TW538141B - Titanium crystal and titanium, and method and apparatus for prodding the same - Google Patents

Abstract

Described is a method and apparatus for producing high purity titanium and high purity titanium so produced. The process contemplates producing titanium sponge in a container and performing titanium fused salt electrolysis in situ in the same container to produce high purity titanium crystal, and where especially low oxygen content is desired, to treat the high purity titanium crystal as produced with iodine.

Description

538141 玖 Description of the invention The present invention relates to a 咼 purity titanium (Ti) crystal and titanium metal, and a method and device for manufacturing high purity titanium crystal and titanium metal. The present invention relates to the manufacture of titanium sponge (Ti Sponge), and electrolysis of titanium fusible salt (Ti Fused Salt) in the same container: Among them, titanium sponge can be used to generate high-purity titanium crystals. Among them, if it is necessary to obtain high-purity titanium crystals with low oxygen content, the obtained high-purity titanium crystals can be treated with iodine (12). At present, high-purity titanium has been widely used in the microelectronics industry to manufacture microprocessors and to be used in similar objects. Microprocessor technology continues to advance (including increasing accumulation and reducing circuit component size), so manufacturers are required to increase the purity of titanium in order to meet wafer manufacturing requirements. In the sputtering process, a high-purity titanium target is used to produce the thin films required for microprocessors, integrated circuits, and flat panel displays. Depending on requirements, the range required for its purity is approximately 99.99% (4N) to 99.99999% (7N). In order to improve the End Usage Property, the content of impurities can be reduced, such as alkali metals including sodium (Na) and potassium (K), heavy metals including iron (Fe), nickel (Ni) and chromium (Cr ), Radioactive materials include uranium (U) and thorium (Th), and gases, especially oxygen. These elements will have a bad influence on the properties of the element, for example, iron pollution will damage the thin film pattern and circuit elements, oxygen will affect the resistance of the deposited layer, sodium and potassium will move from the deposited layer to the transistor and 3057twf3. doc / 008 6 538141 Reduced efficiency, both uranium and plutonium emit alpha particles, which will change the state of nearby solids. A titanium commonly known as "6N" purity has a total impurity (including gas) content of less than about ippm and contains a small amount of oxygen, such as less than about 100 ppm. This purity is currently required by the industry. Using high-purity titanium and reducing the content of impurities can improve the performance of the sputtering process and increase the reliability and speed of the microprocessor or memory element. The current manufacturing process of high-purity titanium includes: (1) In a designed container, TiCl4 is reacted with a reducing agent to generate titanium metal wool. The reducing agent used is, for example, magnesium (Mg) Or 0 sodium: (2) vacuum distillation with a vacuum distillation device (Vacuum Distilling Apparatus) to remove residual salts; or treat the titanium wool with other methods to remove residual Salt. (3) Use an electrolytic cell with molten salt (Electrolytic Cell) to electrolyze titanium metal wool. _ And (4) use an Electron-Beam Furnace or similar high vacuum melting process to melt the titanium. By combining these steps, a titanium sputtering target can be obtained from a metal block (Ingot). Therefore, the main object of the present invention is to provide a high-purity titanium and a device and method for manufacturing high-purity titanium. # The method of the present invention includes reacting titanium tetrachloride with a reducing agent in a container to generate titanium metal wool and molten salts, and then chlorinating the salts in the same container [see equations (2) and (3) )]. The reducing agent includes an alkali metal or an alkaline earth metal. And these titanium metal wools were electrolyzed in the same container to produce titanium crystals. Then, titanium crystals were recovered from the container, and salts were removed from the crystals. The advantage is that the container has a metal surface which can be used as the surface of anti-3057t \ vt3.doc / O08 7 538141. The metal material includes metals with electrochemical activity lower than titanium (refer to chloride electromotive force). sequence). Among them, preferred reducing agents include sodium, magnesium, potassium or lithium or alloys of the above metals. In addition, the preferred metal material of the contact surface of the reactant includes molybdenum, nickel, or molybdenum / nickel alloy. The preferred device of the present invention includes a container that can be maintained in a state filled with air (Ah · Tight) and has other elements for providing the original substance; a cathode; an anode; and a reactant contact surface The metal material on this surface is a metal with electrochemical activity less than that of titanium (refer to the chloride electromotive force sequence). This device can be used to manufacture titanium metal wool and electrolytic molten salts at the same time, so the reduction and electrolysis steps can be performed at the same time; and the products of the reduction reaction need not be removed before the electrolysis step. And the salt produced by the reduction reaction of titanium tetrachloride can be used as a salt bath in the electrolytic process. In another embodiment of the present invention, the above-mentioned high-purity titanium crystals can further react with iodine to generate Til2 and Til4, and can be decomposed into high-purity titanium by heat treatment in a vacuum container, and its oxygen content is less than 50 ppm, and even Less than about 30 ppm. The reaction temperature ranges from 500 ° C to 800 ° C, and the preferred temperature range is from 750 ° C to 775t. The decomposition temperature is 1150 t to 1450 ° C, and the preferred decomposition temperature range is 1300 ° C to 1400 ° C. In addition, the pressure can be 1000 micrometers (Micron), and preferably 値 is 100 to 500 micrometers. A method for manufacturing high-purity titanium crystals, including reacting titanium crystals with iodine to form titanium iodide as described above, decomposing iodide at high temperatures, and reducing the pressure of 3057twi3.doc / 008 8 538141 to produce an oxygen content of less than 50 ppm Of titanium crystals. The process of the present invention can be used to produce high-purity titanium metal wool, which includes Be, Mn, Zr, A1, and V in a total content of less than 1 ppm, and Yb, Zn, Cr, Cd, and Sn in a total content of less than 1 ppm. This process can also be used to manufacture titanium metal wool, which contains Be, Mn, V, Zn, Cr, A1, Yb, Cd, Zr, Sn with a total content of less than 1 ppm. The high-purity titanium crystal obtained according to the method of the present invention contains sodium, potassium, aluminum, iron, chromium and nickel in a total content of less than 1 ppm; U and Th in a total content of less than 1 ppb, and sodium in a total content of less than 10 ppb With potassium, this includes gas and mechanical trapped salts. It is important to note that the titanium described herein may or may not include mechanically trapped salts. Therefore, for example, expressions of titanium purity and impurity content do not consider mechanical trapping of salts in titanium. The term "mechanical trapping of salts" is not limited to sodium chloride, but refers to being physically trapped in holes, cracks or openings generated by the growth of titanium crystals, rather than being melted in a large amount in metals. , Or not alloy with metal. Among them, the methods used in chemical analysis include Glow Discharge Mass Spectroscopy (GDMS) and Furance Atomic Absorption (FAA) for analyzing metals, and LECO gas analysis for analyzing gases, where Includes traceable samples calibrated to the National Institute of Standard and Technology (NIST). In order to make the objectives, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below in conjunction with the accompanying drawings for detailed description, such as 3057twf3.doc / 008 9 538141: Brief description: Figure 1 is a schematic diagram showing the electromotive force sequence of molten salt; Figure 2 is similar to Figure 1, but represents the key element (Window Element) and will remain on the salt bath or anode during the electrolytic process Figure 3 is a schematic diagram of a hybrid cell device; Figure 4 is a cross-sectional view of a receiving air intake system; Figure 5 is a diagram showing the relationship between iron pollution and current density Figure 6 is a diagram showing the relationship between temperature effect and iron discharge in a container with Mo lining; Figure 7 is a schematic diagram showing a Mo-lined container; and Figure 8 is a diagram for processing high purity Diagram of an iodide tank setup for titanium crystals to reduce their oxygen content. Description of pictographs: 1 ·· furnace 2 .metal wool 3: Ti crystal 4: titanium cathode 5: salt bath 6: cathode lead 7: lid 8: ding 014 supply port 3057tw0.doc / 008 538141 9 : Reducing reagent supply port 10: Stainless steel gate valve 11: Titanium-plated Transition Spool 12: Copper current distributor 13: Vacuum line 14: Argon feed line (Feed Pipe) 15: Titanium receiver (Receiver) 1 6: Suction system 17: Heat Jacket 18: Handling receiver 19, 20: Winch equipment 21: Winch Housing 22: Air inlet 23: Vacuum insulated blower (Blower) 24: Insulated valve 25: strainer 26: pipeline heater 27: heating element 28: getter material 29: recovery port Example In the manufacturing process of titanium metal wool, Ding 1 (: 14 can be dissolved with molten sodium (or magnesium) It can produce titanium metal wool and produce by-products such as NaCl (or MgCl2), as shown in reaction formula (1). TiCl2 can be used as 3057tvvt3.doc / 008 Carrier Salt in the electrolytic process, and Ding The 10:12 series is obtained by reacting titanium metal wool with TiCl4, as shown in reaction formula (2). TiCl2 can be reacted with an excess of TiCl4 reacts to produce TiCl3, as shown in reaction formula (3): (1) 4Na (I) + TiCl4 (g)-Ti (s) + 4NaCl (1) or 2Mg ⑴ + TiCl (g > — Ti ⑴ + 2MgCl2 (h (2) TiCI4 (g) + Ti (s)-> 2TiCl2 (1) (3) TiCl2 + TiCl4 (g) — 2TiCl3 (丨) s = solid phase 1 two liquid phases g = gas phase Reaction formulas (2) and (3) are chlorinated salts as a catalyst for electrolysis. The ratio of reaction formula (2) to reaction formula (3) is about 4: 1, and the titanium produced is formed or excessive. The average atomic valence in the metal wool is about 2.2. Other methods can be used to chlorinate the salts to produce the required electrolytic environment. For example, TiCl2W can be directly put into the electrolytic bath. The metal wool can be produced by reducing TiCl4 # The reducing agents include Na, Mg, Ca, K and Li. The reducing agents react in a similar manner as described above. The more common metal wool manufacturing reactions include the Himter process using sodium and the Kroll process using magnesium. The reason is that after the reduction reaction is performed in the container, the electrolytic reaction of the metal wool is directly performed in the container. Therefore, all reduction process steps, related pollution sources, and manufacturing costs can be reduced. In the reduction reaction, salt co-products include electrolytes and negligible water vapor, which is the source of oxygen. And under a single operating environment, metal wool manufacturing can be performed with 3057tvvf3.doc / 008 538141 and molten salt electrolysis.

At present, they are already aware of the possible pollution sources in the conventional process. For example, although Mild Steel does not directly contact the salt bath, it indirectly contaminates the salt bath and titanium crystals. Under the environment of water vapor, salt and heat, the steel is rapidly oxidized, so iron oxide is generated, and the iron oxide is peeled from the main material. If it is not careful enough, and it is impossible to determine that the crystal does not contain other materials besides titanium or titanium ions or substances with less electrochemical activity than titanium, the titanium crystallization process will also cause pollution. Even the surrounding sources of pollution can adversely affect the properties of the crystal. "Ambient pollution, including external impurities that may be in the air, or the environment, or equipment.

The above process can be used to electrolyze metal wool to produce high-purity titanium crystals, including tachygen TiC14, so that the metal wool does not need to be processed before electrolysis, so high-purity titanium can be obtained. In the titanium manufacturing process, molten salt can be used to electrolyze metal wool under the same operating environment, so there is no need to pre-treat or remove the metal wool before the electrolysis step. In addition, Ke Yi performs reduction reaction and electrolytic reaction in the same reaction tank. After a reducing agent, such as sodium, reacts with titanium tetrachloride, titanium metal wool and Nae u are formed, and then the salts are chlorinated, followed by electrolysis. The acid in the titanium crystals was then filtered off and washed with water to remove residual salts, followed by vacuum drying or using a drying step with heated argon. Other dry and dry methods such as freeze drying can also be used. J Single-element reducing agents, such as pure Na, can also replace coincident reducing agents, and are used in a single reaction to make mixtures of fibers and salts. The benefit of mixing the reactants together is that the produced 3057twt3.doc / 008 538141 salts can be melted at low temperatures. For example, when NaK and Na react with TiCl4, the melting temperature of the salt bath mixture is about 660 ° C, while the melting temperature of pure NaCl is about 800t. Controlling the composition of the salt mixture can reduce the operating cost of subsequent electrolysis steps and achieve a wide range of electrolysis temperature operations. The preferred reducing agent in the present invention is sodium because sodium is easier to purify than magnesium. In addition, the hygroscopicity of NaCl is much lower than that of MgCl2:

Purification of TiCl4 and reducing reagents, such as sodium and TiCl4, can be performed in advance to avoid becoming a factor affecting the purity of titanium metal wool. Pretreatment of ^ (: 14 and Na) can make the content of metallic impurities in TiCl4 and Na less than about 1 ppm, preferably less than 0.1 ppm. It can also be used to obtain high-purity rhenium metal wool. The second factor that affects the purity of titanium metal wool is the manufacturing process. The reaction system of Na and TiCl4 is highly exothermic, so it generates a lot of heat. For example, supplying precursors at too high a rate will cause the container to be true The melting rate in the present invention is relatively low, so that the reaction rate between the container, the reactants and the product can be relatively small. And, the better way is to cool the container at the same time to prevent the container from overheating. Wall design is another consideration. The wall must have a large thermal conductivity. For example, the container may have a two- or even three-layer structure, such as an outer stainless steel layer, a major ductile steel layer, and a single layer. The material of the inner layer is the substance whose electrochemical activity of the chloride electromotive force sequence is less than that of titanium, and the material of the preferred inner layer is molybdenum. Another factor is the material. Sexual contact, because the closer the contact, the better the thermal conductivity. 3057tvvf3.doc / 008 538141 The third factor that affects the purity of titanium metal wool is the contact surface of the reactant of the container, which is important for the manufacture of high-purity titanium. Impact. Not all substances are suitable for the reaction to take place. The container substance must not melt at too low a temperature F, nor can it react with the precursors of any product. In the process, the container substance cannot also be fast. Ground and titanium form an alloy, and the reactant contact surface must be less active in the chloride electromotive force sequence than titanium, which will be discussed below. Table 1 and Figure 1 show the chloride electromotive force sequence (EMF sequence), and this sequence How to use it in the device and electrolytic process of the present invention. The electrorefining ability can also be controlled by the selective oxidation process occurring at the anode and the selective reduction process occurring at the cathode. These processes are performed by two It is controlled by the main reaction mechanism. A reaction mechanism is based on the potential sequence (EMF sequence 歹 i j) and the electrolysis reaction generated by it. Another reaction mechanism is based on the inhibition reaction of MCln + nTiCl2 < di > nTiCl3 + M (s), where M represents the impurity element and η represents the valence state when the impurity element forms a chloride salt. In the practical example, the voltage of the electrolytic reaction is about 0.5 volts overvoltage (Overvlotage), and the voltage of the suppression reaction is about 0.3 volts overvoltage. By combining these two reaction mechanisms, and the process that occurs at the anode and cathode And considering Kinetic overvoltage, the key elements of electrorefined titanium (Window Element) can be defined. These key elements are quite sensitive to overvoltage, so they cannot be effectively electrolyzed in industrial applications. Therefore, the electrolysis step cannot effectively solve the problems of M η and V 雑 quality, and can only slightly solve the problem of Cr impurities in general cases. Moreover, in the case of high overvoltages on the electrode 3057t \ vf3.doc / 008 538141, electrolysis is less effective at solving metals close to key boundaries. However, overvoltage is very effective for controlling iron. In addition, other methods must be used to eliminate Ah Mn, Zr *, Be, and V.

The reason for considering the chloride electromotive force sequence in the electrolytic process of Ti is that the test metal, soil test metal and rare earth metal will remain in the molten salt bath. Ti2 + is contained in the molten salt bath, and an inhibitory reaction occurs spontaneously. In the case of iron, because there is sufficient spare energy, even if the anode is pure iron, iron cannot be effectively electrolyzed (from anodizing). Electrolysis can produce titanium crystals with relatively low oxygen content. However, because of its poor storage life, the metal bars obtained from these crystals will not be as pure as those crystals unless stored under vacuum or covered with argon. However, it is currently known that if the titanium iodide process is performed in the same process environment process described above, the oxygen content can be effectively reduced to 30 PPm or less, and the iodine crystal block has a relatively good storage life. Figure 2 shows the refining characteristics of electrolysis and represents impurities that tend to remain on the salt bath or anode. Key elements can be removed or prevented by other methods. By removing these elements from the precursors and blocking them, high-purity titanium can be obtained. The electromotive force sequence of molten salt at operating temperature is very important for the electrolytic process. The electromotive force sequence can be obtained, for example, from the third edition of the JANAF Thermochemical Table, while other older sources include, for example, U.S. Bureau of Minerals Bulletin 605. Figure 1 shows these sequences. For these calculations, some salts evaporate below the melting point of NaCl, or are solid at the melting point of NaCl 3057t \ vt3.doc / 008. In these examples, the electrolytic potential can be obtained by linearly extrapolating to a free formation energy of 1 100K. In each case, potential energy can be obtained from the Nernst equation assuming unit activity and equilibrium. However, in fact, these impurities do not correspond to the actual electrorefining situation because impurities do not have unit activity and are not in equilibrium. So the electromotive force sequence is a limiting condition where each variable is independent of each other. However, the concentration of different impurities must be considered during operation, so the applied voltage can be adjusted to compensate the purity of the raw material and the operating temperature. According to the electric refining process in Table 1, it is as follows:

Elements from Ba to Yb: (1) These elements will remain in the salt bath during the electrolysis step. (2) Low overvoltage is valid. Key elements: Potential energy close to Ti2 + / Ti (Be and Μη): (3) When the overvoltage is reduced, the emission of these elements will increase. (4) The content of these elements in the purchased TiCl4 and Na is quite low. (5) It is easy to remove these elements in the pre-purification step. (6) In the melting step of high vacuum, Mn is easily evaporated first. The potential energy is between Ti2VTi and Ti3 + / Ti2 + (V, A1, and Zr): (1) In practical examples, these elements cannot be efficiently refined in the electrolytic step. (2) Prior to the reduction of metal wool, these elements will preferentially start from 3057twt3.doc / 008 538141

TiCl4 is refined with reducing agents such as sodium. (3) During the high vacuum melting step, A1 is easily evaporated first. The potential energy is close to Ti3 + / Ti2 + (Zr, Cr, and Cd): (1) When the overvoltage decreases, the emission of these elements will increase. (2) The content of these elements in the purchased TiCl4 and Na or Mg is quite low. (3) These elements are easily removed during the pre-purification step. Elements from B to Pt: (1) These elements will remain in the anode or tank residue during the electrolysis step. (2) Low overvoltage is valid. The manufacture of metal wool and the electrolysis of salts are performed in a mixing tank instrument, so there is no need to remove the metal wool from the reduction vessel before the electrolysis step. Among them, the salt co-product of the reduction reaction of the metal wool includes an electrolyte. In this preferred embodiment, the mixing tank includes an iron container (outer layer), which can be used to make and electrolyze titanium wool. The inner wall of the container may include ferrous metal. The ferrous metal is plated with a metal layer having a chloride electromotive force sequence smaller than that of titanium. The metal layer is, for example, Mo, Ni, or Mo / Ni. Depending on the required purity, the container may not be covered with other substances because the container will be covered with a titanium wool material. In order to produce high-purity titanium, molybdenum can be used as a preferred reactant-contacting surface substance in electrolysis. But avoid contacting aluminum with air at high temperature, molybdenum will have better performance. This is because molybdenum oxide has a high vapor pressure, is 3057t \ vf3.docO08 18 538141, and contaminates the electrolytic cell. However, for the production of high-purity titanium, other metals that have higher ductility and are more resistant to oxidation than molybdenum-iron, nickel, and iron-nickel alloys and nickel-molybdenum alloys are particularly useful because they can form , Weldable and stronger than nickel alone, and more ductile than molybdenum. However, the higher the aluminum content in the nickel alloy, the lower the alloy's activity and the higher the purity of the titanium crystal. In terms of electromotive force sequence, manufacturability and oxidation resistance, lead group metals are quite desirable, but the disadvantage is that they are too expensive. In the electrolytic process, it is better to have good electrical contact with the metal wool. The lid, conversion reel, receiver and capstan in the mixed tank can also be made of titanium-plated ductile steel, stainless steel or commercially available pure titanium or titanium alloy. If it is to be made of a relatively pure product, it is better In order to use commercially available pure titanium, these instruments will not be contacted with TiCl4 during the reduction process. The supply line on the lid can be used to add a mixture of sodium (or reducing reagent) and TiCl4 in the reduction reaction and subsequent salt bath chlorination reaction. If magnesium is used as the reducing reagent, the magnesium can be loaded into the tank before the tank lid is closed, or this can be achieved through an opening. Among them, the material of the supply pipeline can be carbon steel, and is equipped with a titanium cover to avoid impurities due to corrosion during the reduction process. The power supply is connected to the current distributor (cathode) and the container (anode). The container is located in a gas furnace or an electric furnace to maintain the temperature required for the reduction electrolysis reaction. And in the highly exothermic reduction step, it is better to cool the air so that the speed of supplying raw materials can be increased. This instrument can also include a winch to raise or lower the cathode and support. Yin 3057t \ vt3.doc / 008 538141 The preferred material for the pole is titanium. The heating element is located on the external receiver to heat the receiver. In addition, when the receiver is evacuated and nitrogen is filled, it can be used to remove the moisture adsorbed in the mixing tank. In addition, the receiver can be electrically isolated from the circuit by other convenient methods, and the receiver can be stationary on, for example, a handling receiver, so the receiver can be located on the tank or in the state of harvesting of titanium crystals. During electrolysis, current can pass through the anode to the cathode, causing accelerated deposition of titanium onto the cathode. Then, the metal wool on the anode is consumed, and the remaining salts are transferred to the fixed tank, and then the reduction reaction is performed in the mixing tank. If the anode is not completely consumed, other suitable methods can be used to recover the residual metal wool. The consumed salts are rich in TiCl2 and can be reacted with other reducing reagents, such as sodium, to obtain titanium wool again. This titanium wool will then undergo other electrolytic or traditional operating steps. Add the reduction test agent used to obtain titanium cations in the same container, which can help the metal wool process and electrolysis steps. At this time, the titanium in the solution will become a cation part, and the salts that are free of titanium can be pumped out. The entire process can then be repeated to increase purity as needed. The amount of high beta-purity titanium produced in alkali metals, heavy metals, radioactive elements, and oxygen is relatively small. In particular, local purity titanium contains Na, K, Ab, Fe, Cr, and Ni with a total weight of less than 1 ppm; U and Th with a total weight of less than Ippb; Na and K with a total weight of less than 10 ppm; and less than 100 ppm. Oxygen, the content of oxygen is even less than 50ppm ◦ In addition, the above method can be used to make titanium crystals. This titanium crystal contains 99.99999 weight percent titanium, excluding gas and mechanical trapped salts 3057tw (3.doc / O0S 20 538141 Moreover, the available is titanium containing 99.9999% by weight, excluding gas and mechanical trapped salts, but including less than 50ppm of salts. In addition, in the 99.99999% by weight titanium crystal, the oxygen content is about Less than 100ppm, even less than 50ppm. In order to improve the purity level, even put the salt bath in a steel container, so as to produce a titanium protective layer in the process of metal wool manufacturing, this layer of protective layer can be effectively used in the early electrolytic operation. Isolate the container wall from the salt bath. This isolation effect will continue until the metal wool is completely consumed. In the subsequent reduction process, a protective layer will be obtained again. Please refer to Figure 3 for a clear understanding of the invention. The mixing tank is used. This mixing tank is suitable for batch mode operation, that is to say, the main body of the mixing tank can be disassembled or appropriately modified in the reduction or electrolysis stage. For batch operation, It uses the same benefits of the process design of the same operating environment, which uses different cover equipment designs during the reduction and electrolysis stages. In batch-type operations, the container can also be cooled after the metal wool process to facilitate the re-assembly of the electrolytic cover equipment. This tank container includes an outer layer, and the outer layer is made of stainless steel, for example, so that it can avoid corrosion in an oxygen environment. The inner layer, this inner layer is made of steel, for example, to increase the integrity of the structure. One layer is made of chloride Metals that are less active than titanium in the electromotive force sequence, such as nickel, nickel alloys, molybdenum, molybdenum-nickel alloys, or layers of non-conductive materials, such as boron nitride, can be covered by an inner layer, such as the surface of a reagent container The material of the cover 7 can include steel, or a thin layer of pure titanium, nickel, molybdenum, or other inactive metals. The container may be mounted with the cover gas furnace or an electric furnace 1

jOSTtvvtj.doc / QOS 538141 and can be supported by a steel frame. Through the reducing reagent supply port 9, a sufficient amount of Na (or other reducing reagent combination) can be added to the container / and fl can be added to the tank through the corresponding supply port 8 until the reaction is completed. After all the reducing reagents have reacted, additional TiCl4 can be added, so that TiCl2 / TiCl3 effective chloride bath 5 can be used, so that the weight percentage of titanium is about 2-12%. During this reaction, the pressure measured near the vessel wall is about 2 psig to 4 psig, and the temperature is about 800-1000 ° C. ◦ The reduction process can be controlled to make the temperature inside the reactor quite low, so it can ensure that Obtain impurities or other non-titanium materials from the container. According to the above procedure, the bottom and part of the container wall can be covered with a layer of titanium metal wool, and the composition on the lid is usually called the superstructure. For example, it can include: non-mirror steel gate valve 10, titanium plating conversion The reel 11, the copper current distributor 12, and the titanium receiver 15 include a heat jacket 17, a carrying receiver 18, and a titanium-plated winch cover 21. As shown in the figure, the above-mentioned upper structure is arranged on the container, and the material of the upper structure may include titanium, stainless steel, molybdenum, nickel, molybdenum-nickel alloy, and alloys of the above metals. In addition, any conventional method can be used to isolate the electrical properties of the superstructure from the circuit. The superstructure of the tank can also be other substances that will not allow corrosion or erosion products to enter the salt bath and contaminate the titanium crystals. Prior to electrolysis, the upper structure of the tank can be evacuated with a vacuum line 13 to make its pressure lower than 10 × 10 · 6 or lower. Combining the pump with the receiver can effectively remove air and water vapor from the surface, so that titanium crystals with low oxygen content can be obtained. After the vacuum step, the vessel can be filled with argon using argon addition line I4. An additional evacuation step can then be performed to further remove 3057twt3.doc 008 538141 moisture from the system. Referring to FIG. 4, the getter system 16 can heat the getter material to circulate the gas in the tank before, during or after the electrolysis process, and can be used to remove residual oxygen in the tank. However, the present invention is not limited to the apparatus used in Fig. 4, and the present invention is also shown to be applied to other similar apparatuses. For example, a convection driven cycle machine can also be used to simplify the instrument, but the relative time efficiency is lost. The vacuum insulated exhaust fan 23 can suck the gas in the tank through the air inlet 22 to the lower suction machine. Titanium crystals, fine titanium particles, lathe machining of titanium blocks, and other materials, such as Zr, will absorb oxygen under appropriate conditions, so they can be used as good getter substances28. Therefore, when these substances are used, no contaminants are introduced into the tank. The getter material can enter the line heater 26 through the titanium screen 25 at the line inlet. The gas in the tank can be heated to about 300 ° C to 800 ° C by the heating element 27 and returned to the receiving gas through the recovery port 29 '. When these materials are used up, use Insulation Valve 24: Insulate the system before adding new materials. The operating temperature is related to the composition of the salt bath. For typical salts, the operating temperature range is from about 650 ° C to 900 ° C. If mixed salts are used, lower operating temperatures can be used in the electrolytic process. # In fact, one of the factors limiting the maximum operating temperature is the eutectic of the container lining material and titanium. For example, a nickel lining forms a eutectic with titanium at about 950 ° C. The winch equipment 19 and 20 are used to lower the pure titanium cathode 4. The winch equipment 19 and .20 inches are connected to the cathode support frame through electrical insulation wires. Depending on the depth of the salt bath and the substrate, different lengths of cathode can be made. Initially, the bottom of the cathode was 3057twf3.doc / 008 23 538141 and the distance from the metal wool was about 15 to 20 inches. This cathode support can be in electrical contact with the circuit sub-panel, so that the circuit completes a loop. In one example, the power supply may connect the cathode lead 6 and the current distribution panel at the same time. DC power supplies can provide voltages of about 0 to 12 volts and amps of 0 to 10,000 amps. The power supply can be operated by voltage or circuit control. The current density varies between individual runs and between runs. Depending on the initial surface area of the cathode, the current density ranges from about 0 "to 0.1 to 1.4 (amps / cm2). It has been experimentally found that lower current densities can result in higher purity titanium crystals because low current densities prevent impurities from being deposited on the cathode. Among them, the preferred current density is about 0.3 (amps / cm2) and less than 0.3 Umps / cm2. However, when titanium crystals are formed, the surface area of the cathode will increase at the same time. Therefore, it is only necessary to accurately measure the current at the beginning of the electrolytic process. The density is sufficient. The data in Table 2A is shown in Figure 5, and Table 2B shows the results of the change in the starting current density from 0.1 (amps / cm2) to 1.9 (amps / cm2). As shown in the table, this data can be the same as the theoretical calculation of current optimization. When the current density in the tank is about 0.3 (amps / cm2), the same properties exist for the chitin crystals obtained from different substances. This result indicates that titanium crystals of high purity can be obtained even if ductile steel is used, if the tank is operated properly and under certain operating restrictions. The use of nickel or molybdenum (or previously mentioned inactive metals) as the container lining can increase the operating range. In one of these-operating embodiments, the voltage can be fixed and then the current can be increased until a set value is reached. In the subsequent steps, the current is fixed and μ. The voltage is reduced. The explanation of these trends includes observing that when the titanium crystal is formed on the 3057t \ vt3.doc / 008 24 538141 cathode and the resistance of the overall current decreases, the current is fixed. When the voltage decreases and the amperage increases at a fixed voltage. And according to the process requirements and anode / salt bath conditions, the variables of the electrolytic process can be changed in the above-mentioned operating range and in the change / fixed control design. After the electrolytic process, the cathode can be inserted into a receiver to isolate the cathode from the salt bath and allow the cathode to cool. During the cooling cycle, argon can be added so that the pressure in the tank is maintained at 0 to 10 psig. It is also preferable to avoid making the receiver pressure below Opsig during the cooling cycle to avoid gas leakage and contamination of titanium crystals. However, when the vessel does not leak gas φ, the pressure can also be lower than Opsig. The cooling cycle is continued until the titanium crystal deposition temperature reaches 100 ° C, preferably 50 ° c. The cathode and the deposited titanium crystals can then be removed from the cathode frame and filter by a method that includes the use of a mild acid solution to remove all surface salts' deposits. Electrolytic salts are usually caused by crystal growth or bridging: general mechanical trapping. Among them, the amount trapped is about 50 to 3000 ppm. Then, the titanium crystal is peeled from the cathode using a physical exfoliation method, and is completely wetted to remove residual salts. The more important point is to remove all the acids that appear on the crystal. The complete removal of the acid is quite β important, as the residual acid will contain impurities in the solution, and a load of evaporated acid will cause the deposition of oxides, which will contaminate the crystal and render the crystal useless. Methods of drying include using a vacuum drying method or passing hot argon through the crystals. It is also useful to use freeze-drying, but at a slower rate. The purpose of drying the crystal is to make the water and gas content less than 0.2 weight 卩:! Minutes, ratio, or reach an undetectable level to obtain higher quality 3057tvvf3.doc / 008 A single reduction reaction can produce sufficient supply An electrolytic reaction of metal wool. During the reaction, impurities less active than titanium in the chloride electromotive force sequence will either remain in the metal wool or leave the solution, and will contaminate the anode or other surfaces. Impurity elements less active than titanium tend to remain in the salts. Among them, the chloride electromotive force sequence has a key (Window) of about 0.5 volts. If the container lining is an inactive metal, this metal will not enter the solution and be deposited on the electrode. When there is no more deposition reaction on the anode, the container is prepared for the next reduction reaction. As mentioned earlier, after the anode no longer has a deposition reaction, an electrolytic reaction is performed. In the electrolytic reaction, sodium remaining in the salt bath can be stripped using sodium, and titanium can be recovered using conventional methods. In addition, after the anode no longer has a deposition reaction, the container is cooled and removed from the instrument. Then, using any conventional removal method, remove the lid and recover any remaining titanium wool. Before cooling the container, the titanium-rich salts can be treated, for example, by reacting with other reducing agents to obtain titanium wool. A preferred method of recovering titanium involves immersing the cathode deposit in a weak mineral acid solution (preferably HC1 or H2S04). Care must be taken to prevent contamination and, if possible, use clean rooms and high-purity reagents. The pH of the solution must be low enough so that all predictable impurities remain in the solution. Then, the cathode deposit is wetted until the water of the nail becomes neutral by the wetting, wherein the wetting step is, for example, using deionized water. It is possible to remove the deposit with the titanium bed, and then perform the wetting process again. If necessary, large pieces of sediment can be crushed using a titanium crusher 3057tvvf3.doc / 008 26 538141. Then, you can use a method of wetting and separating fines, and use deionized water that does not contain any fine particles on the shoulder.撸, +, θ _ work precipitates are also helpful in the wetting step. All crystallization processes involve 4 #, rfi, π, and it is better to perform the steps in a clean environment. For example, the further processing of 莆 t, a ~, the above 駄 crystals, filtration, wetting, drying, suitable for cutting off fine objects, P-__ 一 _____ 'and the steps of assembly should be in clean The room environment is not equal to two steps, and the encapsulation step performed in the environment or the post-J step in a vacuum environment = the transfer step performed should also be in a clean room environment

In progress. The vacuum drying method is a better choice because the freeze drying method takes longer. In addition, if the purity of the argon gas is sufficient, a hot ammonia gas passing method may be used. You can also use hot air, but hot air may cause surface oxidation or even combustion. In order to obtain fairly pure titanium, it is better to dry the surface of the titanium crystals in a vacuum container by vacuum drying. These vessels are vacuum sealed or flushed with argon or even pressurized with argon.

The manufactured titanium crystals have needle-like, dendritic shapes, and some are lentils, flat plates, or blocks. When the electrolytic process is at the α to / 3 conversion temperature, the crystal growth in the direction of the vertical hexagonal axis is the fastest. At the above temperature, the crystal system grows into a cube (Cubic). In order to obtain 7N metal purity and make the oxygen content less than 30 ppm, Ώ] · Use additional purification methods, such as using iodine to process iE according to the following method. Table 3 summarizes the impurities commonly observed in precursors, metal wool, electrolyte crystals, phantoms, and metal nail blocks. Among them, the residual impurities are also listed. * A 4 (emission ratio) ◦ This number indicates that the process steps and source of the material must be carefully | 3057twi3.doc / 008 27 538141 processed to obtain high purity titanium. As mentioned above, elements that need to be completely removed before additional processes include Fe, Cr, Zr, V, A1, Mn, Na, K, Cu,

Ni, U and Th. Proper use of the information provided in Table 3 [J can produce titanium with a weight percentage of 99.99999. Table 4 shows the effect of the additional steps on the above impurities. If a product with very low oxygen content is required, the product can be further refined from the compounding process. The preferred methods include the sequential use of the iodide process and the methods described above. Table 3 lists the refining methods and the amount of impurities in each process stage. It lists the more important elements in electrical engineering applications. Table 3 summarizes the best methods for dealing with these elements. The mixed crystals are then processed using the process described above to remove salts. For titanium sputtering targets, iron is the main contamination because it destroys the sputtered film pattern and circuit elements. In order to obtain 7N purity, the amount of iron contamination on the obtained titanium harrow must be limited to less than 0.01 ppm. A major source of iron is steel containers used to make and electrolyze. Titanium metal wool precursors typically contain less than 5 ppm iron, while subsequent metal wools contain about 50-100 ppm iron. Excessive temperature in the TiCl4 reduction process will cause iron to enter the metal wool from the container wall and affect the purity of titanium. The superstructure of the grooves also produces rust. In this container, the larger purity grades of the crystals contain about 0.2 to 0.4 ppm of iron, and generally the iron content is less than 1 ppm. The sources of pollution in Shao Europe include steel processing equipment and perspiration. With other container substances, the iron content in titanium crystals can be greatly reduced 057twf3.doc / 008 28. For example, the use of nickel and molybdenum containers allows the iron content of titanium crystals to be less than 0.1 ppm. Other materials such as tungsten, lead, and molybdenum / nickel alloys can also be used. When the material used is less active than molybdenum, the iron content in the crystal is controlled by the iron content in the metal wool. Nickel has reasonable cost, easy availability, workability, practicality, suitable nickel-titanium eutectic temperature, and electrochemical inertness based on chloride electromotive force sequences. The use of molybdenum, tungsten, or platinum metals has additional material costs, but these metals are less active and these metals have a higher eutectic temperature with titanium than nickel-titanium. A better electrolytic environment also reduces the amount of iron and other impurities that may be deposited on the cathode. The lower current density (cathode / anode) makes these impurities less contaminated with titanium crystals. The ideal current density is about 0.3 (amps / cm3) or lower. Even when a steel container is used, the discharge ratio obtained under these operating conditions is about 250 to 1 (the use of other container substances can increase the discharge ratio to more than 2000 to 1). In order to make the iron pollution in titanium to the sub-ppm level, the possibility of iron pollution sources in the process equipment and other surrounding environments must be considered. Therefore, all refining tank structures (except vessels) should be composed of titanium or plated with titanium. The only limitation is that in the reaction step, when the temperature is high enough to react with the metal, any titanium in the superstructure cannot contact TiCl4. Otherwise, similarly, any other process equipment that directly contacts the titanium crystal should be made of pure titanium. As shown in Figure 6, the temperature of the electrolysis affects the discharge of iron from the container (Figure 7). When the temperature is lower than 750 ° C, the iron can be effectively avoided. A temperature better than 3057twt3.doc / 008 29 538141 is to use a temperature below 700 ° C. In order to obtain higher purity and even the salt bath in the electrolytic process, LiCl or other salts can be used to obtain lower temperatures. Lowering the temperature can reduce the overall energy required, and also avoid equipment wear or damage. However, because these salts are more hydrophilic than NaCl or KC1 and may contain a large amount of water vapor when purchased, the use of these salts requires additional safety facilities to prevent water vapor from entering. The water vapor dissolved in the salt bath will add oxygen to the refined crystals, so it must be avoided by all possible means. These methods include: 1) prior to use, conventional methods, such as distillation, dry the salt φ in advance; 2) vacuum treatment of the electrolytic bath; 3) the metal wool and the electrolytic bath-cooking; 4) drying The argon gas covers the electrolytic bath; 5) other salts are produced (but not including water vapor) by a co-reduction method, such as mixing 闬 Li and Na in a reduction reaction to produce LiCl + NaCl salts with a lower melting temperature. _ Iodide thermal decomposition is also a method of purifying iron or other metals. In the electron beam melting step, a part of the iron is removed because at the melting point of titanium, iron has a higher vapor pressure than titanium. However, the iodide process discharges most of the metal impurities, which range is about 10 ° /. To 99%, it is mainly based on the ability to discharge oxygen. This will be discussed below. · In recent years, the manufacture of wafers has required the use of titanium with a low oxygen content, since oxygen can hinder the deposition of titanium layers. A method for producing titanium having an oxygen content of less than 100 ppm or even less than 30 ppm will be discussed below. There are many sources of gas and sweat from the metal wool precursor to the electron beam melting step. Both D14 and Na have oxygen in the form of oxides or oxychlorides. Therefore, the oxygen content of metal wool in subsequent processes will be increased. In the process of metal wool 3057twf3.doc / 008 30 538141, there will be additional oxidation reactions, such as the formation of titanium oxide when the residual water in the reduction tank reacts with the metal cotton. The post-electrolytic crystal process includes acid filtration to remove residual salts, so titanium oxide crystals are further added. In addition, if a vacuum reaction tank is not used or residual moisture is not taken into account, oxygen is also introduced into the electron beam melting process. By combining metal process, electrolysis, and electron beam process, titanium crystals and sputtering targets with oxygen content below 100 ppm can be obtained. However, as described below, treating or decomposing titanium iodide with iodine can make the oxygen content less than 50 ppm, and even the content of the electron beam melted material can be less than φ 30 ppm. To obtain titanium with an oxygen content less than 30 ppm You can use iodide thermal decomposition process, this process includes using high-purity titanium crystals as raw materials. The iodide bath consistently produced titanium crystal bars (Bar) with an oxygen content of <30 ppm. Table 5 'Typical results of thermal decomposition of iodide containing titanium crystals. '' The thermal decomposition process of iodide can be connected using the same environment as that used to produce titanium, as described below. In this method, iodine and titanium crystals are reacted according to the following reaction. Each reaction occurs at a wide range of temperatures, but in the operating tank, reactions 6 and 7 occur at a higher temperature than reactions 4 and 5. β (4) Ti (s) + I2 (g) — Til2 (g) (5) Til2 (g) + I2 (g) — Til4 (g) (6) Ti (s) + 2I2 (g)-Til4 ( gi The following unbalanced reaction (Disproportionation Reaction) causes precipitation at the hot filament. (7) Tii4 (g) — Ti (s) + 2I2 (g) 3057twt3.doc / 008 538141 (8) 2TiI2 (g)-&gt; Ti (s) + Til4 (g) It has been found that titanium oxide, which may appear or form in the raw material, does not react with iodine and is not transported to the filament. Moreover, this process may produce High-purity titanium with very low oxygen content. It has been found that by the iodide process, some of the A1, Mn, Cu, and Zr impurities can be reduced. Table 6 lists the use of pure titanium metal wool and 3N to 4N input holes. / Or crystal, the conclusion of the result obtained. The result is that the combination of the iodine process and the metal wool in the same environment produces the crystal as described above. Electron beam melting and other high vacuum melting methods can be removed by removing Titanium is further purified by volatile metal impurities. In general, metals with low melting points and / or high vapor pressures can be removed by electron melting, which is also attributed to electron beam refining For example, the melting point of A1 and Mn in titanium have a higher vapor pressure than titanium, and both of them can be partially removed during the melting of the electron beam. In order to reduce the oxygen content and combine with the melting of the electron beam, many The technology has been proven. The residual water vapor in both the titanium crystal and the melting reaction chamber can be regarded as a source of oxygen and increase the oxygen content of the titanium ingot (Ti Ingot). The degree of high vacuum maintained during the melting is Not enough to remove all remaining water vapor, so additional water vapor removal methods need to be provided. One method involves melting titanium in the bottom of the separate getter furnace to melt the The chamber removes water vapor. The first method is to heat the melting reaction chamber wall and the manhole to increase the water evaporated from the walls and crystals. The result is a controllable electron beam atmospheric pressure, where the oxygen content is Ignored. 3057tvvf3.doc / O08 538141

The effect of Cr on the sputtering film is the same as that of Fe, and for example, to improve the results of the sputtering target, the removal of Cr is very important. In order to reach a metal containing 7N, the Cr content of the completed sputtering target needs to be <0.05 ppm. A small amount of Cr was found in the reduction and electrolytic vessels of TiCl4, Na, metal wool and traditional steel. Interestingly, metal wool usually contains more Ci * than its predecessors, which means that process equipment (such as containers, supply lines, etc.) has become the most important cause of metal wool impurities in metal wool. Because the Cr content is relatively small, no additional purification of TiCl4 is required. The commercially available sodium has a Cr content of about 5 PPm, but higher purity sodium can also be obtained. The high purity sodium has a Cr content of about 1 ppm. Methods for obtaining high-purity titanium include filtering molten sodium to remove metal oxides. For example, nickel pipelines can be used because nickel pipelines do not contain Cr and other metals that occur in steel. The Cr content of the titanium wool obtained by this method is about 0.5 ppm. Only a part of Cr is discharged during the electrolytic process, and the discharge ratio is about 5: 1. In the higher-purity metal wool, the Cr content of titanium crystals is about 0.1 ppm. The iodide process and the electron beam melting process can usually remove Cr, although it is generally predicted that the difference between the vapor pressures of Ti and Cr will not cause purification. The acceptable removal ratio is about 3: 1, and the Cr content of the titanium block can be less than about 0.02 ppm. Also, longer furnace heating time or higher specific electron beam power can also help remove the phenomenon.

In sputtering target applications, pins (Zirconium; Zr) / Vanadium (Vanadium; V) do not cause much problem. However, in order to obtain the 7N substance, the contents of Zr and V 3057t \ vi3.doc / 008 538141 must be less than 0.02 ppm (all of which are 0_04 ppm). Generally purchased sodium contains about 2ppm of Zr and 8ppmV, which can contaminate metal wool. Zr / V cannot be removed by electrorefining, iodide processes, and electron beam melting. The reduction tendency of Zr / V is similar to that of titanium, because only a part of Zr is discharged during the electrolytic process, and V is not discharged at all. Similarly, in the iodide process, Zr / V has properties similar to Ti, so it limits the ability of the refining step. And because of the vapor pressure, Zr / V does not evaporate during the electron beam melting step. One way to reduce the Zr / V content is to refine the metal wool precursor to meet the needs of the titanium block with φ. Generally, Na can be filtered to remove metal oxides, especially calcium oxide generated from CaCl2. The purpose of CaCl2 is to reduce the operating temperature of the NaCl reduction process. The filtration step does not completely remove all gold oxides, especially the rare oxides. Therefore, sodium must be refined through a simple steaming step. In this process, Zr / V can be removed; oxide contaminants are moved to the required level, where the melting and boiling temperatures of Zr / V oxides are higher than titanium. Therefore, a distillation step can be used to prevent other contaminants from entering the sodium. This purification step can obtain sodium with a Zr / V content of less than 0.1 ppm. The subsequent electrorefining process will make the Zr / V in the titanium crystal less than 0.004Ppm in total. Minor pollutants (A, Bmη, Na , K, U, Th, Cu, and Ni): The above-mentioned elements are minor pollutants, because the source of these pollutants can be traced, and S / can be completely removed in different refining steps, so These elements can be classified as minor pollutants. The following are descriptions of each process stage or corresponding precursor, and how to remove these elements. 3057twt3.doc / 008 34 538141

TiCl4 / Na: These metal wool precursors contain a small amount of the above elements, except for the radioactive elements U and Th. Distilled sodium will only partially remove any metal oxides (for example, A1203). However, for the manufacture of 7N titanium, it is not necessary to completely remove the metal oxides. Electrolysis: According to the prediction of thermodynamics, the electrolysis step will not release Cu. However, a part of A1 will be discharged, and a large amount of NΠ. Mn is not discharged at all, and is usually obtained from steel containers for metal wool and electrolytic processes. The use of Ni or Mo lined containers eliminates the Mn contamination of the container wall 6. Titanium crystal filtration: The filtration step is used to remove residual salts on titanium crystals, especially NaCl and KC1, so the Na and K content can be reduced. Iodide process: The above elements cannot be effectively reduced, and Zr, A1 and Mr ^ can only be partially removed. Electron beam melting: Some of the above elements are more volatile than titanium, so they can be used in the electron beam melting step. Completely removed. The content of Ni, U, and Th in the crystal is small, so no additional purification step is required. Basically, the remaining elements are completely removed. Table 7 includes the element's vapor pressure number 値 and its approximate removal ratio. The following examples can be used to further explain the present invention. Example 1 (Mixture Tank Electrolysis) For both the reduction period and the concomitant electrolysis, the mixture tank 巳 was completed. Ductile steel containers have previously been used in the manufacture of four metal wools. Therefore, a Ti-Fe alloy layer appears on the wall. Initially, 4,650 lbs of molten Na has been supplied to the tank container, and t Na is reacted with 11,220 lbs of TiCl4 at an atmospheric pressure containing argon. The resulting solution (Resulting Bath) includes about 2,010 lbs of Ti metal wool. And 11,820 lbs of NaCl, and about 2,040 lbs of TiCl2. Thoroughly cool the container and remove the hemispherical lid used during the reduction. Use a lid designed for electrolysis. Care should be taken to reduce any contamination that may enter the container during cap exchange. Put the container back to the electrolytic place, and the required components (such as the gate valve, the conversion reel, and the current connection) need to be inspected to ensure their vacuum. Heat the furnace to 850 ° C and soak the container About 12 hours. Then increase the temperature to 900T :, and insert a thermowell into the tank container to detect the temperature of the salt bath, which is 825 ° C. The receiver is evacuated to a vacuum of 9 microns. The degree of evacuation usually indicates the balance between the vacuum system and the amount of water and gas absorbed on the inner wall surface of the device. After evacuation, the tank container is filled with argon to a pressure of about 4 psig. This pressure should be maintained during the process. During the insertion of the hot well, the first reaction was performed using a 36-inch anode based on the measured cathode depth. The combined anode was lowered into the salt bath and the power supply was turned on. Initially, the voltage was set at 6 volts and the current was set at 2500 amps. This resulted in an initial current density of about 0.5 amps / cm 2. Then the reaction was performed under the control of current. Table 8 shows the experimental data. When After the anode and titanium crystal deposits have been moved to the receiver and cooled down SOSTtwil.doc / OOS 36 538141, the reaction lasts 66.5 hours. During the cooling cycle, at least initially, this hot crystal is exposed to the tank container This gas may be absorbed by the crystal, such as residual oxygen. During the cooling cycle, pressurized air is used to cool the outside of the receiver to accelerate the effect of the cooling cycle and reduce the time that the crystal is affected by the pollution source. After cooling, the receiver is placed above the Harvesting Station, and the received crystals are lowered into the filtering acid tank. This filtering acid tank contains 0.5% sulfuric acid / 0.5% citric acid. % Acidic solution. Keep the received crystals in the filter tank for about 30 minutes, then transfer them to the same tank and solution and leave them for 17 hours. Once the external salt (Superficial Salt) is removed (delay; Dragout), one of the effects of extending the filtering time is to remove the blocked or mechanically trapped salt to a certain degree. After the filtering cycle, the remaining drag is removed Salt, and the surface of the crystal may be slightly uranium etched, then the obtained titanium is covered with deionized water 3 times.: If there is any acid that has not been washed with water and can cause significant chemical combustion (such as surface oxidation), the It is effectively removed. The titanium crystals are manually removed from the anode, and completely rinsed for about 2 hours by spraying the crystals with deionization. They are dried by blowing hot argon through the crystals until water vapor The content of the content ® is about 0.1% by weight. The samples are analyzed and the results are shown in Table 9. Included in the table are crystals generally produced by the molten salt electrolysis of titanium metal wool in a tough steel container. Comparative Purity Range compared to this example. It is clear from the data that titanium crystals produced under the same environment demonstrate an improved degree of purity. The lower Fe supports this argument, omitting the metal wool process steps of 3057t \ vt3.doc / 〇08 37 538141, which obviously contributes to the Fe contamination of the subsequent crystals. This data also supports that Mo-lined tank vessels will significantly reduce Fe contamination, and allow the manufacture of crystals containing about 0.01 ppm Fe Fe. The lower oxygen was observed due to the decrease in brine gas, where this water-gas system As a source of oxygen. According to calculations, the electrolyte experiment has a current efficiency of over 50%. Another example is crystals of different morphologies. Three clearly distinguishable crystalline structures: flat hexagons, small dendrites, and large natural nuggets. The results of the analysis for oxygen φ are shown in Table 10. It contains standard samples with no special morphology. As expected, the correlation between the surface area-to-weight ratio of the sample and the degree of oxygen content is very high, so increasing the importance of surface area to crystal volume ratio. _ It should be understood that the results shown in Tables 4, 6 and 7 can be increased by increasing the degree of vacuum, using a low current density, increasing the trenching ability, lowering the temperature, increasing the pumping time, providing the container lining and using the same Technology. Example 2 (Iodide Thermal Decomposition) Figure 8 depicts a typical iodide tank used to process high-purity Ti crystals to reduce oxygen content. In this example, all tank elements were initially rinsed with ethanol to reduce the possibility of contamination. The container 2 is placed in the melting furnace 1, and the FL is heated to 150 C for two hours to remove the residual water vapor and remove the reagent.

The Mo lining and Mo strainer 5 are placed in the container 2 and about 13 pounds of Ti product. The body 3 is added between the container wall and the strainer 5 3057twt3.doc / 008 38 538141 with a length of 70cm and a diameter of 0.35cm.

Ti filaments (Filament) 4 and Mo input-through rods (Feed-through Rods) 6, attached to the ceramic input holes (Feed-through) 7 on the lid assembly 8. Vacuum Grease is used for O-ring, and the lid is used to seal the container. Frame all remaining connections (eg vacuum line, argon line, iodine input hole, etc.). Heat the container for 12 hours to about 300 ° C ~ 850 ° C. When the system is evacuated to less than about 10mtorr to remove the residual moisture in the Ti crystal input hole. Subsequently, the temperature of the melting furnace was set to 750 ° C. Electrical wires are attached to the filaments to supply resistance heating filaments to approximately 1300 ° C. Sufficient iodine is delivered to the tank to initiate the reaction 9-the temperature and filaments of the vessel wall are monitored during the maintenance of appropriate reaction conditions. During operation, the lid is cooled with water to protect the integrity of the O-ring. This lasted about 100 hours and produced about 1 650 grams of Ti crystal strips containing less than 30 ppm oxygen. The crystals are estimated to contain between 100 and 200 ppm of oxygen, resulting in a total reduction of more than 70%. Example 3 (Electrolyzed in Mo-lined container) Commercially available pure Mo was manufactured in a container liner with a height of 10 inches and a diameter of 5 inches, and its size matched the container. Ti metal wool, NaCh KC1 and TiCl2 are directly filled into the container, and then the container is placed in the melting furnace. The vessel was evacuated, returned to argon, and heated sufficiently to completely melt the salt bath. After the electrolyte has been melted, commercially available pure Ti anodes are lowered into the salt bath. By maintaining the temperature of the salt bath, the viscosity of the molten mixture can be controlled during electrolysis. After the electrolysis was completed, the container was cooled and the Ti crystals were removed from the container. The Ti crystals were filtered under acidic conditions, and vacuum-dried 乩 3057t \ vl3.doc / 008 39 538141 to analyze metal impurities. Table 11 lists the results of the electrolysis performed on the Mo-lined and Fe vessels. It can be seen that the resulting crystals do not exhibit Mo contamination. However, Fe is significantly contaminated and it is clearly pointed out that MO is a better lining in the production of high-purity Ti. Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. 'Any person skilled in the art can make various modifications and decorations without departing from the spirit and scope of the present invention. The scope of protection of the invention shall be determined by the scope of the attached patent application. 3057tvvf3.doc 008 40

Claims (1)

538141 A system controls multiple current densities during electrolysis. 7. A system for producing high-purity titanium, comprising the device as described in item 1 of the patent application scope and an electron beam melting furnace for purifying the titanium product produced by the device. 8. The device described in item 1 of the patent application scope further includes an electron beam melting furnace. 9. The device according to item 1 of the scope of patent application, which further includes an upper layer structure which can be arranged above the outer layer. The outer layer includes a gate valve, a conversion reel, a current distributor, a heat jacket holder, and a handling Holder * and a winch sleeve. 10. The device according to item 9 of the scope of patent application, wherein the upper structure is composed of titanium, stainless steel, molybdenum, nickel, a molybdenum-nickel alloy, and the above-mentioned alloy. 11. A device for manufacturing high-purity titanium metal, comprising: a tank container; a system filled with a plurality of reactants input into the tank container; an upper structure can be arranged above the tank container; a plurality of control pressure and temperature A system; an electrolysis system that can electrolyze multiple reaction products in the same environment in the tank container; and a getter system, before, during and after the removal of oxygen by electrolysis, via a heated getter substance, The gas generated in the tank container can be circulated. 12. The device according to item 11 of the scope of patent application, wherein the tank * container includes an outer layer containing an antioxidant; and an inner layer is located inside the outer layer 42 538141, and the inner layer has a reactant container made of metal. On the surface, this metal is less reactive than titanium in the chloride electromotive force sequence. 13. The device according to item 11 of the scope of patent application, wherein the superstructure includes a gate valve, a conversion reel, a current distributor, a heat jacket receiver, a handling receiver, and a winch jacket. 14. The device according to item 11 of the scope of patent application, wherein the superstructure is composed of titanium, stainless steel, molybdenum, nickel, a molybdenum-nickel alloy, or the above-mentioned alloy. 15. The device according to item 12 of the scope of patent application, wherein the material of the surface of the reaction container comprises molybdenum, nickel or a molybdenum-nickel alloy. 16. The device according to item 11 of the scope of patent application, further comprising a furnace adapted to receive the tank container. 17. The device according to item 11 of the scope of patent application, wherein the tank container is sealed during the reduction process. 18. The device according to item 11 of the scope of patent application, further comprising a system that controls a plurality of current densities during electrolysis. 19. A system for producing high-purity titanium, comprising a device as described in item 11 of the patent application scope and an electron beam melting furnace for purifying the titanium product produced by the device. 20. A system for producing high-purity titanium, comprising a device as described in item 11 of the scope of patent application and a thermal iodide decomposition system, wherein the titanium produced in the device reacts with iodine. 21. A system for producing high-purity titanium, including the device described in item 11 of the scope of patent application, a thermal iodide decomposition system, and an electronic 43 538141 beam melting furnace. 22. A method for producing high-purity titanium, comprising: reacting titanium tetrachloride and a reducing agent in a container, the reducing agent comprising an alkali metal and / or an alkaline earth metal to form a titanium metal wool and melt Dissolve alkali metal and / or alkaline earth metal salt; chlorinate the molten alkali metal and / or alkaline earth metal salt in the container; keep at least a part of the titanium metal cotton produced in the container as an anode; Under the same environment in the container, the titanium metal wool was electrolyzed to produce a titanium crystal; the titanium crystal in the container was recovered; and the salt was removed from the recovered titanium crystal. 23. The method as described in claim 22 of the scope of patent application, which further comprises adding titanium dichloride to the container to help chlorinate the salt. 24. The method according to item 22 of the scope of patent application, wherein the chlorination of the salt is completed by reacting the titanium tetrachloride with the titanium metal wool in the container. _ 25. The method according to item 24 of the scope of patent application, wherein the titanium metal wool comprises the titanium metal wool generated in the container. 26. The method according to item 22 of the scope of patent application, wherein the container has a reactant contact surface, which is essentially composed of a metal which is electrochemically compared according to the electromotive force sequence of the chloride Titanium is even less active. ^ 27. The method as described in item 26 of the scope of patent application, wherein the metal of the anti-44 538141 application contact surface includes molybdenum, nickel, or an alloy of molybdenum and nickel. 28. The method of claim 22, wherein the reducing agent comprises at least one of sodium, manganese, potassium, calcium, lithium metal and an alloy of these metals. 29. The method of claim 22, wherein the reducing agent comprises sodium. 30. The method according to item 22 of the scope of the patent application, wherein the conditions for electrolyzing the titanium metal wool are in a molten salt in the same container, and the melt includes at least 2% by weight of dissolved titanium. ® 31. The method as described in claim 22, wherein the molten salt is located in the container, and the container includes an electrolyte for electrolyzing the titanium wool in the same container. _ 32. The method as described in item 22 of the scope of patent application, further comprising filtering the deposited titanium crystals under acidic condition and washing with water to remove residual salts. 33. The method described in item 22 of the scope of patent application, further comprising drying the titanium crystal under vacuum, or by washing it away with hot argon, or by freeze-drying. _ 34. The method as described in item 22 of the scope of patent application, wherein after all the reducing agents have been reacted, additional titanium tetrachloride is added to the container to dissolve at 2% to 12% by weight. In titanium, this salt and TiCl2 / TiCl3 are chlorinated. 35. The method as described in claim 22, wherein the container is evacuated before electrolysis. ~ 36. The method as described in item 22 of the scope of patent application, wherein the container 45 538141 is evacuated to less than ίο microns. 37. The method described in item 22 of the scope of patent application, which can be used to generate titanium crystals, the titanium crystals comprising 99.99999% by weight of titanium, but excluding gas and mechanically trapped salts. 38. The method described in item 22 of the scope of patent application, which can be used to generate titanium crystals, the titanium crystals include 99.9999% by weight of titanium, and include less than 50 ppm oxygen, but excluding gas and mechanical trapping ΤΤΤΪΛ 39. The method described in item 22 of the scope of patent application, the titanium metal® cotton includes all of Be, Mn, Zr, A1, and V in a concentration of less than 1 ppm. 40. The method described in item 22 of the scope of the patent application, the titanium metal wool including all of Yb, Zn, Cr, Cd, B and Sn in a concentration of less than 1 ppm. 41. The method as described in item 22 of the scope of the patent application, the titanium metal wool including all concentrations of Be, Mn, V, Zn, Cr, A1, Yb, Cd, Zr, B and Sn. 42. The method as described in item 22 of the scope of patent application, further comprising melting the titanium crystal with an electron beam to form a titanium block of high purity. 43. The method described in item 22 of the scope of the patent application further includes melting the titanium crystals with an electron beam to form a titanium block, which includes 99.99999% by weight of titanium, except for gas. 44. The method described in item 22 of the scope of patent application, further comprising allowing the electron beam to melt the crystal to form a titanium block, the titanium block including 99.99999% by weight of titanium, except for gas, and including less than lOOppm of oxygen. 46 538141 45. The method as described in item 44 of the scope of patent application, wherein the electron beam melting is performed at a pressure of less than 10_2 torr and a melting rate of greater than 15 lbs / hr. 46. A method for manufacturing high-purity titanium, which is essentially composed of 99.999% titanium and oxygen with a concentration of less than 50 ppm, excluding gas and mechanically trapped salts, including : Forming a titanium crystal of high purity, as described in item 22 of the scope of patent application; and processing the titanium crystal and an iodine under a high temperature and reduced pressure in a container to generate a titanium iodide, which decomposes at a high temperature The iodide generates a titanium crystal bar with an oxygen content of less than 50 ppm, wherein the titanium crystal reacts with the iodine at a temperature range of 500 ° C ~ 800 ° C, at a temperature of 1150 ° C ~ 1450 ° C and a high pressure Decompose down to 1000 microns. 47. The method according to item 46 of the scope of patent application, wherein the reaction temperature is 70CTC ~ 775 ° C, and the decomposition temperature is 1300 ° C ~ 140 ° C and the pressure is 100 ~ 500 microns. 48. The method according to item 46, wherein the titanium crystal strip comprises less than 30 ppm of oxygen. 49. The method according to item 46 of the patent application scope further comprises melting the crystal with an electron beam to produce pure purity. 50. The method as described in item 48 of the scope of patent application, wherein the electron beam melting is performed at a pressure lower than 1 (T2torr and the melting rate is greater than I51bs / hr. 51. As in the scope of patent application The method according to item 22, wherein 47 538141 is controlled so that the applied voltage k 'makes the overvoltage of the cathode and the electrode not greater than 5 volts. _ 52. The method according to string gf patent _ item 22, wherein The applied voltage is such that the overvoltages of the cathode and the pole are not greater than Q3 volts. The method described in item 22, wherein the applied voltage k is controlled so that the overvoltages of the cathode and anode are not greater than 0. Volts. 54 ·-a high-purity titanium material, including: at least zirconium or vanadium S; and 99 · 9999 t ·% of Chin, except for gas and mechanically trapped salts. Lu 55 · -species ^ __ materials' include titanium and beryllium, magnesium, chromium, and aluminum with all concentrations less than Ί ppm And f [, except for the salt that is difficult to see. 56. The high-purity Chin material described in No. 54 or 55 of Rugao Patent Fanyi, where the full-time and potassium content of the pure material is less than 1 () ppb. ° 57. The high-purity titanium material described in ^ Patent Specification No. 54 or 55, wherein the content of oxygen in the purity titanium material does not exceed the claw. 58. Such as ^ Patent Specification No. 54 or 55 High-purity titanium materials, including uranium and plutonium with a concentration of less than iPPb in all high-purity materials. 59. Bureau of pure reliance includes at least one of the following:-titanium; sodium with a total concentration of less than 0.75 ppm , Potassium, Ming, iron, chromium, nickel, pins, vanadium, magnesium, copper, uranium, but not gas; and oxygen less than 100 ppm. 60 ·-a kind of thorium purity titanium materials, including: titanium; 48 538141 Sodium, potassium, aluminum, iron, chromium, zirconium, vanadium and nickel in all concentrations less than ol ppm, except for gases and mechanically trapped salts Uranium and plutonium with a total concentration of less than 1 ppb; sodium and potassium with a total concentration of less than 10 ppb; and oxygen of less than or equal to 75 ppm. 61.-a high-purity titanium material, including: 99.999 wt ·% titanium, but Except for gases; all sodium, potassium, aluminum, iron, chromium, nickel, zirconium, vanadium, magnesium, copper, uranium and plutonium in all concentrations less than 0.75 ppm; all uranium and plutonium in concentrations less than 1 ppb; all concentrations less than 10 ppb of sodium and potassium; and 75 ppm or less of oxygen. 62. The high-purity titanium material as described in item 54 of the scope of patent application, including at least one of zirconium and vanadium at least 0 ppm. 63. The high-purity titanium material as described in item 55 of the scope of the patent application, which includes at least one of zirconium and vanadium at least 0.001 ppm. 64. The high-purity titanium material as described in item 56 of the patent application scope, including at least 0.01 ppm of at least one of zirconium and vanadium. 65. The high-purity titanium material as described in item 57 of the patent application scope, including at least 0.01 ppm of at least one of vanadium and vanadium. 66. The high-purity titanium material as described in item 58 of the patent application scope, including at least 0.01 ppm of at least one of zirconium and vanadium. 67. The high-purity titanium as described in item 59 of the patent application scope, including at least 0.01 ppm of at least one of zirconium and vanadium. 49 538141 68. The high-purity titanium material as described in item 60 of the scope of patent application, including at least 0.01 ppm of at least one of vanadium and vanadium. 69. The high-purity titanium material as described in item 61 of the scope of patent application, which includes at least one of zirconium and vanadium at least 0-0.01 ppm. 70. The high-purity titanium material described in item 54 of the scope of patent application, a sputtering composition system comprising the high-purity titanium material. 71. The high-purity titanium material according to item 70 of the application, wherein a thin film can be made from the sputtering composition. 72. The high-purity titanium material described in item 55 of the scope of patent application, a sputtering composition system comprising the high-purity titanium material. 73. The high-purity titanium material according to item 72 of the scope of patent application,-wherein a thin film can be made from the sputtering composition. 74. The high-purity titanium material described in item 56 of the scope of patent application, a sputtering composition system comprising the high-purity titanium material. 75. The high-purity titanium material according to item 74 of the application, wherein a thin film can be made from the sputtering composition. Xin 76. According to the high-purity titanium material described in item 57 of the scope of patent application, a sputtering composition system includes the high-purity titanium material. 77. The high-purity titanium material as described in item 76 of the scope of patent application, wherein a thin film can be made from the splatter composition. 78. According to the high-purity titanium material described in item 58 of the scope of the patent application, a sputtering composition comprises the high-purity titanium material. '79. The high-purity titanium material described in the scope of the patent application No. 78, 50 538141 Wherein the sputtering composition can be made into a thin film 80. If the scope of the patent application is No. 59, the plating composition system includes the high purity titanium. &gt; The high-purity titanium mentioned, ~ splash 81. If the scope of the patent application is 80th, an additional chain * Japanese public goods, the local purity of the ΉΤ system can be made from the sputtering composition into a thin film of titanium 'of which 82. The scope of the patent No. 60 tablet _ A sputtering composition system includes the high-purity titanium material described in the high-purity titanium material. . High purity Lin materials, 84. If the scope of application for patent 6m-beach plating combination _ package _ high purity ^ materials described in Cheng Duqin materials, 85. If the scope of application for patent 84th one, which can be made from the sputtering compound-thin film. Purity lining material, 86. For example, the scope of application for the patent No. 62 I-pendulum plating composition, including materials, materials, and materials 87. For the scope of application for the patent No. 86, which can be prepared from the splatter composition Into-thin film. Purity 88.-A variety of high-purity titanium materials, including to titanium and pins with a total content of less than 0.1 ppm, Ί, '', ～~, but the gas and surface characteristics are fine to earn Y w ^ H and nickel, apply for a patent The high in the range of item 88 includes uranium and thorium (Th) with a total content of less than 1 卯 b. Materials, = _Pleasegroup m_ 88 Describes high purity which includes oxygen at a concentration of not more than 75 ppm. Fu Yi, 51 538141 91. The high-purity titanium material as described in the 88th scope of the patent application, wherein the total content of sodium and potassium is less than 10 ppb.蒌 毚 0.75 92. — High-purity titanium, including at least one of vanadium and vanadium, with a percentage of 99.999% except gas, and a total content of less than Ming, iron, iron, nickel, vanadium, magnesium, copper , Uranium and ppm sodium and potassium thorium. 93. The high-purity titanium material as described in item μ of the patent application scope, including at least 0.01 ppm of at least one of zirconium and vanadium. '94. The high-purity titanium material as described in the 89th scope of the patent application includes at least 0.001 ppm of at least one of zirconium and vanadium. ′ 95. The high purity plutonium as described in Patent Application No. 90 _ includes at least 0.01 ppm of at least one of zirconium and vanadium. Bucket '96. The high purity as described in Application No. 91 _ includes at least 0.001 ppm of at least one of zirconium and vanadium. 97. If applying for the patent Fanol 92, Qi High Purity records at least 0.01 ppm of at least one of zirconium and vanadium ~. 98. If the scope of the patent application is 88: 3, the purpose is to print ten, one-one, one, and one-hundred-thousand-thousands of local purity Chinshu. A sputtering composition system includes the high-purity titanium material. Material 99. For example, the high-purity titanium material described in item 98 of the patent application range, wherein a thin film can be made from the sputtering composition. Fu Ying, 100. As in the scope of the patent application No. 89 _ a sputtering composition is a high-purity titanium material ^, the material is sharp, 101 · as in the scope of the patent application 100 _ where the sputtering The composition can be made into a thin tincture. Purity sharp tree material of 4 wen, 52 3057twf4.doc / 008 102. For example, the scope of application for patent No. 90-sputtering combination_packet_high purity Lin M described the high-purity materials, 103. For the scope of patent application No. 1 Item 02, where the M composition can be made of the high-purity Lin material described above, 104. If the scope of application for the patent is 91_, the sputter plating group includes high-purity money, Wuqi high-purity material, 105 For example, if the scope of the patent application is No. 104_Er :: ,,, and the ratio of the fine-grained material to the fine-grained material is ππ, the high-purity metal material described in J. Jin, where a thin film can be made from the sputtering composition. 106. The plating composition of claim 92 includes the high-purity titanium. -The above-mentioned local purity is as good as 107. The thin film can be made from the sputtering composition as described in the patent application No. 106. -, Purity Drink 3057twf4.doc / 008 53