制备方法与Ce3+对二水硫酸钙晶须形貌的影响

摘要/Abstract

摘要： 本文以稀土石膏为原材料研究了制备方法对硫酸钙晶须(CSW)形貌和结构的影响,并以二水硫酸钙(分析纯)为原材料,CeCl₃·7H₂O为铈源,探究稀土铈的加入对CSW的结构和形貌的影响。利用SEM、XRD、XPS和FL等表征手段对CSW的结构、形貌和组成及其荧光性能等进行表征和分析。研究结果表明:采用微波法可以制备高长径比的CSW,其平均长度为263 μm,平均长径比为39.50。Ce³⁺以原子置换的形式进入CSW,对晶须的晶体结构不产生影响,但改善了CSW的形貌。添加2%(质量分数)的Ce³⁺能够促进晶须向一维生长,使得CSW的长径比显著增加,而过量的Ce³⁺会促使晶须横向生长。研究证明稀土石膏中含有微量的稀土元素Ce,同时发现由稀土石膏制备的CSW具有发射蓝光的特性,这对开发利用稀土石膏具有重要的理论指导意义。

关键词: 稀土铈, 稀土石膏, 硫酸钙晶须, 微波法, 长径比, 荧光性能

Abstract: The calcium sulfate dihydrate whiskers (CSW) were prepared using rare earth gypsum as raw material, and the effects of preparation methods on the morphology and structure of CSW were studied. The effect of rare earth cerium on the structure and morphology of CSW was investigated using pure calcium sulfate dihydrate as raw material and CeCl₃·7H₂O as cerium source. The structure, morphology, composition, and fluorescence properties of CSW were characterized and analyzed by SEM, XRD, XPS and FL. The results show that calcium sulfate dihydrate whiskers with high aspect ratio can be prepared by microwave method, with average length of 263 μm and average aspect ratio of 39.50. Ce³⁺ enters CSW in the form of atomic substitution during the formation of CSW, which does not affect the crystal structure of CSW, but improves the morphology of CSW. When 2% (mass fraction) Ce³⁺ is added, one-dimensional growth of CSW is promoted to make the aspect ratio of CSW increase significantly, while excessive Ce³⁺ leads to the growth of whiskers in the transverse direction. This study proves that rare earth gypsum contains trace amounts of rare earth element Ce. At the same time, it is found that CSW prepared from rare earth gypsum presents the characteristics of emitting blue light, which provides theoretical guidance for the development and utilization of rare earth gypsum.

Key words: rare earth cerium, rare earth gypsum, dehydrate calcium sulfate whisker, microwave method, length to diameter ratio, fluorescence property

中图分类号:

TQ132.3⁺2

吴锦绣, 秦思成, 牛小超, 齐源昊, 柳召刚, 胡艳宏, 冯福山, 李健飞, 张晓伟. 制备方法与Ce³⁺对二水硫酸钙晶须形貌的影响[J]. 人工晶体学报, 2023, 52(9): 1720-1729.

WU Jinxiu, QIN Sicheng, NIU Xiaochao, QI Yuanhao, LIU Zhaogang, HU Yanhong, FENG Fushan, LI Jianfei, ZHANG Xiaowei. Effect of Preparation Method and Ce³⁺ on the Morphology of Calcium Sulfate Dihydrate Whiskers[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(9): 1720-1729.

参考文献

[1] 赵晨阳, 吴丰辉, 瞿广飞, 等. 废石膏制备硫酸钙晶须的高附加值利用前景[J]. 环境化学, 2022, 41(3): 1086-1096.
ZHAO C Y, WU F H, QU G F, et al. The high value-added utilization prospect of calcium sulfate whiskers prepared from waste gypsum[J]. Environmental Chemistry, 2022, 41(3): 1086-1096 (in Chinese).
[2] 黄强, 李程, 周宗科, 等. 掺锶硫酸钙复合骨修复材料的制备及体外特性研究[J]. 生物医学工程学杂志, 2009, 26(3): 575-579.
HUANG Q, LI C, ZHOU Z K, et al. In vitro study of strontium-calcium sulfate compounds as bioactive bone grafted substitute[J]. Journal of Biomedical Engineering, 2009, 26(3): 575-579 (in Chinese).
[3] 杨前昊. 负载介孔二氧化硅MXene复合材料合并3D打印支架协同治疗骨肉瘤促进骨修复[D]. 上海: 上海交通大学, 2020.
YANG Q H. Engineering 2D mesoporous Silica@MXene-integrated 3D-printing scaffolds for combinatory osteosarcoma therapy and bone regeneration[D]. Shanghai: Shanghai Jiao Tong University, 2020 (in Chinese).
[4] 杨红艳, 欧阳俊瑶, 夏蝶, 等. 添加CaSO₄·2H₂O为晶种制备磷石膏半水硫酸钙晶须[J]. 人工晶体学报, 2022, 51(2): 309-315.
YANG H Y, OUYANG J Y, XIA D, et al. Preparation of hemihydrate calcium sulfate whisker with phosphogypsum by adding CaSO₄·2H₂O as crystal seed[J]. Journal of Synthetic Crystals, 2022, 51(2): 309-315 (in Chinese).
[5] 汪潇, 金彪, 王宇斌, 等. 阴离子在脱硫石膏晶须水热结晶中的作用机理[J]. 高等学校化学学报, 2020, 41(3): 473-480.
WANG X, JIN B, WANG Y B, et al. Interaction mechanism of anions in hydrothermal crystallization of desulfurization gypsum whiskers†[J]. Chemical Journal of Chinese Universities, 2020, 41(3): 473-480 (in Chinese).
[6] 邓淋, 俞倩倩. 磷石膏资源化研究现状[J]. 硫酸工业, 2020(7): 1-5+38.
DENG L, YU Q Q. Research status of phosphogypsum resource utilization[J]. Sulphuric Acid Industry, 2020(7): 1-5+38 (in Chinese).
[7] 李强, 刘福立, 尚超, 等. 微波外场强化电石渣制备硫酸钙晶须及其机理分析[J]. 人工晶体学报, 2020, 49(1): 125-130.
LI Q, LIU F L, SHANG C, et al. Preparation of calcium sulfate whiskers by microwave-enhanced carbide slag and its mechanism analysis[J]. Journal of Synthetic Crystals, 2020, 49(1): 125-130 (in Chinese).
[8] 赵博,吴伟,智建国. CeO₂含量对CaO-Al₂O₃精炼渣熔化性能的影响[J/OL]. 中国稀土学报: 1-13[2023-06-28]. http://kns.cnki.net/kcms/detail/11.2365.TG.20220922.1530.004.html.
ZHAO B, WU W, ZHI J G. Effect of CeO₂ content on melting performance of CaO-Al₂O₃refining slag[J/OL]. Journal of the Chinese Society of Rare Earths: 1-13[2023-06-28]. http://kns.cnki.net/kcms/detail/11.2365.TG.20220922.1530.004.html (in Chinese).
[9] ZHOU D, WEI R F, ZHU Y L, et al. Calcium sulfate whisker one-step preparation using semi-dry flue gas desulfurization ash and directional growth control[J]. Journal of Cleaner Production, 2021, 290: 125754.
[10] XIANG G H, LIU T, ZHANG Y M, et al. Synthesis of polypropylene composites with modified calcium sulfate whisker prepared from shale vanadium neutralization slag[J]. Results in Physics, 2018, 10: 28-35.
[11] 徐伟, 李梅, 张栋梁, 等. 稀土石膏常压酸化法制备硫酸钙晶须的研究[J]. 无机盐工业, 2020, 52(8): 66-71.
XU W, LI M, ZHANG D L, et al. Study on preparation of calcium sulfate whisker by atmospheric pressure acidification using rare earth gypsum[J]. Inorganic Chemicals Industry, 2020, 52(8): 66-71 (in Chinese).
[12] 牛小超. 稀土石膏制备硫酸钙晶须及改性[D]. 包头: 内蒙古科技大学, 2021.
NIU X C. Rare earth gypsum preparation calcium sulfate crystal and modified[D]. Baotou: Inner Mongolia University of Science & Technology, 2021 (in Chinese).
[13] LU Y H, JIANG N, LI X W, et al. Effect of inorganic-organic surface modification of calcium sulfate whiskers on mechanical and thermal properties of calcium sulfate whisker/poly(vinyl chloride) composites[J]. RSC Advances, 2017, 7(73): 46486-46498.
[14] 羊道和, 杨玉荣, 易美桂. 柠檬酸对半水硫酸钙晶须形貌稳定性影响[J]. 人工晶体学报, 2019, 48(1): 95-100.
YANG D H, YANG Y R, YI M G. Effect of citric acid on the morphological stability of calcium sulfate hemihydrate whiskers[J]. Journal of Synthetic Crystals, 2019, 48(1): 95-100 (in Chinese).
[15] ZHAO W P, GAO C H, SANG H F, et al. Calcium sulfate hemihydrate whisker reinforced polyvinyl alcohol with improved shape memory effect[J]. RSC Advances, 2016, 6(58): 52982-52986.
[16] JIANG G M, WANG H, CHEN Q S, et al. Preparation of alpha-calcium sulfate hemihydrate from FGD gypsum in chloride-free Ca(NO₃)₂ solution under mild conditions[J]. Fuel, 2016, 174: 235-241.
[17] WANG Y Q, LI Y C, YUAN A, et al. Preparation of calcium sulfate whiskers by carbide slag through hydrothermal method[J]. Crystal Research and Technology, 2014, 49(10): 800-807.
[18] CHEN X J, YANG L C, ZHANG J F, et al. Exploration of As(III)/As(V) uptake from aqueous solution by synthesized calcium sulfate whisker[J]. Chinese Journal of Chemical Engineering, 2014, 22(11/12): 1340-1346.
[19] 谢晴, 蒋美雪, 彭同江, 等. 磷石膏常压酸化法制备无水硫酸钙晶须的实验研究[J]. 人工晶体学报, 2019, 48(6): 1060-1066+1071.
XIE Q, JIANG M X, PENG T J, et al. Experimental study on preparation of anhydrous calcium sulfate whisker by phosphogypsum at atmospheric acidification method[J]. Journal of Synthetic Crystals, 2019, 48(6): 1060-1066+1071 (in Chinese).
[20] PANG X Z, YANG J B, PANG M J, et al. Enhanced C atom adsorption on Cu(111) substrate by doping rare earth element Y for Cu-diamond composites: a first-principles study[J]. Journal of Alloys and Compounds, 2020, 831: 154747.
[21] LI H, JIANG Q, ZHANG J X, et al. Synchronization adsorption of Pb(Ⅱ) and Ce(Ⅲ) by biochar supported phosphate-doped ferrihydrite in aqueous solution: adsorption efficiency and mechanisms[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 648: 129230.
[22] 吴峰, 吴硕琮, 马家玉, 等. 金属离子对水热法制备半水硫酸钙晶须的形貌及粒径的影响[J]. 化工进展, 2018, 37(4): 1536-1543.
WU F, WU S C, MA J Y, et al. Effect of metal ions on crystal morphology and size of calcium sulfate hemihydratewhiskers preparated by hydrothermal method[J]. Chemical Industry and Engineering Progress, 2018, 37(4): 1536-1543 (in Chinese).
[23] ZHANG X M, LI W L, JANG K H, et al. Luminescence enhancement by energy transfer from Ce³⁺ ions in Ba_1.6Ca_0.4P₂O₇∶Ce³⁺∶Tb³⁺ phosphor[J]. Current Applied Physics, 2012, 12(1): 299-302.
[24] YANG Z F, HU Y H, CHEN L, et al. Fluorescence and energy transfer in CaMgP₂O₇∶Ce³⁺, Tb³⁺ phosphor[J]. Materials Science and Engineering: B, 2015, 193: 27-31.
[25] LI M, WU J X, JIA H L, et al. Luminescence properties and energy transfers of NaLa(WO₄)₂∶Sm³⁺∶Ce³⁺ phosphor[J]. Journal of Materials Science: Materials in Electronics, 2019, 30(11): 10465-10474.
[26] 吴锦绣, 李梅, 柳召刚, 等. 超声法合成CePO₄纳米线及发光性能研究[J]. 人工晶体学报, 2015, 44(4): 947-953.
WU J X, LI M, LIU Z G, et al. Preparation and luminescence properties of CePO₄ nanowires by ultrasonic method[J]. Journal of Synthetic Crystals, 2015, 44(4): 947-953 (in Chinese).

制备方法与Ce³⁺对二水硫酸钙晶须形貌的影响

Effect of Preparation Method and Ce³⁺ on the Morphology of Calcium Sulfate Dihydrate Whiskers

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