SiBNC陶瓷纤维前驱体-聚硅硼氮烷的合成与表征

以四氯化硅、三氯化硼、甲胺为原料,使用共缩聚方法制备了SiBNC陶瓷纤维前驱体聚硅硼氮烷。采用FT-IR、NMR、GC-MS和TG分析等,对聚硅硼氮烷的结构、性能和合成机理进行了表征和分析。研究表明该聚硅硼氮烷前驱体的骨架结构由Si-N-B和B-N六元环结构组成,C则主要以N-CH_3和NH-CH_3结构存在。合成得到的前驱体具有良好的溶解性、耐水解性能和可纺性,在105℃的N_2气氛下,经熔融纺丝可得直径约为25μm的前驱体原丝,在N_2气氛中1 000℃时陶瓷产率为60%。     

聚合物陶瓷先驱体材料的合成与应用

概述了作为陶瓷先驱体的四种聚合物f聚碳硅烷(PCS)、聚硅氮烷(PSZ)、聚硼氮烷(PBZ)以及聚硅氧烷(PSO)]的合成与应用,介绍了国内外对该类材料研究的最新进展,并针对先驱体裂解转化陶瓷工艺所存在的局限性以及不足,提出了今后的发展方向.     

氮化硼纤维先驱体聚合物的合成及其表征

以三氯化硼与氯化铵为基础原料合成了三氯环硼氮烷（TCB）,然后将TCB和三氯化硼分别与甲胺反应制得TCB的衍生物（CH3NH）3N3B3H3和B（NHCH3）3单体,将这些衍生物混合后在一定条件下进行缩合反应得到氮化硼先驱体。从合成方法、反应机理及其产物的结构性能表征等方面研究了氮化硼陶瓷纤维的先驱体,并且用IR、NMR、EA．XRD及DSC等表征方法对先驱体的结构、成分及性能进行了分析。结果表明：先驱体中含有B、C、N、H元素,存在CH3、B-N、N—H、G—H、BN六元环等结构单元。最后,对此先驱体进行了试纺丝,并用扫描电镜观察了所得纤维的形态。     

前驱体法制备Si-C-N-M基高性能陶瓷的研究进展

综述了聚合物前驱体热解转化法制备高性能Si-C-N-M基陶瓷的研究进展，着重介绍了3类Si-C-N-B基陶瓷前驱体（主链或侧基含有环硼氮烷或含硼杂环的聚硼硅氮烷、含硼聚硅氮烷和含硼聚硅基碳化二亚胺）及Si-C-N-Al基陶瓷前驱体。     

陶瓷前驱体聚硅氮烷的制备研究进展

综述了合成Si-C-N陶瓷前体聚硅氮烷的一些方法,着重介绍了含金属聚硅氮烷的制备方法,如:含钛聚硅氮烷、铝基聚硅氮烷、铁基聚硅氮烷、锆基聚硅氮烷、硼基聚硅氮烷、钇基聚硅氮烷、铜基聚硅氮烷的制备方法;其次介绍了使用共聚法、超支化法、倍半硅氮烷水解法制备聚硅氮烷的方法。     

纤维用含硼SiC陶瓷先驱体的研究进展

综述了硅硼碳(SiBC)先驱体、硅硼碳氧(SiBCO)先驱体和硅硼碳氮(SiBCN)先驱体等纤维用含硼碳化硅(SiC)陶瓷先驱体的合成方法,分析了不同陶瓷先驱体的组成、结构和性能,比较了几种合成含硼SiC先驱体方法的优缺点,提出了纤维用含硼SiC陶瓷先驱体的合成新思路。     

SiBCN陶瓷先驱体的制备和应用研究进展

综述了SiBCN陶瓷前驱体制备过程中在硅氮烷上引入硼元素的3种方法(采用环硼氮烷引入硼元素、采用硼氢化反应引入硼元素、采用BCl3引入硼元素);介绍了SiBCN陶瓷前驱体在制备介孔骨架、涂覆碳纳米管、制备无定形涂层上的应用;以及先驱体转化的SiBCN陶瓷的结晶化过程及陶瓷结构分析(无定形SiBCN陶瓷的结晶化过程,不同SiBCN陶瓷前驱体生成的陶瓷结构的对比)。     

SiBN陶瓷纤维的脱碳工艺研究

以三氯化硼、六甲基二硅氮烷、三氯硅烷和甲胺为原料,采用多步法合成、聚合得到可纺性良好的聚硼氮硅烷(PBSZ)前驱体,通过熔融纺丝得到前驱体纤维,再经热化学交联得到不熔化纤维;在氨气/氮气(NH_3/N_2)气氛下进行热解脱碳(C)处理制备了硅硼氮(SiBN)陶瓷纤维;研究了NH_3/N_2体积比、气体流量、升温速率、保温时间以及热解温度等对SiBN纤维中C含量的影响,分析了PBSZ的脱C机理。结果表明:较优的热解工艺是NH_3/N_2体积比为3∶1,升温速率为0.5℃/min,600℃和1 000℃分别保温3 h,气体流量为100 m L/min,可制备C质量分数小于0.1%的Si BN陶瓷纤维;NH3对脱C具有积极作用,在热交联反应、自由基反应和脱氢偶合反应的综合作用下,C主要以甲胺和甲烷的形式脱除。     

聚硼硅氮烷固化氰酸酯基耐高温胶粘剂的制备与性能研究

以氰酸酯为基胶,聚硼硅氮烷前驱体为固化剂,复配相应的填料,制备了氰酸酯基耐高温胶粘剂。研究了聚硼硅氮烷用量对氰酸酯固化特性、固化产物的结构变化及固化物热稳定性的影响。研究结果表明：与传统的氰酸酯胶粘剂相比,聚硼硅氮烷催化氰酸酯的固化温度降低了50～100℃;聚硼硅氮烷可以催化氰酸酯在150℃低温固化,20份聚硼硅氮烷催化氰酸酯固化物T_5%最高达到476.3℃。以此为基础制备的耐高温胶粘剂的室温粘接强度最高为16 MPa,400℃老化3 h后粘接强度仍达到12 MPa,表明该胶粘剂具有较好的粘接性能和耐老化性能。本研究制备的胶粘剂凭借较低的固化温度、良好的粘接性能和耐温性,有望用于航空、航天和电子等行业。     

氮化硼的制备及其性能表征

以三氯化硼和氯化铵为原料,在110℃合成三氯环硼氮烷(TCB),将合成的TCB与异丙胺在0℃左右进行胺解反应,将胺解产物在120℃聚合,得到聚硼氮烷高聚物,聚硼氮烷经1 000℃氮化得到氮化硼(BN),对BN的热性能及晶体结构等进行表征。结果表明:通过红外光谱和X射线衍射分析,聚合产物为聚硼氮烷,经1 000℃氮化后,形成BN晶体,晶体结构为斜方晶系;氮化过程存在部分游离碳(C),BN晶体中含有B,N,C元素;聚硼氮烷可溶于二甲基亚砜和N,N-二甲基甲酰胺,可以进行湿法纺丝。     

含硅西佛碱的合成

介绍了含硅西佛碱的合成，制备了8种含硅西佛碱。用^1H—NMR、^13C—NMR对合成的化合物进行表征。目标分子为Ph—CH=NCH2CH2CH2Si(OCH2CH3)3；Ph—CH=NCH2CH2NHCH2CH2CH2Si(OCH2CH3)3；o-HO-Ph—CH—NCH2CH2CH2Si(OCH2CH3)3；o-HO-Ph—CH=NCH2CH2NHCH2CH2CH2Si(OCH2CH3)3；2，4-Cl-Ph—CH=NCH2CH2CH2Si(OCH2CH3)3；2，4-Cl-Ph-CH=NCH2CH2NHCH2CH2CH2Si(OCH2CH3)3；p-NO2-Ph-CH=NCH2CH2CH2Si(OCH2CH3)3；P-NO2-Ph-CH=NCH2CH2NHCH2CH2CH2Si(OCH2CH3)3。     

Preceramic polymer for Si?B?N?C fiber via one‐step condensation of silane,BCl3, and silazane

A preceramic polymer for Si? B? N? C fiber, polyborosilazane, has been synthesized by one‐step condensation reaction of dichloromethylsilane, BCl₃, and hexamethyldisilazane with high yield. The reaction mainly involves the condensation of Si? Cl and B? Cl with N? SiMe₃ followed by SiMe₃Cl evaporation and dehydrogenation between N? H and Si? H. The resulted polymer is a soluble colorless transparent solid with melting point of 70°C and molecular weight of 10,800. The backbone of the polymer is mainly composed of ? Si? N? B‐bridge with some borazine rings. The polymer exhibits good processability and flexible polymer fibers with diameter of 15–20 μm were obtained by melt spinning. Pyrolysis of the as‐synthesized polymer to 1000°C under nitrogen atmosphere results in a ceramic yield of 63 wt %, and the obtained Si? B? N? C ceramic remains fully amorphous up to 1700°C, and only small amount of poorly crystallized BN, Si₃N₄, and SiC phases were observed upon heating at 1850°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of Precursor on Speciation and Nanostructure of SiBCN Polymer‐Derived Ceramics

A comparative structural study of silicon borocarbonitride polymer‐derived ceramics synthesized using polyborosilylcarbodiimide and polyborosilazane precursors is carried out using high‐resolution, multinuclear, one‐ and two‐ dimensional NMR spectroscopy. The polyborosilylcarbodiimide‐derived ceramics contain relatively pure Si₃N₄ and C nanodomains with the BN domains being present predominantly at the interface such that the bonding at the interface consists of Si–N–B, Si–N–C, and B–N–C linkages. In contrast, the structure of the polyborosilazane‐derived ceramics consists of significant amount of mixed bonding in the nearest‐neighbor coordination environments of Si and B atoms leading to the formation of SiC_xN_4?x (0 ≤ x ≤ 4) tetrahedral units and BCN₂ triangular units. The interfacial region between the SiCN and C nanodomains is occupied by the BCN phase. These results demonstrate that the chemistry of the polymeric precursors exerts major influence on the microstructure and bonding in their derived ceramics even when the final chemical compositions of the latter are similar.     

醋酸纤维素的制备及其可纺性研究

以实验室自制的三醋酸纤维素(CTA)为原料,研究其最佳水解条件及水解产物二醋酸纤维素(CDA)的可纺性能。结果表明:60℃下水解时间为4 h,H_2O与CTA的质量比为5∶1,催化剂H_2SO_4的质量分数为CTA的12%,可得到取代度为2.60的CDA。水解产物CDA经湿法纺丝后得到的纤维的干态断裂强度为1.45 c N/dtex,优于目前国内市售的CDA纤维。用FTIR、XRD、TG、SEM对CDA及其纤维进行分析表征,结果显示:CDA经水解和纺丝后结晶度会下降,CDA热分解温度低于CTA和纤维素;SEM照片显示CDA纤维表面有少许沟槽,断面呈圆形结构。     

Stereocomplex formation between enantiomeric poly(lactic acid). VIII. Complex fibers spun from mixed solution of poly(D-lactic acid) and poly(L-lactic acid)

To obtain poly(lactic acid) (PLA) complex fibers, spinning was performed by wet and dry methods from 5–10 g/dL chloroform solutions of poly(D-lactic acid) (PDLA) and poly(L-lactic), both with a viscosity-average molecular weight of 3 × 10⁵. The dope was extruded from a monohole nozzle into coagulation baths from ethanol and chloroform for wet spinning and into a drying column kept at 60°C for dry spinning. Scanning electron microscopic observation of the as-spun fibers showed that the surface of the wet-spun fiber had large basins with diameters of 50–100 μm and many pores with diameters from sub μm to 10 μm, whereas the surface of dry-spun fiber had a microporous structure with the pore diameter of 1–3 μm. The tensile strength of the wet-spun complex fiber was very low and could not be drawn at high temperatures, in contrast to the dry-spun fiber. The tensile strength of dry-spun complex fiber increased upon hot drawing and showed the tensile strength of 94 kg/mm² by drawing at 160°C to the draw ratio of 13. Differential scanning calorimetry revealed that the complex fibers contained both the stereocomplex crystallites (racemic crystallites) and the crystallites of the single polymers, PDLA and PLLA, regardless of the spinning methods. The ratio of the racemic crystallites to the single-polymer crystallites increased with the draw ratio of the complex fiber. © 1994 John Wiley & Sons, Inc.     

液态聚硼硅氮烷的陶瓷化过程

采用Fourier红外光谱、热重–差热以及X射线衍射分析对新型液态SiBNC先驱体进行了结构表征,重点研究了先驱体的陶瓷化过程。结果表明：先驱体以—CH3和—CH=CH2为侧链基团,含有C—H、C=C、Si—H、B—N、N—H、Si—N等化学键;N2气氛保护下的陶瓷产率约为85%,质量损失主要发生在300～800℃;随着温度的升高,聚合物中有机基团逐渐减少,900℃完成无机化转变,得到含有自由碳的非晶态SiBNC陶瓷,1200℃以上非晶态SiBNC陶瓷开始晶化,1500℃得到由C、SiC、Si3N4和BN组成的复相陶瓷。     

纺丝温度对PET/PTT纤维结构与性能的影响

采用质量比为50/50的PET/PTT进行复合纺丝,纺丝速度2 300 m/min,经拉伸1.56倍,生产166dtex/72 f PET/PTT复合纤维,探讨了纺丝温度对PET/PTT复合纤维结构与性能的影响。结果表明:纺丝温度低时,PET/PTT纤维特性黏数高,纤维截面趋向于花生形;纺丝温度高时,纤维特性黏数低,纤维截面呈圆形;选择纺丝温度约275℃时,PET/PTT复合纤维具有良好的力学性能和卷曲性能,卷曲收缩率达39.6%。     

Synthesis and pyrolysis mechanism of a novel polymeric precursor for SiBN ternary ceramic fibers

A novel polymeric precursor polyborosilazane (PBSZ) for SiBN ternary ceramic fibers was successfully synthesized from trichlorosilane (HSiCl₃), boron trichloride (BCl₃) and hexamethyldisilazane (HDMZ) by a simple one step reaction process. The chemical structures and ceramic yield of the PBSZ precursors were investigated by NMR spectroscopy, FT-IR and TGA. The preparation of PBSZ fibers was conducted in a lab-scale melt-spinning equipment at a spinning speed of 130 m/min. SiBN ternary ceramic fibers were obtained after the non-fusible treatment and pyrolysis of PBSZ fibers in an NH₃ atmosphere. The pyrolysis mechanism, high-temperature behavior and morphologies of the SiBN ternary ceramic fibers were investigated by NMR, XRD, TEM and SEM. The obtained SiBN ternary ceramic fibers had good flexibility, and possessed a tensile strength of 0.84 GPa with a diameter of ∼18 μm. Furthermore, these SiBN ceramic fibers exhibited excellent thermal stability, and maintained the amorphous state up to 1600 °C.     

提高1.33dtex缝纫线型涤纶短纤维强、伸度探讨

通过正交实验分析了纺速、拉伸倍率、DF3出口处丝束温度对1.33dtex×38mm缝纫型短纤维强、伸度的影响,结果证明:对成品纤维强度的影响依次为拉伸倍率、纺速、DF3出口温度;对断裂伸长率的影响依次为拉伸倍率、纺速、DF3出口温度。在实际生产中,选用纺速1300m/min、拉伸倍率3.7、DF3出口温度190℃左右的生产工艺,可生产出断裂强度为6.20cN/dtex、断裂伸长率为23%±4%的合格产品。     

扁平纤维纺丝成形研究 Ⅱ.扁平PET纤维喷丝板的设计及产品开发

根据扁平纤维纺丝成形的理论数学模型进行了喷丝板的优化设计,开发了线密度为2.2 dtex,纤维截面长宽比为7.5~8.0的PET扁平纤维。结果表明,选择喷丝板微孔长宽比为14较为合理,调节纺丝温度为286℃,降低环吹风速度为1.1 m/s,环吹风温度26℃,纺丝速度1 000 m/min,纺得的PET扁平纤维的平均长宽比为7.738,断裂强度为4.83 cN/dtex,断裂伸长率为33.6%,各项质量指标达到了预定的要求,纤维截面均匀,手感丰满。