Positron annihilation spectroscopy study of moisture absorption in protective epoxy coatings

Position annihilation spectroscopy (PAS) was used to measure the relative free-volume fraction of protective epoxy coatings before and after exposure to liquid water at room temperature. The relative free volume fraction determined before water exposure was compared to the equilibrium water uptake of each coating and a correlation was found. The relative free-volume fraction of the epoxy coatings decreased slightly after water exposure. This decrease is contrary to the free volume theory of plasticization, but is consistent with the antiplasticization process. Larger decreases in the relative free volume fraction were sought by repeating the water uptake experiments with nitrobenzene which in the bulk, liquid form quenches ortho-positronium (o-Ps). Since the o-Ps lifetime remained approximately constant and the o-Ps intensity decreased after nitrobenzene absorption, nitrcbenzene is believed to be inhibiting the formation of o-Ps in the epoxy free volume cavities. Larger decreases in the relative free volume fractions were found after nitrobenzene exposure than after water exposure. These larger decreases are due to the fact that nitrobenzene is a better inhibitor of o-Ps formation than water in the epoxy free volume cavities. Larger volume fractions of nitrobenzene were absorbed by the coatings than water and were interpreted to be due to interactions between nitrobenzene and the epoxies. © 1993 John Wiley & Sons, Inc.     

Effect of carbon fiber surface functionality on the moisture absorption behavior of carbon fiber/epoxy resin composites

Polyacrylonitrile (PAN)‐based carbon fibers were electrochemically oxidized in aqueous ammonium bicarbonate with increasing current density. The electrochemical treatment led to significant changes of surface physical properties and chemical structures. The oxidized fibers showed much cleaner surfaces and increased levels of oxygen functionalities. However, it was found that there was no correlation between surface roughness and the fiber/resin bond strength, i.e. mechanical interlocking did not play a major role in fiber/resin adhesion. Increases in surface chemical functionality resulted in improved fiber/resin bonding and increased interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composites. The relationship between fiber surface functionality and the hydrothermal aging behavior of carbon fiber/epoxy composites was investigated. The existence of free volume resulted from poor wetting of carbon fibers by the epoxy matrix and the interfacial chemical structure were the governing factors in the moisture absorption process of carbon fiber/epoxy composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Fluorescent labels to study thermal transitions in epoxy/silica composites

The analysis of the fluorescent response from the dansyl moiety as a function of temperature has been used to estimate the thermal transitions in silica particle/epoxy-based composite materials. Silica particles were surface-coated with 3-aminopropyltriethoxysilane (APTES) and 3-aminopropylmethyldiethoxysilane (APDES). 5-Dimethylamino-1-naphtalenesulfonyl chloride (DNS) and 5-dimethylaminonaphthalene-1-(2-aminoehyl)) sulfonamide (DNS-EDA) were selectively attached to the silanized silica particles and to the epoxy matrix respectively. The fluorescence results, interpreted in terms of the model of interpenetrating polymer networks, suggest that (i) independent of the silane coating, the interfacial region is slightly more rigid and heterogeneous than the epoxy bulk and (ii) the interface generated with APTES seems to be more flexible than that obtained with APDES.     

Irreversible effects of moisture on the epoxy matrix in glass-reinforced composites

The irreversible effects of moisture exposure on anhydride-crosslinked epoxy resin films are investigated by means of Fourier-transform infrared spectra. Hydrolytic attack of water at the ester linkages is accelerated in alkaline media and is a mechanically activated process. Matrix hydrolysis is also enhanced in the presence of inorganic fillers.     

Electrical and positron annihilation study on epoxy and epoxy acrylate composites

Epoxy acrylate resin was prepared by endcapping the acrylic acid to epoxy resin backbone in the presence of triphenyl phosphene as catalyst. The structure was elucidated by IR and NMR spectroscopy. Epoxy and epoxy acrylate composites were prepared by mixing different concentrations of mica, magnesium hydroxide and calcium silicate with each epoxy/hardener and epoxy acrylate/styrene mixtures, respectively. The permittivity ε′, dielectric loss ε′′ and loss tangent tan δ were measured for these composites in the frequency range (10²-10⁶ Hz) and at 30 °C. The data obtained were analyzed into two absorption regions related to Maxwell-Wagner effect and to some local molecular motions rather than the main chain motion. The higher values of ε′ and the lower values of tan δ given for the composites containing the epoxy acrylate resin indicate some improvement in the dielectric properties when compared with those containing the epoxy resin. The effect of filler type and filler content on the positron annihilation lifetime and its intensity as well as S-parameter for epoxy and epoxy acrylate composites were also studied. The high values of S-parameter noticed by with increasing filler content indicates some increase in free electrons which lead to an increase in electrical conductivity. The highest value of hardness was obtained in the case of calcium silicate followed by mica and magnesium hydroxide.     

A novel model for quantification of the moisture absorption of polymeric laminated composites

In the present study, a new model was developed that considers the amount of the environmental fluid absorption by different constituents of polymeric laminated composites including fibers, resin, fiber-matrix interphase region, ply interface region, and voids. By knowing the fluid absorption behavior of the composite constituents, the present model can predict the amount of fluid absorption of different constituents of polymeric laminated composites with an arbitrary resin volume fraction and stacking sequence. Test specimens were fabricated by glass fibers and vinyl ester resin. The environmental fluids, examined in this study, were distilled and saline water under different temperatures and salt concentrations. To investigate the absorption behavior of different constituents of polymeric composite, various tests were conducted on fibers, pure cured resin, unidirectional composite specimens, and laminated composites. Based on the results of the tests, a new theoretical model was developed to quantify and predict the amount of fluid absorption of different constituents of laminated polymeric composites. The thickness of the interphase region between the fiber and matrix was also measured using the scanning electron microscope (SEM) images and nano-indentation tests. The consistency of experimental results with the outcomes of the theoretical model indicates the accuracy of the model.     

A mesoscale study of thermal expansion behaviors of epoxy resin and carbon fiber/epoxy unidirectional composites based on periodic temperature and displacement boundary conditions

The thermal expansion behaviors of neat epoxy resin and carbon fiber/epoxy unidirectional (UD) composites were experimentally and numerically studied in this paper. The dynamic mechanical analysis (DMA), thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and thermal conductivity measurement were used to measure the thermo-mechanical properties of epoxy resin at different temperatures. The dilatometer was used to measure the thermal strains and linear CTEs of neat epoxy resin and UD composites. In addition, a mesoscale finite element model based on the periodic temperature and displacement boundary conditions was presented to analyze the thermal expansion behaviors of UD composites. The resin-voids representative volume element (RVE) was used to calculate the thermo-mechanical properties of several kinds of resin-voids mixed matrix. From the results it can be found that the glass transition temperature of epoxy resin, porosity and fiber orientation angle have significant effects on the thermal expansion behaviors of UD composites. The mesoscale finite element analyses (FEA) have obvious advantages than various existing analysis models by comparing their predictive results. The distributions of thermal displacement, thermal stress and thermal strain were extracted between the carbon fiber, resin-voids mixed matrix and their interface, and also between the front and back surfaces of the loading direction, to further investigate thermal expansion structure effects of UD composites. This paper revealed that the mesoscale FEA based on periodic temperature and displacement boundary conditions can be also used for thermal expansion researches of other complex structure composites.     

Variation of the thermal diffusivity of glass and carbon fiber–epoxy composites as a function of water absorption

Polymeric matrix composites can be degraded due to their exposure to wet environments. In this work, the thermal diffusivity of glass and carbon reinforced polymer-matrix composites is determined, and the variability of this property is evaluated as a function of the amount of absorbed water. The results obtained are discussed with respect to the efficiency of the heat exchange capacity of each composite.     

Competitive absorption of epoxy monomers on carbon nanotube: A molecular simulation study

Position restrained (PR) molecular dynamics (MD) simulations were carried out on the bulk models for the two composite systems including epoxy monomers and carbon nanotube (CNT). The pair energies and the radial distribution functions (RDFs) were computed to evaluate the relative strength of the epoxy monomers binding to the CNT. It is found that the aromatic amine binds more strongly to the CNT than does the aliphatic amine. A vivid view indicates the aromatic rings tend to form π‐stacking with the CNT, and the compounds with aromatic rings prefer to wrap the CNT. These simulated results are in good agreement with those obtained previously from the vacuum models. This work demonstrates that curing agents affect the interactions between epoxy resin and CNT. Other comparisons of relative binding strength of epoxy monomers also depend upon the temperature. Further analyses suggest that the aliphatic amine exhibits more strong interactions with epoxy resin than does the aromatic amine, mainly due to the presence of hydrogen bonds (HBs) between them. Thus, the ultimate performance of epoxy‐CNT polymer nanocomposites should be affected by the two reverse interactions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011.     

Contributions of the nanovoid structure to the moisture absorption properties of epoxy resins

Epoxy resins absorb significant quantities of moisture, typically 1 to 7% by weight for various formulations, which can greatly compromise their physical properties. It is known that polarity of the epoxy is a significant factor in determining the ultimate moisture uptake. However, the contribution from molecular topology still remains vague. In this work, the effects of molecular topology are elucidated by synthesizing novel epoxies where the polarity is maintained constant but the topology is systematically altered. The molecular topology is quantified in part via Positron Annihilation Lifetime Spectroscopy (PALS) in terms of the nanometer-sized voids, or nanovoids, that are also commensurate with typical interchain distances. The nanovoids are separated into their absolute zero and thermally fluctuating fractions by performing PALS measurements over a wide range of temperatures. A strong correlation is observed between the absolute zero hole volume fraction and the ultimate moisture uptake. Although the correlation is clear, the absolute zero hole volume fraction alone is not sufficient to predict the ultimate moisture uptake, and network polarity must also be considered. It is surmised that the role of the nanovoids is to open the epoxy matrix and alleviate steric hindrances that may prevent a water molecule from associating with a polar group. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3035–3048, 1998     

Effect of silica content on thermal stability of fumed silica/epoxy composites

Composites of a fumed silica industrial residue and an epoxy resin were prepared and their thermal stability and thermal degradation behaviour were studied by TGA in air. Classical thermal stability parameters, based on the initial decomposition temperature (IDT), temperature of maximum rate of mass loss (T_max) and integral procedure decomposition temperature (IPDT) were calculated before and after subtraction of the filler mass from the TGA curves. Without filler mass subtraction, the thermal stability of the epoxy resin seems to be improved and the mass loss rate was reduced by the addition of fumed silica. Nevertheless, after subtraction of the filler mass, the thermal degradation behaviour of the resin was only slightly affected by the silica content. A possible negative effect of the silica content on the cure was also found.     

Reduction in the moisture absorption of cured MY720/DDS epoxy resins

Thin films of cured MY720/DDS epoxy resins were treated with blocking reagents for hydroxyl, amine, and epoxide functional groups. Infrared spectroscopy (IR) and differential scanning calorimetry (DSC) were used to monitor the progress of the reaction. Treated films were soaked in distilled water at 30°C for 720 h, and the corresponding moisture absorption determined gravimetrically. Samples treated with N-methyl-N-t-butyldimethylsilyl trifluroacetamide (MTBSTFA) containing 1% t-butyldimethylchlorosilane (TBDMCS) in dimethylsulfoxide (DMSO) at 30°C showed a maximum reduction in the IR peak at 3400 cm^?1 (OH and NH) of 39% and a 100% reduction in the epoxide peak at 904 cm, ^?1. The moisture absorption was 1.9%, a reduction of 58% compared to the untreated films (ca. 4.5%). The reactions show dependencies on time and temperature and are diffusion controlled. Samples treated with trimethylsilyl isocyanate (TMSI) in DMSO a 70°C showed 72% reduction in the 3400 cm^?1 IR peak; DSC thermograms do not show an exothermic energy, suggesting that all epoxide groups reacted. These reactions are primarily dependent on time and temperature. The moisture absorption of TMSI treated samples was 1.0% (75% reduction). Samples were also treated with m-trifluoromethyl phenyliscyanate (MTFPI). The reduction in the IR peak at 3400 cm^?1 was 9%, but the moisture absorption was 2.4%—a reduction of 47%.     

Combined effect of zeolite and boric acid on thermal behavior of epoxy composites

The particles of natural zeolite in combination with boric acid were incorporated into the epoxy resin ED-20 in order to improve the thermal stability of epoxy polymer. Epoxy resin was cured using polyethylenepolyamine. Characterization of the epoxy composites was carried out by using Fourier transform infrared spectrometry, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) under flow of air and argon. The thermal behavior of the zeolite/boric acid-based epoxy composites (total percentage 15 mass%) were compared with that of 15 mass% boric acid-based epoxy system and the neat epoxy resin. TG and DSC results revealed that the combination of 5 mass% zeolite and 10 mass% boric acid significantly increased the mid-point temperature and residue, and decreased the maximum decomposition rate of the epoxy composites at the heating.     

Characteristics of kenaf fibre/epoxy composites subjected to thermal degradation

Kenaf fibres are receiving much attention in the natural fibre composite industry due to its potential as polymer reinforcements. However, like all natural fibres, kenaf fibres have lower thermal resistance as compared to synthetic fibres. In this current work, the characteristics of kenaf fibre/epoxy composites, both treated and untreated using alkalization process, exposed to high temperature were studied. Thermogravimetric analysis (TGA) was used to study the thermal decomposition behaviour of treated and untreated kenaf/epoxy composites as well as their components, kenaf fibre and neat epoxy from room temperature up to 600 °C. The weight loss and physical changes of these samples were observed through furnace pyrolysis. Surface morphology of the composites after degradation was observed using scanning electron microscopy (SEM). The results from the TGA showed that the addition of kenaf fibres into the epoxy slightly improves both the charring and thermal stability of the samples. However, it was observed that alkalization causes reduction in these behaviours for the kenaf/epoxy composite. Generally, increased exposure time causes higher weight loss of the composites only up to 150 °C. At higher temperature, duration of exposure has little influence on the weight loss. Fibre-matrix debondings were observed on degraded samples implying mechanical degradation of the composites had occurred.     

Mechanical and thermal properties of epoxy/silicon carbide nanofiber composites

The silicon carbide (SiC) nanofibers (0.1, 0.25, and 0.5 phr), produced by self‐propagating high‐temperature synthesis (SHS), are used to reinforce the epoxy matrix cured with an anhydride hardener. Morphological studies reveal a better dispersion of SiC nanofibers and a good level of adhesion between nanofiber and the matrix in composites with lower (0.1 and 0.25 phr) nanofiber loading. The flexural studies show that a maximum increase in flexural properties is obtained for composites with 0.25 phr SiC nanofiber. The fracture toughness of epoxy is found to increase with the incorporation of SiC nanofibers, and 0.25 phr SiC nanofiber loading shows maximum fracture toughness value. The possible fracture mechanisms that exist in epoxy/SiC nanofiber composites have been investigated in detail. Thermogravimetric analysis reveals that SiC nanofibers are effective fillers to improve the thermal stability of epoxy matrix. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of curing on the glass transition temperature and moisture absorption of a neat epoxy resin

Apparent glass transition temperature (T_g) measurements were made on smaples of a neat epoxy resin that had been cured at four different temperature and for four different times at each temperature. The apparent T_g data increase with cure time toward an asymptote that was dependent on cure temperature. The asymptotic dependence of T_g on cure temperature may be explained by the effect of cure temperature on the reaction rates and available reaction sites. The asymptotic increase with cure time may be understood in terms of the resin's extent of cure. Moisture-conditioning studies were also made and the amount of moisture absorbed was correlated with the extent of cure. The absorbed moisture's interaction with the resin's molecular structure was deduced to by primarily at hydroxyl sites.     

The effect of masked isocyanates on the moisture absorption of MY 720/DDS epoxy resin

Several masked isocyanates were prepared with variations in both the type of isocyanate and masking group. They were characterized by elemental analysis and NMR spectroscopy, and their unblocking temperatures were determined. In general, higher unblocking temperatures were obtained using acyclic and cyclic aliphatic isocyanates and fluorinated phenols. Those with unblocking temperatures in the range of 120–180°C were incorporated into MY 720/DDS epoxy resin prior to cure. Highly fluorinated variations were incompatible with the resin. IR and DSC analyses showed that residual functional groups in the epoxy resin reacted with the masked isocyanates. Reductions in moisture absorption as high as 65% were obtained depending on the masked isocyanate. DMA studies showed that the T_g of the epoxy resin is lowered by incorporation of the masked isocyanate but the elastic modulus (E′) is relatively unchanged at temperatures below T_g.     

Influence of T31 content on combustion and thermal degradation behaviors on flame-retardant epoxy composites

To study the influence of the T31 content on the combustion properties and thermal degradation behaviors of flame-retardant epoxy composites, a series of flame-retardant epoxy composites were prepared using E-44 epoxy resin as matrix, T31 curing agent as curing agent, and intumescent flame retardant (IFR, based on phosphorus acid, melamine, and pentaerythritol) as flame retardant. The influence of T31 content on combustion behaviors and thermal degradation properties of the flame-retardant epoxy composites were studied using cone calorimeter test (CCT) and thermal-gravimetric analysis (TG), respectively. The cone calorimeter test results indicate that the decrease of T31 can significantly decrease the HRR, THR, SPR, and enhance the char residue of the epoxy composites. EP-4 with 7.0 wt% T31 shows the lowest HRR, SPR and the highest char residue. Furthermore, the TG results indicate that the EP-4 has the highest char residue among all the epoxy composites.     

The improvement of thermal stability and adhesion of silicone rubber composites modified by phenolic epoxy resin

The phenolic epoxy resin (F51) was siliconized by KH550 and the product was named as FKS. A hydroxyl-terminated polydimethylsiloxane (HTPDMS) which was modified with FKS was prepared. The siliconization reaction ensured a segment of siloxane on the side chain of F51. FT-IR and ¹H-NMR were employed to confirm the chemical structure of FKS. Morphology observations revealed that the enhancement of mechanical properties of the silicone rubber systems can be attributed to good compatibility between FKS and silicone rubber matrix. Thermogravimetric analysis showed that the residual yield at 800?°C of silicone rubber composites increased significantly when compared with that of neat HTPDMS. The mechanical properties demonstrated that tensile strength and elongation at break of silicone rubber system increased distinctly after modification, especially when 30 phr siliconized F51 were added to the silicone rubber. Shear strength was improved gradually with the addition of FKS. These above observations emphasize the vital effect of FKS on the behavior of modified HTPDMS.     

Surfactant-assisted fabrication of graphene frameworks endowing epoxy composites with superior thermal conductivity

With the rapid growth in electronic device performance,there has been an increasing demand for thermally conductive polymer composites to handle the thermal management issue,thus contributing to the great importance to develop the graphene framework,which is evaluated as the most promising reinforcements for enhancing the thermal conductivity of polymer.Vacuum filtration is a common method to fabricate graphene framework,whereas,it is available to prepare a framework with centimeter-scale thickness by filtrating the graphene-water dispersion,due to the fact of sample cracking caused by the mismatch of surface tension between graphene and water.In this work,a surfactantassisted strategy was proposed by adjusting the surface tension of the water close to that of graphene first,then performing a conventional filtration process,to fabricate graphene framework.As a result,a thick graphene framework(thickness:3 cm)was successfully prepared,and after embedding into epoxy,the framework endows the composite(13.6 wt%)with a high in-plane thermal conductivities of12.4 W/mK,which is equivalent to≈64 times higher than that of neat epoxy.Our method is simple and compatible with the conventional filtration process,suggesting great potential for the mass-production of graphene framework to meet the practical application requirements.