In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skel...In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.展开更多
采用热力学和动力学方法研究了轴承钢GCr15凝固过程中溶质元素偏析、钛夹杂析出规律及影响钛夹杂长大的因素。研究表明:1)GCr15钢在凝固过程中Ti(C_(x)N_(1-x))先于TiN在凝固前沿的固液两相区析出,降低钢液初始Ti、N含量均能推迟Ti(C_(x...采用热力学和动力学方法研究了轴承钢GCr15凝固过程中溶质元素偏析、钛夹杂析出规律及影响钛夹杂长大的因素。研究表明:1)GCr15钢在凝固过程中Ti(C_(x)N_(1-x))先于TiN在凝固前沿的固液两相区析出,降低钢液初始Ti、N含量均能推迟Ti(C_(x)N_(1-x))在凝固前沿的析出。Ti(C_(x)N_(1-x))夹杂中的x值随w(Ti)_(0)下降而下降,但随w(N)_(0)下降而升高。2)凝固冷却速率对GCr15钢中Ti、N元素的凝固偏析影响不大,但对钛夹杂的长大影响显著。随着钢液初始Ti、N含量下降,钛夹杂凝固析出推迟,尺寸变小。采用70 t EAF→EBT→LF→RH→IC(模铸)工艺生产轴承钢GCr15大钢锭,从30 t GCr15钢锭经热锻/轧成的Ф75 mm圆棒上取样,w(T.O)、w(Ti)和w(N)分别为0.0007%、0.0010%、0.0019%。光学显微镜下检测到的钛夹杂是呈土红色的碳氮化钛夹杂;扫描电镜下观察到钢中钛夹杂形状不规则,钛夹杂最大尺寸17.4μm,平均尺寸为9.2μm,这与大吨位模铸锭冷却速率小有关。对大钢锭模铸而言,严格控制各工序钢水增Ti量和增N量,降低钢液中Ti、N含量,推迟钛夹杂在凝固过程中的析出是控制盾构机主轴承圆柱滚子用轴承钢GCr15产品钛夹杂尺寸的有效措施。展开更多
基金supported by Japan Society for the Promotion of Science(JSPS),a Grant-in-Aid for Scientific Research(B)(JP23K23398)(for M.G.)and(JP24K01570)(for K.T.).
文摘In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.
文摘采用热力学和动力学方法研究了轴承钢GCr15凝固过程中溶质元素偏析、钛夹杂析出规律及影响钛夹杂长大的因素。研究表明:1)GCr15钢在凝固过程中Ti(C_(x)N_(1-x))先于TiN在凝固前沿的固液两相区析出,降低钢液初始Ti、N含量均能推迟Ti(C_(x)N_(1-x))在凝固前沿的析出。Ti(C_(x)N_(1-x))夹杂中的x值随w(Ti)_(0)下降而下降,但随w(N)_(0)下降而升高。2)凝固冷却速率对GCr15钢中Ti、N元素的凝固偏析影响不大,但对钛夹杂的长大影响显著。随着钢液初始Ti、N含量下降,钛夹杂凝固析出推迟,尺寸变小。采用70 t EAF→EBT→LF→RH→IC(模铸)工艺生产轴承钢GCr15大钢锭,从30 t GCr15钢锭经热锻/轧成的Ф75 mm圆棒上取样,w(T.O)、w(Ti)和w(N)分别为0.0007%、0.0010%、0.0019%。光学显微镜下检测到的钛夹杂是呈土红色的碳氮化钛夹杂;扫描电镜下观察到钢中钛夹杂形状不规则,钛夹杂最大尺寸17.4μm,平均尺寸为9.2μm,这与大吨位模铸锭冷却速率小有关。对大钢锭模铸而言,严格控制各工序钢水增Ti量和增N量,降低钢液中Ti、N含量,推迟钛夹杂在凝固过程中的析出是控制盾构机主轴承圆柱滚子用轴承钢GCr15产品钛夹杂尺寸的有效措施。
