自由基引发活性聚碳硅烷交联及其在制备SiC纤维中的应用

在基于先驱体聚碳硅烷转化制备SiC陶瓷纤维过程中, 交联过程是保持纤维形貌和提高陶瓷产率的必要条件。本研究以含丙烯酸酯基的聚碳硅烷(A-PCS)为原料, 通过引入自由基热引发剂在热解升温过程中实现原料的交联成型。采用红外光谱仪(FT-IR)和差示扫描量热仪(DSC)研究了引发剂含量对A-PCS交联程度、交联速率以及热降解速率的影响规律; 采用热失重(TG)、元素分析仪和X射线衍射仪(XRD)分析了陶瓷产率、陶瓷产物组成以及无定形态随温度的变化。研究结果表明: 加入自由基热引发剂可提高A-PCS中的丙烯酸酯基的交联速率, 减少交联阶段的热失重; 将质量百分比为1%自由基热引发剂的A-PCS以5 ℃/min升至250 ℃时, 丙烯酸酯基反应完全, 1500 ℃的陶瓷产率为69.5%; 通过静电纺丝加工工艺可获得直径介于2~5 μm的A-PCS原丝, 并通过后续升温热解转化为SiC纤维; 所得SiC纤维形貌规整、无熔并现象, 且随着热解温度的升高从无定形态向结晶形态转变。     

聚甲基硅烷/二乙烯基苯的交联和裂解

本文研究了在不同的交联制度下,不同配比的聚甲基硅烷(PMS)/二乙烯基苯(DVB)对凝胶含量、陶瓷产率、陶瓷显微结构的影响.结果表明:随保温温度的升高,交联体系凝胶含量、陶瓷产率逐渐增大.PMS/DVB配比越小,陶瓷显微结构的缺陷越多.PMS/DVB配比为1/0.2,保温温度为300℃时,陶瓷产率较高,达到80%.XRD分析表明所得陶瓷为β-SiC.     

液态超支化聚碳硅烷的研究进展

液态超支化聚碳硅烷(HBPCS)因具良好的流动性和可自交联性,适用于制备SiC陶瓷基复合材料而倍受青睐。对它的合成、交联、陶瓷化和应用探索等方面的研究动态进行了综述,并展望了其今后的发展趋势。     

超支化聚碳硅烷的掺硼改性与陶瓷化研究

通过二甲基胺硼烷(DMAB)与烯丙基超支化聚碳硅烷(AHPCS)反应合成含硼聚碳硅烷先驱体,后经170℃热交联及高温裂解制备出碳化硅陶瓷。采用傅立叶红外光谱、热重分析、X射线衍射分析及扫描电子显微镜对上述过程进行研究。结果表明,DMAB中的B—H键可分别与AHPCS中的CC键及Si—H键发生硼氢化反应和脱氢偶合反应,从而促进AHPCS的热交联,并显著提高陶瓷产率。此外,硼的引入还可有效抑制β-SiC在高温下的结晶。     

含硼聚碳硅烷的制备及热解行为EI北大核心CSCD

为制备陶瓷产率高、高温性能优良的碳化硅(SiC)陶瓷先驱体,利用频那醇硼烷(PINB)与聚碳硅烷(PCS)的脱氢偶合反应,对聚碳硅烷进行化学改性。改变PINB与PCS的质量比(1∶20、1∶10、1∶5),制备了一系列不同硼(B)含量的含硼聚碳硅烷(PBCS)。通过傅里叶变换红外光谱分析、核磁共振氢谱分析、热重分析以及X射线衍射分析等手段研究了PBCS的组成、结构及热解行为。结果表明,通过B-H键的反应将B元素以PINB骨架形式引入PCS结构;引入B元素可以将PCS的陶瓷产率从78%提高至92%;另外,B元素的引入引起PCS的交联,PBCS的热解过程分3个阶段。同时B元素的引入抑制了SiC晶体的生长,将材料的耐温性能提高至1400℃。     

聚碳硅烷先驱体的交联与陶瓷产率

本文探讨了可提高先驱体陶瓷产率的PCS／DVB交联条件。研究表明聚碳硅烷交联前的性质和状态是影响先驱体陶瓷产率的主要因素。     

含硼聚碳硅烷的制备及热解行为

为制备陶瓷产率高、高温性能优良的碳化硅(SiC)陶瓷先驱体,利用频那醇硼烷(PINB)与聚碳硅烷(PCS)的脱氢偶合反应,对聚碳硅烷进行化学改性。改变PINB与PCS的质量比(1∶20、1∶10、1∶5),制备了一系列不同硼(B)含量的含硼聚碳硅烷(PBCS)。通过傅里叶变换红外光谱分析、核磁共振氢谱分析、热重分析以及X射线衍射分析等手段研究了PBCS的组成、结构及热解行为。结果表明,通过B-H键的反应将B元素以PINB骨架形式引入PCS结构;引入B元素可以将PCS的陶瓷产率从78%提高至92%;另外,B元素的引入引起PCS的交联,PBCS的热解过程分3个阶段。同时B元素的引入抑制了SiC晶体的生长,将材料的耐温性能提高至1400℃。     

添加填料合成SiC（Al）纤维的先驱体聚铝碳硅烷

以聚硅碳硅烷和乙酰丙酮铝为原料,在反应装置的裂解柱中加入填料,在常压下合成了聚铝碳硅烷.结果表明:添加填料使合成聚铝碳硅烷的时间缩短46%,聚铝碳硅烷的从1008增大到2436,分子量的分布变窄,—Si—Si—键的含量低;在N_2气氛中,在400℃以下失重减少,在1200℃陶瓷的产率从65%提高到69%;加入填料可促进—Si—Si—链转化为—Si—C—Si—链,制备出的聚铝碳硅烷纤维在预氧化过程中氧的增重少,预氧化烧成后得到的Si—Al—C—O连续纤维强度为2.1 GPa,在Ar中1800℃烧结可得到致密的SiC(Al)纤维.纤维的结晶行为与不加填料时的类似.     

低氧含量液态超支化聚碳硅烷的合成与陶瓷化研究

以甲醇对氯甲基三氯硅烷(Cl3SiCH2Cl)进行烷氧化反应,然后经过格氏偶联反应和还原反应,制备了低氧含量液态超支化聚碳硅烷(HBPCS)。通过凝胶渗透色谱法(GPC)、核磁共振(NMR)以及元素分析对由此制备的HBPCS进行表征。结果表明,提高烷氧化比例,可以有效抑制溶剂四氢呋喃开环的副反应,降低先驱体氧含量。通过热失重分析(TGA)和X射线衍射(XRD)分别对HBPCS的热性能及相应陶瓷在高温下的结晶行为进行研究。     

活性填料钼在聚碳硅烷转化陶瓷中的应用

研究了活性填料钼(Mo)在聚碳硅烷(PCS)先驱体转化陶瓷中的应用.研究表明,活性填料Mo能有效降低陶瓷素坯的气孔率.Mo可与PCS气态裂解碳氢产物、游离碳和N2气氛反应生成新的化合物,可明显提高PCS的陶瓷产率.当Mo/PCS为25%(vol)时, 坯体的陶瓷产率为100%.Mo还能有效地提高烧成体的强度.     

Preparation of a hyperbranched polycarbosilane precursor to SiC ceramics following an efficient room-temperature cross-linking process

Room-temperature cross-linking of a hyperbranched polycarbosilane (HBPCS) with divinylbenzene (DVB) in the presence of the cyclohexanone peroxide–cobaltous naphthenate (CHP–CN) initiator system was studied. According to the Fourier transform infrared spectroscopy (FT-IR) and ¹H nuclear magnetic resonance (¹H NMR) results, the cross-linking reaction occurred via the vinyl polymerization. The GPC analysis confirmed the molecular weight of the cross-linked HBPCS significantly increased. Thermal behaviors of cross-linked HBPCS and original HBPCS were investigated by thermal gravimetric analysis-differential thermal analysis (TGA–DTA). The TGA results indicated that the ceramic yield of HBPCS remarkably increased by the cross-linking treatment. For the HBPCS/10 wt% DVB system, the maximum of reaction degree of HBPCS was obtained, which might be responsible for the highest ceramic yield of 70.1 wt% at 1000 °C. However, the ceramic yield of the non-crosslinked HBPCS was only 45 wt% at 1000 °C. The evolution of crystal structure of SiC as a function of pyrolysis temperature was traced by means of X-ray diffraction (XRD) and FT-IR. With the pyrolysis temperature increasing, the β-SiC peaks became sharper and the grain size also grew larger. As the DVB content increased, the intensity of β-SiC peaks significantly reduced, indicating smaller β-SiC grain size.     

UV curing behavior of a highly branched polycarbosilane

The UV curing behavior of a highly branched polycarbosilane (HBPCS) was studied by differential scanning photo calorimeter (DPC) measurements. 2-Hydroxy-2-Methyl-Phenyl-Propane-1-one (Photocure-1173) was selected as photoinitiator. In order to accelerate the curing reaction rate of polycarbosilane, acrylic reactive diluent tripropane glycol diacrylate (TPGDA) was also added to the polymer system. The effect of TPGDA content, photoinitiator concentration, temperature, light intensity, and the curing atmosphere was investigated. The results indicated that the TPGDA greatly enhanced the reaction rate of the HBPCS system. The TPGDA content, photoinitiator concentration, temperature, and light intensity had their own optimal values to get the maximum ultimate conversion percentage and the reaction rate. The oxygen atmosphere helped to increase the final conversion percentage though it could retard the reaction rate.     

Production mechanism of polyzirconocarbo- silane using zirconium(IV)acetylacetonate and its conversion of the polymer into inorganic materials

The reaction of polycarbosilane with zirconium(IV)acetylacetonate proceeded at 573 K in nitrogen atmosphere by the condensation reaction of the Si–H bonds in polycarbosilane and the ligands of zirconium(IV)acetylacetonate accompanied by the evolution of acetylacetone, and then the molecular weight increased by the cross-linking reaction with a formation of Si–Zr bond. The obtained polyzirconocarbosilane showed higher ceramic yield than the polycarbosilane. Zirconium contained in the pyrolysed polyzirconocarbosilane was furthermore found to have the effect of inhibiting crystalline grain growth of -type SiC up to high temperature, so Si–Zr–C–O fibre, which was obtained by the use of polyzirconocarbosilane as precursor, showed high tensile strength up to high temperature.     

先驱体转化法制备SiCO陶瓷粉体的氧化性能

以先驱体转化法制备的SiCO陶瓷粉体为原材料,采用热重法研究了粉体在干燥空气中的氧化性能。采用液态聚碳硅烷裂解制备的SiCO 陶瓷粉体平均粒径为7μm,氧化处理温度分别为：900℃、950℃、1000℃、1050℃,氧化时间均为4 h。结果表明：液态聚碳硅烷裂解制备的SiC_{1. 12}O_{0. 12}陶瓷粉体在1173～1373 K、干燥空气中,氧化增重表现为典型的2阶段变化规律：900℃ 下的前80 min至1050℃下的前20 min时间内,材料氧化表现为快速增重趋势;随后较长的氧化时间里,材料内部气孔的氧化由于封孔而停止,氧化反应主要由扩散控制,样品增重不太明显。经计算SiCO陶瓷粉体的氧化活化能为121 kJ/mol,并在此基础上推导了热重法与厚度测量法获得的2种氧化速率常数的转变公式。     

Al作为活性填料对前驱体法复相陶瓷性能的影响

采用微米级Al粉作为活性填料, SiC微粉作为惰性填料, 聚碳硅烷作为陶瓷前驱体制备SiC基复相陶瓷. 研究了热解温度和保温时间对陶瓷产率、线收缩率、力学性能以及微观结构的影响. 研究表明, 由于活性Al粉颗粒在热解过程中与含碳的有机小分子以及反应性气氛发生氮化和碳化反应, 产生体积膨胀效应, 热解陶瓷表现为小收缩、高产率, 可以满足近净尺寸成型的要求. 在1000℃热解保温1h, 线收缩率为0.08%, 陶瓷产率为99.68%, 材料的三点弯曲强度达到293MPa.     

Fabrication and morphological study of converged SiC-TiC fiber mats by electrospinning

Titanium-containing silicon carbide (SiC) fiber mats were fabricated by an electrospinning method followed with a polymer-derived ceramics route. Titanium isopropoxide was used to cross-link into polycarbosilane (PCS) in toluene and xylene contained in the medium. The mat structure, fiber morphology, and crystallization of the fabricated SiC fibrous mat were analyzed by scanning electron microscopy and X-ray diffraction. According to the analysis results, the ceramic yield of the precursor increased significantly because of the high degree of cross-linking in PCS molecular structure.     

活性填料钼在聚碳硅熔转化陶瓷中的应用

研究了活性填料钼（Mo）在聚碳硅烷（PCS）先驱体转化陶瓷中的应用。研究表明,活性填料Mo能有效降低陶瓷素坯的气孔率。Mo可与PCS气态裂解碳氢产物、游离碳和N2气氛反应生成新的化合物,可明显提高PCS的陶瓷产率。当Mo/PCS为25％（vol)时,坯体的陶瓷产率为100％。Mo还有能效地提高烧成体的强度。     

Heterogeneously catalysed crosslinking of polycarbosilane with divinylbenzene

Crosslinking of polycarbosilane (PCS) with divinylbenzene (DVB) is readily accomplished using heterogeneous catalysis with platinum chloride in heptane to provide a silicon carbide precursor that produces a ceramic with significantly reduced oxygen content. The ceramic yield after crosslinking increased from 47% to between 72% and 78%; however, crosslinking may be influenced by dehydrogenative silylation of hydroxyl groups. Solid-state ¹³C NMR spectroscopy of the crosslinked PCS showed peaks assignable to the aromatic group at 144 and 126.7 ppm. Monitoring of the crosslinking reaction by ¹H NMR spectroscopy indicated 40% consumption of the vinyl bonds of DVB within 10 min and complete consumption within 16 h. Infrared spectroscopy showed no increase in the peak at 3,650 cm⁻¹ due to O–H stretching in Si–OH, demonstrating that hydrosilylation crosslinking is a highly effective non-oxidative crosslinking technique. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.