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1.
Hui Zhang  Zhong Zhang  Klaus Friedrich 《Polymer》2008,49(17):3816-3825
Fracture behaviours of nanosilica filled bisphenol-F epoxy resin were systematically investigated at ambient and higher temperatures (23 °C and 80 °C). Formed by a special sol-gel technique, the silica nanoparticles dispersed almost homogenously in the epoxy resin up to 15 vol.%. Stiffness, strength and toughness of epoxy are improved simultaneously. Moreover, enhancement on fracture toughness was much remarkable than that of stiffness. The fracture surfaces taken from different test conditions were observed for exploring the fracture mechanisms. A strong particle-matrix adhesion was found by fractography analysis. The radius of the local plastic deformation zone calculated by Irwin model was relative to the increment in fracture energy at both test temperatures. This result suggested that the local plastic deformation likely played a key role in toughening of epoxy.  相似文献   

2.
Shiqiang Deng  Lin Ye  Jingshen Wu 《Polymer》2008,49(23):5119-5127
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 KIC and 127% in GIC. 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.  相似文献   

3.
We investigated the effect of silica nanoparticles on the mechanical property and fracture toughness of two epoxy systems cured by Jeffamine D230 (denoted J230) and 4,4′-diaminodiphenyl sulfone (denoted DDS), respectively. Toughening mechanisms were identified by a tailor-loaded compact tension method which quantitatively recorded the deformation of a damage zone in the vicinity of a sub-critically propagated sharp crack tip. 20 wt% silica nanoparticles' fraction provided 40% improvement in Young's modulus for both systems; it improved the toughness of J230-cured epoxy from 0.73 to 1.68 MPa m1/2, and for the other system improved from 0.51 to 0.82 MPa m1/2. The nanoparticles not only stiffen, strengthen and toughen epoxy, but reduce the effect of flaws on mechanical performance as well. In both systems, nanosilica particle deformation, internal cavitation and interface debonding were not found, different to previous reports. This could be due to the various hardeners used or different identification techniques employed. The toughening mechanisms of the J230-cured nanocomposite were attributed to the formation and development of a thin dilatation zone and nanovoids, both of which were induced, constrained and thwarted by the stress fields of the silica nanoparticles. Regarding 10 wt% silica-toughen epoxy cured by J230, a thicker and shorter dilatation zone was found, where neither nanoparticles nor nanovoids were observed. With regard to the DDS-cured system, much less dilatation and voids were found due to the hardener used, leading to moderately improved toughness.  相似文献   

4.
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.  相似文献   

5.
T.H. Hsieh  K. Masania  S. Sprenger 《Polymer》2010,51(26):6284-6294
The present paper considers the mechanical and fracture properties of four different epoxy polymers containing 0, 10 and 20 wt.% of well-dispersed silica nanoparticles. Firstly, it was found that, for any given epoxy polymer, their Young’s modulus steadily increased as the volume fraction, vf, of the silica nanoparticles was increased. Modelling studies showed that the measured moduli of the different silica-nanoparticle filled epoxy polymers lay between upper-bound values set by the Halpin-Tsai and the Nielsen ‘no-slip’ models, and lower-bound values set by the Nielsen ‘slip’ model; with the last model being the more accurate at relatively high values of vf. Secondly, the presence of silica nanoparticles always led to an increase in the toughness of the epoxy polymer. However, to what extent a given epoxy polymer could be so toughened was related to structure/property relationships which were governed by (a) the values of glass transition temperature, Tg, and molecular weight, Mc, between cross-links of the epoxy polymer, and (b) the adhesion acting at the silica nanoparticle/epoxy-polymer interface. Thirdly, the two toughening mechanisms which were operative in all the epoxy polymers containing silica nanoparticles were identified to be (a) localised shear bands initiated by the stress concentrations around the periphery of the silica nanoparticles, and (b) debonding of the silica nanoparticles followed by subsequent plastic void growth of the epoxy polymer. Finally, the toughening mechanisms have been quantitatively modelled and there was good agreement between the experimentally-measured values and the predicted values of the fracture energy, Gc, for all the epoxy polymers modified by the presence of silica nanoparticles. The modelling studies have emphasised the important roles of the stress versus strain behaviour of the epoxy polymer and the silica nanoparticle/epoxy-polymer interfacial adhesion in influencing the extent of the two toughening mechanisms, and hence the overall fracture energy, Gc, of the nanoparticle-filled polymers.  相似文献   

6.
Quyen-Huyen Le  Jia-Bin Dai  Lee Luong 《Polymer》2010,51(21):4867-4879
55-nm rubber particles significantly toughened two epoxy systems without loss of Young’s modulus, tensile strength and glass transition temperature. Transmission Electron Microscopy (TEM) showed that the nanoparticles are uniformly dispersed in matrix and have blurred interface with epoxy. 5 wt% rubber nanoparticles increased the critical strain energy release rate (G1c) of Jeffamine D230 (J230)-cured epoxy from 175 J/m2 to 1710 J/m2, while the 10 wt% increased G1c of diaminodiphenyl sulfone (DDS)-cured epoxy from 73 J/m2 to 696 J/m2. This is explained by comparing the surface-surface interparticle distance and total particle surface of nanocomposites with those of composites. The higher the matrix stiffness, the more nanoparticles needed for toughening. Although the 10 wt% J230-cured nanocomposite showed a 50% larger size of stress-whitened zone than the 5 wt% J230-cured nanocomposite, the 5 wt% nanocomposite showed a higher toughness. These nanoparticles were found to pose barriers to the vibration of crosslinked matrix molecules, leading to higher glass transition temperatures. While the matrix shear banding caused by nanoparticle expansion and growth is the major toughening mechanism for the J230-cured nanocomposites, the matrix plastic void growth and deformation are most probably the major mechanisms for the DDS-cured system. Under tensile loading, the nanoparticles in the DDS-cured epoxy created fibrils of 100-200 nm in diameter and 3-5 μm in length. TEM analysis in front of a subcritically propagated crack tip showed a number of voids of 30-500 nm in diameter in the vicinity of the crack, implying that rubber nanoparticles expanded, grew and deformed under loading. Unlike conventional epoxy/rubber composites in which all of the rubber particles in the crack front cavitated under loading, only a portion of the nanoparticles in this study expanded to create voids. Huang and Kinloch’s model developed from composites was found not fit well into these nanocomposites.  相似文献   

7.
B.B. Johnsen  A.C. Taylor 《Polymer》2005,46(18):7352-7369
Thermoplastic/epoxy blends were formed using an amine-cured epoxy polymer and a semi-crystalline thermoplastic: syndiotactic polystyrene (sPS). Complete phase-separation of the initially soluble sPS from the epoxy occurred via ‘reaction-induced phase-separation’ (RIPS) or via ‘crystallisation-induced phase-separation’ (CIPS), depending upon the thermal processing history employed. Dynamic mechanical thermal analysis showed that no sPS was retained dissolved in the epoxy polymer. For RIPS, at concentrations of sPS of up to 8 wt%, the sPS is present solely as spherical particles. However, macro phase-separation, giving a co-continuous microstructure, accompanied by local phase-inversion, dominates the RIPS blends containing more than 8 wt% sPS. In the CIPS blends, the sPS is present as spherulitic particles, and this microstructure does not change over the range of sPS concentrations employed, i.e. from 1 to 12 wt% sPS. The pure epoxy polymer was very brittle with a value of fracture energy, GIc, of about 175 J/m2. However, the addition of the sPS significantly increases the value of GIc, though the toughness of the RIPS and CIPS blends differs markedly. For the RIPS blends, there is a steady increase in the toughness with increasing content of sPS and an apparent maximum value of GIc of about 810 J/m2 is obtained for 8-10 wt% sPS. On the other hand, the measured toughness of the CIPS blends increases relatively slowly with the concentration of sPS, and a maximum plateau value of only about 350 J/m2 was measured in the range of 8-12 wt% sPS. The relationships between the microstructure of the RIPS and CIPS sPS/epoxy blends and the measured fracture energies are discussed. Further, from scanning electron microscopy studies of the fracture surfaces and optical microscopy of the damage zone around the crack tip, the nature of the micromechanisms responsible for the increases in toughness of the blends are identified. For the RIPS blends, (i) debonding of the sPS particles, followed by (ii) plastic void growth of the epoxy matrix are the major toughening micromechanisms. The increase in toughness due to such micromechanisms is successfully predicted theoretically using an analytical model. In the case of the CIPS blends, the increase in the value of GIc results from (i) crack deflection and (ii) microcracking and crack bifurcation.  相似文献   

8.
Toughening mechanisms in epoxy-silica nanocomposites (ESNs)   总被引:1,自引:0,他引:1  
Y.L. Liang 《Polymer》2009,50(20):4895-565
Two types of nanosilica (NS) particles with different average particle sizes (20 nm and 80 nm in diameter, respectively) were used to fabricate epoxy-silica nanocomposites (ESNs) in this study. No significant differences in fracture behavior were observed between the epoxies filled with 20 nm NS particles and the epoxies filled with 80 nm NS particles. Interestingly, both types of NS particles were found to be more efficient in toughening epoxies than micron size glass spheres. As with micron size glass spheres, the fracture toughness of the ESNs were affected by the crosslink density of the epoxy matrix, i.e. a lower crosslinked matrix resulted in a tougher ESN. The increases in toughness in both types of ESNs were attributed to a zone shielding mechanism involving matrix plastic deformation. Moreover, the use of Irwin's formalized plastic zone model precisely described the relationship between the fracture toughness, yield strength and the corresponding plastic zone size of the various ESNs examined.  相似文献   

9.
The effect of rubber nanoparticles on mechanical properties and fracture toughness was investigated. Rubber nanoparticles of 2–3 nm were in situ synthesized in epoxy taking advantage of the reaction of an oligomer diamine with epoxy. The chemical reaction was verified by gel permeation chromatography (GPC) and 1HNMR, and the microstructure was characterized by transmission electron microscope. The rubber nanoparticles caused much less Young's modulus deterioration but toughened epoxy to a similar degree in comparison with their peer liquid rubber that formed microscale particles during curing. Fifteen wt % of rubber nanoparticles increased fracture energy from 140 to 840 J/m2 with Young's modulus loss from 2.85 to 2.49 GPa. The toughening mechanism might be the stress relaxation of the matrix epoxy leading to larger plastic work absorbed at the crack tip; there is no particle cavitation or deformation; neither crack deflection nor particle bridging were observed. The compound containing rubber nanoparticles demonstrates Newtonian liquid behavior with increasing shear rate; it shows lower initial viscosity at low shear rate than neat epoxy; this provides supplementary evidence to NMR and GPC result. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

10.
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 (Tg), coefficient of thermal expansion (CTE), Young's modulus (E), yield stress (σ), fracture energy (GIC) and fracture toughness (KIC), 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 Tg or the yield stress of epoxy resin, i.e. the yield stress and Tg 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.  相似文献   

11.
Epoxy-nanocomposite resins filled with 12-nm spherical silica particles were investigated for their thermal and mechanical properties as a function of silica loading. The nanoparticles were easily dispersed with minimal aggregation for loadings up to 25 wt% as determined using transmission electron microscopy (TEM) and ultra-small-angle X-ray scattering (USAXS). A proportional decrease in cure temperatures and glass transition temperature (for loadings of 10 wt% and above) was observed with increased silica loading. The morphology determined by USAXS is consistent with a zone around the silica particles from which neighboring particles are excluded. The “exclusion zone” extends to 10× the particle diameter. For samples with loadings less than 10 wt%, increases of 25% in tensile modulus and 30% in fracture toughness were obtained. More highly loaded samples continued to increase in modulus, but decreased in strength and fracture toughness. Overall, the addition of nanosilica is shown as a promising method for property enhancement of aerospace epoxy composite resins.  相似文献   

12.
Silica nanoparticles possessing three different diameters (23, 74 and 170 nm) were used to modify a piperidine-cured epoxy polymer. Fracture tests were performed and values of the toughness increased steadily as the concentration of silica nanoparticles was increased. However, no significant effects of particle size were found on the measured value of toughness. The toughening mechanisms were identified as (i) the formation of localised shear-band yielding in the epoxy matrix polymer which is initiated by the silica nanoparticles, and (ii) debonding of the silica nanoparticles followed by plastic void growth of the epoxy matrix polymer. These mechanisms, and hence the toughness of the epoxy polymers containing the silica nanoparticles, were modelled using the Hsieh et al. approach (Polymer 51, 2010, 6284–6294). However, it is noteworthy that previous modelling work has required the volume fraction of debonded silica particles to be measured from the fracture surfaces but in the present paper a new and more fundamental approach has been proposed. Here finite-element modelling has demonstrated that once one silica nanoparticle debonds then its nearest neighbours are shielded from the applied stress field, and hence may not debond. Statistical analysis showed that, for a good, i.e. random, dispersion of nanoparticles, each nanoparticle has six nearest neighbours, so only one in seven particles would be predicted to debond. This approach therefore predicts that only 14.3% of the nanoparticles present will debond, and this value is in excellent agreement with the value of 10–15% of those nanoparticles present debonding which was recorded via direct observations of the fracture surfaces. Further, this value of about 15% of silica nanoparticles particles present debonding has also been noted in other published studies, but has never been previously explained. The predictions from the modelling studies of the toughness of the various epoxy polymers containing the silica nanoparticles were compared with the measured fracture energies and the agreement was found to be good.  相似文献   

13.
In the present work it is shown that low nanoparticle‐loaded polymer composites with improved mechanical performance can be prepared by a conventional melt blending technique in which the nanoparticles are chemically pregrafted by diglycidyl ether of bisphenol‐A (DGEBA). Two composites, each with 2.5 wt% filler, were developed. The first one was obtained by melt blending propylene‐ethylene copolymer (EP) with nanosilica in a co‐rotating sigma internal mixer. The second one was obtained by melt blending the same EP, but with DGEBA grafted nanosilica. The addition of epoxy resin grafted nanosilica to the polymer matrix produced a homogeneous dispersion of particles in the form of micro domains. The results of tensile tests indicate that epoxy resin grafted nanosilica particles (SiO2‐g‐DGEBA) provide EP with stiffening, strengthening, and toughening effects at a 2.5 wt% loading level. This is a much lower level compared to most particulate fillers used for composites. There was no noticeable improvement in the mechanical properties when nanosilica was added to the neat polymer. However, the addition of SiO2‐g‐DGEBA particles to the polymer matrix led to an increase of both elastic modulus and toughness (from 0.36 to 0.54 GPa, and 19.06 to 21.05 MJ/m3, respectively). POLYM. ENG. SCI., 26:806–812, 2005. © 2005 Society of Plastics Engineers  相似文献   

14.
Model diglycidyl ether of bisphenol-A based epoxy resins containing well-dispersed 15 nm block copolymer (BCP) nanoparticles were prepared to study the effect of matrix crosslink density on their fracture behavior. The crosslink density of the model epoxies was varied via the controlled epoxy thermoset technology and estimated experimentally. As expected, it was found that the fracture toughness of the BCP-toughened epoxy is strongly influenced by the crosslink density of the epoxy matrix, with higher toughenability for lower crosslink density epoxies. Key operative toughening mechanisms of the above model BCP-toughened epoxies were found to be nanoparticle cavitation-induced matrix shear banding for the low crosslink density epoxies. The toughening effect from BCP nanoparticles was also compared with core-shell rubber-toughened epoxies having different levels of crosslink density. The usefulness of the present findings for designing toughened thermosetting materials with desirable properties is discussed.  相似文献   

15.
Y.L. Liang 《Polymer》2010,51(21):4880-4890
Two different size nanosilica (NS) particles, nominally 20 nm and 80 nm in diameter, and carboxyl terminated butadiene acrylonitrile (CTBN) were blended into a lightly crosslinked, DGEBA/piperidine epoxy system to investigate the toughening mechanisms in hybrid epoxy-silica-rubber nanocomposites (HESRNs). Adding small amount of NS particles into CTBN toughened epoxies further improved the fracture toughness to a level that could not be achieved by increasing CTBN content alone. Interestingly, this toughening effect is diminished when NS particles clustered at high CTBN contents. In addition, the effect of NS particle size on toughening behavior was not considerable, except the case when NS clustering is observed. According to the SEM and TOM investigations, the plastic zone, which consists of shear banding and matrix dilation, is further enlarged in front of the crack tip in HESRNs. Irwin’s model is used to evaluate the process zone concept and the result indicates that zone shielding is credited for the toughening mechanism in these HESRNs.  相似文献   

16.
The mechanisms of deformation and fracture of isotactic polypropylene filled with CaCO3 particles were studied. Three types of particles with average diameters of 0.07, 0.7, and 3.5 μm were used at filler volume fraction from 0.05 to 0.30. The experiments included slow tensile tests, notched Izod impact tests with varying notch depths, and fracture resistance tests using double-cantilever-beam sample configurations. In slow tension, addition of fillers increased the modulus and decreased the yield stress independently of filler type. The strain at break increased with initial incorporation of fillers but decreased at higher loadings. The 0.7 μm diameter particles improved Izod impact energy up to four times that of the unfilled matrix. The other particles had either adverse or no effect on the impact toughness. The toughening mechanisms at work were plastic deformation of interparticle ligaments following particle-matrix debonding with additional contribution coming from crack deflection toughening. The failure of the 0.07 and 3.5 μm diameter particles to toughen the matrix was attributed to poor dispersion.  相似文献   

17.
The mechanical properties, thermomechanical properties, and fracture mechanic properties of block-copolymer (BCP), core–shell rubber (CSR) particles, and their hybrids in bulk epoxy/anhydride system were investigated at 23 °C. The results show that fracture toughness was increased by more than 268% for 10 wt % BCP, 200% for 12 wt % of CSR particles, and 100% for hybrid systems containing 3 wt % of each, BCP and CSR. The volume content of nanoparticles influences the final morphology and thus influences the tensile properties and fracture toughness of the modified systems. The toughening mechanisms induced by the BCP and CSR particles were identified as (1) localized plastic shear-band yielding around the particles and (2) cavitation of the particles followed by plastic void growth in the epoxy polymer. These mechanisms were modeled using the Hsieh et al. approach and the values of GIc of the different modified systems were calculated. Excellent agreement was found between the predicted and the experimentally measured fracture energies. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48471.  相似文献   

18.
Silica nanoparticles (SN) and epoxidized natural rubber (ENR) were used as binary component fillers in toughening diglycidyl ether of bisphenol A (DGEBA) cured cycloaliphatic polyamine. For a single component filler system, the addition of ENR resulted in significantly improved fracture toughness (KIC) but reduction of glass transition temperature (Tg) and modulus of epoxy resins. On the other hand, the addition of SN resulted in a modest increase in toughness and Tg but significant improvement in modulus. Combining and balancing both fillers in hybrid ENR/SN/epoxy systems exhibited improvements in the Young’s modulus and Tg, and most importantly the KIC, which can be explained by synergistic impact from the inherent characteristics associated with each filler. The highest KIC was achieved with addition of small amounts of SN (5 wt.%) to the epoxy containing 5–7.5 wt.% ENR, where the KIC was distinctly higher than with the epoxy containing ENR alone at the same total filler content. Evidence through scanning electron microscopy (SEM) and transmission optical microscopy (TOM) revealed that cavitation of rubber particles with matrix shear yielding and particle debonding with subsequent void growth of silica nanoparticles were the main toughening mechanisms for the toughness improvements for epoxy. The fracture toughness enhancement for hybrid nanocomposites involved an increase in damage zone size in epoxy matrix due to the presence of ENR and SN, which led to dissipating more energy near the crack-tip region.  相似文献   

19.
Highly cross-linked polyurethanes have a high elastic modulus and creep resistance, but they undergo a brittle fracture below the glass transition temperature. The lack of substantial toughness in these polymers limits their use in practical engineering applications. One method that has shown promise in recent years is the creation of local regions of reduced modulus that absorb strain energy and act to toughen the polymer. For instance, rubbers are typically added to epoxy which phase separate upon polymerization and create local elastic regions that significantly toughen the polymer. Here a variety of two-phase polyurethanes in the form of single inclusions is designed to study the toughening mechanism of the local regions of reduced modulus with an embedded crack. Synthesized heterogeneous polyurethanes show a transition from brittle to ductile behavior in addition to a drastic increase in the maximum load that the polymer can withstand. Fracture mechanics experiments demonstrate that a small reduction in the inclusion's Young's modulus (∼10%) leads to an increase in the toughness by factor of 7 (∼700%). The finite element method and digital image correlation are utilized to study this toughening mechanism. Optical strain measurements confirm the numerical simulation results and possible toughening and strengthening mechanisms.  相似文献   

20.
Composite materials based on 8 wt% yttria partially stabilized zirconia, with additions of gadolinium zirconate, lanthanum lithium hexaaluminate, yttrium aluminum garnet and strontium zirconate were characterized. Samples were fabricated by hot-press sintering at 1550 °C. The effect of the secondary phase content on the mechanical properties of the composites was evaluated. Hardness, elastic modulus and fracture toughness of the fabricated composites were determined by means of depth-sensitive indentation testing. The fracture toughness of the samples as determined by the indentation method was found to increase with increasing YSZ content, reaching 3 MPa·m0.5 for samples with 80 wt% YSZ. The fracture toughness appeared to be affected by thermal expansion coefficient mismatch, crack bridging and crack deflection.  相似文献   

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