SYNTHESIS OF ORGANOMETALLIC PRECURSORS FOR Si/Zr/C/N-BASED CERAMICS

A new kind of organometallic precursor for Si/Zr/C/N-based ceramics was synthesized from the amine exchangereaction of hexamethylcyclotrisilazane (D_3~N) and tetrakis(diethylamino) zirconium (Zr[NEt_2]_4). Pyrolysis was performedunder nitrogen at 800℃ in a tube furnace equipped with a temperature program controller. The highest pyrolytic yield was67.5%.

A New Method to Synthesize Polytitanosilazane as Ceramic Precursor

A new kind of polytitanosilazane precursor PTSZ for Si/C/N/Ti-based ceramic was synthesized from the condensation reaction of silazane lithium salt and titanium tetrachloride (TiCl4). The results indicated that the ceramic yield of PTSZ was much higher than that of corresponding silazane oligomer.

Synthesis of Nd∶GGG Ultrafine Polycrystalline Powders by Sol-Gel Method

Nd∶GGG ultrafine polycrystalline powders for transparent ceramics precursor powder were synthesized by sol-gel method, and sol-gel transformation mechanics was discussed. Nd∶GGG polycrystalline material was analyzed by XRD, SEM and fluorescence spectrum. XRD analysis shows that Nd∶GGG polycrystalline phase is formed at 1000 ℃, and the grain size increases with rising sintering temperature by SEM, and the particle size is about 100 nm. They are used as transparent ceramics precursor powder. Fluorescence spectrum test shows that the strongest fluorescence emission peak is 1061.45 nm for the Nd∶GGG polycrystalline precursor powder, which is the fluorescence-emission of Nd 3+ 4F_ 3/2—4I_ 11/2.

One-pot synthesis and characterization of a new, branched polycarbosilane bearing allyl groups

A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlorosilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials. The resultant polymer, with the approximate formula [SiH1.2(CH3)0.71(CH2CHCH2)0.09CH2]n, has been characterized by 1H, 13C, and 29Si NMR, GPC, TG and elemental analysis. It could be cross-linked thermally at 170 °C in the absence of oxygen. Pyrolysis of the polymer gave a ceramic with a yield of about 70%.

Initial nucleation of amorphous Si–B–C–N ceramics derived from polymer-precursors

Nucleation behavior of amorphous Si–B–C–N ceramics derived from boron-modified polyvinylsilazane procusors was systematically investigated by transmission electron microscopy(TEM) combined with spatially-resolved electron energy-loss spectroscopy(EELS) analysis. The ceramics were pyrolyzed at1000℃ followed by further annealing in N2, and SiC nano-crystallites start to emerge at 1200℃ and dominate at 1500℃. Observed by high-angle annular dark-field imaging, bright and dark clusters were revealed as universal nano-structured features in ceramic matrices before and after nucleation, and the growth of cluster size saturated before reaching 5 nm at 1400℃. EELS analysis demonstrated the gradual development of bonding structures successively into SiC, graphetic BNCxand Si3N4 phases, as well as a constant presence of unexpected oxygen in the matrices. Furthermore, EELS profiling revealed the bright SiC clusters and less bright Si3N4-like clusters at 1200–1400℃. Since the amorphous matrix has already phase separated into SiCN and carbon clusters, another phase separation of SiCN into SiC and Si3N4-like clusters might occur by annealing to accompany their nucleation and growth, albeit one crystallized and another remained in amorphous structure. Hinderance of the cluster growth and further crystallization was owing to the formation of BNCxlayers that developed between SiC and Si3N4-like clusters as well as from the excessive oxygen to form the stable SiO2.

A Novel Method to Synthesize Polyorganozircosilazane

A new kind of polyorganozircosilazane as Si/Zr/C/N-based ceramic precursor was synthesized from the condensation reaction of hexamethylcyclotrisilazane lithium salts (D3NLi) and zirconium tetrachloride (ZrCl4). In the presence of N, N, N, N-tetramethyl ethylene diamine (TMEDA), polyorganozircosilazane was obtained in high yield.

Preparation and Characterization of Polyborosiloxanes and Their Blends with Phenolic Resin as Shapeable Ceramic Precursors

Two polyborosiloxanes （PBSis） with char yield up to 74.13% at 800 ℃ were synthesized by the direct polycondensation of boric acid with phenyltrimethoxysilane in diglyme. The PBSis were characterized by gel permeation chromatography, IR spectroscopy as well as ^1H-, ^29Si- and ^11B-NMR. PBSi modified phenol-formaldehyde resins （PBSi/PFs） were prepared at different PBSi/PF mass ratios and were cured at 150 ℃. The PBSi/PFs were characterized by IR spectroscopy, scanning electron microscopy, thermogravimetric analysis and tensile test. The results revealed that the cured PBSi/PFs had sea-island morphology and higher char yield than the common PF. PBSi/PF blend with PBSi/PF mass ratio of 0.4：1 had char yield up to 70.83% at 800 ℃. The PBSi/PFs had tensile strength similar to PF. The ceramization of PBSi/PFs was also studied. The silicon boron oxycarbide （SiBOC） ceramics formed were characterized by IR spectroscopy and elemental analysis. This method provided a valuable way to prepare easily shapeable polymer blends as ceramic precursors.