孙祥斌,张楠,窦焰,方羊,郑之银,刘荣,崔鹏

• 1:合肥工业大学化学与化工学院
• 2:安徽六国化工股份有限公司

摘要(Abstract)：

以CaSO_4·2H_2O为原料,柠檬酸铵(C_6H_(17)N_3O_7)为添加剂,在水热温度130℃,搅拌速率60r·min~(-1),反应2h的条件下制备α-CaSO_4·0.5H_2O。采用X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、场发射透射电子显微镜(TEM)、热重分析仪(TG)、差热示差扫描量热仪(DSC)、傅里叶红外光谱仪(FT-IR)和X射线光电子能谱测定元素结合能(XPS)表征α-CaSO_4·0.5H_2O晶体的形貌和结构,探讨不同浓度C_6H_(17)N_3O_7对α-CaSO_4·0.5H_2O的晶体和结晶过程的影响。研究结果表明,C_6H_(17)N_3O_7会抑制α-CaSO_4·0.5H_2O沿c轴的生长,随着添加C_6H_(17)N_3O_7浓度的增大,α-CaSO_4·0.5H_2O的形貌由针状向柱状转变,晶体的直径由1.5～2μm增至10～12μm,长径比由80:1～100:1降至2:1～3:1。并且在CaSO_4·2H_2O向α-CaSO_4·0.5H_2O转化过程中,C_6H_(17)N_3O_7的添加导致其诱导时间和转化周期延长,生长速率减慢,晶体的热稳定性提高。

关键词(KeyWords)： 柠檬酸铵;晶型控制剂;半水硫酸钙;结晶

Abstract:

Keywords:

基金项目(Foundation): 安徽省创新环境建设专项资助项目(1606a1003040)

作者(Author): 孙祥斌,张楠,窦焰,方羊,郑之银,刘荣,崔鹏

参考文献(References)：

• [1]JIA C Y,CHEN Q S,ZHOU X,et al.Trace NaCl and Na2EDTA mediated synthesis ofα-calcium sulfate hemihydrate in glycerol-water solution[J].Industrial&Engineering Chemistry Research,2016,55(34):9189-9194.
• [2]DOADRIO J C,ARCOS DCABANAS M V,VALLET R M,et al.Calcium sulphate-based cements containing cephalexin[J].Biomaterials,2004,25(13):2629-2635.
• [3]WANG P,LEE E J,PARK C S,et al.Calcium sulfate hemihydrate powders with a controlled morphology for use as bone cement[J].Journal of the American Ceramic Society,2008,91(6):2039-2042.
• [4]KONG B,GUAN B H,YANG L C,et al.Influence of seed crystal and modifier on the morphology ofα-calcium sulfate hemihydrate prepared by salt solution method in pilot scale[J].Advanced Materials Research,2010,16(70):8-12.
• [5]GUAN B H,JIANG G M,FU H L,et al.Thermodynamic preparation window of alpha calcium sulfate hemihydrate from calcium sulfate dihydrate in non-electrolyte glycerol-water solution under mild conditions[J].Industrial&Engineering Chemistry Research,2011,50(23):13561-13567.
• [6]FU H L,GUAN B H,JIANG G M,et al.Effect of supersaturation on competitive nucleation of caso4 phases in a concentrated cacl2solution[J].Crystal Growth&Design,2017,12(3):1388-1394.
• [7]GUAN B H,SHEN Z X,WU Z B,et al.Effect of pH on the preparation ofα-calcium sulfate hemihydrate from FGD gypsum with the hydrothermal method[J].Journal of the American Ceramic Society,2008,91(12):383-3840.
• [8]CHEN Q S,JIA C Y,LI Y,et al.α-calcium sulfate hemihydrate nanorods synthesis:a method for nanoparticle preparation by mesocrystallization[J].Langmuir,2017,33(9):2362-2369.
• [9]TANG Y B,GAO J M.Investigation of the effects of sodium dicarboxylates on the crystal habit of calcium sulfateα-hemihydrate[J].Langmuir,2017.33(38):9637-9644.
• [10]CHEN Q S,JIANG G M,JIA C Y,et al.A facile method to control the structure and morphology ofα-calcium sulfate hemihydrate[J].Crystengcomm,2015,17(44):8549-8554.
• [11]BOSBACH D,JR M F H.Gypsum growth in the presence of growth inhibitors:a scanning force microscopy study[J].Chemical Geology,1996,132(4):227-236.
• [12]MISRA D N.Interaction of citric acid with hydroxyapatite:surface exchange of ions and precipitation of calcium citrate[J].Journal of Dental Research,1996,75(6):1418-25.
• [13]PHILLIPS B L,LEE Y J,REEDER R J,et al.Organic coprecipitates with calcite:NMR spectroscopic evidence[J].Environmental Science&Technology,2005,39(12):4533-4539.
• [14]LANZóN M,GARCíA-RUIZ P A.Effect of citric acid on setting inhibition and mechanical properties of gypsum building plasters[J].Construction&Building Materials,2012,28(1):506-511.
• [15]SAHA A,LEE J,PANCERA S M,et al.New insights into the transformation of calcium sulfate hemihydrate to gypsum using time-resolved cryogenic transmission electron microscopy[J].Langmuir,2012,28(30):11182-11187.
• [16]CHEN H Y,WANG J,HOU S C,et al.Influence of NH4Cl on hydrothermal formation ofα-CaSO4·0.5H2O whiskers[J].Journal of Nanomaterials,2015,16(1):99-105.
• [17]田萍,宁朋歌,曹宏斌,等.二水硫酸钙在铵盐溶液中溶解度测定及热力学计算[J].过程工程学报,2012,12(4):625-630.TIAN P,NING P G,CAO H B,et al.Solubility measurement of calcium sulfate dihydrate in NH4Cl-(NH4)2SO4 solutions and thermodynamic calculation[J].The Chinese Journal of Process Engineering,2012,12(4):625-630.
• [18]HOU S C,WANG J,XUE T Y,et al.Supersaturation-induced hydrothermal formation ofα-CaSO4·0.5H2O whiskers[J].Crystengcomm,2015,17(10):2141-2146.
• [19]FELDMANN T,DEMOPOULOS G P.Influence of impurities on crystallization kinetics of calcium sulfate dihydrate and hemihydrate in strong hcl-cacl2 solutions[J].Industrial&Engineering Chemistry Research,2013,52(19):6540-6549.
• [20]JIANG G M,CHEN Q S,JIA C Y,et al.Controlled synthesis of monodisperseα-calcium sulfate hemihydrate nanoellipsoids with a porous structure[J].Physical Chemistry Chemical Physics,2015,17(17):11509-11515.
• [21]ZHAO W P,WU Y M,XU J,et al.Effect of ethylene glycol on hydrothermal formation of calcium sulfate hemihydrate whiskers with high aspect ratios[J].Rsc Advances,2015,5(62):50544-50548.
• [22]MAO J W,JIANG G M,CHEN Q S,et al.Influences of citric acid on the metastability ofα-calcium sulfate hemihydrate in CaCl2solution[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2014,443:265-271.
• [23]姚连增.晶体生长基础[M].合肥:中国科学技术大学出版社,1995.YAO L Z.Crystal growth basis[M].Hefei:University of Science and Technology of China Press,1995.