阅读说明：本技术 一种含锰钡白云石连续固溶体晶体及其高温高压合成方法 (Manganese-containing barium dolomite continuous solid solution crystal and high-temperature high-pressure synthesis method thereof ) 是由 翟福强 梁文 李璐 陈西浩 于 2021-06-25 设计创作，主要内容包括：本发明公开了提供一种含锰钡白云石连续固溶体晶体及其高温高压合成方法,使用分析纯的碳酸钡和二水草酸镁以摩尔比1:1研磨混合均匀作为起始原料,通过高温高压反应得到前躯体BaMg(CO-3)-2；使用分析纯的碳酸钡和碳酸锰以摩尔比1:1研磨混合均匀作为起始原料,通过高温高压反应得到前躯体BaMn(CO-3)-2；使用前躯体BaMg(CO-3)-2和前躯体BaMn(CO-3)-2以摩尔比(1-x):x研磨混合均匀作为起始原料,通过高温高压反应得到含锰钡白云石连续固溶体晶体,该固溶体为纯相,锰含量0<x<1,晶体结构和对称性为三方晶系R-3m,无超晶格和氧有序,这为进一步天然发现富锰钡白云石提供重要实验参考。(The invention discloses a barium-containing dolomite continuous solid solution crystal and a high-temperature high-pressure synthesis method thereof, wherein analytically pure barium carbonate and magnesium oxalate dihydrate are ground and uniformly mixed in a molar ratio of 1:1 to serve as initial raw materials, and a precursor BaMg (CO) is obtained through high-temperature high-pressure reaction 3 ) 2 (ii) a Analytically pure barium carbonate and manganese carbonate are ground and uniformly mixed in a molar ratio of 1:1 to serve as initial raw materials, and a precursor BaMn (CO) is obtained through high-temperature high-pressure reaction 3 ) 2 (ii) a Using a precursor BaMg (CO) 3 ) 2 And a precursor BaMn (CO) 3 ) 2 Grinding and uniformly mixing the raw materials according to a molar ratio of (1-x): x to obtain a continuous solid solution crystal containing the manganiferous barium dolomite through high-temperature and high-pressure reaction, wherein the solid solution is a pure phase and has a manganese content of 0<x<1, the crystal structure and symmetry are trigonal R-3m, and no superlattice and oxygen order are provided, which provides for further natural discovery of the manganese-rich barium dolomiteImportant experimental references.)

1. A method for synthesizing a continuous solid solution crystal containing manganese barium dolomite at high temperature and high pressure is characterized by comprising the following steps:

precursor BaMg (CO)₃)₂The preparation of (1):

step 1, using analytically pure barium carbonate BaCO₃And magnesium oxalate dihydrate MgC₂O₄·2H₂Grinding and uniformly mixing O in a molar ratio of 1:1 to serve as an initial raw material;

step 2, pressing the mixture powder in the step 1 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;

and 4, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder to obtain a precursor BaMg (CO)₃)₂；

Precursor BaMn (CO)₃)₂The preparation of (1):

step 5, using analytically pure barium carbonate BaCO₃And manganese carbonate MnCO₃Grinding and uniformly mixing the raw materials as initial raw materials according to the molar ratio of 1: 1;

step 6, pressing the mixture powder in the step 5 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 7, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;

and 8, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder to obtain a precursor BaMn (CO)₃)₂；

Barium-manganese-containing dolomite continuous solid solution Ba (Mg)_1-xMn_x)(CO₃)₂Crystal preparation:

step 9, using the precursor BaMg (CO) obtained in step 4₃)₂And the precursor BaMn (CO) obtained in the step 8₃)₂Grinding and mixing uniformly by using a molar ratio of (1-x): x as a starting material, 0<x<1；

Step 10, pressing the mixture powder in the step 9 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, plugging a cylindrical sample into a platinum tube with the diameter of 5mm and the thickness of 0.1mm, adding 30 mu L of deionized water, sealing the platinum tube by using a welding gun, placing the platinum tube into an h-BN tube, and taking h-BN as a pressure transmission medium;

step 11, assembling the h-BN pipe provided with the sample in the step 6 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;

step 12, after the high-temperature high-pressure reaction is finished, taking out the sample, cutting the platinum tube by using a diamond cutter, and naturally air-drying the sample to obtain the barium manganite-containing dolomite continuous solid solution Ba (Mg)_1-xMn_x)(CO₃)₂And (4) crystals.

2. The method for synthesizing the nephrite continuous solid solution crystal containing the manganin barium under high temperature and high pressure according to claim 1, wherein the manufacturing method of the h-BN tube in the steps 2, 6 and 10 is the same, and the specific operation is as follows: drilling a phi 5mm hole in the center of a phi 10mm h-BN rod on a lathe to form an h-BN tube, inserting a sample into the tube, and sealing two ends of the h-BN tube by using phi 5mm h-BN sheets with the thickness of 2 mm. The method for assembling the h-BN pipe in the high-pressure synthesis assembly block in the steps 3, 7 and 11 is the same, and the specific operations comprise: selecting a pyrophyllite block, and punching a phi 12mm circular through hole in the center of the pyrophyllite block; a circular graphite heating furnace with the outer diameter of 12mm and the inner diameter of phi 10mm is sleeved in the circular through hole; placing a 10mm h-BN tube sealed sample in the middle of a graphite heating furnace; the upper end and the lower end of the round graphite heating furnace are sealed by pyrophyllite plugs.

3. The method for synthesizing the continuous solid solution crystal containing the lithopone at high temperature and high pressure according to claim 1, wherein the reaction conditions at high temperature and high pressure in step 3 are that the pressure is increased to 1GPa, then the temperature is increased to 800 ℃, the pressure and the heat are maintained for 6h, then quenching is carried out, and then the pressure is slowly released.

4. The method for synthesizing the continuous solid solution crystal containing the lithopone at high temperature and high pressure according to claim 1, wherein the reaction conditions of the high temperature and the high pressure in the step 7 are that the pressure is increased to 3GPa, then the temperature is increased to 800 ℃, the pressure is maintained and the temperature is kept for 6h, then quenching is carried out, and then the pressure is slowly released.

5. The method for synthesizing the continuous solid solution crystal containing the lithopone at high temperature and high pressure according to claim 1, wherein the reaction conditions at high temperature and high pressure in step 11 are that the pressure is increased to 3GPa, then the temperature is increased to 850 ℃, the pressure is maintained and the temperature is kept for 48h, then quenching is carried out, and then the pressure is slowly released.

6. The method for synthesizing the continuous solid solution crystal containing the barium manganite at high temperature and high pressure is characterized in that the continuous solid solution Ba (Mg) containing the barium manganite is synthesized in step 12_1-xMn_x)(CO₃)₂The crystal is pure phase, has no other impurities, and has a value of 0<x<1; the crystal structure and symmetry are trigonal crystal system R-3m, no superlattice and oxygen order are generated, and lattice parameters

7. High-temperature high-pressure synthesis of manganese-containing barium dolomiteContinuous solid solution crystal, characterized in that, in step 12, the MnBa Bainite continuous solid solution Ba (Mg)_1-xMn_x)(CO₃)₂The size of the crystal is 50-100 μm, the color of the crystal gradually changes from colorless transparency to blue fluorescence transparency along with the increase of the manganese content x, and the wrappage on the surface of the crystal gradually changes from black to brown.

Technical Field

The invention relates to the field of research of earth science and mineralogy, and relates to a barium manganite-containing dolomite continuous solid solution crystal and a high-temperature high-pressure synthesis method thereof.

Background

Minerals with different chemical compositions usually exist in the same-class phase, which depends on the cation substitution mechanism in the crystal structure, so the same-class relation between the chemical compositions and the crystal structureIs considered to be the core of mineralogical quantification studies. BaMg (CO) white barium marble₃)₂Is discovered successively under different geochemical conditions in the nature, and the chemical composition of the Mg shows that²⁺Ions usually being limited by Mn²⁺And (4) substituting to form the barium dolomite containing manganese with the same phase. Up to now, it has been found naturally that the maximum Mn content of the MnBaBabai marble reaches 20%. In addition, the barium dolomite analog BaMn (CO) has also been found in natural deposits of the sea of Boragina₃)₂. Therefore, the research on the solid solution of the barium dolomite containing manganese and the establishment of the homogeneous-phase class model are necessary conditions for restricting the chemical components of the natural barium dolomite, and are closely related to the geochemical properties such as the indication of the microstructure of the barium dolomite, the distribution of the deposition environment, the source of mineral formation and the like.

The nature of the same phase of the quasicity is entirely dependent on the difference in radius of the replacing cations, due to Mg²⁺-Mn²⁺Radius difference less thanSo Mg is usually observed²⁺-Mn²⁺Binary carbonate continuous solid solutions, e.g. of calcite type (Mg)_1-xMn_x)CO₃Dolomite type Ca (Mg)_1-xMn_x)(CO₃)₂. This indicates that Mg²⁺-Mn²⁺The substitution is mainly composed of (MgO)₆) And (3) controlling a six-coordinate octahedral unit. Therefore, it is presumed that they have the same structural unit (MgO)₆) The barium dolomite type of (A) will have the same substitution mechanism as the known calcite type and dolomite type, and can form a continuous solid solution Ba (Mg) substituted by manganese_1-xMn_x)(CO₃)₂. However, it is not found naturally that the content of manganese x is in the range of 20-100%, whereas the manganese content of the currently artificially synthesized lithopone by solution deposition does not exceed 10%, which results make this speculation questionable. Based on the condition that the intermediate components of the MnBaBaBaBabbin are absent, in order to make up the blank of the existing research, the method for artificially synthesizing the MnBabbin continuous solid solution is explored, and the natural MnBabbin marble and the determination thereof are further discoveredVolume studies provide the necessary experimental support.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: provides a continuous solid solution crystal containing the manganiferous barium dolomite and a high-temperature and high-pressure synthesis method thereof, which are used for filling the deficiency of the middle components of the prior natural manganiferous barium dolomite.

The technical scheme is a method for synthesizing a manganese-containing barium dolomite continuous solid solution crystal at high temperature and high pressure, which comprises the following steps:

precursor BaMg (CO)₃)₂The preparation of (1):

step 1, using analytically pure barium carbonate BaCO₃And magnesium oxalate dihydrate MgC₂O₄·2H₂Grinding and uniformly mixing O in a molar ratio of 1:1 to serve as an initial raw material;

step 2, pressing the mixture powder in the step 1 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;

step 4, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder

Obtaining precursor BaMg (CO)₃)₂；

Precursor BaMn (CO)₃)₂The preparation of (1):

step 5, using analytically pure barium carbonate BaCO₃And manganese carbonate MnCO₃Grinding and uniformly mixing the raw materials as initial raw materials according to the molar ratio of 1: 1;

step 6, pressing the mixture powder in the step 5 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 7, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;

step 8, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder

Obtaining precursor BaMn (CO)₃)₂；

Barium-manganese-containing dolomite continuous solid solution Ba (Mg)_1-xMn_x)(CO₃)₂Crystal preparation:

step 9, using the precursor BaMg (CO) obtained in step 4₃)₂And the precursor BaMn (CO) obtained in the step 8₃)₂Grinding and mixing uniformly by using a molar ratio of (1-x): x as a starting material, 0<x<1；

Step 10, pressing the mixture powder in the step 9 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, plugging a cylindrical sample into a platinum tube with the diameter of 5mm and the thickness of 0.1mm, adding 30 mu L of deionized water, sealing the platinum tube by using a welding gun, placing the platinum tube into an h-BN tube, and taking h-BN as a pressure transmission medium;

step 11, assembling the h-BN pipe provided with the sample in the step 6 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;

step 12, after the high-temperature high-pressure reaction is finished, taking out the sample, cutting the platinum tube by using a diamond cutter,

naturally air-drying the sample to obtain the continuous solid solution Ba (Mg) containing the manganese barium dolomite_1-xMn_x)(CO₃)₂And (4) crystals.

Further, the manufacturing method of the h-BN pipe in the steps 2, 6 and 10 is the same, and the specific operation is as follows: drilling a phi 5mm hole in the center of a phi 10mm h-BN rod on a lathe to form an h-BN tube, inserting a sample into the tube, and sealing two ends of the h-BN tube by using phi 5mm h-BN sheets with the thickness of 2 mm. The method for assembling the h-BN pipe in the high-pressure synthesis assembly block in the steps 3, 7 and 11 is the same, and the specific operations comprise: selecting a pyrophyllite block, and punching a phi 12mm circular through hole in the center of the pyrophyllite block; a circular graphite heating furnace with the outer diameter of 12mm and the inner diameter of phi 10mm is sleeved in the circular through hole; placing a 10mm h-BN tube sealed sample in the middle of a graphite heating furnace; the upper end and the lower end of the round graphite heating furnace are sealed by pyrophyllite plugs.

Further, the high-temperature and high-pressure reaction conditions in the step 3 are that the pressure is increased to 1GPa, then the temperature is increased to 800 ℃, the pressure and heat preservation are carried out for 6 hours, then quenching is carried out, and then the pressure is slowly released. And 7, under the high-temperature and high-pressure reaction condition, increasing the pressure to 3GPa, then increasing the temperature to 800 ℃, maintaining the pressure and preserving the heat for 6 hours, quenching, and then slowly releasing the pressure. And 11, under the high-temperature and high-pressure reaction condition, increasing the pressure to 3GPa, then increasing the temperature to 850 ℃, maintaining the pressure and preserving the heat for 48 hours, quenching, and then slowly releasing the pressure.

Further, step 12 is conducted to obtain a continuous solid solution of barium dolomite containing manganese (Ba) (Mg)_1-xMn_x)(CO₃)₂The crystal is pure phase, has no other impurities, and has a value of 0<x<1; the crystal structure and symmetry are trigonal crystal system R-3m, no superlattice and oxygen order are generated, and lattice parameters

Further, step 12 is conducted to obtain a continuous solid solution of barium dolomite containing manganese (Ba) (Mg)_1-xMn_x)(CO₃)₂The size of the crystal is 50-100 μm, the color of the crystal gradually changes from colorless transparency to blue fluorescence transparency along with the increase of the manganese content x, and the wrappage on the surface of the crystal gradually changes from black to brown.

The invention has the advantages that:

in 1961, barium dolomite was first discovered in Green River Format in Wyoming, USA, and then widely observed throughout the world. In 2009, barium dolomite Ba (Mg) with a manganese content of 20% was found in the dense-rock ore bed of Kremikovtsi, bulgaricus_0.8Mn_0.2)(CO₃)₂It is the barium dolomite solid solution with the highest manganese content at present. In 2012, a new carbonate was found in native sedimentary rock in the sea of porpoise, and its composition was determined to be BaMn (CO)₃)₂. Mineralogical studies show that Mg²⁺-Mn²⁺Substitution enables the formation of binary carbonate continuous solid solutions in calcite-and dolomite-type structures, from which it is speculated that the manganiferous barium dolomite should also be a continuous solid solution. However, the absence of the native manganese-rich 20-100% sample questioned this view. Therefore, the artificial synthesis of barium white containing manganese is developedThe method of marble is based on quantitative studies to obtain solid solutions of different manganese contents. Chang synthesized BaMg (CO) in 1964 for the first time by using a high-temperature high-pressure solid-phase method₃)₂And BaMn (CO)₃)₂Powder crystals, but subsequent repetition of this method and experimental conditions by Schmidt et al, revealed that the product was impure and BaCO was present₃And Mn₃O₄And (3) impurity phase. Lippmann was deposited in 1973 using a hydrothermal method to obtain pure BaMg (CO)₃)₂Crystals, and subsequent researchers have synthesized BaMn (CO) by this method₃)₂Powder crystals and attempts to synthesize the manganiferous barium dolomite. However, hydrothermal synthesis of the Mn-containing blanc fixe hardly exceeds 10%, which is lower than the Mn content found naturally in the Mn-containing blanc fixe. Based on the present natural findings and artificial synthetic results, mineralogical studies have been questioned, in the barium dolomite structure, Mg²⁺-Mn²⁺Substitutions may have limited solid solubility, i.e. no continuous solid solution can be formed, but the specific reason is not at all clear.

Based on the unsolved problems of the mineralogy, the innovation point of the invention is that the continuous solid solution Ba (Mg) containing the MnBa dolomite is synthesized for the first time_1-xMn_x)(CO₃)₂Crystals of manganese with a manganese content of 0<x<1, the experimental result shows that the manganiferous barium dolomite can form a continuous solid solution, and the solid solubility behavior of the manganiferous barium dolomite is completely phase-diagram with that of calcite type and dolomite type. The method has the advantages that the method utilizes the continuous solid solution crystal of the manganiferous barium dolomite to determine the evolution of the barium dolomite crystal structure and the Raman spectrum along with the change of the manganese content, and establishes the calibration relation of the manganese content, the crystal structure parameter and the Raman frequency shift, thereby providing important experimental reference for further discovering the manganiferous barium dolomite with the manganese content of 20-100 percent in the future. In addition, the current solution deposition is difficult to obtain the barium-containing dolomite, so that researchers cannot obtain the deposition product constant of the barium-containing dolomite. Compared with the prior art, the method can be characterized in that the continuous solid solution crystal containing the manganese barium dolomite is used as an initiator to be dissolved to form a solid-liquid saturated solution, the ion concentration of the saturated solution is tested by controlling the dissolving condition, the change relation of the solubility product constant along with the manganese content-pH value-temperature is determined, the precipitation product constant is further determined, and different manganese is conjecturedNatural mineralization condition of barium dolomite.

Detailed Description

Example 1:

high-temperature high-pressure synthesis of manganese-containing barium dolomite solid solution Ba (Mg)_0.9Mn_0.1)(CO₃)₂A method of crystallizing comprising the steps of:

step 1, using analytically pure barium carbonate BaCO₃And magnesium oxalate dihydrate MgC₂O₄·2H₂Grinding and uniformly mixing O in a molar ratio of 1:1 to serve as an initial raw material;

step 2, pressing the mixture powder in the step 1 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 1GPa, then raising the temperature to 800 ℃, maintaining the pressure and the temperature for 6 hours, quenching, and then slowly releasing the pressure;

and 4, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder to obtain a precursor BaMg (CO)₃)₂；

Step 5, using analytically pure barium carbonate BaCO₃And manganese carbonate MnCO₃Grinding and uniformly mixing the raw materials as initial raw materials according to the molar ratio of 1: 1;

step 6, pressing the mixture powder in the step 5 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 7, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 3GPa, then raising the temperature to 800 ℃, maintaining the pressure and the temperature for 6h, quenching, and then slowly releasing the pressure;

and 8, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder to obtain a precursor BaMn (CO)₃)₂；

Step 9, using the precursor BaMg (CO) obtained in step 4₃)₂And the precursor BaMn (CO) obtained in the step 8₃)₂Grinding and uniformly mixing the raw materials as initial raw materials according to a molar ratio of 9: 1;

step 10, pressing the mixture powder in the step 9 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, plugging a cylindrical sample into a platinum tube with the diameter of 5mm and the thickness of 0.1mm, adding 30 mu L of deionized water, sealing the platinum tube by using a welding gun, placing the platinum tube into an h-BN tube, and taking h-BN as a pressure transmission medium;

step 11, assembling the h-BN pipe provided with the sample in the step 6 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 3GPa, then raising the temperature to 850 ℃, maintaining the pressure and the temperature for 48 hours, quenching, and then slowly releasing the pressure;

step 12, after the high-temperature high-pressure reaction is finished, taking out the sample, cutting the platinum tube by using a diamond cutter, and naturally air-drying the sample to obtain the barium manganite-containing dolomite continuous solid solution Ba (Mg)_0.9Mn_0.1)(CO₃)₂And (4) crystals. The crystal is pure phase, has no other impurities, has a crystal size of 50-100 μm, is colorless and transparent, and has black surface coating.

Example 2:

high-temperature high-pressure synthesis of manganese-containing barium dolomite solid solution Ba (Mg)_0.8Mn_0.2)(CO₃)₂A method of crystallizing comprising the steps of:

step 1, using analytically pure barium carbonate BaCO₃And magnesium oxalate dihydrate MgC₂O₄·2H₂Grinding and uniformly mixing O in a molar ratio of 1:1 to serve as an initial raw material;

step 2, pressing the mixture powder in the step 1 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 1GPa, then raising the temperature to 800 ℃, maintaining the pressure and the temperature for 6 hours, quenching, and then slowly releasing the pressure;

and 4, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder to obtain a precursor BaMg (CO)₃)₂；

Step 5, using analytically pure barium carbonate BaCO₃And manganese carbonate MnCO₃Grinding and uniformly mixing the raw materials as initial raw materials according to the molar ratio of 1: 1;

step 6, pressing the mixture powder in the step 5 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 7, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 3GPa, then raising the temperature to 800 ℃, maintaining the pressure and the temperature for 6h, quenching, and then slowly releasing the pressure;

and 8, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder to obtain a precursor BaMn (CO)₃)₂；

Step 9, using the precursor BaMg (CO) obtained in step 4₃)₂And the precursor BaMn (CO) obtained in the step 8₃)₂Grinding and uniformly mixing the raw materials as initial raw materials according to a molar ratio of 8: 2;

step 10, pressing the mixture powder in the step 9 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, plugging a cylindrical sample into a platinum tube with the diameter of 5mm and the thickness of 0.1mm, adding 30 mu L of deionized water, sealing the platinum tube by using a welding gun, placing the platinum tube into an h-BN tube, and taking h-BN as a pressure transmission medium;

step 11, assembling the h-BN pipe provided with the sample in the step 6 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 3GPa, then raising the temperature to 850 ℃, maintaining the pressure and the temperature for 48 hours, quenching, and then slowly releasing the pressure;

step 12, after the high-temperature high-pressure reaction is finished, taking out the sample, cutting the platinum tube by using a diamond cutter, and naturally air-drying the sample to obtain the continuous solid containing the barium manganite dolomiteMelt Ba (Mg)_0.8Mn_0.2)(CO₃)₂And (4) crystals. The crystal is pure phase, has no other impurities, has a crystal size of 50-100 μm, is colorless and transparent, and has black surface coating.

Example 3:

high-temperature high-pressure synthesis of manganese-containing barium dolomite solid solution Ba (Mg)_0.1Mn_0.9)(CO₃)₂A method of crystallizing comprising the steps of:

step 1, using analytically pure barium carbonate BaCO₃And magnesium oxalate dihydrate MgC₂O₄·2H₂Grinding and uniformly mixing O in a molar ratio of 1:1 to serve as an initial raw material;

step 2, pressing the mixture powder in the step 1 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 1GPa, then raising the temperature to 800 ℃, maintaining the pressure and the temperature for 6 hours, quenching, and then slowly releasing the pressure;

and 4, after the high-temperature high-pressure reaction is finished, taking out the sample, stripping off gold foil on the surface of the sample, and grinding the sample into powder to obtain a precursor BaMg (CO)₃)₂；

Step 5, using analytically pure barium carbonate BaCO₃And manganese carbonate MnCO₃Grinding and uniformly mixing the raw materials as initial raw materials according to the molar ratio of 1: 1;

step 6, pressing the mixture powder in the step 5 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, wrapping a cylindrical sample by using a gold foil with the thickness of 0.02mm as a sample, placing the sample in an h-BN tube, and using the h-BN as a pressure transmission medium;

step 7, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 3GPa, then raising the temperature to 800 ℃, maintaining the pressure and the temperature for 6h, quenching, and then slowly releasing the pressure;

step 8, after the high-temperature high-pressure reaction is finished, the sample is putTaking out the sample, stripping off gold foil on the surface of the sample, and grinding into powder to obtain a precursor BaMn (CO)₃)₂；

Step 9, using the precursor BaMg (CO) obtained in step 4₃)₂And the precursor BaMn (CO) obtained in the step 8₃)₂Grinding and uniformly mixing the raw materials as initial raw materials according to a molar ratio of 9: 1;

step 10, pressing the mixture powder in the step 9 into a cylinder with the diameter of 5 multiplied by 3mm by using a tablet press, plugging a cylindrical sample into a platinum tube with the diameter of 5mm and the thickness of 0.1mm, adding 30 mu L of deionized water, sealing the platinum tube by using a welding gun, placing the platinum tube into an h-BN tube, and taking h-BN as a pressure transmission medium;

step 11, assembling the h-BN pipe provided with the sample in the step 6 in a high-pressure synthesis assembly block, placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, namely boosting the pressure to 3GPa, then raising the temperature to 850 ℃, maintaining the pressure and the temperature for 48 hours, quenching, and then slowly releasing the pressure;

step 12, after the high-temperature high-pressure reaction is finished, taking out the sample, cutting the platinum tube by using a diamond cutter, and naturally air-drying the sample to obtain the barium manganite-containing dolomite continuous solid solution Ba (Mg)_0.1Mn_0.9)(CO₃)₂And (4) crystals. The crystal is pure phase, has no other impurities, has a crystal size of 50-100 μm, is blue, fluorescent and transparent, and has a brown surface coating.

In all the above embodiments, the manufacturing methods of the h-BN tubes in the steps 2, 6 and 10 are the same, and the specific operations are as follows: drilling a phi 5mm hole in the center of a phi 10mm h-BN rod on a lathe to form an h-BN tube, inserting a sample into the tube, and sealing two ends of the h-BN tube by using phi 5mm h-BN sheets with the thickness of 2 mm. The method for assembling the h-BN pipe in the high-pressure synthesis assembly block in the steps 3, 7 and 11 is the same, and the specific operations comprise: selecting a pyrophyllite block, and punching a phi 12mm circular through hole in the center of the pyrophyllite block; a circular graphite heating furnace with the outer diameter of 12mm and the inner diameter of phi 10mm is sleeved in the circular through hole; placing a 10mm h-BN tube sealed sample in the middle of a graphite heating furnace; the upper end and the lower end of the round graphite heating furnace are sealed by pyrophyllite plugs.

The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.