CN115786737B - Method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition - Google Patents
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Abstract
The invention belongs to the technical field of ultra-pure titanium preparation, and particularly relates to a method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition. Comprising the following steps: communicating the refining chamber with a vessel containing the condensed higher titanium halide; placing the crude titanium and the substrate into a refining chamber, and then vacuumizing; heating the container to raise the vapor pressure of the high-valence titanium halide to 72-177 Pa, stopping vacuumizing, controlling the pressure of the refining chamber through the vapor pressure of the high-valence titanium halide, and reacting to generate low-valence titanium halide when the high-valence titanium halide in the refining chamber contacts crude titanium; when the low-valence titanium halide contacts the substrate, the low-valence titanium halide is thermally decomposed to generate halogen gas and high-purity low-oxygen titanium is deposited on the surface of the substrate; the halogen gas reacts to generate low-valence titanium halide again when contacting with crude titanium; the above-mentioned processes are circularly reciprocated to continuously produce high-purity low-oxygen titanium. The invention can obtain titanium material with purity of more than 5N5, oxygen content of less than 80ppm and density of more than 98.5 percent, and has little consumption of high-value halide and low refining cost.
Description
Technical Field
The invention belongs to the technical field of ultra-pure titanium preparation, and particularly relates to a method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition.
Background
High purity Ti and its compounds such as TiW, tiN, tiSi have excellent thermal conductivity, electrical conductivity, inertness to general wiring metals and dielectric layer materials, good adhesion, and resistance to diffusion of the wiring materials into the dielectric layer, so high purity Ti and its partial compounds are excellent diffusion barrier materials. In addition, due to the characteristics of high recoverable strain, large deformation, corrosion resistance, biocompatibility and the like, the NiTi shape memory alloy is used as a micro actuator in a micro-electromechanical system, such as a micro valve, a micro pump, a micro clamp, a micro sensor and the like, and is successfully applied to the fields of aerospace, biomedical, industrial process control, electronic instruments and the like. Titanium in the above applications requires extremely high purity, in particular extremely low oxygen content. In chip manufacture, abnormal discharge is caused by gas elements such as O, C, N, H and the like during sputtering, particles in a sputtering chamber are increased, so that a film bulges and the formed film is uneven; fe. The heavy metal impurities such as Ni, cr and the like can cause lattice defects of the silicon substrate, and meanwhile, the leakage current on the PN junction is increased and the service life of carriers is reduced; the high activity of alkali metal impurity ions such as Na, K and the like can cause movable ion pollution, the movable ion pollution can migrate to an oxide layer interface of a gate structure, the threshold voltage required for starting a transistor is changed, and the device is disabled; u, th and other radioactive impurities can cause soft failure of the device, cause accidental switching of the transistor in an on-off state, and cause change of storage capacity of the data storage element. The introduction of impurities can change the phase transition temperature in the NiTi memory alloy, the addition of metals Zr and Hf positioned below Ti and metals Pd and Pt positioned below Ni in the periodic table of elements can lead to the rising of the initial temperature point of martensitic transformation, and the effect after the addition of element V, cr, mn, fe, co positioned between Ti and Ni is the opposite; o, C impurities can be combined with Ti, so that not only is the stoichiometric ratio of local positions in the NiTi memory alloy changed and the martensitic transformation initial temperature is changed, but also particles are generated, and the fatigue life of the NiTi memory alloy is reduced; o can also improve the brittleness of the NiTi memory alloy and reduce the working performance of the NiTi memory alloy as a micro-actuator. However, titanium does not exist in nature as a pure substance, but rather, titanium has a very high chemical activity. Titanium and many metals are mutually solid-solved, even infinite solid solution can be formed, and the bonding energy of Ti-O is 2.12eV and the bonding energy of Ti-Ti is 2.56eV are very close, so that titanium has extremely high chemical affinity to oxygen, and therefore, the high-purity low-oxygen-content refining of titanium is very challenging.
At present, the high-purity titanium mainly has the following preparation modes: (1) Crohn's method and its improvement. The refining efficiency of the Kroll method is low, even though the purity of raw materials and the reaction process are controlled carefully, elements on the wall of the reaction vessel still enter titanium in the furnace, so that only the titanium in the central range can keep high purity, and further refining technology is still required for removing impurities, so that only 10% -15% of the titanium raw materials can be truly used as high-purity titanium. CN101984101a improves the kroll process and can produce a small amount of solid high purity titanium with purity of 5N and oxygen content of 120 ppm. (2) an electrolytic refining method. The electrolytic refining can effectively reduce the oxygen content in the high-purity titanium, but the electrolytic process is complex, the control difficulty is high, the effect of removing metal elements with the electrode potential close to that of Ti is poor, the grain structure of the electrolytic titanium is greatly influenced by process parameters, the porosity of the grains can improve the salt inclusion rate, and the impurity content such as O, H is increased. CN104928722a proposes a method for preparing high purity titanium by molten salt electrolysis, the purity can reach more than 4N5, and the oxygen content is unknown. (3) iodination method. The traditional iodination method using tungsten wire as a matrix and hot wire has been reported more, and the tungsten wire is used as the matrix, so that the deposition speed is low, the production capacity is small, and the tungsten wire has the risk of fracture along with the increase of the deposition time. CN101003861a proposes an improved iodination process with a single use of crude titanium of 87.5%, a purity of more than 4N and an oxygen content of less than 500 ppm. In summary, in the existing preparation method of high-purity titanium, high-purity titanium is difficult to prepare with high purity, low oxygen content, high efficiency, high utilization rate and high stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition, which has high refining efficiency on crude titanium, and the purity of the pure titanium obtained by refining is high (the purity is more than 99.9995 percent), the oxygen content is low (the oxygen content is less than 80 ppm) and the density is high (the density is more than 98.5 percent).
Specifically, the invention provides the following technical scheme:
a method for preparing high purity low oxygen titanium using chemical vapor transport deposition comprising:
1) Preparing a refining chamber and a container filled with condensed high-valence titanium halide, and communicating the refining chamber and the container filled with condensed high-valence titanium halide with each other;
2) Placing the crude titanium and the substrate into the refining chamber, and then vacuumizing;
3) Heating to make the temperature of the crude titanium reach and stabilize at 800-1100 ℃ and the temperature of the matrix reach and stabilize at 1200-1550 ℃;
4) Heating the container filled with the condensed high-valence titanium halide to improve the vapor pressure of the condensed high-valence titanium halide to be 72-177 Pa, stopping vacuumizing, and allowing the gaseous high-valence titanium halide to enter the refining chamber under the action of the vapor pressure and controlling the pressure of the refining chamber;
5) The higher titanium halide entering the refining chamber reacts to produce gaseous lower titanium halide when contacting the crude titanium;
6) The gaseous low-valence titanium halide is heated when contacting the substrate so that the gaseous low-valence titanium halide is subjected to decomposition reaction to generate halogen gas and deposit high-purity low-oxygen titanium on the surface of the substrate;
7) The halogen gas reacts to generate gaseous low-valence titanium halide again when contacting the crude titanium;
8) The processes in the steps 6) and 7) are circularly and reciprocally carried out, so that high-purity low-oxygen titanium is continuously generated.
According to the preparation method provided by the invention, the high-valence condensed titanium halide in a container communicated with the refining chamber is heated to be in a gaseous state, so that the high-valence condensed titanium halide is introduced into the refining chamber to carry out a vapor transport reaction (see the diagram shown in figure 1), namely, the low-temperature synthesis and the high-temperature decomposition reaction realize the transfer of titanium from a raw material end (crude titanium, synthetic titanium halide) to a product end (high-purity low-oxygen titanium, titanium halide decomposition). The process is continuously and spontaneously circulated, and after the crude titanium is completely consumed, heating is stopped, and natural cooling is performed, so that refined high-purity low-oxygen titanium is obtained, and the raw material utilization rate reaches more than 99%.
The pressure in the refining chamber in the preparation method is determined by the vapor pressure of the high-valence titanium halide, and the invention discovers that the pressure in the refining chamber is kept at 72-177 Pa by controlling the vapor pressure of the titanium halide, so that the stable control of the pressure in the system can be realized, the high-efficiency and stable growth of the titanium in the refining process can be ensured, and the obtained high-purity low-oxygen titanium has low oxygen content and high density.
In addition, in the method, only a small amount of high-value titanium halide is introduced into the refining chamber, so that the refining reaction can be ensured to be carried out stably for a long time, and the consumption of the high-value titanium halide is very small.
Specifically, taking halogen I as an example, the following reaction occurs:
on crude titanium at relatively low temperatures, the following synthesis reactions occur:
Ti+Til 4 → 2TiI 2
Ti+2I → TiI 2
TiI 2 after reaching the high temperature matrix, the following decomposition reaction occurs:
TiI 2 → Ti+2I
from the above reaction, it can be seen that Ti passes through TiI 2 For transport, ti is generally transported by TiI in conventional iodination 4 Transport TiI 4 The temperature required for the thermal decomposition reaction is high, and impurities are easily introduced from the reaction vessel and pyrolyzed together with titanium tetraiodide. And TiI 2 Is lower than TiI 4 By controlling the temperature of the substrate and the crude titanium, the TiI is utilized 2 The purpose of transporting Ti can effectively reduce the impurities possibly introduced into the reactor and improve the refining effect.
Preferably, in step 2), the vacuum is applied to less than 1X 10 -3 Pa。
Preferably, in step 2), the substrate is a metal having a melting point higher than 1600 ℃.
Further preferably, the substrate is pure titanium, pure molybdenum, pure tantalum or pure niobium, more preferably pure titanium.
Further preferably, the purity of the matrix is not less than 99.9%.
Preferably, in step 2), the crude titanium has a purity of 99.9% or more and an oxygen content of 400ppm or less.
Preferably, the higher titanium halide is selected from TiF 4 、TiCl 4 、TiBr 4 、TiI 4 One or more of the following.
Preferably, the higher titanium halide is TiI 4 In step 4) the vessel containing the condensed higher titanium halide is heated to 130-145 ℃. The vapor pressure of the higher titanium halide is determined by the heating temperature of the vessel containing the higher titanium halide in the condensed state.
The invention also provides high-purity low-oxygen titanium which is prepared by the preparation method.
The high-purity low-oxygen titanium is used as a target material, can avoid a smelting process, reduce O pollution, is used as a shape memory alloy raw material, can effectively control the phase transition temperature, and can be used for manufacturing chips or manufacturing NiTi memory alloy films or other equipment and devices with extremely low requirement on the oxygen content of titanium.
The invention has the advantages that:
the invention provides a method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition, which can obtain block titanium materials with different shapes and with the purity of more than 5N5, the oxygen content of less than 80ppm and the density of more than 98.5 percent; the consumption of high-value halide is low, and the refining cost is low; the deposition rate is high, and the utilization rate of crude titanium is high; the process flow is short, the control is simple, and the refining effect stability is high; the full-closed circulation process has almost no emission and is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the process for preparing high purity low oxygen titanium by chemical vapor transport deposition.
FIG. 2 is a schematic diagram showing the construction of a device for producing high purity low oxygen titanium as prepared in example 1; wherein 1-power supply, 2-heating element, 3-substrate, 4-coarse titanium, 5-refining chamber, 6-vacuum pump, 7-valve, 8-resistance heater, 9-halide vessel.
FIG. 3 is a microstructure of high purity low oxygen titanium prepared in example 1, with a scale of 1mm.
Detailed Description
The invention is illustrated by the following preferred embodiments. It will be appreciated by those skilled in the art that the examples are provided for illustration only and are not intended to limit the scope of the invention.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, which are used for illustrating the present invention but are not intended to limit the scope of the present invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
A method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition, wherein the device is shown in figure 2, and comprises the following specific steps:
TiI having a purity of 99.9995% and an oxygen content of 160ppm was used as a base material, and TiI having a purity of 99.9% was used 4 As a transport agent, crude titanium 477 g having a purity of 99.99% and an oxygen content of 310ppm was refined. The heating element (2), the base body (3) and the coarse titanium (4) are coaxially arranged in the refining chamber. Vacuum is applied to the refining chamber (5) by a vacuum pump (6) to 2.9X10 -4 pa, then heating the heating element (2) with the power supply (1), heating the substrate (3) until its temperature is balanced at 1250 ℃, and the crude titanium (4) temperature is stabilized at 900 ℃. After the temperature in the refining chamber (5) had stabilized, 9g of TiI in the halide vessel (9) was heated using a resistance heater (8) 4 Heating the transport agent, and closing the valve (7) after the temperature of the heater reaches 137 ℃ to enable the TiI to be 4 And the mixture enters a refining chamber (5), a system formed by mutually communicating the refining chamber (5) and a halide container (9) is in a closed state, the air pressure in the refining chamber is quickly stabilized to 111 Pa (absolute pressure), 476g of refined titanium is precipitated on a substrate after 3 hours of growth, the thickness is 1.57mm, the purity is 99.99958% (C, H, O, N gap elements are not considered in the purity calculation, the same is true), the oxygen content is 78ppm, the density is 98.9%, and the coarse titanium utilization rate is 99.8%.
FIG. 3 is a microstructure of the high purity low oxygen titanium prepared in example 1 in the thickness direction, wherein the lower part of the dotted line is a pure titanium matrix, and the upper part is refined high purity low oxygen titanium. It can be seen that the refined high-purity low-oxygen titanium directly grows on the pure titanium substrate in an epitaxial manner, no interface exists between the high-purity low-oxygen titanium and the pure titanium substrate, defects such as holes and the like are not found in the whole thickness direction, and good compactness is shown.
Comparative example 1
A method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition comprises the following specific steps:
TiI having a purity of 99.9995% and an oxygen content of 160ppm was used as a base material, and TiI having a purity of 99.9% was used 4 As a transport agent, crude titanium 400 g having a purity of 99.99% and an oxygen content of 260ppm was refined. The heating element (2), the base body (3) and the coarse titanium (4) are coaxially arranged in the refining chamber (5). Vacuum is applied to the refining chamber (5) by a vacuum pump (6) to 7.0X10 -4 pa, then heating the heating element (2) with the power supply (1), heating the substrate (3) until its temperature is balanced at 1330 ℃, and the crude titanium (4) temperature is stabilized at 1000 ℃. After the temperature in the refining chamber (5) has stabilized, 8g of TiI in the halide vessel (9) is heated by means of a resistance heater (8) 4 Heating the transport agent, and closing the valve (7) after the temperature of the heater reaches 160 ℃ to ensure that the TiI 4 And (3) entering a refining chamber (5), and enabling a system formed by mutually communicating the refining chamber (5) and a halide container (9) to be in a closed state, wherein the air pressure in the refining chamber is stabilized to 405 Pa (absolute pressure), and 398g of refined titanium is separated out from a substrate after 2 hours of growth, wherein the thickness is 1.28mm, the purity is 99.99953%, the oxygen content is 100ppm, the density is 96.8%, and the coarse titanium utilization rate is 99.5%.
Comparative example 2
A method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition comprises the following specific steps:
TiI having a purity of 99.9% was used with titanium having a purity of 99.5% and an oxygen content of 780ppm as a base material 4 As a transport agent, 447g of crude titanium having a purity of 99.5% and an oxygen content of 780ppm was refined. The heating element (2), the base body (3) and the coarse titanium (4) are coaxially arranged in the refining chamber (5). Vacuum is pumped to 2.0X10 by using a vacuum pump (6) to the refining chamber (5) -4 pa, followed by heating with a power supply (1)The element (2) is heated up and the substrate (3) is heated until its temperature is balanced at 1280 ℃ and the temperature of the crude titanium (4) is stabilized at 960 ℃. After the temperature in the refining chamber (5) has stabilized, 8g of TiI in the halide vessel (9) is heated by means of a resistance heater (8) 4 Heating the transport agent, and closing the valve (7) after the temperature of the heater reaches 122 ℃ to ensure that the TiI 4 And the mixture enters a refining chamber (5), a system formed by mutually communicating the refining chamber (5) and a halide container (9) is in a closed state, the air pressure in the refining chamber is quickly stabilized to 43 Pa (absolute pressure), 445g of refined titanium is separated out from a substrate after 2 hours of growth, the thickness is 1.4mm, the purity is 99.958%, the oxygen content is 340ppm, the density is 98.7%, and the utilization rate of crude titanium is 99.6%.
TABLE 1 impurity content and content of refined titanium in example 1 and comparative examples 1-2
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for preparing high purity low oxygen titanium by chemical vapor transport deposition, comprising:
1) Preparing a refining chamber and a container filled with condensed high-valence titanium halide, and communicating the refining chamber and the container filled with condensed high-valence titanium halide with each other;
2) Placing the crude titanium and the substrate into the refining chamber, and then vacuumizing; the matrix is metal with the melting point higher than 1600 ℃;
3) Heating to make the temperature of the crude titanium reach and stabilize at 800-1100 ℃ and the temperature of the matrix reach and stabilize at 1200-1550 ℃;
4) Heating the container filled with the condensed high-valence titanium halide to improve the vapor pressure of the condensed high-valence titanium halide to be 72-177 Pa, stopping vacuumizing, and allowing the gaseous high-valence titanium halide to enter the refining chamber under the action of the vapor pressure and controlling the pressure of the refining chamber;
5) The higher titanium halide entering the refining chamber reacts to produce gaseous lower titanium halide when contacting the crude titanium;
6) The gaseous low-valence titanium halide is heated when contacting the substrate so that the gaseous low-valence titanium halide is subjected to decomposition reaction to generate halogen gas and deposit high-purity low-oxygen titanium on the surface of the substrate;
7) The halogen gas reacts to generate gaseous low-valence titanium halide again when contacting the crude titanium;
8) The processes in the steps 6) and 7) are circularly and reciprocally carried out, so that high-purity low-oxygen titanium is continuously generated.
2. The method for preparing high purity low oxygen titanium using chemical vapor transport deposition according to claim 1, wherein in step 2), the vacuum is drawn to less than 1 x 10 -3 Pa。
3. The method for preparing high purity low oxygen titanium using chemical vapor transport deposition according to claim 1, wherein the substrate is pure titanium, pure molybdenum, pure tantalum, or pure niobium.
4. The method for producing high purity low oxygen titanium using chemical vapor deposition according to claim 1, wherein the purity of the substrate is not lower than 99.9%.
5. The method for producing high purity low oxygen titanium using chemical vapor transport deposition according to claim 1 or 2, wherein in step 2), the purity of the crude titanium is 99.9% or more and the oxygen content is 400ppm or less.
6. Use according to claim 1 or 2A method for preparing high-purity low-oxygen titanium by chemical vapor transport deposition, which is characterized in that the high-valence titanium halide is selected from TiF 4 、TiCl 4 、TiBr 4 、TiI 4 One or more of the following.
7. The method for preparing high purity low oxygen titanium using chemical vapor transport deposition according to claim 1 or 2, wherein the high valence titanium halide is TiI 4 In step 4) the vessel containing the condensed higher titanium halide is heated to 130-145 ℃.
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| TW373026B (en) * | 1997-06-06 | 1999-11-01 | Shigenori Okudaira | Method for refining titanium and apparatus to produce the refined titanium |
| CN100475990C (en) * | 2007-01-23 | 2009-04-08 | 遵义钛业股份有限公司 | Method and equipment for producing high-purified titanium |
| AU2010252965B2 (en) * | 2009-05-29 | 2013-05-23 | Hitachi Metals, Ltd. | Method for producing titanium metal |
| CN103221558B (en) * | 2010-11-22 | 2014-08-20 | 日立金属株式会社 | Device for producing titanium metal, and method for producing titanium metal |
| CN102808091B (en) * | 2011-06-01 | 2015-12-02 | 攀钢集团有限公司 | A kind of preparation method of high purity titanium |
| CN103773974A (en) * | 2012-10-18 | 2014-05-07 | 西安交大京盛科技发展有限公司 | Preparation method of high purity titanium |
| CN104947152B (en) * | 2014-03-31 | 2017-12-26 | 晟通科技集团有限公司 | The method that fused-salt electrolytic refining method prepares high purity titanium |
| CN110198798B (en) * | 2016-10-21 | 2022-11-29 | 通用电气公司 | Titanium alloy material production by reduction of titanium tetrahalide |
| CN111112636A (en) * | 2020-02-21 | 2020-05-08 | 朱鸿民 | Titanium-aluminum alloy powder and preparation method thereof |
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