CN114086256B - Preparation method of enstatite single crystal with high calcium, high manganese and high water content - Google Patents
Preparation method of enstatite single crystal with high calcium, high manganese and high water content Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-calcium high-manganese high-water content enstatite single crystal, which comprises the following steps: preparing a mixture cylinder sample by taking solid magnesium nitrate hexahydrate powder, solid calcium nitrate tetrahydrate powder, solid manganese (II) nitrate tetrahydrate powder, liquid tetraethoxysilane and absolute ethyl alcohol concentration as starting raw materials according to the stoichiometry of enstatite; preparing a water source wafer by taking solid natural serpentine powder, solid natural birnessite powder and solid natural hydrated lime powder as raw materials; placing water source wafers at two ends of the mixture cylinder sample; putting the mixture cylindrical sample and the water source wafer into a gold-palladium alloy sample tube for high-temperature and high-pressure reaction to prepare high-calcium high-manganese high-water-content enstatite single crystals; the method solves the technical blank of preparing the high-calcium, high-manganese and high-water content enstatite single crystal so as to obtain large-particle experimental samples of the high-calcium, high-manganese and high-water content enstatite single crystal.
Description
Technical Field
The invention belongs to the technical field of mineral single crystal sample synthesis under high temperature and high pressure conditions, and particularly relates to a preparation method of a high-calcium high-manganese high-water-content enstatite single crystal.
Background
Enstatite (molecular formula: Mg) 2 [Si 2 O 6 ]) Belonging to the chain structure silicate and is a subspecies in the family of the epidesmine. The clinoptilolite group minerals are composed of a series of complex systems of iron magnesium silicate solid solutions, and enstatite is pyroxene which is an important magnesium end-member component. In enstatite of chain structure, the complex anion is [ SiO ] 4 ]The tetrahedrons are connected with each other at the common angle top, and the tetrahedrons extend infinitely along a one-dimensional direction. In the crystal structure of enstatite, chain siloxane backbones are linked to each other by divalent magnesium cations other than the backbones. Enstatite is a rock-making mineral which is second to olivine and is the second most important to be widely present in the upper mantle area of the earth, the upper mantle area of the moon and the valance area of mars, the surface of the enstatite is often exposed in rocks such as basic and super-basic rocks, layered invaded rocks, igneous rocks and metamorphic rocks, and is an important marker mineral for researching the cause of rock, and the main production sites are Australia, Burma, India and south Africa.
The chemical general formula of the enstatite mineral can be represented as X 2 [T 2 O 6 ]In addition, the X group cations in enstatite of the aeonite family are usually divalent metal magnesium ions, and also contain a certain amount of Ca 2+ 、Mn 2+ 、Fe 2+ 、Na + 、Li + And other impurities, mainly occupy the M2 position in the crystal structure. The T group ions being mainly positive quadrivalentThe silicon ions (2) occupy tetrahedral positions corresponding to the silicon-oxygen skeleton. Mg as a result of metal cations at lattice sites 2+ With numerous impurity ions (Ca) 2+ 、Mn 2+ 、Fe 2+ 、Na + 、Li + Etc.), equivalent or aliovalent, complete or incomplete substitution of the isomorphs can occur, thus revealing a wide variety and complex compositions of enstatite minerals containing different impurity ions on the earth's surface. Generally, there are four main homogeneous, pleomorphic variants of enstatite under high temperature conditions: crude enstatite (stabilized at 1GPa and 1557 ℃ of 1000 ℃ C., Pbcn type structure with orthorhombic system), enstatite (630 ℃ C., Pbca type structure with orthorhombic system) and high-temperature monoclinic enstatite (f) ((b))>980 ℃, C2/C type structure having monoclinic system) and low-temperature monoclinic enstatite: (<630 ℃ of P2 with monoclinic system 1 Type/c structure).
The metal element calcium and the element manganese, the atomic numbers of which are respectively 20 and 25. Calcium metal is the most active element in alkaline earth metals, is second to oxygen, silicon, aluminum and iron, and is most abundant and widely distributed in the earth crust, wherein the first ten elements are positioned at the fifth position (3 percent), and mostly exist in a free state or a combined state. The element manganese is located in a fourth period VIIB group, belongs to typical transition group metal elements, and comprises visible main manganese-containing minerals such as pyrolusite, hausmannite, manganese nodule and the like. Generally, in the mantle, water is present in the structure of a nominally anhydrous silicate mineral in the form of lattice point defects. Recent studies of water solubility experiments in nominally anhydrous minerals in the upper mantle under high temperature and pressure conditions have shown that while pyroxene is much lower in mineral content than olivine in the region of the earth's mantle, the solubility of water in pyroxene is much higher than olivine and pyroxene is likely to be the predominant water storage mineral in the upper mantle depth range. In-situ experiments and theoretical calculation results of the prior pyroxene such as electrical conductivity, dielectric constant, ultrasonic elastic wave velocity, thermal conductivity, thermal diffusion coefficient, synchrotron radiation micro-region single crystal X-ray diffraction spectrum, confocal micro-Raman spectrum, high-resolution Brillouin scattering spectrum, vacuum Fourier transform infrared spectrum and the like under the conditions of high temperature and high pressure show that trace water contained in the mineral rock can improve or reduce the physical migration property of the pyroxene by several orders of magnitude. Generally, in the prior art, synthesis methods such as a high-temperature chemical precipitation method, a high-temperature hydrothermal method, a high-temperature sol-gel method and the like are adopted, all the prepared pure enstatite single crystals are water-free, and the particle size of the product pure enstatite single crystals is relatively small (generally in nanometer order of magnitude). Therefore, the method for effectively synthesizing the large-particle high-calcium, high-manganese and high-water-content enstatite single crystal meets the scientific research requirements of various high-temperature and high-pressure laboratory simulations, and particularly the research on the preferred orientation and crystal axis anisotropy of the single crystal mineral lattice under high pressure becomes more urgent.
The invention content is as follows:
the technical problem to be solved by the invention is as follows: the preparation method of the high-calcium high-manganese high-water content enstatite single crystal is provided, so as to solve the technical blank of the preparation of the high-calcium high-manganese high-water content enstatite single crystal in the prior art, and obtain large-particle experimental samples of the high-calcium high-manganese high-water content enstatite single crystal.
The technical scheme of the invention is as follows:
a preparation method of a high-calcium high-manganese high-water content enstatite single crystal comprises the following steps: preparing a mixture cylinder sample by taking solid magnesium nitrate hexahydrate powder, solid calcium nitrate tetrahydrate powder, solid manganese (II) nitrate tetrahydrate powder, liquid tetraethoxysilane and absolute ethyl alcohol concentration as starting raw materials according to the stoichiometry of enstatite; preparing a water source wafer by taking solid natural serpentine powder, solid natural birnessite powder and solid natural hydrated lime powder as raw materials; placing water source wafers at two ends of the mixture cylinder sample; the mixture cylinder sample and the water source wafer are put into a gold-palladium alloy sample tube to carry out high-temperature high-pressure reaction to prepare the enstatite single crystal with high calcium, high manganese and high water content.
The preparation method of the mixture cylinder sample specifically comprises the following steps:
step 1, putting 55 ml of absolute ethyl alcohol into a 250 ml wide-mouth glass bottle;
step 2, according to enstatite ((Mg, Ca, Mn) 2 Si 2 O 6 ) Stoichiometrically weighing 10 g of solid magnesium nitrate hexahydrate powder, 50 mg of solid calcium nitrate tetrahydrate powder and 40 mg of solid manganese (II) nitrate tetrahydrate powder and adding the mixture into an anhydrous ethanol solution;
step 3, adding 9.1376 ml of liquid ethyl orthosilicate into 55 ml of absolute ethyl alcohol by using a pipette gun;
step 4, adding a magnetic stirring rotor into the wide-mouth bottle, and sealing the mouth of the wide-mouth bottle by using a plastic film with the thickness of 0.5 mm;
step 5, placing the wide-mouth bottle on a high-temperature magnetic stirring hot plate, and stirring the wide-mouth bottle for 20 hours at room temperature and at the rotating speed of 940 revolutions per minute;
step 6, opening the plastic film seal of the wide-mouth bottle, adding 45 ml of concentrated nitric acid solution with the concentration of 69-70 percent into the mixed solution, and sealing the mouth of the wide-mouth bottle
Step 7, binding countless small holes of 0.1mm on the surface of the plastic film;
step 8, placing the wide-mouth bottle on a high-temperature magnetic stirring hot plate, increasing the temperature of the hot plate to 86 ℃, and stirring the mixed solution for 25 hours at 86 ℃ and 1068 rpm;
step 9, removing the plastic film at the mouth of the wide-mouth bottle, and adjusting the temperature of the high-temperature magnetic stirring hot plate to 113 ℃ until the mixed solution in the whole wide-mouth bottle is completely evaporated to dryness;
step 10, taking out the magnetic stirring rotor, taking out all mixed powder in the wide-mouth bottle by using a medicine spoon, and putting the mixed powder in a platinum crucible;
step 11, placing the platinum crucible filled with the mixture powder in a high-temperature muffle furnace, heating to 1020 ℃ at a heating rate of 760 ℃/h, and roasting for 1.6 hours; naturally cooling to room temperature and taking out mixture sample powder;
step 12, grinding and uniformly mixing the powder of the mixture sample in an agate mortar, pressing the mixture into a round piece with the diameter of 14.8mm multiplied by 7.6mm on a tablet press, overlapping the three pieces together, and placing the round piece in a platinum crucible;
step 13, connecting the platinum crucible containing the wafer-shaped mixture sample with platinum wires to the wall of the platinum crucible, suspending the platinum crucible in the middle of a high-temperature oxygen atmosphere furnace with an open bottom end, and filling a mixed gas of hydrogen, argon and carbon dioxide at the top end;
step 14, placing a cup of 700 ml of cold water of secondary deionized water under the furnace body of the oxygen atmosphere furnace;
step 15, heating the platinum crucible filled with the wafer-shaped mixture sample to 1690 ℃ at a heating rate of 680 ℃/h, and roasting at constant temperature for 35 minutes to melt the platinum crucible into glassy enstatite;
step 16, introducing 10 amperes of current into the platinum wire connected with the platinum crucible wall, fusing the platinum wire under the action of the current, and further enabling the platinum crucible containing the sample to fall into cold water of secondary deionized water from a hearth of an oxygen atmosphere furnace so as to realize direct quenching of the sample at high temperature to obtain enstatite glass with uniform components;
step 17, taking the quenched enstatite glass out of the platinum crucible, and grinding the enstatite glass into uniform sample powder in an agate mortar;
step 18, pressing the powder sample into a cylinder with the diameter of 3.8mm multiplied by 3.4mm to obtain a mixture cylinder sample.
The method for preparing the water source wafer by taking solid natural serpentine powder, solid natural birnessite powder and solid natural hydrated lime powder as raw materials comprises the following steps: the natural serpentine, the birnessite and the hydrated lime in a weight ratio of 4:3:1 are used as water sources and are put on a tablet machine to be pressed into two round tablets with phi of 3.8mm and 0.2 mm.
The method for preparing the enstatite single crystal with high calcium, high manganese and high water content by putting the mixture cylinder sample and the water source wafer into the gold-palladium alloy sample tube for high-temperature and high-pressure reaction comprises the following steps: placing the gold-palladium alloy tube filled with the mixture cylindrical sample and the water source wafer on a Kawai-1000t multi-surface top large cavity press, setting the pressure increasing rate and the temperature increasing rate to be 2.0 GPa/h and 50 ℃/min respectively, increasing the pressure and the temperature to be 7.0GPa and 1100 ℃ respectively, and performing hot-pressing sintering for 18 hours at constant temperature and constant pressure; after the constant temperature and the constant pressure are carried out for 18 hours, the temperature in the sample cavity is reduced from 1100 ℃ to room temperature at the cooling rate of 5 ℃/minute, and after the temperature is reduced to the room temperature, the pressure in the sample cavity is reduced from 7.0GPa to normal pressure at the pressure reduction rate of 0.7 GPa/hour; and after the high-temperature high-pressure preparation reaction is finished, taking out the obtained experimental sample from the sample cavity, opening the gold-palladium alloy sample tube by adopting a diamond slicing machine, and selecting the enstatite single crystal under a microscope.
During high-temperature and high-pressure reaction, the temperature in the high-pressure sample cavity is calibrated by B-type high-temperature platinum-rhodium noble metal thermocouples, each group of high-temperature platinum-rhodium noble metal thermocouples is composed of two platinum-rhodium alloy wires with different materials, and the chemical components of the positive electrode (BP) of the thermocouple are as follows: pt 70％ Rh 30％ (ii) a Negative electrode (BN) chemical composition of thermocouple: pt 94％ Rh 6％ (ii) a And the diameters of the corresponding positive and negative platinum-rhodium alloy wires BP and BN are 0.2mm, and each group of high-temperature platinum-rhodium noble metal thermocouples are symmetrically arranged on the upper side and the lower side of the outer wall of the sample cavity of the gold-palladium alloy tube, so that the temperature calibration in the sample cavity is realized.
The invention has the beneficial effects that:
the invention organically combines the related subject backgrounds of crystallography, mineralogy, magma petrography, sedimentary petrography, metamorphic petrography, high-grade geochemistry, planetary geology, meteority, high-pressure mineral physics and the like, namely the principle that a high-calcium, high-manganese and high-water content enstatite single crystal is slowly formed under the redox condition of the earth mantle. Adopting Kawai-1000t multi-surface top large cavity high-temperature high-pressure experimental equipment in a laboratory to simulate the formation process of a high-calcium, high-manganese and high-water content enstatite single crystal under the condition of high temperature and high pressure, wherein the invention relates to the following main chemical reaction equations:
2[Mg(NO 3 ) 2 ·6H 2 O]+2[Ca(NO 3 ) 2 ·4H 2 O]+2[Mn(NO 3 ) 2 ·4H 2 O]+2C 8 H 20 O 4 Si→[(Mg,Ca,Mn) 2 Si 2 O 6 ]+12(NH 3 ·H 2 O)+16CO+18H 2 O+10O 2
5[Mg 6 Si 4 O 10 (OH) 8 ]→12Mg 2 SiO 4 +2[Mg 3 (Si 4 O 10 )(OH) 2 ]+18H 2 O2[Mg 3 (Si 4 O 10 )(OH) 2 ]→3Mg 2 Si 2 O 6 +2SiO 2 +2H 2 O
Mn(OH) 2 →MnO+H 2 O
2Mn(OH) 2 →Mn 2 O 3 +H 2 O+H 2
[Ca(OH) 2 ]→CaO+H 2 O
the invention selects solid magnesium nitrate hexahydrate (molecular formula: Mg (NO)) 3 ) 2 ·6H 2 O), which provides magnesium element indispensable for synthesizing high-calcium, high-manganese and high-water content enstatite single crystals. Calcium nitrate tetrahydrate (molecular formula: Ca (NO): in solid state as starting material 3 ) 2 ·4H 2 O), which provides an indispensable calcium element for synthesizing high-calcium, high-manganese and high-water content enstatite single crystals. Solid manganese (II) nitrate tetrahydrate of starting material (formula: Mn (NO)) 3 ) 2 ·4H 2 O), provides the manganese element indispensable for synthesizing a high-calcium, high-manganese and high-water content enstatite single crystal. Liquid tetraethoxysilane (molecular formula: C) as starting material 8 H 20 O 4 Si), which provides the silicon element essential for the synthesis of high calcium, high manganese and high water content enstatite single crystals. Natural serpentine (formula: Mg) in solid state as starting material 6 Si 4 O 10 (OH) 8 ) When the temperature is increased to 615 ℃ under the condition of 7.0GPa, the serpentine undergoes a first dehydration reaction, and the dehydration product is forsterite (Mg) 2 SiO 4 ) And talc (molecular formula: mg (magnesium) 3 (Si 4 O 10 )(OH) 2 ) (ii) a When the temperature is increased to 802 ℃ under the condition of 7.0GPa, the first dehydration product talc can undergo a second dehydration reaction, and the dehydration product is enstatite (molecular formula: Mg) 2 Si 2 O 6 ) And quartz (molecular formula: SiO 2 2 ) Mineral combination of forsterite, enstatite and quartz can well control the high-pressure sample cavityThe silicon activity in the body, while releasing large amounts of water. The selected initial raw material sheet pyrolusite [ molecular formula: mn (OH) 2 Also known as manganite]Also belongs to a typical manganese-containing water-containing mineral, the pyrolusite carries out a first dehydration reaction at the temperature of 300 ℃ to generate pyrolusite (MnO); when the temperature is increased to 560 ℃, a second dehydration reaction occurs to produce Mn 2 O 3 While releasing large amounts of water. Selected starting material slake (molecular formula: Ca (OH)) 2 ) Also typical of hydrated minerals containing calcium, hydrated lime undergoes a dehydration reaction at a temperature of 580 c to produce quicklime (CaO), releasing a large amount of water. Natural serpentine, pyrolusite and hydrated lime of water-containing minerals are placed in the high-pressure sample cavity according to a certain proportion, dehydration reaction can be carried out under the conditions of high temperature and high pressure, a large amount of water is generated, and a good water source is provided for synthesizing the high-calcium, high-manganese and high-water content enstatite single crystal. Adding concentrated nitric acid into the reaction product to generate NH 3 ·H 2 O, CO and O 2 Are all volatile substances.
The method needs to synthesize the enstatite single crystal with higher calcium content (5000-6000ppm wt%), manganese content (4000-5000ppm wt%) and water content (3000-4000ppm wt%), and the synthesized sample contains the enstatite single crystal with calcium content, manganese content and water content which are matched with the geoid mantle of the earth, mars, waterstars and the like, and the enstatite single crystal is widely applied to the high-temperature high-pressure research of the experimental simulation of the physicochemical properties of substances of the geoid mantle under the high-temperature high-pressure condition. Compared with the natural meteorite sample which may have impurities of calcium ions and manganese ions similar to each other, in the preparation process of the high-calcium high-manganese and high-water content enstatite single crystal, the laboratory environment is pure, the sample is in a sealed environment and does not contact with the impurities, the obtained high-calcium high-manganese and high-water content enstatite single crystal is a pure substance and has good chemical stability, and important experimental sample guarantee is provided for measuring physical property parameters of the high-calcium high-manganese and high-water content enstatite single crystal, particularly researching the crystal axis anisotropy and the crystal lattice preferred orientation of single crystal minerals under high pressure.
Compared with the artificially synthesized pure enstatite single crystal which can be seen by the former people, the preparation method of the invention adopts a high-temperature chemical sedimentation method, a high-temperature hydrothermal method, a high-temperature sol-gel method and other synthesis methods, has the obvious advantages of simple operation process, short reaction time and the like, and the obtained enstatite single crystal has the superior performances of high purity, large size, stable chemical performance and the like, and particularly, the calcium content, the manganese content and the water content are high and controllable. The particle size of the enstatite single crystal is large, the sample requirements of diamond on high-temperature and high-pressure experimental simulation of electrical properties, elastic properties, spectral properties, diffusion properties and the like on anvil equipment under the conditions of high temperature and high pressure can be completely met, the method provides important experimental sample guarantee for measuring physical property parameters of high-calcium, high-manganese and high-water content enstatite single crystals, particularly researching the preferred orientation of single crystal mineral lattices and the anisotropy of crystal axes under high pressure, and breaks through the technical bottleneck of synthesis of the existing enstatite single crystals.
The specific implementation mode is as follows:
the preparation method specifically comprises the following steps:
solid magnesium nitrate hexahydrate powder (purity: > 99.99%), solid calcium nitrate tetrahydrate powder (purity: > 99.99%), solid manganese (II) nitrate tetrahydrate powder (purity: > 99.99%), liquid ethyl orthosilicate (purity: > 99.99%), solid natural serpentine powder (purity: > 99%), solid natural sheet birnessite powder (purity: > 99%), solid natural hydrated lime powder (purity: > 99%) and anhydrous ethanol concentration (concentration: > 99.9%) were used as starting materials.
Step 1, putting 55 ml of absolute ethyl alcohol into a 250 ml wide-mouth glass bottle.
Step 2, according to enstatite ((Mg, Ca, Mn) 2 Si 2 O 6 ) Stoichiometry, accurately weighing high-purity 10 g of solid magnesium nitrate hexahydrate powder, high-purity 50 mg of solid calcium nitrate tetrahydrate powder and high-purity 40 mg of solid manganese (II) nitrate tetrahydrate powder on a high-precision analytical balance, and carefully adding 55 ml of anhydrous ethanol solutionIn the liquid.
And 3, carefully adding 9.1376 ml of high-purity liquid tetraethoxysilane into 55 ml of absolute ethyl alcohol by using a pipette according to the stoichiometry of the enstatite.
And 4, adding a magnetic stirring rotor into the wide-mouth bottle containing the anhydrous ethanol mixed solution of solid magnesium nitrate hexahydrate, solid calcium nitrate tetrahydrate, solid manganese (II) nitrate tetrahydrate and liquid ethyl orthosilicate, and sealing the mouth of the wide-mouth bottle by using a thick plastic film with the thickness of 0.5 mm to prevent the initial solution in the wide-mouth bottle from being sprayed out in the high-speed stirring process so as to influence the synthesis precision of the sample.
And step 5, placing the wide-mouth bottle filled with the sealed initial mixed liquid and the magnetic stirring rotor on a high-temperature magnetic stirring hot plate, and stirring the high-temperature magnetic stirring hot plate for 20 hours at room temperature and 940 revolutions per minute in order to dissolve the magnesium nitrate hexahydrate, the calcium nitrate tetrahydrate, the manganese (II) tetrahydrate and the liquid tetraethoxysilane of the initial materials in the absolute ethyl alcohol solution so as to realize full dissolution and no residue between the materials.
And 6, opening the plastic film seal of the wide-mouth bottle, adding 45 ml of concentrated nitric acid solution with the concentration of 69-70% into the mixed solution for accelerating the occurrence of the preparation reaction of the enstatite, and sealing the seal of the plastic film so as to prevent the initial solution in the wide-mouth bottle from splashing in the high-temperature stirring process and further influence the synthesis precision of the sample.
Step 7, pricking small holes of 0.1mm on the surface of the film by using a sharp-mouthed forceps so as to generate NH (hydrogen) for reaction 3 ·H 2 O, CO and O 2 When volatile matter volatilizees more easily, can also avoid the concentrated nitric acid in the wide-necked bottle to spout at the high-speed stirring process simultaneously to influence the synthetic precision of sample.
And 8, placing the wide-mouth bottle on a high-temperature magnetic stirring hot plate, increasing the temperature of the hot plate to 86 ℃, and stirring the mixed solution at high temperature and high speed for 25 hours at the rotating speed of 1068 rpm at 86 ℃ so that all the initial reagents are fully dissolved in the mixed solution of the anhydrous ethanol and the concentrated nitric acid.
And 9, removing the sealing film of the sealing opening, and increasing the temperature of the high-temperature magnetic stirring hot plate to 113 ℃ until the mixed solution in the whole wide-mouth bottle is completely evaporated to dryness.
And step 10, taking out the magnetic stirring rotor, mixing all the powder in the wide-mouth bottle by using a medicine spoon, carefully taking out all the powder, and placing the powder in a platinum crucible.
And 11, placing the platinum crucible filled with the mixture powder in a high-temperature muffle furnace, raising the temperature to 1020 ℃ at the heating rate of 760 ℃/hour, roasting for 1.6 hours, and mainly removing residual nitric acid and organic matters in the mixture powder through high-temperature calcination.
Slowly and naturally cooling to room temperature, and taking out mixture sample powder.
And step 12, grinding and uniformly mixing the calcined powder mixture sample in an agate mortar, pressing the mixture into a wafer with the diameter of 14.8mm multiplied by 7.6mm on a tablet machine, overlapping the three wafers together, and placing the wafer in a platinum crucible.
And step 13, connecting the platinum crucible containing the wafer-shaped mixture sample with platinum wires to the wall of the platinum crucible, suspending the platinum crucible in the middle of a high-temperature oxygen atmosphere furnace with an open bottom end, and filling a mixed gas of hydrogen, argon and carbon dioxide at the top end to realize the purpose of controlling the oxygen atmosphere in the furnace body in the high-temperature calcination process.
A cup of 700 ml of cold water of secondary deionized water is placed under the furnace body of the oxygen atmosphere furnace, so as to realize the purpose of directly quenching the sample at high temperature.
And step 14, raising the temperature of the platinum crucible filled with the disc-shaped mixture sample to 1690 ℃ at the heating rate of 680 ℃/h, and roasting at constant temperature for 35 minutes to melt the platinum crucible into glassy enstatite. Generally, the melting point of enstatite is 1610 ℃, and when the temperature is higher than 1610 ℃, enstatite can take on a glassy state. The high-temperature roasting process for controlling the oxygen atmosphere aims at: the invention realizes the synthesis of large-particle high-calcium, high-manganese and high-water content enstatite single crystals and provides purer mixture initial material enstatite glass; the valence state of the valence element metal manganese in the product can be better controlled by high-temperature calcination under the oxygen atmosphere condition; the relatively short firing time is due to the rapid melting of enstatite into the glass phase at temperatures above 1610 c and the total evaporation of possible residual water, organics, nitric acid, etc. that affect sample preparation.
And step 15, after the sample is roasted at the temperature of 1690 ℃ for 35 minutes, introducing high-power current of 10 amperes to the platinum wire connected with the wall of the platinum crucible, fusing the platinum wire under the action of the high-power current, and instantly dropping the platinum crucible filled with the sample into cold water of secondary deionized water from a hearth of an oxygen atmosphere furnace to realize direct quenching of the sample at high temperature to obtain the enstatite glass with uniform components, wherein the aim of rapid quenching is to well store the glass-state enstatite sample at high temperature.
And step 16, taking the enstatite glass quenched by cold water of secondary deionized water out of the platinum crucible, and fully grinding the enstatite glass in an agate mortar to obtain uniform sample powder.
Step 17, putting the powder sample on a tablet press, pressing the powder sample into a cylinder with the diameter of phi 3.8mm multiplied by 3.4mm (height), and adopting natural serpentine (molecular formula: Mg: 3: 1) with the weight ratio of 4:3:1 to obtain the enstatite with high water content 6 Si 4 O 10 (OH) 8 ) And pyrolusite (molecular formula: mn (OH) 2 Also known as manganite) and slaked lime (molecular formula: ca (OH) 2 ) As a water source. The natural serpentine, the birnessite and the hydrated lime are typical water-containing minerals, and can be subjected to dehydration reaction at the temperature higher than 802 ℃ under the set pressure of 7.0GPa, so that the natural serpentine, the birnessite and the hydrated lime are widely applied to common mineral combinations for providing water sources in high-temperature and high-pressure experimental simulation. The natural serpentine is selected because the dehydrated product of the hydrous minerals under high temperature and high pressure releases enough water to be used for synthesizing the enstatite with high water content to provide a water source, and simultaneously generates a large amount of forsterite, enstatite and quartz, so that the silicon activity in the preparation process of the enstatite single crystal with high calcium, high manganese and high water content in the sample cavity under the conditions of high temperature and high pressure can be well controlled. In addition, natural serpentine, manganosite and hydrated lime in a weight ratio of 4:3:1 are selected as waterThe source and the dehydration reaction products are magnesium-containing silicate minerals (forsterite and enstatite) and oxides (quartz, pyrolusite, manganese sesquioxide and quicklime) which do not react with the enstatite sample, so that the pollution problem in the sample preparation process is effectively avoided.
And step 18, placing the natural serpentine, the manganous sheet and the hydrated lime which provide a water source in a weight ratio of 4:3:1 on a tablet press, pressing the natural serpentine, the manganous sheet and the hydrated lime into two round sheets with the diameter of phi 3.8mm (diameter) multiplied by 0.2mm (thickness), sequentially placing the two round sheets at two ends of a sample, and sealing the sample and the two water source sheets (the natural serpentine, the manganous sheet and the hydrated lime which provide the water source in a weight ratio of 4:3: 1) in a gold-palladium alloy sample tube with the diameter of phi 3.8mm (inner diameter) multiplied by 4.0mm (height) and the wall thickness of 0.1mm, wherein the gold-palladium alloy tube is an optimal sealing material which can effectively prevent water from escaping from the sample tube in the sample preparation process under the conditions of high temperature and high pressure.
The enstatite is one of important magnesium-containing silicate minerals in the earth and other kinds of epicyclical mantle areas, in order to truly simulate the growth environment of the earth and other kinds of epicyclical mantle deep enstatite and invert the temperature and pressure conditions of steady existence of enstatite mineral phases, a gold-palladium alloy tube filled with a sample and two water source pieces (natural serpentine, sheet manganite and slaked lime which provide a water source with a weight ratio of 4:3: 1) is placed on a Kawai-1000t multi-surface top large-cavity press, the pressure increasing rate and the temperature increasing rate are set to be 2.0 GPa/hour and 50 ℃/minute respectively, the pressure and the temperature are increased to be 7.0GPa and 1100 ℃ respectively, and hot-pressing sintering is carried out, and the reaction time is constant temperature and pressure for 18 hours.
According to the invention, the temperature in the high-pressure sample cavity is accurately calibrated by adopting the B-type high-temperature platinum-rhodium noble metal thermocouple, and the high-temperature platinum-rhodium noble metal thermocouple has the advantages of high accuracy, strong stability, wide temperature measurement range, long service life, high upper temperature measurement limit and the like, and is widely applied to temperature measurement of glass, ceramics, industrial salt bath furnaces and the like. The high-temperature platinum-rhodium thermocouple is a noble metal thermocouple which is common in numerous high-temperature high-pressure mineral physics research laboratories at home and abroad, the highest temperature can be realized to be 2315 ℃, and each group of high-temperature platinum-rhodium noble metal thermocouples is composed of platinum-rhodium alloy wires with different materials; chemical composition of positive electrode (BP) of thermocouple：Pt 70％ Rh 30％ (ii) a Negative electrode (BN) chemical composition of thermocouple: pt 94％ Rh 6％ (ii) a The diameter of each corresponding positive and negative electrode platinum rhodium alloy wire (BP and BN): 0.2mm), and each group of high-temperature platinum-rhodium noble metal thermocouples are symmetrically arranged on the upper side and the lower side of the outer wall of the sample cavity of the gold-palladium alloy tube, so that the temperature in the sample cavity can be accurately calibrated.
And step 19, under the condition that the pressure is 7.0GPa, when the temperature rises to 802 ℃, the natural serpentine, the birnessite and the hydrated lime which are sealed at two ends of the gold-palladium alloy sample tube and provide water sources according to the weight ratio of 4:3:1 can perform dehydration reaction to release enough water and provide good water sources. Meanwhile, under the conditions of high temperature and high pressure, the serpentine and the hydrated lime undergo dehydration reaction to generate a large amount of forsterite, enstatite, quicklime and quartz mineral combination, and the silicon activity in the preparation process of the enstatite single crystal with high calcium, high manganese and high water content in the sample cavity under the conditions of high temperature and high pressure can be well controlled.
And 20, after the constant temperature and the constant pressure are carried out for 18 hours, reducing the temperature in the sample cavity from 1100 ℃ to room temperature at a cooling rate of 5 ℃/minute, and compared with the heating rate (50 ℃/minute) of sample preparation, the slow constant-pressure cooling rate is more favorable for the crystal growth of the large-particle enstatite single crystal.
And after the temperature in the sample cavity is reduced to the room temperature, reducing the pressure in the sample cavity from 7.0GPa to normal pressure at the pressure reduction rate of 0.7 GPa/h.
After the high-temperature high-pressure preparation reaction is finished, taking out the obtained experimental sample from the sample cavity, opening the gold-palladium alloy sample tube by adopting a diamond slicer, and selecting the enstatite single crystal under a high-power Ahlinbus microscope.
The obtained enstatite single crystal is a single phase and has no other impurity phase; detecting with Electron Probe (EPMA), and obtaining enstatite single crystal with molecular formula of Mg 2 [Si 2 O 6 ](ii) a The calcium content and the manganese content in the obtained enstatite single crystal are 5427ppm wt% and 4085ppm wt% respectively according to the detection result of a multifunctional ion mass spectrometer (ICP-MS); vacuum Fourier transformBy converting infrared spectrum (FT-IR) detection results, the obtained enstatite has higher water content of 3819ppm wt%.
The obtained high calcium, high manganese and high water content enstatite single crystal is an orthorhombic system, the space group is Pbcn (No.60), and the lattice parameter is
Unit cell volume of
The average particle size was 201 microns and the maximum particle size was 472 microns.
The high-calcium, high-manganese and high-water content enstatite single crystal obtained by the method has the advantages of high purity, large size, stable chemical property and the like, and particularly, the calcium content, the manganese content and the water content are high and controllable. Finally, the calcium content of the correspondingly obtained high-calcium, high-manganese and high-water content enstatite single crystal samples is from 5000ppm wt percent to 6000ppm wt percent by changing the chemical agent amount of the added initial substance solid calcium nitrate tetrahydrate powder from 46.0691 mg to 55.2829 mg; finally, the manganese content in the correspondingly obtained high-calcium, high-manganese and high-water content enstatite single crystal samples was from 4000ppm wt% to 5000ppm wt% by changing the chemical reagent amount of the solid manganese (II) nitrate tetrahydrate powder of the starting material added from 39.1742 mg to 48.9678 mg; by changing the weight ratio of the water-containing minerals, namely the natural serpentine powder, the natural bixbyite powder and the natural hydrated lime powder, which provide water sources and the different heights of the two corresponding water source pieces, the total water amount generated by the dehydration reaction of the water-containing minerals enclosed in the gold-palladium alloy sample tube is controlled, and finally, the water content in the high-calcium, high-manganese and high-water-content enstatite single crystal samples is adjusted. The obtained high-calcium, high-manganese and high-water content enstatite single crystal can completely meet the requirement of physical experiment simulation of minerals in the earth and other geostationary mantle areas under the high-temperature and high-pressure conditions, breaks through the technical bottleneck of the existing synthesis of enstatite single crystals, and provides an important experimental sample support for researching the crystal lattice preferred orientation and crystal axis anisotropy of single crystal minerals in the earth and other geostationary mantle areas under the high-temperature and high-pressure conditions.
Claims (2)
1. A preparation method of enstatite single crystal with high calcium, high manganese and high water content is characterized in that: the preparation method comprises the following steps: preparing a mixture cylindrical sample by taking solid magnesium nitrate hexahydrate powder, solid calcium nitrate tetrahydrate powder, solid manganese (II) nitrate tetrahydrate powder, liquid tetraethoxysilane and absolute ethyl alcohol as starting raw materials according to the stoichiometric ratio of the enstatite; preparing a water source wafer by taking solid natural serpentine powder, solid natural birnessite powder and solid natural hydrated lime powder as raw materials; placing water source wafers at two ends of the mixture cylinder sample; placing the mixture cylindrical sample and a water source wafer into a gold-palladium alloy sample tube to perform high-temperature and high-pressure reaction to prepare high-calcium high-manganese high-water-content enstatite single crystals;
the preparation method of the mixture cylinder sample specifically comprises the following steps:
step 1, putting 55 ml of absolute ethyl alcohol into a 250 ml wide-mouth glass bottle;
step 2, according to the enstatite (Mg, Ca, Mn) 2 Si 2 O 6 Weighing 10 g of solid magnesium nitrate hexahydrate powder, 50 mg of solid calcium nitrate tetrahydrate powder and 40 mg of solid manganese (II) nitrate tetrahydrate powder into the anhydrous ethanol solution according to a stoichiometric ratio;
step 3, adding 9.1376 ml of liquid ethyl orthosilicate into 55 ml of absolute ethyl alcohol by using a pipette gun;
step 4, adding a magnetic stirring rotor into the wide-mouth bottle, and sealing the mouth of the wide-mouth bottle by using a plastic film with the thickness of 0.5 mm;
step 5, placing the wide-mouth bottle on a high-temperature magnetic stirring hot plate, and stirring the wide-mouth bottle for 20 hours at room temperature and at the rotating speed of 940 revolutions per minute;
step 6, opening the plastic film seal of the wide-mouth bottle, adding 45 ml of concentrated nitric acid solution with the concentration of 69 ‒ 70 percent into the mixed solution, and sealing the mouth of the wide-mouth bottle
Step 7, binding countless small holes of 0.1mm on the surface of the plastic film;
step 8, placing the wide-mouth bottle on a high-temperature magnetic stirring hot plate, increasing the temperature of the hot plate to 86 ℃, and stirring the mixed solution for 25 hours at 86 ℃ and 1068 rpm;
step 9, removing the plastic film at the mouth of the wide-mouth bottle, adjusting the temperature of the high-temperature magnetic stirring hot plate to 113 ℃ until the mixed solution in the whole wide-mouth bottle is completely evaporated to dryness;
step 10, taking out the magnetic stirring rotor, taking out all mixed powder in the wide-mouth bottle by using a medicine spoon, and putting the mixed powder in a platinum crucible;
step 11, placing the platinum crucible filled with the mixture powder in a high-temperature muffle furnace, heating to 1020 ℃ at a heating rate of 760 ℃/h, and roasting for 1.6 hours; naturally cooling to room temperature and taking out mixture sample powder;
step 12, grinding and uniformly mixing the powder of the mixture sample in an agate mortar, pressing the mixture into round pieces with the diameter of 14.8mm multiplied by 7.6mm on a tablet press, overlapping the three pieces together, and placing the round pieces in a platinum crucible;
step 13, connecting the platinum crucible containing the wafer-shaped mixture sample with platinum wires, suspending the platinum crucible in the middle of a high-temperature oxygen atmosphere furnace with an open bottom end, and filling a mixed gas of hydrogen, argon and carbon dioxide at the top end;
step 14, placing a cup of 700 ml of cold water of secondary deionized water under the furnace body of the oxygen atmosphere furnace;
step 15, heating the platinum crucible filled with the wafer-shaped mixture sample to 1690 ℃ at a heating rate of 680 ℃/h, and roasting at constant temperature for 35 minutes to melt the platinum crucible into glassy enstatite;
step 16, leading 10 amperes of current to the platinum wire connected with the platinum crucible wall, fusing the platinum wire under the action of the current, and further enabling the platinum crucible filled with the sample to fall into cold water of secondary deionized water from a hearth of an oxygen atmosphere furnace so as to realize direct quenching of the sample at high temperature to obtain enstatite glass with uniform components;
step 17, taking the quenched enstatite glass out of the platinum crucible, and grinding the enstatite glass into uniform sample powder in an agate mortar;
step 18, pressing the powder sample into a cylinder with the diameter of phi 3.8mm multiplied by 3.4mm to obtain a mixture cylinder sample;
the method for preparing the water source wafer by taking solid natural serpentine powder, solid natural birnessite powder and solid natural hydrated lime powder as raw materials comprises the following steps: the natural serpentine, the birnessite and the hydrated lime in a weight ratio of 4:3:1 are used as water sources and are placed on a tablet press to be pressed into two round pieces with the diameter of phi 3.8mm multiplied by 0.2 mm;
the method for preparing the enstatite single crystal with high calcium, high manganese and high water content by putting the mixture cylinder sample and the water source wafer into the gold-palladium alloy sample tube for high-temperature and high-pressure reaction comprises the following steps: placing the gold-palladium alloy tube filled with the mixture cylindrical sample and the water source wafer on a Kawai ‒ 1000t multi-surface top large cavity press, setting the pressure increasing speed and the temperature increasing speed to be 2.0 GPa/h and 50 ℃/min respectively, increasing the pressure and the temperature to be 7.0GPa and 1100 ℃ respectively, and performing hot-pressing sintering for 18 hours at constant temperature and constant pressure; after the constant temperature and the constant pressure are carried out for 18 hours, the temperature in the sample cavity is reduced from 1100 ℃ to room temperature at the cooling rate of 5 ℃/minute, and after the temperature is reduced to the room temperature, the pressure in the sample cavity is reduced from 7.0GPa to normal pressure at the pressure reduction rate of 0.7 GPa/hour; and after the high-temperature high-pressure preparation reaction is finished, taking out the obtained experimental sample from the sample cavity, opening the gold-palladium alloy sample tube by adopting a diamond slicer, and selecting the enstatite single crystal under a microscope.
2. The method for producing a high-calcium, high-manganese, and high-water content enstatite single crystal according to claim 1, characterized in that: when the high-temperature and high-pressure reaction is carried out, the temperature in the high-pressure sample cavity is calibrated by B-type high-temperature platinum-rhodium noble metal thermocouples, each group of high-temperature platinum-rhodium noble metal thermocouples is composed of two platinum-rhodium alloy wires with different materials, and the positive electrode BP of the thermocouple is chemically formedDividing into: pt 70% Rh 30% (ii) a Negative electrode BN chemical composition of thermocouple: pt 94% Rh 6% (ii) a And the diameters of the corresponding positive and negative platinum-rhodium alloy wires BP and BN are 0.2mm, and each group of high-temperature platinum-rhodium noble metal thermocouples are symmetrically arranged on the upper side and the lower side of the outer wall of the sample cavity of the gold-palladium alloy tube, so that the temperature calibration in the sample cavity is realized.
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| ZA2022/05474A ZA202205474B (en) | 2021-11-19 | 2022-05-18 | Method for preparing high-calcium, high-manganese and high-water single-crystal enstatite |
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| CN107447257A (en) * | 2017-09-04 | 2017-12-08 | 中国科学院地球化学研究所 | A kind of method for growing manganese spar monocrystalline at high temperature under high pressure |
| CN107640787A (en) * | 2017-09-04 | 2018-01-30 | 中国科学院地球化学研究所 | A kind of method for preparing mangandolomite at high temperature under high pressure |
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| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
| CN107447257A (en) * | 2017-09-04 | 2017-12-08 | 中国科学院地球化学研究所 | A kind of method for growing manganese spar monocrystalline at high temperature under high pressure |
| CN107640787A (en) * | 2017-09-04 | 2018-01-30 | 中国科学院地球化学研究所 | A kind of method for preparing mangandolomite at high temperature under high pressure |
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