacement and the correlations established between stress intensity factor, K_Ic, yield stress and type of crack growth suggest that the extent of crack tip blunting largely governs the relative toughness of the epoxy materials and induces transitions in the types of crack growth observed. A quantitative expression is then presented which successfully describes the fracture toughness values over a wide range of temperatures and rates. The two parameters in this expression are shown to be material constants and therefore provide a unique failure criterion. They can be viewed simply as curve-fitting parameters but they may also have some significance in terms of a critical stress that must act over a critical distance ahead of the crack tip to produce crack growth.     

Microstructural,mechanical, and thermal characteristics of recycled cellulose fiber‐halloysite‐epoxy hybrid nanocomposites

Epoxy hybrid‐nanocomposites reinforced with recycled cellulose fibers (RCF) and halloysite nanotubes (HNTs) have been fabricated and investigated. The dispersion of HNTs was studied by synchrotron radiation diffraction (SRD) and transmission electron microscopy (TEM). The influences of RCF/HNTs dispersion on the mechanical properties and thermal properties of these composites have been characterized in terms of flexural strength, flexural modulus, fracture toughness, impact toughness, impact strength, and thermogravimetric analysis. The fracture surface morphology and toughness mechanisms were investigated by SEM. Results indicated that mechanical properties increased because of the addition of HNTs into the epoxy matrix. Flexural strength, flexural modulus, fracture toughness, and impact toughness increased by 20.8, 72.8, 56.5, and 25.0%, respectively, at 1 wt% HNTs load. The presence of RCF dramatically enhanced flexural strength, fracture toughness, impact strength, and impact toughness of the composites by 160%, 350%, 444%, and 263%, respectively. However, adding HNTs to RCF/epoxy showed only slight enhancements in flexural strength and fracture toughness. The inclusion of 5 wt% HNTs into RCF/epoxy ecocomposites increased the impact toughness by 27.6%. The presence of either HNTs or RCF accelerated the thermal degradation of neat epoxy. However, at high temperature, samples reinforced with RCF and HNTs displayed better thermal stability with increased char residue than neat resin. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

自修复聚合物材料用微胶囊

Microcapsules with dicyclopentadiene (DCPD) as core material and urea formaldehyde resin as wall material used for making self-healing polymer material were prepared with the in-situ polymerization method. The effect of microcapsules on the fracture toughness of epoxy resin was studied. The addition of microcapsules into epoxy resin results in the decrease of fracture toughness. When microcapsule content was kept constant, as the microcapsule size increased the fracture toughness of the epoxy resin decreased linearly and the percentage of decrease compared to the neat epoxy without microcapsules increased linearly. Moreover, the fracture toughness of the material decreases linearly with the increase of microcapsule content.     

Deformation and fracture behaviour of a rubber-toughened epoxy: 1. Microstructure and fracture studies

The microstructure and fracture behaviour of an unmodified and a rubber-modified epoxy have been studied. Values of the stress intensity factor, K_Ic, at the onset of crack growth, the type of crack growth, and the detailed nature of the associated fracture surfaces have been ascertained. Both materials exhibit essentially the same types of crack growth but the values of K_Ic for the rubber-modified material were usually significantly higher than those for the nmodified epoxy. The mechanisms for this increased toughness have been considered and a mechanism that accounts for all the observed characteristics has been proposed.     

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.     

Dispersed microfibril‐dominated deformation and fracture behaviors of linear low density polyethylene/isotactic polypropylene blends

Linear low density polyethylene/isotactic polypropylene (LLDPE/iPP) blends, with oriented microfibrils of iPP dispersed in the nearly isotropic LLDPE matrix, has been prepared via melt extrusion drawing and subsequent thermal treatment at 160°C to melt LLDPE matrix. The presence of oriented microfibrils of iPP in the LLDPE/iPP blends not only promotes the homogenous deformation, with no drop of nominal stress around yield point, but also enhances the fracture toughness significantly. The specific Essential Work of Fracture w_e, which is a pure crack resistance parameter per ligament area unit, is 24.7 and 33.6 N/mm for the blends with 15 and 30 wt % microfibrils of iPP, respectively. Moreover, with the deduced deformation parameters, such as true yield stress and strain hardening modulus, the relationship between deformation parameters and fracture toughness is explored. It is demonstrated that the fracture toughness can be well correlated with the ratio of true yield stress to strain hardening modulus σ_ty/G, and either a decrease in yield stress or an increase in strain hardening can improve fracture toughness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1291–1298, 2007     

The fracture toughness and stress corrosion cracking characteristics of an anhydride-hardened epoxy adhesive

The toughness and stress corrosion cracking characteristics of an epoxy resin (DER 332) hardened with hexahydrophthalic anhydride (HHPA) were investigated. The epoxy was studied in both the bulk and bond form, and its properties were compared with an amine-hardened (tetraethylene pentamine, TEPA) system. The toughness, ??_Ic, of the anhydride system varied less as a function of ratio of hardener-to-resin content and postcure temperature than it did in the TEPA-hardened system. Like the latter, however, its toughness in the bulk and bond forms could not be correlated, but ??_Ic of the joints was dependent on tensile modulus and/or yield strength of the bulk epoxy. Both systems were also toughened in the vicinity of the crack tip by water for short-time loading, but their long-time load carrying capability was reduced by a water environment. The anhydride hardened system was more sensitive to strength loss in water than the amine system. The fracture morphology for the two systems was the same, i.e., fast cracking occurred cohesively near the center of the bond, and slow cracking occurred at the interface.     

Influence of multiwalled carbon nanotubes on the processing behavior of epoxy powder compositions and on the mechanical properties of their fiber reinforced composites

This study reports the preparation of advanced carbon fiber composites with a nanocomposite matrix prepared by dispersing multiwall carbon nanotubes (CNTs) in a powder type epoxy oligomer with two different processing techniques (1) master batch dilution technique and (2) direct mixing (with the help of twin‐screw extruder in both cases). The master batch technique shows a better efficiency for the dispersion of the CNTs aggregates. The rheological results demonstrate that the incorporation of the CNTs into the epoxy oligomer leads, as expected, to a marked increase in the viscosity and of the presence of a yield stress point that also depends on the processing technique adopted. Carbon fiber (CFRP) and glass fiber (GFRP) composite materials were produced by electrostatic spraying of the epoxy matrix formulations on the carbon and glass fabric, respectively, followed by calendering and mold pressing. The mechanical properties of the obtained epoxy/CNT‐matrix composite materials, such as interlaminar fracture toughness, flexural strength, shear storage and loss moduli are discussed in terms of the processing techniques and fabric material. The incorporation of 1 wt% CNTs in the epoxy matrix results in a relevant increase of the fracture toughness, flexural strength and modulus of both CFRP and GFRP. POLYM. COMPOS., 37:2377–2383, 2016. © 2015 Society of Plastics Engineers     

Mechanical properties of phenolphthalein polyether ketone: Yield stress,young's modulus,and fracture toughness

A series of tensile and three-point bending studies was conducted at various temperatures and loading rates using phenolphthalein polyether ketone (PEK-C). Yield stress, Young's modulus, fracture toughness, and crack opening displacement data were obtained for various conditions. In general, both yield stress and Young's modulus increase with decreasing temperature. However, the relationships between fracture toughness, loading rate, and temperature are very complex. This behavior is due to the simultaneous intersection of viscoelasticity and localized plastic deformation. The increased yield stress is the main factor contributing to the reduction in fracture toughness and crack opening displacement. The relationship between fracture toughness and yield stress are discussed. © 1995 John Wiley & Sons, Inc.     

Fracture toughness of an epoxy system

The fracture toughness of epoxy used in the bulk and adhesive form was measured by a previously developed technique. The uniform double cantilever-beam specimen, which was described earlier, was modified to a tapered beam, which simplified the experimental procedure and calculations for obtaining toughness measurements. by varying the ratio of hardener to resin and post-cure temperature on a single epoxy system (DER 332-TEPA), it was found that the toughness of the epoxy used in either bulk or bond form varied by a factor of approximately five. A particular combination of composition and post-curing temperature generally yielded higher toughness in the bulk than in the bond form. This was not always the case, however. At high post-cure temperatures, where the bonds were very tough, their toughness exceeded that of the bulk material. Hence, it does not appear possible to predict joint toughness from bulk toughness measurements. The toughness of joints was found to be a single-valued function of tensile modulus. For the bulk material, on the other hand, the toughness obtained on the epoxy having a specific modulus depended on the combination of composition and post-cure temperature. Joint toughness for any combination of composition and post-cure temperature depended only on the cracking rate. If the epoxy was the type that caused cracks to jump rapidly, the epoxy was tough and vice versa. For a particular epoxy system, toughness was increased by driving the crack at an increasing rate.     

Synergistic Toughening in Ternary Silica/Hollow Glass Spheres/Epoxy Nanocomposites

Herein, the fracture toughness of ternary epoxy systems containing nanosilica and hollow glass microspheres (HGMS) is investigated. The experimental measurements reveal synergistic fracture toughness in some hybrid compositions: The incorporation of 10 phr of HGMS and nanosilica alone modify the fracture toughness of epoxy by 39% and 91%, respectively. However, use of 10 phr hybrid modifier can enhance the fracture toughness of the resin up to 120%. Observations reveal different toughening mechanisms for the blends i.e., plastic deformation for silica nanoparticles and crack bifurcation for HGMS. Both of these toughening mechanisms additively contribute to the synergism in ternary epoxies.     

Structure-property relationships in rubber-toughened epoxies

Epoxies toughened with two reactive liquid rubbers, an epoxy-terminated butadiene acrylonitrile rubber (ETBN) and an amino-terminated butadiene acrylonitrile rubber (ATBN), were prepared and studied in terms of their structure property relationships. A two-phase structure was formed, consisting of spherical rubber particles dispersed in an epoxy matrix. A broad distribution of rubber particles was observed in all the materials with most of the particles ranging in size from 1 to 4 μm, but some particles exceeding 20 μm were also found. Impact strength, plane strain fracture toughness (K_IC), and fracture energy (G_IC) were increased, while Young's modulus and yield strength decreased slightly with increasing rubber content and volume fraction of the dispersed phase. Both G_IC and K_IC were found to increase with increasing apparent molecular weight between crosslinks and decreasing yield strength. The increased size of the plastic zone at the crack tip associated with decreasing yield strength could be the cause of the increased toughness. An ATBN-toughened system containing the greatest amount of epoxy sub-inclusion in the rubbery phase demonstrated the best fracture toughness in this series. In the present systems, rubber-enhanced shear deformation of the matrix is considered to be the major toughening mechanism. Curing conditions and the miscibility between the liquid rubber and the epoxy resin determine the phase morphology of the resulting two-phase systems. Kerner's equation successfully describes the modulus dependence on volume fraction for the two-phase epoxy materials.     

Silicon Carbide Platelet/Alumina Composites: II, Mechanical Properties

The mechanical properties, i.e., Young's modulus, fracture toughness, and flexural strength, of SiC-platelet/Al₂O₃ composites with two different platelet sizes were studied. Both Young's modulus and the fracture toughness of composites using small platelets (12 μm) increased with increasing SiC volume fraction. Maximum values for toughness and Young's modulus of 7.1 MPa·m^1/2 and 421 GPa were obtained for composites containing 30 vol% platelets. Composites fabricated using larger platelets (24 μm), however, showed spontaneous microcracking at SiC volume fractions of ≤0.15. The presence of microcracks decreased Young's modulus and the fracture toughness substantially. Two types of radial microcracks were identified by optical microscopy and found to be consistent with a residual stress analysis. Anisotropy in fracture toughness was identified with a crack length indentation technique. Cracks propagating in a plane parallel to platelet faces experienced the least resistance, which was the the lowest toughness plane in platelet composites with preferred orientation. Enhanced fracture toughness was found in the plane parallel to the hot-pressing direction, but no anisotropy in toughness was observed in this plane. The flexural strength of alumina showed a decrease from 610 to 480 MPa for a 30 vol% composite and was attributed to the presence of the platelets.     

Toughening epoxies with halloysite nanotubes

An experimental attempt was made to characterize the fracture behaviour of epoxies modified by halloysite nanotubes and to investigate toughening mechanisms with nanoparticles other than carbon nanotubes (CNTs) and montmorillonite particles (MMTs). Halloysite-epoxy nanocomposites were prepared by mixing epoxy resin with halloysite particles (5 wt% and 10 wt%, respectively). It was found that halloysite nanoparticles, mainly nanotubes, are effective additives in increasing the fracture toughness of epoxy resins without sacrificing other properties such as strength, modulus and glass transition temperature. Indeed, there were also noticeable enhancements in strength and modulus for halloysite-epoxy nanocomposites because of the reinforcing effect of the halloysite nanotubes due to their large aspect ratios. Fracture toughness of the halloysite particle modified epoxies was markedly increased with the greatest improvement up to 50% in K_IC and 127% in G_IC. Increases in fracture toughness are mainly due to mechanisms such as crack bridging, crack deflection and plastic deformation of the epoxy around the halloysite particle clusters. Halloysite particle clusters can interact with cracks at the crack front, resisting the advance of the crack and resulting in an increase in fracture toughness.     

Synergetic effect of carbon nanofibers and short carbon fibers on the mechanical and fracture properties of epoxy resin

The effects of carbon nanofibers (CNFs) and combinations of CNFs with microsized short carbon fibers (SCFs) on the mechanical and fracture properties of epoxy resin were investigated. The combined use of CNFs and SCFs leads to significant synergy in the mechanical and fracture properties. The composites reinforced with the combined multiscale fillers exhibit much higher modulus, strength and fracture toughness than the composites reinforced solely with either micro- or nanofillers. The mechanisms of such synergism were analyzed by fracture studies using scanning electron microscopy. The release of overstresses near to SCFs by stress transfer and redistribution, realized by CNFs, was traced to the synergistic effects observed.     

Critical stress intensity factor of epoxy mortar

Fracture behavior of epoxy mortar was investigated in Mode I fracture using single edge notched beams with varying notch depth and beam thickness. The beams were loaded in both 3-point and 4-point bending. Influence of polymer content and temperature on the fracture behavior of epoxy mortar was studied using uniform Ottawa 20–30 sand. The polymer content was varied between 10 percent and 18 percent of the total weight of the composite. The temperature was varied between 22°C and 120°C. The flexural strength of the polymer mortar increases with increase in polymer content while the flexural modulus goes through a maximum. The critical stress intensity factor (K_IC) was determined by several methods including compliance method (based on crack mouth opening displacement) and finite element analysis. The K_IC for epoxy mortar increases with increase in polymer content and epoxy mortar strength but decreases with increase in temperature. The critical stress intensity factor of epoxy mortar is represented in terms of polymer content and polymer strength or stiffness. Numerical tests based on random sampling and stratified sampling procedures were performed to substantiate the experimentally observed fracture toughness values of epoxy mortar.     

Mode I interlaminar fracture toughness of Nylon 66 nanofibrilmat interleaved carbon/epoxy laminates

Carbon/epoxy laminates interleaved with laboratory scale electrospun Nylon 66 nanofibrilmat and spunbonded nonwoven mats were investigated. The effect of the nanoscale fibers on the fracture toughness of the composite under pure Mode I loading was evaluated. It was shown that the nanofibrilmat is responsible for a major interlaminar fracture toughness improvement, as high as 255–322%, compared to a noninterleaved carbon/epoxy reference laminate. We further studied the improvement mechanism of the electrospun nanofibrilmat compared to a commercial spunbonded nonwoven Nylon 66 mat. A combination of two interlayer fracture mechanisms responsible for the toughness improvement is suggested: the first is related to the high energy dissipated by bridged thermoplastic nanofibers and the second is attributed to the generation of a plastic zone near the crack tip. The interlaminar fracture mechanisms of both electrospun nanofibrilmat and the nonwoven mat interleaving was analyzed and discussed. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers