Preparation and Phase Formation Mechanism of β-ZnS Transparent Ceramics

doi:10.11901/1005.3093.2024.521

Chinese Journal of Materials Research

2025, Vol. 39

Issue (12): 927-934 DOI: 10.11901/1005.3093.2024.521

ARTICLES

Current Issue | Archive | Adv Search

Preparation and Phase Formation Mechanism of β-ZnS Transparent Ceramics

LI Hongxiao, LI Huanyong(

), ZHANG Xuan

School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China

Cite this article:

LI Hongxiao, LI Huanyong, ZHANG Xuan. Preparation and Phase Formation Mechanism of β-ZnS Transparent Ceramics. Chinese Journal of Materials Research, 2025, 39(12): 927-934.

Download:

HTML

PDF(6701KB)
Export: BibTeX | EndNote (RIS)

Abstract

ZnS transparent ceramics with free wurtzite phase α-ZnS were successfully prepared through hot-pressing sintering by 30 MPa at 830 ^oC, using the as-synthesized β-ZnS nanopowders and KX (X = Br, I, Cl) as raw material. It was found that halides KX, as the additives, play the crucial role in the sintering process of ZnS transparent ceramics. Both halides KBr and KI not only promote the rapid growth of grain by generating a liquid phase, but also effectively inhibit the size-induced low-temperature phase transition of the nanopowder cubic phase β-ZnS to the hexagonal one. However, KCl promotes the formation of α-ZnS with an adverse impact on ZnS transparent ceramics. A mechanism of alkali metal halides KX inhibiting the size-induced low-temperature phase transition of ZnS nanoparticles was rationally proposed by combining X-ray diffraction results, microstructure, composition distribution and photoluminescence spectra of ZnS ceramics with the ionic radii of Br^-, I^-, and Cl^-.

Key words: inorganic non-metallic materials ZnS transparent ceramics hot-press sintering low-temperature phase transition sintering additive

Received: 31 December 2024

ZTFLH:

TB321

Fund: National Natural Science Foundation of China(51572220);Natural Science Basic Research Program of Shaanxi(2021JM-057)

Corresponding Authors: LI Huanyong, Tel: 13572263608, E-mail: lihuanyong@nwpu.edu.cn

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	LI Hongxiao
	LI Huanyong
	ZHANG Xuan

URL:

https://www.cjmr.org/EN/10.11901/1005.3093.2024.521 OR https://www.cjmr.org/EN/Y2025/V39/I12/927

Fig.1 XRD pattern and SEM image of ZnS nanopowders

Fig.2 XRD patterns of ZnS transparent ceramics with various amount of additive KX (X = Cl, Br, I): (a) ZnS-A: 0.5%KBr, (b) ZnS-B:1.5%KBr, (c) ZnS-C:3.0%KBr, (d) ZnS-D: 3.0%KCl, (e) ZnS-E: 3.0%KI

Fig.3 SEM images of ZnS transparent ceramics with various amount of additive KX (X = Cl, Br, I) (a) ZnS-A: 0.5%KBr, (b)ZnS-B: 1.5%KBr, (c) ZnS-C: 3.0%KBr, (d) ZnS-D: 3.0%KCl, (e) ZnS-E: 3.0%KI; (c1-e1) EDS energy spectra of elements map in (c-e), (c2-e2) the enlarged views of K and X in (c1-e1)

Fig.4 Schematic illustration of mechanism on inhibiting low-temperature phase transition of ZnS nanocrystals (a) mixture of β-ZnS and KBr, (b) KBr molecular layer via spontaneous diffusion, (c) KBr liquid molecular layer and α-ZnS nucleus on ZnS nanopartical surface, (d) ZnSKBr melt dissolving α-ZnS nuclues, (e) β-ZnS nuclei from ZnSKBr melt, (f) β-ZnS grains from melt

Fig.5 PL spectra of ZnS ceramics under 365 nm UV excitation at room temperature (Insert: luminous samples)

Fig.6 IR spectra of as-sintered ZnS transparent ceramics (a) ZnS-C, (b) ZnS-D, (c) ZnS-E

[1]	Xiao Z H, Yu S J, Li Y M, et al. Materials development and potential applications of transparent ceramics: a review [J]. Mater. Sci. Eng., 2020, 139R: 100518
[2]	Durand G R, Hakmeh N, Dorcet V, et al. New insights in structural characterization of transparent ZnS ceramics hot-pressed from nanocrystalline powders synthesized by combustion method [J]. J. Eur. Ceram. Soc., 2019, 39(10): 3094 doi: 10.1016/j.jeurceramsoc.2019.03.033
[3]	Choi B H, Kim D S, Lee K T, et al. Highly IR transparent ZnS ceramics sintered by vacuum hot press using hydrothermally produced ZnS nanopowders [J]. J. Am. Ceram. Soc., 2020, 103(4): 2663 doi: 10.1111/jace.v103.4
[4]	Xu L G, Guo S, Ralchenko V, et al. Progress in infrared transparencies under opto electro thermo and mechanical environments [J]. Surf. Sci. Technol., 2023, 1(1): 2 doi: 10.1007/s44251-023-00002-9
[5]	Li Y Y, Wu Y Q. Transparent and luminescent ZnS ceramics consolidated by vacuum hot pressing method [J]. J. Am. Ceram. Soc., 2015, 98(10): 2972 doi: 10.1111/jace.2015.98.issue-10
[6]	Lee K T, Choi B H, Woo J U, et al. Microstructural and optical properties of the ZnS ceramics sintered by vacuum hot-pressing using hydrothermally synthesized ZnS powders [J]. J. Eur. Ceram. Soc., 2018, 38(12): 4237 doi: 10.1016/j.jeurceramsoc.2018.05.018
[7]	Qadri S B, Skelton E F, Hsu D, et al. Size-induced transition-temperature reduction in nanoparticles of ZnS [J]. Phys. Rev., 1999, 60B(13) : 9191
[8]	Li C Y, Pan Y B, Kou H M, et al. Densification behavior, phase transition, and preferred orientation of hot-pressed ZnS ceramics from precipitated nanopowders [J]. J. Am. Ceram. Soc., 2016, 99(9): 3060 doi: 10.1111/jace.2016.99.issue-9
[9]	Li C Y, Xie T F, Dai J W, et al. Hot-pressing of zinc sulfide infrared transparent ceramics from nanopowders synthesized by the solvothermal method [J]. Ceram. Int., 2018, 44(1): 747 doi: 10.1016/j.ceramint.2017.09.242
[10]	Yeo S Y, Kwon T H, Park C S, et al. Sintering and optical properties of transparent ZnS ceramics by pre-heating treatment temperature [J]. J. Electroceram., 2018, 41(1): 1 doi: 10.1007/s10832-018-0137-y
[11]	Li H Y, Ren X Y, Xi P F, et al. Influence of NaX (X = Cl, Br, I) additive on phase composition, thermostability and high infrared performances of γ-La₂S₃ transparent ceramics [J]. Ceram. Int., 2020, 46(7): 9145 doi: 10.1016/j.ceramint.2019.12.164
[12]	Huang F, Banfield J F. Size-dependent phase transformation kinetics in nanocrystalline ZnS [J]. J. Am. Chem. Soc., 2005, 127(12): 4523 pmid: 15783236
[13]	Xie Y C, Wang C B, Tang Y Q. Dispersion capacities of KCl and NaCl in zeolites [J]. Acta Phy. Chim. Sin., 1993, 9(6): 735
	谢有畅, 汪传宝, 唐有祺. KCl、NaCl在分子筛载体上的分散阈值研究 [J]. 物理化学学报, 1993, 9(6): 735
[14]	Xie Y C, Tang Y Q, Spontaneous monolayer dispersion of oxides and salts onto surfaces of supports: applications to heterogeneous catalysis [J]. Adv. Catal., 1990, 37: 1
[15]	Wang K X, Yang X W, Zhao B Y, et al. ⁷Li MAS NMR studies on LiCl/γ-Al₂O₃ [J]. Acta Phy. Chim. Sin., 1997, 13(3): 196
	王凯旋, 杨夏万, 赵璧英等. LiCl/γ-Al₂O₃的⁷Li MAS NMR研究 [J]. 物理化学学报, 1997, 13(3): 196
[16]	Wachs I E. Recent conceptual advances in the catalysis science of mixed metal oxide catalytic materials [J]. Catal. Today, 2005, 100(1-2): 79 doi: 10.1016/j.cattod.2004.12.019
[17]	Liang L H, Shen C M, Du S X, et al. Increase in thermal stability induced by organic coatings on nanoparticles [J]. Phys. Rev., 2004, 70B(20) : 205419
[18]	Dick K, Dhanasekaran T, Zhang Z Y, et al. Size-dependent melting of silica-encapsulated gold nanoparticles [J]. J. Am. Chem. Soc., 2002, 124(10): 2312 pmid: 11878986
[19]	Chen S, Liu W M. Preparation and characterization of surface-coated ZnS nanoparticles [J]. Langmuir, 1999, 15(23): 8100 doi: 10.1021/la9906875
[20]	Zhang H Z, Huang F, Gilbert B, et al. Molecular dynamics simulations, thermodynamic analysis, and experimental study of phase stability of zinc sulfide nanoparticles [J]. J. Phys. Chem., 2003, 107B: 13051
[21]	Tiwary C S, Sricastava C, Kumbhakar P. Onset of sphalerite to wurtzite transformation in ZnS nanoparticles [J]. J. Appl. Phys., 2011, 110(3): 034908
[22]	Dutta B, Deb D, Bhattacharya S. Electroactive phase nucleation and isothermal crystallization kinetics in ionic liquid-functionalized ZnS nanoparticle-ingrained P(VDF-HFP) copolymer nanocomposites [J]. J. Mater. Sci., 2019, 54(4): 2990 doi: 10.1007/s10853-018-3027-4
[23]	Prior K A, Bradford C, Davidson I A, et al. Metastable II-VI sulphides: Growth, characterization and stability [J]. J. Cryst. Growth, 2011, 323(1): 114121
[24]	Gupta S K, Mao Y B. Recent developments on molten salt synthesis of inorganic nanomaterials: a review [J]. J. Phys. Chem., 2021, 125C(12) : 6508
[25]	Sahraei R, Aval G M, Goudarzi A. Compositional, structural, and optical study of nanocrystalline ZnS thin films prepared by a new chemical bath deposition route [J]. J. Alloy. Compd., 2008, 466(1-2): 488 doi: 10.1016/j.jallcom.2007.11.127
[26]	Penn R L, Banfield J F. Imperfect oriented attachment: dislocation generation in defect-Free nanocrystals [J]. Science, 1998, 281(5379): 969 pmid: 9703506
[27]	Hapiuk D, Masenelli B, Masenelli-Varlot K, et al. Oriented attachment of ZnO nanocrystals [J]. J. Phys. Chem., 2013, 117C(19) : 10220
[28]	Sarkar H, Raj A, Kumar L, et al. Bulk-sized (~50 μm) faceted wurtzite crystals via non-classical mesocrystalline growth assembly [J]. J. Mater. Res., 2024, 39: 3294 doi: 10.1557/s43578-024-01463-w
[29]	Ghica D, Nistor S V, Nistor L C, et al. Structural phase transformations in annealed cubic ZnS nanocrystals [J]. J. Nanopart. Res., 2011, 13(9): 4325 doi: 10.1007/s11051-011-0379-y
[30]	Ooshita K, Inoue T, Sekiguchi T, et al. Flux growth of ZnS single crystals and their characterization [J]. J. Cryst. Growth, 2004, 267(1-2): 74 doi: 10.1016/j.jcrysgro.2004.03.067
[31]	Zahabi S, Jamali H, Bakhshi S R, et al. Comparing infrared transmission of zinc sulfide nanostructure ceramic produced via hot pressure and spark plasma sintering methods [J]. Int. J. Appl. Ceram. Technol., 2022, 19(3): 1319 doi: 10.1111/ijac.v19.3
[32]	Liu M Y, Wang S F, Wang C H, et al. Understanding of electronic and optical properties of ZnS with high concentration of point defects induced by hot pressing process: The first-principles calculations [J]. Comput. Mater. Sci., 2020, 174: 109492 doi: 10.1016/j.commatsci.2019.109492
[33]	Shannon R D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides [J]. Acta Cryst. Sect. A: Found. Cryst., 1976, 32(5): 751
[34]	Pelleg J. Diffusion in Ceramics [M]. Cham: Springer, 2016: 86
[35]	Kang S J L. Sintering: Densification, Grain Growth and Microstructure [M]. Amsterdam: Butterworth-Heinemann, 2005: 173
[36]	Parker S G, Pinnell J E. Molten flux growth of cubic zinc sulfide crystals [J]. J. Cryst. Growth, 1968, 3-4: 490 doi: 10.1016/0022-0248(68)90207-8
[37]	Zhang W, Zeng X H, Liu H F, et al. Synthesis and investigation of blue and green emissions of ZnS ceramics [J]. J. Lumin., 2013, 134: 498 doi: 10.1016/j.jlumin.2012.07.039
[38]	Singhal S, Chawla A K, Nagar S, et al. Photoluminescence measurements in the phase transition region of Zn_1-_x Cd_xS films [J]. J. Nanopart. Res., 2010, 12(4): 1415 doi: 10.1007/s11051-009-9687-x
[39]	Hong J W, Jung W K, Choi D H. Effect of porosity and hexagonality on the infrared transmission of spark plasma sintered ZnS ceramics [J]. Ceram. Int., 2020, 46(10): 16285 doi: 10.1016/j.ceramint.2020.03.185
[40]	Chlique C, Merdrignac-Conanec O, Hakmeh N, et al. Transparent ZnS ceramics by sintering of high purity monodisperse nanopowders [J]. J. Am. Ceram. Soc., 2013, 96(10): 3070 doi: 10.1111/jace.2013.96.issue-10
[41]	Chen Y Z, Zhang L, Zhang J, et al. Fabrication of transparent ZnS ceramic by optimizing the heating rate in spark plasma sintering process [J]. Opt. Mater., 2015, 50: 36 doi: 10.1016/j.optmat.2015.03.058
[42]	Abdi A, Davar F. Hot pressing sintering of zinc sulfide microsphere decorated with nanorods synthesized by the simple refluxing method [J]. Ceram. Int., 2020, 46(13): 21107 doi: 10.1016/j.ceramint.2020.05.186

[1]	ZHAN Jie, CHEN Xiaojiang, ZOU Zhili, SU Xingdong, XIE Shiyu, JIANG Liang, WANG Jinling, WANG Lielin. Preparation of Nano Ag⁰@ACF Material and Its Adsorption Performance for Gaseous Iodine[J]. 材料研究学报, 2025, 39(9): 673-682.
[2]	SHI Yuanji, CHENG Cheng, ZHANG Haitao, HU Daochun, CHEN Jingjing, LI Junwan. Nanoscale Analysis of Material Removal Behavior of β-SiC Semiconductor Devices during Sliding Wear[J]. 材料研究学报, 2025, 39(9): 701-711.
[3]	ZHOU Yingying, ZHANG Yingxian, DAN Zhuoya, DU Xu, DU Haonan, ZHEN Enyuan, LUO Fa. Influence of La Doping on Microwave Absorption Properties of YFeO₃ Ceramics[J]. 材料研究学报, 2025, 39(8): 561-568.
[4]	GENG Ruiwen, YANG Zhijiang, YANG Weihua, XIE Qiming, YOU Jinjing, LI Lijun, WU Haihua. Molecular Dynamics Simulation of Subsurface Damage of 6H-SiC Bulk Materials Induced by Grinding with Nano-sized Diamond Particles[J]. 材料研究学报, 2025, 39(8): 603-611.
[5]	LIU Zhihua, WANG Mingyue, LI Yijuan, QIU Yifan, LI Xiang, SU Weizhao. Preparation and Photocatalytic Performance of 1T/2H O-MoS₂@S-pCN Composite Catalyst in Degradation of Hexavalent Chromium and Ciprofloxacin[J]. 材料研究学报, 2025, 39(7): 551-560.
[6]	HAN Leilei, WANG Wentao, WU Yun, CHEN Jiajun, ZHAO Yong. High Temperature Growth Process of YBCO Superconducting Solder by Fluorine-free Chemical Solution Method[J]. 材料研究学报, 2025, 39(6): 474-480.
[7]	YUAN Xinyu, SHI Fei, LIU Jingxiao, ZHANG Haojie, YANG Dayi, WANG Meiyu, REN Ming. Effect of Er₂O₃ Addition on Crystallization Behavior and Properties of Lithium Disilicate Glass Ceramics[J]. 材料研究学报, 2025, 39(6): 455-462.
[8]	CHEN Shiyu, LI Wei, KUANG Haiyan, GAO Shaowei, PANG Dongfang. Dielectric-, Ferroelectric- and Piezoelectric-property of Lu³⁺ Doped 0.67BiFeO₃-0.33BaTiO₃ Lead-free Piezoelectric Ceramics[J]. 材料研究学报, 2025, 39(4): 272-280.
[9]	LIANG Honghua, CHEN Jiangchao, ZHENG Wenyu, WU Haining, HUANG Yicong, YI Zhuoyan, PANG Dazhi, JIANG Kunpeng, ZHU Guisheng, XU Huarui. Synthesis and Performance of a Novel Quasi-solid-state Electrolyte PHCN Based on Polyvinylidene Fluoride-hydrogenated Acrylate Incorparated with Mesoporous Spherical g-C₃N₄[J]. 材料研究学报, 2025, 39(12): 935-944.
[10]	XU Zhanyuan, ZHAO Wei, SHI Xiangshi, ZHANG Zhenyu, WANG Zhonggang, HAN Yong, FAN Jinglian. Effect of Composition Adjustment on Structure and Magnetic Properties of Soft Magnetic MnZn Ferrites[J]. 材料研究学报, 2025, 39(1): 55-62.
[11]	DENG Xiaolong, WANG Shanshan, DAI Xinxin, LIU Yi, HUANG Jinzhao. Preparation and Performance of Electrocatalyst of Amorphous FeOOH Covered Layered Double Hydroxide CoFeAl-Heterostructure for Efficient Overall Water Splitting in Alkaline Solution[J]. 材料研究学报, 2025, 39(1): 71-80.
[12]	ZHANG Wei, ZHANG Jie. Toughening Mechanism of B₄C-Al₂O₃ Composite Ceramics[J]. 材料研究学报, 2024, 38(8): 614-620.
[13]	CHEN Shijie, BAO Mengfan, LIN Na, YANG Haiqin, MAO Aiqin. Effect of Zn Content on Lithium Storage Properties of Rock Salt Type High Entropy Oxides[J]. 材料研究学报, 2024, 38(7): 508-518.
[14]	YUAN Xinzhong, WANG Cunjing, YAO Peng, LI Qiong, MA Zhihua, LI Pengfa. Preparation of N and O Co-doped Carbon Materials by Salt Sealing Method for Electrode of Supercapacitors[J]. 材料研究学报, 2024, 38(7): 529-536.
[15]	WANG Wei, CHANG Wenjuan, LV Fanfan, XIE Zelei, YU Chengcheng. Preparation and Tribological Properties of Fluorinated Boron Nitride Nanosheets Water-based Additive[J]. 材料研究学报, 2024, 38(6): 410-422.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed