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氟硼铍酸钾KBe2 BO3 F2(KBBF)晶体是至今发现可相位匹配的倍频波长最短的晶体之一。采用 TG-DSC热分析技术研究了KBBF的热分解动力学特性,发现其分解为单向非可逆的过程。利用 Doyle 法和 Kissinger法求得了KBBF热分解反应的活化能E和指前因子A分别为440.988 kJ/mol 和1.414×1019 s-1。通过 Coats-Red-fern方程的线性回归处理并结合 Malek法和反应前后的扫描电镜图建立了 KBBF 的热分解动力学方程,研究发现KBBF的热分解动力学过程符合R3机理,即球形对称的三维相界面反应模型。

KBe2 BO3 F2 (KBBF)is currently one of the practical ultraviolet nonlinear optical (NLO)crystals with shortest wave-length which can be phase-matched.The thermal decomposition characteristics of KBBF were studied by TG-DSC thermal analysis,the result showed that the process was an irreversible one-way reaction.The ac-tivation energy E and pre-exponential factor A were calculated by Doyle and Kissinger methods,and the values were 440.988 kJ/mol and 1.414 × 1019 s-1 respectively.According to the results of linear regressions of Coats-Redfern equation,combined with Malek method and SEM images before and after reaction,the differential equation was de-duced.The study showed that the thermal decomposition process of KBBF belonged to spherical symmetric three-di-mensional phase interface reaction (R3 ).

参考文献

[1] Wang JY.;Zhang CQ.;Liu YG.;Zhang JX.;Hu XB.;Jiang MH.;Chen CT.;Wu YC.;Xu ZY..Growth and properties of KBe2BO3F2 crystal[J].Journal of Materials Research,200310(10):2478-2485.
[2] Dingyuan Tang;Younan Xia;Bochuang Wu.Growth of a new UV nonlinear optical crystal: Kbe_2(BO_3)F_2[J].Journal of Crystal Growth,20011/2(1/2):125-129.
[3] 洪海平;林绮;周淑琴;金祥凤.KBBF晶体的热膨胀[J].化学通报,1994(12):51-52,64.
[4] Liu, X.W.;Feng, Y.L.;Li, H.R.;Zhang, P.;Wang, P..Thermal decomposition kinetics of magnesite from thermogravimetric data (Conference Paper)[J].Journal of thermal analysis and calorimetry,20121(1):407-412.
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