采用原位溶剂热法合成了2种混合有机阳离子杂化甲酸盐(CH(NH_(2))_(2))[RE(HCOO)_(4)](RE=Y、Er)。这2种材料是同构的(手性空间群C222_(1)),并具有有趣的类钙钛矿结构。进行了包括线性和非线性光学特性在内的光物理研究。(CH(NH_(2))_(2...采用原位溶剂热法合成了2种混合有机阳离子杂化甲酸盐(CH(NH_(2))_(2))[RE(HCOO)_(4)](RE=Y、Er)。这2种材料是同构的(手性空间群C222_(1)),并具有有趣的类钙钛矿结构。进行了包括线性和非线性光学特性在内的光物理研究。(CH(NH_(2))_(2))[Y(HCOO)_(4)]和(CH(NH_(2))_(2))[Er(HCOO)_(4)]分别表现出5.59和5.61 e V的宽光学带隙,对应于222和221 nm的紫外吸收边缘。粉末倍频测量表明,(CH(NH_(2))_(2))[Y(HCOO)_(4)]和(CH(NH_(2))_(2))[Er(HCOO)_(4)]的倍频效应分别是基准KH_(2)PO_(4)(KDP)的0.32和0.37倍。测量得到(CH(NH_(2))_(2))[Y(HCOO)_(4)]和(CH(NH_(2))_(2))[Er(HCOO)_(4)]的双折射率分别为0.013和0.015。第一性原理研究表明,2个π共轭的(CH(NH_(2))_(2))^(+)和HCOO^(-)基团是光学性质的主要贡献者。展开更多
The relationships of crystal type, crystallization speed, purity, grain size and shape of rare earth carbonate with precipitation and crystallization conditions are very important for the production of rare earth carb...The relationships of crystal type, crystallization speed, purity, grain size and shape of rare earth carbonate with precipitation and crystallization conditions are very important for the production of rare earth carbonate with high efficiency, high quality and low cost. It is necessary for us for further understand the crystallization process mechanism and the factors effect on the crystallization. In the present paper, the crystallization characteristic, composition and crystal phase type of yttrium carbonates or ammonium yttrium carbonates precipitated from yttrium chloride solution using ammonium bicarbonate as precipitant were determined by chemical analysis, X ray powder diffraction and the pH situ determination. It was found that the crystal phase type was dominated by the feed molar ratio of ammonium bicarbonate to yttrium chloride, and the crystallization speed and the crystal composition were also influenced by temperature, feed manner and aging period etc. When precipitating and aging under lower temperature, crystallization is easy to take place in the high feed molar ratio zone, and when increasing temperature, crystallization will take place both in lower and higher feed molar ratio zones. The results show that spherical yttrium carbonate with tengerite type crystal phase can be formed within the temperature 30～70℃ when feed molar ratio of ammonium bicarbonate to yttrium chloride is less than 4, and that a rhombus flake crystal, which possesses the composition of ammonium yttrium quasi double carbonate and a new XRD pattern, is formed when the feed molar ratio is over 4. Their compositions can be represented as (NH4)aY(CO3)b(OH)c·nH2O, a< 1, 1< b< 2, c=3+a-2b. A fine crystal of ammonium yttrium double carbonate with the formula of (NH4)Y(CO3)2·H2O can also be obtained as using an enough amount of ammonium bicarbonate and aging enough time.展开更多
文摘采用原位溶剂热法合成了2种混合有机阳离子杂化甲酸盐(CH(NH_(2))_(2))[RE(HCOO)_(4)](RE=Y、Er)。这2种材料是同构的(手性空间群C222_(1)),并具有有趣的类钙钛矿结构。进行了包括线性和非线性光学特性在内的光物理研究。(CH(NH_(2))_(2))[Y(HCOO)_(4)]和(CH(NH_(2))_(2))[Er(HCOO)_(4)]分别表现出5.59和5.61 e V的宽光学带隙,对应于222和221 nm的紫外吸收边缘。粉末倍频测量表明,(CH(NH_(2))_(2))[Y(HCOO)_(4)]和(CH(NH_(2))_(2))[Er(HCOO)_(4)]的倍频效应分别是基准KH_(2)PO_(4)(KDP)的0.32和0.37倍。测量得到(CH(NH_(2))_(2))[Y(HCOO)_(4)]和(CH(NH_(2))_(2))[Er(HCOO)_(4)]的双折射率分别为0.013和0.015。第一性原理研究表明,2个π共轭的(CH(NH_(2))_(2))^(+)和HCOO^(-)基团是光学性质的主要贡献者。
文摘The relationships of crystal type, crystallization speed, purity, grain size and shape of rare earth carbonate with precipitation and crystallization conditions are very important for the production of rare earth carbonate with high efficiency, high quality and low cost. It is necessary for us for further understand the crystallization process mechanism and the factors effect on the crystallization. In the present paper, the crystallization characteristic, composition and crystal phase type of yttrium carbonates or ammonium yttrium carbonates precipitated from yttrium chloride solution using ammonium bicarbonate as precipitant were determined by chemical analysis, X ray powder diffraction and the pH situ determination. It was found that the crystal phase type was dominated by the feed molar ratio of ammonium bicarbonate to yttrium chloride, and the crystallization speed and the crystal composition were also influenced by temperature, feed manner and aging period etc. When precipitating and aging under lower temperature, crystallization is easy to take place in the high feed molar ratio zone, and when increasing temperature, crystallization will take place both in lower and higher feed molar ratio zones. The results show that spherical yttrium carbonate with tengerite type crystal phase can be formed within the temperature 30～70℃ when feed molar ratio of ammonium bicarbonate to yttrium chloride is less than 4, and that a rhombus flake crystal, which possesses the composition of ammonium yttrium quasi double carbonate and a new XRD pattern, is formed when the feed molar ratio is over 4. Their compositions can be represented as (NH4)aY(CO3)b(OH)c·nH2O, a< 1, 1< b< 2, c=3+a-2b. A fine crystal of ammonium yttrium double carbonate with the formula of (NH4)Y(CO3)2·H2O can also be obtained as using an enough amount of ammonium bicarbonate and aging enough time.
