KR101560455B1 - LCD Glass METHOD OF MANUFACTURING AN OXIDE DISPERSION STRENGTHENED PLATINUMRHODIUM ALLOYS MATERIALS USING SPARK PLASMA SINTERING FOR LIQUID CRYSTAL DISPLAY GLASS MANUFACTURING - Google Patents
LCD Glass METHOD OF MANUFACTURING AN OXIDE DISPERSION STRENGTHENED PLATINUMRHODIUM ALLOYS MATERIALS USING SPARK PLASMA SINTERING FOR LIQUID CRYSTAL DISPLAY GLASS MANUFACTURING Download PDFInfo
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- oxide
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- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 title claims description 26
- 239000011521 glass Substances 0.000 title abstract description 7
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 title abstract description 6
- 239000000463 material Substances 0.000 title description 22
- 238000002490 spark plasma sintering Methods 0.000 title description 15
- 239000004973 liquid crystal related substance Substances 0.000 title 1
- 229910000629 Rh alloy Inorganic materials 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000005728 strengthening Methods 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000002074 melt spinning Methods 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000010948 rhodium Substances 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- UXVUXLQXLAHKAB-UHFFFAOYSA-N oxoplatinum;rhodium Chemical compound [Rh].[Pt]=O UXVUXLQXLAHKAB-UHFFFAOYSA-N 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000005242 forging Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000005097 cold rolling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims 2
- 229910052693 Europium Inorganic materials 0.000 claims 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 1
- 229910001260 Pt alloy Inorganic materials 0.000 abstract description 12
- 238000012805 post-processing Methods 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000005275 alloying Methods 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 8
- 238000005482 strain hardening Methods 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
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- 238000001887 electron backscatter diffraction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
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- 239000002033 PVDF binder Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- 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
- C22C1/0466—Alloys based on noble metals
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/50—Treatment under specific atmosphere air
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
More particularly, the present invention relates to the production of an oxide dispersion strengthened platinum-rhodium alloy used as an LCD glass manufacturing apparatus, and more particularly, to a method of manufacturing a platinum alloy thin plate by melt spinning, , And a method for manufacturing a novel dispersion-strengthening platinum-rhodium alloy material in which oxide is finely dispersed at a high density through post-processing after ensuring density using a discharge plasma sintering method (SPS).
The present invention can be used for the purpose of reducing the processing time and cost in comparison with the conventional platinum-rhodium alloy manufacturing process using the hot press used for securing the density.
Description
The present invention relates to a process for producing a high-density oxide dispersion-strengthening (PVDF) resin for use in platinum devices (crucibles, bushings, stirrers) More particularly, the present invention relates to a method of producing a platinum-rhodium alloy having enhanced dispersion of oxides by melt spinning, followed by heat treatment, discharge plasma sintering (SPS), forging, To a new manufacturing method for manufacturing a high-density oxide dispersion strengthening type platinum-rhodium alloy material through post-processing such as rolling.
Platinum having a high melting point, chemical resistance and corrosion resistance is easy to process at room temperature and high temperature, and is excellent in volatility, so that it is used in various industries despite expensive materials. Particularly, along with the recent growth of the LCD industry, the use of platinum materials having high strength is increasing for manufacturing materials and devices for manufacturing high quality glass for LCD.
In order to improve the strength of pure platinum, a platinum material which has been conventionally alloyed with an element such as gold (Au) or rhodium (Rh) and solidified by platinum has been mainly used. However, recent price changes of alloying elements used as reinforcing elements have been replaced by platinum alloy materials which are cheaper than these alloys and dispersed and strengthened with oxides having excellent high temperature creep characteristics.
In order to solve the above problems of the platinum-rhodium materials strengthened by employment, platinum alloy materials in which oxides are formed and dispersed using elements superior to rhodium have been developed. The platinum alloy containing such an oxide is known to exhibit a high high temperature creep strength because it has a small grain growth and small deformation even when used at a high temperature of 1200 ° C or higher for a long time and has crystallized grains while being interrupted by recrystallization due to oxides .
On the other hand, the conventional designed oxide dispersion strengthening type platinum-rhodium alloy is produced by preparing platinum-rhodium alloy powder by using plasma or melt spinning method, ensuring density through hot press, then hot working (forging, rolling) , And a final heat treatment to obtain an oxide dispersion strengthened platinum-rhodium alloy sheet. However, the pressure sintering process such as a hot press in the above process has a disadvantage of high cost due to an increase in the process time. Accordingly, there is a need for a new manufacturing method that shortens the process time and reduces the manufacturing cost.
DISCLOSURE Technical Problem The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide a method for manufacturing a platinum-rhodium alloy in which oxides having excellent high temperature strength and creep characteristics are dispersed, a metal thin plate is manufactured using melt spinning The produced thin plate is produced by a high-density oxide dispersion strengthening type platinum-rhodium alloy by the discharge plasma sintering (SPS) method, thereby reducing the processing time and the manufacturing cost thereby to manufacture a high density oxide dispersion strengthening type platinum- .
In order to achieve the above-mentioned object, the present invention provides a method for producing a platinum-rhodium-oxide alloy ingot comprising: (a) preparing an alloy ingot for platinum-rhodium-oxide by adding rhodium and an alloy- (b) preparing a platinum-rhodium alloy thin plate by melt spinning on the prepared platinum-rhodium-oxide alloy ingot; (c) oxidizing the alloyed element for oxide by performing an oxidation heat treatment on the prepared thin plate of platinum-rhodium alloy; (d) laminating or grinding the oxidized heat treated thin plate to improve density by discharge plasma sintering (SPS); And (e) post-processing the sintered body. The present invention also provides a method of manufacturing a platinum-rhodium alloy for enhancing dispersion of oxides for LCD glass.
According to a preferred embodiment of the present invention, the step (b) comprises the steps of charging and melting a platinum-rhodium alloy ingot into a melt spinning equipment, rotating the melt at a constant speed by pressurized injection of argon gas through a nozzle And then cooled and brought into contact with the surface of the wheel to be produced.
According to another preferred embodiment of the present invention, the step (d) may be a high-temperature compression molding by a spark plasma sintering (SPS) method. At this time, at a temperature of 1200 ° C. to 1400 ° C. for 5 to 20 minutes It is preferably carried out under a pressure of 10 MPa to 50 MPa.
According to another preferred embodiment of the present invention, it is preferable that the post-processing step of the step (e) is carried out by one or more processes selected from the group consisting of hot working, cold working and recrystallization heat treatment of the sintered body.
In the present invention, in the production of an oxide dispersion strengthening type platinum-rhodium alloy having excellent creep and high temperature strength, by using a discharge plasma sintering method (SPS) instead of the conventional hot press sintering method, a high- It is possible not only to produce a dispersion-strengthening platinum-rhodium alloy sheet material, but also to remarkably shorten the processing time and cost.
FIG. 1 is a process flow diagram of a method for manufacturing an oxide dispersion enhanced platinum-rhodium alloy according to an embodiment of the present invention.
FIG. 2 is a process flow chart comparing a conventional method and a method for manufacturing an oxide dispersion strengthening type platinum-rhodium alloy according to the present invention.
FIG. 3 is a graph showing the relative density values of the oxide dispersion strengthening type platinum-rhodium alloy prepared in each of Comparative Examples (conventional methods) and Examples, respectively.
4 is an EBSD analysis photograph of the oxide dispersion strengthening type platinum-rhodium alloy produced in the example.
5 is a TEM photograph of the oxide dispersion-strengthening platinum-rhodium alloy thin sheet produced in the examples.
6 is an analysis photograph showing the crystal grain size of an oxide dispersion strengthening type platinum-rhodium alloy produced according to the present invention (Example -6b) and the conventional method (Comparative Example 6a).
7 is a graph showing the results of high temperature (800 ° C) tensile strength of an oxide dispersion strengthening type platinum-rhodium alloy produced according to the present invention (Example 7b) and the conventional method (Comparative Example 7a).
Hereinafter, the present invention will be described in detail.
Conventionally, when a platinum-rhodium alloy having high density and high strength and having high strength is dispersed, a sintering process for securing the density was carried out using a hot press. However, since the HP process has a long process time, the manufacturing time and cost are high.
Accordingly, the present invention is characterized in that a high-density oxide dispersion strengthening type platinum-rhodium alloy sheet material is produced in a short time by replacing the conventional hot sintering method (SPS) with a discharge press-sintering method (SPS).
Spark plasma sintering (SPS) is a method of applying sintering by applying a DC pulse current in a direction parallel to a pressing direction while pressing a powder or a sheet material in a single axis, and applying pressure, a low voltage and a large current to the powder or plate material It is a sintering method in which the high energy of plasma generated instantaneously by the spark generated at this time is applied to electric field diffusion, thermal diffusion and the like. This discharge plasma sintering method has a lower sintering temperature of about 200 to 500 DEG C than the conventional hot compression method and can complete sintering in a short time including a temperature rise and a holding time, It is easy to handle and low running cost. It is also advantageous in that it is not necessary to be skilled in sintering technology, and it is applicable to materials that are difficult to process at high temperature and ovary solubility.
In the present invention, unlike the conventional method, a platinum-rhodium alloy ingot produced in a vacuum or an inert atmosphere is produced in the form of a thin plate of platinum alloy by melt spinning, and then the alloy element Can be sufficiently performed in a shorter time.
Accordingly, in the present invention, a high-density oxide dispersion strengthening type platinum-rhodium alloy sheet material having a level equivalent to that of the conventional method can be produced in a short time, and the effect of shortening the process time and cost can be obtained.
≪ Method for producing high-density oxide dispersion strengthening type platinum-rhodium alloy material >
Hereinafter, a method for producing a high-density oxide dispersion strengthening type platinum-rhodium alloy material according to the present invention will be described. However, the present invention is not limited to the following production methods, and the steps of each process may be modified or optionally mixed as required.
The method for producing an oxide dispersion strengthening type platinum-rhodium alloy material according to the present invention comprises the steps of: preparing a platinum alloy thin plate by melt spinning an alloy ingot for platinum-rhodium-oxide; subjecting the prepared platinum alloy thin plate to oxidation heat treatment and discharge plasma Followed by sintering and post-processing.
(1) a step (S10) of producing an alloy ingot for platinum-rhodium-oxide by adding rhodium and an alloy element for an oxide to a target platinum; (2) a step (S20) of charging a melt-spinning apparatus with an alloy ingot for platinum-rhodium-oxide and melting the melt to manufacture a thin metal sheet by melt spinning; (3) oxidizing the thin plate material to oxidize the oxide thin film by performing an oxidative heat treatment (S30); (4) a step (S40) of increasing the density through lamination or pulverization of the oxidized thin plate and sintering by discharge plasma; And (5) a step (S50) of producing a final oxide dispersion strengthening type platinum-rhodium alloy material through post-processing such as forging, rolling and final heat treatment.
Hereinafter, the manufacturing method will be described separately for each step.
(1) First, an ingot of a platinum-rhodium-oxide alloy is prepared by adding rhodium of the aimed composition and a strengthening element for an oxide to high purity platinum (S10).
In the first step, an alloy ingot for platinum-rhodium-oxide is produced in a vacuum or an inert atmosphere.
In the platinum-rhodium alloy material according to the present invention, the rhodium content of the alloying element added may be appropriately adjusted within the conventional range known in the art, and for example, in the range of 5 to 20% by weight based on 100% . When the rhodium content is less than 5 wt%, the solid solution strengthening effect by adding rhodium can not be obtained. When the rhodium content is more than 20 wt%, the strength is increased and cracks occur in the post- There is a drawback that the improvement is rather deteriorated.
In addition, at least one kind of metal element added as the alloy element for oxide can be used without limitations in the conventional metal components used in the conventional platinum alloy. Generally, the kinds of alloying elements to be added can be selected in various ways, and it is selected as an oxide element which is stable even at a high temperature of 1400 ° C. or more and has a higher degree of oxidation compared to platinum and gold without deteriorating the corrosion resistance in view of the applications used in the glass industry . Accordingly, non-limiting examples of the alloying element for use as an oxide include zirconium (Zr), samarium (Sm), yttrium (Y), hafnium (Hf), and mixed forms of at least one.
The amount of the alloying element for the oxide to be added at this time is not particularly limited, but is preferably in the range of 0.02 wt% to 0.8 wt%. If the content of the oxide-based alloy element is less than 0.02% by weight, the dispersion strengthening effect is insignificant. When the content is more than 0.8% by weight, the creep strength is improved, but the dispersion strengthening effect by the residual dispersed particles is increased, . Therefore, it is preferable that the amount of the alloying element for rhodium and oxide is selected within a range in which workability can be maximized while enhancing solid solution strengthening and dispersion strengthening effect.
Particularly, since the above-described alloy element for oxide is superior in oxidation property to platinum or rhodium, it is difficult to control the content of the oxide element by oxidation and vaporization in the case of dissolving in air, so it is preferable to perform dissolution in a vacuum or an inert atmosphere.
(2) The alloyed ingot for platinum-rhodium-oxide produced is charged into a melt-spinning machine and melted, and a thin metal plate is produced by melt spinning. (S20).
In the present invention, an alloy ingot for platinum-rhodium-oxide is formed into a thin metal plate by melt spinning.
In a preferred example of the second step, a platinum-rhodium alloy ingot produced through vacuum melting is charged into a melt spinning machine and melted, and the melt is flowed by pressurized injection of argon gas through a nozzle, The metal foil can be manufactured by contacting and cooling the rotating wheel surface.
More specifically, the nozzle is installed in the melt spinning equipment before the melt spinning process, the ingot is charged, and the ingot charged under high vacuum (10 -4 Torr) is melted. When the molten ingot is completely melted, argon gas (Ar gas) is injected into the melt on the surface of a rotating wheel (for example, a Cu wheel) rotating at a constant speed to inject platinum alloy thin plate.
Here, the rotating speed of the rotating wheel is not particularly limited, but may be in the range of 500 to 3000 rpm, for example. Also, the pressurized injection range of the argon gas may be in the range of 0.1 to 1.0 MPa, but is not particularly limited thereto.
At this time, as a usable material of the mold mounted on the ingot, a material having a high melting point can be used without limitation, and a quartz crucible or a graphite mold is preferably used.
The size and thickness of the thin metal plate manufactured in the above step can be adjusted according to the wheel speed, the injection pressure, the distance to the nozzle, and the like. In one example, the width of the platinum-rhodium alloy sheet may be in the range of about 3 to 10 mm, and the thickness may be in the range of 100 μm or less, preferably in the range of 5 to 100 μm.
(3) The produced thin plate of platinum is subjected to an oxidation heat treatment to produce a thin plate which is subjected to oxidation treatment of the oxide element (S30).
In the third step, internal oxidation is performed to form and disperse oxides of the additive elements for the oxides in the platinum alloy thin sheet produced by the melt spinning method. Atmospheric heat treatment can be used to form and disperse oxides in a short time.
The heat treatment conditions are not particularly limited. For example, the heat treatment is preferably performed at a temperature of 800 to 1200 ° C for 1 to 12 hours. If the temperature of the heat treatment is less than 800 ° C or less than 1 hour, the oxidation of the alloy element for the oxide may not be sufficient. If the temperature exceeds 1200 ° C for 12 hours, the dispersion strengthening effect due to coarsening of the oxide of the alloy element is deteriorated There are disadvantages.
Since the shape to be manufactured is a thin plate, it is preferable that the alloy is produced in the form of a thin plate so that oxidation of the alloying element which can be easily oxidized in a shorter time can be sufficiently performed.
(4) An oxidized platinum alloy thin plate material is laminated or pulverized, charged into a molding mold, and spark plasma sintering is performed to improve density to manufacture a sintered body (S40).
In the present invention, discharge plasma sintering (SPS) is performed in place of hot pressing to ensure a high density of the sintered body.
As described above, the discharge plasma sintering method refers to sintering the high energy of the hot discharge plasma instantaneously generated by the spark discharge by the action of heat diffusion, electric field diffusion or the like, and the conventional hot press or HIP it is advantageous in that it can be sintered or sintered in a short time or at a lower temperature than a sintering process such as a hot isostatic press. In addition, since the temperature can be raised rapidly, the growth of particles can be controlled and a dense sintered body can be obtained in a short time.
In a preferred example of the fourth step, the platinum alloy thin plate material as the oxidized shape is laminated or pulverized and charged into a mold, and then electric energy and a large current in the form of pressure and a direct current pulse are applied to the powder material, (SPS) which effectively applies and sinters high energy of a discharge plasma instantaneously generated by the interdischarge phenomenon by thermal diffusion and electric field diffusion or the like.
The sintering conditions applicable at this time are preferably a pressure of 10 to 50 MPa for 5 to 20 minutes in a temperature range of 1200 to 1400 캜.
If the sintering temperature is less than 1200 ° C or the sintering time and pressure are low, a high-density sintered body can not be obtained. If the temperature is 1400 ° C and the sintering time is more than 20 minutes, . Also, high pressures are undesirable because they can lead to the risk of applied molds and equipment.
In general, the sintered body produced by the sintering method may have a target density range of about 80 to 90%. The sintered body produced by the discharge plasma sintering (SPS) of the present invention has a sintered body of about 86.2% Can be represented by the relative density.
(5) The sintered body produced by the discharge plasma sintering method is subjected to post-treatment to finally produce an oxide dispersion strengthening platinum-rhodium alloy material (S50).
In the fifth step, the post-processing may be performed by one or more processes selected from the group consisting of hot working, cold working and recrystallizing heat treatment of the sintered body. Preferably, the hot working, the cold working and the recrystallizing heat treatment are sequentially performed.
Here, in the hot working step, it is important to secure the density close to the theoretical density. As a non-limiting example of applicable hot working processes for this purpose, hot rolling or hot forging can be used.
In the case of the oxide dispersion strengthening type platinum-rhodium prepared through hot working, it is preferable to have a relative density of 98% or more. In the case of a material having a relative density of 98% or less, pores remaining in the hot working are not removed even if a relative density of 99% or more is ensured due to subsequent cold working, And the like) is likely to occur.
The processing temperature during the hot working may be appropriately adjusted within a range generally known to those skilled in the art. For example, the working temperature is preferably in the range of 1,000 to 1400 ° C. When the processing temperature is less than 1000 ° C, cracks tend to occur during hot working and it is difficult to secure a high density. When the processing temperature is higher than 1400 ° C, the characteristics of the oxide dispersion strengthening platinum- It can be degraded.
After the hot working, it is also preferable to carry out a heat treatment to prevent the occurrence of cracks during cold working, and to perform cold working to obtain a recrystallized heat treated structure through thickness control and final heat treatment.
At this time, the reduction ratio in cold rolling is preferably 40 to 90%. If the reduction rate is less than 40%, the processing stress is low and recrystallization may not occur even after the heat treatment. If the reduction rate exceeds 90%, the material is likely to be broken due to high processing stress.
As the conditions for performing the recrystallization heat treatment after the cold working, it is preferable to carry out the heat treatment in the atmosphere for oxidation of the oxide element in the temperature range of 1,200 ° C to 1400 ° C for 1 to 5 hours.
Recrystallization of the microstructure can be suppressed when the recrystallization heat treatment conditions are less than 1200 ° C. and less than 1 hour, and when the temperature is higher than 1400 ° C. and more than 5 hours, the crystal grains and oxides are coarsened, have.
The relative density of the final product produced through the post-processing step described above is preferably 99% or more.
The present invention provides a platinum-rhodium alloy material for strengthening dispersion of oxides for the production of an LCD glass produced by the above-described method.
It has been found that the platinum-rhodium alloy material for strengthening the oxide dispersion has a relative density equivalent to that of a platinum-rhodium alloy material produced by a conventional hot press, and the elongated grains are retained even after the
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.
[Example]
In order to produce a Pt-Rh-Zr ingot using a vacuum high-frequency induction melting furnace, 3R5 grade PtRh10 and 3N grade Zr were added to produce an ingot. At this time, the target compositions of the constituents of the ingot are Pt_89.7 wt%, Rh_10 wt% and Zr_0.3 wt%, and specific contents of the impurity-containing trace components are shown in Table 1 below. In this case, when the unit is converted to ppm, 1/10000 is converted into wt%.
Melting spinning was used for the ingot produced by vacuum melting. The ingot was charged into the nozzle of the melt spinning equipment, and then the molten material flowing down by pressurizing the Ar gas was mixed with Cu The surface of the wheel was cooled to produce a thin metal plate.
The prepared platinum thin plate was heat treated at 1000 ℃ for 1 hour in order to form and disperse the oxide added elements. As a result of TEM analysis of the oxide dispersion-strengthening platinum-rhodium alloy thin sheet produced by the present invention, it was found that Zr oxide particles of about 200 nm which are visible in white were dispersed (see FIG. 5).
Spray plasma sintering (SPS) was carried out at 1400 ℃ for 15 min at 2 ton pressure to obtain the density by laminating or milling the manufactured thin plate. After that, hot forging and cold rolling were carried out to obtain high density, The final oxide dispersion strengthened platinum-rhodium alloy was prepared through heat treatment at 1200 ℃ for 1 hour.
FIG. 3 shows changes in relative density for each process for the high-density oxide dispersion strengthened platinum-rhodium alloy material prepared as described above.
FIG. 4 shows the cross-sectional EBSD analysis results of the high-density oxide dispersion strengthened platinum-rhodium alloy material prepared above. From these results, it can be seen that the elongated grains are retained even after the heat treatment.
[Comparative Example]
500gr of Pt - 10wt% Rh - 0.3wt% Zr ingot was prepared by using a vacuum high - frequency induction melting furnace. For the prepared ingot, a vacuum pump attached to the plasma equipment was used to produce powder, and the pressure was reduced to 10 -3 torr. Ar was used as a reaction gas to form a plasma, the ingot was melted and the plasma power was further increased Powder. The final prepared powder was collected in the chamber and quenching part to obtain final Pt-10wt% Rh-0.3wt% Zr powder. Carbon contamination was confirmed by the use of graphite mold. In order to remove it, The Pt-10 wt% Rh-0.3 wt% Zr powder from which the carbon was removed was obtained by heat treatment.
The powder thus prepared was put into a square shaped carbon mold and heat-treated at 1300 ° C for 2 hours in an argon (Ar) atmosphere to prepare a molded body. The oxide was formed in the atmosphere at 1400 ° C for 2 hours Heat treatment was performed. In order to ensure high density, the oxidized specimens were sintered at 1300 ℃ for 2 hours under pressure of 20 MPa. To ensure ultra - high density, the hot - rolled, cold - rolled and heat - A rhodium material was prepared.
[Property evaluation]
The properties of the platinum-rhodium alloy materials produced in the examples and the comparative examples were evaluated as follows.
As a result of the high temperature (800 캜) tensile test, the platinum-rhodium alloy prepared in the comparative example exhibited 170 MPa (see Fig. 7A) (See FIG. 7B). Therefore, it was confirmed that the platinum-rhodium alloy of the present invention manufactured by the discharge plasma sintering method (SPS) had a higher tensile strength than the conventional method.
As a result of comparing the sizes of the crystal grains, the average crystal grain sizes of the platinum-rhodium alloy prepared in Comparative Examples and Examples were 23.3 탆 and 23.1 탆, respectively (see Table 2).
Therefore, the platinum-rhodium alloy material for strengthening the oxide dispersion of the present invention exhibits a grain size equivalent to that of a platinum-rhodium alloy material produced by a conventional hot press, and has a higher high temperature tensile strength (See Figs. 6 to 7).
(Comparative Example)
(Example)
Claims (12)
(b) preparing an alloy thin plate for platinum-rhodium-oxide using the melt spinning method on the prepared alloy ingot for platinum-rhodium-oxide;
(c) oxidizing the alloy element for oxide by performing the oxidation heat treatment at a temperature of 800 to 1200 ° C. for 1 to 12 hours in an atmospheric environment, thereby producing the platinum-rhodium alloy thin plate;
(d) laminating or pulverizing the oxidized heat-treated thin plate, and then densifying the compact by high-temperature compression molding by discharge plasma sintering (SPS) at a temperature of 1200 to 1400 ° C for 10 to 50 MPa for 5 to 20 minutes; And
(e) subjecting the sintered body to recrystallization heat treatment at 1200 to 1400 ° C for 1 to 5 hours under hot forging, cold rolling and atmospheric conditions
Wherein the molar ratio of the platinum-rhodium alloy to the platinum-rhodium alloy is in the range of 1: 1 to 1: 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130129043A KR101560455B1 (en) | 2013-10-29 | 2013-10-29 | LCD Glass METHOD OF MANUFACTURING AN OXIDE DISPERSION STRENGTHENED PLATINUMRHODIUM ALLOYS MATERIALS USING SPARK PLASMA SINTERING FOR LIQUID CRYSTAL DISPLAY GLASS MANUFACTURING |
| PCT/KR2013/009983 WO2015064808A1 (en) | 2013-10-29 | 2013-11-06 | Oxide dispersion strengthened platinum-rhodium alloy manufacturing method for manufacturing lcd glass by using spark plasma sintering |
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| KR1020130129043A KR101560455B1 (en) | 2013-10-29 | 2013-10-29 | LCD Glass METHOD OF MANUFACTURING AN OXIDE DISPERSION STRENGTHENED PLATINUMRHODIUM ALLOYS MATERIALS USING SPARK PLASMA SINTERING FOR LIQUID CRYSTAL DISPLAY GLASS MANUFACTURING |
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| CN110106386B (en) * | 2019-05-08 | 2021-02-12 | 昆明贵金属研究所 | Preparation method of oxide-reinforced platinum-rhodium-based composite wire and platinum-rhodium-based composite wire |
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