Studies on thermal, mechanical and morphological behaviour of caprolactam blocked methylenediphenyl diisocyanate toughened bismaleimide modified epoxy matrices

Diglycidyl ether of bisphenol A epoxy resin (DGEBA, LY 556) was toughened with 5%, 10% and 15% (by wt) of caprolactam blocked methylenediphenyl diisocyanate (CMDI) using 4,4′-diaminodiphenylmethane (DDM) as curing agent. The toughened epoxy resin was further modified with chemical modifier N,N′-bismaleimido-4,4′-diphenylmethane (BMI). Caprolactam blocked methylenediphenyl diisocyanate was synthesized by the reaction of caprolactam with methylenediphenyl diisocyanate in presence of carbon tetrachloride under nitrogen atmosphere. Thermal properties of the developed matrices were characterized by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), heat distortion temperature (HDT) and dynamic mechanical analysis (DMA). Mechanical properties like tensile strength, flexural strength and impact strength were tested as per ASTM standards. The glass transition temperature (T_g) and thermal stability were decreased with increase in the percentage incorporation of CMDI. The thermomechanical properties of caprolactam blocked methylenediphenyl diisocyanate toughened epoxy resin were increased by increasing the percentage incorporation of bismaleimide. The values of impact strength for epoxy resin were increased with increase in the percentage concentration of CMDI. The homogeneous morphology of CMDI toughened epoxy resin and bismaleimide modified CMDI toughened epoxy resin system were ascertained from scanning electron microscope (SEM).     

Preparation and characterization of bismaleimide/1,3-dicyanatobenzene modified epoxy intercrosslinked matrices

An intercrosslinked network of cyanate ester (CE)-bismaleimide (BMI) modified epoxy matrix system was made by using epoxy resin, 1,3-dicyanatobenzene and bismaleimide (N,N^′-bismaleimido-4,4^′-diphenyl methane) with diaminodiphenylmethane as curing agent. BMI-CE-epoxy matrices were characterised using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterised for their mechanical properties such as tensile strength, flexural strength and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of cyanate ester into epoxy resin improves the toughness and flexural strength with reduction in tensile strength and glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of cyanate ester as well as BMI modified epoxy resin show an unimodal reaction exotherm. Electrical properties were studied as per ASTM method and the morphology of the BMI modified epoxy and CE-epoxy systems were studied by scanning electron microscope.     

Efficient Entrapment of Oxirane Ring Containing Compounds in Thermally Stable Poly(urea-formaldehyde) Polymer Shell Wall

This article aims to address the problems associated with the encapsulation of oxirane ring containing compounds in poly(urea-formaldehyde) (PUF) shell for application in self-healing composite systems. The main objectives were to produce non-agglomerated, stable microcapsules, and to control the pH drop during the encapsulation via oil-in-water emulsion polymerization. In the modified method; two stage additions of urea and formaldehyde monomers, core to shell ratio, weight percent and combination of two surfactants/emulsifiers were altered to produce the desired product. Analysis was done with optical microscope (OM), scanning electron microscopy (SEM), FTIR, particle size analyzer, and thermogravimetric analysis (TGA). The pH drop was confirmed by using a common epoxy resin, an epoxy functionalized polydimethylsiloxane (E-PDMS), and epoxidized palm oil (EPO) as cores. The modified oil-in-water emulsion polymerization of PUF was effective in preventing the pH drop during the encapsulation and a product stable for more than 3 months with less agglomeration was produced. The method produced microcapsules having diameters less than 100 μm at lower agitation rates. The modified method is only applicable to epoxy resin and not for compounds like amine hardeners. The use of stable microcapsules in self-healing coatings can lead towards cost reduction implied for repair and maintenance purposes.     

Coaxial electrospinning core-shell fibers for self-healing scratch on coatings

Polystyrene (PS) fibers with core-shell structure were prepared by coaxial electrostatic spinning using liquid epoxy or curing agent as the core and PS solution as the shell. Scratch self-healing coatings were realized by using the healant-loaded core-shell fibers in the matrix.     

Mechanical properties of UV‐curable carbon fiber‐reinforced polymer composite patch: Repair evaluation of damaged aluminum alloy

Epoxy resin composite patches reinforced by carbon fiber were prepared through ultraviolet (UV)–curing method, and the damaged aluminum alloy plates are rapidly repaired by means of adhesively bonding method. Mechanical properties of the composite patches and damaged aluminum alloy plates before and after repair were studied by experiment and numerical simulation. Results indicated that the tensile properties of carbon fiber/epoxy resin composite patches presented the tendency of first increase and then decrease with the increase of layer numbers of reinforced fiber. The composite patches with two layers fiber showed the best tensile properties, and the tensile strength and modulus reached 1.13 GPa and 27.79 GPa, respectively. However, the bending strength of composite patches decreased with the increase of layer numbers. Results of performance evaluation on the mechanical properties of damaged aluminum alloy plates repaired by the two layers carbon fiber/epoxy resin composite patches showed that the repair efficiency of tensile and bending properties of the repaired aluminum alloys reached more than 83% and 160%, respectively, compared with the undamaged aluminum alloys. Besides, results of numerical simulation showed that the stress intensity factor (SIF) of the crack tip on repaired aluminum alloy plates decreased significantly in comparison with the unrepaired aluminum alloy plates, which further revealing the reinforced mechanism of composite patches on the bending properties of repaired aluminum alloy plates.     

Micromechanical assessment of PMMA microcapsules containing epoxy and mercaptan as self-healing agents

Mechanical properties of microcapsule shell have great influence on microcapsule suitability as a mechanical trigger in a self-healing composite. The elastic modulus and hardness of polymethyl methacrylate (PMMA) microcapsules containing epoxy prepolymer (EC 157) and pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) as healing agents were investigated using nanoindentation technique. The influence of the PMMA average molecular weight (M_W), the kind of core material, and the mechanical mixing rate on the mechanical properties of the microcapsule shell were studied using the Taguchi experimental design approach. The results indicated that the most important factors which affect the elastic modulus and the hardness of microcapsules shell are the Mw of PMMA and the kind of core material. The average elastic modulus of PMMA shell of epoxy and mercaptan-loaded microcapsules was found between 2.386 and 3.495 GPa. The hardness of PMMA shell of healing agent microcapsules was obtained in the range of 0.064–0.219 GPa. This constitutes essential knowledge in order to design capsules with tailored properties for self-healing materials.     

Synthesis and characterization of novel polythiourethane hardeners for epoxy resins

A novel thiol-terminated polythiourethanes were synthesized from low-molecular-weight di- and multifunctional mercaptans and diisocyanates and employed as curing agent of epoxy resin. The curing reaction of epoxy resin and thermal properties of cured products were investigated with differential scanning calorimetry. Evaluation of climatic ageing resistance was made by the change in mechanical properties. Mechanical studies indicated that the application of polythiourethane has toughening effect and significantly increases ageing resistance of the cured resins. The results of this study indicate that molecular structure and functionality of polythiourethane oligomers are of critical importance in governing the curing mechanism, structure of the network and final properties of epoxy compositions.     

Synthesis of a novel epoxy resin containing naphthalene moiety and properties of its cured polymer with phenol novolac

A new epoxy resin (Bis-ENA) containing naphthalene structure linked with a 1,4-bis(isopropylidene)phenylene was synthesized and was confirmed by elemental analysis, infrared spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. To estimate the effect of naphthalene moiety on the cured polymer, an epoxy resin (Bis-EP) having phenyl moiety was synthesized, and curing behaviors of Bis-ENA and Bis-EP with phenol novolac were evaluated by differential scanning calorimetry. The incorporation of naphthalene structure into the resin backbone increased the curing temperature and reduced the curing reactivity. Thermal properties of the cured polymers obtained from Bis-ENA and Bis-EP with phenol novolac were examined by thermomechanical analysis and dynamic mechanical analysis. Mechanical properties and moisture resistance were evaluated by flexural strength, flexural modulus, and moisture absorption measurements. The cured polymer obtained from Bis-ENA showed higher glass transition temperature, higher flexural modulus, lower thermal expansion, and lower moisture absorption than that from Bis-EP. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3063–3069, 1999     

Epoxy/amine‐functionalized short‐length vapor‐grown carbon nanofiber composites

Short length vapor‐grown carbon nanofibers (VGCNFs) were functionalized with 4‐aminobenzoic acid in polyphosphoric acid/phosphorous phentoxide medium via “direct” Friedel‐Crafts acylation reaction to afford aminobenzoyl‐functionalized VGCNFs (AF‐VGCNFs). The AF‐VGCNFs as a cocuring agent were mixed with epoxy resin by simple mechanical stirring in methanol which was added to help efficient mixing. After evaporation of methanol, 4,4′‐methylenedianiline as a curing agent was added to the mixture, which was then cured at elevated temperatures. The resultant composites displayed uniform dispersion of AF‐VGCNFs into cured epoxy matrix. During curing process, the amine functionalities on AF‐VGCNF together with 4,4′‐methylenedianiline were expected to be involved in covalent attachment to the epoxy resin. As a result, both tensile modulus and strength of the composites were improved when compared with those of pure epoxy resin. Thus, the AF‐VGCNFs play a role as an outstanding functional additive, which could resolve both dispersion and interfacial adhesion issues at the same time by functionalization of VGCNFs and covalent bonding between the additive and matrix, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7473–7482, 2008     

Effect of Oil Palm and Jute Fiber Treatment on Mechanical Performance of Epoxy Hybrid Composites

In this work, oil palm empty fruit bunch (EFB) and jute fibers were treated with 2-hydroxy ethyl acrylate (2-HEA) to improve interfacial bonding of oil palm EFB and jute fibers with epoxy matrix. Hybrid composites were fabricated by incorporation of modified oil palm EFB and jute fibers into an epoxy matrix by the hand lay-up technique. Mechanical (flexural and impact) and morphological properties of modified hybrid composites were measured. Results indicated that flexural and impact properties of modified fiber–reinforced hybrid composites improved as compared to untreated hybrid composites due to better fiber/matrix interfacial bonding, which was confirmed by scanning electron microscopy. We confirmed that treated oil palm/jute hybrid composite may be fabricated by advanced techniques such as resin transfer molding, extrusion, and injection molding for industrial applications in the automotive sector.     

双酚A型环氧改性R-122环氧树脂的研究

用双酚A环氧树脂(E-44)改性脂环类环氧树脂(R-122),通过对改性R-122环氧树脂力学性能和热性能的测定,探讨了固化工艺,固化荆体系对改性R-122环氧树脂韧性的影响。结果表明：改性R-122环氧树脂冲击强度提高40％,弯曲强度提高75％,断裂能提高81％,而热变形温度和玻璃化转变温度基本不变。R-122树脂基复合材料随E-44的加入冲击强度和弯曲强度分别提高12％和18％。     

Experimental investigation of the healing properties of the microvascular channels-based self-healing glass fibers/epoxy composites containing the three-part healant

In this study, the self-healing ability of the E-glass fibers/epoxy composites based on microvascular channels under flexural and tensile loading was investigated by a three-part healant. The fabrication of the microvascular channels was conducted through embedding the solid preforms and removing them. The epoxy resin and premix anhydride hardener-CuBr₂ (2-Methylimidazole) as the healing agents were used to study the self-healing ability of the composites at different healing times (4, 7 and 11 days) and various volume fractions for recovering the tensile (2.5, 4 and 8 vol%) and flexural (2, 3.2 and 3.7 vol%) strength. The optimum recovered tensile strength belonged to the composite containing the 4 vol% healant. The obtained healing efficiencies of this composite after 4, 7 and 11 days were 57, 68 and 69%, respectively. In the flexural test, the composite with the 3.2 vol% healant had the maximum healing efficiencies of 3, 46 and 44%, as compared with other composites. By using the field emission scanning electron microscopy and energy dispersed spectroscopy analysis, the healing ability of the composite was confirmed by this healing system.     

Thermo-reversible MWCNTs/epoxy polymer for use in self-healing and recyclable epoxy adhesive

A self-healing and recyclable carbon tube/epoxy adhesive was prepared by epoxy monomer with Diels-Alder(DA) bonds, diethylenetriamine and polyethyleneimine modified multi-wall carbon nanotubes(MWCNTs). The self-healing and recyclable ability was attained by thermally reversible Diels-Alder reaction between furan and maleimide in the epoxy monomer. By controlling the molar ratio of furfuryl glycidyl ether and 4,4′-methylenebis(N-phenylmaleimide), the glass transition temperature and mechanical properties of MWCNTs/epoxy adhesives were varied. The self-healing properties of MWCNTs/epoxy polymers were evaluated by lap shear experiment and the results showed that the MWCNTs/epoxy adhesives exhibited enhanced mechanical properties and excellent self-healing ability under heat stimulus. The healing efficiency was related to the molecule mobility and the conversion of DA reaction between furan and maleimide. The MWCNTs/epoxy adhesives also displayed excellent recyclable ability by transforming into soluble polymer under heating. These materials offer a wide range of possibilities to produce materials with healing and recyclable ability and have the potential to bring great benefits to our daily lives by enhancing the safety, performance, and lifetime of products.     

Aligned electrospun cellulose fibers reinforced epoxy resin composite films with high visible light transmittance

Uniaxially oriented cellulose nanofibers were fabricated by electrospinning on a rotating cylinder collector. The fiber angular standard deviation (a parameter of fiber orientation) of the mats was varied from 65.6 to 26.2^o by adjusting the rotational speed of the collector. Optically transparent epoxy resin composite films reinforced with the electrospun cellulose nanofibrous mats were then prepared by the solution impregnation method. The fiber content in the composite films was in the range of 5–30 wt%. Scanning electron microscopy studies showed that epoxy resin infiltrated and completely filled the pores in the mats. Indistinct epoxy/fiber interfaces, epoxy beads adhering on the fiber surfaces, and torn fiber remnants were found on the fractured composite film surfaces, indicating that the epoxy resin and cellulose fibers formed good interfacial adherence through hydrogen-bonding interaction. In the visible light range, the light transmittance was 88–92% for composite films with fiber loadings of 16–32 wt%. Compared to the composite films reinforced with 20 wt% randomly oriented fibers, the mechanical strength and Young’s modulus of the composite films reinforced with same amount of aligned fibers increased by 71 and 61%, respectively. Dynamical mechanical analysis showed that the storage moduli of the composite films were greatly reinforced in the temperature above the glass transition temperature of the epoxy resin matrix.     

纳米木质素/二氧化硅基微胶囊的制备及在自愈合涂层中的应用

利用磷酸化改性木质素/二氧化硅复合纳米颗粒(PAL/SiO₂)作为壁材包埋活性组分异佛尔酮二异氰酸酯(IPDI)制备微胶囊(PAL/SiO₂-IPDI). 通过加入少量反应活性更高的聚合多甲基多二异氰酸酯(PMDI), 与水反应形成聚脲, 以增加微胶囊的壁厚. 采用光学显微镜、 扫描电子显微镜(SEM)和激光粒度分析仪(DLS)研究了PAL/SiO₂复合纳米粒子掺杂量, 水油比和剪切速率对微胶囊表面形貌、 粒径和壁厚的影响. 结果表明, 所制备的微胶囊呈现规整球形, 壁厚为2.36~3.50 μm, 平均粒径为40.3~201.5 μm. IPDI作为芯材包埋在微胶囊中, 芯材含量约为82.8%. 将制备的PAL/SiO₂-IPDI微胶囊添加到环氧树脂中得到自愈合环氧树脂涂层. 其在高盐浓度溶液中的抗侵蚀测试结果显示, 添加质量分数4%的PAL/SiO₂-IPDI微胶囊的环氧树脂涂层在划破后能够快速愈合, 显著降低基底的腐蚀电流和腐蚀速率. 纳米压痕实验表明, 环氧涂层的硬度为249.99 MPa, 而添加PAL/SiO₂-IPDI微胶囊后硬度增加到302.98 MPa, 弹性模量也有提高.     

Effect of Non-Woven Carbon Nanofiber Mat Presence on Cure Kinetics of Epoxy Nanocomposites

Summary : An investigation was carried out into the cure kinetics of carbon nanofiber (CNF) mat-epoxy nanocomposites, composed of bisphenol-A based epoxy resin and diethylene triamine as a curing agent. It was observed that the rate of cure reaction for CNF mat-epoxy nanocomposites was higher than that for neat epoxy resin at low curing temperatures and the presence of the CNF mat produced the maximum influence at a certain curing temperature and time. At high curing temperature and long curing times, the effect of CNF mat on the cure rate was insignificant. The CNF mat-epoxy composite exhibited somewhat lower value of activation energy than that of the neat epoxy system at the beginning of the curing stage. The weight fraction of CNF mat also affected the cure reaction of epoxy nanocomposites at the same curing temperature. As the amount of CNF mat increased, the cure rate was higher at the same cure time. However, at high CNF mat loading, the cure reaction was retarded since the amount of epoxy and hardener decreased dramatically at high CNF contents together with the hindering effect of the CNF mat on the diffusion of epoxy resin and the curing agent, leading to lower crosslinking efficiency. Although the curing efficiency of epoxy nanocomposites dropped at high CNF mat content, the glass transition temperature (T_g) was still high due to the ultra-high strength of the CNF mat. The cure kinetics of CNF mat-epoxy nanocomposites was in good agreement with Kamal's model.     

Cure behavior and thermal stability of an epoxy: new bismaleimide blends for composite matrices

A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends.     

Benzoxazine modified diglycidyl ether of bisphenol-a/silicon/siliconized epoxy hybrid polymer matrices: Mechanical,thermal, electrical and morphological properties

Benzoxazines modified epoxy hybrid polymer matrices were developed using benzoxazines (CB_DDM and BMPB_DDM) and epoxy resins (DGEBA, SE and EP-HTPDMS) to make them suitable for high performance applications. The benzoxazine-epoxy hybrid polymer matrices were prepared via in-situ polymerization and were investigated for their thermal, thermo-mechanical, mechanical, electrical and morphological properties. Two types of skeletal modified benzoxazines namely 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane benzoxazine (CB_DDM) and bis(4-maleimidophenyl) benzoxazine (BMPB_DDM) were synthesized by reacting paraformaldehyde and 4,4′-diaminodiphenylmethane with 1,1-bis (3-methyl-4-hydroxyphenyl)cyclohexane and N-(4-hydroxyphenyl)maleimide respectively. Epoxy resins viz., diglycidyl ether of bisphenol-A (DGEBA), silicon incorporated epoxy (SE) and siliconized epoxy resin (EP-HTPDMS) were modified with 5, 10 and 15 wt% of benzoxazines using 4,4′-diaminodiphenylmethane as a curing agent at appropriate conditions. The chemical reaction of benzoxazines with the epoxy resin was carried out thermally and the resulting product was analyzed by FT-IR spectra. The glass transition temperature, curing behavior, thermal stability, char yield and flame resistance of the hybrid polymers were analysed by means of DSC, TGA and DMA. Mechanical properties were studied as per ASTM standards. The benzoxazines modified epoxy resin systems exhibited lower values of dielectric constant and dielectric loss with an enhanced values of of arc resistance, glass transition temperatures, degradation temperatures, thermal stability, char yield, storage modulus, tensile strength, flexural strength and impact strength.     

Synthesis of a novel phosphorus‐containing curing agent and its effects on the flame retardancy,thermal degradation and moisture resistance of epoxy resins

A novel phosphorus‐containing compound diphenyl‐(1, 2‐dicarboxylethyl)‐phosphine oxide defined as DPDCEPO was synthesized and used as a flame retardant curing agent for epoxy resins (EP). The chemical structure of the prepared DPDCEPO was well characterized by Fourier transform infrared spectroscopy, and ¹H, ¹³C and ³¹P nuclear magnetic resonance. The DPDCEPO was mixed with curing agent of phthalic anhydride (PA) with various weight ratios into epoxy resins to prepare flame retardant EP thermosets. The flame retardant properties, combustion behavior and thermal analysis of the EP thermosets were respectively investigated by limiting oxygen index (LOI), vertical burning tests (UL‐94), cone calorimeter measurement, dynamic mechanical thermal analysis and thermogravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of the char residues for EP thermosets were respectively investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS). The water resistant properties of the cured EP were evaluated by putting the samples into distilled water at 70°C for 168 hr. The results revealed that the EP/20 wt% DPDCEPO/80 wt% PA thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value was as high as 33.2%. The cone test results revealed that the incorporation of DPDCEPO effectively reduced the combustion parameters of the epoxy resin thermosets, such as heat release rate and total heat release. The dynamic mechanical thermal analysis test demonstrated that the glass transition temperature (Tg) decreased with the increase of DPDCEPO content. The TGA results indicated that the incorporation of DPDCEPO promoted the decomposition of epoxy resin matrix ahead of time and led to a higher char yield and thermal stability at high temperatures. The surface morphological structures and analysis of the XPS of the char residues of EP thermosets revealed that the introduction of DPDCEPO benefited the formation of a sufficient, compact and homogeneous char layer with rich flame retardant elements on the epoxy resin material surface during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After water resistance tests, the EP/20 wt% DPDCEPO/80 wt% PA thermosets retained excellent flame retardancy, and the moisture adsorption of the EP thermosets decreased with the increase of DPDCEPO content in EP thermosets because of the existence of the P–C bonds and the rigid aromatic hydrophobic structure in DPDCEPO. Copyright © 2015 John Wiley & Sons, Ltd.     

Creation of a nanovascular network by electrospun sacrificial nanofibers for self-healing applications and its effect on the flexural properties of the bulk material

Composites, increasingly significant due to their excellent properties, are prone to failure over time. Self-healing materials are being developed to extend their lifetime. Despite continuous progress, the effect of introducing such healing feature on the mechanical properties of the neat material is mainly overlooked. Therefore, we created a nanocomposite and a nanovascular network by pullulan sacrificial nanofibers, and analysed the flexural properties in comparison to the neat matrix. A parameter analysis of the electrospinning process allowed production of tailored pullulan nanofibers. Their introduction showed no effect on the strength and modulus of the epoxy matrix. On removal of the pullulan nanofibers, the properties of the resultant nanovascularized epoxy were somewhat reduced relative to the neat epoxy depending on volume fraction and diameter of the nanochannels. Interestingly, the decrease of mechanical properties of the nanovascular epoxy is lower than by introducing microcapsules, and opens potential for a more appropriate introduction of self-healing systems in polymeric matrices.