石墨烯/腰果酚改性酚醛树脂基碳纤维纸基复合材料制备及性能研究

利用石墨烯和腰果酚对酚醛树脂进行改性,制得石墨烯/腰果酚改性酚醛树脂(GCP),并将自制碳纤维原纸浸渍于此树脂中,制备得到石墨烯/腰果酚改性酚醛树脂基碳纤维纸基复合材料(GCPC)。利用热重分析仪对GCP进行了分析;并利用四探针测试仪、万能试验机和多孔材料分析仪,研究了GCPC的电学性能、力学性能、孔径分布以及孔隙率。结果表明,随着石墨烯和腰果酚用量的增加,GCPC的力学强度和导电性能得以提高;随着石墨烯用量的增加,孔隙率下降,小孔比例增加;而随着腰果酚用量的增加,孔隙率上升,小孔比例减少,且当腰果酚的质量分数为20%时,碳纤维纸基复合材料的拉伸强度为38.17 MPa,体积电阻率为18.46 mΩ·cm,孔隙率67.46%。     

腰果酚改性甲阶酚醛树脂的合成及其泡沫性能研究

用腰果酚代替部分苯酚改性酚醛树脂,制备可发性甲阶酚醛树脂。并讨论了腰果酚替代量对改性酚醛树脂性能及其泡沫性能的影响,通过红外光谱仪、热重分析仪对树脂结构及热稳定性进行表征,运用万能电子试验机对甲阶酚醛树脂泡沫的力学性能进行了研究。结果表明:当腰果酚替代量为10%时,制得的树脂黏度为4650mPa·s,树脂中游离苯酚含量从6.72%降为5.45%,游离甲醛含量从1.17%降为0.68%,甲阶酚醛树脂泡沫压缩强度达到最大值0.20MPa,但树脂热稳定性及甲阶酚醛树脂泡沫阻燃性有所下降。     

腰果酚改性酚醛树脂泡沫的制备

在碱性条件下,以腰果酚部分代替苯酚与甲醛反应制得腰果酚改性酚醛树脂,并以该树脂为原料制备腰果酚改性酚醛树脂泡沫。结果表明:当苯酚/腰果酚物质的量比为9/1、缩聚反应温度90℃、催化剂加入量为苯酚和腰果酚总质量4%时,所得树脂黏度为25 Pa·s,符合最佳发泡黏度范围。当苯酚/腰果酚物质的量比为9/1时,改性树脂在400℃时的残炭量(94.6%)要比未改性树脂的残炭量高7.1%,压缩强度由改性前的0.08 MPa提高到改性后的0.14 MPa。扫描电镜结果表明:在相同条件下,改性后的酚醛树脂泡沫泡孔更为均匀。     

腰果酚改性酚醛泡沫树脂的研究

采用腰果酚作增韧剂对酚醛泡沫树脂进行增韧改性。通过改变反应温度、反应时间、催化剂用量等合成酚醛树脂并制备酚醛泡沫。测定其拉伸强度、固含量、红外光谱图并进行可发泡性试验,最终得到改性酚醛泡沫的最佳工艺条件。实验发现当腰果酚代替量(质量分数)35%,反应温度为100℃,反应时间为3.5 h,催化剂二水合草酸用量为1.65 g时,酚醛树脂的性能最好,拉伸强度为1.8MPa,且发泡效果比较好。     

摩擦材料用改性酚醛树脂的制备及应用

用三聚氰胺、腰果酚、粉末丁腈橡胶对酚醛树脂进行了改性,并将其用作摩擦材料的基体树脂。探讨了腰果酚、三聚氰胺用量等因素对改性酚醛树脂性能的影响,并对各摩擦制动材料的摩擦磨损、热衰退等性能进行了研究。结果表明:腰果酚、丁腈橡胶改性酚醛树脂(YX-PF)与三聚氰胺、腰果酚改性酚醛树脂(SY-PF)的热分解温度比普通酚醛树脂分别提高了57℃和91℃,且摩擦磨损性能优良。另外,加入丁腈橡胶可进一步提高SY-PF的综合性能。     

腰果酚制备可发性酚醛树脂的合成工艺研究

以苯酚、腰果酚、甲醛为原料,NaOH为催化剂,乙二醇为助剂,合成了可发性酚醛树脂,通过粘度,固含量,韧性测试研究了原料的配比,腰果酚替代苯酚的比例,催化剂用量,反应时间,反应温度及乙二醇用量对合成树脂性能的影响并通过IR,TG分析对树脂结构及耐热性进行了表征。结果表明,适宜的反应条件为:F/P比(甲醛与总酚物质的量比值)1.6,腰果酚替代量20%,催化剂用量1%,反应时间3 h,反应温度80℃,乙二醇质量分数10%～15%。以腰果酚制备的CPF树脂耐热性变化不明显,拉伸强度为22.34 MPa,断裂伸长率3.08%,冲击强度3.56 kJ/m2,较PF树脂有很大提高。     

树脂制备工艺对腰果酚改性酚醛树脂胶接性能影响研究

采用腰果酚、苯酚和甲醛为原料,氨水为催化剂,制备了三种腰果酚含量40%的热固性腰果酚改性酚醛树脂:腰果酚-甲醛/苯酚-甲醛共混酚醛树脂(CF-PF)、腰果酚-苯酚-甲醛共聚酚醛树脂(PCF-A)和混酚(腰果酚-苯酚-双酚)-甲醛共聚酚醛树脂(PCF-B)。借助DSC、TGA、剪切强度等手段对合成树脂性能进行了表征。DSC分析结果表明:三种改性树脂中PCF-B树脂的固化反应活性最高,初始温度、峰温和终温分别为146℃、190℃和259℃,固化反应活性顺序是PCF-BPCF-ACF-PF。TGA结果表明,PCF-A和PCF-B树脂的耐热性能相当,2%和5%失重温度分别是340℃左右和400℃左右,CF-PF树脂耐热性能较低,2%和5%失重温度分别为316℃和376℃。PCF-B的室温和150℃剪切强度分别为8.31MPa和7.74MPa,较PF树脂分别提高27%和71%,增韧效果明显;CF-PF的高温粘接性能最好,250℃和300℃剪切强度分别为5.07MPa和5.15MPa,分别是PF树脂250℃和300℃剪切强度的96%和141%。     

环氧腰果酚/硅氧烷对酚醛树脂及泡沫性能的影响

以环氧腰果酚(ECD)为酚原,替代部分苯酚,同时引入1,3-双(氨丙烷基)四甲基二硅醚(APTMDS),合成改性酚醛树脂,进而制备改性酚醛泡沫。分析APTMDS添加量一定时,ECD替代苯酚量对改性树脂的结构、游离酚含量、游离醛含量、黏度以及热稳定性的影响,研究ECD替代苯酚量对改性泡沫压缩强度、弯曲强度、易碎性能以及燃烧性能的影响。结果表明,当APTMDS添加量一定时,改性树脂体系的游离酚含量随着ECD的替代量的增加而呈下降趋势,游离醛随着ECD的替代量的增加而呈上升趋势,改性树脂体系的黏度随着ECD的替代量的增加有所上升。改性酚醛泡沫的压缩和弯曲强度有很大程度的提高,当ECD替代量为4%(wt)时,改性泡沫的压缩和弯曲强度最大,分别为0.281和0.363 MPa,与纯酚醛泡沫相比,分别提高了91.16%和62.05%。改性酚醛泡沫粉碎率有所降低,当ECD替代苯酚量为12%时,改性酚醛泡沫的粉碎率最小,19.81%,与纯酚醛泡沫相比,下降了24.13%。改性后的酚醛泡沫的阻燃性能略有下降。     

腰果酚改性焦油粗酚酚醛泡沫塑料的研究

为降低酚醛泡沫塑料的成本,改善其性能,以焦油粗酚、苯酚、多聚甲醛为原材料,腰果酚为改性剂,合成可发性腰果酚改性焦油粗酚酚醛树脂,发泡制备出腰果酚改性焦油粗酚酚醛泡沫塑料。研究了腰果酚用量对改性焦油粗酚酚醛泡沫塑料保温性能、阻燃性能、吸水率、力学性能和耐热稳定性等的影响,并通过傅立叶变换红外光谱仪对合成改性焦油粗酚酚醛树脂进行了表征,通过生物显微镜、热重分析仪对改性焦油粗酚酚醛泡沫塑料的微观结构和耐热稳定性进行表征。结果表明,腰果酚的加入使改性焦油粗酚酚醛泡沫塑料的综合性能有较大改善,当腰果酚占混合酚的质量分数为15%时,改性焦油粗酚酚醛泡沫塑料的综合性能最佳,吸水率为4.51%,压缩强度为0.31 MPa,弯曲强度为0.55 MPa,导热系数为0.036 W/(m·K),极限氧指数为35.2%。改性焦油粗酚酚醛泡沫塑料的保温、阻燃性能和耐热稳定性较好,泡孔致密均匀。     

腰果酚基环氧树脂的制备及其硅烷化改性

采用从腰果壳油中提炼出来的腰果酚为原料,在乙酸锌的催化下生成腰果酚基酚醛树脂(CN),随后利用CN在苄基三乙基氯化铵(TEBAC)的催化下进一步合成腰果酚基环氧树脂(CNE),最后对CNE进行有机硅改性,制备了有机硅改性环氧树脂(SICNE)。研究结果表明:将CNE和SICNE与三乙烯四胺(TETA)固化后,由于反应性硅氧烷基链段的引入使树脂涂层附着力由1级提升为0级,水接触角由73.5°升至112.7°。     

改性纳米碳化硅/聚氨酯弹性体复合材料的制备

采用KH-560与KH-550反应得到新的硅烷偶联剂改性纳米碳化硅(SiC);再以2,4-甲苯二异氰酸酯(TDI)、聚氧化丙烯醚二醇(PPG2000)为原料合成预聚体,改性纳米SiC为填料、3,3’-二氯-4,4’-二氨基二苯甲烷(MOCA)为扩链剂,制备了改性纳米SiC/聚氨酯弹性体(PUE)复合材料。讨论了改性前后的纳米SiC添加量对复合材料的力学性能、耐磨性能和热稳定性的影响,并用扫描电镜分析了改性前后的纳米SiC在基体中的分散性。结果表明,改性后的纳米SiC在基体中的分散性优于纳米SiC,当改性纳米SiC质量分数为9%时,改性纳米SiC/PUE复合材料的力学性能达到最佳,耐磨性能明显改善,热失重温度提高了33℃。     

Cu-SiC磨具制备及其性能表征

笔者描述了铜-碳化硅磨具的制备过程,采用热压成形法制备了Cu-SiC磨具。该磨具主要由铜粉、酚醛环氧树脂和碳化硅磨料组成。研究了树脂、碳化硅与辅助磨料的种类、组成对磨具性能的影响。结果表明:当加入适量铜粉,复合材料磨损率会下降、耐磨性能会提高,被磨削表面不易出现凹痕、孔洞;但是铜粉添加过量时,磨具磨损率会增加。较佳配方组成为:35wt%树脂、45wt%碳化硅、15.56wt%铜粉、4.44wt%白刚玉。     

Properties of SiC-Si made via binder jet 3D printing of SiC powder,carbon addition,and silicon melt infiltration

We report the physical and mechanical properties of ceramic composite materials fabricated by binder jet 3D printing (BJ3DP) with silicon carbide (SiC) powders, followed by phenolic resin infiltration and pyrolysis (IP) to generate carbon, and a final reactive silicon melt infiltration step. After two phenolic resin infiltration and pyrolysis cycles; porosity was less than 2%, Young's modulus was close to 300 GPa, and the flexural strength was 517.6 ± 24.8 MPa. However, diminishing returns were obtained after more than two phenolic resin infiltration and pyrolysis cycles as surface pores in carbon were closed upon the formation of SiC, resulting in reaction choking and residual-free carbon and porosity. The instantaneous coefficient of thermal expansion of the composite was found to be independent of the number of phenolic IP cycles and had values of between 4.2 and 5.0 ppm/°C between 300 and 1000℃, whereas the thermal conductivity was found to have a weak dependence on the number of phenolic IP cycles. While the manufacturing procedures described here yielded highly dense, gas impermeable, siliconized SiC composites with properties comparable to those of bulk siliconized silicon carbide processed according to conventional techniques, BJ3DP enables the manufacture of objects with complex shape, unlike conventional techniques.     

A microstructural study of carbon–carbon composites impregnated with SiC filaments

Porous multidirectional carbon/carbon composite obtained by pulse chemical vapour infiltration (PCVI) was impregnated with silicon carbide (SiC) derived from pyrolysis of polymethylsiloxane resin (PMS). The impregnation process was made to improve oxidation resistance and mechanical properties of MD C/C composite. The resin was used as a source of silicon carbide component of the composite forming after heat treatment above 1000 °C. During this process SiC thin filaments were formed inside the porous carbon phase. The aim of this work was to investigate the structure and microstructure of the constituents of carbon composite obtained after pyrolysis of SiC PMS precursor. Microscopic observations revealed that during careful heat treatment of crosslinked polymethylsiloxane resin up to 1700 °C, the filaments (diameter 200–400 nm) crystallized within porous carbon phase. The filaments were randomly oriented on the composite surface and inside the pores. FTIR spectra and XRD analysis of the modified C/C composite showed that filaments had silicon carbide structure with the crystallite size of silicon carbide phase of about 45 nm. The Raman spectra revealed that the composite contains two carbon components distinctly differing in their structural order, and SiC filaments present nanocrystalline structure.     

环氧树脂/碳化硅复合材料的热性能及韧性

采用碳化硅作为增强剂制备了环氧树脂/碳化硅复合材料,考察了复合材料的热学及力学性能。实验结果表明,碳化硅的添加使环氧树脂的玻璃化温度提高。当碳化硅添加质量分数为3%时,复合材料的韧性与纯环氧树脂相比提高了35%。     

腰果酚/聚乙烯醇改性酚醛树脂的制备

以腰果酚、聚乙烯醇作为苯酚与甲醛缩聚的改性剂,研究了腰果酚和聚乙烯醇的用量,催化剂类型和用量等对其性能的影响。结果表明:改性酚醛树脂的最佳条件为:苯酚、腰果酚、聚乙烯醇、甲醛的最佳摩尔比为0.85:0.32:0.02:1,最佳的催化剂为苯磺酸,用量为4.5%。     

腰果酚/聚乙烯醇改性酚醛树脂的制备

以腰果酚、聚乙烯醇作为苯酚与甲醛缩聚的改性剂,研究了腰果酚和聚乙烯醇的用量,催化剂类型和用量等对其性能的影响。结果表明:改性酚醛树脂的最佳条件为:苯酚、腰果酚、聚乙烯醇、甲醛的最佳摩尔比为0.85:0.32:0.02:1,最佳的催化剂为苯磺酸,用量为4.5%。     

碳化硅增强摩阻材料的制备及性能表征

选用不饱和树脂作为基体材料,偶联剂处理过的碳化硅作为填料,制备具有较好耐磨性和较高摩擦系数的聚合物基复合摩阻材料。实验结果表明:粒径400目的碳化硅作为摩阻材料的填料效果最佳,其添加量为10%时,该复合材料具有较低的磨损率,添加量为7%时,该复合材料的摩擦系数达到最大值。结合扫描电镜(SEM)和理论分析说明,硬度大的碳化硅作为磨料,起到了抵抗磨损和基本变形产生磨损的双重作用,并产生了微切削和犁沟效应,改变了材料的摩擦系数。     

Manufacture and characterisation of a low cost carbon fibre reinforced C/SiC dual matrix composite

A porous two-dimensional C/C composite was produced via the polymer pyrolysis route using phenolic resin as the matrix precursor and polyacrilonitrile- (PAN-) or pitch-based carbon fibres as reinforcement. The resulting C/C composites were then densified using a modified polysilane followed by pyrolysis to convert the polymer into silicon carbide, sealing the pores in the C/C composite. Aiming to increase the ceramic yield of the infiltrated polysilane and to reduce its volumetric shrinkage during pyrolysis the polymer’s curing behaviour was modified by catalytic addition of 0.1% dicobaltoctacarbonyl [Co₂(CO)₈]. The densification procedure is very efficient in sealing cracks in the C/C composite with SiC. The obtained carbon fibre reinforced C/SiC dual matrix composites were subjected to flexural tests and dynamic mechanical analysis. The flexural and visco-elastic properties of the composite are dominated by the strength of the fibre/matrix interface rather than by the fibre strength or modulus. A correlation between the mechanical loss factor (tan δ) and the fracture behaviour of the composite is suggested.     

Phenolic foams modified by cardanol through bisphenol modification

In this study, cardanol, a natural phenol, has been applied to toughen phenolic foam by bisphenol modification. In order to verify the occurrence of Friedel–Craft alkylation between cardanol and phenol on the side chain, FTIR, and NMR had been used to characterize the bisphenol successfully. With the introduction of cardanol, the viscosity of prepolymers increased. The SEM results demonstrated that the some cells with increasingly large size existed, when the dosage of cardanol increased. With respect to the mechanical properties, phenolic foams modified by 10 wt % cardanol increased by 22% in flexural strength and 28% in bending modulus compared to pure phenolic foams, which indicates that the incorporation of cardanol does improve the toughness of phenolic foams. In addition, the effects of different dosage of cardanol on the apparent density and thermal stability of phenolic foams were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39942.