Stability of crack propagation in epoxy resins

The propagation of cracks in epoxy resins has been studied using a linear elastic fracture mechanics approach and a double torsion testing geometry. Under constant crosshead displacement rate conditions cracks are found to propagate in an unstable ‘stick-slip’ manner at high temperatures and with low rates of testing whereas at lower temperatures and using higher rates of loading propagation is more stable and cracks propagate in a continuous manner. The presence of liquid water tends to cause a transition from stable to unstable propagation at room temperature. The influence of specimen geometry upon crack stability is also discussed.     

Very slow crack growth during osmosis in epoxy and in polyester resins

It has been demonstrated that osmotic pressure filled cracks in both epoxy and polyester resins are elastic cracks. Use of classical formulas for elastic cracks has enabled estimates to be made of the time dependence of Young's modulus for both resins. Use of linear elastic fracture mechanics formulas has enabled stress intensity factors to be determined from measurements of crack profiles. Radical crack growth rates are small, in the range 10^?12–10^?9 ms^?1 for hot water tests, and remain constant over a wider range of stress intensity factor, from 0.3 to 0.8 MPa.m^1/2. To a first approximation, constant radial growth rate is compatible with a diffusion controlled mechanism. However, analysis of the data indicates an activation energy of ～50 kcal. Some evidence is presented for concluding that, in polyesters at least, the true nature of crack propagation can be by way of slip/stick.     

Improvement of the Adhesive Fracture Toughness of Bonded Aluminum Joints Using E-Glass Fibers at Cryogenic Temperature

Fracture toughness and crack resistance of aluminum adhesive joints were measured at the cryogenic temperature of ?150°C, with respect to the orientation and volume fraction of the E-glass fibers in the epoxy adhesive. Cleavage tests on the DCB (Double Cantilever Beam) adhesive joints were performed using two different test rates of 1.67 × 10^?2 and 8.33 × 10^?4 mm/s to observe the crack propagation trends. From the experiments, it was found that the DCB joints bonded with the epoxy adhesive reinforced with E-glass fibers not only showed a stable crack propagation with a low crack propagation speed, but also higher fracture toughness and crack resistance than those of the DCB joints bonded with the unreinforced epoxy adhesive at a cryogenic temperature of ?150°C.     

Strain dependent energy dissipation in multi-scale carbon fiber composites containing carbon nanofibers

This study investigates strain dependent energy dissipation characteristics in carbon nanofiber (CNF) reinforced carbon fiber epoxy composites (multi-scale composites) by characterizing their viscoelastic properties and vibrational damping response. The air damping effect on the energy dissipation characteristics is also examined. The viscoelastic properties of epoxy containing two weight fractions (3 and 5 wt%) of added CNFs were characterized using dynamic mechanical analysis. Carbon fiber layers were then infiltrated with the two epoxy resins containing the CNFs to form multi-scale composites. A strain dependent loss factor behavior of the multi-scale composites was observed in the dynamic cyclic testing due to CNF’s stick–slip friction, showing a 53% increase in loss factor for the composites containing 5 wt% CNFs. The beam vibration test results also indicated an improvement in loss factor for the multi-scale composite beams relative to those without the CNF addition in the first two resonant frequencies. The multi-scale composite beams exhibit an increase in loss factor, up to 43%, at high amplitude excitation, while a reduction in loss factor was seen at low amplitude. These observed strain dependent damping characteristics seem to result from both the stick–slip friction and the air damping effect.     

Adhesive Properties of Epoxy Resin with Chromic Hardener

Cohesive and adhesive properties have been compared of epoxy resins crosslinked either with chromic‐based hardener or with conventional amine‐type hardener. Higher cohesive parameters, such as yield strength, Young's modulus and impact resistance were observed for the material cured with chromic hardener. The adhesive strength of metal‐metal joints (steel‐aluminium) has been also found to be higher for chromic hardener containing epoxy compared to conventional curing systems. The time dependencies of adhesive strength after thermal treatment at 140°C of the joints showed a higher thermal resistance of the epoxy with chromic hardener when compared to the amine cured resin.     

Correlation between nodular morphology and fracture properties of cured epoxy resins

Various bulk epoxy resin formulations, based on diglycidyl ether of bisphenol A (DGEBA) and cured with diethylene triamine (DETA) were studied. Methods of linear elastic fracture mechanics were employed and all systems were characterized by the corresponding values of the critical strain energy release rate for crack initiation and crack arrest. Fracture morphology was studied by scanning electron microscopy and transmission electron microscopy of carbon—platinum surface replicas. An apparent correlation between morphology and ultimate mechanical properties has been found. All fracture surfaces are shown to be characterized by distinct nodular morphology. Nodules, ranging in size from 15–45 nm, represent the sites of higher crosslink density in an inhomogeneous network structure. Fracture surfaces were further characterized by three crack propagation zones. A smooth, brittle fracture zone was preceded and followed by crack initiation and crack arrest zones, respectively. An apparent plastic flow was confined to the initiation and arrest regions. No crazing phenomenon was seen in the initiation zone; instead a step-like fracture was observed, typified by the ‘flow’ of internodular matrix during step formation. Local plastic deformation in the initiation zone and the corresponding value of critical strain energy release rate, G_Ic, were correlated with the nodular morphology. The size of nodules was found to vary with the curing agent concentration, thus allowing us to establish a fundamental correlation between the nodular morphology and the ultimate mechanical properties of epoxy resins.     

Comparison of fracture behavior between acrylic and epoxy adhesives

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

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.     

Improving the crack resistance of bulk molding compounds and sheet molding compounds

Fiber-reinforced plastics exhibit two types of mechanical failure: gross fracture and microcracking. Gross fracture involves both matrix and fiber failures. Principal resistance to crack propagation derives from partial decoupling of fibers and then stressing, remove finite volumes of them to fracture. Classical concepts of fracture mechanics can be applied to such composites, though modifications of methodology to treat anisotropy and other special effects are required. Microcracking occurs principally in the matrix phase and usually accompanies cyclic fatigue, drop impact, bending, or rapid cooling from molding temperatures. It lowers composite stiffness, environmental resistance and may reduce strength. Matrix resins require high fracture toughness to minimize or eliminate microcracking. This paper discusses cracking in bulk molding compounds and sheet molding compounds, complex materials containing high percentages of glass fibers and calcium carbonate filler. Microcracking can be greatly reduced by tire addition of small amounts of a rubber to the polyester matrix. Various tests such as impact, bending, acoustic emission and crack propagation demonstrate the improved toughness properties which result. No sacrifice of original strength characteristics occurs, and markedly improved resistance to damage has been noted with rubber modified epoxy and polyester matrix resins.     

Mode-l Fracture Behaviour of Adhesive Joints. Part II. Stress Analysis and Constraint Parameters

The constraint effect on the fracture behaviour of a rubber-modified epoxy was investigated using compact tension (CT) adhesive joints. An elastic-plastic finite element analysis was conducted to evaluate the stress distribution ahead of the crack tip in the bulk adhesive and adhesive joints of different bond thickness. The models with sharp and finite radius crack tips were evaluated in the analyses. The constraint effect of adherends on the stress triaxiality ahead of the crack tip in the adhesive joints were discussed. The constraint parameters were investigated using the J-Q theory and the J-CTOD relationship. It was found that as the adhesive thickness was increased, the stress triaxiality ahead of the crack tip was relieved by the remarkable deformation of the adhesive material. Similarly, the crack tip constraint was reduced with increasing bond thickness so that the fracture energy increased towards the value of the bulk adhesive. A higher constraint was associated with a lower fracture energy and vice versa. Furthermore, the J-integral did not have a unique relationship with the crack-tip opening displacement (CTOD) for different adhesive bond thickness, as this depends on the constraint around the crack tip. The results of this study will help improve reliability assessment of adhesive joints in engineering applications.     

Toughening mechanisms of rubber modified thin film epoxy resins

An epoxy terminated polybutadiene (ETPB) was synthesized and utilized to enhance the toughening of an epoxy system, in both bulk and coating states. In the first step, the fracture energy of the modified samples was determined using a single edge notched type specimen in a three point bending (SEN3PB) geometry. The effective toughening mechanisms of bulk epoxy specimens were examined using scanning electron microscopy (SEM). The results showed that plastic void growth, cavitation and shear yielding mechanisms were the main toughening mechanisms of the bulk epoxy systems. In the next step, mechanical properties (i.e. impact resistance, flexibility, cupping resistance and hardness) and adhesion of the thin film specimens were evaluated in accordance to the amount of synthesized ETPB. The results showed that the mechanical properties of the ETPB modified epoxy resins considerably improved. In all cases, it was found that the improvement of the mechanical properties reached a maximum at 7.5 wt.% and then began to decrease with further increase in ETPB content. The effective toughening mechanisms in the modified thin films were also examined using SEM and compared to the bulk types. In contrast to the bulk types, the results showed that crack arresting and shear yielding were active mechanisms in thin films. The contribution of these mechanisms led to the improvement of adhesion and mechanical properties by energy dissipation.     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. II. Suppression of sharkskin by addition of adhesive resins

Standing on a hypothesis that the sharkskin of a polymer with a narrow molecular weight distribution at extrusion processing originates from a stick‐slip of the polymer at the die wall, the suppression of the sharkskin was tried by means of suppressing the slip by the addition of adhesives. To polypropylene (PP)‐type resins with narrow molecular weight distributions such as a PP‐type thermoplastic elastomer, PER and a controlled rheology PP were added small amounts of adhesives such as maleated PP, maleated PER, reactive polyolefin oligomers, ethylene/ethylacrylate/maleic anhydride (MAH) copolymer, ethylene/vinyl acetate copolymer, and styrene/MAH copolymer, and their melt fracture behaviors at capillary extrusion were observed. It was found that the sharkskin of the PP‐type resins with narrow molecular weight distributions was suppressed by the addition of the adhesive resins with good adhesion to metal. The suppressive effect of the sharkskin was generally the more remarkable by the higher loading of the adhesives with the higher MAH content. This is the direction of increasing adhesion. From this fact, it was assumed that the sharkskin of the PP‐type resins with narrow molecular weight distribution does not originate from a periodic growth and relaxation of tensile stress at the extrudate surface but from a stick‐slip at the die wall. Based on this mechanism, it may be said that the sharkskin can be suppressed by both ways of directions of promoting and suppressing the slip at the die wall. The former way is the previously known method, and the latter way is the method proposed in the present study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2120–2127, 2002     

The Effect of Tungsten Sulfide Fullerene-Like Nanoparticles on the Toughness of Epoxy Adhesives

In this work the effect of inorganic fullerene-like (closed cages) nanoparticles of tungsten disulfide (IF-WS₂) on the mechanical properties and especially on the toughness of epoxy resins, was studied. The epoxy resin used was the well-known DGEBA (di-glycidyl ether of bis-phenol A) cured with polyamidoamine. The epoxy/IF-WS₂ nanocomposites were prepared by applying a high shear mixing to obtain a uniform dispersion and homogeneous distribution of the IF nanoparticles in the epoxy matrix. Two mixing procedures were used — a low shear of short duration and high shear with a long mixing time. The resulting epoxy nanocomposites were first characterized for their shear and peel strength using appropriate bonded joints. The experimental results demonstrate that enhanced shear strengths and shear moduli were achieved, together with a significant increase in the peel strengths at low concentrations of the IF-WS₂ nanoparticles (more than 100% increase at 0.5 wt% IF-WS₂). Above the threshold value of 0.5% IF-WS₂ the peel strength decreased sharply. The fractured surfaces of the bonded joints were examined by transmission and scanning electron microscopy in order to characterize the fracture mechanisms and analyze the dispersion level of the nanoparticles within the polymer. The electron micrographs indicated that the presence of the nanoparticles in the epoxy matrix induced fracture mechanisms which were different from those observed in the pristine epoxy phase. These mechanisms included: crack deflection; crack bowing; and crack pinning. Evidence for a chemical interaction between the nanoparticles and the epoxy were obtained by infrared measurements in the attenuated total transmittance mode. The data suggests the formation of new carbon–oxygen–sulfur bonds, which are most likely due to the reaction of the outermost sulfur layer of the IF nanoparticles with the reactive epoxy groups. The observed simultaneous increase in both shear and peel strengths at very low IF-WS₂ concentrations, found in this work, could lead to the development of high performance adhesives and to new types of structural and ballistic fiber nanocomposites.     

Stick—slip friction as a method of powder flow characterization

We have made use of a previously ignored quantity, stick—slip friction, in determining powder flow properties. Stick-slip friction can easily be measured with a Table Model Instron or similar device. The stick—slip friction of most powders can be measured with greater accuracy and precision than any type of angle of repose measurements. Stick—slip friction values for a set of plastic powders were related to the particle size, flow properties and tensile strength. While stick—slip friction may not be universally relatable to flow behavior, it does hold promise for more limited sample tests.     

Aging and performance of structural film adhesives. II. Comparison of two nitrile–epoxy systems

The room-temperature aging of two nitrile rubber–epoxy adhesives has been examined. Both are 121°C curing systems, based on DGEBA-type epoxy resins, one of which has been available for about 15 years while the other is a more recent development. It has been found that hydrolysis of the epoxide and polymerization both occur slowly, reducing the epoxide content and solubility. A major reduction in honeycomb peel strength of joints made with aged material was evident in the older system and to a lesser extent in the newer adhesive. This is a result of diminished adhesive flow. Tensile strength was less affected by aging.     

Adhesive bonding of polyvinylidene fluoride: Effect of curing agent in PVF2 surface modification

—We have shown that certain amine and amide curing agents for epoxy resins modify the surface properties of the fluoropolymer polyvinylidene fluoride (PVF₂), thereby permitting the formation of strong adhesive joints. When PVF₂ is exposed to these curing agents at the temperatures used in preparing adhesive joints (~70°C), discoloration (darkening) occurs with concomitant gelation. This suggests that there is dehydrofluorination followed by crosslinking. Infrared spectroscopy has been used to follow the course of these reactions. In effect, the curing agent serves a dual function. It reacts with the fluoropolymer both to modify the surface region and to crosslink the epoxy resin.     

Effect of short chain branching on the viscoelastic behavior during fatigue fracture of medium density ethylene copolymers

A method to determine viscoelastic changes in medium density polyethylene (MDPE) pipe specimens associated with the crack tip during fatigue crack initiation (FCI) and propagation (FCP) experiments is described. The load-displacement curves are analyzed to obtain the phase angle, δ. Changes in δ are related to the number of cycles of crack initiation of three different MDPE copolymers: hexene (H), butene (B), and methyl pentene (MP) copolymers. These changes are related to craze formation and growth at the notch tip, leading to crack initiation and to the irreversible work, W_i, expended on them. Within a given material, step wise increments in δ distinguish the onset of crack initiation and the brittle-to-ductile transition in crack growth. The magnitudes of tan δ and W_i are noted to be in quantitative agreement with the resistance of the three copolymers to FCI and brittle propagation that rank in the order: isobutyl (MP) > ethyl (B) > butyl (H). Similar crystallinity of the three copolymers insinuates a hypothesis that variance in the nature of chain entanglements associated with the respective branch type might be accountable for the observed differences in viscoelastic character. The final stage of failure by ductile tearing is dominated by large scale plastic flow that seemingly overshadows the material differences governing time dependent brittle fracture.     

Fatigue Crack Growth in Epoxy/Aluminum and Epoxy/Steel Joints

The fatigue crack growth rate within epoxy/aluminum and epoxy/steel joints was evaluated as a function of a) type of surface pretreatment, b) water soak, c) fatigue cycle rate (Hz), d) adhesive thickness and e) type of epoxy adhesive.

For both adherends, aluminum and steel, a significant improvement in the fatigue behavior was obtained by use of a mercaptoester coupling agent. After an 8-day, 57°C water soak, the metal surfaces which were pretreated with coupling agent (CA) or by phosphoric acid anodization (PAA) still resulted in cohesive failure, while the controls had higher crack growth rate and showed greater scatter. The room-temperature cure matrix with CA-treated aluminum showed a less dramatic improvement, probably because of a known difference in the application procedure. For the steel joints and room-temperature adhesive the improvement in the fatigue behavior of CA-treated samples was maintained after the 8-day hot water soak. No significant change was found in the fatigue crack growth rate over a frequency range of 1 to 5 Hz, but a significant change was found as a function of the bondline thickness. The room temperature curing adhesive evaluated herein exhibited a much lower fatigue resistance than a heat-cured commercial structural adhesive FM-73.     

Fatigue Crack Growth in Epoxy/Aluminum and Epoxy/Steel Joints

The fatigue crack growth rate within epoxy/aluminum and epoxy/steel joints was evaluated as a function of a) type of surface pretreatment, b) water soak, c) fatigue cycle rate (Hz), d) adhesive thickness and e) type of epoxy adhesive.

For both adherends, aluminum and steel, a significant improvement in the fatigue behavior was obtained by use of a mercaptoester coupling agent. After an 8-day, 57°C water soak, the metal surfaces which were pretreated with coupling agent (CA) or by phosphoric acid anodization (PAA) still resulted in cohesive failure, while the controls had higher crack growth rate and showed greater scatter. The room-temperature cure matrix with CA-treated aluminum showed a less dramatic improvement, probably because of a known difference in the application procedure. For the steel joints and room-temperature adhesive the improvement in the fatigue behavior of CA-treated samples was maintained after the 8-day hot water soak. No significant change was found in the fatigue crack growth rate over a frequency range of 1 to 5 Hz, but a significant change was found as a function of the bondline thickness. The room temperature curing adhesive evaluated herein exhibited a much lower fatigue resistance than a heat-cured commercial structural adhesive FM-73.     

Influence of crack speed on fracture energy in amorphous and rubber toughened amorphous polymers

Abstract

To study the influence of the crack speed at initiation on measurements of the toughness of amorphous polymers such as polycarbonate (PC) and rubber toughened poly(methyl methacrylate) (RTPMMA), ‘compact tension’ specimens were tested at a medium loading rate (0·6 m s^-1 ). The specimens were equipped to allow location of the position of the crack tip and to trigger a photograph on passage of the crack. The experimental procedure was validated using PC for which the crack speed was found to change suddenly over very short distances, owing to stick–slip propagation. Conversely, fracture tests on RTPMMA showed that the acceleration of the crack tip, due to the decrease in fracture energy with crack speed, is controlled by a process zone, the size of which did not allow the systematic use of linear elastic fracture mechanics. The rapid crack propagation regime in RTPMMA corresponds to a propagation stabilised at the macroscopic crack branching velocity. This constant crack speed corresponds to frustrated microbranching and leads to non-unique values of the fracture energy at the macroscopic branching velocity.