CN112239886A - Artificial alumina doped color gem and production method thereof - Google Patents
Artificial alumina doped color gem and production method thereof Download PDFInfo
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- CN112239886A CN112239886A CN201910659642.5A CN201910659642A CN112239886A CN 112239886 A CN112239886 A CN 112239886A CN 201910659642 A CN201910659642 A CN 201910659642A CN 112239886 A CN112239886 A CN 112239886A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
- C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/20—Aluminium oxides
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Abstract
The invention provides an artificial alumina doped colored gem and a production method thereof. The color gemstones prepared by the invention comprise at least one of purple gemstones, green gemstones and orange gemstones. The invention designs various colored jewel formulas, combines the production method of the invention, and the manufactured jewel has large volume and bright color, effectively solves the problem of high bubble proportion in the prior jewel production, obviously reduces the burst rate, has large size, and can be manufactured into various industrial products, accessories, ornaments and the like by cutting and processing various parts.
Description
Technical Field
The invention relates to the technical field of gem production, in particular to an artificial alumina doped colored gem and a production method thereof.
Background
At present, the technique for synthesizing color gem is mainly flame fusion method, also known as Verneuil process. The prepared fine powder of the raw materials leaks from a pipe orifice, is uniformly sprayed in oxyhydrogen flame to be melted, and is then condensed and crystallized on the top layer of a seed crystal or a pear-shaped monocrystal; the growth of the pear crystals starts from a cone melted at the top, the base of the pear crystals descends and rotates in the growth process so as to ensure that the melting surface of the pear crystals grows layer by layer at a proper temperature, and the artificial gem crystallized while rotating has arc growth grains or color bands like the sing-slip grains and the characteristics of bead-shaped and tadpole-shaped bubbles and the like; the method does not need a crucible, and can prepare and synthesize various artificial gemstones such as ruby, sapphire, spinel, rutile, artificial strontium titanate and the like at low cost.
The process has high yield and relatively simple preparation, but because the temperature gradient of oxyhydrogen flame is large, the longitudinal temperature gradient and the transverse temperature gradient of a crystal layer are large, so that the quality of the grown sapphire crystal is poor, and bubbles are distributed too much and disorderly; the temperature of the flame gas cannot be controlled to be stable, and the temperature change caused by the temperature cannot generate larger internal stress on the crystal, so that the dislocation density of the crystal is higher; the raw material can not be completely melted and crystallized into crystals when being melted in flame, and about 30 percent of powder is lost; on one hand, the jewel of the flame fusion method has smaller volume, on the other hand, the phenomenon of uneven and not gorgeous color also exists, and the conditions for processing products such as large-size windows, ornaments, artware and the like are not met.
At present, no large-size colored gem crystal and related products appear in the market, and the gem has high bubble proportion and high explosion rate.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a large-sized artificial alumina doped colored gemstone and a method for producing the same, which are used to solve the problems of the prior art, such as small volume, poor color, many bubbles, easy generation of cracks, high explosion rate, etc.
To achieve the above and other related objects, a first aspect of the present invention provides an artificial alumina-doped colored gemstone, which comprises Al as a raw material2O3And a coloring element, wherein the colored gemstones comprise at least one of purple gemstones, green gemstones and orange gemstones, and the coloring element of the purple gemstones is selected from at least one of V, Ti; the coloring element of the green gem is at least one of V, Ni, Ti and Co; the coloring element of the orange gem is selected from Cr, Ni and TiAt least one of them.
In some embodiments of the invention, each color-imparting element is incorporated into the Al in the form of a simple substance or an oxide2O3In (1).
In some embodiments of the invention, the oxide of the chromogen element V is selected from VO (grey), V2O3(Black), VO2(deep blue), V2O5(reddish yellow).
In some embodiments of the invention, the oxide of the chromogen Ti is selected from TiO, TiO2(white) Ti2O3(reddish brown or reddish brown), Ti3O4At least one of (black).
In some embodiments of the invention, the oxide of the chromogen element Ni is selected from NiO (normally green, heated yellow), Ni2O3(black), NiO2At least one of (black).
In some embodiments of the invention, the oxide of the chromogen Co is selected from CoO (sometimes a grey-green powder, sometimes pink), Co2O3(black and gray powder, decomposition at 895 ℃), Co3O4(gray or black solid, decomposition to CoO at 900 ℃ C. and 950 ℃ C.).
In some embodiments of the invention, the oxide of the chromogen Cr is selected from Cr2O3(dark green crystals or black powder), CrO2(Black), CrO3(dark red orthorhombic crystals).
In some embodiments of the invention, the purple gemstone comprises Al in the weight of each chromogen2O3V is less than or equal to 1 ‰ in weight ratio2O5≤10‰，0≤Ti2O3Less than or equal to 5 thousandths; preferably 1% o.ltoreq.V2O5≤8‰，0.5‰≤Ti2O3Less than or equal to 3 thousandths; more preferably, 2 ‰ V2O5≤5‰，0.5‰≤Ti2O3≤1.5‰。
V2O5Is based on the weight of Al2O3The weight ratio can be 1 per thousand, 1.2 per thousand, 1.4 per thousand, 1.6 per thousand, 1.8 per thousand, 2 per thousand, 2.2 per thousand, 2.4 per thousand, 2.6 per thousand, 2.8 per thousand, 3 per thousand, 3.2 per thousand, 3.4 per thousand, 3.6 per thousand, 3.8 per thousand, 4 per thousand, 4.2 per thousand, 4.4 per thousand, 4.6 per thousand, 4.8 per thousand, 5 per thousand, 5.5 per thousand, 6 per thousand, 6.5 per thousand, 7 per thousand, 7.5 per thousand, 8 per thousand, 8.5 per thousand, 9 per thousand, 9.5 per thousand, 10 per thousand and the like.
Ti2O3Is based on the weight of Al2O3The weight ratio can be 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
In some embodiments of the invention, the green stone comprises Al in weight per chromogen2O3V is less than or equal to 1 ‰ in weight ratio2O5≤10‰，0‰≤Ti2O3≤5‰，0‰≤NiO≤5‰，0‰≤Co3O4Less than or equal to 5 thousandths; preferably 1% o.ltoreq.V2O5≤5‰，0‰≤Ti2O3≤3‰，0‰≤NiO≤3‰，0‰≤Co3O4Less than or equal to 4 thousandths; more preferably, 1 ‰ V2O5≤3‰，0‰≤Ti2O3≤2‰，0‰≤NiO≤3‰，0‰≤Co3O4Not more than 3 per mill, the above Ti2O3Can be replaced by TiO2，Co3O4CoO may be substituted.
V2O5Is based on the weight of Al2O3The weight ratio can be 1 per thousand, 1.2 per thousand, 1.4 per thousand, 1.6 per thousand, 1.8 per thousand, 2 per thousand, 2.2 per thousand, 2.4 per thousand, 2.6 per thousand, 2.8 per thousand, 3 per thousand, 3.2 per thousand, 3.4 per thousand, 3.6 per thousand, 3.8 per thousand, 4 per thousand, 4.2 per thousand, 4.4 per thousand, 4.6 per thousand, 4.8 per thousand, 5 per thousand, 5.5 per thousand, 6 per thousand, 6.5 per thousand, 7 per thousand, 7.5 per thousand, 8 per thousand, 8.5 per thousand, 9 per thousand, 9.5 per thousand, 10 per thousand and the like.
Ti2O3Is based on the weight of Al2O3The weight ratio can be 0, 0.1 per thousand, 0.2 per thousand, 0.3 per thousand, 0.4 per thousand, 0.5 per thousand, 0.6 per thousand, 0.7 per thousand, 0.8 per thousand, 0.9 per thousand, 1 per thousand, 1.1 per thousand, 1.2 per thousand, 1.3 per thousand, 1.4 per thousand, 1.5 per thousand, 1.6 per thousand, 1 per thousand7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
NiO weight of Al2O3The weight ratio can be 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
Co3O4Is based on the weight of Al2O3The weight ratio can be 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
In some embodiments of the invention, the orange gemstone comprises Al in weight per chromogen2O30% o or less of Cr in weight ratio2O3≤10‰，0‰≤Ti2O3Not more than 5 thousandths, not less than 0 thousandths and not more than 5 thousandths of NiO; preferably 0.1 ‰ Cr2O3≤5‰，0‰≤Ti2O3Not more than 3 per mill, not less than 0 per mill and not more than 3 per mill of NiO; more preferably, 0.1 ‰ Cr2O3≤2‰，0‰≤Ti2O3≤2‰，0‰≤NiO≤2‰。
Cr2O3Is based on the weight of Al2O3The weight ratio can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, etc.
Ti2O3Is based on the weight of Al2O3The weight ratio can be 0, 0.1 per thousand, 0.2 per thousand, 0.3 per thousand, 0.4 per thousand, 0.5 per thousand, 0.6 per thousand, 0.7 per thousand, 0.8 per thousand, 0.9 per thousand, 1 per thousand, 1.1 per thousand, 1.2 per thousand, 1.3 per thousand, 1.4 per thousand, 1.5 per thousand, 1.6 per thousand, 1.7 per thousand, 1.8 per thousand1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
NiO weight of Al2O3The weight ratio can be 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
The coloring formula mentioned above is only required to be capable of providing the coloring ions, and the raw material containing the coloring elements can be in powder, granule and the like, and the purity can be different, and the valence state of the coloring ions is not particularly limited.
The second aspect of the present invention provides a method for producing the colored gemstone, comprising the steps of:
1) charging: the raw materials are loaded into a container of a pulling furnace according to the formula, seed crystals are fixed above the container, and protective gas is introduced.
2) And (3) heating: heating to the temperature above the melting point of the raw materials to melt the raw materials.
3) Growing: lifting the seed crystal for growth, wherein the lifting speed is 0.5-4mm/h, and the rotating speed is 2-10 rpm;
4) cooling: after the growth is finished, the gem is pulled out of the liquid level, and the temperature is reduced to obtain a color gem product.
In some embodiments of the present invention, in the step 1), the protective gas is at least one selected from an inert gas and nitrogen, so as to prevent oxidation of the crucible, and nitrogen is generally selected, so that the cost is low.
The inert gas is at least one selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe).
In some embodiments of the present invention, in the step 1), the introducing of the protective gas includes any one of the following manners: a. continuously introducing protective gas from the bottom of the equipment, and continuously discharging the protective gas from the upper end of the equipment; b. after the hearth is vacuumized, inert gas is filled, the micro positive pressure is kept at 0.02-0.04MPa, and the pressure is kept by air discharge in the temperature rising process until the pressure is stable.
In some embodiments of the invention, in the step 1), when the protective gas is introduced, the gas flow is kept at 10-25L/min, the gas is introduced from the bottom of the device, and the gas is continuously exhausted from the upper part of the device.
In some embodiments of the invention, in the step 2), the temperature rise time is 1-2h or more than 7 h.
In some embodiments of the present invention, in step 2), the temperature rise time is 7 hours or more, preferably 7 to 10 hours, and more preferably 7 to 8 hours.
In some embodiments of the invention, in step 3), the pull rate is 1.2-2 mm/h.
The drawing speed may be specifically 0.5mm/h, 0.8mm/h, 1.0mm/h, 1.2mm/h, 1.3mm/h, 1.4mm/h, 1.5mm/h, 1.6mm/h, 1.7mm/h, 1.8mm/h, 1.9mm/h, 2.0mm/h, 2.2mm/h, 2.4mm/h, 2.6mm/h, 2.8mm/h, 3.0mm/h, 3.2mm/h, 3.4mm/h, 3.6mm/h, 3.8mm/h, 4.0mm/h, or the like.
In some embodiments of the invention, in step 3), the rotation speed is 2 to 9rpm, more preferably 3 to 6rpm, and more preferably 4 rpm.
The rotation speed may be specifically 2rpm, 3rpm, 4rpm, 5rpm, 6rpm, 7rpm, 8rpm, 9rpm, 10rpm, or the like.
In some embodiments of the invention, in step 3), the crystal shoulder angle is 80-120 ° and the diameter is 80-180 mm.
In some embodiments of the invention, in step 3), the gemstone is pulled out of the liquid level at a speed of 600-.
As mentioned above, the artificial alumina doped colored gemstone and the production method thereof have the following beneficial effects: the invention designs various color gem formulas, combines the production method of the invention, and the prepared color gem has large volume and bright color, effectively solves the problem of high bubble proportion in the existing color gem production, obviously reduces the burst rate, has large size, and can be made into various industrial products, accessories, ornaments and the like by cutting and processing various parts.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to absolute pressures.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The Czochralski method, the CZ method for short, was first introduced in 1918 by Czochralski. In 1964, Poladino and Rotter applied the CZ method to the growth of sapphire single crystal, and successfully grown sapphire crystal with higher quality. The raw material is heated to a melting point and then melted to form molten soup, and then a single crystal seed crystal is contacted with the surface of the molten soup, so that supercooling is formed on a solid-liquid interface between the seed crystal and the molten soup due to temperature difference. The melt then begins to solidify on the surface of the seed crystal and grows a single crystal of the same crystal structure as the seed crystal. The crystal seed is simultaneously pulled up at a very slow speed and rotates at a certain rotating speed, and the melt is gradually solidified on a liquid-solid interface of the crystal seed along with the upward pulling of the crystal seed, so that an axisymmetric single crystal bar is formed. During the pulling-up process, a crystal Neck (Neck), a crystal Shoulder (Shoulder), a crystal Body (Body) and a crystal tail are respectively grown through the adjustment of controlling the pulling-up speed. Each portion has its purpose, and the growth of the neck is mainly used to eliminate dislocation. Because the crystal growth process is complex and the dislocation generation amount is not easy to be controlled, most of the crystal growth processes take dislocation elimination as a main choice. After the crystal neck grows, the pulling speed needs to be slowed down to increase the crystal diameter to the required size, and the step is crystal shoulder growth. When the crystal diameter is increased to a desired size, the crystal is pulled up at a constant speed, and the crystal diameter of the portion is fixed, that is, the crystal body portion. Since this portion is intended to be a material of an industrial substrate, care is required for growth. When the crystal grows up, the crystal bar is required to be separated from the molten liquid, the pulling speed is increased, the diameter of the crystal bar is reduced until the crystal bar becomes a point, and the crystal bar is separated from the molten liquid. The step is crystal tail growth, and aims to avoid the defects of dislocation, slip lines and the like of the crystal bar caused by thermal stress generated when the crystal bar is quickly separated from the molten liquid and the thermal stress generated when the crystal bar is separated.
The method comprises loading iridium or molybdenum crucible into a crystal growth furnace, adjusting the position of the crucible, checking the state of the thermal field insulator, and ensuring the thermal insulation performance (such as deformation and crack) of the thermal field; after cleaning, alumina raw materials and coloring elements are filled, and the raw materials such as doped coloring powder or particles are placed in the middle of the crucible and cannot be exposed in the air or contact the crucible wall; before and during heating, continuously introducing protective gas such as nitrogen or keeping a micro-positive pressure state in the furnace, and heating for 1-10 hours; after the materials are dissolved, the seed crystals are continuously placed down to gradually contact the liquid surface, after the seed crystals contact the liquid surface, the seed crystals are required not to be condensed or melted too fast, the most suitable growth starting power is found by adjusting the power, and then the automatic pulling growth stage is carried out; the main process parameters of automatic growth are 0.5-4mm/h of pulling and 2-10rpm of rotation, and the growth process comprises seeding: ensuring that the seed crystal is not rapidly enlarged or melted back; shoulder expanding: the angle of the shoulder is 80-120 degrees; and (3) isometric growth: the diameter of the equal diameter is 80mm-180 mm; and (3) providing a gem: pulling the jewel to be separated from the liquid level at the speed of 600-; after 24-60 hours of cooling and natural cooling for more than 24 hours, the gem can be taken out after opening the furnace, and the large-size artificial alumina doped color gem with the diameter of more than 5-15 kilograms is prepared, the diameter of the prepared gem is 100-180mm, and the length of the equal-diameter part is 80-300 mm.
It should be noted that the type of the pulling furnace is not limited by the specific type in the embodiment, and pulling furnaces of the same type are all suitable for the present invention.
The method for calculating the bubble proportion of the colored gem prepared by the following embodiments is as follows: the volume was calculated from the diameter of the bubble, and the bubble volume was divided by the total volume of the equal diameter portion of the gem stone to obtain the bubble content ratio (total volume of bubble ÷ total volume of gem stone) × 100%.
Burst rate is defined as follows: in the grown gem single crystal, the number of the cracked gem single crystal accounts for the percentage of the total number of the gems.
In the following examples, the production directions of the gemstones are all in the A direction, and the formula of the invention is also suitable for the growth of colored gemstones in the R direction, the M direction and the C direction, namely, the formula of the invention is suitable for the growth of gemstones in various directions.
Generally, colored gemstones other than ruby are commonly referred to as sapphire.
In the following embodiments, the bubble proportion and the explosion ratio of the prepared gem are obtained by statistics after annealing, the factors influencing the bubble proportion mainly include hearth cleanliness, growth starting temperature, transmission stability of pulling rotation, raw material purity, automatic control precision and the like, the factors influencing the explosion ratio mainly include the single crystallinity of seed crystals, growth starting temperature, heat preservation condition of a temperature field and the like, and in production practice, the higher the specific gravity of doped elements is, the deeper the color is, the higher the bubble proportion and the explosion ratio are, the higher the production cost is, and the corresponding types and doping amounts of the doped elements are generally considered according to the requirements of customers on color depth.
Example 1
In this example, purple gemstones were produced by using a Czochralski crucible, the equipment model of the Czochralski furnace was PACER S-10 (AJAX TOCCO), and the steps of heating, temperature adjustment, growth, temperature reduction and cooling of the raw materials and the doping elements were carried out by using an iridium crucible and induction heating with a copper coil. The same pulling furnace as in the present example was used in the subsequent examples.
The purple gem comprises the following raw materials: block Al with purity of 99.99%2O3Powdery V with purity of 99.9%2O5Powdery Ti with purity of 99.9%2O3，V2O5Is based on the weight of Al2O32 per mill of weight, Ti2O3Is based on the weight of Al2O30.7 per mill of weight, Al2O3The block-shaped transparent raw material prepared by the flame method is purchased from the market.
The production method comprises the following steps:
1) charging: cleaning a hearth and a furnace shell of the equipment, checking the heat preservation performance of the hearth and a heat preservation brick, adjusting the position of a crucible, and ensuring that the crucible is stable and is positioned in the center of the hearth; loading according to the designed weight of the raw materials and the doping elements, and covering the crucible cover with the heater and the semicircular bricks; covering the upper furnace shell and the furnace cover; connecting each circulating water pipe and opening a water valve; seed crystals are loaded into the seed crystal clamp, are arranged on the equipment lifting frame and fixed, and are lowered to the position above the semicircular brick; and introducing nitrogen protective gas from the vent hole at the bottom of the hearth half an hour before heating, so that the air in the furnace is extruded by nitrogen, and the flow rate of the nitrogen is 25L/min.
2) And (3) heating: and (3) increasing the power of the equipment to 67kw according to the temperature rise time of 1.5 hours, recording data, observing the melting condition of the raw materials in the furnace through a semicircular brick observation port, gradually lowering the seed crystal to ensure that the seed crystal is not melted and is not solidified until the seed crystal is contacted with the liquid level, and keeping the state.
3) Growing: after the temperature is adjusted, a program is set to enable the equipment to enter an automatic growth state. The weight of the crystal is monitored by a weight sensor, and when the crystal grows, main parameters are set as follows: the pulling speed of the seed crystal is 1.5mm/h, the seed crystal is pulled at a constant speed during growth, the quality of the gem is improved, the growth speed is stabilized, the rotating speed is 4rpm, the shoulder angle is 90 degrees, the diameter is 110mm, the diameter of the crucible is 203mm, and the diameter of the seed crystal is 10 mm.
4) Cooling: when the weight of the gem reaches the expected weight, the device can be directly intervened to enter a cooling state, the gem is pulled out of the liquid level, the gem is pulled at a speed of 600mm/h to be separated from the liquid level, the pulling height is 60-80mm, when the pulling is stopped, the weight of the weight sensor is observed, and if the weight is stable, the gem is separated from the liquid level. After the liquid level is lifted, the jewel enters a natural cooling state, and the cooling time is set to be 55 hours.
5) Opening the furnace: after the equipment is powered off, the furnace can be opened after being cooled for more than 24 hours, the gem is taken out, the annealing operation is carried out, and the specific process of annealing is as follows: putting the jewels in an annealing furnace in order, heating to 1800 ℃ within 40 hours, keeping the temperature for more than 24 hours, cooling for 50 hours, and then opening the furnace. The sapphire single crystal with excellent quality is obtained, the bubble content of the sapphire is 5%, no explosion is caused, the diameter is 110 +/-5 mm, the equal diameter length is 100mm, the shoulder angle is 90 degrees, the weight is 5.1 kilograms, the bubbles are intensively distributed near the central axis of the A direction, the axis of the A direction is used as the center, the maximum distance is 20mm, the minimum distance is 5mm, the whole sapphire is transparent, and the utilization rate is as high as 95%. The annealing operations in the subsequent examples are the same as in this example.
TABLE 1 influence of purple gem process parameters on product performance
According to the experiment, V2O5The condition that the gem cannot grow up and the bubbles are increased sharply can occur when the concentration is too high. Too fast pulling results in crystallization rate not following the pulling rate, resulting in misalignment, bubbles, and other defects.
Example 2
In the production of the green gem, an iridium crucible is selected, and the steps of heating, temperature adjustment, growth, cooling and cooling of the raw material and the doping elements are carried out by utilizing the induction heating of a copper coil.
The green gem comprises the following raw materials: block Al with purity of 99.99%2O3Powdery V with purity of 99.95%2O5Powdery Ti with purity of 99.9%2O3NiO with the purity of 99.9 percent,co of 99.9% purity3O4；V2O5Is based on the weight of Al2O31 per mill of weight, Ti2O3Is based on the weight of Al2O30.5 per mill of the weight, the weight of NiO accounts for Al2O32% o by weight, Co3O4Is based on the weight of Al2O32 per mill of weight, Al2O3Is a flame method blocky transparent raw material.
The production method comprises the following steps:
1) charging: cleaning a hearth and a furnace shell of the equipment, checking the heat preservation performance of the hearth and a heat preservation brick, adjusting the position of a crucible, and ensuring that the crucible is stable and is positioned in the center of the hearth; loading according to the designed weight of the raw materials and the doping elements, and covering the crucible cover with the heater and the semicircular bricks; covering the upper furnace shell and the furnace cover; connecting each circulating water pipe and opening a water valve; seed crystals are loaded into the seed crystal clamp, are arranged on the equipment lifting frame and fixed, and are lowered to the position above the semicircular brick; and introducing nitrogen protective gas from the vent hole at the bottom of the hearth half an hour before heating, so that the air in the furnace is extruded by nitrogen, and the flow rate of the nitrogen is 20L/min.
2) And (3) heating: and (3) increasing the power of the equipment to 65kw according to the temperature rise time of 1.5 hours, paying attention to record data, observing the melting condition of the raw materials in the furnace through a semicircular brick observation port, gradually lowering the seed crystal to ensure that the seed crystal is not melted and is not solidified until the seed crystal is contacted with the liquid level, and keeping the state.
3) Growing: after the temperature is adjusted, a program is set to enable the equipment to enter an automatic growth state. The weight of the crystal is monitored by a weight sensor, and when the crystal grows, main parameters are set as follows: the pulling speed of the seed crystal is 1.2mm/h, the seed crystal is pulled at a constant speed during growth, the quality of the gem is improved, the growth speed is stabilized, the rotating speed is 4rpm, the shoulder angle is 90 degrees, the diameter is 115mm, the diameter of the crucible is 203mm, and the diameter of the seed crystal is 10 mm.
4) Cooling: when the weight of the gem reaches the expected weight, the device can be directly intervened to enter a cooling state, the gem is pulled out of the liquid level, the gem is pulled at a speed of 600mm/h to be separated from the liquid level, the pulling height is 60-80mm, and when the pulling is stopped, the weight of the weight sensor is observed, and the weight is stable, which indicates that the gem is separated from the liquid level. After the liquid level is lifted, the jewel enters an automatic cooling state, and the cooling time is set to be 55 hours.
5) Opening the furnace: after the equipment is powered off, the furnace can be opened after being cooled for more than 24 hours, the jewel is taken out, annealing operation is carried out, the red single crystal jewel with excellent quality is obtained, the jewel has the advantages that the bubble content is 5%, the jewel is free from cracking, the diameter is 115mm, the equal diameter length is 270mm, the shoulder angle is 90 degrees, the weight is 5 kilograms, the bubbles are intensively distributed near the A-direction central axis, the A-axis is taken as the center, the maximum distance is 20mm, the minimum distance is 2mm, the jewel is wholly transparent, and the utilization.
TABLE 2 influence of Green Gem technological parameters on product performance
Example 3
In the production of the orange gem, an iridium crucible is selected, and the steps of heating, temperature adjustment, growth, cooling and cooling of raw materials and doping elements are carried out by utilizing copper coil induction heating.
The raw materials of the sapphire comprise: block Al with purity of 99.99%2O3NiO powder with purity of 99.95 percent and Ti powder with purity of 99.9 percent2O3Powdery Cr with purity of 99.99%2O3(ii) a NiO weight of Al2O30.5 per mill of Ti2O3Is based on the weight of Al2O30.5 per mill of Cr2O3Is based on the weight of Al2O30.2 per mill of weight, Al2O3Is a flame method blocky transparent raw material.
The production method comprises the following steps:
1) charging: cleaning a hearth and a furnace shell of the equipment, checking the heat preservation performance of the hearth and a heat preservation brick, adjusting the position of a crucible, and ensuring that the crucible is stable and is positioned in the center of the hearth; loading according to the designed weight of the raw materials and the doping elements, and covering the crucible cover with the heater and the semicircular bricks; covering the upper furnace shell and the furnace cover; connecting each circulating water pipe and opening a water valve; seed crystals are loaded into the seed crystal clamp, are arranged on the equipment lifting frame and fixed, and are lowered to the position above the semicircular brick; and introducing nitrogen protective gas from the vent hole at the bottom of the hearth half an hour before heating, so that the air in the furnace is extruded by nitrogen, and the flow rate of the nitrogen is 25L/min.
2) And (3) heating: and (3) increasing the power of the equipment to 63kw according to the temperature rise time of 1.5 hours, paying attention to record data, observing the melting condition of the raw materials in the furnace through a semicircular brick observation port, gradually lowering the seed crystal to ensure that the seed crystal is not melted and is not solidified until the seed crystal is contacted with the liquid level, and keeping the state.
3) Growing: after the temperature is adjusted, a program is set to enable the equipment to enter an automatic growth state. The weight of the crystal is monitored by a weight sensor, and when the crystal grows, main parameters are set as follows: the pulling speed of the seed crystal is 1.5mm/h, the pulling speed is gradually reduced in the growth process, the quality of the gem is improved, the growth speed is stabilized, the rotating speed is 4rpm, the shoulder angle is 90 degrees, the diameter is 11.0mm, the diameter of the crucible is 200mm, and the diameter of the seed crystal is 10 mm.
4) Cooling: when the weight of the gem reaches the expected weight, the device can be directly intervened to enter a cooling state, the gem is pulled out of the liquid level, the gem is pulled at a speed of 600mm/h to be separated from the liquid level, the pulling height is 80mm, and when the pulling is stopped, the weight of the weight sensor is observed, and the weight is stable, which indicates that the gem is separated from the liquid level. After the liquid level is lifted, the jewel enters an automatic cooling state, and the cooling time is set to be 55 hours.
5) Opening the furnace: after the equipment is powered off, the furnace can be opened after being cooled for more than 24 hours, the gem is taken out, annealing operation is carried out, the yellow single crystal gem with excellent quality is obtained, the gem bubble accounts for 6 percent, no crack exists, the diameter is 110 +/-5 mm, the equal diameter length is 160mm, the shoulder angle is 90 degrees, the weight is 12 kilograms, the bubbles are intensively distributed near the A-direction central axis, the A-axis is taken as the center, the maximum distance is 20mm, the minimum distance is 5mm, the gem is wholly transparent, and the utilization rate is as high as 95 percent.
TABLE 3 Table of the influence of orange gemstone process parameters on product performance
As can be seen from tables 1 to 3, the content of the color-causing component affects the weight of the single crystal gemstone, the bubble ratio, the explosion ratio, the degree of color flamboyance, and the like.
According to the comparative research and development data in tables 1-3, it can be found that the more the dominant color element is doped, the higher the concentration is, the darker the color of the gem is, but as the color of the gem is deepened, the bubble proportion is also improved, the growth stability is reduced, and the associated polycrystal and explosion are also correspondingly improved, so that the content of the doped element is reasonably designed, and the proper pulling speed and rotation speed are matched to produce the high-quality colored gem.
In conclusion, the formula of the raw materials of the gem is reasonably designed, the large-size gems with different colors are obtained by the pulling method, bubbles are obviously reduced, the color is bright, and materials at different parts can be made into various ornaments, accessories and the like by cutting.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. An artificial alumina doped colored gemstone, characterized in that: the raw material comprises Al2O3And a coloring element, wherein the colored gemstones comprise at least one of purple gemstones, green gemstones and orange gemstones, and the coloring element of the purple gemstones is selected from at least one of V, Ti; the coloring element of the green gem is at least one of V, Ni, Ti and Co; the coloring element of the orange gem is at least one of Cr, Ni and Ti.
2. The artificial alumina doped colored gemstone according to claim 1, wherein: the color-forming elements are doped into the Al in the form of simple substance or oxide2O3In (1).
3. The artificial alumina doped colored gemstone according to claim 2, wherein: the oxide of the chromogen V is selected from VO and V2O3、VO2、V2O5At least one of (1).
4. The artificial alumina doped colored gemstone according to claim 2, wherein: the oxide of the chromogen Ti is selected from TiO and TiO2、Ti2O3、Ti3O4At least one of (1).
5. The artificial alumina doped colored gemstone according to claim 2, wherein: the oxide of the coloring element Ni is selected from NiO and Ni2O3、NiO2At least one of (1).
6. The artificial alumina doped colored gemstone according to claim 2, wherein: the oxide of the coloring element Co is selected from CoO and Co2O3、Co3O4At least one of (1).
7. The artificial alumina doped colored gemstone according to claim 2, wherein: the oxide of the chromogen Cr is selected from Cr2O3、CrO2、CrO3At least one of (1).
8. The artificial alumina doped colored gemstone according to claim 2, wherein: in the purple gem, Al is contained according to the weight of each coloring raw material2O3V is less than or equal to 1 ‰ in weight ratio2O5≤10‰，0≤Ti2O3Less than or equal to 5 thousandths; preferably 1% o.ltoreq.V2O5≤8‰，0.5‰≤Ti2O3Less than or equal to 3 thousandths; more preferably, 2 ‰ V2O5≤5‰，0.5‰≤Ti2O3≤1.5‰；
And/or, in the green gem, Al is accounted by the weight of each chromogen2O3V is less than or equal to 1 ‰ in weight ratio2O5≤10‰，0‰≤Ti2O3≤5‰，0‰≤NiO≤5‰，0‰≤Co3O4Less than or equal to 5 thousandths; preferably 1% o.ltoreq.V2O5≤5‰，0‰≤Ti2O3≤3‰，0‰≤NiO≤3‰，0‰≤Co3O4Less than or equal to 4 thousandths; more preferably, 1 ‰ V2O5≤3‰，0‰≤Ti2O3≤2‰，0‰≤NiO≤3‰，0‰≤Co3O4≤3‰；
And/or, in the orange gem, Al is accounted by the weight of each chromogen2O30% o or less of Cr in weight ratio2O3≤10‰，0‰≤Ti2O3Not more than 5 thousandths, not less than 0 thousandths and not more than 5 thousandths of NiO; preferably 0.1 ‰ Cr2O3≤5‰，0‰≤Ti2O3Not more than 3 per mill, not less than 0 per mill and not more than 3 per mill of NiO; more preferably, 0.1 ‰ Cr2O3≤2‰，0‰≤Ti2O3≤2‰，0‰≤NiO≤2‰。
9. The method for producing artificial alumina doped colored gemstones according to any one of claims 1 to 8, comprising the steps of:
1) charging: the raw materials are loaded into a container of a pulling furnace according to the formula amount, seed crystals are fixed above the container, and protective gas is introduced;
2) and (3) heating: heating to a temperature higher than the melting point of the raw materials to melt the raw materials;
3) growing: lifting the seed crystal for growth, wherein the lifting speed is 0.5-4mm/h, and the rotating speed is 2-10 rpm;
4) cooling: after the growth is finished, the gem is pulled out of the liquid level, and the temperature is reduced to obtain a color gem product.
10. The method of producing as claimed in claim 9, further comprising at least one of the following features:
A1) in the step 1), the protective gas is at least one selected from inert gas and nitrogen;
A2) in the step 1), the method for introducing the protective gas comprises any one of the following methods: a. continuously introducing protective gas from the bottom of the equipment, and continuously discharging the protective gas from the upper end of the equipment; b. after the hearth is vacuumized, inert gas is filled, the micro positive pressure is kept at 0.02-0.04MPa, and the pressure is kept by air discharge in the temperature rising process until the pressure is stable.
A3) In the step 1), when protective gas is introduced, the gas flow is kept at 10-25L/min, gas is introduced from the bottom of the equipment, and gas is continuously discharged from the upper part of the equipment;
A4) in the step 2), the temperature rise time is 1-2h or more than 7 h;
A5) in the step 2), when the temperature rise time is more than 7 hours, the temperature rise time is preferably 7-10 hours, and more preferably 7-8 hours;
A6) in the step 3), the pulling speed is 1.2-2 mm/h;
A7) in the step 3), the rotating speed is 2-9rpm, more preferably 3-6rpm, and more preferably 4 rpm;
A8) in the step 3), the angle of the shoulder part of the crystal is 80-120 degrees, and the diameter is 80-180 mm;
A9) in the step 3), the gem is pulled out of the liquid level at the speed of 600-.
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