JPS6220269B2 - - Google Patents
Info
- Publication number
- JPS6220269B2 JPS6220269B2 JP59246318A JP24631884A JPS6220269B2 JP S6220269 B2 JPS6220269 B2 JP S6220269B2 JP 59246318 A JP59246318 A JP 59246318A JP 24631884 A JP24631884 A JP 24631884A JP S6220269 B2 JPS6220269 B2 JP S6220269B2
- Authority
- JP
- Japan
- Prior art keywords
- corrosion
- titanium
- alloys
- alloy
- ruthenium
- 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 29
- 238000005260 corrosion Methods 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 229910001069 Ti alloy Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910000990 Ni 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
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910002787 Ru-Ni Inorganic materials 0.000 description 1
- 229910002793 Ru–Ni Inorganic materials 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni 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
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 238000004519 manufacturing process Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum 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
な酸化性腐食性環境、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の厳しい腐食
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ルテニウム及びニツケ
ルを含有することを特徴と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。
元 素 組成範囲（wt％）
ルテニウム 0.005〜0.2未満
ニツケル 0.01〜2.0
チタン balance
ルテニウムの下限を0.005wt％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、0.005wt％以上このましくは
0.01wt％以上が必要とされる。又、ルテニウムの
上限を0.2wt％未満としたのは、それ以上の添加
は耐食性の効果が飽和し、又ルテニウムに費用が
かかりすぎ経済的でないためである。
ニツケルの下限を0.01wt％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0.1wt％以上が必要とさ
れる。又ニツケルの上限を2.0wt％以下としたの
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
なることにより、好ましくは1.0wt％以下であ
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.16に示す。
No.６〜No.11は、Ti―Ru―Ni合金においてNiの
添加量を変化させたものである。Ni添加量が
0.01wt％（No.６）において既にその効果はみられ
ているが、0.06wt％以上ではとくにはつきりと腐
食速度が減つており、No.３との比較においてNi
添加の効果がはつきりとうかがえる。これより、
Niの添加量はその下限を0.01wt％とし、また上限
を2.0wt％としたのはこれより多くでは加工性が
著しく劣ることによる。
次に、No.12〜No.16はTi―Ru―Ni合金において
Ruの添加量を変化させたものである。0.01Ru wt
％（No.12）ではつきりと腐食速度が減つており、
No.４との比較においてRu添加の効果がはつきり
とうかがえる。これより、Ruの添加量はその下
限を0.005wt％とし、また上限を0.2wt％未満とし
たのはこれより多くでは耐食性の効果が飽和し、
又添加するルテニウムに費用がかかりすぎること
による。
第２表、第３表は、５％H2SO4及び５％HClで
の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。
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下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も強い耐食性を有す
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。又、
ニツケル、ルテニウムの含有量が少ないため加工
性は純チタンなみであり、しかも安価に製造でき
ることになる。これより、本発明合金は既存の耐
食性チタン合金の欠点をなくし、しかもよりすぐ
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。
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 and corrosive environments such as seawater and other corrosive environments containing chlorides. On the other hand, hydrochloric acid
Non-oxidizing acids such as sulfuric acid do not exhibit as much power 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 based on these circumstances, and is particularly effective in severe 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 invention relates to a titanium-based alloy characterized by containing ruthenium and nickel that exhibits the following properties. Its composition range is as follows. Element Composition range (wt%) Ruthenium 0.005 to less than 0.2 Nickel 0.01 to 2.0 Titanium balance The lower limit of ruthenium is set at 0.005wt% because the improvement in corrosion resistance is small and impractical if the addition amount is less than 0.005wt. % or more preferably
0.01wt% or more is required. Furthermore, the upper limit of ruthenium is set to less than 0.2 wt% because if it is added more than that, the corrosion resistance effect will be saturated and ruthenium will be too expensive, making it uneconomical. The lower limit of nickel is set at 0.01 wt% because if the addition amount is less than this, the improvement in corrosion resistance is small and is not practical, and preferably 0.1 wt% or more is required. The upper limit of nickel is set to 2.0wt% or less because the effect does not change much even if more than this is added, and the processability decreases and manufacturing becomes difficult, so it is preferably 1.0wt% or less. . 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 16. Nos. 6 to 11 are Ti--Ru--Ni alloys in which the amount of Ni added is changed. Ni addition amount
The effect is already seen at 0.01wt% (No. 6), but at 0.06wt% or more, the corrosion rate and corrosion rate are particularly reduced, and compared with No. 3, Ni
The effect of the addition is clearly visible. Than this,
The lower limit of the amount of Ni added is set at 0.01 wt%, and the upper limit is set at 2.0 wt% because the processability is significantly inferior when the amount is higher than this. Next, No. 12 to No. 16 are Ti-Ru-Ni alloys.
The amount of Ru added was changed. 0.01 Ru wt
% (No. 12), the corrosion rate decreased sharply,
A comparison with No. 4 clearly shows the effect of Ru addition. From this, the lower limit of the amount of Ru added is set at 0.005wt%, and the upper limit is set at less than 0.2wt% because the corrosion resistance effect is saturated if the amount is higher than this.
Another reason is that the ruthenium added is too expensive. Tables 2 and 3 show the results of corrosion tests with 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. 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. Furthermore, the alloy of the present invention has excellent corrosion resistance as well as 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 extremely corrosive non-oxidizing acids such as hydrochloric acid and sulfuric acid, and also has excellent resistance to crevice corrosion.It also has good hydrogen absorption resistance. Are better. or,
Because the content of nickel and ruthenium is low, its workability is comparable to that of pure titanium, and it can be manufactured at a low cost. This shows that the alloy of the present invention is a completely new titanium alloy that eliminates the drawbacks of existing corrosion-resistant titanium alloys and has even better corrosion resistance.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
ニツケル0.01重量％以上2.0重量％以下、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 less than 0.2% by weight,
A titanium-based alloy with excellent corrosion resistance, consisting of 0.01% to 2.0% by weight of nickel, the balance being titanium and unavoidable impurities.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24631884A JPS61127844A (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 |
|---|---|---|---|
| JP24631884A JPS61127844A (en) | 1984-11-22 | 1984-11-22 | Titanium alloy having superior corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61127844A JPS61127844A (en) | 1986-06-16 |
| JPS6220269B2 true JPS6220269B2 (en) | 1987-05-06 |
Family
ID=17146768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24631884A Granted JPS61127844A (en) | 1984-11-22 | 1984-11-22 | Titanium alloy having superior corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61127844A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014115845A1 (en) | 2013-01-25 | 2014-07-31 | 新日鐵住金株式会社 | Titanium alloy having excellent corrosion resistance in environment containing bromine ions |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0689423B2 (en) * | 1985-11-05 | 1994-11-09 | 住友金属工業株式会社 | Titanium alloy with excellent corrosion resistance |
| 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 |
| US8741217B2 (en) | 2005-12-28 | 2014-06-03 | Nippon Steel & Sumitomo Metal Corporation | Titanium alloy for corrosion-resistant materials |
| JP3916088B2 (en) * | 2005-12-28 | 2007-05-16 | 住友金属工業株式会社 | Titanium alloy for corrosion resistant materials |
| JP5379752B2 (en) | 2010-06-29 | 2013-12-25 | 株式会社神戸製鋼所 | Titanium alloy with excellent intergranular corrosion resistance |
-
1984
- 1984-11-22 JP JP24631884A patent/JPS61127844A/en active Granted
Non-Patent Citations (4)
| Title |
|---|
| A NEW CORROSION RESISTANT TITANIUM ALLOY TI-38A FOR HIGH TEMPERATURE BRINE SERVICE=1974 * |
| CORROSION=1968 * |
| CORROSION=1975 * |
| JOURNAL OF THE ELECTROCHEMICAL SOCIETY=1959 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014115845A1 (en) | 2013-01-25 | 2014-07-31 | 新日鐵住金株式会社 | Titanium alloy having excellent corrosion resistance in environment containing bromine ions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61127844A (en) | 1986-06-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |