LU502064B1

LU502064B1 - Preparation method of ternary sulfide-based ceramic powder

Info

Publication number: LU502064B1
Application number: LU502064A
Authority: LU
Inventors: Kelun Xia; Jierong Gu; Guang Jia; Xiang Shen; Miaomiao Wu
Original assignee: Ningbo Inst Of Oceanography; Univ Ningbo
Priority date: 2021-12-17
Filing date: 2022-05-11
Publication date: 2022-11-17
Also published as: CN114014664A

Abstract

The present disclosure relates to the technical field of infrared transparent ceramics, in particular to a preparation method of a ternary sulfide-based ceramic powder. The preparation method includes: in a protective gas, mixing a source A, a source B, a source S, and a milling ball for high-energy ball milling to obtain a ternary sulfide-based ceramic powder with a chemical composition of AB2S4, where in the AB2S4, A is an alkaline earth metal, and B is a lanthanide metal; the source A includes an alkaline earth metal elementary substance and/or an alkaline earth metal sulfide, the source B includes a lanthanide metal elementary substance and/or a lanthanide metal sulfide, and the source S includes one or more of the alkaline earth metal sulfide, the lanthanide metal sulfide and a sulfur elementary substance.

Description

BL-5468 PREPARATION METHOD OF TERNARY SULFIDE-BASED CERAMIC POWDER 7502068

TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of infrared transparent ceramics, in particular to a preparation method of a ternary sulfide-based ceramic powder.

BACKGROUND ART

[0002] Infrared transparent ceramic, as a newly developed infrared optical material with high density, few defects, wide transmission band, high transmittance, high hardness, and desirable wear resistance, has gradually become a main material used for infrared windows and fairings of various devices such as aircrafts and detectors. At present, the most researched infrared transparent ceramics include oxide ceramics (such as ALOs;, Y20s3, and ZrO»), nitride ceramics (such as Si3N4 and AION), sulfide ceramics (such as ZnS), and fluoride ceramics (such as MgF). However, with the gradual complexity of infrared detection application scenarios in recent years, comprehensive properties of the above ceramic materials, including mechanical properties and infrared transmittance properties, have been unable to meet the requirements for use. Therefore, it is urgent to develop a ceramic material with desirable mechanical properties, wide infrared transmission range and high transmittance to fill the technology and application gaps.

[0003] Ternary sulfide-based infrared transparent ceramic, as an excellent material for improving performances of the infrared windows and fairings, has an infrared transmittance cut-off wavelength of 20 um and a transmittance of not less than 50% at a long-wave infrared band of 8 um to 14 um. Compared with other infrared transparent ceramics, the ternary sulfide-based infrared transparent ceramic is very suitable as a next-generation material for the infrared windows and fairings due to high hardness (570 kg/mm?), high flexural strength (49 MPa), and excellent resistance to rain and sand erosion.

[0004] A first step to obtain the ternary sulfide-based infrared transparent ceramic is to prepare a pure ternary sulfide-based ceramic powder. Currently, the ternary sulfide-based ceramic powder is prepared by vulcanizing a precursor at high temperature for a long time, where a vulcanization medium used is hydrogen sulfide or carbon disulfide gas. Although the ternary sulfide-based ceramic powder with a higher purity can be prepared, the method has great potential safety hazards because of a highly toxic, flammable and explosive sulfide gas used.

SUMMARY

[0005] In view of this, the present disclosure provides a preparation method of a ternary sulfide-based ceramic powder. The preparation method has safety, high efficiency, simple 1

BL-5468 operations and low-cost raw materials. 17008086

[0006] To achieve the above objective, the present disclosure provides the following technical solutions.

[0007] The present disclosure provides a preparation method of a ternary sulfide-based ceramic powder, including the following steps:

[0008] in a protective gas, mixing a source À, a source B, a source S, and a milling ball for high-energy ball milling to obtain a ternary sulfide-based ceramic powder with a chemical composition of AB2S4, where in the AB2S4, A is an alkaline earth metal, and B is a lanthanide metal; the source À includes an alkaline earth metal elementary substance and/or an alkaline earth metal sulfide, the source B includes a lanthanide metal elementary substance and/or a lanthanide metal sulfide, and the source S includes one or more of the alkaline earth metal sulfide, the lanthanide metal sulfide and a sulfur elementary substance; and in the source A, the source B, and the source S, an alkaline earth metal element, a lanthanide metal element, and a sulfur element satisfy a stoichiometric ratio of the three elements in the ternary sulfide-based ceramic powder.

[0009] Preferably, in the AB»S4, A may be selected from the group consisting of Mg, Ca, and Ba; and B may be selected from the group consisting of La, Pr, and Gd.

[0010] Preferably, the chemical composition of the ternary sulfide-based ceramic powder may be any one selected from the group consisting of MgLazS4, CaLazS4, SrLazS4, BaLazS4, MgGd»S4, CaGd»S4, SrGd2S4, and BaGd»S4.

[0011] Preferably, a total mass of the source A, the source B, and the source S, and a mass of the milling ball may have a ratio of 1:(10-100).

[0012] Preferably, the milling ball may have a diameter of 5 mm to 12 mm.

[0013] Preferably, the high-energy ball milling may be conducted at 200 r/min to 800 r/min for greater than or equal to 6 h.

[0014] Preferably, the preparation method may further include the following step after the high-energy ball milling: annealing an obtained high-energy ball-milled material in vacuum or a protective gas to obtain the ternary sulfide-based ceramic powder; where

[0015] the annealing 1s conducted at 600°C to 1,100°C for 4 h to 12 h.

[0016] Preferably, the source A, the source B, and the source S each may have a particle size of less than 100 um, and a purity of greater than or equal to 99.9%.

[0017] Preferably, the annealing may be conducted at a heating rate of 5°C/min to 50°C/min from a room temperature to a working temperature.

[0018] Preferably, the protective gas may be independently one or more selected from the group consisting of Ar, N, and He.

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[0019] The present disclosure provides a preparation method of a ternary sulfide-based ceramic 202064 powder, including the following steps: in a protective gas, mixing a source A, a source B, a source S, and a milling ball for high-energy ball milling to obtain a ternary sulfide-based ceramic powder with a chemical composition of AB>S4, where in the AB»S4, A is an alkaline earth metal, and B is a lanthanide metal; the source A includes an alkaline earth metal elementary substance and/or an alkaline earth metal sulfide, the source B includes a lanthanide metal elementary substance and/or a lanthanide metal sulfide, and the source S includes one or more of the alkaline earth metal sulfide, the lanthanide metal sulfide and a sulfur elementary substance. In the source A, the source B, and the source S, an alkaline earth metal element, a lanthanide metal element, and a sulfur element satisfy a stoichiometric ratio of the three elements in the ternary sulfide-based ceramic powder. In the preparation method, the alkaline earth metal element, lanthanide metal element and sulfur element in the source A, source B and source S meet the stoichiometric ratio of the three elements in the ternary sulfide-based ceramic powder; in the protective gas, the source A, source B and source S are provided with energy by a high-energy impact from the high-energy ball milling, and the ternary sulfide-based ceramic powder is directly obtained by solid solution compounding. In the present disclosure, the ternary sulfide-based ceramic powder with fine particle size and uniformity can be prepared by the preparation method. The preparation method does not require toxic and dangerous gas such as hydrogen sulfide or carbon disulfide, and has ensured safety, high efficiency, simple operations and low-cost raw materials. Therefore, the present disclosure is suitable for a small amount of laboratory preparation and industrial mass production, and is expected to promote the further development of use technology of the infrared transparent ceramics.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIG 1 shows an X-ray diffraction (XRD) phase detection diagram of a CaLazS4 ceramic powder synthesized by a high-energy ball milling method in Example 1 of the present disclosure;

[0021] FIG 2 shows an electron microscope photograph of the CaLazS4 ceramic powder synthesized by the high-energy ball milling method in Example 1 of the present disclosure; and

[0022] FIG 3 shows a particle size distribution diagram of the CaLa:S4 ceramic powder synthesized by the high-energy ball milling method in Example 1 of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0023] The present disclosure provides a preparation method of a ternary sulfide-based ceramic powder, including the following steps:

[0024] in a protective gas, mixing a source A, a source B, a source S, and a milling ball for 3

BL-5468 high-energy ball milling to obtain a ternary sulfide-based ceramic powder with a chemical 799 composition of AB2S4, where in the AB2S4, A is an alkaline earth metal, and B is a lanthanide metal; the source A includes an alkaline earth metal elementary substance and/or an alkaline earth metal sulfide, the source B includes a lanthanide metal elementary substance and/or a lanthanide metal sulfide, and the source S includes one or more of the alkaline earth metal sulfide, the lanthanide metal sulfide and a sulfur elementary substance; and in the source A, the source B, and the source S, an alkaline earth metal element, a lanthanide metal element, and a sulfur element satisfy a stoichiometric ratio of the three elements in the ternary sulfide-based ceramic powder.

[0025] In the present disclosure, unless otherwise specified, the raw materials used are all commercially-available products well known to those skilled in the art.

[0026] In the present disclosure, the chemical composition of the ternary sulfide-based ceramic powder is AB2S4, where in the AB‚S4, A is an alkaline earth metal; and B is a lanthanide metal.

[0027] In the present disclosure, in the AB2S4, A is preferably selected from the group consisting of Mg, Ca, and Ba; and B is preferably selected from the group consisting of La, Pr, and Gd.

[0028] In the present disclosure, the chemical composition of the ternary sulfide-based ceramic powder is preferably any one selected from the group consisting of MgLarS4, CaLazS4, SrLazS4, Bal.axS4, MgGd»S4, CaGd,S4, SrGd2S4, and BaGd, Ss.

[0029] In a specific example of the present disclosure, the chemical composition of the ternary sulfide-based ceramic powder is preferably the Mgla,S4 or the CaLazS4.

[0030] In the present disclosure, the source A includes an alkaline earth metal elementary substance and/or an alkaline earth metal sulfide.

[0031] In the present disclosure, the source B includes a lanthanide metal elementary substance and/or a lanthanide metal sulfide.

[0032] In the present disclosure, the source S includes one or more of the alkaline earth metal sulfide, the lanthanide metal sulfide and an sulfur elementary substance.

[0033] In the present disclosure, in the source A, the source B, and the source S, an alkaline earth metal element, a lanthanide metal element, and a sulfur element satisfy a stoichiometric ratio of the three elements in the ternary sulfide-based ceramic powder.

[0034] In the present disclosure, the source A, the source B and the source S each include preferably the alkaline earth metal sulfide and the lanthanide metal sulfide.

[0035] In a specific example of the present disclosure, the source A, the source B and the source S each include preferably CaS and La,Ss.

[0036] In a specific example of the present disclosure, the source A, the source B and the source S each include preferably CaS and Gd,Ss.

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[0037] In the present disclosure, the source A, the source B and the source S each include 202064 preferably the alkaline earth metal sulfide, the lanthanide metal elementary substance and the sulfur elementary substance.

[0038] In a specific example of the present disclosure, the source A, the source B and the source S each include preferably CaS, La and S.

[0039] In the present disclosure, the source A, the source B and the source S each include preferably the alkaline earth metal elementary substance, the lanthanide metal elementary substance and the sulfur elementary substance.

[0040] In a specific example of the present disclosure, the source A, the source B and the source S each include preferably Mg, La and S.

[0041] In the present disclosure, the source A, the source B, and the source S each have a particle size of preferably less than 100 um.

[0042] In the present disclosure, the source A, the source B, and the source S each have a purity of preferably greater than or equal to 99.9%.

[0043] In the present disclosure, the milling ball is preferably made of tungsten carbide.

[0044] In the present disclosure, the milling ball has a diameter of 5 mm to 12 mm, more preferably 6 mm to 11mm, and most preferably 10 mm.

[0045] In the present disclosure, a total mass of the source A, the source B, and the source S, and a mass of the milling ball have a ratio of preferably 1:(10-100), more preferably 1:(10-50).

[0046] In the present disclosure, the source A, the source B, the source S and the milling ball are mixed preferably in a high-energy ball milling tank in a protective gas, where the protective gas includes preferably one or more selected from the group consisting of Ar, No and He, more preferably Ar and/or Na.

[0047] In the present disclosure, the high-energy ball milling is conducted at preferably 200 r/min to 800 r/min, more preferably 450 r/min to 650 r/min.

[0048] In the present disclosure, the high-energy ball milling is conducted for preferably greater than or equal to 6 h, more preferably 30 h to 50 h.

[0049] In the present disclosure, the high-energy ball milling is conducted in a protective gas, where the protective gas includes preferably one or more selected from the group consisting of Ar, N; and He, more preferably Ar and/or No.

[0050] In the present disclosure, the high-energy ball milling is preferably conducted by forward-reverse-rotation alternative high-energy ball milling, where each forward-rotation high-energy ball milling is conducted preferably for 30 min, and each reverse-rotation high-energy ball milling is conducted preferably for 30 min.

[0051] In the present disclosure, the high-energy ball milling is conducted preferably in a

BL-5468 high-energy ball mill, and the high-energy ball mill is preferably a planetary high-energy ball 7094 mill.

[0052] In the present disclosure, a high-energy ball-milled material is obtained after the high-energy ball milling; preferably, the high-energy ball-milled material is sieved to obtain the ternary sulfide-based ceramic powder. There is no special requirement for a specific implementation of the sieving, as long as the ternary sulfide-based ceramic powder and the milling ball can be separated.

[0053] In the present disclosure, a high-energy ball-milled material is obtained after the high-energy ball milling; preferably, the high-energy ball-milled material is sieved to obtain an initial ceramic powder; further, the initial ceramic powder is preferably annealed in vacuum or a protective gas to obtain the ternary sulfide-based ceramic powder.

[0054] In the present disclosure, the annealing is conducted at preferably 600°C to 1,100°C, more preferably 650°C to 1,000°C.

[0055] In the present disclosure, the annealing is conducted at a heating rate of preferably 5°C/min to 50°C/min, more preferably 10°C/min to 30°C/min from a room temperature to a working temperature.

[0056] In the present disclosure, the annealing is conducted for preferably 4 h to 12 h, more preferably 4 h.

[0057] In the present disclosure, the annealing is conducted in preferably vacuum or a protective gas.

[0058] In the present disclosure, the annealing is conducted at a vacuum degree of preferably less than 2x107 Pa.

[0059] In the present disclosure, the protective gas during the annealing includes preferably an inert gas and/or a reducing gas; and the inert gas is preferably Ar, and the reducing gas is preferably Hs S.

[0060] In the present disclosure, vacuum annealing can further eliminate lattice distortion of the initial ceramic powder caused by high-energy impact, to purify the initial ceramic powder.

[0061] The technical solutions in the present disclosure are clearly and completely described below in conjunction with examples of the present disclosure.

[0062] Example 1

[0063] In a glove box under an argon atmosphere, 3.2318 g of a CaS powder (particle size < 100 um, purity > 99.9%), 12.4463 g of a La powder (particle size < 100 um, purity > 99.9%), and

4.3219 g of an S powder (particle size < 100 um, purity > 99.9%) were mixed well, and an obtained mixed powder was put into a high-energy ball milling tank together with 200 g of a tungsten carbide milling ball with a diameter of 10 mm, followed by sealing and locking well.

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[0064] The high-energy ball milling tank was installed on a high-energy ball mill, and 502068 high-energy ball milling was conducted for 40 h in a mode of alternatively forward-reverse rotation at 500 r/min.

[0065] The milling ball and the mixed powder were separated by sieving, and the mixed powder was put into a crucible for annealing in a vacuum annealing furnace. The annealing was conducted at a vacuum degree of 3x10” Pa and at 800°C for 4 h; and the mixed powder was cooled to room temperature and taken out, to obtain a ternary sulfide-based ceramic powder with a chemical composition of CaLazS4.

[0066] FIG 1 shows an XRD phase detection diagram of the Cala;S; ceramic powder synthesized by the high-energy ball milling method in this example. It can be concluded from FIG 1 that the CaLazS4 ceramic powder is successfully synthesized in this example.

[0067] FIG 2 shows an electron microscope photograph of the CaLazS4 ceramic powder synthesized by the high-energy ball milling method in Example 1 of the present disclosure; and FIG 3 shows a particle size distribution diagram of the CaLazS4 ceramic powder synthesized by the high-energy ball milling method in Example 1 of the present disclosure. It can be concluded from FIG 2 and FIG 3 that the ternary sulfide-based ceramic powder prepared by the preparation method provided in this example has a fine and uniform particle size.

[0068] Example 2

[0069] In a glove box under an argon atmosphere, 3.2448 g of a CaS powder (particle size < 100 um, purity > 99.9%) and 16.7552 g of a La;Ss powder (particle size < 100 um, purity > 99.9%) were mixed well, and an obtained mixed powder was put into a high-energy ball milling tank together with 200 g of a tungsten carbide milling ball with a diameter of 10 mm, followed by sealing and locking well.

[0070] The high-energy ball milling tank was installed on a high-energy ball mill, and high-energy ball milling was conducted for 50 h in a mode of alternatively forward-reverse rotation at 500 r/min.

[0071] The milling ball and the mixed powder were separated by sieving, and the mixed powder was put into a crucible for annealing in a vacuum annealing furnace. The annealing was conducted at a vacuum degree of 3x10” Pa and at 800°C for 4 h; and the mixed powder was cooled to room temperature and taken out, to obtain a ternary sulfide-based ceramic powder with a chemical composition of CaLazS4.

[0072] The test results are similar to those in Example 1.

[0073] Example 3

[0074] In a glove box under an argon atmosphere, 1.1302 g of a Mg powder (particle size < 100 um, purity > 99.9%), 12.9186 g of a La powder (particle size < 100 um, purity > 99.9%), and 7

BL-5468

5.9512 g of an S powder (particle size < 100 um, purity > 99.9%) were mixed well, and an 502068 obtained mixed powder was put into a high-energy ball milling tank together with 200 g of a tungsten carbide milling ball with a diameter of 10 mm, followed by sealing and locking well; the high-energy ball milling tank was installed on a high-energy ball mill, and high-energy ball milling was conducted for 30 h in a mode of alternatively forward-reverse rotation at 600 r/min.

[0075] The milling ball and the mixed powder were separated by sieving, and the mixed powder was put into a crucible for annealing in a vacuum annealing furnace. The annealing was conducted at a vacuum degree of 3x10 Pa and at 850°C for 4 h; and the mixed powder was cooled to room temperature and taken out, to obtain a ternary sulfide-based ceramic powder with a chemical composition of MgLarS4.

[0076] The test results are similar to those in Example 1.

[0077] Example 4

[0078] In a glove box under an argon atmosphere, 1.6592 g of a CaS powder (particle size < 100 um, purity > 99.9%), and 18.3408 g of a Gd, S; powder (particle size < 100 um, purity > 99.9%) were mixed well, and an obtained mixed powder was put into a high-energy ball milling tank together with 200 g of a tungsten carbide milling ball with a diameter of 10 mm, followed by sealing and locking well; the high-energy ball milling tank was installed on a high-energy ball mill, and high-energy ball milling was conducted for 30 h in a mode of alternatively forward-reverse rotation at 600 r/min.

[0079] The milling ball and the mixed powder were separated by sieving, and the mixed powder was put into a crucible for annealing in a vacuum annealing furnace. The annealing was conducted at a vacuum degree of 3x10 Pa and at 900°C for 4 h; and the mixed powder was cooled to room temperature and taken out, to obtain a ternary sulfide-based ceramic powder with a chemical composition of GaGd»S4.

[0080] The test results are similar to those in Example 1.

[0081] The above descriptions are merely preferred implementations of the present disclosure. It should be noted that a person of ordinary skill in the art may further make several improvements and modifications without departing from the principle of the present disclosure, but such improvements and modifications should be deemed as falling within the protection scope of the present disclosure.

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Claims

BL-5468 LU502064 CLAIMS

1. A preparation method of a ternary sulfide-based ceramic powder, comprising the following steps: in a protective gas, mixing a source A, a source B, a source S, and a milling ball for high-energy ball milling to obtain a ternary sulfide-based ceramic powder with a chemical composition of AB»S4, wherein in the AB»S4, A is an alkaline earth metal, and B is a lanthanide metal; the source A comprises an alkaline earth metal elementary substance and/or an alkaline earth metal sulfide, the source B comprises a lanthanide metal elementary substance and/or a lanthanide metal sulfide, and the source S comprises one or more of the alkaline earth metal sulfide, the lanthanide metal sulfide and a sulfur elementary substance; and in the source A, the source B, and the source S, an alkaline earth metal element, a lanthanide metal element, and a sulfur element satisfy a stoichiometric ratio of the three elements in the ternary sulfide-based ceramic powder.

2. The preparation method according to claim 1, wherein in the AB2S4, A is selected from the group consisting of Mg, Ca, and Ba; and B is selected from the group consisting of La, Pr, and Gd.

3. The preparation method according to claim 1 or 2, wherein the chemical composition of the ternary sulfide-based ceramic powder is any one selected from the group consisting of MgLarS4, CaLarS4, SrLazS4, BaLarS4, MgGd, Ss, CaGd, Ss, SrGd, Ss, and BaGd, Ss.

4. The preparation method according to any one of claims 1 to 3, wherein a total mass of the source A, the source B, and the source S, and a mass of the milling ball have a ratio of 1:(10-100).

5. The preparation method according to claim 1, wherein the milling ball has a diameter of 5 mm to 12 mm.

6. The preparation method according to claim 1, wherein the high-energy ball milling is conducted at 200 r/min to 800 r/min for greater than or equal to 6 h.

7. The preparation method according to claim 1, further comprising the following step after the high-energy ball milling: annealing an obtained high-energy ball-milled material in vacuum 9

BL-5468 LU502064 or a protective gas to obtain the ternary sulfide-based ceramic powder; wherein the annealing is conducted at 600°C to 1,100°C for 4 h to 12 h.

8. The preparation method according to any one of claims 1 to 3, wherein the source A, the source B, and the source S each have a particle size of less than 100 um, and a purity of greater than or equal to 99.9%.

9. The preparation method according to claim 7, wherein the annealing is conducted at a heating rate of 5°C/min to 50°C/min from a room temperature to a working temperature.

10. The preparation method according to claim 1 or 7, wherein the protective gas is independently one or more selected from the group consisting of Ar, N, and He.