Biodegradable biocomposites from poly(butylene adipate‐co‐terephthalate) and miscanthus: Preparation,compatibilization, and performance evaluation

Miscanthus fibers reinforced biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) matrix‐based biocomposites were produced by melt processing. The performances of the produced PBAT/miscanthus composites were evaluated by means of mechanical, thermal, and morphological analysis. Compared to neat PBAT, the flexural strength, flexural modulus, storage modulus, and tensile modulus were increased after the addition of miscanthus fibers into the PBAT matrix. These improvements were attributed to the strong reinforcing effect of miscanthus fibers. The polarity difference between the PBAT matrix and the miscanthus fibers leads to weak interaction between the phases in the resulting composites. This weak interaction was evidenced in the impact strength and tensile strength of the uncompatibilized PBAT composites. Therefore, maleic anhydride (MAH)‐grafted PBAT was prepared as compatibilizer by melt free radical grafting reaction. The MAH grafting on the PBAT was confirmed by Fourier transform infrared spectroscopy. The interfacial bonding between the miscanthus fibers and PBAT was improved with the addition of 5 wt % of MAH‐grafted PBAT (MAH‐g‐PBAT) compatibilizer. The improved interaction between the PBAT and the miscanthus fiber was corroborated with mechanical and morphological properties. The compatibilized PBAT composite with 40 wt % miscanthus fibers exhibited an average heat deflection temperature of 81 °C, notched Izod impact strength of 184 J/m, tensile strength of 19.4 MPa, and flexural strength of 22 MPa. From the scanning electron microscopy analysis, better interaction between the components can be observed in the compatibilized composites, which contribute to enhanced mechanical properties. Overall, the addition of miscanthus fibers into a PBAT matrix showed a significant benefit in terms of economic competitiveness and functional performances. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45448.     

体育器材用CFRPA6复合材料的制备及其性能

采用碳纤维(CF)改性聚酰胺(PA)6,从而获得PA 6/CF复合材料。结果表明:CF被浓硝酸氧化后,表面会引入碳氮、碳氧等极性基团,增加了PA 6与CF的界面反应活性;CF经浓硝酸处理后表面有许多沟槽出现,增大的表面积对PA 6与CF间机械锁合有利;随着浓硝酸处理CF时间的延长,复合材料的悬臂梁缺口冲击强度略有提高,拉伸强度提高较大;CF被过度氧化时,复合材料的缺口冲击强度、拉伸强度均降低;经浓硝酸氧化处理后,增强了CF界面黏结效果,CF被PA 6紧密包覆,断裂时两者有黏结现象发生;未经浓硝酸处理的样条在纤维拔出后会留下大量空洞,经浓硝酸处理后CF表面极性基团增加,提高了CF与基体树脂的黏结强度。     

Covalent functionalization of carbon fiber with poly(acrylamide) by reversible addition–fragmentation chain transfer polymerization for improving carbon fiber/epoxy interface

A novel method was developed for grafting poly(acrylamide) (PAAM) on to the carbon fiber (CF) surface via reversible addition–fragmentation chain transfer (RAFT) polymerization to improve the interaction between carbon fibers and epoxy matrix in the composites system. The carbon fibers were first treated with nitric acid and γ‐methacryloxypropyltrimethoxy silane (KH570). Then, the PAAM was grafting onto the carbon fiber surface via RAFT polymerization. The resulted carbon fibers functionalized with PAAM (CF‐PAAM) were characterized by FTIR, XPS, and TGA, and the results revealed that CF‐PAAM were synthesized successfully. The introduction of PAAM chains could make the fiber surface rougher and introduce a large numbers of –NH₂ groups, which can improve the interfacial adhesion in the composites. The microbond test results showed that the interfacial shear strength (IFSS) of the composites reinforced by CF‐PAAM has been enhanced about 107%. POLYM. COMPOS., 38:27–31, 2017. © 2015 Society of Plastics Engineers     

Grafting starch nanocrystals onto the surface of sisal fibers and consequent improvement of interfacial adhesion in sisal reinforced starch composite

Starch nanocrystals (SNCs) were obtained by the hydrolysis of waxy starch and used to improve the interfacial adhesion of a composite of sisal fibers and starch. Sisal fibers were first treated with acrylic acid (AA), and the modified fibers were then reacted with SNCs to form ester groups. The grafted fibers were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The FTIR and XPS results showed that the SNCs were successfully grafted onto the surface of SF-AA, and an ester linkage was formed during the reaction of AA with the SNCs. The SEM analysis showed that the SNCs were distributed over the fiber surface. Tensile tests and pull-out tests were also performed utilizing a two-parameter Weibull distribution analysis to study the effect of the grafted SNCs on the mechanical and interfacial properties. Compared to the untreated fibers, the interfacial shear strength of the grafted SNCs fibers increased by 79.3%. Therefore, the structural similarity between starch and the SNCs contributed towards their compatibility and improved interfacial properties, with the introduction of SNCs being used as an alternative material for fiber surface modification. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47202.     

The effects of surface treatments of fibers on the interfacial properties in single-fiber composites

The interfacial properties between fibers and the matrix contribute to the overall properties in high performance composites. Plasma treatments (Ar, O₂, CF₄/O₂, N₂/H₂) have been performed on carbon fibers to improve the fiber-matrix interaction. The treatment efficiency was checked by the single-fiber technique, while the surface chemistry and morphology were characterized by X-ray photoelectron spectroscopy (XPS), static secondary ion mass spectroscopy (SSIMS), and scanning electron microscopy (SEM). The O₂- and N₂/H₂-plasma treatments proved most effective both for introducing oxygen-containing functionalities at the fiber surface and for improving the interfacial shear strength of carbon fiber/epoxy composites. A relationship between the oxygen concentration at the fiber surface and the interfacial shear strength is demonstrated.     

New Coupling Agents as Adhesion Promoters at the Poly(Phenylene Sulfide)/Glass Interface-Studies with Micro and Macro Composites

Carboxy-functionalized poly(phenylene sulfide) having different molar masses and amount of the functional group were prepared in order to be used with γ-aminopropyltriethoxysilane as surface treatment of E-glass fibers. These grafted polymer chains act as connecting chains in order to improve the interfacial shear strength of the PPS-glass interface. According to their chemical nature, which is the same as the PPS matrix, and their ability to crystallize in the same crystalline form as the pure PPS, a continuum of bonding from the fiber surface to the bulk matrix is achieved. A chemical linkage is established at the glass surface by means of hydrolyzed ethoxysilane groups of the γ-APS and from the formation of amide units resulting from the reaction of amine functions of the silane and the carboxylic groups of the modified PPS. A “physical” linkage is expected between the grafted PPS and the PPS chains by means of entanglements and co-crystallization. A large improvement of the interfacial shear strength measured from the microdroplet test is observed when a modified-PPS having a medium molar mass and a low amount of functional groups is used in comparison with untreated or silane-treated glass fibers. This improvement is also observed for short glass fibers/PPS composite materials. In fact, a large improvement is obtained on mechanical properties such as the tensile, flexural, and impact strengths.     

Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments

Interests in improving poor interfacial adhesion in carbon fiber‐reinforced polymer (CFRP) composites has always been a hotspot. In this work, four physicochemical surface treatments for enhancing fiber/matrix adhesion are conducted on carbon fibers (CFs) including acid oxidation, sizing coating, silane coupling, and graphene oxide (GO) deposition. The surface characteristics of CFs are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, interfacial shear strength, and interlaminar shear strength. The results showed that GO deposition can remarkably promote fiber/matrix bonding due to improved surface reactivity and irregularity. In comparison, epoxy sizing and acid oxidation afford enhancement of IFSS owing to effective molecular chemical contact and interlocking forces between the fiber and the matrix. Besides, limited covalent bonds between silane coupling and epoxy matrix cannot make up for the negative effects of excessive smoothness of modified CFs, endowing them inferior mechanical properties. Based on these results, three micro‐strengthening mechanisms are proposed to broadly categorize the interphase micro‐configuration of CFRP composite, namely, “Etching” “Coating”, and “Grafting” modifications, demonstrating that proper treatments should be chosen for combining optimum interfacial properties in CFRP composites. POLYM. ENG. SCI., 59:625–632, 2019. © 2018 Society of Plastics Engineers     

Enhancement of surface adhesion between thermoplastic resin and carbon fiber using polymer colloids

To enhance the interfacial adhesion between carbon fiber and thermoplastic resin, poly(methyl methacrylate) (PMMA) particles were adsorbed on the carbon fiber. It was found that positively charged PMMA particles were readily adsorbed on the carbon fiber, and the interfacial shear strength between the modified carbon fiber and the resin was enhanced. In addition, the interaction between the carbon fiber coated with particles to the PMMA resin would be improved, and the surface adhesion between them was strengthened.     

Improving delamination resistance of carbon fiber reinforced polymeric composite by interface engineering using carbonaceous nanofillers through electrophoretic deposition: An assessment at different in-service temperatures

In this article, modification of carbon fiber surface by carbon based nanofillers (multi-walled carbon nanotubes [CNT], carbon nanofibers, and multi-layered graphene) has been achieved by electrophoretic deposition technique to improve its interfacial bonding with epoxy matrix, with a target to improve the mechanical performance of carbon fiber reinforced polymer composites. Flexural and short beam shear properties of the composites were studied at extreme temperature conditions; in-situ cryo, room and elevated temperature (−196, 30, and 120°C respectively). Laminate reinforced with CNT grafted carbon fibers exhibited highest delamination resistance with maximum improvement in flexural strength as well as in inter-laminar shear strength (ILSS) among all the carbon fiber reinforced epoxy (CE) composites at all in-situ temperatures. CNT modified CE composite showed increment of 9% in flexural strength and 17.43% in ILSS when compared to that of unmodified CE composite at room temperature (30°C). Thermomechanical properties were investigated using dynamic mechanical analysis. Fractography was also carried out to study different modes of failure of the composites.     

New Coupling Agents as Adhesion Promoters at the Poly(Phenylene Sulfide)/Glass Interface-Studies with Micro and Macro Composites

Carboxy-functionalized poly(phenylene sulfide) having different molar masses and amount of the functional group were prepared in order to be used with γ-aminopropyltriethoxysilane as surface treatment of E-glass fibers. These grafted polymer chains act as connecting chains in order to improve the interfacial shear strength of the PPS-glass interface. According to their chemical nature, which is the same as the PPS matrix, and their ability to crystallize in the same crystalline form as the pure PPS, a continuum of bonding from the fiber surface to the bulk matrix is achieved. A chemical linkage is established at the glass surface by means of hydrolyzed ethoxysilane groups of the γ-APS and from the formation of amide units resulting from the reaction of amine functions of the silane and the carboxylic groups of the modified PPS. A “physical” linkage is expected between the grafted PPS and the PPS chains by means of entanglements and co-crystallization. A large improvement of the interfacial shear strength measured from the microdroplet test is observed when a modified-PPS having a medium molar mass and a low amount of functional groups is used in comparison with untreated or silane-treated glass fibers. This improvement is also observed for short glass fibers/PPS composite materials. In fact, a large improvement is obtained on mechanical properties such as the tensile, flexural, and impact strengths.     

The Temperature Dependence of Interfacial Shear Strength for Various Polymeric Matrices Reinforced with Carbon Fibers

The influence of temperature on the interfacial shear strength between epoxy thermoset matrices and surface treated, carbon AS4 as well as with surface treated and sized AS4-C carbon fibers was investigated. The thermoset matrices all consisted of DGEBA epoxy resin cured with different amine curing agents resulting in matrices with a range of behavior from brittle, elastic to ductile, plastic. For all systems, the results indicate that the interfacial shear strength (ISS) decreases with increasing temperature and as the T_g of the matrix is approached, a large corresponding decrease in the interfacial shear strength is seen. Moreover, the AS4-C (epoxy sized) system revealed a distinct decrease in interfacial shear strength at temperatures lower than the bulk matrix T_g indicating the formation of an interphase layer of composition different from the bulk matrix. Linear superposition methods were used to generate a master curve for the different matrix materials reinforced with the AS4 fibers. These results allow the prediction of ISS at any temperature.     

Temperature Dependence of Interfacial Shear Strength in SiC-Fiber-Reinforced Reaction-Bonded Silicon Nitride

The interfacial shear strength of AVCO SCS-6 SiC-fiber-reinforced reaction-bonded Si₃N₄ (RBSN) composites was studied as a function of temperature. Fiber "push-through" experiments were conducted with a diamond indenter and a high-temperature microhardness tester. The interfacial shear strength was variable and depended mostly on interfacial bonding at low temperatures (5 to 18 MPa at room temperature) and frictional forces at high temperatures (12 to 32 MPa at 1300°C). The frictional component is attributed to the surface roughness of the fibers. The interfacial shear strength increased with temperature, because of the relief of residual stresses arising from the thermal expansion mismatch between fiber and matrix. Because of the composite nature of these fibers, a number of interfaces were tested in each experiment. The interface which debonded and slid was not always the same. Interfacial fracture took place either between the two outermost carbon layers of the SCS-6 fibers, or between the SiC core and the innermost of the two outer carbon layers. The outermost carbon layer of the fiber always stayed bonded to the Si₃N₄ matrix.     

表面处理对玻纤/碳纤增强橡胶基密封复合材料性能的影响

采用压延成张工艺制备碳纤维和玻璃纤维混杂增强非石棉橡胶基密封复合材料(NAFC),以横向抗拉强度作为表征混杂增强橡胶基密封材料中纤维与橡胶界面粘结性能的指标.通过扫描电镜(SEM)对材料横向拉伸试样断口进行形貌分析,及对材料的耐油、耐酸、耐碱性能进行测试,探讨了不同表面处理工艺对纤维与基体界面粘结效果的影响.研究结果表明,对玻璃纤维采用偶联剂KH-550浸渍后涂覆环氧树脂涂层,对碳纤维在空气氧化后涂覆环氧树脂涂层,可有效增强纤维、基体的界面粘结,所制得的混杂纤维增强复合材料具有较好的机械性能和耐介质性能.     

The Effect of Surface Treatment on the Strength and Adhesion Characteristics of Phoenix dactylifera-L(Date Palm) Fibers

ABSTRACT

There is a growing interest in the use of natural/bio-fibers as reinforcing components for thermoplastics and thermosets. However, they do suffer from a few limitations, such as lower compatibility with relatively hydrophobic polymer matrixes. Thus, improvement of the interface and interphase interactions in natural fiber–polyester composites is essential. In this research date palm (Phoenix dactylifera-L) fibers were modified by surface treatment using chemical method in order to improve their adhesion to polyester matrixes. Alkaline treatment, as an example of dissolution and treatment with silane coupling agents were performed. Furthermore, a combination treatment of alkaline and silane coupling agents was also carried out. Fiber modifications were monitored by Scanning Electron Microscopy (SEM). In addition to that, the improvement of adhesion and strength between date palm–modified fibers and polyester matrix was investigated by single filament pull-out test as well as tensile tests. It was found, from interfacial shear strength values, that substantial improvements in fiber-matrix compatibility have been achieved. According to single filament pull-out test results, interfacial shear strength increased for all treated fibers as compared to non-treated fibers. Particularly, combination of alkaline and silane coupling agents resulted in substantial adhesion improvement to the polyester matrix in comparison to the untreated fibers and fibers treated by alkaline and silane methods only.     

Interfacial adhesion of plasma‐treated carbon fiber/poly(phthalazinone ether sulfone ketone) composite

Interfacial adhesion between fiber and matrix has a strong influence on composite mechanical performance. To exploit the reinforcement potential of the fibers in advance composite, it is necessary to reach a deeper understanding on the relation between fiber surface treatment and interfacial adhesion. In this study, air plasma was applied to modify carbon fiber (CF) surface, and the capability of plasma grafting for improving the interfacial adhesion in CF/thermoplastic composite was discussed and also the mechanism for composite interfacial adhesion was analyzed. Results indicated that air plasma treatment was capable of increasing surface roughness as well as introducing surface polar groups onto CF; both chemical bonding and mechanical interaction were efficient in enhancements of interlaminate shear strength of CF/PPESK composite, while mechanical interaction has a dominant effect on composite interfacial adhesion than chemical bonding interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

左旋多巴胺处理对芳纶表面结构与性能的影响

利用L-3,4-二羟基苯丙氨酸(L-DOPA)的氧化自聚合,在杂环芳纶表面修饰聚L-3,4-二羟基苯丙氨酸(PDOPA)活性涂层来提高芳纶的表面活性及耐紫外辐照性能。结果表明:改性后芳纶表面粗糙度显著提高,同时,PDOPA涂层上大量的羧基、羟基等活性单元均有利于增强与环氧树脂的机械锁合力,改性后芳纶/环氧树脂复合材料的界面剪切强度提高了32.0%。此外,上述改性过程对杂环芳纶本身力学性能影响较小,纤维的拉伸强度保持率可以达到100%,基本实现了无损改性。同时,由于PDOPA的保护作用,改性后芳纶的耐紫外辐射性能显著提高;经过168 h紫外线辐照处理后,其拉伸强度保持率可达到92.5%,显著提升了杂环芳纶的耐紫外线辐照特性。     

强氧化介质中碳纤维拉伸性能与微观结构的变化

以实验室自制碳纤维为原料,研究了碳纤维在浓HNO3及不同浓度的浓H2SO4/浓HNO3强氧化介质中的性能与结构变化。结果表明,浓HNO3单独氧化时,碳纤维强度较未处理前有所增加,模量变化不大;在浓H2SO4和浓HNO3的共同氧化作用下,碳纤维强度和模量均随着处理时间的延长不断下降,且随着浓H2SO4体积分数的增加下降加快。XRD分析结果表明,浓HNO3的氧化作用主要影响平行于纤维轴向的微观尺寸,而浓H2SO4的氧化主要在纤维的片层堆叠方向起作用。     

超高相对分子质量聚乙烯纤维的表面改性研究

选择乙烯-醋酸乙烯酯共聚物作为表面改性剂,将其溶解在二甲苯中制成复合萃取液,对超高相对分子质量聚乙烯(UHMWPE)冻胶纤维进行萃取,经干燥和超倍拉伸制得表面改性UHMWPE纤维。对改性前后纤维的表面化学结构、结晶性能、表面粘接性能和力学性能进行了比较。结果表明:加入表面改性剂后,纤维表面引入了极性基团,结晶形态不变,纤维与树脂的抗界面剪切强度大大增加,纤维的力学性能变化不大。     

阳极氧化及上浆过程中PAN基碳纤维表面形态结构的演变

采用阳极氧化法对PAN基碳纤维的表面进行改性,然后使用上浆剂对纤维表面进行上浆处理。使用扫描电镜、原子力显微镜、X射线光电子能谱仪等分析了处理过程中碳纤维表面形态结构的变化,研究了阳极氧化及上浆处理对碳纤维的拉伸强度及其与环氧树脂间界面剪切强度(IFSS)的影响。结果表明:阳极氧化处理后,碳纤维表面平均粗糙度从48.0 nm增大到90.5 nm,而上浆后碳纤维平均粗糙度下降到32.3nm;经阳极氧化处理后,碳纤维表面碳(C)元素含量降低,氧(O)、氮(N)元素含量增加,—OH基团含量由14.43%增加到39.32%,而上浆后纤维表面—OH基团含量变化不大;在阳极氧化过程中随着氧化程度的提高,碳纤维的拉伸强度逐渐降低,但其IFSS逐渐升高;上浆对碳纤维拉伸强度影响不大,但上浆剂中较高的活性基团使得其IFSS进一步提高。     

电化学氧化处理对碳纤维及EP复合材料性能的影响

利用电化学氧化法对碳纤维（CF）进行表面改性处理,并将改性CF用于改性环氧树脂（EP）,研究了CF处理前后纤维复丝拉伸强度和EP／CF复合材料的力学性能。结果表明,氧化处理改善了CF与基体的粘结性;经电化学氧化处理后CF的表面羟基含量提高39．96％,羧基／酯基含量提高141．06％,活性碳原子数增加34．28％;随着氧化电流密度的增加,CF复丝的拉伸强度和复合材料的层间剪切强度均呈现先增大后减小的变化趋势,当电流密度为0．2A／m^2时,复合材料的层间剪切强度提高31．70％。