CN104919065A - Method for recovering indium-tin alloy from ito target scrap and methods for producing indium oxide-tin oxide powder and ito target - Google Patents
Method for recovering indium-tin alloy from ito target scrap and methods for producing indium oxide-tin oxide powder and ito target Download PDFInfo
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- CN104919065A CN104919065A CN201380057963.9A CN201380057963A CN104919065A CN 104919065 A CN104919065 A CN 104919065A CN 201380057963 A CN201380057963 A CN 201380057963A CN 104919065 A CN104919065 A CN 104919065A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F2009/001—Making metallic powder or suspensions thereof from scrap particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Provided is a method for reducing ITO target scrap containing indium and tin, by using a reduction gas, and recovering an indium-tin alloy being a raw material for an ITO target, while maintaining the composition ratio of the metal components in the ITO, in a reduction furnace. Provided is a technology: for recovering an indium-tin alloy from a high-purity indium oxide-tin-containing scrap generated during production or after use of an ITO sputtering target; for using same as an indium oxide-tin oxide powder; and for producing an ITO target having the indium oxide-tin oxide powder as a raw material therefor. In other words, the technology reduces the scrap to an alloy as is, uses same in ITO production while maintaining the composition of the obtained alloy, and thereby simplifies the control and adjustment of the composition during the production stage. In addition, the process is simplified by oxide reduction being the only the indium-tin recycling, and production costs can be reduced in comparison to conventional technology. In addition, the byproduct can be water only, therefore handling and generation of toxic substances are reduced and, as a result, the load on the environment can be reduced.
Description
Technical field
The waste material (hereinafter referred to as " ITO waste material ") containing high-purity mangesium oxide indium-stannic oxide that the present invention relates to producing during manufacture ITO (indium oxide-tin oxide) sputtering target or after use ITO sputtering target reduces, recovery indium-tin alloy, and be made into indium oxide-tin oxide powder, then with the method for this indium oxide-tin oxide powder for raw material manufacture ITO target.
Background technology
In recent years, ITO sputtering target is widely used in the transparent conducting film, gas sensor etc. of liquid crystal indicator, in most cases uses to utilize the film of sputtering method to form means to form film on substrate etc.
This to utilize the film of sputtering method to form means are a kind of excellent methods, but use sputtering target when forming such as transparent conducting film, and this target also anisotropically consumes.
Usually part violent for the part consumption of this target is called erosion portion, proceed sputtering operation until the consumption in this erosion portion carry out and support target backboard be about to peel off.Then, the target more renewed.
Therefore, remain a large amount of non-erosion portion, i.e. untapped target part in the sputtering target after using, these become waste material entirely.In addition, when manufacturing ITO sputtering target, also can produce waste material from polishing powder, cutting powder.
ITO sputter target material uses high purity material, and price is also high, therefore usually carries out recovery indium from such waste material.
As this indium recovery method, use the method for the wet type purifying such as composite acid dissolution method, ion exchange method, solvent extration in the past.
Be such as following method: after ITO waste material is cleaned and pulverized, be dissolved in hydrochloric acid, in lysate, pass into hydrogen sulfide, with the form of sulfide precipitation except impurity such as dezincify, tin, lead, copper, then add ammonia wherein to neutralize, reclaim with the form of indium hydroxide.
But, there are the following problems for the indium hydroxide obtained by the method: filterableness is poor and manipulation require is long-time, the impurity such as Si, Al are many, and the indium hydroxide generated makes particle diameter, size-grade distribution produce variation according to its neutrality condition and aging condition etc., when manufacturing ITO target therefore, stably can not keep the characteristic of ITO target.
Due to above-mentioned situation, a kind of recovery method of indium as described below is proposed: it comprises and utilizes hydrochloric acid ITO obtained the operation of indiumchloride solution containing indium waste material dissolves and in this indiumchloride solution, add aqueous sodium hydroxide solution thus to make in waste material the operation that contained tin removes with the form of stannic hydroxide before the present inventor, after removing this stannic hydroxide, zinc is utilized to replace from solution, recovery indium, then by this displacement, the sponge indium reclaimed is dissolved and produces thick indium metal together with solid sodium hydroxide, then further by this thick indium metal electrolytic purification, thus obtain high purity indium (see patent documentation 1).By the method, efficiently and stably highly purified indium can be reclaimed.
But, utilize in the operation of electrolytic purification recovery indium above-mentioned, need the operation that the metallics of separating out at cathodic electricity is cast, now exist and produce the such problem of the oxidiferous waste material (foundry scrap) floated on casting metal.
In the past, if this foundry scrap just cannot process without the operation of dissolving with hydrochloric acid, pH regulator, zinc reduction, the such electrolytic purification of anode casting, there is the problem of cost rising.
In order to solve this problem, in the operation of recovery indium from the ITO waste material produced during manufacture ITO sputtering target or after use ITO sputtering target, propose the method (patent documentation 2) of Footwall drift indium effectively a kind of foundry scrap from producing when casting the metallics of separating out at cathodic electricity.But, in this case, owing to being the object of this restriction of foundry scrap containing suboxide floated on casting metal, therefore there is the problem that shortcoming versatility is such.
In addition, as the technology that indium is carried out to high purity or reclaims, disclose following document, but all there is the such problem of complex procedures.Illustrated as a reference.
Patent Document 3 discloses a kind of purification process of indium, it is the method for the high purity indium manufacturing the raw material being used as compound semiconductor, and the method comprises is undertaken reducing by the positive trivalent indium oxide existed in indium and becomes the operation of the oxide compound of positive monovalence and under the second Heating temperature, remove the operation of residual impurity after making it evaporate.
In patent documentation 4, disclose a kind of method from ITO waste recovery indium, wherein, utilize reducing gas to reduce to ITO waste material at 750 ~ 1200 DEG C and obtain indium metal, then electrolytic purification being carried out to this indium.
Patent Document 5 discloses a kind of recovery method of indium, it is the method from IXO waste recovery indium, and the method comprises: pulverized by IXO waste material, mix with carbon dust, put it into reduction furnace and carry out heat reduction, zinc is expelled to the operation outside system simultaneously with the form of steam; With the operation of the thick indium obtained in this operation being carried out to electrolytic purification.
Patent Document 6 discloses following method: utilize the extraction agent of solvation extraction type to be 1 ~ 12N to concentration of hydrochloric acid and the hydrochloric acid soln that indium concentration is below 20g/L containing indium extracts, then utilize pH be 0 ~ 6 diluted acid strip, then activated carbon treatment carried out to it and remove oil content, then carry out electrowinning or neutralization and obtain oxyhydroxide, then utilize that carbon or hydrogen carry out reducing or utilize sulfuric acid to carry out dissolving, electrolysis, thus recovery indium.
Patent Document 7 discloses a kind of method from scrap concrete indium, it uses plasma furnace, and arranges the splash condenser making the indium condensation of gaseous phase.
Patent Document 8 discloses following method: reduced in reducing atmosphere by the block containing Indium sesquioxide, stannic oxide, produce indium-tin alloy anode, then carry out twice indium electrolytic purification, thus reclaim high purity indium and thick tin.
In addition, as the Indium sesquioxide of raw material, the technology of stannic oxide powder that create ITO target, present inventors have proposed following patent.
Patent Document 9 discloses a kind of manufacture method of Indium sesquioxide, it is characterized in that, be that anode carries out electrolysis with indium, the indium hydroxide obtained thus is calcined.
Patent Document 10 discloses a kind of manufacture method of stannic oxide, it is characterized in that, carry out electrolysis using tin as anode, the metastannic acid obtained thus is calcined.
These are that starting raw material is metal simple-substance and manufactures the technology of respective oxide compound.
In addition, the manufacture method of the manufacture method as ITO target or the indium oxide-tin oxide powder as its raw material, the present inventor proposes following patent.
In patent documentation 11, as the manufacture method of ITO target, it is characterized in that, the dispersion soln obtained making indium hydroxide disperse and dispersion soln metastannic acid being disperseed and obtains are obtained by mixing blending dispersion solution, make this blending dispersion solution dry, then carry out roasting, the formed body of the oxide compound mixed powder obtained thus is sintered.
Patent documentation 12 relates to a kind of manufacture method of indium oxide-tin oxide powder, it is characterized in that, carries out electrolysis using the alloy of indium and tin as anode, and calcine the mixed sediment of obtained indium hydroxide and metastannic acid it.This patent is also that the former produces the dispersion soln of indium hydroxide and metastannic acid individually, the latter for the manufacture method as the indium of anode and the alloy of tin without any specific descriptions.
As mentioned above, in the past, the recovery of ITO is the operation based on wet type, therefore there are the following problems: use harmful chemical such as acid, alkali, suitable process etc. is also needed to isolated by product, relatively large to the load (result is for tackling the cost of the problems referred to above) of environment.In addition, the object indium that mainly unit take-back cost is high that ITO reclaims, separates with tin and carries out separation and purification.Tin additionally reclaims sometimes individually.
Therefore, in the operation using the elemental metals reclaimed, generate Indium sesquioxide, mix with the stannic oxide prepared in addition; Or use after the metal simple-substance prepared in addition is made alloy, therefore all there is the problem needing each weighing and allotment metal simple-substance or oxide compound such in any one method.
In the manufacture method of the oxide compound of the raw material as ITO, describe in patent documentation 10, patent documentation 12 using the alloy of tin or indium and tin as anode and electrolysis is carried out to it can adopt the electrolytic process utilizing usual so-called flat ripple, but in fact cause passivation owing to producing metastannic acid on surface, can not stable electrolysis be carried out.Therefore, embodiment all becomes the electrolytic process (PR electrolytic process) making polar cycle sex-reversal.
In addition, in patent documentation 11, for the problem of the passivation of tin described before, from the viewpoint of cost, dissolving precipitated method is favourable.Think on the other hand, for indium, electrolytic process is good, and thus manufacture method is contrary, even if the manufacture method using the indium oxide-tin oxide powder of the alloy of indium and tin is possible technically, and also cannot be practical.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-69544 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-241865 publication
Patent documentation 3: Japanese Laid-Open Patent Publication 63-250428 publication
Patent documentation 4: Japanese Unexamined Patent Publication 7-145432 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2002-3961 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2002-201026 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2009-293065 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2011-208216 publication
Patent documentation 9: Japanese Unexamined Patent Publication 6-171937 publication
Patent documentation 10: Japanese Unexamined Patent Publication 6-199523 publication
Patent documentation 11: Japanese Unexamined Patent Publication 2001-303239 publication
Patent documentation 12: Japanese Unexamined Patent Publication 6-329415 publication
Summary of the invention
Invent problem to be solved
ITO target is highly purified except a part of impurity be mixed in its manufacturing process, and in purification procedures in the past, main purpose is the tin of removing as one of raw material.It should be noted that, in indium recovery in the past, purification procedures, in order to the reactivity improved when carrying out acidleach, mechanical disintegration is carried out to ITO, but this operation becomes further source of pollution, also have and make the one side that indium reclaims, purification procedures becomes complexity.
The present inventor changes to idea so far, not thinks that the impurity that produces and impurely remove and be mixed in ITO target manufacturing process and tin also reclaim with the form of alloy simultaneously and uses the indium oxide-tin oxide manufacture method of this indium-tin alloy significantly can simplify the ITO manufacturing process comprising recovery together with indium.
Therefore, conduct in-depth research, found that: do not carry out pulverizing, machinery, the chemical treatment such as acidleach, only reduce in the reducing gas atmosphere of high temperature, can not produce and impurely the form of tin with alloy together with indium be reclaimed simultaneously, in addition, the composition of indium-tin alloy can keep the metal ratio of original ITO waste material.
Then, when carrying out electrolysis using obtained indium-tin alloy as anode, as the condition not making anode passivation, need the feed rate of electrolytic solution and electrolysis area, current value, electrolysis time relation meet certain specify in scope, by making it suitable, carry out electrolysis using indium-tin alloy as anode while passivation can not occur.
Then, roasting is carried out to obtained electrolysate, thus obtains indium oxide-tin oxide, then carry out granulation, shaping, sintering, can produce thus and ITO target equal when using metal simple-substance as starting raw material.
The present invention, by the reduction making the recovery of indium-Xi be only oxide compound, makes operation simplify thus, reduce manufacturing cost compared with previous methods.In addition, by product is only water, thereby inhibiting the process of objectionable impurities, generation, because this reducing the load to environment.
For the means of dealing with problems
That is, the invention provides following invention.
1) method for recovery indium-tin alloy, wherein, utilizes reducing gas to reduce to ITO target waste material in reduction furnace, and is incorporated as the indium-tin alloy of the raw material into ITO target next time in the state of the ratio of components keeping the metal ingredient in ITO.
2) as above-mentioned 1) as described in the method for recovery indium-tin alloy, it is characterized in that, in reduction furnace, in-furnace temperature is set as 750 ~ 1200 DEG C, use hydrogen as reducing gas, and hydrogen import volume is set as relative to the ITO target waste material of every 1kg be that 500 ~ 1,000L reduces.
3) a kind of manufacture method of indium oxide-tin oxide powder, it is characterized in that, by electrolytic process by above-mentioned 1) and 2) in reclaim indium-tin alloy make indium hydroxide-metastannic acid mixture, then roasting carried out to it and obtain indium oxide-tin oxide powder, and obtain the raw material of ITO target under the state of composition keeping the metal ingredient in ITO.
4) a kind of manufacture method of ITO target, it is characterized in that, to above-mentioned 3) in manufacture indium oxide-tin oxide powder carry out further granulation, shaping, sintering, and under the state of ratio of components keeping the metal ingredient in ITO, manufacture ITO target by the waste material containing high-purity mangesium oxide indium-stannic oxide produced during manufacture ITO sputtering target or after use ITO sputtering target.
5) as above-mentioned 3) as described in the manufacture method of indium hydroxide-metastannic acid mixture, it is characterized in that, regulate the amount to electrolyzer supply electrolytic solution to make to set up 0.01 ~ 100.0 (Lm between the feed rate of electrolytic solution and electrolysis area, current value, electrolysis time
2)/(Amin) relation.
Invention effect
The present invention has can provide the excellent results of following technology: from the waste recovery indium-tin alloy containing high-purity mangesium oxide indium-stannic oxide produced during manufacture ITO sputtering target or after use ITO sputtering target, and be made into indium oxide-tin oxide powder, then manufacture ITO target using this indium oxide-tin oxide powder as raw material.That is, waste material is directly reduced to alloy, and manufactures for ITO under the state of composition keeping the alloy obtained, simplify control and the adjustment of the composition in manufacturing process thus.
In addition, make the recovery of indium-Xi be only the reduction of oxide compound, have thus and make operation simplify, the such effect of manufacturing cost can be cut down compared with previous methods.In addition, by product can be made to be only water, therefore have can suppress objectionable impurities process, generation, thus reduce the such excellent results of the load of environment.
Accompanying drawing explanation
Fig. 1 is the explanatory view distinguishing the operation of recovery indium and tin with ITO waste material for raw material in the past.
The figure that the summary of Fig. 2 to the manufacturing process of ITO sputtering target is in the past described.
Fig. 3 represents the manufacturing process of ITO sputtering target of the present application and the explanatory view of the summary of recovery process, in described manufacturing process, with ITO waste material for raw material, through gas reduction operation, manufacture indium-tin alloy, then be made into indium oxide-tin oxide powder through electrolysis, calcining process, then it engaged with backboard through granulation, shaping, sintering circuit and obtains ITO sputtering target; In described recovery process, using use after target and obtained by this ITO sputtering target manufacturing process processing bits again as the raw material of ITO sputtering target.
Embodiment
The present invention relates to the technology again manufacturing ITO target using ITO sintered compact waste material (target after use, processing scrap stock) as raw material, summary is as described below.
Specifically, utilize reducing gas to reduce to ITO waste material, reclaim with the form of indium-tin alloy.Then, using the indium-tin alloy of this recovery as anode, use SUS metal sheet as negative plate, electrolytic solution uses ammonium nitrate, carries out electrolysis and generates indium hydroxide-metastannic acid mixture.Then by this mixture filtered and recycled, through dried powder, indium oxide-tin oxide powder is manufactured.Granulation, shaping, sintering thus make ITO sintered compact are carried out to the indium oxide-tin oxide powder so obtained.Be made into the size of regulation by processing such as cut-out, grindings, and engage with backboard, thus manufacture ITO target.
Fig. 3 represents and utilizes reducing gas to reduce to ITO target waste material in reduction furnace, keep ITO metal ingredient ratio of components state under recovery indium-tin alloy, and use it to manufacture the method for ITO sputtering target outline figure.
Waste material is directed in the reduction furnace that ITO target waste material is reduced, and imports hydrogen in this reduction furnace.During reduction, utilize heating unit that above-mentioned waste material is adjusted to 750 ~ 1200 DEG C, and above-mentioned oxide compound waste material is reduced.Hydrogen import volume is set as relative to the ITO target waste material of every 1kg be that 500 ~ 1,000L reduces.
So, do not carry out pulverizing, machinery, the chemical treatment such as acidleach, only utilize and reduce in the reducing gas atmosphere of high temperature, can not produce and impurely the form of tin with alloy together with indium be reclaimed simultaneously, in addition, the composition of indium-tin alloy can keep the metal ratio of original ITO waste material, and this is extremely important from the viewpoint of what utilize easy method to carry out the recovery of ITO waste material.
Recovery method based on above indium metal-Xi has following feature: compared with the past can easily and reclaim at an easy rate.Indium-tin alloy that use obtains as negative plate as anode, use SUS metal sheet, carries out electrolysis, generates indium hydroxide-metastannic acid mixture in electrolyzer.By its filtration drying, roasting and obtain indium oxide-tin oxide powder.Then, through granulation, shaping, sintering circuit and manufacture ITO target.
In order to not make anode passivation in electrowinning process, by the feed rate (L) of electrolytic solution and electrolysis area (m
2), the relation of current value (A), electrolysis time (min) is set to (feed rate L × electrolysis area m of electrolytic solution
2)/(current value A × electrolysis time min) time, circulation electrolytic solution makes to reach 0.01 ~ 100.0 (Lm
2)/(Amin).At this, this electrolysis area refers to for the indium configured abreast in a cell-tin alloy positive plate and negative plate, indium-tin alloy positive plate, relative with negative plate double-edged total area.
So, as the condition not making anode passivation using obtained indium-tin alloy when anode carries out electrolysis, the electrolysis area of suitable adjustment unit quantity of electricity (current value × time) and electrolyte content (feed rate of electrolytic solution), carry out electrolysis using indium-tin alloy as anode while passivation can not occur thus, be extremely important in this respect.
Embodiment
Next, embodiment is described.It should be noted that, the present embodiment is for illustration of an example of invention, but the present invention is not restricted to these embodiments.That is, alternate manner contained in technical conceive of the present invention and distortion is comprised.
As the example of ITO target manufacture method of the present invention, from the waste recovery indium-tin alloy containing high-purity mangesium oxide indium produced during manufacture ITO sputtering target or after use ITO sputtering target, anode is it can be used as to carry out electrolysis, obtained indium hydroxide-metastannic acid mixture is carried out to roasting and obtains indium oxide-tin oxide powder, and to its carry out granulation, shaping, sintering and manufacture ITO target, based on embodiment 1 ~ 5, above-mentioned operation is described.
It should be noted that, to drop into the hydrogen of 492L with the ITO that theory reaction gauge is specially every 1kg for reducing ITO and the amounts of hydrogen that drops into.In addition, for ITO reactivity described later and hydrogen reducing reaction efficiency, such as, when the half 500g carried out in the ITO of the 1kg reacted reacts (obtaining indium stannum alloy 412g), ITO reactivity may be calculated 50%.
In addition, in order to reduce 500g ITO and used up hydrogen is 492L × 500g/1kg=246L, in this case, hydrogen reducing reaction efficiency may be calculated 50%.As long as the ratio being so 492L with the ITO of every 1kg imports hydrogen, then ITO reactivity described later and hydrogen reducing efficiency are identical value.
(embodiment 1)
ITO waste material 5,000g (metal ingredient 4,210g) is put into reduction furnace, and the hydrogen circulated 5L/ minute, was warming up to 1 with two hours, 000 DEG C simultaneously, then kept 16 hours.After stopping heating, the weight alloy reclaimed in the returnable in stove is 3,760g, and reactivity is 91%.In addition, part residue is remained in reaction vessel.
Utilize x-ray fluorescence analysis (XRF:X-ray Fluorescence Analysis) method to measure as the indium of main component and the constituent concentration of tin in the alloy reclaimed, result is In grade is 90.02 % by weight, Sn grade is 9.98 % by weight.In addition, inductively coupled plasma luminescence spectrometer method (ICP:Inductively Coupled Plasma luminescence spectrometer method) is utilized to measure the concentration of other impurity element in this alloy, result is the Ni detecting 2ppm, in addition, Cd, Cu, Fe are < 1ppm, Al, Bi, Cr, Pb, Sn, Zn be < 5ppm, Si, Ti, Zr is < 10ppm, and all dirt element beyond Ni is lower than lower limit of quantitation.
Using the indium-tin alloy of this recovery as anode, carry out electrolysis and generate indium hydroxide-metastannic acid mixture.The flow strength (electrolyte supply speed) of electrolytic solution is now adjusted to 1.0 (Lm
2)/(Amin).Then filtered and recycled is carried out to this mixture, through dried powder, thus produce indium oxide-tin oxide powder.Stannic oxide grade in the indium oxide-tin oxide powder obtained is 10.21 % by weight.
The indium oxide-tin oxide powder so obtained is carried out after the fine adjustment of composition granulation, shaping, sintering, thus produce ITO sintered compact.The density of the sintered compact obtained is 7.132g/cm
3, be highdensity material, be suitable for target, be therefore made into the size of regulation by processing such as cut-out, grindings, and engage with backboard and produce ITO target, result obtains the no problem target of quality.
(embodiment 2)
ITO waste material 5,000g (metal ingredient 4,210g) is put into reduction furnace, and the hydrogen circulated 10L/ minute, was warming up to 1 with two hours, 000 DEG C simultaneously, then kept 6 hours.After stopping heating, the weight alloy reclaimed in the returnable in stove is 3,960g, and reactivity is 96%.In addition, in reaction vessel, part residue is remained.
The grade of the main component element in the alloy reclaimed and Remaining impurity levels are analyzed respectively by analytical procedure similarly to Example 1, result is that the In grade in this alloy is 90.63 % by weight, Sn grade is 9.37 % by weight, other defects inspecting is to the Ni of 2ppm, and Al, Bi, Cd, Cu, Cr, Fe, Pb, Si, Ti, Zn, Zr are all lower than lower limit of quantitation in addition.
Using the indium-tin alloy of this recovery as anode, carry out electrolysis and generate indium hydroxide-metastannic acid mixture.The flow strength (electrolyte supply speed) of electrolytic solution is now adjusted to 2.0 (Lm
2)/(Amin).Then filtered and recycled is carried out to this mixture, through dried powder, produce indium oxide-tin oxide powder.Stannic oxide grade in the indium oxide-tin oxide powder obtained is 9.53 % by weight.Granulation, shaping, sintering are carried out after the fine adjustment of composition to the indium oxide-tin oxide powder so obtained, thus produces ITO sintered compact.
The density of the sintered compact obtained is 7.135g/cm
3, be highdensity material, be suitable for target, be therefore made into the size of regulation by processing such as cut-out, grindings, and engage with backboard and produce ITO target, result obtains the no problem target of quality.
(embodiment 3)
ITO waste material 10,000g (metal ingredient 7,480g) is put into reduction furnace, and the hydrogen circulated 10L/ minute, was warming up to 1 with two hours, 000 DEG C simultaneously, then kept 8 hours.
After stopping heating, the weight alloy reclaimed in the returnable in stove is 7,780g, and reactivity is 94%.In addition, in reaction vessel, part residue is remained.The grade of the main component element in the alloy reclaimed and Remaining impurity levels are analyzed respectively by analytical procedure similarly to Example 1, result is Fe, Ni that the In grade in this alloy is 90.65 % by weight, Sn grade is 9.35 % by weight, other defects inspecting goes out each 2ppm, in addition, Al, Bi, Cd, Cu, Cr, Pb, Si, Ti, Zn, Zr are all lower than lower limit of quantitation.
Using the indium-tin alloy of this recovery as anode, carry out electrolysis and generate indium hydroxide-metastannic acid mixture.The flow strength (electrolyte supply speed) of electrolytic solution is now adjusted to 1.0 (Lm
2)/(Amin).Then filtered and recycled is carried out to this mixture, through dried powder, produce indium oxide-tin oxide powder.Stannic oxide grade in the indium oxide-tin oxide powder obtained is 9.89 % by weight.Granulation, shaping, sintering are carried out after the fine adjustment of composition to the indium oxide-tin oxide powder so obtained, thus produces ITO sintered compact.
The density of the sintered compact obtained is 7.128g/cm
3, be highdensity material, be suitable for target, be therefore made into the size of regulation by processing such as cut-out, grindings, and engage with backboard and produce ITO target, result obtains the no problem target of quality.
(embodiment 4)
ITO waste material 24,000g (metal ingredient 19,780g) is put into reduction furnace, and the hydrogen circulated 40L/ minute, was warming up to 1 with one hour, 000 DEG C, then kept 5 hours.After stopping heating, the weight alloy reclaimed in the returnable in stove is 14,064g, and reactivity is 71%.In addition, in reaction vessel, part residue is remained.The grade of the main component element in the alloy reclaimed and Remaining impurity levels are analyzed respectively by analytical procedure similarly to Example 1, result is that the In grade in this alloy is 90.19 % by weight, Sn grade is 9.81 % by weight, other defects inspecting is to Fe, Ni of each 3ppm, in addition, Al, Bi, Cd, Cu, Cr, Pb, Si, Ti, Zn, Zr are all lower than lower limit of quantitation.
Using the indium-tin alloy of this recovery as anode, carry out electrolysis and generate indium hydroxide-metastannic acid mixture.The flow strength (electrolyte supply speed) of electrolytic solution is now adjusted to 2.0 (Lm
2)/(Amin).Then filtered and recycled is carried out to this mixture, through dried powder, produce indium oxide-tin oxide powder.Stannic oxide grade in the indium oxide-tin oxide powder obtained is 10.15 % by weight.
Granulation, shaping, sintering are carried out after the fine adjustment of composition to the indium oxide-tin oxide powder so obtained, thus produces ITO sintered compact.The density of the sintered compact obtained is 7.138g/cm
3, be highdensity material, be suitable for target, be therefore made into the size of regulation by processing such as cut-out, grindings, and engage with backboard and produce ITO target, result obtains the no problem target of quality.
(embodiment 5)
ITO waste material 24,000g (metal ingredient 19,780g) is put into reduction furnace, and the hydrogen circulated 10L/ minute, was warming up to 1 with one hour, 000 DEG C simultaneously, then kept 20 hours.After stopping heating, the weight alloy reclaimed in the returnable in stove is 16,986g, and reactivity is 86%.In addition, in reaction vessel, part residue is remained.Grade and the Remaining impurity levels of the main component element in the alloy reclaimed are analyzed by analytical procedure similarly to Example 1, result is the Ni that the In grade in this alloy is 90.32 % by weight, Sn grade is 9.68 % by weight, other impurity detects Fe, 5ppm of Cu, 3ppm of 1ppm respectively, in addition, Al, Bi, Cd, Cr, Pb, Si, Ti, Zn, Zr are all lower than lower limit of quantitation.
Using the indium-tin alloy of this recovery as anode, carry out electrolysis and generate indium hydroxide-metastannic acid mixture.The flow strength (electrolyte supply speed) of electrolytic solution is now adjusted to 1.0 (Lm
2)/(Amin).Then filtered and recycled is carried out to this mixture, through dried powder, produce indium oxide-tin oxide powder.Stannic oxide grade in the indium oxide-tin oxide powder obtained is 10.32 % by weight.
Granulation, shaping, sintering are carried out after the fine adjustment of composition to the indium oxide-tin oxide powder so obtained, thus produces ITO sintered compact.The density of the sintered compact obtained is 7.135g/cm
3, be highdensity material, be suitable for target, be therefore made into the size of regulation by processing such as cut-out, grindings, and engage with backboard and produce ITO target, result obtains the no problem target of quality.
Industrial applicability
The invention provides following technology: from the waste recovery indium-tin alloy containing high-purity mangesium oxide indium produced during manufacture ITO sputtering target or after use ITO sputtering target, and be made into indium oxide-tin oxide powder, then manufacture ITO target using this indium oxide-tin oxide powder as raw material.That is, waste material is directly reduced to alloy, and for the manufacture of ITO under the state of composition keeping the alloy obtained, simplifies control and the adjustment of the composition in manufacturing process thus.In addition, make the recovery of indium-Xi be only the reduction of oxide compound, have thus and make operation simplify, the such effect of manufacturing cost can be cut down compared with previous methods.In addition, by product is only water, therefore have can suppress objectionable impurities process, generation, thus can reduce the such excellent results of the load of environment.The target of manufacture like this is equal with the situation taking metal simple-substance as starting raw material.
Claims (5)
1. a method for recovery indium-tin alloy, wherein, utilizes reducing gas to reduce to ITO target waste material in reduction furnace, and is incorporated as the indium-tin alloy of the raw material into ITO target next time in the state of the ratio of components keeping the metal ingredient of ITO.
2. the method for recovery indium-tin alloy as claimed in claim 1, is characterized in that, in reduction furnace, in-furnace temperature is set as 750 ~ 1200 DEG C, use hydrogen as reducing gas, and hydrogen import volume is set as the ITO target waste material of every 1kg is that 500 ~ 1,000L reduces.
3. the manufacture method of an indium oxide-tin oxide powder, it is characterized in that, by electrolytic process, the indium-tin alloy reclaimed in claim 1 and 2 is made indium hydroxide-metastannic acid mixture, then roasting carried out to it and obtain indium oxide-tin oxide powder, and obtain the raw material of ITO target under the state of composition keeping the metal ingredient in ITO.
4. the manufacture method of an ITO target, it is characterized in that, granulation, shaping, sintering are carried out further to the indium oxide-tin oxide powder manufactured in claim 3, under the state of ratio of components keeping the metal ingredient in ITO, manufacture ITO target by the waste material containing high-purity mangesium oxide indium-stannic oxide produced during manufacture ITO sputtering target or after use ITO sputtering target.
5. the manufacture method of indium hydroxide-metastannic acid mixture as claimed in claim 3, is characterized in that, it is 0.01 ~ 100.0 (Lm that circulation electrolytic solution makes relative to the feed speed of current value, electrolysis area, the electrolytic solution of time
2)/(Amin).
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| Application Number | Priority Date | Filing Date | Title |
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| JP2013006806 | 2013-01-18 | ||
| JP2013-006806 | 2013-01-18 | ||
| PCT/JP2013/080994 WO2014112198A1 (en) | 2013-01-18 | 2013-11-18 | Method for recovering indium-tin alloy from ito target scrap and methods for producing indium oxide-tin oxide powder and ito target |
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| CN104919065A true CN104919065A (en) | 2015-09-16 |
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| JP (1) | JP5913639B2 (en) |
| KR (1) | KR20150046336A (en) |
| CN (1) | CN104919065A (en) |
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| CN114635044A (en) * | 2022-03-21 | 2022-06-17 | 宁波东大神乐电工合金有限公司 | Process for recovering silver from silver tin oxide and indium oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5916806B2 (en) * | 2013-07-25 | 2016-05-11 | 株式会社野田修護商店 | Metal chip drying method and metal chip drying apparatus using the same |
| GB201419244D0 (en) | 2014-10-29 | 2014-12-10 | Kings Metal Fiber Technologies | Use of alumina-chromium alloy in heat treatment |
| CN104711426B (en) * | 2014-11-21 | 2017-09-01 | 株洲冶炼集团股份有限公司 | A kind of useless methods of the target through reducing electroextraction indium tin of ITO |
| CN104711638B (en) * | 2014-11-21 | 2017-04-19 | 株洲冶炼集团股份有限公司 | Method for extracting indium and tin from waste ITO targets through reduction and electrolysis |
| CN111606353B (en) * | 2020-06-03 | 2022-04-26 | 福建阿石创新材料股份有限公司 | Method for recovering ITO powder from ITO target grinding waste liquid |
| CN114231743B (en) * | 2021-11-11 | 2022-10-21 | 广东先导稀材股份有限公司 | Method for preparing indium tin alloy by reducing ITO waste target at high temperature |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5417816A (en) * | 1992-12-09 | 1995-05-23 | Nikko Kyodo, Ltd. | Process for preparation of indium oxide-tin oxide powder |
| JP2011208216A (en) * | 2010-03-30 | 2011-10-20 | Jx Nippon Mining & Metals Corp | Method of recovering indium and tin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2736498B2 (en) * | 1993-05-26 | 1998-04-02 | 株式会社ジャパンエナジー | Method for producing indium oxide-tin oxide powder |
| JP3203587B2 (en) * | 1993-11-22 | 2001-08-27 | 株式会社ジャパンエナジー | How to recover indium |
| JP4210713B2 (en) * | 2007-02-16 | 2009-01-21 | 日鉱金属株式会社 | Method for recovering valuable metals from scrap containing conductive oxides |
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2013
- 2013-11-18 JP JP2014557339A patent/JP5913639B2/en active Active
- 2013-11-18 KR KR1020157008240A patent/KR20150046336A/en active Search and Examination
- 2013-11-18 CN CN201380057963.9A patent/CN104919065A/en active Pending
- 2013-11-18 WO PCT/JP2013/080994 patent/WO2014112198A1/en active Application Filing
- 2013-11-20 TW TW102142235A patent/TWI583798B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5417816A (en) * | 1992-12-09 | 1995-05-23 | Nikko Kyodo, Ltd. | Process for preparation of indium oxide-tin oxide powder |
| JP2011208216A (en) * | 2010-03-30 | 2011-10-20 | Jx Nippon Mining & Metals Corp | Method of recovering indium and tin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114635044A (en) * | 2022-03-21 | 2022-06-17 | 宁波东大神乐电工合金有限公司 | Process for recovering silver from silver tin oxide and indium oxide |
| CN114635044B (en) * | 2022-03-21 | 2024-02-09 | 宁波东大神乐电工合金有限公司 | Silver recovery process of silver tin oxide and indium oxide |
Also Published As
| Publication number | Publication date |
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| JP5913639B2 (en) | 2016-05-11 |
| JPWO2014112198A1 (en) | 2017-01-19 |
| KR20150046336A (en) | 2015-04-29 |
| WO2014112198A1 (en) | 2014-07-24 |
| TWI583798B (en) | 2017-05-21 |
| TW201430142A (en) | 2014-08-01 |
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