氮化硼的细粉和泡沫已经由分子前体制备,用作甲烷催化转化中的贵金属载体。已经测试了源自硼嗪的不同前体。使用衍生自三氯硼嗪(TCB)的前体获得最佳结果,该前体在室温下与氨反应,然后加热到1800°C,生成比表面积大于300 m 2 g -1的BN粉和微米级球形纹理。在相似的条件下使用聚硼氮烯获得了可比的结果。氨基硼嗪衍生的前体不能产生如此高的比表面积陶瓷,但BN的微观结构类似于具有结晶表皮和无定形内部的泡沫。这些差异与前体转化为BN的化学机理有关。聚卤代哌嗪和聚硼嗪通过气固反应生成BN,而氨基硼嗪聚合物可保持蜡状直至高温,这有利于玻璃状泡沫。由BN载体和铂组成的催化剂已通过两种途径制备:从前体的混合物中或通过BN粉末的浸渍导致不同的催化剂。
Porous boron nitride supports obtained from molecular precursors.
摘要:
Boron nitride (BN) porous samples have been prepared in order to be used as noble metal catalyst support from various molecular precursors, using classical thermal methods to expand and preceramise the precursors. Three types of precursors have been tested: ammonia borane, polyborazylene and several aminoborazines and derived polymers. Using trimethylamino borazine (MAB) and MAB polymers, the surface of the foams was shown to be decreasing when the polymerisation advancement of the precursor increased meanwhile the crystallisation of the samples decreased. All the samples issued from MAB presented the same SEM morphology: large pores with a glassy skin surface covering a disorganised inner part, hidden under the thin homogeneous BN skin, which appeared through the sample breaks. This was related to the melting property of MAB polymers which imbedded the internal part of the sample and avoided its expansion. Attempts were made, using the bulkier amino group as anilino- and benzylaminoborazine to enhance the porosity of the samples using a precursor with a lower ceramic yield. The change in the specific area was not important. However, a surface of 30 m(2) g(-1) was currently obtained. The ability of the precursor to lead to high specific area seemed to be correlated to the expansion possibilities of the precursor in the solid state prior to fusion. Foams exhibiting a surface of more than 50 m(2) g(-1) have been obtained when polyborazylene based precursor was pyrolysed. (C) 2002 Elsevier Science B.V. All rights reserved.
Structural and Mechanical Behavior of Boron Nitride Fibers Derived from Poly[(Methylamino)Borazine] Precursors: Optimization of the Curing and Pyrolysis Procedures
作者:Pascaline Toutois、Philippe Miele、Sylvain Jacques、David Cornu、Samuel Bernard
DOI:10.1111/j.1551-2916.2005.00685.x
日期:2006.1
A series of boron nitride fibers were prepared by varying the tension applied on a same lot of poly(methylamino)borazine fibers during their pyrolytic conversion at 1800°C. Their microstructure/microtexture was studied by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy investigations. Such analyses showed that ceramic fibers presented good crystallinity, but crystallites oriented along the fiber axis with fiber stress. It is most interesting that stretching was essentially effective during the pyrolysis to 1000°C, preventing fiber crimping, and decreasing the fiber diameter. Therefore, the fiber strength increased, while the fiber modulus also increased because of an improvement of the basal layer orientation along the fiber axis.
Zirconiumdiboride was synthesized by pyrolysis of a novel polymeric precursor. Phase compositions and microstructures of the formed ceramic were characterized. It was found that a precursor with B/Zr molar ratio of 2 can completely transform into zirconiumdiboride by heating in an inert atmosphere with temperatures above 1500 degrees C. However, the initial formation temperature of zirconium diboride
dBoron nitride thin fibres have been obtained using the melt drawn technique from a new molecular precursor prepared by reacting borazine (HBNH)(3) with trimethylamino-borazine (CH3NHBNH)(3), (MAB). Borazine reacted very slowly with MAB at room temperature but this reaction was very enhanced when heated. Polymers have been prepared with different borazine/MAB ratio and. several reaction temperatures and times. According to the precursor properties required for the melt drawing technique, the best results were obtained with copolymer prepared with a borazine/MAB molar ratio of 90/10 heated at 75 degreesC for 36 h. Its glass transition was 22.5 degreesC and no decomposition occurred up to 100 degreesC. The ceramic yield was 78%, however the ceramisation, even under an ammonia atmosphere, was very slow up to 300 degreesC. Using a spinning machine, a mother fibre was easily extruded at 85 degreesC under a 40 daN pressure with a diameter of about 200 pin but its mechanical properties were too low to allow stretching of this crude fibre to lower its diameter down to 20 mum without a lot of breaks. After a chemical and thermal treatment up to 1800 degreesC, samples of BN fibres have been obtained. If the diameter from the crude fibres was thin enough, short samples of a thin ceramic BN fibre have been obtained, but if the diameter of the crude fibre was to important, the ceramisation yield to catastrophic defects on the surface of the fibre. Theses results were related to the low glass transition of the copolymer and to the poor reactivity of the crude fibre during the preceramisation treatment as showed by TGA. (C) 2002 Elsevier Science B.V. All rights reserved.