Preparation and properties of bio‐based epoxy montomorillonite nanocomposites derived from polyglycerol polyglycidyl ether and ε‐polylysine

Glycerol polyglycidyl ether (GPE) and polyglycerol polyglycidyl ether (PGPE) were cured with ε‐poly(L ‐lysine) (PL) using epoxy/amine ratios of 1 : 1 and 2 : 1 to create bio‐based epoxy cross‐linked resins. When PGPE was used as an epoxy resin and the epoxy/amine ratio was 1 : 1, the cured neat resin showed the greatest glass transition temperature (T_g), as measured by differential scanning calorimetry. Next, the mixture of PGPE, PL, and montomorillonite (MMT) at an epoxy/amine ratio of 1 : 1 in water was dried and cured finally at 110°C to create PGPE‐PL/MMT composites. The X‐ray diffraction and transmission electron microscopy measurements revealed that the composites with MMT content 7–15 wt % were exfoliated nanocomposites and the composite with MMT content 20 wt % was an intercalated nanocomposite. The T_g and storage modulus at 50–100°C for the PGPE‐PL/MMT composites measured by DMA increased with increasing MMT content until 15 wt % and decreased at 20 wt %. The tensile strength and modulus of the PGPE‐PL/MMT composites (MMT content 15 wt %: 42 and 5300 MPa) were much greater than those of the cured PGPE‐PL resin (4 and 6 MPa). Aerobic biodegradability of the PGPE‐PL in an aqueous medium was ～ 4% after 90 days, and the PGPE‐PL/MMT nanocomposites with MMT content 7–15 wt % showed lower biodegradability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of reinforcement of sustainable β‐CaSiO3 nanoparticles in bio‐based epoxy resin system

The β‐CaSiO₃ nanoparticles (NPs) were prepared using calcium carbonate from egg shells and silica as precursors. These NPs were incorporated (1–4 wt %) into bio‐based epoxy resin to fabricate nanocomposites. Thermal and mechanical tests were carried out on these composites. The results of dynamic mechanical analysis showed significant improvement in the storage modulus of 1 and 2 wt % composites. The thermomechanical analysis data revealed ～19 and 20% of reduction in coefficient of thermal expansion for 1 wt % of CaSiO₃ before and after glass transition as compared to the neat epoxy system. Thermogravimetric analysis results also showed delayed thermal degradation of the composites by significant amounts (17–35°C) for 5% of decomposition, a proportional increase in residues corresponding to the loading concentrations. The flexure tests showed significant improvements in strength (17–36%), modulus (5–33%), and toughness for 1–4 wt % of reinforcement of β‐CaSiO₃ NPs. Theoretical calculations of the reinforcement effect on the flexure modulus of the composites agree well with the experimental values. The scanning electron micrograph of the fractured surfaces revealed better interfacial interactions in the composites and enhancements in crack path deflections over the neat specimen. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40867.     

Amino-functionalized carbon nanotubes for effectively improving the mechanical properties of pre-impregnated epoxy resin/carbon fiber

Pre-impregnated carbon fiber/epoxy resin (CF/epoxy prepreg) gained its popularity for significant stress applications, especially in the aerospace industry, owing to its excellent resistance and low specific mass. However, these CF/epoxy prepregs have a tendency to crack propagation. A solution for the prepregs fragility is the addition of carbon nanotubes (CNTs), especially those functionalized with amino groups, reinforcing the material due to its exceptional mechanical properties. In this work, the influence of the carbon chain length of two different amino-functionalized CNTs from diverse backgrounds (commercial and laboratory growth CNTs) is studied. The nanofillers were added in CF/epoxy prepregs by dry spraying without solvent aid. CNTs' samples were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, transmission electron microscopy, and thermogravimetric analysis (TGA), while the composites were analyzed by TGA, dynamic-mechanical analysis, and field emission scanning electron microscopy. The various surface treatment occurred at different levels according to the CNTs background, and all samples exhibited a distinct behavior. These differences were also observed in the composites' thermomechanical performance: CNTs functionalized with larger carbon chain amine presented the best results, with an increase of almost 100% in the storage moduli (E'), confirming the efficiency of amino-functionalized CNTs in the reinforcement of CF/epoxy prepregs.     

Impact of water absorption on the creep performance of epoxy/microcrystalline cellulose composites

Recently, considerable effort has been made to study cellulose/epoxy composites. However, there is a gap when it comes to understanding the post-conditioning anomalous effect of moisture uptake on their mechanical and dynamic-mechanical properties, and on their creep behavior. In this work, up to 10.0 wt% microcrystalline cellulose (MCC) was incorporated into epoxy resin by simple mixing and sonication. Epoxy/MCC composites were fabricated by casting in rubber silicone molds, and rectangular and dog-bone test specimens were produced. The moisture uptake, dynamic mechanical, chemical, tensile, and creep behavior were evaluated. The incorporation of MCC increased the water diffusion coefficient. The changes in storage modulus and glass transition temperature, combined with Fourier-transform infrared spectroscopy analysis, evidenced that water sorption in epoxies causes both plasticization and additional resin crosslinking, although the latter is prevented by the addition of MCC. The creep strain of the composites increased by 60% after conditioning, indicating that plasticization induced by water sorption plays an important role in the long-term properties of the composites.     

Preparation,morphology, and properties of silane‐modified MWCNT/epoxy composites

Both epoxy resin and acid‐modified multiwall carbon nanotube (MWCNT) were treated with 3‐isocyanatopropyltriethoxysilane (IPTES). Scanning electron microscopy (SEM) and transmission electronic microscope (TEM) images of the MWCNT/epoxy composites have been investigated. Tensile strength of cured silane‐modified MWCNT (1.0 wt %)/epoxy composites increased 41% comparing to the neat epoxy. Young's modulus of cured silane‐modified MWCNT (0.8 wt %)/epoxy composites increased 52%. Flexural strength of cured silane‐modified MWCNT (1.0 wt %)/epoxy composites increased 145% comparing to neat epoxy. Flexural modulus of cured silane‐modified MWCNT (0.8 wt %)/epoxy composites increased 31%. Surface and volume electrical resistance of MWCNT/epoxy composites were decreased with IPTES‐MWCNT content by 2 orders and 6 orders of magnitude, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and thermal,electrical, and morphological properties of multiwalled carbon nanotubeand epoxy composites

Multiwalled carbon nanotube (MWCNT)/epoxy composites are prepared, and the characteristics and morphological properties are studied. Scanning electron microscopy microphotographs show that MWCNTs are dispersed on the nanoscale in the epoxy resin. The glass‐transition temperature (T_g) of MWCNT/epoxy composites is dramatically increased with the addition of 0.5 wt % MWCNT. The T_g increases from 167°C for neat epoxy to 189°C for 0.5 wt % CNT/epoxy. The surface resistivity and bulk resistivity are decreased when MWCNT is added to the epoxy resins. The surface resistivity of CNT/epoxy composites decreases from 4.92 × 10¹² Ω for neat epoxy to 3.03 × 10⁹ Ω for 1 wt % MWCNT/epoxy. The bulk resistivity decreases from 8.21 × 10¹⁶ Ω cm for neat epoxy to 6.72 × 10⁸ Ω cm for 1 wt % MWCNT/epoxy. The dielectric constant increases from 3.5 for neat epoxy to 5.5 for 1 wt % MWCNT/epoxy. However, the coefficient of thermal expansion is not affected when the MWCNT content is less than 0.5 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1272–1278, 2007     

Study on synthesis of polyurethane‐epoxy composite emulsion

The stable polyurethane‐epoxy composite emulsion with the epoxy‐amine oligomer (DEA‐EP) and the epoxy resin oligomer has been prepared by step‐growth polymerization and controlled crosslinking technique. The emulsion forming transparent films can be cured at room temperature with trimethylolpropane tris (1‐ethyleneimine) propionate (TMPTA‐AZ). The DEA‐EP structure and its reaction with urethane prepolymers were proved by Fourier transform infrared spectra (FTIR). The studies on particle size, the particle size distribution, viscosity, and the films' transmittance (Tr) indicated that both trimethylol propane (TMP) and DEA‐EP contributed to improving the resin blends' compatibility and reducing the viscosity. The epoxy resin content can increase up to 20.0 wt % (based on the total content of the polyurethane and epoxy resin) and the emulsion was still stable. The data from the tensile test experiments showed that with the epoxy content increasing, the tensile strength (σ_b) and Young's modulus were proportionately raised, but the elongation at break (ε_b) decreased. Tensile tests also revealed that introducing TMPTA‐AZ as an outside‐crosslinker can increase the tensile strength. By adding 0.3 wt % of TMPTA‐AZ, the ε_b reduced from 429% to 371% and the σ_b increased from 4.4 to 13.73 MPa; by adding 1.8 wt % of TMPTA‐AZ, ε_b of the film was 67% of ε_b of the film with 0.3 wt % of TMPTA‐AZ, but its σ_b was 24.77 MPa and 180% of σ_b of the film with 0.3 wt % of TMPTA‐AZ. The cured films possessed excellent water and toluene resistance: water uptake (48 h, 3.1%; degree of curing: 70%), toluene uptake (210 h, 8%. degree of curing: 70%). Better properties of the composite emulsion will confer it as a potential application in low volatile industrial coatings. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Interface engineering for the improvement of mechanical and thermal properties of covalent functionalized graphene/epoxy composites

Functionalized reduced graphene oxide (GO)/epoxy composites are fabricated through solution mixing. GO is functionalized using 3‐amino‐1,2,4‐triazole (TZ) in presence of potassium hydroxide (KOH). KOH is expected to serve dual role as catalyst for nucleophilic addition reaction between GO and TZ, and also as reducing agent. The grafting of TZ moiety on GO is confirmed by Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. The prepared composites show remarkable improvement in mechanical and thermal stability. The fracture toughness of the composites (critical stress intensity factor, K_IC) achieved from single edge notched bending testing is improved by ～111% against pure epoxy at 0.1 wt % loading of TZ functionalized GO. Further, the tensile strength and Young's modulus are improved by ～30.5% and 35%, respectively. Thermal stability of the composites as investigated by thermogravimetric analysis showed 29 °C rise in onset degradation temperature for 0.1 wt % TZ functionalized GO incorporated composite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46124.     

Relationship between viscoelastic properties and gelation in the epoxy/phenol‐novolac blend system with N‐benzylpyrazinium salt as a latent thermal catalyst

A study of viscoelastic properties and gelation in epoxy/phenol‐novolac blend system initiated with 1 wt % of N‐benzylpyrazinium hexafluoroantimonate (BPH) as a latent cationic thermal initiator was performed by analysis of rheological properties using a rheometer. Latent behavior was investigated by measuring the conversion as a function of curing temperature using traditional curing agents, such as ethylene diamine (EDA) and nadic methyl anhydride (NMA) in comparison to BPH. In the relationship between viscoelastic properties and gelation of epoxy/phenol‐novolac blend system, the time of modulus crossover was dependent on high frequency and cure temperature. The activation energy (E_c) for crosslinking from rheometric analysis increased within the composition range of 20–40 wt % phenol‐novolac resin. The 40 wt % phenol‐novolac (N40) to epoxy resin showed the highest value in the blend system, due to the three‐dimensional crosslinking that can take place between hydroxyl groups within the phenol resin or epoxides within the epoxy resin involving polyaddition of the initiator with BPH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2299–2308, 2001     

Blends of epoxy resin with amine‐terminated polyoxypropylene elastomer: Morphology and properties

A liquid diglycidyl ether of bisphenol A (DGEBA) epoxy resin is blended in various proportions with amine‐terminated polyoxypropylene (POPTA) and cured using an aliphatic diamine hardener. The degree of crosslinking is varied by altering the ratio of diamine to epoxy molecules in the blend. The mixture undergoes almost complete phase separation during cure, forming spherical elastomer particles at POPTA concentrations up to 20 wt %, and a more co‐continuous morphology at 25 wt %. In particulate blends, the highest toughness is achieved with nonstoichiometric amine‐to‐epoxy ratios, which produce low degrees of crosslinking in the resin phase. In these blends, the correlation between G_IC and plateau modulus (above the resin T_g), over a wide range of amine‐to‐epoxy ratios, confirms the importance of resin ductility in determining the fracture resistance of rubber‐modified thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 427–434, 1999     

Investigation of mechanical properties of alumina nanoparticle‐loaded hybrid glass/carbon‐fiber‐reinforced epoxy composites

This research work investigates the tensile strength and elastic modulus of the alumina nanoparticles, glass fiber, and carbon fiber reinforced epoxy composites. The first type composites were made by adding 1–5 wt % (in the interval of 1%) of alumina to the epoxy matrix, whereas the second and third categories of composites were made by adding 1–5 wt % short glass, carbon fibers to the matrix. A fourth type of composite has also been synthesized by incorporating both alumina particles (2 wt %) and fibers to the epoxy. Results showed that the longitudinal modulus has significantly improved because of the filler additions. Both tensile strength and modulus are further better for hybrid composites consisting both alumina particles and glass fibers or carbon fibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39749.     

Study of dynamically cured PP/MAH‐g‐PP/talc/epoxy composites

In the present study, an epoxy resin was dynamically cured in a polypropylene (PP)/maleic anhydride–grafted PP (MAH‐g‐PP)/talc matrix to prepare dynamically cured PP/MAH‐g‐PP/talc/epoxy composites. An increase in the torque at equilibrium showed that epoxy resin in the PP/MAH‐g‐PP/talc composites had been cured by 2‐ethylene‐4‐methane‐imidazole. Scanning electron microscopy analysis showed that MAH‐g‐PP and an epoxy resin had effectively increased the interaction adhesion between PP and the talc in the PP/talc composites. Dynamic curing of the epoxy resin further increased the interaction adhesion. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had higher crystallization peaks than did the PP/talc composites. Thermogravimetric analysis showed that the addition of MAH‐g‐PP and the epoxy resin into the PP/talc composites caused an obvious improvement in the thermal stability. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best thermal stability of all the PP/talc composites. The PP/MAH‐g‐PP/talc/epoxy composites had better mechanical properties than did the PP/MAH‐g‐PP/talc composites, and the dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best mechanical properties of all the PP/talc composites, which can be attributed to the better interaction adhesion between the PP and the talc. The suitable content of epoxy resin in the composites was about 5 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Rheological,mechanical, and electrical properties of Sr0.7Bi0.2TiO3 modified BaTiO3 ceramic and its composites

Porous BaTiO₃-based relaxor ferroelectric ceramics with lamellar structure were achieved by ice templating method, and the rheological properties of ceramic slurry for freeze casting were deeply studied. Epoxy resin was then backfilled to generate ceramic–epoxy resin composites. Ceramic–epoxy composites with a lamellar structure were obtained when using a slurry with a ceramic content of 45 wt.%. The nanoindentation results showed that the introduction of ceramic materials into the epoxy resin can significantly improve the penetration resistance and hardness of the material. The dielectric and ferroelectric properties of the composites were also characterized. The interaction between the highly coupled dipoles in the polymers results in a decrease in the breakdown field strength of the composite. The dielectric constant reached up to ∼800. At 220 kV/cm, W_rec = 0.62 J/cm³, and η was ∼80%. At low frequencies, W_rec was ∼0.16 J/cm³, which indicated good stability.     

Epoxy composites reinforced by different size silica nanoparticles

Three series of epoxy/SiO₂ composites, containing 0.3–7 wt % nanosized SiO₂ with different specific surface area, were prepared by solution blending. The resulting composites exhibit the higher glass transition temperature (T_g) than that of pure epoxy. The T_g of composite showed a maximum increment of 35.3°C by the addition of 7 wt % A300. The trade name of A300 is Aerosil 300. It is one of the fumed silica nanoparticles products of Degussa. The decomposition temperatures (T_d) of composites were always higher than that of pure epoxy and showed a maximum increment of 20.8°C by the addition of 5 wt % A300. The light transmittance of composites was as a function of the SiO₂ content and size. The water permeability of composites decreased with increasing SiO₂ content and the 7 wt % A300 composite exhibits a maximum decrement percentage of 35.6%. The T_g, T_d, storage modulus, and water‐vapor barrier property are as a function of the SiO₂ content and size. These properties increased as the content of SiO₂ increased. The finer SiO₂ are more effective in increasing the T_g, T_d, and water‐vapor barrier property. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and thermal properties of waterborne epoxy composites containing cellulose nanocrystals

Cellulose nanocrystals (CNCs) are reinforcing fillers of emerging interest for polymers due to their high modulus and potential for sustainable production. In this study, CNC-based composites with a waterborne epoxy resin matrix were prepared and characterized to determine morphology, water content, and thermal and mechanical properties. While some CNC aggregation was observed, the glass transition temperature (T_g) and modulus for the composites increased with increasing CNC content. Relative to neat epoxy, at 15 wt.% CNC the storage modulus increased by 100%, the T_g increased from 66.5 °C to 75.5 °C, and tensile strength increased from 40 MPa to 60 MPa, suggesting good adhesion between epoxy and CNC surfaces exposed to the matrix. Additionally, no additional water content resulting from CNC addition were observed. These results provide evidence that CNCs can improve thermomechanical performance of waterborne epoxy polymers and that they are promising as reinforcing fillers in structural materials and coatings.     

Acceleration Effect of Dynamic Covalent Chains in a Hard Epoxy Resin on Its Thermally Induced Deformation and Healing Behavior

The dynamic covalent chain polyester oligomer PCG5 is prepared and applied to epoxy thermoset. Preliminary tests including pattern stamping, healing, shape memory, indentation, and adhesion test of the cured epoxy resin show that PCG5 can accelerate deformation, crack-healing, and transesterification rates at high temperatures. The transesterification rate and activation energy are quantitatively determined by a newly developed TGA method in the authors' group. This method is used to further realize a virtual acceleration mechanism of PCG5 in the transesterification reaction with cured epoxy resins, pointing out that the increase in cross-link density and ester concentration improves the mobility of structure units and collision of ester groups. Moreover, introduction of PCG5 doesn't sacrifice glass transition temperatures (T_g) of the cured epoxy resin and strengthens the fiber composites. An 85% recovery in storage modulus and an 88% recovery in tensile strength are achieved after 10 000 cycle's fatigue tests.     

Surfactant-Assisted Dispersion of MWCNTs in Epoxy Resin Used in CFRP Strengthening Systems

The epoxy resin used as the bonding agent in carbon fiber-reinforced polymer (CFRP) strengthening systems was modified by the infusion of multiwalled carbon nanotubes (MWCNTs). Two types of surfactants, Triton X-100 and C₁₂E₈, were used to disperse the nanotubes in the epoxy resin employing ultrasonic mixing. Dynamic mechanical analysis and tensile tests were conducted to study the effect of the surfactant-assisted dispersion of nanotubes on the thermal and mechanical properties of epoxy composites. The morphology of the epoxy composites was interpreted using scanning electron microscopy (SEM). Moreover, the effect of surfactant treatment on the structure of nanotubes was investigated by Fourier transform infrared (FT-IR). Based on the experimental results, the tensile strength and the storage modulus of the epoxy resin were increased by 32% and 26%, respectively, by the addition of MWCNTs. This was attributed to the homogeneous dispersion of nanotubes in the epoxy resin according to the SEM images. Another reason for the enhancement in the tensile properties was the reinforced nanotube/epoxy interaction as a result of the surfactant anchoring effect which was proved by FT-IR. A moderate improvement in the glass transition temperature (T _g) was recorded for the composite fabricated using Triton X-100, which was due to the restricted molecular motions in the epoxy matrix. To characterize the temperature-dependent tensile behavior of the modified epoxy composites, tensile tests were conducted at elevated temperatures. It was revealed that the MWCNT modification using surfactant substantially improves the tensile performance of the epoxy adhesive at temperatures above the T _g of the neat epoxy.     

Controlling water permeability of composite films of polylactide acid,cellulose, and xyloglucan

To test the hypothesis that the introduction of a hydrophilic hemicellulose would affect viscoelastic properties and increase water permeability, xyloglucan (XG) was adsorbed onto the surface of microcrystalline cellulose (MCC) in water dispersion prior to the extrusion of 79–80 wt % polylactide acid (PLA), 20 wt % MCC, and 0–1 wt % XG. For comparison, composites of PLA, MCC, and non‐absorbed XG were produced. Analysis of thermal properties showed no differences for glass‐transition or melting temperatures, but the crystallinity of the films increased with the addition of MCC and XG. Storage modulus of the composite materials increased with XG content; however, at higher humidities storage modulus decreased, probably because of lower interfacial adhesion. Water permeability through the films increased more with the addition of XG adsorbed to the MCC than with the MCC and XG simply mixed in the same amounts. © 2014 The Authors. Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41219.     

Effects of high nano‐SiO2 contents on properties of epoxy‐modified polybenzoxazine

High‐performance nanosilica composites based on epoxy‐modified polybenzoxazine matrices are developed. Chemorheological study of benzoxazine–epoxy resin mixtures reveals that processing window of the benzoxazine resin (BA‐a) is substantially broadened with an addition of the liquid epoxy. Glass transition temperature (T _g) of the BA‐a copolymerized with epoxy resin shows a synergistic behavior with a maximum T _g value (174°C) at the benzoxazine–epoxy mass ratio of 80:20. The copolymer at this composition is also used as a matrix for nano‐SiO₂ composites. A very low melt viscosity of the benzoxazine–epoxy mixtures promotes good processability with the maximum attainable nano‐SiO₂ loading up to 35 wt%. From scanning electron microscopy investigation, fracture surface of the 35 wt% nano‐SiO₂‐filled benzoxazine–epoxy composite reveals relatively homogeneous distribution of the nano‐SiO₂ in the copolymer with good particle wet‐out. In addition, very high reinforcing effect was also observed in such high content of the nano‐SiO₂, i.e., about 2.5 times in modulus improvement. This improvement is attributed to the strong bonding between the copolymer matrix and the nano‐SiO₂ through ether linkage as confirmed by Fourier‐transform infrared investigation. POLYM. COMPOS., 38:2261–2271, 2017. © 2015 Society of Plastics Engineers     

Thermal and dynamic mechanical behavior of epoxy composites reinforced with post-consumed yerba mate

Yerba mate (YM) is widely consumed in Latin American countries, and its residues can be used as bio-resources such as reinforced in epoxy composites. The present work aims to produce epoxy resin composites and evaluate the influence of post-consumed YM as reinforcement. The concentrations of YM used were 5, 10, and 20% (wt/wt). Chemical, thermal, morphological, and dynamic mechanical behaviors were explored. The YM incorporation did not influence chemically on the epoxy structure and a pull-out phenomenon was observed as YM content increased. The YM at lower concentrations (5 and 10%) led to higher values of activation energies calculated from model-free isoconversional methods. On the other hand, the composite e/YM 20 wt% improved all dynamic-mechanical properties. YM proved to be a suitable and cheap reinforcement for epoxy resin.