本文選題：碳纖維 + 氧化石墨烯�。� 參考：《哈爾濱工業(yè)大學(xué)》2017年博士論文

【摘要】：隨著現(xiàn)代航空航天技術(shù)的進(jìn)步,具有高馬赫數(shù)的新型高超聲速航天飛行器已經(jīng)成為世界軍事大國研究重點(diǎn),X系列空天飛行器成為其中的代表。而熱防護(hù)系統(tǒng)作為其重要子系統(tǒng)之一,它成為制約高超飛行器服役能力的關(guān)鍵技術(shù)。針對服役環(huán)境,對系統(tǒng)所采用的材料提出了具有輕質(zhì)、耐高溫、抗氧化燒蝕及高可靠性的基本特征,以滿足熱防護(hù)系統(tǒng)的需求。而連續(xù)碳纖維增強(qiáng)陶瓷基復(fù)合材料所制備的多孔材料,由于其較高的孔隙率,較低的密度,良好的高溫穩(wěn)定性使其成為重要的候選材料之一,此外做為新型的剛性多孔陶瓷基隔熱材料,SiBCN陶瓷的引入相較于傳統(tǒng)的SiOC陶瓷能進(jìn)一步提高其耐熱性。連續(xù)碳纖維增強(qiáng)復(fù)合材料具有高強(qiáng)度、高硬度、低比重和耐化學(xué)腐蝕等優(yōu)點(diǎn),在過去幾十年一直是材料學(xué)科研究的熱點(diǎn),由于其杰出的力學(xué)性能在航空航天、汽車及國防等領(lǐng)域有著廣泛的應(yīng)用。相較于傳統(tǒng)的金屬或者合金材料,碳纖維復(fù)合材料還具有更好的面內(nèi)拉伸性能以及密度更低的優(yōu)勢。由于碳纖維與基體之間存在弱界面限制了碳纖維復(fù)合材料性能的發(fā)揮。本論文主要研究了氧化石墨烯接枝改性碳纖維(CF-g-GO)三維織物和納米二氧化硅改性碳纖維(CF-g-nanosilica)三維織物兩種復(fù)合增強(qiáng)體;并以此為基礎(chǔ)結(jié)合原位聚合法和先驅(qū)體浸漬裂解法,經(jīng)過浸漬和高溫?zé)峤獾裙に?合成了兩種新型的CF-g-GO/SiBCN-Ⅰ和CF-gnanosilica/SiBCN-Ⅱ陶瓷基復(fù)合材料,并研究了兩種復(fù)合材料的制備工藝方法,探討了兩種復(fù)合材料的化學(xué)基團(tuán)組成、元素分布及含量等變化規(guī)律,并對其機(jī)械性能及熱物理性能進(jìn)行了研究。采用3-氨丙基三乙氧基硅烷和3-縮水甘油醚氧基丙基三甲氧基硅烷兩種硅烷偶聯(lián)劑分別修飾氧化石墨烯和碳纖維,通過開環(huán)反應(yīng)制備了氧化石墨烯接枝改性碳纖維復(fù)合增強(qiáng)體。研究了碳纖維/氧化石墨烯雜化結(jié)構(gòu)的合成工藝及接枝氧化石墨烯前后碳纖維界面化學(xué)組成及微觀組織的變化。FTIR、XPS及SEM等分析測試結(jié)果表明了氧化石墨烯被高效的接枝到碳纖維表面。單絲拉伸測試表明接枝氧化石墨烯能一定程度上彌合碳纖維表面由于氧化作用而產(chǎn)生的缺陷,使改性碳纖維自身的拉伸強(qiáng)度和斷裂功能得到提高,同時(shí)起到增加纖維表面的粗糙度和增強(qiáng)界面機(jī)械咬合的作用。以1,4-對苯二異氰酸酯為單體合成了大分子偶聯(lián)劑聚異氰酸酯(PPDI),采用二氧化硅納米顆粒為增強(qiáng)相,結(jié)合異氰酸酯與羥基的親核加成反應(yīng)制備了二氧化硅納米顆粒改性碳纖維復(fù)合材料,研究了碳纖維/納米二氧化硅雜化結(jié)構(gòu)的合成機(jī)理及接枝前后碳纖維界面化學(xué)組成及微觀組織演變規(guī)律。通過測試分析結(jié)果表明納米二氧化硅被均勻有序的包覆在碳纖維表面,并且通過改變反應(yīng)條件可實(shí)現(xiàn)對纖維表面二氧化硅納米顆粒的接枝率及接枝密度的有效調(diào)控。納米二氧化硅改性碳纖維力學(xué)測試結(jié)果表明,不同納米二氧化硅接枝量會(huì)影響碳纖維的拉伸性能,其中當(dāng)碳纖維和納米二氧化硅質(zhì)量比5:1時(shí),改性碳纖維力學(xué)性能最好,其拉伸強(qiáng)度和斷裂功分別提高至3.74GPa和34.25J/m3,與碳纖維原絲相比,其拉伸強(qiáng)度和斷裂功分別提高了45%和132%。結(jié)合AFM測試結(jié)果表明,二氧化硅納米顆粒接枝到碳纖維表面,不僅極大地增加了碳纖維的表面粗糙度及比表面積,還有效地改善了碳纖維的機(jī)械性能。以氧化石墨烯接枝改性連續(xù)碳纖維為增強(qiáng)體,以甲基三氯硅烷、三氯化硼和六甲基二硅氮烷三種小分子為單體,在改性碳纖維三維織物表面經(jīng)過原位聚合、熱解等工藝制備了CF-g-GO/Si BCN-Ⅰ陶瓷基復(fù)合材料。經(jīng)測試分析表明復(fù)合材料主要由Si、B、C和N四種元素構(gòu)成,其鍵接方式主要有B-N鍵、Si-N鍵和Si-C鍵三種共價(jià)鍵。采用熱重分析法測試了CF-g-GO/SiBCN-Ⅰ陶瓷基復(fù)合材料在空氣氣氛下的抗氧化性能。結(jié)果表明在1400°C時(shí)其失重率為26%,這是由于在溫度700~836°C范圍SiBCN中BN及部分纖維發(fā)生了氧化,并生成了氧化硅玻璃相和氧化硼玻璃相,玻璃相的生成阻止了復(fù)合材料的進(jìn)一步氧化。通過對不同密度復(fù)合材料的壓縮測試表明,復(fù)合材料的壓縮模量和壓縮強(qiáng)度隨著密度的增加而增加,經(jīng)過四次浸漬裂解循環(huán)后,復(fù)合材料的壓縮性能達(dá)到最好,其x/y方向壓縮強(qiáng)度和壓縮模量分別為5.56±0.52MPa和87.92±8.13MPa,z方向壓縮強(qiáng)度和壓縮模量分別為0.91±0.32MPa和35.10±5.07MPa。以納米二氧化硅改性連續(xù)碳纖維三維織物為增強(qiáng)體,采用三氯硅烷、三氯化硼和六甲基二硅氮烷三種單體,制備了另外一種CF-g-nanosilica/SiBCN-Ⅱ陶瓷基復(fù)合材料。研究結(jié)果表明,采用SiBCN-Ⅱ型先驅(qū)體所制備的復(fù)合材料有更好的力學(xué)性能,同樣經(jīng)過四次浸漬裂解循環(huán)后,所得復(fù)合材料的x/y方向壓縮強(qiáng)度和壓縮模量分別為7.36±0.67MPa和223.53±16.15MPa,z方向壓縮強(qiáng)度和壓縮模量分別為0.92±0.25MPa和46.4±9.31MPa,明顯高于采用SiBCN-Ⅰ所合成的復(fù)合材料,這主要是由于SiBCN-Ⅱ在1400°C熱解后擁有更高的陶瓷產(chǎn)率及高溫穩(wěn)定性所致。采用熱失重測試方法研究了CF-g-nanosilica/SiBCN-Ⅱ陶瓷基復(fù)合材料的在空氣中的動(dòng)態(tài)氧化行為。結(jié)果表明,該復(fù)合材料的氧化行為主要分為三個(gè)階段:第一階段,當(dāng)溫度在28~826°C時(shí),復(fù)合材料未發(fā)生明顯氧化;第二階段為826~900°C時(shí),樣品失重速率驟升,主要是因?yàn)樘祭w維表面包覆的SiBCN多元陶瓷中BN發(fā)生了氧化反應(yīng),生成B2O3和NO2氣體,氣體揮發(fā),導(dǎo)致陶瓷中出現(xiàn)孔隙,從而引起纖維氧化而導(dǎo)致失重;第三階段為900~1200°C,隨著溫度升高,SiBCN中Si和B分別發(fā)生氧化生成了玻璃態(tài)的氧化硅及氧化硼彌合了氧化過程中產(chǎn)生的缺陷,有效地保護(hù)了纖維在高溫氧化環(huán)境中不受損傷。因此通過接枝二氧化硅納米顆粒和表面包覆SiBCN陶瓷先驅(qū)體均能有效地提高碳纖維在高溫環(huán)境中的抗氧化性能。
[Abstract]:With the progress of modern aerospace technology, a new type of hypersonic spacecraft with high Maher number has become the focus of the world's military power research. The X series airspace vehicle has become one of the representative. As one of its important subsystems, thermal protection system has become the key technology to restrict the service ability of the hypervehicle. The basic features of the materials used in the system are light, high temperature resistant, antioxidation and high reliability, to meet the requirements of the thermal protection system. The porous material prepared by continuous carbon fiber reinforced ceramic matrix composites is made by its high porosity, low density and good high temperature stability. One of the important candidates, in addition to a new type of rigid porous ceramic based insulation, the introduction of SiBCN ceramics is more heat-resistant than traditional SiOC ceramics. Continuous carbon fiber reinforced composites have the advantages of high strength, high hardness, low specific gravity and chemical corrosion resistance. In the past few decades it has been a material subject. Because of its outstanding mechanical properties, it has a wide range of applications in aerospace, automotive and national defense fields. Compared to traditional metal or alloy materials, carbon fiber composites have better tensile properties and lower density. The weak interface between carbon fiber and matrix restricts carbon fiber. In this paper, two kinds of composites reinforced with graphene oxide graft modified carbon fiber (CF-g-GO) and nano silica modified carbon fiber (CF-g-nanosilica) fabric are mainly studied in this paper. On this basis, the technology of in-situ polymerization and precursor impregnation cracking, impregnation and high temperature pyrolysis are used as the basis. Two new types of CF-g-GO/SiBCN- I and CF-gnanosilica/SiBCN- II ceramic matrix composites were synthesized, and the preparation methods of two kinds of composites were studied. The chemical group composition, the distribution and content of the two kinds of composite materials were discussed. The mechanical properties and the thermal physical properties of the two composites were studied. Graphene oxide and carbon fibers were modified by two silane coupling agents, which were two kinds of silane coupling agents, such as triethoxy silane and glycidyl triethyl trimethoxy silane, respectively. The carbon fiber reinforced carbon fiber reinforced polymer was prepared by the ring opening reaction. The synthesis process of carbon fiber / graphene oxide hybrid structure and the grafted graphene oxide were studied. The chemical composition and microstructure change of the carbon fiber interface.FTIR, XPS and SEM show that the graphene oxide is efficiently grafted onto the surface of carbon fiber. The tensile test of monofilament shows that the graft copolymer can partly bridge the defects of the carbon fiber surface due to oxidation, and make the modified carbon fiber itself. The tensile strength and fracture function are improved, at the same time, the roughness of the fiber surface and the mechanical occlusal of the interface are increased. The macromolecule coupling agent (PPDI) is synthesized by 1,4-, and the silica nanoparticles are used as the enhanced phase, and the nucleophilic addition reaction of isocyanate and hydroxyl group is made. Silica nanoparticles modified carbon fiber composites were prepared. The synthesis mechanism of carbon fiber / nano silica hybrid structure and the chemical composition and microstructure evolution of carbon fibers before and after grafting were studied. The results showed that the nano silica was coated on the surface of carbon fiber uniformly and orderly. The change of reaction conditions can effectively control the grafting ratio and the grafting density of silica nanoparticles on the fiber surface. The mechanical test results of nano silica modified carbon fiber show that the grafting amount of different nano silica will affect the tensile properties of carbon fibers, of which carbon fiber and nano silica are modified when the mass ratio is 5:1. The tensile strength and fracture work of its tensile strength and fracture work were improved to 3.74GPa and 34.25J/m3 respectively. The tensile strength and fracture work of the carbon fiber were increased by 45% and 132%. respectively compared with the carbon fiber precursor. The results showed that the grafting of silica nanoparticles onto the surface of carbon fibers not only greatly increased the surface roughness and specific surface of carbon fibers. The mechanical properties of carbon fibers were effectively improved. CF-g-GO/Si BCN- I ceramics were prepared on the surface of modified carbon fiber three-dimensional fabric by in-situ polymerization, pyrolysis and other processes by using methyl three chlorosilane, three boron chloride and six methyl two silanane as monomers. Based on the test and analysis, the composite material is mainly composed of four elements, Si, B, C and N. The bonding mode is mainly composed of B-N, Si-N and Si-C bonds. The thermogravimetric analysis is used to test the anti oxygen properties of CF-g-GO/SiBCN- I ceramic matrix composites in air atmosphere. The results show that the weight loss rate is 26% at 1400 degree C. This is due to the oxidation of BN and some fibers in the range SiBCN of temperature 700~836 C, and the formation of the silica glass phase and the boron oxide glass phase. The formation of the glass phase prevents the further oxidation of the composites. The compression modulus and compressive strength of the composite materials are determined by the compression test of different density composites. The compression strength and modulus of x/y direction are 5.56 + 0.52MPa and 87.92 + 8.13MPa, respectively, and the compressive strength and compression modulus of the Z direction are 0.91 + 0.32MPa and 35.10 + 5.07MPa. respectively, and the nano silica modified continuous carbon fibers are woven in three dimensional fabric. Another kind of CF-g-nanosilica/SiBCN- II ceramic matrix composite was prepared by using three chlorosilane, three boron chloride and six methyl two silicanitane. The results showed that the composites prepared by the SiBCN- type II precursor had better mechanical properties, and the composite after four cycles of lysis was also obtained. The compressive strength and compression modulus of the material in x/y direction are 7.36 + 0.67MPa and 223.53 + 16.15MPa respectively. The compressive strength and compression modulus of the Z direction are 0.92 + 0.25MPa and 46.4 + 9.31MPa respectively, which are obviously higher than those synthesized by SiBCN- I. This is mainly due to the higher ceramic yield and high temperature stability of SiBCN- II after the pyrolysis of 1400 degrees. The dynamic oxidation behavior of CF-g-nanosilica/SiBCN- II ceramic matrix composites in the air was studied by the method of thermal weight loss test. The results showed that the oxidation behavior of the composite was mainly divided into three stages: the first stage, when the temperature was 28~826 C, the composite material had no obvious oxidation; the second stage was 826~900 degree C. When the weight loss rate of the sample rises suddenly, it is mainly because the oxidation reaction of BN in the SiBCN multicomponent ceramic coated on the carbon fiber surface generates B2O3 and NO2 gas, and the gas volatilization leads to the appearance of pores in the ceramics, which causes the fiber oxidation to cause weightlessness. The third stage is 900~1200 C, with the increase of temperature, Si and B occur respectively in SiBCN. The glass state of silicon oxide and boron oxide bridge the defects produced in the oxidation process and effectively protect the fibers from being damaged in the high temperature oxidation environment. Therefore, the oxidation resistance of carbon fibers in high temperature environment can be effectively improved by grafting silica nanoparticles and coating SiBCN ceramic precursors on the surface.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB332

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