Cryogenic microcracking of rubber toughened composites

This study investigated the influence of carboxyl‐terminated butadiene acrylonitrile (CTBN) liquid rubbers on the microcracking response of polymeric composite materials to cryogenic cycling. Matrices of carbon fiber/epoxy prepregs were modified with different concentrations of two CTBN liquid rubbers. The glass transition temperature and the interlaminar shear strength of the laminate systems were depressed as a result of the presence of CTBN in the epoxy phase. An increase in total rubber concentration with the continuous phase was found to decrease and in some cases eliminate microcracking in laminates exposed to cryogenic cycling.     

Rubber modification of low temperature cure cyanate ester matrices and the performance in glass fabric composites

Low temperature cure cyanate ester resin systems were developed and modified with epoxy‐terminated butadiene acrylonitrile rubber (ETBN) and impregnated into woven glass fabric. Mode I and mode II interlaminar fracture toughness values of the cured laminates were evaluated as a function of rubber concentration. Mode I fracture toughness increased to almost twice that of the unmodified system, while mode II fracture toughness remained essentially unchanged. Composite samples were subjected to aging experiments in water and the absorption/desorption behavior was investigated as was the effect on thermal performance. The presence of rubber was found to reduce the rate of matrix deterioration but also caused a substantial increase in water uptake. It was found that although the addition of rubber to the matrices decreased the unconditioned (dry) T_g all specimens showed the same reduction in T_g, after equilibrium water absorption.     

Predictive modeling of microcracking in carbon‐fiber/epoxy composites at cryogenic temperatures

The temperature at which microcracking occurred in symmetrical cross‐ply carbon‐fiber/epoxy composite materials was predicted with a yield‐stress‐based failure model. A fracture mechanics analysis of the in situ strength of the ply groups in a composite material was combined with a compound beam determination of thermal stress development to create the predictive model. This approach, unlike many other models, incorporated the change in the material properties with temperature with the room‐temperature properties of the laminate to predict the low‐temperature behavior of the ply groups. Dynamic mechanical analysis was used to assess microcracking at cryogenic temperatures through the observation of discontinuities in the material properties during failure. Four different material systems were studied, and the model accurately predicted the onset temperature for microcracking in three of the four cases. It was shown that the room‐temperature properties of a fiber‐reinforced polymeric composite laminate, appropriately modified to account for property variations at low temperatures, could be used to predict transverse microcracking as a response to thermal stresses at cryogenic temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1104–1110, 2004     

Cure temperature effects on cryogenic microcracking of polymeric composite materials

A model prepreg system was used to evaluate the effect of cure temperature on microcracking in polymeric composite materials exposed to cryogenic cycling. Symmetic and unsymmetric carbon fiber/epoxy laminates were fabricated to examine the development of thermal stresses and microcracks at cryogenic temperatures. The residual strains and theoretical curvatures of the laminates were calculated from the composite properties and correlated with the microcrack density and experimentally observed curvatures. Higher cure temperatures resulted in higher stress free temperatures and residual strains in the laminates, which corresponded directly to increased levels of microcracking.     

Fracture of an epoxy polymer containing recycled elastomeric particles

The fracture behavior of elastomer-modified epoxy was investigated using compact-tension geometry. The elastomeric modifiers included a liquid carboxyl-terminated butadiene acrylonitrile and solid rubber particles of different sizes which were obtained from recycled automobile tires. When used with solid rubber alone, no significant improvement in the fracture toughness was observed. However, when used in combination with the liquid rubber modifier, it was observed that the fracture toughness of these hybrid epoxies was higher than that of those toughened with liquid rubber alone. This synergistic effect is explained in terms of crack deflection and localized shear yielding. Furthermore, we observed a slight improvement in the fracture toughness as the size of the solid rubber particles increased. Although using a combination of both reactive rubber liquids and solid rubber particles as toughening agents had been investigated previously, in this study, the solid rubber particles used were from recycled rubber tires. Therefore, we have clearly demonstrated an application of producing high-quality engineering epoxy systems using toughening modifiers that are relatively low in cost and created higher-value products for recycled solid rubber. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 271–277, 1997     

Interaction of toughening mechanisms in a hybrid epoxy system

Interaction between different toughening mechanisms is studied using a heat treated hybrid system, consisting of carboxyl‐terminated butadiene acrylonitrile (CTBN) rubber and EXPANCEL (expandable hollow microspheres) as modifiers for an epoxy resin. It was found that the fracture toughness of the hybrid system is higher than that of either individually EXPANCEL‐ or CTBN‐modified system for a given content of modifier, although the maximum toughness was not substantially high compared with maxima of single modifier systems. Microscopic examination revealed that damage zone due to CTBN particles ahead of the crack reduces due to the presence of EXPANCEL particles and nevertheless its fracture toughness increased. A possibility was deduced that the cavitation due to CTBN assists with promoting compressive stresses around EXPANCEL particles ahead of the crack tip, resulting in increase in fracture toughness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4470–4475, 2006     

Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

Effect of rubber hardness on the properties of fiber reinforced plastic composites made by the newly proposed rubber pressure molding technique

The effect of rubber hardness on the properties of fiber‐reinforced plastic (FRP) composites is investigated in order to know the optimum composition of rubber mold used in rubber pressure molding (RPM) technique. A matching die set was used in RPM method, where the die was made of hard metal like steel and the punch from the flexible rubber like material, natural rubber. The use of flexible rubber punch generates and applies hydrostatic pressure on the surface of FRP composites. The hardness of rubber mold was controlled by incorporating carbon black as a filler material in the matrix of natural rubber and varied from 0 to 75 phr (per hundred rubber) in steps of 15 phr. Burn test, tension test, interlaminar shear test and interlaminar fracture toughness tests were conducted on the FRP composites to measure the void content, presence of delamination, tensile strength, inter laminar shear strength and inter laminar fracture toughness. The results are compared with the FRP composites made by conventional technique to evaluate the performance of RPM technique. It is observed that the laminates produced by RPM technique with different filler content in natural rubber mold show significant improvement in mechanical properties except interlaminar shear strength. POLYM. COMPOS., 28:618–630, 2007. © 2007 Society of Plastics Engineers     

Use of surface modified recycled rubber particles for toughening of epoxy polymers

The objective of this research is to investigate the feasibility of using surface treated recycled rubber particles for toughening of epoxy polymers. These particles are obtained through grinding of scrap tires followed by oxidizing the surface of the particles in a reactive gas atmosphere. Surface treated recycled rubber particles with a nominal particle size of approximately 75 μm and a commonly used reactive liquid elastomer, CTBN, have been incorporated in a DGEBA epoxy resin. It has been shown that the recycled rubber particles are not as effective as CTBN in toughening of the epoxy matrix. However, blending of the two modifiers results in a synergistic toughening. Microscopy reveals that, when used alone, recycled rubber particles simply act as large stress concentrators and modestly contribute to toughening via crack deflection and microcracking. In the presence of micron size CTBN particles, which cavitate and induce massive shear yielding in the matrix, however, the recycled particles “stretch” the plastic deformation to distances far from the crack tip. This mechanism causes plastic zone branching and provides an unexpectedly high fracture toughness value. This study, therefore, provides a practical approach for manufacturing engineering polymer blends utilizing the surface modified recycled rubber particles.     

Epoxidized natural rubber/epoxy blends: Phase morphology and thermomechanical properties

Epoxidized natural rubbers (ENRs) were prepared. ENRs with different concentrations of up to 20 wt % were used as modifiers for epoxy resin. The epoxy monomer was cured with nadic methyl anhydride as a hardener in the presence of N,N‐dimethyl benzyl amine as an accelerator. The addition of ENR to an anhydride hardener/epoxy monomer mixture gave rise to the formation of a phase‐separated structure consisting of rubber domains dispersed in the epoxy‐rich phase. The particle size increased with increasing ENR content. The phase separation was investigated by scanning electron microscopy and dynamic mechanical analysis. The viscoelastic behavior of the liquid‐rubber‐modified epoxy resin was also evaluated with dynamic mechanical analysis. The storage moduli, loss moduli, and tan δ values were determined for the blends of the epoxy resin with ENR. The effect of the addition of rubber on the glass‐transition temperature of the epoxy matrix was followed. The thermal stability of the ENR‐modified epoxy resin was studied with thermogravimetric analysis. Parameters such as the onset of degradation, maximum degradation temperature, and final degradation were not affected by the addition of ENR. The mechanical properties of the liquid‐natural‐rubber‐modified epoxy resin were measured in terms of the fracture toughness and impact strength. The maximum impact strength and fracture toughness were observed with 10 wt % ENR modified epoxy blends. Various toughening mechanisms responsible for the enhancement in toughness of the diglycidyl ether of the bisphenol A/ENR blends were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39906.     

Preformed particle toughening of epoxy‐based film adhesive systems: The effect of particle size and chemistry

A new family of particulate modifiers was incorporated into an epoxy‐based model film adhesive system and the performance was evaluated. The particulate modifiers were selected to include a range of particle sizes, chemistry, and functionality. Thermal analysis, lap shear, and fracture energy tests were performed to characterize the performance of the adhesives. The mechanisms of failure for the adhesives were analyzed in relation to the particle modifier characteristics. Significant differences were found for mode I fracture energy when comparing adhesively joined composite specimens in cocured and bonded situations. Large preformed particle modified adhesives had nearly the same G_IC values for both cocured and bonded applications, while the G_IC values for the much smaller core‐shell particle modified adhesives differed significantly. All particle modified adhesives provided an improvement in mode II fracture toughness over that of the control such that the laminates failed either in compression (through‐thickness direction) or through delamination of the prepreg plies.     

Effect of morphology and refractive index on toughness and clarity balance of MBS modified vinyl bottles

Impact modifiers are used to enhance the toughness of rigid vinyl by providing a dispersed rubbery phase to absorb impact energy and prevent fracture of the otherwise brittle matrix. MBS impact modifiers are complex core//shell polymer structures based on specially prepared butadiene/styrene rubber latices with multiple stages of acrylic and other polymers grafted to them. In addition to providing a rubbery dispersed phase to improve to improve the toughness of vinyl, these structures also maintain clarity by matching the refractive index of the rubber particles with that of the vinyl matrix. Data will be present showing the effect of the rubber morphology, particle size and refractive index on the balance of impact strength and clarity of MBS modified vinyl packaging formulations.     

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.     

Morphology and properties of an epoxy alloy system containing thermoplastics and a reactive rubber

A novel approach for toughening thermosetting epoxy matrices using both thermoplastics and liquid reactive rubbers as modifiers has been investigated. The network structure of the modified epoxy systems was characterized using dynamic mechanical analysis, and the morphology of the multiphase structure was examined using scanning electron microscopy (SEM). To investigate the continuity of the phase domains, the constituents in the phase domains were positively identified using solving etching and RuO₄ staining techniques for transmission electron microscopy (TEM). The fracture toughness of the modified and basic epoxy samples was measured using compact tension (CT) specimens. Quite limited toughness improvement was achieved for the epoxy modified with only the PSu thermoplastic, or the liquid rubber by itself. However, the fracture toughness was found to increase dramatically when a proper combination of both the liquid reactive rubber and thermoplastic was simultaneously incorporated into the epoxy. Toughening by using dual modifiers resulted in maximum improvement of fracture toughness with minimal compromises in processability and T_g depression by rubbers.     

Effects of Rubber Addition to an Epoxy Resin and Its Fiber Glass‐Reinforced Composite

Epoxy resins are considered as one of the most important class of thermosetting polymers and find extensive use in various fields. However, these materials are characterized by a relatively low toughness. In this respect, many efforts have been made to improve the toughness of cured epoxy resins. In this work, samples of epoxy resin diglycidyl ether of bisphenol‐A and fiber glass‐reinforced composite of this polymer with and without liquid carboxyl‐terminated butadiene acrylonitrile (CTBN) copolymer were prepared to assess the effect of CTBN rubber on the properties of polymeric and composite laminate specimens. The addition of CTBN into the polymeric specimens led to a decrease in the glass transition temperature, fracture stress (from 70.39 to 56.34 MPa), and tensile elasticity modulus (from about 3.51 to 2.65 GPa), accompanied by an increase in elongation (from 2.47 to 5.64%). However, the degradation temperature of the polymeric system was not modified. Infrared analysis evidenced the occurrence of chemical reaction between the two components, and scanning electron microscopy results suggested rubber particles deformation as the prevailing toughening mechanism. The rubber addition in the composite specimens, promoted an increase simultaneous in fracture stress and in elongation at fracture. The elasticity tensile modulus has not changed. This probably results from the increased deformation capacity of the matrix, which prevents its premature cracking, and better adhesion between fibers and matrix observed in the CTBN‐modified composite laminates. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Interlaminar fracture toughness of woven fabric composite laminates with carbon nanotube/epoxy interleaf films

The Mode I interlaminar fracture behavior of woven carbon fiber/epoxy composite laminates incorporating partially cured carbon nanotube/epoxy composite films has been investigated. Laminates with films containing carbon nanotubes (CNTs) in the as‐received state and functionalized with polyamidoamine were evaluated, as well as laminates with neat epoxy films. Double‐cantilever beam (DCB) specimens were used to measure G_Ic, the critical strain energy release rate (fracture toughness) versus crack length. Post‐fracture microscopic inspection of the fracture surfaces was performed. Results show that initial fracture toughness was improved with the amino‐functionalized CNT/epoxy interleaf films, but the important factor appears to be the polyamidoamine functionalization, not the CNTs. The initial fracture toughness remained relatively unaffected with the incorporation of neat epoxy and as‐received CNT/epoxy interleaf films. Plateau fracture toughness was unchanged with the use of functionalized CNT/epoxy interleaf films, and was reduced with the use of neat epoxy and as‐received CNT/epoxy interleaf films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Toughening modification of (Acrylonitrile‐styrene‐acrylic copolymer)/(α‐Methylstyrene‐acrylonitrile copolymer) binary blend via using different impact modifiers

In this work, different impact modifiers such as acrylic resin impact modifier, chlorinated polyethylene (CPE), nitrile rubber, powdered nitrile rubber, and hydrogenated nitrile rubber, were chosen to improve the toughness of (acrylonitrile‐styrene‐acrylic copolymer)/(α‐methylstyrene‐acrylonitrile copolymer) (ASA/α‐MSAN) binary blend. The blend ratios of the ASA/(α‐MSAN)/(impact modifier) ternary system were 30/70/20 and 70/30/20 by mass, respectively. The results showed that the impact strength significantly increased, nearly 30 times (22.59 kJ·m^?2, 22.26 kJ·m^?2, and 25.24 kJ·m^?2) compared with that of control samples (0.80 kJ·m^?2) when nitrile rubber, powdered nitrile rubber, or hydrogenated nitrile rubber was added to the ASA/(α‐MSAN) (30/70) matrix, respectively. Moreover, the impact strength of ASA/(α‐MSAN) (70/30) was dramatically enhanced to 46 kJ·m^?2 with the addition of 20 parts by weight per hundred parts of resin of chlorinated polyethylene. The toughness of ASA/(α‐MSAN) with or without impact modifiers was also characterized via fracture energy calculated from stress‐strain curves. The results were perfectly consistent with that of impact strength. The results of dynamic mechanical analysis demonstrated the existence of α‐MSAN (glass transition temperature at approximately 140°C). The heat distortion temperature was barely changed, indicating the addition of impact modifiers barely affects the heat resistance. J. VINYL ADDIT. TECHNOL., 22:326–335, 2016. © 2014 Society of Plastics Engineers     

Fracture testing and toughening of epoxy resins

The tapered cantilever cleavage and the single-edge-notch tension fracture toughness tests have been shown to give similar results for several cured epoxy resin systems. Methods for the calculation of fracture energy and critical stress intensity factors are described and discussed. These tests have been used to study the influence of rubber modifiers (“Hycar” CTBN and “Blendex” 311) on the toughness of a conventional epoxy resin (“Epikote” 828) reacted with anhydride curing agents. The modifiers used increase fracture energies and stress intensity factors by factors of approximately 5 and 2 respectively.     

Mechanical behavior and structure of rubber modified vinyl ester resins

Vinyl esters are used widely as thermoset matrix materials for reinforced composites; however, they suffer from low‐impact resistance. Substantial enhancement of the toughness of brittle polymers may be achieved by dispersing elastomeric inclusions or rubber particles in the polymer matrix, inducing multiple crazing and shear yielding of the matrix. The main objectives of this work are morphological characterization of vinyl ester/reactive rubber systems and investigation of the mechanical and fracture behavior of these systems. Additional studies focused on rubber endcapped vinyl ester in the absence and presence of added reactive rubber. The initial compatibility of the liquid rubber with the liquid resin was studied. This is a key factor, along with cure conditions, in determination of the possible morphologies, namely, the degree of phase separation and particle size. The initial rubber/resin compatibility was found poor and all attempts to improve it by means of surfactants or ultrasonic treatment have not been successful. The flexure mechanical and fracture behavior of the cured resin/rubber systems was investigated. Three basic types of crack propagation behavior, stable, unstable, and stick‐slip, were observed. Fracture toughness of various resin/rubber systems was evaluated and was found to increase with increased content of rubbery second‐phase material. However, there is some payoff in stiffness and flexural strength of the cured resins. The addition of rubber does not affect the resin toughness at impact conditions. Analysis and interpretation of fractures morphology show that both multiple crazing and external cavitation play an important role in the fracture mechanism of the rubber modified specimens. No shear yielding is evident. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 647–657, 1999     

Combined effect of specific nucleation and rubber dispersion on morphology and mechanical behavior of isotactic polypropylene

This study aims to explore the joint effects of specific β‐nucleation and rubber dispersion on morphology and mechanical behavior of materials derived from isotactic polypropylene. A β‐nucleator (N,N′‐dicyclohexylnaphthalene‐2,6‐dicarboxamide) and an amorphous EPM rubber were used for the modification of isotactic polypropylene. Four samples were investigated: neat polypropylene, the same polymer modified with 0.03 wt % of β‐nucleator or with 15 wt % of dispersed rubber particles, and finally polypropylene containing both the β‐nucleator and the rubber particles. Tensile and impact behavior were followed at room and cryogenic temperatures. It has been observed that the β‐nucleation and rubber modification have brought about a similar macroscopic softening effect on the tensile mechanical behavior. Microscopy of fracture surfaces, however, has shown different toughening mechanisms caused by specific nucleation on one hand and by rubber dispersion on the other. While a distinct synergy effect of nucleation and rubber modification on the resulting toughness was found at low temperature, no such cooperative effect manifested itself at room temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3539–3546, 2007