Effects of metal ions on the morphology of calcium sulfate hemihydrate whiskers by hydrothermal method

doi:10.1007/s11705-017-1665-8

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (4) : 545-553 https://doi.org/10.1007/s11705-017-1665-8

RESEARCH ARTICLE

Effects of metal ions on the morphology of calcium sulfate hemihydrate whiskers by hydrothermal method

Tianjie Liu, Hao Fan, Yanxia Xu, Xingfu Song(

), Jianguo Yu

National Engineering Research Center for Integrated Utilization of Salt Lake Resources, East China University of Science and Technology, Shanghai 200237, China

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Abstract

The effects of Na⁺, Mg²⁺, Al³⁺ and Fe³⁺ ion concentrations on the crystal morphology of calcium sulfate hemihydrate whiskers formed via a hydrothermal method have been studied. In the presence of Al³⁺ concentrations higher than 1×10⁻³ mol/L the whiskers were significantly shorter and thicker and the presence of Mg²⁺ and Fe³⁺ resulted in shorter whiskers. The presence of Na⁺ did not affect the morphology of the whiskers. Through elemental analysis, it was determined that Mg²⁺ and Al³⁺ were selectively adsorbed on the surfaces of the crystals, whereas Fe³⁺ underwent a hydrolysis reaction to form a brown precipitate which decreased the ion concentration in the solution. These results indicate that in raw materials used for the industrial preparation of calcium sulfate whiskers, Al³⁺ and Fe³⁺ should be removed and the Mg²⁺ concentration should be less than 8 × 10⁻³ mol/L in order to obtain pure whiskers with high aspect ratios.

Keywords metal ions morphology calcium sulfate hemihydrate whiskers hydrothermal method selective adsorption

Corresponding Author(s): Xingfu Song

Just Accepted Date: 19 June 2017 Online First Date: 26 September 2017 Issue Date: 06 November 2017

Cite this article:

Tianjie Liu,Hao Fan,Yanxia Xu, et al. Effects of metal ions on the morphology of calcium sulfate hemihydrate whiskers by hydrothermal method[J]. Front. Chem. Sci. Eng., 2017, 11(4): 545-553.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1665-8
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I4/545

Tab.1 Concentrations of metal ion impurities in the experimental solutions

Fig.1 Experimental procedure for the preparation of calcium sulfate whiskers by a hydrothermal method

Fig.2 The XRD patterns of the calcium sulfate prepared with different concentrations of metal ions ((a) Na⁺; (b) Mg²⁺; (c) Al³⁺; (d) Fe³⁺). The red vertical lines (Fig. 2(a)) denote the positions of diffraction peaks in the standard PDF 41-0224 for crystalline calcium sulfate HH

Fig.3 Theoretical crystal habit of calcium sulfate hemihydrate predicted by the attachment energy method

Fig.4 Effect of the Na⁺ concentration on the calcium sulfate morphology ((a) average length and average diameter; (b) average aspect ratio) and SEM photos (Na⁺: (c) 0 mmol/L; (d) 24 mmol/L; (e) 40 mmol/L)

Fig.5 Effect of the Mg²⁺concentration on the calcium sulfate morphology ((a) average length and average diameter; (b) average aspect ratio) and SEM photos (Mg²⁺: (c) 4 mmol/L; (d) 12 mmol/L; (e) 20 mmol/L)

Fig.6 Effect of the Al³⁺ concentration on the calcium sulfate morphology ((a) average length and average diameter; (b) average aspect ratio) and SEM photos (Al³⁺: (c) 1 mmol/L; (d) 6 mmol/L; (e) 10 mmol/L)

Fig.7 Effect of the Fe³⁺ concentration on the calcium sulfate morphology ((a) average length and average diameter; (b) average aspect ratio) and SEM photos (Fe³⁺: (c) 2 mmol/L; (d) 6 mmol/L; (e) 10 mmol/L)

Fig.8 EDS analysis of the products prepared with different metal ion concentrations

Fig.9 Influence of Mg²⁺ and Al³⁺ on the XPS spectra of calcium sulfate HH whiskers ((a) Mg 1s peaks; (b) S 2p peaks; (c) Al 2p peaks; (d) S 2p peaks)

Fig.10 Effect of ion concentration on impurity ion uptake by the calcium sulfate products

Fig.11 Stereoscopic microscope photos of the calcium sulfate whiskers prepared with and without Fe³⁺ ((a) 0 mmol/L Fe³⁺; (b) 10 mmol/L Fe³⁺) and SEM photo ((c) pH= 1, 10 mmol/L Fe³⁺)

1	Wang H, Mu B, Ren J , Jian L, Zhang J, Yang S . Mechanical and tribological behaviors of PA66/PVDF blends filled with calcium sulphate whiskers. Polymer Composites, 2009, 30(9): 1326–1332
2	Wang J, Yang K, Lu S . Preparation and characteristic of novel silicone rubber composites based on organophilic calcium sulfate whisker. High Performance Polymers, 2011, 23(2): 141–150
3	Zhang Y, Wang G, Miao M , Shi L. Dual-surface modification of calcium sulfate whisker with sodium hexametaphosphate/silica and use as new water-resistant reinforcing fillers in papermaking. Powder Technology, 2015, 271: 1–6
4	Yuan W, Cui J, Cai Y , Xu S. A novel surface modification for calcium sulfate whisker used for reinforcement of poly (vinyl chloride). Journal of Polymer Research, 2015, 22(9): 173
5	Luo K B, Li H P, Tan Y X. Study on the preparation of calcium sulfate whisker by hydrothermal method. Advanced Materials Research, 2013, 602: 1369–1372
6	He H, Dong F, He P , Xu L. Effect of glycerol on the preparation of phosphogypsum-based CaSO4·0.5H2O whiskers. Journal of Materials Science, 2014, 49(5): 1957–1963
7	Zhao W, Wu Y, Xu J , Gao C. Effect of ethylene glycol on hydrothermal formation of calcium sulfate hemihydrate whiskers with high aspect ratios. RSC Advances, 2015, 5(62): 50544–50548
8	Mao X, Song X, Lu G , Sun Y, Xu Y, Yu J . Control of crystal morphology and size of calcium sulfate whiskers in aqueous HCl solutions by additives: Experimental and molecular dynamics simulation studies. Industrial & Engineering Chemistry Research, 2015, 54(17): 4781–4787
9	Xu A Y, Li H P, Luo K B, Xiang L. Formation of calcium sulfate whiskers from CaCO3-bearing desulfurization gypsum. Research on Chemical Intermediates, 2011, 37(2): 449–455
10	Wang X, Jin B, Yang L , Zhu X. Effect of CuCl2 on hydrothermal crystallization of calcium sulfate whiskers prepared from FGD gypsum. Crystal Research and Technology, 2015, 50(8): 633–640
11	Wang Y, Li Y, Yuan A , Yuan B, Lei X, Ma Q , Han J, Wang J. Preparation of calcium sulfate whiskers by carbide slag through hydrothermal method. Crystal Research and Technology, 2014, 49(10): 800–807
12	Yang L, Wu Z, Guan B , Fu H, Ye Q. Growth rate of a-calcium sulfate hemihydrate in K-Ca-Mg-Cl-H2O systems at elevated temperature. Journal of Crystal Growth, 2009, 311(20): 4518–4524
13	Guan B, Yang L, Wu Z . Effect of Mg2+ ions on the nucleation kinetics of calcium sulfate in concentrated calcium chloride solutions. Industrial & Engineering Chemistry Research, 2010, 49(12): 5569–5574
14	Li Z, Demopoulos G P. Effect of NaCl, MgCl2, FeCl2, FeCl3, and AlCl3 on solubility of CaSO4 phases in aqueous HCl or HCl+CaCl2 solutions at 298 to 353 K. Journal of Chemical & Engineering Data, 2006, 51(2): 569–576
15	Song X, Sun S, Zhang D , Wang J, Yu J. Synthesis and characterization of magnesium hydroxide by batch reaction crystallization. Frontiers of Chemical Science and Engineering, 2011, 5(4): 416–421
16	Li F, Liu J, Yang G , Pan Z, Ni X, Xu H , Huang Q . Effect of pH and succinic acid on the morphology of α-calcium sulfate hemihydrate synthesized by a salt solution method. Journal of Crystal Growth, 2013, 374: 31–36
17	Song X, Tong K, Sun S , Sun Z, Yu J. Preparation and crystallization kinetics of micron-sized Mg(OH)2 in a mixed suspension mixed product removal crystallizer. Frontiers of Chemical Science and Engineering, 2013, 7(2): 130–138
18	Wang X, Yang L, Zhu X , Yang J. Preparation of calcium sulfate whiskers from FGD gypsum via hydrothermal crystallization in the H2SO4-NaCl-H2O system. Particuology, 2014, 17(6): 42–48
19	Hou S, Wang J, Wang X , Chen H, Xiang L. Effect of Mg2+ on Hydrothermal Formation of α-CaSO4·0.5H2O Whiskers with High Aspect Ratios. Langmuir, 2014, 30(32): 9804–9810
20	Xin Y, Hou S C, Xiang L, Yu Y . Adsorption and substitution effects of Mg on the growth of calcium sulfate hemihydrate: An ab initio DFT study. Applied Surface Science, 2015, 357: 1552–1557
21	Feldmann T, Demopoulos G P. Influence of impurities on crystallization kinetics of calcium sulfate dihydrate and hemihydrate in strong HCl-CaCl2 solutions. Industrial & Engineering Chemistry Research, 2013, 52(19): 6540–6549
22	Mao X, Song X, Lu G , Sun Y, Xu Y, Yu J . Effects of metal ions on crystal morphology and size of calcium sulfate whiskers in aqueous HCl solutions. Industrial & Engineering Chemistry Research, 2014, 53(45): 17625–17635
23	Miao M, Feng X, Wang G , Cao S, Shi W, Shi L . Direct transformation of FGD gypsum to calcium sulfate hemihydrate whiskers: Preparation, simulations, and process analysis. Particuology, 2015, 19(2): 53–59
24	Zhao W, Gao C, Zhang G , Xu J, Wang C, Wu Y . Controlling the morphology of calcium sulfate hemihydrate using aluminum chloride as a habit modifier. New Journal of Chemistry, 2016, 40(4): 3104–3108
25	Rashad M M, Mahmoud M H H, Ibrahim I A, Abdel-Aal E A. Crystallization of calcium sulfate dihydrate under simulated conditions of phosphoric acid production in the presence of aluminum and magnesium ions. Journal of Crystal Growth, 2004, 267(1): 372–379
26	Kruger A, Focke W W, Kwela Z, Fowles R . Effect of ionic impurities on the crystallization of gypsum in wet-process phosphoric acid. Industrial & Engineering Chemistry Research, 2001, 40(5): 1364–1369
27	Lü P, Fei D, Dang Y . Effects of calcium monohydrogenphosphate on the morphology of calcium sulfate whisker by hydrothermal synthesis. Canadian Journal of Chemical Engineering, 2014, 92(10): 1709–1713
28	Guan B, Yang L, Wu Z , Shen Z, Ma X, Ye Q . Preparation of α-calcium sulfate hemihydrate from FGD gypsum in K, Mg-containing concentrated CaCl2 solution under mild conditions. Fuel, 2009, 88(7): 1286–1293
29	Singh N B, Middendorf B. Calcium sulphate hemihydrate hydration leading to gypsum crystallization. Progress in Crystal Growth and Characterization of Materials, 2007, 53(1): 57–77
30	Dumazer G, Narayan V, Smith A , Lemarchand A A . Modeling gypsum crystallization on a submicrometric scale. Journal of Physical Chemistry C, 2009, 113(4): 1189–1195
31	Seyama H, Soma M. X-ray photoelectron spectroscopic study of montmorillonite containing exchangeable divalent cations. Journal of the Chemical Society, Faraday Transactions 1. Physical Chemistry in Condensed Phases, 1984, 80(1): 237–248
32	Arata K, Hino M. Solid catalyst treated with anion: XVIII. Benzoylation of toluene with benzoyl chloride and benzoic anhydride catalysed by solid superacid of sulfate-supported alumina. Applied Catalysis, 1990, 59(1): 197–204
33	Bourcier W L, Knauss K G, Jackson K J. Aluminum hydrolysis constants to 250 °C from boehmite solubility measurements. Geochimica et Cosmochimica Acta, 1993, 57(4): 747–762
34	Bottero J Y, Cases J M, Fiessinger F, Poirier J E . Studies of hydrolyzed aluminum chloride solutions. 1. Nature of aluminum species and composition of aqueous solutions. Journal of Physical Chemistry, 1980, 84(22): 2933–2939
35	Subrt J, Bohácek J, Stengl V , Grygar T , Bezdicka P . Uniform particles with a large surface area formed by hydrolysis of Fe2(SO4)3 with urea. Materials Research Bulletin, 1999, 34(6): 905–914
36	Musić S, Orehovec Z, Popović S , Czakó-Nagy I . Structural properties of precipitates formed by hydrolysis of Fe3+ ions in Fe2(SO4)3 solutions. Journal of Materials Science, 1994, 29(8): 1991–1998

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