JPH0820809A - Production of chromium-base alloy powder - Google Patents
Production of chromium-base alloy powderInfo
- Publication number
- JPH0820809A JPH0820809A JP17773794A JP17773794A JPH0820809A JP H0820809 A JPH0820809 A JP H0820809A JP 17773794 A JP17773794 A JP 17773794A JP 17773794 A JP17773794 A JP 17773794A JP H0820809 A JPH0820809 A JP H0820809A
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- platinum group
- base alloy
- chromium oxide
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 239000000843 powder Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 27
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 33
- 239000011651 chromium Substances 0.000 claims description 32
- 229910052804 chromium Inorganic materials 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000006229 carbon black Substances 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001513 hot isostatic pressing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- -1 Of these Chemical compound 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐蝕性、耐磨耗性に優
れたすぐれたクロム基合金粉末の製造法に関する。さら
に詳しくは、白金族、特に白金、パラジウム、ルテニウ
ムの一種以上を含み、残部がクロムからなる合金粉末の
製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a chromium-based alloy powder having excellent corrosion resistance and abrasion resistance. More specifically, it relates to a method for producing an alloy powder containing one or more members of the platinum group, particularly platinum, palladium and ruthenium, with the balance being chromium.
【０００２】[0002]
【従来の技術】白金族に属する金属元素を他の金属成
分、例えばチタンに少量添加してその耐蝕性を向上させ
る試みは従来から実施されており、代表的な合金として
チタンーパラジウム合金が、熱交換機等の高腐食環境下
に置かれる化学プラントの構成素材として利用されてい
る。しかし、白金族に属する金属元素は極めて高価であ
ることから、その経済性を考慮すればこれに用いる量は
必然的に制限される。2. Description of the Related Art Attempts have been made to add a small amount of a metal element belonging to the platinum group to other metal components such as titanium to improve its corrosion resistance. A typical alloy is a titanium-palladium alloy. It is used as a constituent material for chemical plants placed in highly corrosive environments such as heat exchangers. However, since the metal elements belonging to the platinum group are extremely expensive, the amount used for them is necessarily limited in consideration of their economic efficiency.
【０００３】従来、チタンやニッケルを基とした合金の
製造法は、各成分を混合溶解して均一組成の合金を得る
溶解法が基本とされており、添加元素が少量の場合はそ
の均一性については特に留意することもない。しかし、
クロムを基とした合金を製造するに際しては、クロムの
融点が１９２０℃と高く、又、蒸気圧が極めて高いこと
から前記した溶解法をこれに適応すると、ルツボなどの
容器からの不純物の混入や蒸発損失による収率の低下な
どの問題があった。Conventionally, a method of manufacturing an alloy based on titanium or nickel is based on a melting method in which each component is mixed and melted to obtain an alloy having a uniform composition. There is no particular concern about But,
When a chromium-based alloy is produced, the melting point of chromium is as high as 1920 ° C. and the vapor pressure is extremely high. Therefore, if the above-mentioned melting method is applied to this, contamination of impurities such as crucibles from the container and There was a problem such as a decrease in yield due to evaporation loss.
【０００４】そこで、クロム基合金の製造については溶
解法に代えて粉末冶金的な手法が検討されている。一般
に粉末冶金法により少量の添加物を合金内に均一に分散
させるにはメカニカルアロイングなどの特殊な処理が有
効とされているが、クロム基合金の場合、不純物の混入
はその加工性を著しく悪化させることから、不純物の混
入の可能性の高いこのような特殊処理の適応は困難であ
り、結局、一般的な混合、成型、焼結又は熱間静水圧プ
レスによるクロム基合金焼結体を得た後、これを熱処理
により添加元素を熱拡散させて均一性のある合金成型体
を得ている。Therefore, for the production of chromium-based alloys, a powder metallurgical method has been studied instead of the melting method. Generally, special treatment such as mechanical alloying is effective to uniformly disperse a small amount of additives in the alloy by powder metallurgy, but in the case of chromium-based alloys, the inclusion of impurities significantly improves its workability. It is difficult to apply such a special treatment that is likely to be mixed with impurities because it deteriorates, and in the end, general mixing, molding, sintering or hot isostatic pressing of a chromium-based alloy sintered body is performed. After being obtained, this is heat-treated to thermally diffuse the additional element to obtain a uniform alloy molded body.
【０００５】このように白金族元素を含むクロム基合金
成型体の製造についてはエネルギーを多大に必要とする
とともに経済性の面、更に、処理対象物の形状（大き
さ）の制限など多くの問題がある。As described above, the production of a chromium-based alloy molded body containing a platinum group element requires a large amount of energy, is economical, and has many problems such as the limitation of the shape (size) of the object to be treated. There is.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、不純
物が少なく組成の均一な白金族元素を含むクロム基合金
成型体の製造法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a chromium-based alloy molded body containing a platinum group element having a uniform composition with a small amount of impurities.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上記課題
の解決のため種々検討を行った結果、ある種の還元法に
より目的とするクロム基合金粉末を得ることを見出し本
発明を完成した。Means for Solving the Problems As a result of various studies for solving the above problems, the present inventors have found that the desired chromium-based alloy powder can be obtained by a certain reduction method, and completed the present invention. did.
【０００８】即ち本発明は、白金族元素の一種以上と酸
化クロム、炭材の混合物を熱還元し、次いで水素還元す
ることを特徴とするクロム基合金粉末の製造法に関する
ものである。次に本発明を以下に詳述する。That is, the present invention relates to a method for producing a chromium-based alloy powder, which comprises thermally reducing a mixture of one or more platinum group elements, chromium oxide and carbonaceous material, and then hydrogen-reducing the mixture. Next, the present invention will be described in detail below.
【０００９】本発明の主原料には高純度の酸化クロムと
炭材を用いる。純度の高い合金粉末を得るためには原料
の純度についても十分留意する必要がある。本発明で用
いる酸化クロムは、例えば無水クロム酸を焼成したもの
が純度が高く好ましいが、酸化クロムの製造方法につい
ては特に制限されるものではない。この酸化クロムの純
度はＣｒ2 Ｏ3 として９９．９％以上が好ましく、特に
鉄、鉛、銅などの重金属不純物は、これらの合計で１０
０ppm 以下であることが好ましい。High-purity chromium oxide and carbonaceous materials are used as the main raw materials of the present invention. In order to obtain a highly pure alloy powder, it is necessary to pay sufficient attention to the purity of the raw materials. The chromium oxide used in the present invention is preferably one obtained by burning chromic anhydride, for example, because of its high purity, but the method for producing chromium oxide is not particularly limited. The purity of this chromium oxide is preferably 99.9% or more as Cr 2 O 3 , and especially heavy metal impurities such as iron, lead and copper are 10% in total.
It is preferably 0 ppm or less.
【００１０】金属クロムの製造法には、酸化クロムを金
属アルミニウムで熱還元するいわゆるテルミット法と、
高炭素フェロクロムを硫酸で溶解して得られるクロム明
礬精製液から電解採取する電解法がある。金属クロムは
耐熱性、耐蝕性の向上を目的として超合金などの添加材
として主に用いられているが、耐熱性、耐蝕性に優れた
特性を持ちながら主に添加材として用いられているの
は、金属クロムの脆性による機械加工性に劣るためであ
る。しかし、金属クロムに含まれる不純物、特に酸素お
よび窒素などのガス成分を低減させることによってその
機械加工性が著しく向上するため高純度金属クロムを主
原料としてその良好な耐熱性、耐蝕性を生かした用途が
広がりつつある。特に硫酸、塩酸などの酸性水溶液に対
して金属クロムは良好な耐蝕性を示すが、さらに高温度
条件が加わるなど過酷な環境下においては、白金族元素
を含むクロム基合金が金属クロム単体より一段と優れた
耐蝕性を示す。The method for producing metallic chromium includes a so-called thermit method in which chromium oxide is thermally reduced with metallic aluminum,
There is an electrolysis method in which high carbon ferrochrome is electrolyzed from a purified chrome alum solution obtained by dissolving it in sulfuric acid. Metallic chromium is mainly used as an additive material for superalloys and the like for the purpose of improving heat resistance and corrosion resistance, but it is mainly used as an additive material while having excellent heat resistance and corrosion resistance. Is due to the poor machinability due to the brittleness of metallic chromium. However, since the machinability is remarkably improved by reducing the impurities contained in the metallic chromium, especially the gas components such as oxygen and nitrogen, the good heat resistance and the corrosion resistance were made by using the high purity metallic chromium as the main raw material. Applications are expanding. In particular, metallic chromium shows good corrosion resistance to acidic aqueous solutions such as sulfuric acid and hydrochloric acid, but under severe conditions such as the addition of high temperature conditions, chromium-based alloys containing platinum group elements are much more prominent than metallic chromium alone. Shows excellent corrosion resistance.
【００１１】本発明で用いる炭材は、カーボンブラッ
ク、黒鉛のいずれも使用可能であるが炭材中の灰分が１
０００ppm 以下のものが好ましい。用いる炭材の量は、
酸化クロム中の酸素を還元するに必要な理論量の９８〜
９９％が好ましい。これは原料中に炭材が残存すると後
述する水素還元工程で炭材がそのまま原料中に残存し、
目的とする純度の金属クロムが得られないからである。The carbonaceous material used in the present invention may be either carbon black or graphite, but the ash content in the carbonaceous material is 1
It is preferably 000 ppm or less. The amount of carbonaceous material used is
The theoretical amount of 98 to reduce oxygen in chromium oxide
99% is preferable. This is because when the carbonaceous material remains in the raw material, the carbonaceous material remains as it is in the raw material in the hydrogen reduction step described below.
This is because metallic chromium having a desired purity cannot be obtained.
【００１２】本発明で合金成分として用いる白金族元素
は、ルテニウム、ロジウム、パラジウム、オスミウム、
イリジウム、白金であるが、これらの中でもルテニウ
ム、パラジウム、白金が得られる合金の耐蝕性を向上さ
せる上で好ましい。これらは金属粉、酸化物、硝酸塩の
形で添加するが、例えば金属粉を添加する際、そのもの
の粒度が１００μm 以下のものが均一な混合状態の合金
粉末を得る上で好ましい。又、これらの添加量は、添加
元素の合計で０．１重量％以上好ましくは０．５重量％
以上である。この量が０．１重量％より少ないと得られ
る合金粉末の十分な耐蝕性が得られず、又、５重量％以
上では添加量に見合った効果が得られず経済的にも問題
となる。従って添加量の上限は２重量％が目安となる。Platinum group elements used as alloy components in the present invention include ruthenium, rhodium, palladium, osmium,
Of these, iridium and platinum are preferable, among which ruthenium, palladium, and platinum are preferable for improving the corrosion resistance of the obtained alloy. These are added in the form of metal powders, oxides, and nitrates. For example, when the metal powders are added, those having a particle size of 100 μm or less are preferable in order to obtain an alloy powder in a uniform mixed state. The total amount of these elements added is 0.1% by weight or more, preferably 0.5% by weight.
That is all. If this amount is less than 0.1% by weight, sufficient corrosion resistance of the obtained alloy powder cannot be obtained, and if it is 5% by weight or more, the effect corresponding to the added amount cannot be obtained, which is economically problematic. Therefore, the upper limit of the amount added is 2% by weight.
【００１３】本発明は、以上述べたような酸化クロム、
炭材、白金族元素を所定の量配合し混合したものを、堅
型プレス等の方法で任意の大きさに成型し加熱炉を用い
て真空熱還元を行う。この時の処理条件は１３５０〜１
４５０℃の温度範囲で、真空度３〜１０Torr、８〜１６
時間が好ましい。この処理条件で処理温度が１４５０℃
より高く、又、真空度が３Torrより高い場合は、生成し
たクロムの蒸発損失が大きく目的とする組成、純度のも
のを得ることが困難である。又、逆に上記した範囲より
温度、減圧度が低い場合も、還元が不十分でやはり目的
とする組成、純度のものを得ることが困難である。The present invention provides the chromium oxide as described above,
A mixture of a predetermined amount of carbonaceous material and platinum group elements is mixed and molded into a desired size by a method such as a rigid press, and vacuum thermal reduction is performed using a heating furnace. The processing conditions at this time are 1350-1
Vacuum degree 3-10 Torr, 8-16 in the temperature range of 450 ° C
Time is preferred. The processing temperature is 1450 ° C under these processing conditions.
When the degree of vacuum is higher and the degree of vacuum is higher than 3 Torr, it is difficult to obtain a desired composition and purity because of large evaporation loss of chromium produced. On the contrary, when the temperature and the degree of reduced pressure are lower than the above ranges, the reduction is insufficient and it is difficult to obtain the desired composition and purity.
【００１４】このような真空熱還元によって１〜２重量
％の酸素が生成物中に残存するが添加した白金族元素を
所定量含むクロム基合金のスポンジ状生成物が得られ
る。By such vacuum thermal reduction, 1 to 2% by weight of oxygen remains in the product, but a sponge product of a chromium-based alloy containing a predetermined amount of added platinum group element is obtained.
【００１５】上記の方法で得たクロム基合金は次に水素
による熱還元を行う。この際の処理条件は、水素圧で１
気圧の場合、処理温度１５００〜１６００℃、処理時間
６〜８時間である。又、水素圧２０〜５０mmHgの減圧下
でも可能で、この場合処理温度１３５０〜１４５０℃、
処理時間１２〜２０時間である。このような処理条件の
下限より下の温度、時間では還元が不十分で生成物中に
酸素が残存する可能性が高い。The chromium-based alloy obtained by the above method is then subjected to thermal reduction with hydrogen. The processing condition at this time is 1 hydrogen pressure.
In the case of atmospheric pressure, the processing temperature is 1500 to 1600 ° C. and the processing time is 6 to 8 hours. It is also possible under a hydrogen pressure of 20 to 50 mmHg, in which case the treatment temperature is 1350 to 1450 ° C.
The processing time is 12 to 20 hours. If the temperature and time are below the lower limit of such treatment conditions, reduction is insufficient and oxygen is likely to remain in the product.
【００１６】以上の炭素、水素の熱還元処理で得た白金
族元素を含むクロム基合金はスポンジ状の粒度１０〜５
０μm の粉体の塊で、通常の粉砕方法、例えば振動ミル
等で粉砕する。なお、この粉砕時にもし不純物が混入し
た場合は粉砕物を硫酸、硝酸などで洗浄することにより
高純度のクロム基合金粉末とすることができる。The chromium-based alloy containing the platinum group element obtained by the above thermal reduction treatment of carbon and hydrogen has a sponge particle size of 10 to 5
The powder mass of 0 μm is crushed by a usual crushing method, for example, a vibration mill. If impurities are mixed during this pulverization, the pulverized product can be washed with sulfuric acid, nitric acid or the like to obtain a high-purity chromium-based alloy powder.
【００１７】このようにして得られたクロム基合金粉末
は白金族元素をそれらの合計で０．１〜５重量％含み、
これら以外の成分ではクロムが９９．８％以上である。The chromium-based alloy powder thus obtained contains platinum group elements in a total amount of 0.1 to 5% by weight,
Other than these components, chromium is 99.8% or more.
【００１８】本発明で得たクロム基合金粉末は直接熱間
静水圧プレスや熱間圧延などにより耐蝕性の優れた均一
組成の合金成型体とすることができる。The chromium-based alloy powder obtained in the present invention can be directly formed into an alloy compact having a uniform composition with excellent corrosion resistance by hot isostatic pressing or hot rolling.
【００１９】[0019]
【実施例】無水クロム酸を焼成して得た純度９９．９８
％の酸化クロム１０００ｇに対して固定炭素量９９．９
％の黒鉛２３７ｇを加え、さらに粒度１００μm 以下の
金属ルテニウムを３．４２ｇ加えて十分混合し加圧成型
したものを真空加熱炉で１４００℃、真空度５Torrで１
６時間処理し、さらに減圧還元炉で１４００℃圧力４０
mmHgで１６時間処理し得られた生成物を振動ミルで粒度
１４４μm 以下に粉砕し、８０℃の１５重量％硝酸水溶
液で洗浄して０．５Ｒｕの高純度クロム基合金を得た
（実施例１）。この粉末の主な成分の分析値を表１に示
す（単位 PPm）。Example: Purity 99.98 obtained by firing chromic anhydride
% Fixed carbon amount 99.9% to chromium oxide 1000 g
% Graphite 237 g, and further metal ruthenium 3.42 g with a particle size of 100 μm or less was added, thoroughly mixed, and pressure-molded, and the result was 1400 ° C. in a vacuum heating furnace at a vacuum degree of 5 Torr.
Treated for 6 hours, and further reduced pressure reduction furnace at 1400 ℃ pressure 40
The product obtained by treatment with mmHg for 16 hours was pulverized with a vibration mill to a particle size of 144 μm or less, and washed with a 15 wt% nitric acid aqueous solution at 80 ° C. to obtain a high-purity chromium-based alloy of 0.5 Ru (Example 1 ). The analytical values of the main components of this powder are shown in Table 1 (unit: PPm).
【００２０】[0020]
【表１】 さらに、実施例１の金属ルテニウムの代わりに硝酸パラ
ジウムを６．６４ｇ加えて実施例１と同様の処理を行
い、０．７Ｐｄの高純度クロム基合金を得た（実施例
２）。この粉末の主な成分の分析値を表２に示す（単位
PPm）。[Table 1] Further, in place of the metal ruthenium of Example 1, 6.64 g of palladium nitrate was added and the same treatment as in Example 1 was performed to obtain a 0.7 Pd high-purity chromium-based alloy (Example 2). The analytical values of the main components of this powder are shown in Table 2 (unit:
PPm).
【００２１】[0021]
【表２】 実施例１、２の合金粉末を夫々ステンレス容器に充填
し、十分真空排気して封止したものを１２００℃、１０
００気圧で熱間静水圧加工して夫々の合金成型体を得
た。さらに、白金族元素を添加しない高純度クロム粉単
独およびこの高純度クロム粉に金属ルテニウムを０．５
重量％になるように混合したものを夫々前記と同様の条
件で熱間静水圧加工して夫々の成型体とし、これらを用
いて常温における塩酸水溶液中の腐食状況を比較した。
結果を表３に示す。[Table 2] Each of the alloy powders of Examples 1 and 2 was filled in a stainless steel container, sufficiently evacuated, and sealed.
Each of the alloy molded bodies was obtained by hot isostatic pressing at 00 atm. Further, the high-purity chromium powder alone without adding the platinum group element and 0.5% of ruthenium metal to this high-purity chromium powder.
Each of the mixed materials so as to have a weight percentage was subjected to hot isostatic pressing under the same conditions as described above to form respective molded bodies, and the corrosion state in the hydrochloric acid aqueous solution at room temperature was compared using these molded bodies.
The results are shown in Table 3.
【００２２】[0022]
【表３】 なお、腐食速度：１mm／Ｙ＝３．２×１０-11 ms-1で、
一般に０．１mm／Ｙ以下を耐食材とされている。[Table 3] The corrosion rate is 1 mm / Y = 3.2 × 10 −11 ms −1 ,
Generally, 0.1 mm / Y or less is regarded as a food resistant material.
【００２３】さらに、実施例１、２の合金粉末を夫々電
気亜鉛鍍金ラインの通電ロール（ロール寸法：径３６０
mm×長さ１８００mm、鋼板厚さ：０．４〜１．６mm）を
熱間静水圧加工により作製し、従来品であるニッケル基
合金（Ｎｉ−22Ｃｒ− 9Ｍｏ− 3.5Ｎｂ）の通電ロール
（形状は同上）との腐食消耗量を比較した。結果を結果
を表４に示す。Further, each of the alloy powders of Examples 1 and 2 was applied to a current-carrying roll of an electrogalvanizing line (roll size: diameter 360).
mm x length 1800 mm, steel plate thickness: 0.4 to 1.6 mm) was produced by hot isostatic pressing, and a conventional nickel-based alloy (Ni-22Cr-9Mo-3.5Nb) energizing roll (shape) The same as above). The results are shown in Table 4.
【００２４】[0024]
【表４】 [Table 4]
【００２５】[0025]
【発明の効果】本発明で得た合金粉末は、従来のように
金属単体を夫々混合し成型し焼成などの拡散処理を施す
ことなく、合金粉末を直接熱間静水圧プレスや熱間圧延
などにより耐蝕性の優れた均一組成の合金成型体とする
ことができる。EFFECTS OF THE INVENTION The alloy powder obtained by the present invention is directly hot isostatic pressed or hot rolled without subjecting the alloy powder to the conventional mixing and molding of the individual metals and performing diffusion treatment such as firing. As a result, an alloy molded body having a uniform composition with excellent corrosion resistance can be obtained.
Claims (3)
の混合物を熱還元し、次いで水素還元することを特徴と
するクロム基合金粉末の製造法。1. A method for producing a chromium-based alloy powder, which comprises thermally reducing a mixture of one or more platinum group elements, chromium oxide, and carbonaceous material, and then reducing with hydrogen.
ムである請求項１記載の製造法。2. The method according to claim 1, wherein the platinum group element is platinum, palladium or ruthenium.
炭材を用いて熱還元する請求項１又は２記載の製造法。3. The production method according to claim 1, wherein the carbon material is thermally reduced by using an amount of carbonaceous material that allows a part of oxygen of chromium oxide to remain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17773794A JPH0820809A (en) | 1994-07-07 | 1994-07-07 | Production of chromium-base alloy powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17773794A JPH0820809A (en) | 1994-07-07 | 1994-07-07 | Production of chromium-base alloy powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0820809A true JPH0820809A (en) | 1996-01-23 |
Family
ID=16036248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17773794A Pending JPH0820809A (en) | 1994-07-07 | 1994-07-07 | Production of chromium-base alloy powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0820809A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1102651A4 (en) * | 1998-08-06 | 2003-02-12 | Eramet Marietta Inc | PURE CHROME RECOVERY |
| CN102211201A (en) * | 2011-05-16 | 2011-10-12 | 西安交通大学 | Method for preparing Pt, Pd and Pt-M (M is Cu, Ag and Pd) alloy nanoparticles |
| CN103357884A (en) * | 2013-07-07 | 2013-10-23 | 合肥工业大学 | Method for preparing porous nano-iron by brown iron ore |
| CN103962568A (en) * | 2014-04-15 | 2014-08-06 | 昆明理工大学 | Method for preparing reduction chromium powder through microwave heating |
| JP2016532783A (en) * | 2013-09-02 | 2016-10-20 | プランゼー エスエー | Powder metallurgy parts |
-
1994
- 1994-07-07 JP JP17773794A patent/JPH0820809A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1102651A4 (en) * | 1998-08-06 | 2003-02-12 | Eramet Marietta Inc | PURE CHROME RECOVERY |
| CN102211201A (en) * | 2011-05-16 | 2011-10-12 | 西安交通大学 | Method for preparing Pt, Pd and Pt-M (M is Cu, Ag and Pd) alloy nanoparticles |
| CN103357884A (en) * | 2013-07-07 | 2013-10-23 | 合肥工业大学 | Method for preparing porous nano-iron by brown iron ore |
| JP2016532783A (en) * | 2013-09-02 | 2016-10-20 | プランゼー エスエー | Powder metallurgy parts |
| US10211465B2 (en) | 2013-09-02 | 2019-02-19 | Plansee Se | Powdered metal component |
| CN103962568A (en) * | 2014-04-15 | 2014-08-06 | 昆明理工大学 | Method for preparing reduction chromium powder through microwave heating |
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