ORGANOMETALLIC SOL-GEL CHEMISTRY OF METAL SULFIDES
ORGANOMETALLIC SOL-GEL CHEMISTRY OF METAL SULFIDES
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DOI：
10.1016/0022-3093(90)90095-4
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发表时间：
1990-05-01
影响因子：
3.5
通讯作者：
PANTANO, CG
中科院分区：
文献类型：
--
作者：
GUITON, TA;CZEKAJ, CL;PANTANO, CG
本文综述了与金属硫化物溶胶/凝胶加工相关的有机金属化学。它重点关注 ZnS 的合成，其中评估了不同类别前体的溶解/凝胶行为。这些涉及硫醇锌/硫醇化合物前体与硫化氢或有机多硫化物的反应。仅确定了两个产生聚合物残留物或凝胶的反应。其中一种使用五聚体物质 - [EtZn(SBut)]5 - 在与受控数量的 H2S 反应后产生无定形纤维状 ZnS 残留物。随后在流动的 H2S 下对该残留物进行热处理，形成 β-ZnS 粉末和 α-ZnS 单晶须的混合物。另一种表现出溶胶/凝胶行为的反应使用多硫化物 - (BzS)2S - 将硫传递到 Et2Zn 前体。在这种情况下，形成了透明的高粘度溶液。该溶液胶凝并干燥形成呈现玻璃化转变的无定形固体。在较高温度下，生成细晶粒的ZnS。这种化学物质是否可以用于陶瓷的溶胶/凝胶加工仍有待确定；即，残余物的净成型，然后在 H2S 中固结/转化以产生 ZnS 陶瓷，或者在五聚体反应的情况下，产生 ZnS 晶须增强的 ZnS 复合材料。
This paper reviews organometallic chemistry relevant to the sol/gel processing of metal sulfides. It focuses on the synthesis of ZnS wherein different classes of precursors were evaluated for their solution/gelation behavior. These involved the reaction of Zn-thiolate/mercaptide compound precursors with hydrogen sulfide or organo-polysulfides. Only two reactions were identified where polymeric residues or gels were created. One of these used a pentamer species — [EtZn(SBut)]5— which yielded an amorphous, fibrous ZnS residue after reaction with controlled quantities of H2S. A subsequent heat-treatment of this residue under flowing H2S created a mixture of β-ZnS powder and α-ZnS single crystal whiskers. The other reaction exhibiting sol/gel behavior used a polysulfide — (BzS)2S — to deliver sulfur to the Et2Zn precursor. In this case, a clear high viscosity solution was created. This solution gelled and dried to form an amorphous solid which exhibited a glass transition. At higher temperature, a fine-grained ZnS was generated. It remains to be determined whether this chemistry can be used for sol/gel processing of ceramics; i.e., net-shaping of the residue, and then consolidation/transformation in H2S to create a ZnS ceramic, or in the case of the pentamer reaction, a ZnS whisker-reinforced ZnS composite.