CN114014664A - Preparation method of ternary sulfide ceramic powder - Google Patents

Preparation method of ternary sulfide ceramic powder Download PDF

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CN114014664A
CN114014664A CN202111554744.4A CN202111554744A CN114014664A CN 114014664 A CN114014664 A CN 114014664A CN 202111554744 A CN202111554744 A CN 202111554744A CN 114014664 A CN114014664 A CN 114014664A
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ceramic powder
sulfide
alkaline earth
earth metal
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贾光
沈祥
夏克伦
顾杰荣
仵苗苗
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Ningbo Institute Of Oceanography
Ningbo University
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Ningbo Institute Of Oceanography
Ningbo University
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Priority to LU502064A priority patent/LU502064B1/en
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Abstract

The invention relates to the technical field of infrared transparent ceramics, in particular to a preparation method of ternary sulfide ceramic powder. The preparation method provided by the invention is characterized in that in protective gas, the A source, the B source, the S source and grinding balls are mixed for high-energy ball milling to obtain the chemical composition AB2S4The ternary sulfide ceramic powder of (AB)2S4Wherein A is an alkaline earth metal and B is a lanthanide metal; the source A comprises an alkaline earth metal simple substance and/or an alkaline earth metal sulfide, the source B comprises a lanthanide metal simple substance and/or a lanthanide metal sulfide, and the source S is one or more of an alkaline earth metal sulfide, a lanthanide metal sulfide and a simple substance sulfur. The alkaline earth metal elements, lanthanide series metal elements and sulfur elements in the A source, the B source and the S source meet the stoichiometric ratio of the three elements in the ternary sulfide ceramic powder. The present invention providesThe preparation method is safe and efficient, and has simple operation and low raw material cost.

Description

Preparation method of ternary sulfide ceramic powder
Technical Field
The invention relates to the technical field of infrared transparent ceramics, in particular to a preparation method of ternary sulfide ceramic powder.
Background
The infrared transparent ceramics are a new developed infrared optical material, and have gradually become the main material used for infrared device windows and fairings of various aircrafts, detectors and the like due to the advantages of high density, few defects, wide transmission waveband, high transmittance, high hardness, good abrasion resistance and the like. Currently, most studied infrared transparent ceramics have oxide ceramics (Al)2O3、Y2O3、ZrO2Etc.), nitride ceramics (Si)3N4AlON, etc.), sulfide ceramics (ZnS, etc.), fluoride ceramics (MgF, etc.). However, with the gradual complication of infrared detection application scenes in recent years, the comprehensive properties of the ceramic material, specifically including mechanical properties and infrared transmittance, cannot meet the use requirements, and the development of a ceramic material with good mechanical properties, a wide infrared transmittance range and a high transmittance is urgently needed to fill the technical gap and the application gap.
The ternary sulfide infrared transparent ceramic is an excellent material for improving the performance of an infrared window and a fairing, the infrared transmission cut-off wavelength of the ternary sulfide infrared transparent ceramic reaches 20 micrometers, and the transmittance of the ternary sulfide infrared transparent ceramic is more than 50% in a long-wave infrared band of 8-14 micrometers. Compared with other infrared transparent ceramics, the ternary sulfide ceramics has high hardness (570 Kg/mm)2) The material has high bending strength (49MPa) and outstanding rain, wind and sand erosion resistance, and is very suitable for being used as a new-generation infrared window and fairing material.
The first step of obtaining the ternary sulfide infrared transparent ceramic is to prepare pure ternary sulfide ceramic powder, the method adopted for preparing the ternary sulfide ceramic powder at present is to carry out long-time vulcanization on a precursor at high temperature, and a used vulcanization medium is hydrogen sulfide or carbon disulfide gas. Although the method can prepare the ternary sulfide ceramic powder with higher purity, the used sulfide gas is extremely toxic, flammable and explosive, and has larger potential safety hazard.
Disclosure of Invention
In view of the above, the invention provides a preparation method of ternary sulfide ceramic powder, which is safe and efficient, and has simple operation and low raw material cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of ternary sulfide ceramic powder, which comprises the following steps:
in protective gas, mixing A source, B source, S source and grinding balls for high-energy ball milling to obtain AB with chemical composition2S4The ternary sulfide ceramic powder of (AB)2S4Wherein A is an alkaline earth metal and B is a lanthanide metal; the source A comprises an alkaline earth metal simple substance and/or an alkaline earth metal sulfide, the source B comprises a lanthanide metal simple substance and/or a lanthanide metal sulfide, the source S comprises one or more of an alkaline earth metal sulfide, a lanthanide metal sulfide and a sulfur simple substance, and the alkaline earth metal element, the lanthanide metal element and the sulfur element in the source A, the source B and the source S meet the stoichiometric ratio of three elements in the ternary sulfide ceramic powder.
Preferably, the AB is2S4A in (A) is Mg, Ca or Ba; the AB is2S4B in (3) is La, Pr or Gd.
Preferably, the chemical composition of the ternary sulfide ceramic powder is MgLa2S4、CaLa2S4、SrLa2S4、BaLa2S4、MgGd2S4、CaGd2S4、SrGd2S4And BaGd2S4Any one of them.
Preferably, the mass ratio of the total mass of the A source, the B source and the S source to the grinding ball is 1 (10-100).
Preferably, the diameter of the grinding ball is 5-12 mm.
Preferably, the rotating speed of the high-energy ball milling is 200-800 r/min, and the time of the high-energy ball milling is more than or equal to 6 h.
Preferably, the high energy ball mill further comprises: annealing the obtained high-energy ball-milling material in vacuum or protective gas to obtain ternary sulfide ceramic powder;
the heat preservation temperature of the annealing treatment is 600-1100 ℃, and the heat preservation time of the annealing treatment is 4-12 hours.
Preferably, the particle sizes of the A source, the B source and the S source are independently less than 100 mu m, and the purities of the A source, the B source and the S source are independently more than or equal to 99.9 percent.
Preferably, the heating rate from room temperature to the heat preservation temperature of the annealing treatment is 5-50 ℃/min.
Preferably, the protective gas is Ar and N independently2And He.
The invention provides a preparation method of ternary sulfide ceramic powder, which comprises the following steps: in protective gas, mixing A source, B source, S source and grinding balls for high-energy ball milling to obtain AB with chemical composition2S4The ternary sulfide ceramic powder of (AB)2S4Wherein A is an alkaline earth metal and B is a lanthanide metal; the source A comprises an alkaline earth metal simple substance and/or an alkaline earth metal sulfide, the source B comprises a lanthanide metal simple substance and/or a lanthanide metal sulfide, and the source S comprises one or more of an alkaline earth metal sulfide, a lanthanide metal sulfide and a simple substance sulfur. The alkaline earth metal elements, lanthanide series metal elements and sulfur elements in the A source, the B source and the S source meet the stoichiometric ratio of the three elements in the ternary sulfide ceramic powder. According to the preparation method provided by the invention, alkaline earth metal elements, lanthanide series metal elements and sulfur elements in the A source, the B source and the S source meet the stoichiometric ratio of three elements in the ternary sulfide ceramic powder, a high-energy ball milling method is adopted in protective gas, high-energy impact during high-energy ball milling is utilized to provide energy for the A source, the B source and the S source, and the ternary sulfide ceramic powder is obtained by direct solid solution combination. The preparation method provided by the invention can be used for preparing the ternary sulfide ceramic powder with fine and uniform granularity. The preparation method provided by the invention does not use toxic and dangerous gas of hydrogen sulfide or carbon disulfide, is safe and efficient, is simple to operate,The raw material cost is low, the method is suitable for small-amount preparation in a laboratory and industrial batch production, and the further development of the application technology of the infrared transparent ceramics is expected to be promoted.
Drawings
FIG. 1 is a schematic diagram of the synthesis of CaLa by high energy ball milling method in example 1 of the present invention2S4XRD phase detection diagram of the ceramic powder;
FIG. 2 is a schematic diagram of the synthesis of CaLa by high-energy ball milling method in example 1 of the present invention2S4Electron microscope photographs of the ceramic powder;
FIG. 3 is a schematic diagram of the synthesis of CaLa by high-energy ball milling method in example 1 of the present invention2S4The particle size distribution of the ceramic powder.
Detailed Description
The invention provides a preparation method of ternary sulfide ceramic powder, which comprises the following steps:
in protective gas, mixing A source, B source, S source and grinding balls for high-energy ball milling to obtain AB with chemical composition2S4The ternary sulfide ceramic powder of (AB)2S4Wherein A is an alkaline earth metal and B is a lanthanide metal; the source A comprises an alkaline earth metal simple substance and/or an alkaline earth metal sulfide, the source B comprises a lanthanide metal simple substance and/or a lanthanide metal sulfide, the source S comprises one or more of an alkaline earth metal sulfide, a lanthanide metal sulfide and a sulfur simple substance, and the alkaline earth metal element, the lanthanide metal element and the sulfur element in the source A, the source B and the source S meet the stoichiometric ratio of three elements in the ternary sulfide ceramic powder.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art, unless otherwise specified.
In the invention, the chemical composition of the ternary sulfide ceramic powder is AB2S4The AB2S4Wherein A is an alkaline earth metal and B is a lanthanide metal.
In the present invention, the AB is2S4A in (A) is preferably Mg, Ca or Ba; the AB is2S4B in (3) is preferably La, Pr or Gd.
In the present inventionThe chemical composition of the ternary sulfide ceramic powder is preferably MgLa2S4、CaLa2S4、SrLa2S4、BaLa2S4、MgGd2S4、CaGd2S4、SrGd2S4、BaGd2S4Any one of them.
In a specific embodiment of the present invention, the chemical composition of the ternary sulfide ceramic powder is preferably MgLa2S4Or CaLa2S4。
In the present invention, the a source includes an alkaline earth metal element and/or an alkaline earth metal sulfide.
In the present invention, the B source includes a lanthanide metal simple substance and/or a lanthanide metal sulfide.
In the present invention, the S source includes one or more of an alkaline earth metal sulfide, a lanthanide metal sulfide, and elemental sulfur.
In the invention, the alkaline earth metal elements, lanthanide series metal elements and sulfur elements in the A source, the B source and the S source meet the stoichiometric ratio of three elements in the ternary sulfide ceramic powder.
In the present invention, the a source, B source and S source preferably include alkaline earth metal sulfides and lanthanide metal sulfides.
In a specific embodiment of the present invention, the A source, B source and S source particularly preferably comprise CaS and La2S3。
In a particular embodiment of the invention, the A, B and S sources particularly preferably comprise CaS and Gd2S3。
In the present invention, the a source, the B source, and the S source preferably include an alkaline earth metal sulfide, a lanthanoid metal simple substance, and a sulfur simple substance.
In a specific embodiment of the present invention, the a source, B source and S source particularly preferably include CaS, La and S.
In the present invention, the a source, the B source, and the S source preferably include an alkaline earth metal element, a lanthanoid metal element, and a sulfur element.
In a specific embodiment of the present invention, the a source, B source and S source particularly preferably include Mg, La and S.
In the present invention, the particle size of the A source, B source and S source is independently preferably < 100 μm.
In the present invention, the purities of the A source, B source and S source are independently preferably 99.9% or more.
In the present invention, the material of the grinding beads is preferably tungsten carbide.
In the invention, the diameter of the grinding ball is 5-12 mm, more preferably 6-11 mm, and most preferably 10 mm.
In the invention, the mass ratio of the total mass of the A source, the B source and the S source to the grinding ball is preferably 1 (10-100), and more preferably 1 (10-50).
In the present invention, the source A, source B and source S and the grinding balls are preferably mixed in a high energy ball mill tank, the mixing is carried out in a protective gas, and the protective gas preferably comprises Ar and N2And He, more preferably Ar and/or N2。
In the invention, the rotation speed of the high-energy ball mill is preferably 200-800 r/min, and more preferably 450-650 r/min.
In the invention, the time of the high-energy ball milling is preferably not less than 6 hours, and more preferably 30-50 hours.
In the present invention, the high energy ball milling is performed in a protective gas, preferably comprising Ar, N2And He, more preferably Ar and/or N2。
In the invention, the high-energy ball milling mode is preferably positive and negative rotation alternative high-energy ball milling, the time of each positive rotation high-energy ball milling is preferably 30min, and the time of each negative rotation high-energy ball milling is preferably 30 min.
In the present invention, the high-energy ball milling is preferably carried out in a high-energy ball mill, which is particularly preferably a planetary high-energy ball mill.
In the invention, the high-energy ball grinding material is obtained after the high-energy ball milling, and the high-energy ball grinding material is preferably screened to obtain the ternary sulfide ceramic powder. The screening method has no special requirements on the specific implementation mode of screening, and the ternary sulfide ceramic powder can be separated from the grinding balls.
In the invention, the high-energy ball grinding material is obtained after the high-energy ball milling, the high-energy ball grinding material is preferably screened to obtain initial ceramic powder, and the invention also preferably comprises annealing treatment of the initial ceramic powder in vacuum or protective gas to obtain the ternary sulfide ceramic powder.
In the invention, the heat preservation temperature of the annealing treatment is preferably 600-1100 ℃, and more preferably 650-1000 ℃.
In the invention, the heating rate from the room temperature to the heat preservation temperature of the annealing treatment is preferably 5-50 ℃/min, and more preferably 10-30 ℃/min.
In the invention, the heat preservation time of the annealing treatment is preferably 4-12 h, and more preferably 4 h.
In the present invention, the annealing treatment is preferably performed in a vacuum or a protective gas.
In the present invention, the degree of vacuum at the time of the annealing treatment is preferably < 2X 10-5Pa。
In the present invention, the protective gas in the annealing treatment preferably includes an inert gas and/or a reducing gas, and in the present invention, the inert gas is preferably Ar, and the reducing gas is preferably H2S。
The invention can further eliminate the lattice distortion of the initial ceramic powder caused by high-energy impact through vacuum annealing treatment, and purify the initial ceramic powder.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
In a glove box in argon atmosphere, 3.2318g of CaS powder (the grain diameter is less than 100 mu m, the purity is more than or equal to 99.9 percent), 12.4463g of La powder (the grain diameter is less than 100 mu m, the purity is more than or equal to 99.9 percent) and 4.3219g S powder (the grain diameter is less than 100 mu m, the purity is more than or equal to 99.9 percent) are uniformly mixed, and then the mixture and 200g of tungsten carbide grinding balls with the diameter of 10mm are put into a high-energy ball milling tank for sealing and locking;
mounting a high-energy ball milling tank on a high-energy ball mill, and performing high-energy ball milling for 40 hours at a rotating speed of 500r/min in a positive and negative rotation alternate operation mode;
sieving to separate the ball powder, loading the powder into a crucible, and annealing in a vacuum annealing furnace. Vacuum degree of 3X 10-5Pa, the heat preservation temperature is 800 ℃, the heat preservation time is 4 hours, the mixture is cooled to the room temperature and taken out to obtain the chemical composition CaLa2S4The ternary sulfide ceramic powder.
FIG. 1 shows the synthesis of CaLa by high-energy ball milling method according to this example2S4The XRD phase detection diagram of the ceramic powder can be obtained from FIG. 1, and CaLa is successfully synthesized in the embodiment2S4The ceramic powder of (1).
FIG. 2 is a schematic diagram of the synthesis of CaLa by high-energy ball milling method in example 1 of the present invention2S4Electron microscope photographs of the ceramic powder; FIG. 3 is a schematic diagram of the synthesis of CaLa by high-energy ball milling method in example 1 of the present invention2S4The particle size distribution of the ceramic powder. As can be seen from fig. 2 and 3, the ternary sulfide ceramic powder prepared by the preparation method provided by this embodiment has a fine and uniform particle size.
Example 2
In a glove box under argon atmosphere, 3.2448 g of CaS powder (particle size < 100 μm, purity ≥ 99.9%) and 16.7552 g of La were mixed2S3Uniformly mixing the powder (the particle size is less than 100 mu m, the purity is more than or equal to 99.9 percent), and then putting the powder and 200g of tungsten carbide grinding balls with the diameter of 10mm into a high-energy ball milling tank for sealing and locking;
mounting a high-energy ball milling tank on a high-energy ball mill, and performing high-energy ball milling for 50 hours at a rotating speed of 500r/min in a positive and negative rotation alternate operation mode;
sieving to separate the ball powder, loading the powder into a crucible, and annealing in a vacuum annealing furnace. Vacuum degree of 3X 10-5Pa, the heat preservation temperature is 800 ℃, the heat preservation time is 4 hours, the mixture is cooled to the room temperature and taken out to obtain the chemical composition CaLa2S4The ternary sulfide ceramic powder.
The test results were similar to example 1.
Example 3
In a glove box in argon atmosphere, 1.1302g of Mg powder (the grain diameter is less than 100 mu m, the purity is more than or equal to 99.9 percent), 12.9186g of La powder (the grain diameter is less than 100 mu m, the purity is more than or equal to 99.9 percent) and 5.9512g S powder (the grain diameter is less than 100 mu m, the purity is more than or equal to 99.9 percent) are uniformly mixed, and then the mixture and 200g of tungsten carbide grinding balls with the diameter of 10mm are put into a high-energy ball milling tank for sealing and locking; mounting a high-energy ball milling tank on a high-energy ball mill, and performing high-energy ball milling for 30 hours at a rotating speed of 600r/min in a positive and negative rotation alternate operation mode;
sieving to separate the ball powder, loading the powder into a crucible, and annealing in a vacuum annealing furnace. Vacuum degree of 3X 10-5Pa, keeping the temperature at 850 ℃, keeping the temperature for 4 hours, cooling to room temperature and taking out to obtain the MgLa with the chemical composition2S4The ternary sulfide ceramic powder.
The test results were similar to example 1.
Example 4
In a glove box under argon atmosphere, 1.6592 g of CaS powder (particle size < 100 μm, purity ≥ 99.9%) and 18.3408 g of Gd2S3Uniformly mixing the powder (the particle size is less than 100 mu m, the purity is more than or equal to 99.9 percent), and then putting the powder and 200g of tungsten carbide grinding balls with the diameter of 10mm into a high-energy ball milling tank for sealing and locking; mounting a high-energy ball milling tank on a high-energy ball mill, and performing high-energy ball milling for 30 hours at a rotating speed of 600r/min in a positive and negative rotation alternate operation mode;
sieving to separate the ball powder, loading the powder into a crucible, and annealing in a vacuum annealing furnace. Vacuum degree of 3X 10-5Pa, the temperature is kept at 900 ℃, the temperature is kept for 4 hours, the mixture is cooled to the room temperature and taken out to obtain the chemical composition of GaGd2S4The ternary sulfide ceramic powder.
The test results were similar to example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of ternary sulfide ceramic powder is characterized by comprising the following steps:
in protective gas, mixing A source, B source, S source and grinding balls for high-energy ball milling to obtain AB with chemical composition2S4The ternary sulfide ceramic powder of (AB)2S4Wherein A is an alkaline earth metal and B is a lanthanide metal; the source A comprises an alkaline earth metal simple substance and/or an alkaline earth metal sulfide, the source B comprises a lanthanide metal simple substance and/or a lanthanide metal sulfide, the source S comprises one or more of an alkaline earth metal sulfide, a lanthanide metal sulfide and a sulfur simple substance, and the alkaline earth metal element, the lanthanide metal element and the sulfur element in the source A, the source B and the source S meet the stoichiometric ratio of three elements in the ternary sulfide ceramic powder.
2. The method of claim 1, wherein the AB is in the form of a powder2S4A in (A) is Mg, Ca or Ba; the AB is2S4B in (3) is La, Pr or Gd.
3. The production method according to claim 1 or 2, wherein the chemical composition of the ternary sulfide ceramic powder is MgLa2S4、CaLa2S4、SrLa2S4、BaLa2S4、MgGd2S4、CaGd2S4、SrGd2S4And BaGd2S4Any one of them.
4. The production method according to any one of claims 1 to 3, wherein the ratio of the total mass of the A source, the B source and the S source to the mass of the grinding balls is 1 (10 to 100).
5. The method of claim 1, wherein the grinding balls have a diameter of 5 to 12 mm.
6. The preparation method of claim 1, wherein the rotation speed of the high-energy ball mill is 200-800 r/min, and the time of the high-energy ball mill is not less than 6 h.
7. The method of claim 1, further comprising, after the high energy ball milling: annealing the obtained high-energy ball-milling material in vacuum or protective gas to obtain ternary sulfide ceramic powder;
the heat preservation temperature of the annealing treatment is 600-1100 ℃, and the heat preservation time of the annealing treatment is 4-12 hours.
8. The method according to any one of claims 1 to 3, wherein the particle size of the A source, the B source and the S source is independently < 100 μm, and the purity of the A source, the B source and the S source is independently 99.9% or more.
9. The method according to claim 7, wherein a temperature increase rate from room temperature to the holding temperature of the annealing treatment is 5 to 50 ℃/min.
10. The method of claim 1 or 7, wherein the shielding gas is independently Ar, N2And He.
CN202111554744.4A 2021-12-17 2021-12-17 Preparation method of ternary sulfide ceramic powder Pending CN114014664A (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
US6793875B1 (en) * 1997-09-24 2004-09-21 The University Of Connecticut Nanostructured carbide cermet powders by high energy ball milling
CN101513674A (en) * 2009-04-02 2009-08-26 济南大学 L1<2>-TiAl3 intermetallic compound nano powder and preparation method thereof
CN102992767A (en) * 2012-11-19 2013-03-27 西安理工大学 Preparation method for high-purity Ti3AlC2 block material
CN113149651A (en) * 2021-05-28 2021-07-23 武汉理工大学 High-energy ball milling and SPS sintering CaLa2S4Preparation method of infrared transparent ceramic
CN113788677A (en) * 2021-09-28 2021-12-14 上海电机学院 High-entropy sesqui-rare earth sulfide ceramic material and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6793875B1 (en) * 1997-09-24 2004-09-21 The University Of Connecticut Nanostructured carbide cermet powders by high energy ball milling
CN101513674A (en) * 2009-04-02 2009-08-26 济南大学 L1<2>-TiAl3 intermetallic compound nano powder and preparation method thereof
CN102992767A (en) * 2012-11-19 2013-03-27 西安理工大学 Preparation method for high-purity Ti3AlC2 block material
CN113149651A (en) * 2021-05-28 2021-07-23 武汉理工大学 High-energy ball milling and SPS sintering CaLa2S4Preparation method of infrared transparent ceramic
CN113788677A (en) * 2021-09-28 2021-12-14 上海电机学院 High-entropy sesqui-rare earth sulfide ceramic material and preparation method and application thereof

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