Environmental stress-corrosion cracking of fiberglass: lessons learned from failures in the chemical industry

Fiberglass reinforced plastic (FRP) composite materials are often used to construct tanks, piping, scrubbers, beams, grating, and other components for use in corrosive environments. While FRP typically offers superior and cost effective corrosion resistance relative to other construction materials, the glass fibers traditionally used to provide the structural strength of the FRP can be susceptible to attack by the corrosive environment. The structural integrity of traditional FRP components in corrosive environments is usually dependent on the integrity of a corrosion-resistant barrier, such as a resin-rich layer containing corrosion resistant glass fibers. Without adequate protection, FRP components can fail under loads well below their design by an environmental stress-corrosion cracking (ESCC) mechanism when simultaneously exposed to mechanical stress and a corrosive chemical environment. Failure of these components can result in significant releases of hazardous substances into plants and the environment. In this paper, we present two case studies where fiberglass components failed due to ESCC at small chemical manufacturing facilities. As is often typical, the small chemical manufacturing facilities relied largely on FRP component suppliers to determine materials appropriate for the specific process environment and to repair damaged in-service components. We discuss the lessons learned from these incidents and precautions companies should take when interfacing with suppliers and other parties during the specification, design, construction, and repair of FRP components in order to prevent similar failures and chemical releases from occurring in the future.     

A study of the corrosion resistance of glass fibre reinforced polymers

Specific interactions between chemical environments (hydrochloric acid, sulphuric acid and distilled water) and glass fibre cause stress corrosion cracking in the glass fibre surface. The etching of the glass fibre gives rise to an extraction process. Axial or spiral cracks can then be observed. These effects depend on the fibre diameter, the etching time and the chemical environment and cause a drop in tensile stresses. The glass fibre crumbles with increasing etching time.Strict etching procedures lead to definite extraction processes and crack structures in the glass fibres and will be discussed in connection with strength tests.In addition to investigations of individual elements, e.g. glass fibres, it is also possible that whole glass fibre reinforced composites are damaged during service under the influence of aggressive surrounding media. In such cases, circular or spiral-shaped cracks can also be observed preferentially in the glass fibre. The fibres can then no longer contribute to an increase in strength and the result is the untimely failure of the composite material.     

Effect of Seawater and Warm Environment on Glass/Epoxy and Glass/Polyurethane Composites

A study of the durability of fiber reinforced polymer (FRP) materials in seawater and warm environment is presented in this paper. The major objective of the study is to evaluate the effects of seawater and temperature on the structural properties of glass/epoxy and glass/polyurethane composite materials. These effects were studied in terms of seawater absorption, permeation of salt and contaminants, chemical and physical bonds at the interface, degradation in mechanical properties, and failure mechanisms. Test parameters included immersion time, ranging from 3 months to 1 year, and temperature including room temperature and 65°C. Seawater absorption increased with immersion time and with temperature. The matrix in both composites was efficient in protecting the fibers from corrosive elements in seawater; however moisture creates a dual mechanism of stress relaxation—swelling—mechanical adhesion, and breakdown of chemical bonds between fiber and matrix at the interface. It is observed that high temperature accelerates the degradation mechanism in the glass/polyurethane composite. No significant changes were observed in tensile strength of glass/epoxy and in the modulus of both glass/epoxy and glass/polyurethane composites. However, the tensile strength of the glass/polyurethane composite decreased by 19% after 1 year of exposure to seawater at room temperature and by 31% after 1 year of exposure at 65°C. Plasticization due to moisture absorption leads to ductile failure in the matrix, but this can be reversed in glass/polyurethane composites after extended exposure to seawater at high temperature where brittle failure of matrix and fiber were observed.     

Processing and hygrothermal effects on viscoelastic behavior of glass fiber/epoxy composites

Fiber reinforced epoxy composites are used in a wide variety of applications in the aerospace field. These materials have high specific moduli, high specific strength and their properties can be tailored to application requirements. In order to screening optimum materials behavior, the effects of external environments on the mechanical properties during usage must be clearly understood. The environmental action, such as high moisture concentration, high temperatures, corrosive fluids or ultraviolet radiation (UV), can affect the performance of advanced composites during service. These factors can limit the applications of composites by deteriorating the mechanical properties over a period of time. Properties determination is attributed to the chemical and/or physical damages caused in the polymer matrix, loss of adhesion of fiber/resin interface, and/or reduction of fiber strength and stiffness. The dynamic elastic properties are important characteristics of glass fiber reinforced composites (GRFC). They control the damping behavior of composite structures and are also an ideal tool for monitoring the development of GFRC’s mechanical properties during their processing or service. One of the most used tests is the vibration damping. In this work, the measurement consisted of recording the vibration decay of a rectangular plate excited by a controlled mechanism to identify the elastic and damping properties of the material under test. The frequency amplitude were measured by accelerometers and calculated by using a digital method. The present studies have been performed to explore relations between the dynamic mechanical properties, damping test and the influence of high moisture concentration of glass fiber reinforced composites (plain weave). The results show that the E’ decreased with the increase in the exposed time for glass fiber/epoxy composites specimens exposed at 80^∘C and 90% RH. The E’ values found were: 26.7, 26.7, 25.4, 24.7 and 24.7 GPa for 0, 15, 30, 45 and 60 days of exposure, respectively.     

Strain-rate dependence of the tensile strength of glass fibers

It is well known that the strength of glass fibers increases with increasing strain rate. Consequently, impact strength of glass fiber is competitive with that of carbon fiber. This strengthening phenomenon is well recognized for bulk glass. Strain-rate dependence of the strength for bulk glass was described by considering slow crack growth in glass. The analytical model that considered the slow crack growth of glass is proposed to predict the strength of glass fibers. The proposed model considered the stress corrosion limit and a constant crack velocity region. Calculations showed almost same results with the previous model, however, some differences were confirmed. To discuss the validity of the analysis, tensile tests of E-glass fiber bundles were conducted at various strain rates. It was observed that the fracture behaviors differ with the strain rates. Experimental results showed that the strength of E-glass fibers increased with increasing strain rate. Furthermore, we confirmed that the analytical results were in good agreement with the experimental results. The strain-rate dependence of the strength of glass fibers was successfully predicted by considering the slow crack growth in glass.     

Modeling Strength Degradation of Fiber-Reinforced Ceramic-Matrix Composites Subjected to Cyclic Loading at Elevated Temperatures in Oxidative Environments

In this paper, the strength degradation of non-oxide and oxide/oxide fiber-reinforced ceramic-matrix composites (CMCs) subjected to cyclic loading at elevated temperatures in oxidative environments has been investigated. Considering damage mechanisms of matrix cracking, interface debonding, interface wear, interface oxidation and fibers fracture, the composite residual strength model has been established by combining the micro stress field of the damaged composites, the damage models, and the fracture criterion. The relationships between the composite residual strength, fatigue peak stress, interface debonding, fibers failure and cycle number have been established. The effects of peak stress level, initial and steady-state interface shear stress, fiber Weibull modulus and fiber strength, and testing temperature on the degradation of composite strength and fibers failure have been investigated. The evolution of residual strength versus cycle number curves of non-oxide and oxide/oxide CMCs under cyclic loading at elevated temperatures in oxidative environments have been predicted.     

Tensile creep behavior of 3-D woven Si-Ti-C-O fiber/SiC-based matrix composite with glass sealant

The present work investigates the tensile creep behavior (deformation and rupture) at 1100–1300°C in air of a 3-D woven Si-Ti-C-O (Tyranno) fiber/SiC-based matrix composite with and without glass sealant. The composite contained Si-Ti-C-O fibers with an additional surface modification in order to improve interface properties. Although a significant decrease in tensile strength was observed in the unsealed composite beyond 1000°C in air (and attributed to oxidation of the fiber/matrix interface), the composite with glass sealant possessed excellent mechanical properties for short-term (<1 hr.) exposure in air. In this study, tensile creep testing was conducted at 1100–1300°C in air and the effect of glass sealant on medium- and long-term strength was investigated. In addition, chemical stability of the glass sealant was evaluated by X-ray diffraction analysis (XRD) and energy dispersive X-ray spectrometer (EDS). The creep rupture behavior of the composite with glass sealant under long-term exposure is suggested to depend on several factors including decomposition, evaporation, and crystallization of the glass sealant material, in addition to the applied stress.     

玻璃纤维/环氧树脂复合材料与镀层界面的Ni颗粒强化工艺

针对玻璃纤维/环氧树脂复合材料与镀层结合界面强度低的问题,基于复合材料/镀层间的机械互锁原理及传统塑料基体化学镀工艺,提出通过增强颗粒的桥接作用,增加含有增强颗粒的过渡层来强化镀层界面的复合材料金属化方法。对金属化后的玻璃纤维/环氧树脂复合材料试件采用拉伸试验法测量镀层的结合强度,并通过截面和断面的显微观测,分析了增强颗粒对于镀层界面的强化机制;同时获得了玻璃纤维/环氧树脂复合材料表面粗糙度和增强颗粒质量分数对含有过渡层的镀层结合强度的影响规律。结果表明:采用上述金属化方法可以显著提高镀层的界面强度,与传统的金属化工艺制备试件相比,玻璃纤维/环氧树脂复合材料在不同表面粗糙度下,镀层结合强度平均提高161%;同时,镀层的结合强度随着增强颗粒质量分数的增加,呈现先增大后减小的趋势,当增强颗粒的质量分数为50%时,镀层的结合强度达到最大。      

不同热氧环境对T800碳纤维/环氧树脂复合材料力学性能的影响EI北大核心CSCD

不同热氧环境(70,130,190℃)对碳纤维复合材料的性能有着重要的影响。分析了不同热氧环境下T800碳纤维/环氧树脂复合材料的失重特性,并对比了老化前后的表面形貌、红外光谱、动态力学性能和层间剪切性能。结果表明:在热氧老化初始阶段,质损率急速上升,老化温度越高质量损失越快;试样表面形貌随热氧温度的升高其破坏程度逐渐加剧,在190℃老化后,纤维表面树脂脱落严重,纤维与纤维之间出现裂缝空隙,无树脂填充,在此老化温度下,试样发生了不可逆化学变化;试样的玻璃化转变温度会随老化温度的升高而变大,但内耗呈现先降低后增大再降低的趋势,在70,130,190℃热氧老化后试样剪切强度分别提高6.0%,13.7%和2.1%。相关实验结果和实验现象可为后续研究新型国产T800碳纤维/环氧复合材料提供数据参考。     

Tensile-force-induced delamination of polymeric coatings in tightly jacketed double-coated optical fibers

To maintain the mechanical strength, the glass fiber of optical fibers is coated by polymeric materials during the fabrication process. However, when the external tensile-force-induced shear stress at the interface of the glass fiber and primary coating is larger than its adhesive stress, the polymeric coatings will be delaminated from the glass fiber and optical fiber will lose its mechanical strength. In this article, the tensile-force-induced delamination of polymeric coatings in tightly jacketed double-coated optical fibers is investigated. To minimize the coating's delamination, the tensile-force-induced shear stress at the interface of the glass fiber and primary coating should be reduced. The method to minimize such a shear stress is to select suitable polymeric coatings as follows. The Poisson's ratio of the primary coating and the Young's moduli of the secondary coating and jacket should be increased, but the Young's modulus of the primary coating and thickness of the secondary coating should be decreased. On the other hand, the thickness of the primary coating has an optimal value. The selection of the adhesive shear stress between the glass fiber and primary coating in the minimization of the coating's delamination is also discussed.     

Damage characterisation of glass/textile fabric polymer hybrid composites in sea water environment

The results of the experimental analysis carried out on the glass/textile fabric reinforced hybrid composites under normal condition and sea water environments have been reported. The critical stress intensity factor, interlaminar shear strength and impact toughness have been evaluated, both in interlaminar and translaminar directions. The specimen preparation and the experimentations were carried out according to the ASTM standards. Results have revealed that the damage in hybrid composite under sea water environment is entirely different. The characterising parameters have shown changes in their magnitudes with the variation in immersion time. The nature of fracture as a function of the reinforcement volume, loading and environmental conditions has been analyzed with the aid of scanning electron microscopy. The SEM analysis has shown that the fibers pull out, matrix cracking and also the nature of crack growth is different in sea water environment. The fracture in individual fiber has also been identified.     

Coupling ability of silane grafted poly(propene) at glass fibers/poly(propene) interface

Isotactic copolymers of propene and dienes were synthesized through Ziegler–Natta catalysis and functionalized with silanes through Speier catalysis, either at one end of linear chains or at the end of short ramifications. Fibers/matrix coupling can be obtained with such polymers in one hand, through chemical bonding with the glass surface OH functions and in the other hand by cocrystallization with the poly(propylene) matrix. The grafting ability of the coupling agents (CAs) onto glass surface was studied by the sessile drop technique after solvent washing. For ramificated poly(propene)s it is possible to adjust the surface free energy with the silane content. Adhesion of the poly(propene) matrix on the sized fibers was evaluated by the microtension test. The CAs characteristics required to promote adhesion between the fibers and matrix are discussed as a function of their chemical nature and structure. The more important interfacial shear stress was obtained with poly(propene-co-8.5%methyloctadiene-g-chlorodimethylsilane) showing that a compromise must be found between the silane content and polymer crystallinity.     

偶联剂处理对玻璃纤维/尼龙复合材料力学性能的影响

采用KH-550 和KH-570 两种不同的偶联剂处理玻璃纤维, 得到的玻璃纤维增强铸型(MC) 尼龙复合材料( GFRMCN) 的力学性能差别很大。经过KH-570 处理GFRMCN 力学性能降低, 而经过KH₂550 处理能有效提高其力学性能; KH₂550 质量分数与处理的玻璃纤维质量分数之间符合定量关系式, 含量为0. 2 %时, GFRMCN的弯曲强度提高了35 % , 弯曲模量提高了72 % , 拉伸强度提高了46 % , 弹性模量提高了88 % , 冲击强度提高了41 %。KH-550 偶联剂在玻璃纤维与尼龙基体之间形成良好界面结合, 达到增强效果; 而未经处理的玻璃纤维断裂时从基体中拔出, 玻纤与尼龙界面相当于缺陷, 使MC 尼龙性能下降。      

浸泡腐蚀对玻璃纤维-空心玻璃微珠/环氧树脂复合泡沫材料弯曲性能的影响

制备了不同纤维质量分数的玻璃纤维-空心玻璃微珠/环氧树脂复合泡沫材料。通过三点弯曲试验研究了纤维质量分数对复合泡沫材料力学性能的影响。将复合泡沫材料试件置于蒸馏水和海水中浸泡,研究了浸泡腐蚀对试件弯曲性能的影响,并结合扫描电镜照片分析其原因。研究表明:纤维质量分数越高,玻璃纤维-空心玻璃微珠/环氧树脂复合泡沫材料的吸湿率越大,且在蒸馏水中的吸湿率较海水中的更大。试件的弯曲强度随纤维质量分数增加而增大,当纤维质量分数为10%时达到最大,比未添加纤维的试件增强了51%,之后则随纤维质量分数增加逐渐降低。浸泡腐蚀降低了试件的弯曲性能,其中海水浸泡后的试件弯曲性能最低。玻璃纤维-空心玻璃微珠/环氧树脂复合泡沫材料弯曲强度降低的直接原因是浸泡腐蚀使得部分玻璃微珠和玻璃纤维与环氧树脂基体间的界面层受到破坏。     

Strength degradation of glass fibers at high temperatures

This article presents an experimental investigation into the effects of temperature and heating time on the tensile strength and failure mechanisms of glass fibers. The loss in strength of two glass fiber types (E-glass and Advantex^®, a boron-free version of E-glass) was investigated at temperatures up to 650 °C and heating times up to 2 h. The tensile properties were measured by fiber bundle testing, and the maximum strength was found to be temperature and time dependent. The higher softening point of the Advantex^® fibers is reflected in superior high-temperature performance. A phenomenological model is presented for calculating the residual strength of glass fiber bundles as functions of temperature and time. The strength reduction mechanism was determined by single-fiber testing. Fracture mirror sizes on the E-glass fibers were related to the fiber strength after high-temperature treatment. Based on fracture mirror measurements, it was established that (1) the mirror constant of the glass, which reflects the network structure, does not change during heat treatment and (2) the strength degradation is a result of larger surface flaws present after heat treatment.     

Improved mechanical property of foam glass composites toughened by glass fiber

The mechanically improved foam glass composite toughened by glass fiber was prepared by sintering technique, using waste sodium-calcium silicon flat glass powder as main raw materials. In this study, the preparation and properties of the samples were characterized by differential thermal analysis (DTA), field-emission scanning electron microscopy (FESEM) and mechanical property test. The specific strength of the composite was defined for the first time, and applied into the investigation of mechanical property. The results show that the specific improved bending strength of 10.45-22.26 MPa/(g cm^− 3), and the specific compressive strength of 30.45-34.34 MPa/(g cm^− 3) can be displayed when sintered at 790-815 °C with the addition of 5-25 wt.% glass fiber. Good correlations between the microstructure (in particular the fiber distribution), the high specific strength and the high modulus of elasticity of glass fibers.     

Molecular characterization of glass fiber surface coatings for thermosetting polymer matrix/glass fiber composites

Model multi-component glass fiber sizings, with formulations based upon current patent disclosures, were prepared to model the full coating packages used in commercial glass fiber manufacture. The sizings consisted of silane coupling agent, film former, and emulsifying surfactant in water and were applied to glass fibers prepared directly from molten glass. Fibers were analyzed before and after acetone extraction. The analyses of the extract solutions, with the fiber analysis, were used to determine the quantity and quality of the physically and chemically adsorbed layers. It was found that all three species remain on the fiber after extraction and that both coupling agent and surfactant concentrations in the coatings are higher than in the applied sizing. The impact of these species on the polymer composite/glass fiber interphase is discussed.     

混杂短纤维增强尼龙1010的热水老化

本文研究了经80℃热水老化2600小时的短碳纤维和玻璃纤维混杂增强尼龙1010复合材料的性能与结构变化,并对复合材料中的纤维长度分布进行了统计.研究表明,纤维长度减小主要发生在挤出造粒阶段.碳纤维与玻璃纤维的长度分布差异不大.混杂增强的尼龙1010复合材料在许多力学性能和摩擦磨损行为上表现出正的“混杂效应”.热水老化后仍然存在这种情况.热水老化使尼龙1010的分子量降解,降解率随玻璃纤维含量增加而增大.老化使尼龙1010晶粒增大,但并无形成球晶.热水老化后复合材料的力学性能保留率随玻璃纤维含量增加而下降.热水老化使玻璃纤维与尼龙1010之间的界面粘结受到严重破坏,界面剪切强度严重下降.碳纤维与尼龙的界面粘结所受的破坏轻一些.     

Comparison of chemical vapor deposition and chemical grafting for improving the mechanical properties of carbon fiber/epoxy composites with multi-wall carbon nanotubes

By engineering the fiber/matrix interface, the properties of the composite can be changed significantly. In this work, we increased the effective surface area of the fiber/matrix interface, to facilitate additional stress transfer between fibers and matrix, by grafting carbon nanotubes on to carbon fibers (in the form of carbon fabric) by two different methods: (1) chemical vapor deposition (CVD) method and (2) a purely chemical method. With the CVD process, carbon nanotubes (CNT) were directly grown on carbon fiber substrate using chemical vapors. For the chemical method, CNT with carboxyl groups were grafted on functionalized carbon fiber via a chemical reaction. The morphology of CNT/carbon fibers was examined by scanning electron microscope (SEM) which revealed uniform coverage of carbon fibers with CNT in both of CVD method and chemical grafting method. CNT-grafted woven carbon fibers were used to make carbon/epoxy composites, and their mechanical properties were measured using three-point bending and tension tests which showed that those with CNT-grafted carbon fiber reinforcements using the CVD process has 11 % higher tensile strength compared to those containing carbon fibers modified with the chemical method. Also, composites with CNT-grafted carbon fibers with chemical method showed 20 % higher tensile strength compared to composites with unmodified carbon fibers. The results of tensile test revealed that both CVD and chemical grafting could significantly improve the mechanical properties of the carbon fiber composites.     

Evaluation of mechanical properties of banana and sisal fiber reinforced epoxy composites: Influence of glass fiber hybridization

In this work, the effect of glass fiber hybridization with the randomly oriented natural fibers has been analyzed. The banana (B), sisal (S) fibers were chopped and woven E-glass (G) synthetic fibers were reinforced with epoxy matrix. Nine different kinds of laminates were prepared in the following stacking sequence of B, S, BS, G/B/G, G/S/G, G/BS/G, G/B/G/B/G, G/S/G/S/G and G/BS/G/BS/G. Mechanical properties like tensile strength, flexural strength and impact strength were evaluated and compared. Interfacial analysis was also carried out with the help of Scanning Electron Microscope (SEM) to study the micro structural behavior of the tested specimen. It was observed that the addition of two and three layer of glass fiber can improve the tensile strength by a factor of 2.34 and 4.13 respectively. The flexural properties were enhanced on banana–sisal fiber with two layers of glass fibers rather than three layers and the laminate with sisal and three glass ply offers better impact strength.