Viscoelastic and Processing Effects on the Fiber-Matrix Interphase Strength. Part III. The Effects of Postcure

A novel method for tailoring the interphase of carbon fiber-polymer composites by resistive electric heating is presented. The single-fiber fragmentation test is used to investigate the adhesion and fracture properties of the interphase. Electric resistive heating is shown to increase adhesion and toughness at the interphase region. In analyzing the results, the strength and fracture energy of the interphase are related to the thermal postcure conditions created by resistive electric heating. For this purpose, a difference analysis method is used to obtain a numerical solution for the heat conduction problem in the single-fiber test specimen and the temperature distributions are determined. Improvements obtained by using resistive electric heating of the carbon fiber are compared with those obtained by postcuring of the whole sample via convective thermal postcuring. The results obtained using these two different postcure methods seem to be similar.     

Adhesion: Comparison Between Physico-chemical Expected and Measured Adhesion of Oxygen-plasma-treated Carbon Fibers and Polycarbonate

The adhesive interaction between oxygen-plasma-treated, polyacrylonitrile-based, high-tensile-strength carbon fibers and a polycarbonate matrix has been studied. Several models have been used to predict the impact of the plasma treatment process on the strength of adhesion between both jointing partners. These approaches have been the thermodynamic work of adhesion which was calculated from the solid surface tensions, based on the results of contact angle measurements versus test liquids, the contact angle which was directly obtained via polycarbonate melt droplets on single carbon fibers and the zeta (?)-potential data provided by streaming potential measurements. The results have been compared with the interfacial shear strength determined from the single-fiber fragmentation test. Additionally, the single-fiber tensile strength of the oxygen-plasma-treated carbon fibers was determined.

We confirmed that any physico-chemical method on its own fails to describe exactly the measured adhesion. However, for the investigated system, the conscientious interpretation of the data obtained from wetting measurements, in conjunction with the thermodynamic approach, is sufficient to predict the success of a modification technique which has been applied to one component in order to improve adhesion.     

Effect of postmold curing on plastic IC package reliability

Nearly all IC encapsulating compounds require a postcure treatment to ensure integrated circuit (IC) package reliability. The issue of postcuring and this effect on IC package reliability performance are considered in this article. We examined the development of various encapsulating compounds' properties with various durations of postcure time. It was found that the mechanical strength, glass transition, and adhesion strength were increased with increasing duration of postcure time compared to as-molded samples. However, these properties could reach ultimate values after postcuring for 1–2 h. It was also seen that the moisture uptake was increased for samples that have been post-mold-cured due to increased crosslinking density causing a large free volume in the glassy polymer matrix. C-mode scanning acoustic microscopy (C-SAM) analyses were performed to investigate the effect of the duration of postcure time on the IC package reliability and they show a good relationship with the evolution of the compound's properties during the postcure process. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2187–2193, 1998     

Adhesion: Comparison Between Physico-chemical Expected and Measured Adhesion of Oxygen-plasma-treated Carbon Fibers and Polycarbonate

The adhesive interaction between oxygen-plasma-treated, polyacrylonitrile-based, high-tensile-strength carbon fibers and a polycarbonate matrix has been studied. Several models have been used to predict the impact of the plasma treatment process on the strength of adhesion between both jointing partners. These approaches have been the thermodynamic work of adhesion which was calculated from the solid surface tensions, based on the results of contact angle measurements versus test liquids, the contact angle which was directly obtained via polycarbonate melt droplets on single carbon fibers and the zeta (ς)-potential data provided by streaming potential measurements. The results have been compared with the interfacial shear strength determined from the single-fiber fragmentation test. Additionally, the single-fiber tensile strength of the oxygen-plasma-treated carbon fibers was determined.

We confirmed that any physico-chemical method on its own fails to describe exactly the measured adhesion. However, for the investigated system, the conscientious interpretation of the data obtained from wetting measurements, in conjunction with the thermodynamic approach, is sufficient to predict the success of a modification technique which has been applied to one component in order to improve adhesion.     

The influence of the interphase on composite properties: Poly(ethylene-co-acrylic acid) and poly(methyl vinyl ether-co-maleic anhydride) electrodeposited on graphite fibers

The electrodeposition of saturated copolymers onto carbon fibers is investigated, focusing particular attention on improvement of shear and impact properties of the corresponding composites. Carbon fibers are electrocoated with poly(ethylene-co-acrylic acid) and poly(methyl vinyl ether-co-maleic anhydride) from aqueous media, and fabricated into epoxy composites. The results of interlaminar shear strength (ILSS) tests, initially employed to assess fibermatrix adhesion, are vitiated by the occurrence of mixed-mode failure. Interfacial shear strength (IFSS) is hence evaluated by stressing single-fiber composite specimens to obtain ultimate aspect ratios of the fiber fragments. The data are combined with fiber strengths by a recently developed statistical theory (1) to yield a distribution for IFSS. Both copolymer interphases improve fiber-matrix bonding to an extent greater even than that obtained with commercial fiber surface treatment. Good fiber-matrix adhesion is further apparent from SEM studies of fractured ILSS test specimens. A key to this improved adhesion is the interpenetration of matrix resin and interphase polymer, revealed by electron microprobe analysis (2). Notched Izod impact strength is also increased over uncoated-fiber composites. These copolymer interphases behave as deformable interlayers, absorbing impact energy and blunting the growing crack tip. Further energy is absorbed in deflecting the crack through a more tortuous path. Simultaneous improvements in impact and shear strengths are thus obtained, which may be further enhanced by optimizing the electrodeposition parameters and the coating thickness. The influence of the interphase on composite properties is better understood from this study, paving the way for refinement in interphase design.     

CHARACTERIZATION, PROPERTIES, AND PROCESSING OF LARC PETI-5® AS A HIGH-TEMPERATURE SIZING MATERIAL: III. ADHESION ENHANCEMENT OF CARBON/BMI COMPOSITES

A phenylethynyl-terminated imide oligomer (LaRC PETI-5®) with a number average molecular weight of 2500 g/mol has been applied onto the surfaces of PAN-based carbon fiber tows and woven carbon fabrics as a sizing material to introduce an interphase between the fiber and matrix in carbon/BMI composites. The adhesion between the fiber and matrix was enhanced by the presence of a properly processed LaRC PETI-5® interphase. The results showed that when LaRC PETI-5® was sized and processed at 150°C, the interfacial shear strength (IFSS) of unidirectional IM7/BMI composite measured by using a microindentation technique and the interlaminar shear strength (ILSS) of a carbon/BMI composite measured by short beam shear test were markedly improved by about 35% and 66%, respectively, in comparison with the unsized counterparts. The adhesion enhancement strongly depends not only on the presence or absence of LaRC PETI-5® sizing interphase but also on the temperature profile applied to the sizing before composite fabrication. Both of these factors critically influence the physical and chemical state of the sizing material. Scanning electron microscopic observations of the composite fracture surfaces support the improved interfacial property of carbon/BMI composites.     

Residual Stresses in Microcomposites and Macrocomposites

Existing models for built-in residual stresses in composite materials are reviewed and discussed. In particular, the thermal longitudinal stress present in the fiber prior to a single-fiber fragmentation experiment is studied using various model composite data. It is found that this stress is typically compressive in nature and that, quantitatively, it depends on the fiber content, the degree of undercooling, and the thermoelastic constants of the fiber and the matrix. In the case of single-fiber composites (or microcomposites), the thermal longitudinal stress present in the fiber is high enough to either induce fiber sinewave buckling (such as in E-glass/epoxy), or extensive fiber fragmentation (such as in graphite HM/polypropylene) that may then be used to measure the dependence of compressive fiber strength upon length. This has to be accounted for in quantitative models that calculate interfacial adhesion parameters using single-fiber tests, such as the fragmentation test or the microbond test. Implications for high fiber content composites (or macrocomposites) are discussed.     

一种新型高光注塑模具加热方法的模拟和实验研究

采用电加热方式的高光注塑模具可以有效消除传统注塑成型过程中塑料件的熔接痕、浮纤、银纹等缺陷。然而直接将电加热棒插入模具孔中,由于间隙处的空气,大大降低了传热速度,提出一种新型电加热方法,通过在电加热棒与模具之间填充一种导热液,改变电加热棒与模具之间的接触状况,建立三维传热模型,并通过模拟和实验研究,证明了这种方法可以提高40%的加热效率,同时还能降低电加热棒内部40%的温度。     

Effects of curing agent and carbon black filler loading on carbonization behavior of phenolic‐carbon black composites

The effects of curing agent (p‐toluene sulfonic acid, PTSA) concentration, i.e., 1.0, 1.5, 2.0, 2.5, and 3.0 wt% on neat phenolic resin (in absence of carbon black) were investigated through the measurement of density, weight loss, linear shrinkage, and mechanical properties under compression mode to understand the carbonization behavior of carbon–carbon composite. The study was carried out after curing, postcuring, and carbonization. Also, thermogravimetric analysis was used to study the effects of curing agent concentration on thermal stability and kinetic parameters (i.e., activation energy, order of decomposition, pre‐exponential term, etc). The kinetic parameters were evaluated by using four single heating rate techniques namely Friedman, Coats‐Redfern, Freeman‐Carroll, and Chang methods. Further, to study the effects of both carbon black filler loading and carbonization temperature, phenolic‐carbon black composites were prepared at the loading of 10, 20, 30, 40 wt% using 1.5 wt% of PTSA. These were also investigated through density, weight loss, and shrinkage measurements after curing, postcuring, and carbonizing at the temperature of 600, 1000, and 1400°C in nitrogen atmosphere. To analyze the evolution of carbon phase X‐ray diffraction study was carried out for the carbonized samples. Finally, cured, postcured and carbonized composite samples were subjected to compression tests to study the compression strength and modulus. POLYM. COMPOS., 31:2069–2078, 2010. © 2010 Society of Plastics Engineers     

Characterization of interfacial toughness in carbon fiber/epoxy resin composite subjected to water aging using single‐fiber fragmentation method in an energy‐based model

The toughness of the interphase between carbon fibers and epoxy resin was characterized by the interfacial fracture energy, which was derived from the modified Wagner‐Nairn‐Detassis (WND) model, considering the moisture swelling stress. The characterization was used to evaluate the changes of interphase bonding before and after water aging, including boiling water and 70°C water immersion. The effects of the water aging on the parameters in WND model were analyzed. The mechanism of interphase degradation under water aging was interpreted considering the change of interphase thickness, which was measured using the dynamic nanomechanical mapping method. It is shown that the single‐fiber fragmentation test with the proposed energy‐based model can quantify the degradation of interphase toughness after water aging. For the studied system, the interphase thickness has a close relationship with the interfacial fracture energy, indicating that the swelling of the resin matrix and interphase results in an increase in interphase thickness and a decrease in interphase bonding property. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Role of functional groups on the microwave attenuation and electric resistivity of activated carbon fiber cloth

Virgin activated carbon fiber cloth (ACFC) samples with select degrees of activation/porosity were treated with nitric and sulfuric acids or with hydrogen. Composition, microwave attenuation constant and electric resistivity results for these samples are provided. On average, acid treatment resulted in a 677% increase in oxygen content, 89% decrease in microwave attenuation constant, and 3200% increase in electrical resistivity when comparing these properties to the corresponding ones in the virgin samples. However, hydrogen treatment resulted in a 72% decrease in oxygen content, 50% increase in microwave attenuation constant, and 63% decrease in electrical resistivity, when comparing these properties to the corresponding ones in the virgin samples. These results indicate that conduction loss dominates over the polarization loss for microwave attenuation in ACFC. Increasing the oxygen content reduces the ACFC’s ability to absorb microwaves and is expected to make ACFC more difficult to heat with microwaves. However, decreasing the oxygen content allows the ACFC to heat more readily by resistive heating. Since microwave and resistive heating techniques depend on the microwave attenuation constant and electric resistivity, respectively, controlling the density of functional groups of ACFC can significantly affect the thermal regeneration of ACFC depending on the method used to heat the ACFC.     

Comparative study of interlaminar fracture toughness of GFRP with different fiber surface treatments

This investigation is focused on the influence of glass fiber surface treatment on the interlaminar fracture toughness of unidrectional laminates. Three different fiber surface treatments were considered: polyethylene treated fibers to get poor adhesion, silance treated fibers to get good bond strength, and industrial fibers without special treatments with the coupling agents. The interlaminar fracture behavior of unidirectional glass fiber reinforced composites with different fiber surface treatments has been investigated in mode I, mode II, and for the fixed mixed mode I/II ratio 1.33. Double cantilever beam (DCB), end notched flexure (ENF), and mixed mode flexure (MMF) specimens were used. The data obtained from these tests were analyzed by using different analytical approaches and the finite element method. For the fibers treated with the silane coupling agent, a value about 2.5 times higher of mode II interlaminar fracture toughness for crack initiation was obtained in comparison with the polyethylene sized composite. For the composite made from the industrial fibers, a value about 2 times higher was obtained. Because of extensive fiber bridging and pullout in the composites with poor fiber/matrix adhesion, the results of mode I and mixed mode I/II tests did not characterize the interphase quality. In order to determine the interphase quality, the mode II tests are recommended.     

Interfacial Bond Strength in SiC/C/SiC Composite Materials, As Studied by Single-Fiber Push-Out Tests

The interfacial characteristics of SiC/C/SiC composites with different fiber-coating bond strengths have been investigated using single-fiber push-out tests. Previous studies have shown that weak or strong bonds can be obtained by using as-received or treated fibers, respectively, and that the stress-strain behavior is improved with the treated fibers. This effect results from multiple branching of the cracks within the interphase. The model used to extract interfacial characteristics from nanoindentation and microindentation tests does not consider the presence of an interphase. However, the results highlight the significant effect of the interphase on the interfacial parameters, as well as the effect of roughness along the sliding surfaces. For the composite with treated fibers, the uncommon upward curvature of the push-out curves is related to different modes of crack propagation in the interphase. Different techniques are required to analyze the interfacial properties, such as nanoindentation and microindentation with push-out and push-back tests.     

Comparison between microwave and conventional thermal reactivations of spent activated carbon generated from vinyl acetate synthesis

Microwave and traditional thermal reactivations of activated carbon (AC) used as catalyst support in vinyl acetate synthesis have been investigated. Experiments have been carried out by using a single mode microwave device (MW) operating at 2450 MHz and a conventional electric furnace (CF) under steam and CO₂ atmosphere, respectively. The surface properties of the spent AC and the reactivated samples were characterized by means of N₂ adsorption and SEM, and compared the effects of different heating mechanisms and activating agents on the adsorption capacities and pore structures of the reactivated AC. These results indicated that the AC obtained by microwave irradiation showed higher adsorption capacities for iodine, methylene blue (MB) and acetate acid, higher BET surface areas and mesoporosity than those obtained by conventional thermal heating. The reactivated samples activated by steam had a narrower and more extensive microporosity as well as higher BET than those activated by carbon dioxide under the same heating equipment. From the results, it was concluded that microwave heating combined with steam as an activating agent could remarkably increase the reactivating efficiency compared to the traditional thermal heating.     

Combining Different Frequencies for Electrical Heating of Saturated and Unsaturated Soil Zones

In situ electrical heating of soil was studied applying different frequencies: low‐frequency energy for resistive heating and radio‐frequency energy for dielectric heating. Steep temperature gradients were observed for each heating mode under the condition of the coexistence of saturated and unsaturated soil zones. By combining the two heating modes, this undesired effect can be avoided, thus allowing efficient soil remediation especially when organic phases are accumulated at the capillary fringe. A parallel application of both frequencies was demonstrated as the most suitable method to reduce temperature gradients. By using electronic filters, both electric fields can be established by only one electrode array. This innovative concept is especially applicable for optimizing thermal remediation of light non‐aqueous phase liquid contaminations or realizing thermally‐enhanced electrokinetic removal of heavy metals.     

间隙对电热变模温高光注塑模具加热效率的影响

采用电热方式的高光注塑模具可以有效消除传统注塑成型过程中塑件的熔接痕、浮纤、银纹等缺陷。高光注塑成型技术要求对模具温度的快速动态控制,然而在电加热高光注塑成型中,电加热棒与模具安装孔之间不可避免地存在间隙,间隙层内的空气大大阻碍热量向模具传递。研究了电加热棒与模具安装孔之间的间隙对电热变模温加热效率的影响,构建了电加热高光注塑模具的三维热响应分析模型,利用有限元分析软件ANSYS进行了三维瞬态传热分析,得到了在不同间隙下的模具表面和电加热棒内部的热响应曲线,并通过大量实验证明了理论分析和模拟方法的正确性。结果表明,加热相同时间,间隙量越小,模具表面温度越高,电加热棒内部温度越低,加热效率越高,相较于间隙在0.32 mm,间隙在0.05 mm加热到60 s的模具表面温度至少高出50%,电加热棒内部的温度至少低55%。隙量对模具加热效率的影响并非成线性关系,而是间隙量在越小的区间,加热效率对间隙更加敏感,研究结果为电热变模温高光模具结构设计和电加热棒的选用提供依据。     

Correlation Between Chemical Composition and Adherence of Cr and Co Coatings Deposited by Electric Arc

This paper presents the adhesive strength of FeCr and FeCoCr coatings produced by electric arc thermal spray process on carbon steel plates. Carbon steels are not resistant to corrosion and several methods are used in surface engineering to protect them from aggressive environments such as the marine one. The main objective of this work is the evaluation of the mechanical and metallurgical properties of coatings produced by thermal spray on carbon steel. Five chemical compositions were tested in order to give a large panel of possibility. Coatings were characterized by several methods to result in a screening of performance. The physical properties of coatings were also evaluated by adhesion quantification, using pull-off test, and microhardness measurement. The assessment of microstructural morphology by X-ray diffraction (XRD) and scanning electron microscopy (SEM) was made. The open circuit potential was monitored to evaluate the corrosion tendency. SEM results showed uniformity in the deposited layer and low amount of oxide and porosity. The adhesive strength of FeCoCr alloy coatings was higher than other coating conditions. In the immersion test, all sealed conditions presented high corrosion potential. Semi-quantitative phase calculation was performed by the Rietveld method using XRD. The presence of FeCr, FeCo, and austenite phases was determined. Based on the performed characterizations, the findings suggested that the FeCrCo deposition, with an epoxy sealing, is suitable to be used as an efficient coating of carbon steel in aggressive corrosive environments.     

Conversion of plastic/cellulose waste into composites. I. Model of the interphase

This article proposes a mechanism for a significant improvement in the mechanical performance of a simulated waste fraction, composed of an immiscible low-density polyethylene (LDPE) and high-impact polystyrene (HIPS) blend (70:30 proportion), when chemithermomechanical pulp (CTMP) fibers and maleic acid anhydride grafted styrene–ethylene/butylene–styrene block copolymer (MAH-SEBS) were added. SEM micrographs of composites showed an increased contact between the continuous LDPE phase and CTMP fibers when the functionalized compatibilizer (MAH-SEBS) was used. By employing a model study using LDPE and regenerated cellulose, we investigated the interphase properties between the plastic phase and the cellulosic component. The model study utilized ESCA, FTIR, and contact angle analysis to follow the reaction between the cellulose surface and the functionalized compatibilizer. All three methods showed that MAH-SEBS was bonded to the surface of the cellulose. The single-fiber fragmentation test showed that the adhesion between cellulose fibers and the plastic matrix was significantly improved for MAH-SEBS–modified samples. The effect of enhanced adhesion on increased mechanical properties of cellulose composites is also discussed, and a prediction of composite strength given, based on interfacial adhesion promotion and fiber properties. © 1995 John Wiley & Sons, Inc.     

氟化物体系熔盐电解制钕存在问题及改进建议

介绍了氯化物熔盐体系、钕镁中间合金法、钙热真空还原氟化钕法和氟化物体系熔盐电解氧化钕法等制取金属钕的工艺,说明了它们的优缺点。提出了稳定和降低金属钕中碳含量的方法,建议提高单炉电流强度、扩大设备,扩大品种向铁舍金引申。用上挂圆桶型阳极取代石墨电解槽、石墨电极单相电弧加热取代电解槽外部硅碳棒加热装置可取得较好效果。     

Influence of Cure Conditions on the Adhesion of Rubber Compound to Brass-plated Steel Cord. Part I. Cure Temperature

The effect of the cure temperature of rubber compound on the adhesion with brass-plated steel cord was investigated in conjunction with the formation, growth and degradation of the adhesion interphase formed between the rubber compound and brass-plated steel cord. With increasing cure temperature from 130°C to 190°C, the pull-out force after cure decreased linearly. This decrease in adhesion force at higher temperature may be explained by the limitation of the mass transfer of vulcanizing agents into the adhesion interphase and/or rubber compound near the adhesion interphase, resulting in a deficiency of sulfur due to the fast cure of the rubber compound which significantly retards the diffusion of vulcanizing chemicals. Also, at a high temperature, an adhesion interphase with a ZnS-rich layer, which may act as a barrier to copper diffusion for the formation of the adhesion interphase of copper sulfide, was formed. After thermal aging of the adhesion samples, the pull-out force decreased in comparison with that of the unaged. The decrease of pull-out force after thermal aging stemmed mainly from the decline of the tensile properties after thermal aging. The adhesion property after humidity aging was completely different from that after thermal aging. With increase in the cure temperature to 160°C, the pull-out force increased. But further increase in the cure temperature caused a decline in pull-out force. This phenomenon can be explained by the degradation of the adhesion interphase. At lower cure temperatures, a severe growth of copper sulfide and a large extent of dezincification were observed in the adhesion interphase. At higher cure temperatures, a significant growth of copper sulfide in the adhesion interphase appeared. The proper formation of the adhesion interphase and good physical properties of the rubber compound at a moderate cure temperature can result in high retention of adhesion properties.