JPS6220268B2 - - Google Patents
Info
- Publication number
- JPS6220268B2 JPS6220268B2 JP59246317A JP24631784A JPS6220268B2 JP S6220268 B2 JPS6220268 B2 JP S6220268B2 JP 59246317 A JP59246317 A JP 59246317A JP 24631784 A JP24631784 A JP 24631784A JP S6220268 B2 JPS6220268 B2 JP S6220268B2
- Authority
- JP
- Japan
- Prior art keywords
- corrosion
- alloy
- titanium
- alloys
- amount
- 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.)
- Expired
Links
- 230000007797 corrosion Effects 0.000 claims description 30
- 238000005260 corrosion Methods 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910010977 Ti—Pd Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
チタンは、その耐食性が優れているため、従来
の耐食性金属に替わつて広く工業用材料として使
われるようになつてきたが、特に硝酸、クロム
酸、塩素酸、二酸化塩素、又は塩素酸塩等のよう
な酸化性腐食環境、並びに海水その他塩化物を含
む腐食環境において優れている。一方、塩酸、硫
酸などのような非酸化性酸においては、上記のよ
うな環境ほど優れた威力を発揮しない。そのた
め、この点を改良した既存の合金としてTi―Pd
合金、Ti―Ni合金、Ti―Ni―Mo合金（特願昭50
―37435）などが一部使用されているが、Ti―Pd
合金は、高価なパラジウムを使用しているため値
段が高いという欠点があり、Ti―Ni合金、Ti―
Ni―Mo合金は、加工性が悪いという欠点がある
ため広く利用されるにはいたつていないのが現状
である。
以上の点から、チタンは優れた耐食性を有して
いるとはいえ過酷な腐食環境下では、まだ多くの
問題をのこしており、又同時にこれらに対し一部
改善されたチタン合金も開発されてはいるが多く
の欠点を有しており十分でない。
本発明は、これらの状況を踏まえ見いだされた
ものであり、特に非酸化性の酸など厳しい腐食環
境で威力を発揮すると同時に、塩素イオンが存在
する溶液においてしばしば発生する隙間腐食にも
おおいに威力を発揮するチタン基合金に関するも
のである。
その組成範囲は、以下のとおりである。
Due to its excellent corrosion resistance, titanium has come to be widely used as an industrial material in place of conventional corrosion-resistant metals. Excellent in oxidizing corrosive environments such as seawater and other corrosive environments containing chlorides. On the other hand, non-oxidizing acids such as hydrochloric acid and sulfuric acid do not exhibit as good an effect as in the above environment. Therefore, Ti-Pd is an existing alloy that improves this point.
Alloy, Ti-Ni alloy, Ti-Ni-Mo alloy (patent application 1972)
-37435) are used in some cases, but Ti-Pd
Alloys have the disadvantage of being expensive because they use expensive palladium, and Ti--Ni alloys, Ti--
Currently, Ni--Mo alloys have not been widely used because they have the disadvantage of poor workability. From the above points, although titanium has excellent corrosion resistance, it still has many problems in harsh corrosive environments, and at the same time, titanium alloys with some improvements in these problems have also been developed. However, it has many drawbacks and is not sufficient. The present invention was discovered in light of these circumstances, and is particularly effective in harsh corrosive environments such as non-oxidizing acids, and at the same time is highly effective against crevice corrosion that often occurs in solutions containing chlorine ions. This relates to titanium-based alloys that exhibit the following properties. Its composition range is as follows.
【表】
ルテニウムの下限を0.005wt％以上とするの
は、この添加量未満では耐食性の向上が小さく実
用的でないためであり、このましくは0.01wt％以
上が必要とされる。又、ルテニウムの上限を
2.0wt％以下としたのは、それより上の添加量で
は加工性が悪くなるためである。
タングステンの下限を0.005wt％以上とするの
は、この添加量未満では耐食性の向上が小さく実
用的でないためであり、好ましくは0.01wt％以上
が必要とされる。又上限を0.5wt％以下とするの
は、これより多く添加すると加工性の低下及び製
造が難しくなるためである。
モリブデンの下限を0.01wt％以上とするのは、
この添加量未満では耐食性の向上が小さく実用的
でないためである。又上限を1.0wt％以下とする
のは、これより多く添加してもその効果があまり
かわらないことと、加工性の低下及び製造が難し
くなるためである。
次に、本発明のチタン合金を従来の耐食性チタ
ン合金と比較しその有効性を説明することにす
る。試験した腐食環境は、全面腐食では
1.5％HCl、沸騰状態
2.1％H2SO4、沸騰状態
3.5％H2SO4、沸騰状態
であり、隙間腐食では
4.10％NaCl、PH＝6.1、沸騰状態
で行なつた。
第１表に１％H2SO4の結果を示す。
純Ti及び既存の耐食性チタン合金をNo.１〜No.
５に示し、本発明合金をNo.６〜No.19に示す。
No.６〜No.９は、Ti―Ru―Ｗ合金においてＷの
添加量を変化させたものである。Ｗ添加量が
0.01wt％（No.６）において既にＷ添加の効果が認
められているが、添加量を増すにしたがいより一
層の効果が得られている。No.10〜No.12は、Ruの
添加量を変化させたものであるが、Ruの添加量
が増すにしたがい耐食性が向上している。
次に、No.13〜No.15はTi―Ru―Mo合金において
Moの添加量を変化させたものである。0.01Mo
wt％（No.13）において既にMo添加の効果が認め
られる。No.16〜No.18は、Ruの添加量を変化させ
たものであるが、その添加量が増すにしたがい耐
食性が向上しているのがわかる。
No.19は、チタン、ルテニウム、タングステン、
モリブデンを添加した合金であるが、四元合金に
することにより一層優れた耐食性チタン合金がで
きていることがわかる。
第２表、第３表は、５％H2SO4及び５％HClで
腐食試験結果が示されている。１％H2SO4と比較
した場合、腐食環境がきびしいため腐食速度は全
体的に上昇しているが、本発明合金が従来よりあ
る耐食性チタン合金より優れていることにかわり
はない。
以上の結果より、TiにRu、ＷもしくはRu、Mo
もしくはRu、Mo、Ｗを添加した場合非常に優れ
た耐食性チタン合金ができることがわかるが、特
に、既存の耐食性チタン合金（No.１〜No.５）との
比較においてはつきりと認識することができ、本
発明合金の有効性がわかる。
次に、隙間腐食試験結果を第４表に示す。
純チタン、Ti―0.15Pd合金は、１日を経ずし
て隙間腐食をおこしている。Ti―0.8Ni―0.3Mo
は、２日間をへたのち隙間腐食を起こしている。
これに比べ、本発明合金はどれもそれ以上の耐隙
間腐食性を有していることがわかる。
また本発明合金は、以上の耐食性の他、耐水素
吸収性にもすぐれている。第５表にその試験結果
を示す。
本データーは、対極に白金をもちい、極間電圧
を6.0Vとして供試材の表面より水素の泡を出し
水素吸収を行なわせたものである。
純チタンにくらべ明らかに本発明合金の方が水
素吸収量が少ないことがわかる。
以上、本発明合金は塩酸、硫酸等の非常に腐食
力が強い非酸化性酸に対して強い耐食性を有する
と共に隙間腐食においても優れた抵抗力をもつて
おり、また耐水素吸収性にも優れている。これよ
り、本発明合金は既存の耐食性チタン合金よりす
ぐれた耐食性を有している全く新しいチタン合金
であることがわかる。[Table] The lower limit of ruthenium is set at 0.005wt% or more because if the addition amount is less than this, the improvement in corrosion resistance is small and is not practical, and preferably 0.01wt% or more is required. Also, the upper limit of ruthenium
The reason why the amount is set at 2.0wt% or less is that if the amount added is higher than that, the processability will deteriorate. The reason why the lower limit of tungsten is set to 0.005 wt% or more is because if the addition amount is less than this, the improvement in corrosion resistance is small and is not practical, and preferably 0.01 wt% or more is required. The reason why the upper limit is set to 0.5 wt% or less is because adding more than this decreases processability and makes manufacturing difficult. The lower limit of molybdenum is 0.01wt% or more because
This is because if the addition amount is less than this, the improvement in corrosion resistance is small and is not practical. The reason why the upper limit is set to 1.0 wt% or less is that the effect does not change much even if added in a larger amount than this, and processability decreases and manufacturing becomes difficult. Next, the effectiveness of the titanium alloy of the present invention will be explained by comparing it with conventional corrosion-resistant titanium alloys. The corrosion environments tested were 1.5% HCl, 2.1% H 2 SO 4 in a boiling state, 3.5% H 2 SO 4 in a boiling state for general corrosion, and 4.10% NaCl, PH = 6.1, in a boiling state for crevice corrosion. I did it. Table 1 shows the results for 1% H 2 SO 4 . Pure Ti and existing corrosion-resistant titanium alloys No. 1 to No.
The alloys of the present invention are shown in Nos. 6 to 19. Nos. 6 to 9 are Ti—Ru—W alloys in which the amount of W added is changed. The amount of W added is
The effect of W addition has already been observed at 0.01wt% (No. 6), but as the amount added increases, even more effects are obtained. In No. 10 to No. 12, the amount of Ru added was changed, and the corrosion resistance improved as the amount of Ru added increased. Next, No. 13 to No. 15 are Ti-Ru-Mo alloys.
The amount of Mo added was changed. 0.01Mo
The effect of Mo addition is already recognized at wt% (No. 13). In Nos. 16 to 18, the amount of Ru added was varied, and it can be seen that the corrosion resistance improved as the amount added increased. No.19 is titanium, ruthenium, tungsten,
Although this is an alloy containing molybdenum, it can be seen that a titanium alloy with even better corrosion resistance can be produced by making it into a quaternary alloy. Tables 2 and 3 show the corrosion test results for 5% H 2 SO 4 and 5% HCl. When compared with 1% H 2 SO 4 , the corrosion rate is generally higher due to the harsher corrosive environment, but the alloy of the present invention is still superior to conventional corrosion-resistant titanium alloys. From the above results, it can be concluded that Ti has Ru, W or Ru, Mo.
Alternatively, it can be seen that when Ru, Mo, and W are added, a very excellent corrosion-resistant titanium alloy can be produced, but it is especially clear when compared with existing corrosion-resistant titanium alloys (No. 1 to No. 5). This shows the effectiveness of the alloy of the present invention. Next, the crevice corrosion test results are shown in Table 4. Pure titanium and Ti-0.15Pd alloys undergo crevice corrosion in less than a day. Ti―0.8Ni―0.3Mo
After 2 days, crevice corrosion occurred.
In comparison, it can be seen that all the alloys of the present invention have higher crevice corrosion resistance. In addition to the corrosion resistance described above, the alloy of the present invention also has excellent hydrogen absorption resistance. Table 5 shows the test results. In this data, platinum was used as the counter electrode, and the voltage between the electrodes was set to 6.0V, and hydrogen bubbles were generated from the surface of the test material to absorb hydrogen. It can be seen that the amount of hydrogen absorbed by the alloy of the present invention is clearly lower than that of pure titanium. As described above, the alloy of the present invention has strong corrosion resistance against highly corrosive non-oxidizing acids such as hydrochloric acid and sulfuric acid, and also has excellent resistance to crevice corrosion.It also has excellent hydrogen absorption resistance. ing. This shows that the alloy of the present invention is a completely new titanium alloy that has better corrosion resistance than existing corrosion-resistant titanium alloys.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
及びタングステン0.005重量％以上0.5重量％以下
もしくはモリブデン0.01重量％以上1.0重量％以
下の一種または二種を含有し、残部チタン及び不
可避的不純物からなる耐食性に優れたチタン基合
金。1 Ruthenium 0.005% by weight or more and 2.0% by weight or less,
A titanium-based alloy with excellent corrosion resistance, containing one or both of the following: and 0.005% to 0.5% by weight of tungsten or 0.01% to 1.0% by weight of molybdenum, with the remainder being titanium and unavoidable impurities.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24631784A JPS61127843A (en) | 1984-11-22 | 1984-11-22 | Titanium alloy having superior corrosion resistance |
| US06/796,839 US4666666A (en) | 1984-11-22 | 1985-11-12 | Corrosion-resistant titanium-base alloy |
| GB08528183A GB2167769B (en) | 1984-11-22 | 1985-11-15 | Corrosion-resistant titanium-base alloy |
| DE19853541223 DE3541223A1 (en) | 1984-11-22 | 1985-11-21 | CORROSION-RESISTANT TITANIUM BASED ALLOY |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24631784A JPS61127843A (en) | 1984-11-22 | 1984-11-22 | Titanium alloy having superior corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61127843A JPS61127843A (en) | 1986-06-16 |
| JPS6220268B2 true JPS6220268B2 (en) | 1987-05-06 |
Family
ID=17146753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24631784A Granted JPS61127843A (en) | 1984-11-22 | 1984-11-22 | Titanium alloy having superior corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61127843A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0784632B2 (en) * | 1986-10-31 | 1995-09-13 | 住友金属工業株式会社 | Method for improving corrosion resistance of titanium alloy for oil well environment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5858428A (en) * | 1981-10-02 | 1983-04-07 | Yamatake Honeywell Co Ltd | Three-wire temperature sensor |
-
1984
- 1984-11-22 JP JP24631784A patent/JPS61127843A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5858428A (en) * | 1981-10-02 | 1983-04-07 | Yamatake Honeywell Co Ltd | Three-wire temperature sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61127843A (en) | 1986-06-16 |
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