Influence of Submicron TiO2 Particles on the Mechanical Properties and Fracture Characteristics of Cured Epoxy Resin

Submicron titanium dioxide (TiO₂) was used in different weight fractions as a toughening agent for amine-cured epoxy resin. After the use of X-ray photoelectron spectroscopy (XPS), which confirmed that the TiO₂ particles were evenly distributed in the cross-linked epoxy resin matrix, the composites were characterized by tensile and impact testing, followed by scanning electron microscopy of the fracture surfaces. The results indicated that the submicron TiO₂ toughening particles markedly improved the mechanical properties of the cured epoxy resin compared to the untoughened epoxy resin. The optimal properties were achieved at a TiO₂ concentration of 4 wt. %, at which point the toughness and the impact resistance values increased by 65% and 60%, respectively. The results also indicated that an increase in the amount of TiO₂ causes a decrease in toughness. Stress whitening, out-of-plane flaking, and thumbnail markings were the major visible features of the toughening mechanisms.

It is suggested that, at 4 wt. % of the submicron TiO₂ particles, microvoids are developed in the epoxy matrix. These microvoids are able to absorb some of the deformation work applied to the material, and thus enhance the toughness of the material. On increasing the TiO₂ content in the matrix (> 4 wt. %), the submicron particles got closer to each other and the microvoids were converted to macrovoids, which may act as stress concentrating flaws, leading to the deterioration of the mechanical properties of the epoxy resin.     

Study of ionic polymer toughening epoxy resin

In this study, PEL [copolymer of poly(propylene) oxide (PPO) and poly(ethylene oxide) (PEO)] toughening epoxy resin with ionic charge was used to produce an interpenetrating action between the cross‐linking network structure of the epoxy resin and the PEL additive. Fourier transform infrared (FTIR) analysis of the toughening epoxy resin revealed that ? NCO disappeared at 2400 cm^?1, ? NH appeared at 3300 cm^?1, and ? C?O appeared at 1750 cm^?1. These results indicate that a urethane bond was produced. Dynamic mechanical analysis (DMA) and mechanical testing results indicated that as the level of PEL increased, the compatibility between the epoxy resin and PEL also increased. In addition, the compatibility was improved because the addition of cornate hardener produced a graft phenomenon. The tensile property, impact strength, and fracture toughness of PEL toughening epoxy resin all had a tendency to improve. The tensile strength, impact strength, and fracture toughness (K_IC value) were most improved when 30 phr cornate was added. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3740–3751, 2002     

A toughened epoxy resin by silica nanoparticle reinforcement

Within this study the influence of adding 5 vol % of silica nanoparticles, obtained via a sol–gel process, on an Araldite‐F epoxy was investigated. To characterize toughening effects, compact tension specimens were used to obtain K_IC and G_IC. Additionally, tensile strength and E‐Modulus were measured as well as differential scanning calorimetry and dynamic mechanical thermal analysis were carried out to evaluate the influence on the thermal properties of the epoxy because of addition of the particles. Electronic microscopy was used to check dispersion quality and fracture surfaces, in transmission mode and scanning mode, respectively. The addition of 5 vol %. silica‐nanoparticles could improve the stiffness and the toughness of an epoxy resin at the same time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1849–1855, 2006     

Graphene/nanorubber reinforced electrically conductive epoxy composites with enhanced toughness

Graphene platelets (electrically conductive 2D filler) and rubber nanoparticles (0D soft filler) can work together to develop electrically conductive and toughened epoxy composite adhesives. In this study, complementing effect between graphene platelets (GnPs) and rubber nanoparticles (RnPs) within an epoxy matrix is reported. In the 3-phase composite adhesive, the 2D graphene platelets form global conductive network and rubber nanoparticles provide a viscoelastic phase inside the epoxy, both complementing each other to develop electrically conductive and toughened epoxy composite adhesives. Fracture toughness (K_1c) and critical strain energy release rate (G_1c) of the epoxy were augmented by 422% and 872%, respectively by adding 1 wt% RnPs and it recorded electrical percolation threshold at 0.78 vol% GnP. Also, the Young's modulus and strength of epoxy/1 wt% RnP composite were promoted from 1.57 to 2.32 GPa when 1 wt% GnP is added. Scanning electron microscopy analysis was conducted to investigate the toughening mechanism of epoxy/RnP/GnP and epoxy/GnP composites. Lap shear strength tests on epoxy composite adhesives confirm the reinforcement effect of GnPs and toughness effect of RnPs.     

Synthesis and characterization of chlorinated soy oil based epoxy resin/glass fiber composites

Composites with good toughness properties were prepared from chemically modified soy epoxy resin and glass fiber without additional petroleum based toughening agent. Chlorinated soy epoxy (CSE) resin was prepared from soybean oil. The CSE was characterised by spectral, and titration method. The prepared CSE was blended with commercial epoxy resin in different ratios and cured at 85°C for 3 h, and post cured at 225°C for 2 h using m‐phenylene diamine (MPDA) as curing agent. The cure temperatures of epoxy/CSE/MPDA with different compositions were found to be in the range of (151.2–187.5°C). The composite laminates were fabricated using epoxy /CSE/MPDA‐glass fiber at different compositions. The mechanical properties such as tensile strength (248–299 MPa), tensile modulus (2.4–3.4 GPa), flexural strength (346–379 MPa), flexural modulus (6.3–7.8 GPa) and impact strength (29.7–34.2) were determined. The impact strength increased with the increase in the CSE content. The interlaminor fracture toughness (G_IC) values also increased from 0.6953 KJ/m² for neat epoxy resin to 0.9514 KJ/m² for 15%CSE epoxy‐modified system. Thermogravimetric studies reveal that the thermal stability of the neat epoxy resin was decreased by incorporation of CSE. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Silica/poly(styrene-alt-maleic anhydride) hybrid particles as a reactive toughener for epoxy resin

Amino-modified silica nanoparticles (SiO₂─NH₂) were first prepared by hydrolytic condensation of tetraethyl orthosilicate and 3-aminopropylmethyldiethoxysilane. Then, organic–inorganic hybrid particles (SiO₂─SMA) were prepared by the amidation reaction between SiO₂─NH₂ and poly(styrene-alt-maleic anhydride) (SMA). Subsequently, SiO₂─SMA particles were employed for modifying bisphenol-A epoxy/anhydride thermoset. Compared with pure cured epoxy, the modified epoxy thermosets with only 1 wt % of SiO₂─SMA particles could achieve a simultaneous toughening and reinforcing performance. The tensile strength, impact strength, and fracture toughness of epoxy thermoset were increased by 14.1, 44.3, and 114.4%, respectively. Moreover, the modification also improved the thermal stability of epoxy thermosets, and the modulus and glass transition temperature of cured resin were not sacrificed. It can be attributed to the rigid structure of SiO₂, as well as the anhydride and carboxyl groups onto the surface of SiO₂─SMA particles participating in the epoxy curing reaction and effectively enhancing the crosslinking density of epoxy thermoset.     

Toughening of aromatic diamine-cured epoxy resins by poly(butylene phthalate)s and the related copolyesters

Aromatic polyesters, prepared by the reaction of aromatic dicarboxylic acids and 1,4-butanediol, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulfone. These polyesters contained poly(butylene phthalate)s (PBP), poly(butylene phthalate-co-butylene isophthalate)s, poly(butylene phthalate-co-butylene terephthalate)s, and poly(butylene phthalate-co-butylene 2,6-naphthalene dicarboxylate)s. All aromatic polyesters used in this study were soluble in the epoxy resin without solvents and were found to be effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PBP (MW 16,300) led to a 120% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 1996 John Wiley & Sons, Inc.     

Synergistic toughening of epoxy resin by CTBN and CM-β-CD

Carboxymethyl-β-cyclodextrin (CM-β-CD) and carboxyl terminated liquid nitrile rubber (CTBN) were used as binary component fillers in toughening the epoxy resin (E-54). For a single component filler system, the addition of CTBN resulted in significantly improved fracture toughness but reduction of glass transition temperature (T_g) and modulus of epoxy resin. On the other hand, the addition of CM-β-CD resulted in a modest increase in modulus and T_g, and significant improvement in toughness. This work provides a promising route of nanocomposites with excellent toughness. Besides the mechanism of synergistic toughening in this project was explained, and the major toughening mechanisms were attributed to interfacial micro-cracks, energy dissipation of CM-β- CD. This work gives us a further understanding of the modification effect of β- CD.     

Synthesis and characterization of fluorinated poly(etherimide)s toughening for carbon fiber‐reinforced epoxy composites

Novel‐fluorinated poly(etherimide)s (FPEIs) with controlled molecular weights were synthesized and characterized, which were used to toughen epoxy resins (EP/FPEI) and carbon fiber‐reinforced epoxy composites (CF/EP/FPEI). Experimental results indicated that the FPEIs possessed outstanding solubility, thermal, and mechanical properties. The thermally cured EP/FPEI resin showed obviously improved toughness with impact strength of 21.1 kJ/m² and elongation at break of 4.6%, respectively. The EP/FPEI resin also showed outstanding mechanical strength with tensile strength of 91.5 MPa and flexural strength of 141.5 MPa, respectively. The mechanical moduli and thermal property of epoxy resins were not affected by blending with FPEIs. Furthermore, CF/EP/FPEI composite exhibited significantly improved toughness with Mode I interlaminar fracture toughness (G_IC) of 899.4 J/m² and Mode II interlaminar fracture toughness (G_IIC) of 1017.8 J/m², respectively. Flexural properties and interlaminar shear strength of the composite were slightly increased after toughening. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Preparation and properties of TiO2‐filled poly(acrylonitrile‐butadiene‐styrene)/epoxy hybrid composites

Poly (acrylonitrile‐butadiene‐styrene) (ABS) was used to modify diglycidyl ether of bisphenol‐A type of epoxy resin, and the modified epoxy resin was used as the matrix for making TiO₂ reinforced nanocomposites and were cured with diaminodiphenyl sulfone for superior mechanical and thermal properties. The hybrid nanocomposites were characterized by using thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA), universal testing machine (UTM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The bulk morphology was carefully analyzed by SEM and TEM and was supported by other techniques. DMA studies revealed that the DDS‐cured epoxy/ABS/TiO₂ hybrid composites systems have two T_gs corresponding to epoxy and ABS rich phases and have better load bearing capacity with the addition of TiO₂ particles. The addition of TiO₂ induces a significant increase in tensile properties, impact strength, and fracture toughness with respect to neat blend matrix. Tensile toughness reveals a twofold increase with the addition of 0.7 wt % TiO₂ filler in the blend matrix with respect to neat blend. SEM micrographs of fractured surfaces establish a synergetic effect of both ABS and TiO₂ components in the epoxy matrix. The phenomenon such us cavitation, crack path deflection, crack pinning, ductile tearing of the thermoplastic, and local plastic deformation of the matrix with some minor agglomerates of TiO₂ are observed. However, between these agglomerates, the particles are separated well and are distributed homogeneously within the polymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Toughening of aromatic diamine-cured epoxy resins by modification with hybrid modifiers composed of N-phenylmaleimide–styrene copolymers and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers

Hybrid modifiers composed of N-phenylmaleimide–styrene copolymers (PMS), and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers (PMSH) containing pendent p-hydroxyphenyl groups as functionalities, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulphone. The hybrid modifiers were effective in toughening the epoxy resin. When using the modifier composed of 10 wt% PMS (M?_w 313000) and 2.5 wt% PMSH (2.5 mol% p-hydroxystyrene units, M?_w 316000), the fracture toughness (K_IC) for the modified resins increased 100% with no deterioration in the flexural properties and the glass transition temperature. The improvement in toughness of the epoxy resins was attained because of the co-continuous phase structure and the improvement in interfacial adhesion. The toughening mechanism is discussed in terms of the morphological characteristics of the modified epoxy resin systems.     

Toughening of aromatic diamine-cured trifunctional epoxy resins by modification with N-phenylmaleimide–styrene copolymers containing pendant p-hydroxyphenyl groups

N-Phenylmaleimide (PMI)–N-(p-hydroxy)phenylmaleimide (HPMI)–styrene (St) terpolymers (HPMS), containing pendant p-hydroxyphenyl (HP) groups, were prepared and used to improve the toughness of triglycidyl aminocresol epoxy resin cured with p,p′-diaminodiphenyl sulfone. HPMS was effective as a modifier for the toughening of the epoxy resin. When using 15 wt % of HPMS (1.0 mol % HP unit, M_w 129,000), the fracture toughness (K_IC) for the modified resin increased 190% with a medium loss of flexural strength. The toughening of epoxies could be attained because of the cocontinuous phase structure of the modified resins. The decrease in flexural strength was suppressed to some extent by introducing a functional group into the modifier. The toughening mechanism was discussed in terms of the morphological behavior of the modified epoxy resin system. © 1995 John Wiley & Sons, Inc.     

Toughening of Epoxy Adhesives by Nanoparticles

With the emergence and commercialization of nanoparticles, new opportunities have emerged for toughening of epoxy adhesives using nanoparticles without sacrificing strength, rigidity and glass transition temperature, as is the case with conventional elastomeric tougheners. Inorganic Fullerene-like tungsten disulfide (IF-WS₂) nanoparticles and functionalized nano-POSS (Polyhedral-Oligomeric-Sil-Sesquioxane) were used to study the effects of nanoparticles on the toughening and mechanical properties of low and high temperature curing epoxy systems. Experimental results indicated that IF-WS₂ increased the fracture toughness by more than 10 fold in both epoxy systems at very low concentrations (0.3–0.5 wt%) while increasing its storage modulus and preserving its glass transition temperature. Epoxy functionalized POSS demonstrated an increase in toughness in addition to preserving rigidity and thermal properties at higher concentrations (3 wt%). It was postulated that chemical interaction of the sulfide and the epoxy matrix and the inherent properties of WS₂ were the decisive factors with respect to the outstanding nano-effect in the case IF-WS₂.     

Photosynthesis and application of polyfunctional poly(n-butyl acrylate) elastomers for use in epoxy resin toughening

Medium molecular weight, novel polyfunctional elastomers, namely epoxy groups on poly(n-butylacrylate) (ETPnBA) and carboxyl groups on poly(n-butylacrylate) (CTPnBA) were photosynthesized for evaluation as the toughening agents in epoxy resins. The effect of the functionality and kind of functional group of the elastomers upon the toughening of epoxy resins modified with these rubbery copolymers as a second phase was investigated by tensile tests, impact test, and electron microscopy. It was found that there exists an optimum functionality of elastomers for maximum impact resistance in epoxy groups (ETPnBA) and carboxyl groups (CTPnBA) copolymer-modified systems. Studies on morphology of the modified epoxy resin system indicated that the better toughening effects of multiple distribution of particle sizes. The aggregation of rubber particles occurring in carboxyl group CTPnBA modified epoxy resin caused a loss of toughness.     

Tertiary-amine-terminated polybutadiene and butadiene acrylonitrile: Synthesis and application in the modification of epoxy resins

Two tertiary-amine-terminated liquid rubbers (TATPB and TATBN) containing polybutadiene and butadiene acrylonitrile are successfully synthesized and used in the modification of epoxy networks. By taking advantage of the flexibility of rubbers, the toughness of epoxy resin has been significantly improved. The addition of 60 phr TATPB and TATBN increased the impact strength of epoxy resins from 12.2 to 59.8 and 92.0 KJ/m², respectively. Meanwhile, due to the dual role of tertiary amine of TATPB and TATBN in catalysis and curing for epoxies, their T_g values shifted from 87.7 to 102.0 and 95.7°C, respectively. TATPB with a smaller polarity improves the toughness of the epoxy resin slightly less than TATBN with a larger polarity, but the former is more effective in increasing the T_g values. This study demonstrates a novel strategy to enhance the toughness of epoxy composites as well as improve the high temperature resistance by designing the end-structure of toughening agents.     

Mode I and Mode II delamination resistance and mechanical properties of woven glass/epoxy–PU IPN composites

The effect of polyurethane on the mechanical properties and Mode I and Mode II interlaminar fracture toughness of glass/epoxy composites were studied. Polyurethanes (PU) synthesized using polyols and toluene diisocyanate were employed as modifier for epoxy resin by forming interpenetrating polymer network. The PU/Epoxy IPN was used as matrix material for GFRP. PU modified epoxy composite laminates having varying PU contents were prepared. The effect of PU content on the mechanical properties like interlaminar fracture toughness (Mode I, G_1c and Mode II, G_IIc), tensile strength, flexural strength, and Izod impact strength were studied. The morphological studies were conducted on the fractured surface of the composite specimen by scanning electron microscopy (SEM). Tensile strength, flexural strength, and impact strength of PU‐modified epoxy composite laminates were found to increase inline with interlaminar fracture toughness (G_1c and G_IIc) with increasing PU content to a certain limit and then it was found to decrease with increase in PU content. It was observed that toughening of epoxy with PU increases the Mode I and Mode II delamination toughness up to 17 and 120% higher than that of untoughened composite specimen, respectively. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of diphenylsilanediol modified epoxy resin and curing agent

A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (T_g), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.     

Toughening of epoxy resins by modification with aromatic polyesters

Aromatic polyesters, prepared by the reaction of phthalic or isophthalic acids and α,ω-alkanediols, were used to reduce the brittleness of bisphenol-A diglycidyl ether epoxy resin cured with methyl hexahydrophthalic anhydride. These polyesters were effective as modifiers for toughening of the epoxy resin system. The most suitable composition for modification of the epoxy resins was inclusion of 20 wt % of poly(ethylene phthalate) (MW 7200), which resulted in a 150% increase in the fracture toughness (K_IC) of the cured resin at no expense of its mechanical properties. The effectiveness of poly(alkylene phthalate)s as modifiers decreased with increasing the chain length of alkylene units. The toughening mechanism was discussed based on the morphological and dynamic mechanical behaviors of the modified epoxy resin system.     

Preparation of novel soluble poly(ester imide)s containing a trimellitimide moiety and their use as modifiers for aromatic diamine‐cured epoxy resin

Poly(ester imide)s, prepared by the reaction of phthalic anhydride, N‐(4‐carboxyphenyl) trimellitimide and 1,2‐ethanediol, were used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone (DDS). The poly(ester imide)s include poly(ethylene phthalate‐co‐ethylene N‐(1,4‐phenylene) trimellitimide dicarboxylate)s (PESIs) having 10, 20 and 30 mol% trimellitimide (TI) units, respectively. PESIs having 10 and 20 mol% TI units were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PESI (20 mol% TI unit, M _W 19300 g mol^?1) led to a 55% increase in the fracture toughness (K_IC) of the cured resin (with an increase in flexural strength and modulus) and the modified resin had a particulate morphology. PESI having 30 mol% TI units was not effective because of degradation of the modifier by DDS. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviour of the modified epoxy resin system. © 2001 Society of Chemical Industry     

Epoxy-functionalized polysiloxane reinforced epoxy resin for cryogenic application

The poor cryogenic mechanical properties of epoxy resins restrict their extensive application in cryogenic engineering fields. In this study, a newly synthesized epoxy-functionalized polysiloxane (PSE) is used to improve the cryogenic mechanical properties of bisphenol-F epoxy resin. The Fourier transform infrared spectra and nuclear magnetic resonance confirm the formation of epoxy-functionalized –Si–O–Si– molecular chain. The surface free energy test results show that the PSE has a better compatibility with epoxy resin. The mechanical test results show that the cryogenic tensile strength, failure strain, fracture toughness, and impact strength of epoxy resin is improved significantly by adding the suitable amounts of PSE. Compared to the neat epoxy resin, the maximum tensile strength (196.92 MPa, an improvement of 11.2%), failure strain (2.97%, an improvement of 33.8%), fracture toughness (3.05 MPa·m^1/2, an improvement of 30.7%) and impact strength (40.55 kJ m⁻², an improvement of 14.8%) at cryogenic temperature (90 K) is obtained by incorporating 10 wt % PSE into the neat epoxy resin. Moreover, the results also indicated that the tensile strength, Young's modulus, and fracture toughness of epoxy resin with the same PSE content at 90 K are higher than that at room temperature (RT). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46930.