Manufacture and characterisation of a low cost carbon fibre reinforced C/SiC dual matrix composite

A porous two-dimensional C/C composite was produced via the polymer pyrolysis route using phenolic resin as the matrix precursor and polyacrilonitrile- (PAN-) or pitch-based carbon fibres as reinforcement. The resulting C/C composites were then densified using a modified polysilane followed by pyrolysis to convert the polymer into silicon carbide, sealing the pores in the C/C composite. Aiming to increase the ceramic yield of the infiltrated polysilane and to reduce its volumetric shrinkage during pyrolysis the polymer’s curing behaviour was modified by catalytic addition of 0.1% dicobaltoctacarbonyl [Co₂(CO)₈]. The densification procedure is very efficient in sealing cracks in the C/C composite with SiC. The obtained carbon fibre reinforced C/SiC dual matrix composites were subjected to flexural tests and dynamic mechanical analysis. The flexural and visco-elastic properties of the composite are dominated by the strength of the fibre/matrix interface rather than by the fibre strength or modulus. A correlation between the mechanical loss factor (tan δ) and the fracture behaviour of the composite is suggested.     

The thermal characteristics of epoxy resin: Design and predict by using molecular simulation method

Trial-and-error approaches for experimentally designing and optimizing the polymer matrix for advanced composites are time-consuming and expensive. The simulation for curing behavior and structure–property relationships of epoxy resins can provide a guideline for designing resin matrix which will possess desirable properties. So far there are few reports in which the accuracy of the molecular simulation for the different amine-epoxy systems are addressed. In this paper, an atomistic modeling technique was used to theoretically investigate the curing and thermal transition behavior of two epoxy resin matrices containing amine curing agent with different chemical structures i.e. diaminodiphenyl methane (DDM)/diglycidyl-4,5-epoxycyclohexane-1,2-dicarboxylate (TDE85) and diaminodiphenyl sulfone (DDS)/TDE85 to give help for designing high heat-resistant epoxy matrix. The simulated results successfully predicted that the reaction process was catalyzed in the early stage of the curing and the slight modification in the diamine structure resulted in significant change in the curing and glass transition behavior of epoxy resin. As the bridging group of diamine changed from methylene to sulphone, the reactivity of diamine toward epoxy declined and the glass transition temperature increased from about 190 °C to about 230 °C. This simulated method presented a good agreement with experimental data, and can be used to design and predict high performance resin matrix for advanced composites.     

A new method to improve the stability,tensile strength,and heat resistant properties of shape‐memory epoxy resins: Two‐stages curing

In this article, we design a new thermal curing method: two‐stage curing. The purpose of using this approach is to maintain the excellent shape‐memory property of epoxy resin system after first stage curing, and the material can be folded in small size to storage or transportation and recovery its original shape commodiously by heating temperature. Then, after second stage curing, the stability, glass transition temperature(T_g), and tensile strength of material can be improved effectively. For this aim, a series of mixtures have been prepared. Differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), tensile test, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and fold‐deploy shape‐memory test have been used to characterize the feasibility of two‐stage curing process, curing degree, tensile strength, morphology, thermodynamic properties, and shape‐memory performance of these polymers. DSC results show that two independent curing stages can be achieved successfully. Tensile tests and DMA results suggest that tensile strength and heat resistance have been improved after the second curing stage. SEM results reveal that the addition of latent curing agent do not change the fracture mechanism. Furthermore, the fold‐deploy shape‐memory tests prove that the composites after first stage curing possess eximious shape‐memory property. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39882.     

Polymerization shrinkage,stress, and degree of conversion in silorane‐ and dimethacrylate‐based dental composites

To compare two kind of resin‐based dental composites, the polymerization shrinkage, contraction stress (CS), and degree of conversion (DC) of four dimethacrylate‐based and one silorane‐based composite were investigated. To determine shrinkage, the composites were packed, respectively, into a cylindrical cavity in human teeth and imaged using X‐ray microcomputed tomography to determine the precise volume before and 30 min after photopolymerization. To determine CS, the sample was applied in a similarly sized cylinder in a universal testing machine and monitored for 30 min. FTIR spectroscopy was used to determine DC. The volumetric shrinkage (range: 1.1–3.1%) and maximum CS (range: 1.2–3.5 MPa) differed significantly among the tested composites but not the final DC (range: 62.3–69.1%). The silorane‐based composite displayed the lowest volumetric shrinkage and CS of all composites. No correlation was observed between the stress and volumetric shrinkage values of the dimethacrylate‐based composites. A moderate correlation was found between stress and DC (r = 0.836), which was significant at 20 and 40 s. The silorane‐based composite exhibited superior shrinkage behavior compared with conventional dimethacrylate composites with comparable polymerization kinetics. The CS was dependent on multiple variables, including the volumetric shrinkage, DC, and curing rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and physical properties of photopolymer/SiO2 nanocomposite for rapid prototyping system

A photopolymer material was applied in liquid rapid prototyping (RP) machine. The prototype fabricated from photopolymer was difficult for storage due to volumetric shrinkage and deformation during curing. The prototype fabricated from photopolymer suffers from the volumetric shrinkage during curing and the continuing deformation for a creeping period after curing. Therefore, we used nano‐SiO₂ as a major additive to modify the physical properties of photopolymer. We also added appropriate dispersant to make nanoparticles distribute uniformly in order to reduce the phase separation in composite material. The experimental results showed that photopolymer/SiO₂ nanocomposite can improve tensile strength and hardness by about 50% and offers better dimensional stability. Photopolymer/SiO₂ nanocomposite can also increase the degradation temperature and shorten manufacturing time for RP processing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The influence of post‐cure on properties of carbon/phenolic resin cured composites and their final carbon/carbon composites

Two‐dimensional (2D) carbon/carbon (C/C) composites were prepared with phenol‐formaldehyde resin and graphite fabric. After curing, polymer composites were post‐cured in air at 160°C and 230°C for several hours and then all polymer composites were carbonized up to 1500°C. The effect of post‐cure on the microstructure and fracture behavior of the resultant carbon/carbon composites was studied. The post‐cure process was characterized by weight loss. This process promoted the crosslinking and condensation reactions and led to the formation of long‐chain, cross‐linked polymeric structures in the matrix. The post‐cured composites had a greater density than the unpost‐cured composite. This study indicates that a longer post‐curing time and higher post‐curing temperature would limit the shrinkage for the post‐cured composites during carbonization. The improvement in linear shrinkage was 22% to 44%. This process also limited the formation of open pores and decreased the weight loss of the resultant C/C composites. The resultant C/C composites developed from post‐cured composites had a greater flexural strength by 7 to 26% over that developed from unpost‐cured composite.     

Preparation and properties of UV-cured epoxy acrylate/glycidyl-POSS coatings

Epoxy acrylate (EA)/glycidyl-polyhedral oligomeric silsesquioxane (G-POSS) nanocomposites were synthesized via in situ ultraviolet initiated polymerization. XRD analysis indicates that G-POSS and EA are miscible and can form uniform composites. SEM micrographs show that the G-POSS particles (<500 nm in diameter) disperse uniformly in the polymer matrix. The EA/G-POSS nanocomposites exhibit heterogeneous morphology. FTIR analysis confirms the curing reaction is quite complete, and there are no chemical reactions between G-POSS and EA during the UV-curing process. The carbon–carbon double-bond conversion vs time profiles confirm that the addition of G-POSS improves the UV-curing rates of nanocomposites. The glass transition temperature (T _g) of nanocomposites were obtained by DMA. T _g reaches to the maximum at the loading of 1 wt% and then decreases with the increasing G-POSS loadings. The thermal stability, impact resistance, and flexibility of nanocomposites are all enhanced by the incorporation of G-POSS.     

Chemical shrinkage and diffusion-controlled reaction in a cresol novolac epoxy

The reaction kinetics with a diffusion control mechanism, as well as the volumetric change upon curing, of a cresol novolac epoxy/o-cresol-formaldehyde novolac hardener system were studied. Simple equations to model the change in linear coefficients of thermal expansion with reacting thermosetting system conversion were also derived. Based on the heat of the reaction of monomeric monofunctional model compounds, the true degree of conversion of this crosslinking epoxy system can be obtained. The reaction is then modeled as a reaction of shifting order: it first reacts autocatalytically and later switches into diffusion control. The reaction in the diffusion-controlled region can be modeled by an n-th order kinetic equation with its rate constant described by a WLF-type equation. Both experimental linear coefficients of thermal expansion above and below the glass transition temperature decrease linearly with the degree of conversion, which agrees with the derived equations. The importance of chemical shrinkage upon curing is also discussed.     

环氧树脂基复合材料的微波固化研究

微波固化具有速度快、固化均匀、效率高等优点,在聚合物特别是环氧树脂基复合材料的固化加工方面有很大潜力。本文介绍了微波加热原理以及环氧复合材料微波固化工程的基本理论,并对国内外环氧树脂基复合材料微波固化的最新研究进展及应用现状进行了综述。     

Aromatic phosphorodiamidate curing agent for epoxy resin coating with flame-retarding properties

Two organophosphorus-based diamines containing aromatic moieties has been synthesized and used as a curing and flame retarding agent for epoxy resin coatings. This agent functions not only as a crosslinking materials in the Epon 828 epoxy resin curing process but also as a fire retarding compound to produce thin films or composites upon curing. Phenyl phosphonic ethylene diamine diamide (PPEDD) was synthesized via condensation of phenylphosphonic dichloride (PPDC and ethylenediamine (EDA)). Likewise, phenyl phosphonic p-phenylene diamine diamide (PPPDD) was synthesized via condensation of PPDC and p-phenylenediamine (PDA). Kinetics studies of the curing reaction of the two phosphorodiamidates were carried out in comparison with the corresponding non-phosphorus containing reference crosslinking agents, EDA and PDA. Thermal stability of the cured epoxy were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Moreover, flame retardant properties of the materials was investigated by limiting oxygen index (LOI) measurements. The results show that epoxy resin cured with phosphorodiamidate possesses higher thermostability than that of the non-phosphorus containing counterpart. This is evident by a significantly higher amount of char formed upon burning. More importantly, the LOI of 27 and 31 was observed in the PPEDD-cured epoxy resin and PPPDD-cured epoxy resin compared with those prepared from non-phosphorus curing agents (20 for EDA and 21 for PDA). This was obtained only with approximately 2–3 wt.% of phosphorus content.     

Properties and processing characteristics of dielectric-filled epoxy resins

A family of casting composites, epoxy resins with mineral fillers, having a range of electrical properties, are being developed. In such composites, the dielectric constant is controlled primarily by varying the filler material in composition and proportions. The present work reports on the mechanical properties of composites made with two types of filler, an alumina powder (XA3500 from ALCOA) and a BaTiO₃/TiO₂ ceramic powder (ATD-50 from Ampex). Dependence of mechanical properties on curing agents was also determined. Filler contents from 0 to 40 percent volume were used. Epoxy systems contained single epoxy resin with both amine and anhydride hardeners. Processing of the anhydride-cured systems was easier than that of the amine-based systems because of their lower viscosity and longer gel time of the former. However, the anhydride-cured systems required higher processing temperatures. Curing kinetics and molecular bonding were investigated using a combination of differential scanning calorimetry, dynamic mechanical thermal analysis, and scanning electron microscopy. Activation energies of 11.2 kcal/mole and 12.1 kcal/mole were obtained for the curing of the amine-based and the anhydride-based composites respectively, and a small difference in the glass transition temperature was also observed. These effects can be attributed to the difference in the structure of the curing agents. The epoxy resin cured with NMA is less ductile compared with those cured with MTHPA or MHHPA due to slight chemical modification on the ring structures. This dependence of ductility on curing agent was observed in specimens with different filler contents. Although the presence of the filler materials was found to enhance the mechanical properties of the epoxy, the fracture mode in these materials is still brittle.     

Molecular composites based on thermosetting matrix polymers: Poly(p-phenyleneterephthalamide)-epoxy

Poly(p-phenyleneterephthalamide) (PPTA) reinforced molecular composites that utilize a thermosetting epoxy as the matrix polymer have been prepared by an in situ polymerization process. The properties of these molecular composites were compared with those of Kevlar pulp-filled composites that utilized the same matrix formulation. Study of the curing reactions of these systems using Fourier transform infrared, dynamic mechanical analysis, and nuclear magnetic resonance spectroscopy indicated some differences in the reactivity and ultimate polymer structure of these two systems. A comparison of the properties indicated increased tensile strength, modulus, and heat resistance for the molecularly reinforced material over the conventional fiber-filled system. Examination of the morphology of the molecular composite system showed that aggregated PPTA molecules are formed during the in situ polymerization process. This aggregation phenomenon was found to be due to formation of a liquid crystalline polymer solution during processing and final cure. These findings indicate the possibilities that exist in molecular composite processing for simultaneous control of the properties of the matrix and the reinforcement.     

Experimental modeling of the cure behavior of a formulated blend of DGEBA epoxy and C12‐C14 glycidyl ether as a reactive diluent

Microwave curing of polymer matrix composites has been suggested as an attractive substitute for conventional thermal curing. Formulations of epoxy and reactive diluents have the advantage of better wettability and uniform fiber impregnation. However, higher peak exotherms in large masses, and thus thermal overshoot, presents a challenge for cure cycle optimization. Therefore, building a reliable curing model will not only predict the behavior of these materials during actual processing, but also facilitate numerical modeling of the process and comparison of other resin formulations. In this study the effect of the reactive diluent on the isothermal cure kinetics of low viscosity epoxy was investigated using differential scanning calorimetry (DSC). A formulated blend of diglycidyl ether of bisphenol A (DGEBA) and C₁₂–C₁₄ aliphatic glycidyl was cured using diethylene triamine as the curing agent. Using a standardized procedure, ISO 113571‐5, the epoxy formulation was isothermally cured at several temperatures and the heat flow monitored and recorded. Using the heat flow data from DSC, the rate of cure was determined experimentally and a proper autocatalytic model with a total order of about 2.3 was fit to describe the process. Least‐square regression and isoconversion methods were used to find the model parameters and the activation energy, respectively. The accuracy of the model shows fine correlation with experimental data. By comparison to other epoxy resin without diluents, the analysis of the data shows that the reactive diluent increased the curing rate, while the values of activation energy and process parameters remained within the typical values of epoxy formulations. Based on these data, the future use of these types of resins in nonthermal curing of epoxy matrix composites is discussed. POLYM. COMPOS., 26:593–603, 2005. © 2005 Society of Plastics Engineers     

Physical properties and shrinkage of epoxy resins cured with lactams

In order to reduce the shrinkage of epoxy resin during the curing process, lactam is incorporated into epoxy in a copolymerization reaction. In this study, various amounts of lactams and BF₃-MEA were added to epoxy, and the volume shrinkage of polymerization was investigated. It was found that shrinkage decreases with the increase of the lactam content and with the lactam ring size as well. Infrared spectroscopic analysis, scanning electronic microscopic analysis, and mechanical tests were used to investigate the structure and properties of the copolymers. The results show that the incorporation of caprolactam leads to an increase in tensile strength and elongation, but the Izod impact strength is not improved.     

Optimization and numerical simulation analysis for molded thin‐walled parts fabricated using wood‐filled polypropylene composites via plastic injection molding

Plastic injection molding is discontinuous and a complicated process involving the interaction of several variables for control the quality of the molded parts. The goal of this research was to investigate the optimal parameter selection, the significant parameters, and the effect of the injection‐molding parameters during the post‐filling stage (packing pressure, packing time, mold temperature, and cooling time) with respect to in‐cavity residual stresses, volumetric shrinkage and warpage properties. The PP + 60 wt% wood material is not suitable for molded thin‐walled parts. In contrast, the PP + 50 wt% material was found to be the preferred type of lignocellulosic polymer composite for molded thin‐walled parts. The results showed the lower residual stresses approximately at 20.10 MPa and have minimum overpacking in the ranges of ?0.709% to ?0.174% with the volumetric shrinkage spread better over the part surface. The research found that the packing pressure and mold temperature are important parameters for the reduction of residual stresses and volumetric shrinkage, while for the reduction of warpage, the important processing parameters are the packing pressure, packing time, and cooling time for molded thin‐walled parts that are fabricated using lignocellulosic polymer composites. POLYM. ENG. SCI., 55:1082–1095, 2015. © 2014 Society of Plastics Engineers     

Characteristics of murta bast fiber reinforced epoxy composites

The growing global concern over environment protection has led to the application of natural fiber reinforced polymer composites as alternative materials in manufacturing sectors. Various natural fibers are therefore being explored for reinforcement of polymer matrices. In the present work, murta bast fibers of varying length and weight percent are mixed randomly with the epoxy matrix and the composites are prepared from these mixtures by using the hand lay‐up method. The composites are characterized on the basis of density, thermal gravimetric analysis, infrared spectroscopy, scanning electron microscopy, tensile strength, flexural strength, compressive strength, impact strength, and Rockwell hardness studies. Tensile, flexural, and compressive moduli of the composites are also determined. The tensile strength of the composite was analyzed in the light of the different analytical models. Composites containing 30 weight % fibers of length 25 or 35 mm have the optimum mechanical properties. Murta bast fiber has the characteristics to become a good natural material for reinforcement. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44142.     

Stress‐initiated void formation during cure of a three‐dimensionally constrained thermoset resin

During cure of epoxy resins, polymerization induces an increase in mechanical properties, which is accompanied by a volumetric shrinkage. When the resin is cured in a constrained mold to which it adheres, tensile stresses will hence develop, which may exceed the stremgth of the resin at a given curing stage. Voids will then form. The origin and governing parameters of void formation are studied using an epoxy resin cured in a three‐dimensionally constrained glass mold following isothermal cure cycles. Two types of voids are shown to appear during cure, one early in the process and a second around the gelation point. A viscoelastic analysis of the material stress state over the whole range of cure is performed. Both the viscoelastic modulus obtained from a time‐cure‐temperature superposition and the volumetric shrinkage, which was continuously measured by density change, are taken into account. A value for the critical internal stress at void initiation is thus proposed. This criterion can be used to provide guidelines for tailoring the material properties toward an increase of the critical stress for void initiation. Also, since during theprocessing of composite materials, cases may arise where the resin cures within the interstices left between consolidated fibres that do not move, this critical stress failure criterion can be of use in the eastablishment of a process window providing guidelines for the production of void free composites.     

Manufacturing and mechanical response optimization of epoxy resin/Luffa Cylindrica composite

The present investigation pertains to the existent possibilities of the fibrous natural material Luffa Cylindrica (LC) as reinforcement to thermoset resins. The main purpose was the manufacturing of an engineering material that would, simultaneously, lead to a more sustainable world. In an effort to optimize the final mechanical properties, semi‐ green Epoxy Resin/Luffa Cylindrica (ER/LC) composites were manufactured, applying a number of different manufacturing parameters combinations. The manufacturing parameters taken into account were: (a) fiber chemical treatments; (b) the external applied pressure during curing; (c) number of plies; (d) stacking sequence effect; (e) LC's structural characteristics; and (f) the influence of fiber weight fraction on composite's behavior. The elastic flexural response of the composite polymer was found improved with respect to neat polymer's response due to fibers' nature and the applied manufacturing optimization process. This improvement was reflected to material's stiffness which optimally increased by 48% for a mechanically applied pressure of 4.6 kPa during curing. Additionally, LC fibers chemically treated with Acetone/ CH₃COOH 1 wt % led to stiffness' improvement up to 30%. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41992.     

Cure shrinkage characterization of an epoxy resin system by two in situ measurement methods

Dimensional accuracy of composites manufacturing is a major issue for part producers, especially when tight tolerances are required. One of the main causes of dimensional variations is the resin volumetric changes during the cure. In this article, volumetric cure shrinkage of a one part epoxy system was characterized using two different methods. First, a modified rheology method was used to measure the volumetric cure shrinkage after the gel point. Second, a gravimetric method measured the shrinkage over the entire cure. A linear relationship between the volumetric cure shrinkage and the degree‐of‐cure was deduced from the results and the resin cure kinetic models. Results show a good agreement between the two techniques. POLYM. COMPOS., 31:1603–1610, 2010. © 2009 Society of Plastics Engineers     

Synthesis and characterization of a novel heat resistant epoxy resin based on N,N′-bis(5-hydroxy-1-naphthyl)pyromellitic diimide

A novel epoxy resin containing imide and naphthyl groups was synthesized, and characterized using NMR, NMR, FT-IR spectra and elemental analyses. The curing behavior was investigated with differential scanning calorimetry (DSC) using 4,4′-diaminodiphenylsulfone (DDS) as curing agent. The physical properties of the cured polymer were evaluated with dynamic thermal mechanical analysis (DMTA) and thermogravimetric analysis (TGA). The results showed that the cured polymer exhibited higher glass transition temperature (T_g) and better thermal stability compared with those commercial available heat resistant epoxy resins.