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Exploring the effect of block copolymer architecture and concentration on the microstructure, electrical conductivity and rheological properties of PP/PS blend nanocomposites 探讨嵌段共聚物的结构和浓度对PP/PS共混纳米复合材料微观结构、电导率和流变性能的影响
Pub Date : 2022-04-12 DOI: 10.1186/s42252-022-00031-x
Lilian Azubuike, Uttandaraman Sundararaj

The interface between polymer matrices and nanofillers is critical for efficient interaction to achieve the desired final properties. In this work, block copolymers were utilized to control the interface and achieve optimum interfacial interaction. Specifically, we studied the compatibilizing effects of styrene-ethylene/butadiene-styrene (SEBS) and styrene-ethylene/propylene (SEP) block copolymers on the morphology, conductivity, and rheological properties of polypropylene-polystyrene (PP/PS) immiscible blend with 2 vol% multiwall carbon nanotube (MWCNT) at different blend compositions of PP/PS 80:20, 50:50 and 20:80.

MWCNTs induced co-continuity in PP/PS blends and did not obstruct with the copolymer migration to the interface. Copolymers at the interface led to blend morphology refinement. Adding block copolymers at a relatively low concentration of 1 vol% to compatibilize the PP/PS 80:20 blend substantially increased the electrical conductivity from 5.15*10−7S/cm for the uncompatibilized blend to 1.07*10−2S/cm for the system with SEP and 1.51*10−3S/m for the SEBS system. These values for the compatibilized blends are about 4 orders of magnitude higher due to the interconnection of the droplet domains. For the PP/PS 50:50 blend, the SEBS copolymer resulted in a huge increase in conductivity at above 3 vol% concentration (conductivity increased to 3.49*10−3S/cm from 5.16*10−7S/cm). Both the conductivity and the storage modulus increased as the SEBS copolymer content was increased. For the PP/PS 20:80 blend, we observed an initial decrease in conductivity at lower copolymer concentrations (1–3 vol%) and then an increase in conductivity to values higher than the uncompatibilized system, but only at a higher copolymer concentration of 10 vol%. The triblock copolymer (SEBS), which had 60 wt% PS content, shows a more significant increase in rheological properties compared to the diblock copolymer (SEP). The morphology shows that the interaction between MWCNT and PS is stronger than the interaction between MWCNT and PP, hence there is selective localization of the nanofiller in the PS phase as predicted by Young’s equation and by molecular simulation.

聚合物基体和纳米填料之间的界面对于有效相互作用以获得所需的最终性能至关重要。在这项工作中,利用嵌段共聚物来控制界面并实现最佳的界面相互作用。具体而言,我们研究了苯乙烯-乙烯/丁二烯-苯乙烯(SEBS)和苯乙烯-乙烯/丙烯(SEP)嵌段共聚物在PP/PS 80:20、50:50和20:80的不同共混比例下对聚丙烯-聚苯乙烯(PP/PS)非混相共混体系与2 vol%多壁碳纳米管(MWCNT)的形态、电导率和流变性能的增容作用。MWCNTs诱导PP/PS共混物的共连续性,并且不会阻碍共聚物向界面的迁移。共聚物在界面处导致共混形貌的细化。在PP/PS 80:20共混体系中加入较低浓度(1 vol%)的嵌段共聚物,使共混体系的电导率从未共混体系的5.15*10−7S/cm大幅提高到含SEP体系的1.07*10−2S/cm和含SEBS体系的1.51*10−3S/m。由于液滴域的相互连接,共混物的这些值大约高出4个数量级。对于PP/PS 50:50共混物,SEBS共聚物在3 vol%浓度以上时,电导率大幅提高(电导率从5.16*10 - 7S/cm增加到3.49*10 - 3S/cm)。随着SEBS共聚物含量的增加,电导率和存储模量均增加。对于PP/PS 20:80共混物,我们观察到共聚物浓度较低(1-3 vol%)时,电导率开始下降,然后电导率增加到高于未相容体系的值,但只有在共聚物浓度较高(10 vol%)时才会增加。三嵌段共聚物(SEBS)的PS含量为60%,与二嵌段共聚物(SEP)相比,其流变性能有更显著的提高。形貌分析表明,MWCNT与PS的相互作用强于MWCNT与PP的相互作用,因此,正如杨氏方程和分子模拟预测的那样,纳米填料在PS相中存在选择性定位。
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引用次数: 2
Carbon composites from iron-chelating pyridine nitrogen-rich coordinated nanosheets for oxygen reduction 氧还原用铁螯合吡啶富氮配位纳米片碳复合材料
Pub Date : 2022-03-14 DOI: 10.1186/s42252-022-00030-y
Bing Zhang, Hele Guo, Longsheng Zhang, Xu Zhang, Chao Zhang, Tianxi Liu

The exploration of a noble-metal-free and nitrogen-doped carbon (M–N/C) composite electrocatalyst for the oxygen reduction reaction (ORR) remains a great challenge. The activities of the M–N/C composite electrocatalysts are mainly affected by the metal active sites, pyridinic nitrogen, and graphitic nitrogen. In the present work, the iron-coordinated self-assembly is proposed for the preparation of iron-chelating pyridine nitrogen-rich coordinated nanosheet (IPNCN) composites as electrocatalysts. Due to the highly conjugated structure of the IPNCN precursor, the pyridine nitrogen elements at both ends of the tetrapyrido [3,2-a:2',3'-c:3'',2''-h:2''',3'''-j] phenazine (TP) provide the multiple ligands, and the coordination interactions between the irons and the pyridine nitrogen further improve the thermodynamic stability, where the metal active sites and nitrogen elements are uniformly distributed in the whole structure. The resultant IPNCN composites exhibit excellent ORR performance with an onset potential of 0.93 V and a half potential of 0.84 V. Furthermore, the IPNCN composite electrocatalysts show the higher methanol resistance and electrochemical durability than the commercial Pt/C catalysts. It could be convinced that the as-designed IPNCN composite catalysts would be a promising alternative to the noble metal Pt-based catalysts in the practical applications.

探索无贵金属和掺氮碳(M-N /C)复合电催化剂用于氧还原反应(ORR)仍然是一个巨大的挑战。M-N /C复合电催化剂的活性主要受金属活性位、吡啶氮和石墨氮的影响。本文提出用铁配位自组装法制备铁螯合吡啶富氮配位纳米片复合材料作为电催化剂。由于IPNCN前驱体的高共轭结构,四吡啶[3,2-a:2',3'-c:3'',2' -h:2'',3'' -j]吩嗪(TP)两端的吡啶氮元素提供了多重配体,铁与吡啶氮之间的配位相互作用进一步提高了热力学稳定性,金属活性位点和氮元素均匀分布在整个结构中。所得的IPNCN复合材料表现出优异的ORR性能,起始电位为0.93 V,半电位为0.84 V。此外,IPNCN复合电催化剂表现出比商用Pt/C催化剂更高的耐甲醇性能和电化学耐久性。可以相信,所设计的IPNCN复合催化剂在实际应用中有望取代贵金属pt基催化剂。
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引用次数: 0
Superhydrophobic micro-nanofibers from PHBV-SiO2 biopolymer composites produced by electrospinning 静电纺丝法制备PHBV-SiO2生物聚合物复合材料超疏水微纳米纤维
Pub Date : 2022-02-24 DOI: 10.1186/s42252-022-00029-5
Saad Rabbani, Reza Jafari, Gelareh Momen

Electrospinning is a relatively simple technique for producing continuous fibers of various sizes and morphologies. In this study, an intrinsically hydrophilic poly(3-hydroxybutarate-co-3-hydroxyvalerate) (PHBV) biopolymer strain was electrospun from a solution under optimal processing conditions to produce bilayers of beadless micro-fibers and beaded nano-fibers. The fibrous mats produced from the pure PHBV solution exhibited hydrophilicity with complete wetting. Incorporation of polydimethylsiloxane (PDMS) treated silica into the electrospinning solutions resulted in a non-wetting state with increased fiber roughness and enhanced porosity; however, the fiber mats displayed high water droplet-adhesion. The SiO2–incorporated fibrous mats were then treated with stearic acid at an activation temperature of 80 °C. This treatment caused fiber surface plasticization, creating a tertiary hierarchical roughness owing to the interaction of PHBV chains with the polar carboxyl groups of the stearic acid. Scanning electron microscopy was used to assess the influence of the electrospinning process parameters and the incorporation of nanoparticles on surface morphology of the fibers; energy dispersive X-ray spectroscopy confirmed the presence of SiO2 nanoparticles. Fourier transform infrared spectroscopy was performed to study the incorporation of SiO2 and the interaction of stearic acid with PHBV at various concentrations. The chemical interaction between stearic acid and PHBV was confirmed, while SiO2 nanoparticles were successfully incorporated into the PHBV fibers at concentrations up to 4.5% by weight. The incorporation of nanoparticles and plasticization altered the thermal properties of PHBV and a decrease in crystalline fraction was observed. The stearic acid modified bilayers produced from the micro-nano-fibrous composites showed very low water droplet sticking, a roll off angle of approximately 4° and a high static contact angle of approximately 155° were achieved.

Graphical Abstract

静电纺丝是一种生产各种尺寸和形态的连续纤维的相对简单的技术。在本研究中,在最佳工艺条件下,从溶液中静电纺丝制备了一种具有亲水性的聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)生物聚合物菌株,制备了双层无头微纤维和珠状纳米纤维。由纯PHBV溶液制备的纤维席具有完全润湿的亲水性。将聚二甲基硅氧烷(PDMS)处理过的二氧化硅掺入静电纺丝溶液中,使纤维处于非润湿状态,纤维粗糙度增加,孔隙率提高;然而,纤维垫表现出较高的水滴粘附性。然后用硬脂酸在80℃的活化温度下处理二氧化硅纤维垫。这种处理导致纤维表面塑化,由于PHBV链与硬脂酸的极性羧基相互作用而产生三级层次粗糙度。采用扫描电镜观察了静电纺丝工艺参数和纳米颗粒掺入对纤维表面形貌的影响;能量色散x射线光谱证实了SiO2纳米颗粒的存在。傅里叶变换红外光谱研究了SiO2的掺入以及硬脂酸与PHBV在不同浓度下的相互作用。硬脂酸与PHBV之间的化学相互作用得到了证实,而二氧化硅纳米颗粒以4.5%的重量浓度成功地掺入到PHBV纤维中。纳米颗粒的掺入和塑化改变了PHBV的热性能,晶体分数降低。由硬脂酸修饰的微纳纤维复合材料制备的双层膜具有极低的水滴粘附,滚脱角约为4°,静态接触角约为155°。图形抽象
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引用次数: 1
Emerging, hybrid & smart composites 新兴复合材料、混合材料和智能复合材料
Pub Date : 2021-12-31 DOI: 10.1186/s42252-021-00028-y
Christophe Binetruy, Véronique Michaud
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引用次数: 0
Sustainable polymer composites: functionality and applications 可持续聚合物复合材料:功能与应用
Pub Date : 2021-10-21 DOI: 10.1186/s42252-021-00027-z
Fengwei Xie
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引用次数: 0
Ionic liquid-plasticised composites of chitosan and hybrid 1D and 2D nanofillers 壳聚糖与 1D 和 2D 混合纳米填料的离子液体塑化复合材料
Pub Date : 2021-09-26 DOI: 10.1186/s42252-021-00026-0
Pei Chen, Fengwei Xie, Fengzai Tang, Tony McNally

The focus of this research was to study the effect of combining nanofillers with different geometry and surface chemistry on the structure and properties of biopolymers as an alternative to traditional plastics. How the inclusion of 2D graphene oxide (GO) or reduced GO (rGO) combined with 1D sepiolite (SPT) or cellulose nanocrystals (CNCs) affect the structure and properties of chitosan and chitosan/carboxymethyl cellulose (CMC) materials was investigated. A 3D interconnected microstructure formed, composed of GO and SPT due to the strong interactions between these hydrophilic nanofillers. The chitosan/CMC/GO/SPT composite had the highest tensile strength (77.5 ± 1.2 MPa) and Young’s modulus (1925.9 ± 120.7 MPa). For the un-plasticised matrices, hydrophobic rGO nanosheets generally hindered the interaction of SPT or CNCs with the polysaccharides (chitosan and CMC) and consequently, composite properties were mainly determined by the rGO. However, for the chitosan matrix plasticised by 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), rGO + CNCs or rGO + SPT disrupted polymer chain interactions more effectively than the nanofillers when added alone and resulted in the chitosan being more plasticised, as shown by increased chain mobility, ductility, and surface hydrophilicity. For the [C2mim][OAc]-plasticised chitosan/CMC matrix, the advantages of including hybrid fillers, rGO + CNCs or rGO + SPT, were also obtained, resulting in higher thermal stability and surface hydrophobicity.

Graphical Abstract

本研究的重点是研究不同几何形状和表面化学性质的纳米填料组合对生物聚合物结构和性能的影响,以替代传统塑料。研究了二维氧化石墨烯(GO)或还原型 GO(rGO)与一维海泡石(SPT)或纤维素纳米晶体(CNC)的结合如何影响壳聚糖和壳聚糖/羧甲基纤维素(CMC)材料的结构和性能。由于这些亲水性纳米填料之间的强烈相互作用,形成了由 GO 和 SPT 组成的三维互连微结构。壳聚糖/CMC/GO/SPT 复合材料具有最高的拉伸强度(77.5 ± 1.2 兆帕)和杨氏模量(1925.9 ± 120.7 兆帕)。对于未塑化基质,疏水性 rGO 纳米片通常会阻碍 SPT 或 CNC 与多糖(壳聚糖和 CMC)的相互作用,因此复合材料的性能主要由 rGO 决定。然而,对于用 1-乙基-3-甲基咪唑醋酸盐([C2mim][OAc])塑化的壳聚糖基质,与单独添加纳米填料相比,rGO + CNCs 或 rGO + SPT 能更有效地破坏聚合物链的相互作用,并使壳聚糖的塑化程度更高,这表现在链的流动性、延展性和表面亲水性都有所提高。对于[C2mim][OAc]塑化壳聚糖/CMC基质,加入混合填料(rGO + CNCs 或 rGO + SPT)也具有优势,可获得更高的热稳定性和表面疏水性。
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引用次数: 0
The journey of polycarbonate-based composites towards suppressing electromagnetic radiation 聚碳酸酯基复合材料抑制电磁辐射的历程
Pub Date : 2021-07-31 DOI: 10.1186/s42252-021-00025-1
Kumari Sushmita, Giridhar Madras, Suryasarathi Bose

Electronic devices’ widespread usage has led to a new form of pollution, known as electromagnetic (EM) pollution, causing serious problems like equipment malfunctioning and affecting its reliability. This review article presents a comprehensive literature survey on the various polycarbonate (PC)-based materials for electromagnetic interference (EMI) shielding applications comprising of PC-based composites, blend composites, foams, and more recently, multilayered architectures. Following the state-of-the-art literature available from the previous decade, it is apparent that the properties (conductivity, permittivity and permeability) of nanofiller/fillers and nanocomposite processing/fabrication techniques control the EMI shielding properties in PC-based materials. Researchers have explored a variety of fillers, but high aspect ratio carbonaceous nanofillers have gained significant attention. Through morphological modifications of PC composites, one can obtain a percolation threshold as low as 0.021 wt% of carbon nanotubes (CNTs). However, higher connectivity of conductive filler need not necessarily lead to high EMI shielding performance. Thus, detailed insight into the shielding mechanism is also highlighted. This review article will help researchers design PC-based materials with superior EMI shielding performance coupled with good mechanical stability.

电子设备的广泛使用导致了一种新的污染形式,即电磁(EM)污染,造成设备故障等严重问题,并影响其可靠性。这篇综述文章全面介绍了用于电磁干扰(EMI)屏蔽应用的各种聚碳酸酯(PC)材料,包括 PC 基复合材料、共混复合材料、泡沫材料以及最新的多层结构。根据前十年的最新文献,纳米填料/填充物的特性(电导率、介电常数和磁导率)以及纳米复合材料的加工/制造技术显然控制着 PC 基材料的 EMI 屏蔽特性。研究人员对各种填料进行了探索,但高纵横比碳质纳米填料获得了极大关注。通过对 PC 复合材料进行形态改性,人们可以获得低至 0.021 wt% 的碳纳米管(CNT)渗流阈值。然而,导电填料的连接性越高,并不一定就能带来高 EMI 屏蔽性能。因此,本文还强调了对屏蔽机理的详细见解。这篇综述文章将帮助研究人员设计出具有优异 EMI 屏蔽性能和良好机械稳定性的 PC 基材料。
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引用次数: 0
Effects of curing on emulsion cold mix asphalts and their extracted binder 养护对乳化液冷混沥青及其萃取粘结剂的影响
Pub Date : 2021-06-12 DOI: 10.1186/s42252-021-00024-2
Amélie Thiriet, Vincent Gaudefroy, Emmanuel Chailleux, Jean-Michel Piau, Frédéric Delfosse, Christine Leroy

This paper focuses on the physicochemical changes that happen in cold mix asphalts during curing, and more specifically, while and after transitioning to different simulated seasons. Several tests were carried out in order to better grasp the influence of the weather (temperature and humidity) on the curing of such materials. The mechanical behaviour of the mix was assessed using oedometer tests. The physicochemical evolutions of extracted binders, such as oxidation and rheology, were evaluated. The results show stiffening of the mix and ageing of the binder linked to a higher temperature and a lower humidity. A low temperature and high moisture seem to slow down these evolutions. However the binder behaviour does not explain the whole mix behaviour as the kinetics between them are not always similar. Thus other mechanisms are yet to be found and taken into account to fully understand cold mix asphalts behaviour.

本文重点研究了冷拌沥青在养护过程中,特别是在过渡到不同模拟季节期间和之后发生的物理化学变化。为了更好地掌握天气(温度和湿度)对这类材料固化的影响,进行了几次试验。混合料的力学性能是用粘度计试验评估的。评价了萃取粘合剂的理化演变,如氧化和流变性。结果表明,较高的温度和较低的湿度与混合料的硬化和粘结剂的老化有关。低温和高湿度似乎减缓了这些进化。然而,粘结剂的行为并不能解释整个混合行为,因为它们之间的动力学并不总是相似的。因此,其他机制尚未被发现和考虑,以充分了解冷混合沥青的行为。
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引用次数: 6
Investigation of the effect of tufts contribution on the in-plane mechanical properties of flax fibre reinforced green biocomposite 簇对亚麻纤维增强绿色生物复合材料面内力学性能影响的研究
Pub Date : 2021-04-08 DOI: 10.1186/s42252-021-00019-z
M. Rashid, J. L. Hanus, K. Chetehouna, K. Khellil, Z. Aboura, N. Gascoin

Traditional laminated composites have fibres oriented only in the in-plane of the laminate due to their manufacturing process, and are therefore very susceptible to transverse cracking and delamination from out-of-plane actions. Delamination can considerably reduce the load bearing capacity of a structure hence several reinforcement solutions, based on the principle to add out-of-plane reinforcement to the 2D fabric, have been explored to enhance the delamination resistance. However, the usual textile technologies for Z-reinforcement such as weaving, knitting, stitching, z-pinning, and tufting generates perturbations that may alter the in-plane mechanical properties. Although tufting is a single needle and single thread based one side stitching (OSS) technique which can incorporate almost tension free through the thickness reinforcement in a material, various types of microstructural defects may be created during the manufacturing process and lead to a degradation of the in-plane properties of the composite. Moreover, due to awareness in environmental concerns, the development and use of eco-friendly biocomposites to replace synthetic ones has been increasing.

This research work investigates the effect on in plane mechanical properties of adding through the thickness reinforcement (TTR) by tufting in a flax based composite laminate to improve the transversal strength. The glass fibre tufted laminates of 550?g/m2 flax fibre were moulded using a 38% biobased thermoset resin by vacuum bag resin transfer moulding (VBRTM). The tufted and un-tufted in-plane mechanical properties of green biocomposite were determined in tension, compression and shear in accordance with ASTM 3039, ASTM D7137 and EN ISO 14130, using universal INSTRON 1186 and MTS 20?M testing machines. The quantification of the in-plane mechanical properties established a reduction of the in plane tensile mechanical properties, due to tufting, whereas the reduction effects are marginal in compression. As expected, the glass fibre tufts strength the connection between core and skin of the composite so that the interlaminar shear strength, deduced from flexural tests with small span-to-thickness ratio, is increased. Thanks to Digital Image Correlation (DIC) performed during shear tests, an increase in interlaminar shear modulus is highlighted.

由于传统的层压复合材料的制造工艺,其纤维仅在层压板的平面内取向,因此非常容易受到平面外作用的横向开裂和分层。分层会大大降低结构的承载能力,因此,基于在二维织物中添加面外加固的原理,探索了几种增强方案来增强结构的抗分层能力。然而,通常用于z型增强的纺织技术,如编织、针织、缝合、z型钉钉和簇绒,会产生可能改变面内机械性能的扰动。虽然簇绒是一种基于单针和单线的单侧缝合(OSS)技术,可以通过材料中的厚度增强几乎不受张力,但在制造过程中可能会产生各种类型的微结构缺陷,并导致复合材料的平面内性能退化。此外,由于对环境问题的认识,开发和使用生态友好型生物复合材料来取代合成材料已经越来越多。本文研究了在亚麻基复合材料层合板中加入厚度增强剂(TTR)以提高横向强度对其平面力学性能的影响。玻璃纤维簇绒层压板550?g/m2亚麻纤维采用38%生物基热固性树脂真空袋树脂转移模塑(VBRTM)成型。按照ASTM 3039、ASTM D7137和EN ISO 14130,使用通用的INSTRON 1186和MTS 20?M台试验机。平面内力学性能的量化确定了由于簇绒而导致的平面内拉伸力学性能的降低,而压缩时的降低效应是边际的。正如预期的那样,玻璃纤维簇增强了复合材料芯层和表层之间的连接,从而提高了从小跨厚比弯曲试验中得出的层间抗剪强度。由于在剪切测试期间进行了数字图像相关(DIC),层间剪切模量的增加被突出显示。
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引用次数: 6
Surface functionalization of thermoset composite for infrared hybrid welding 红外复合焊接热固性复合材料的表面功能化
Pub Date : 2021-04-06 DOI: 10.1186/s42252-021-00021-5
Henri Perrin, Grégory Mertz, Noha-Lys Senoussaoui, Loïc Borghini, Sébastien Klein, Régis Vaudemont

Fusion assembly is a highly promising technique for joining thermoplastic composite to thermoset composites, enabling the use of both the most affordable composite material and process for each substructure. However, some major challenges need to be addressed such as functionalizing the thermoset composite surface through co-curing with an appropriate thermoplastic interlayer or realizing a fast and robust welding process that meets all quality and mechanical requirements. In this paper, we investigated the potential of polyetheretherketone (PEEK) and its amorphous (PEEK A) and semicristalline (PEEK SC) states as interlayer materials, co-cured onto thermoset composites. A surface preparation involving the atmospheric plasma process demonstrated that both PEEK state materials can be used as interlayer with favorable adhesion properties. The influence of the plasma treatment on surface properties and morphology was also experimentally characterized.

融合组装是一种非常有前途的技术,用于连接热塑性复合材料和热固性复合材料,可以为每个子结构使用最经济实惠的复合材料和工艺。然而,一些主要的挑战需要解决,例如通过与适当的热塑性中间层共固化来使热固性复合材料表面功能化,或者实现满足所有质量和机械要求的快速坚固的焊接工艺。本文研究了聚醚醚酮(PEEK)及其非晶态(PEEK A)和半晶态(PEEK SC)作为热固性复合材料共固化层间材料的潜力。一种涉及大气等离子体工艺的表面制备表明,这两种PEEK状态的材料都可以用作具有良好粘附性能的中间层。实验还表征了等离子体处理对表面性能和形貌的影响。
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引用次数: 4
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Functional Composite Materials
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