JPS61291958A - Titanium material having high corrosion resistance - Google Patents
Titanium material having high corrosion resistanceInfo
- Publication number
- JPS61291958A JPS61291958A JP13143585A JP13143585A JPS61291958A JP S61291958 A JPS61291958 A JP S61291958A JP 13143585 A JP13143585 A JP 13143585A JP 13143585 A JP13143585 A JP 13143585A JP S61291958 A JPS61291958 A JP S61291958A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- titanium material
- zirconium
- corrosion resistance
- spraying
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高耐食性チタン材、特にチタン材表面にジル
コニウムを溶射してなる高耐食性チタン材に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a highly corrosion-resistant titanium material, particularly to a highly corrosion-resistant titanium material obtained by thermally spraying zirconium onto the surface of the titanium material.
（従来の技術）
チタン材、特に純チタン材は、軽量かつ高耐食性を有す
る゛材料として、用途が拡大されつつある。(Prior Art) Titanium materials, especially pure titanium materials, are being used increasingly as materials that are lightweight and have high corrosion resistance.
しかし、環境によって、耐食性が異なり、使用環境とし
ては主に中性に限られ、例えば、還元性の酸（塩酸、硫
酸等）の中で高耐食性は示さない。However, the corrosion resistance varies depending on the environment, and the usage environment is mainly limited to neutral environments. For example, it does not show high corrosion resistance in reducing acids (hydrochloric acid, sulfuric acid, etc.).
酸化性の強い硝酸等では、使用されている例があるが、
濃度、溶液の経時変化等によっては、耐食性が著しく劣
化することがある。There are examples where it is used with strongly oxidizing nitric acid, etc.
Depending on the concentration, changes over time of the solution, etc., corrosion resistance may deteriorate significantly.
チタン材が硝酸プラント用に適用された例もあるが、腐
食を抑えるためには環境の管理が必要である。つまり、
純硝酸中（濃度４５％程度）では、耐食性は良くないに
もかかわらず、この環境にＣｒ６°イオンを添加すると
、チタン材の耐食性が向上する。There are examples of titanium materials being used in nitric acid plants, but environmental management is required to prevent corrosion. In other words,
Although corrosion resistance is not good in pure nitric acid (concentration of about 45%), adding Cr6° ions to this environment improves the corrosion resistance of titanium materials.
このように環境を管理すれば、チタン材の耐食性確保は
可能である。しかしながら、環境の管理といっても局限
された系内のそれであればともかり、一般的には開放状
態にあるためその管理は困難で、かつ費用のかかるもの
であり、実用的とはいえない。By managing the environment in this way, it is possible to ensure the corrosion resistance of titanium materials. However, environmental management is not only limited to a limited system, but is generally open, making it difficult and expensive to manage, making it impractical. .
（発明が解決しようとする問題点）
ここに、本発明の目的は、チタン材そのものの耐食性を
高めることによりすぐれた耐食性材料を提供することで
ある。(Problems to be Solved by the Invention) An object of the present invention is to provide an excellent corrosion-resistant material by increasing the corrosion resistance of the titanium material itself.
本発明の別の目的は、チタン材に表面処理を施すことに
よって、チタン材の材質そのものを変えることなく、そ
の耐食性を高めた耐食性チタン複合材料を提供すること
である。Another object of the present invention is to provide a corrosion-resistant titanium composite material whose corrosion resistance is improved by subjecting the titanium material to surface treatment without changing the quality of the titanium material itself.
（問題点を解決するための手段）
本発明は上述の目的を達成するために種々検討・を重ね
たところ、チタン材の表面に、ジルコニウムを溶射する
ことにより、腐食環境におけるチタン材の使用可能な範
囲が広がることを知見した。(Means for Solving the Problems) In order to achieve the above-mentioned object, the present invention has been made after various studies and studies. By spraying zirconium onto the surface of titanium material, titanium material can be used in a corrosive environment. We found that the range of
つまりジルコニウムそれ自体は、硝酸中では、高耐食性
を有するがチタンよりもかなり高価である。Thus, zirconium itself has high corrosion resistance in nitric acid, but is considerably more expensive than titanium.
チタンにジルコニウムを溶射すると、素地がかなり露出
していても、チタン素地の腐食電位が変わるため、極め
て高い耐食性を存するようになるのである。When zirconium is thermally sprayed onto titanium, the corrosion potential of the titanium substrate changes, even if the substrate is exposed to a large extent, resulting in extremely high corrosion resistance.
したがって、上述のような手段によれば環境側を管理す
ることなく、広範囲の条件にてチタンが使用可能となる
。Therefore, according to the above-mentioned means, titanium can be used under a wide range of conditions without environmental management.
ここに、本発明の要旨とするところは、チタン材表面に
ジルコニウムを溶射してなる高耐食性チタン材である。The gist of the present invention is a highly corrosion-resistant titanium material formed by thermally spraying zirconium onto the surface of the titanium material.
なお４．好ましくはチタン材表面の５％以上を溶射ジル
コニウムにより被覆することにより、十分な耐食性が得
られる。Note 4. Preferably, sufficient corrosion resistance can be obtained by coating 5% or more of the surface of the titanium material with thermally sprayed zirconium.
（作用）
次に、本発明を好適態様により具体的に示すと、まず、
チタン材としては通常耐食性チタンあるいはチタン合金
として使われているものであれば特に制限ないが、その
例として工業用純チタン材の板および管があり、この表
面にジルコニウム溶射を行うに先立って機械的にあるい
は化学的に表面酸化皮膜を除去して表面の活性化を行う
。真空中あるいは還元雰囲気中で加熱するだけでもよい
。(Function) Next, to specifically illustrate the present invention in preferred embodiments, first,
The titanium material is not particularly limited as long as it is normally used as corrosion-resistant titanium or titanium alloy, but examples include plates and pipes made of industrially pure titanium. The surface is activated by removing the surface oxide film either physically or chemically. It is also possible to simply heat in vacuum or in a reducing atmosphere.
このようにして表面調製したチタン材表面にジルコニウ
ム、一般に工業用純ジルコニウムを適宜手段で溶射する
。プラズマ溶射、還元炎を使った火炎溶射等、いずれで
あってもよい。Zirconium, generally industrially pure zirconium, is thermally sprayed onto the surface of the titanium material prepared in this manner by an appropriate means. Any method such as plasma spraying or flame spraying using a reducing flame may be used.
このときの溶射被覆割合は一般にチタン材表面の５％以
上であれば良いが、被覆割合が大きくなればなる程、耐
食性は高くなるが、ある程度以上になるとその効果は飽
和する。経済的観点からは好ましくは３０〜８０％であ
る。In general, the thermal spray coating ratio at this time should be 5% or more of the surface of the titanium material, and the higher the coating ratio, the higher the corrosion resistance, but beyond a certain point, the effect is saturated. From an economic point of view, it is preferably 30 to 80%.
表面被覆率は、溶射時の被覆用材料の供給量および溶射
速度をコントロールすることにより調節できる。The surface coverage can be adjusted by controlling the amount of coating material supplied during thermal spraying and the thermal spraying speed.
なお、チタンもしくはジルコニウムとしては純Ｔｉ （
たとえば５Ｔ４０．５Ｔ５０．５Ｔ７０） もしくは
純Ｚｒを主として用いるが、これらの合金を使用する場
合にはそれぞれＴｉ−６Ａβ−４ｖもしくはジルカロイ
２やジルカロイ４が望ましい。Note that titanium or zirconium is pure Ti (
For example, 5T40.5T50.5T70) or pure Zr is mainly used, but when these alloys are used, Ti-6Aβ-4v or Zircaloy 2 or Zircaloy 4 is preferable, respectively.
それぞれについて代表的例を第１表および第２表に示す
。Representative examples of each are shown in Tables 1 and 2.
第１表 チタンの成分
（ｖｔ％）
第２表 ジルコニウムの成分
また、母材、溶射材の組合せが工業用純チタン材と純ジ
ルコニウムとのときは耐食性向上の効果が最も著しい。Table 1 Components of titanium (vt%) Table 2 Components of zirconium Also, when the combination of base material and thermal spraying material is industrially pure titanium material and pure zirconium, the effect of improving corrosion resistance is most remarkable.
すなわち、純チタン材に純ジルコニウムの溶射塗膜が付
着すると、純チタン材の素地つまり、溶射塗膜に覆われ
ていない部分の腐食電位も上昇して、不働態域に移行し
耐食性が向上する。この効果は、一般に、塗膜の被覆率
が表面積比５％以上からかなり表われはじめるのである
。In other words, when a sprayed coating of pure zirconium adheres to a pure titanium material, the corrosion potential of the base of the pure titanium material, that is, the part not covered by the sprayed coating, also increases, shifting to a passive region and improving corrosion resistance. . Generally, this effect begins to become noticeable when the coating film coverage is 5% or more relative to the surface area.
添付図面の第１図は、チタン材表面に表面被覆率はぼ２
０％近い割合でジルコニウム溶射皮膜を設けた場合の様
子を模式的に示す説明図であるが、第２図のその一部拡
大図より明らかなように、あたかもチタン母地中にジル
コニウムが分散したようになっている。Figure 1 of the attached drawings shows that the surface coverage of the titanium material is approximately 2.
This is an explanatory diagram schematically showing the situation when a zirconium sprayed coating is applied at a ratio of nearly 0%. It looks like this.
したがって、本発明にあってはチタン材表面を全面に亘
って被覆する必要はなく、また各材料の組合せもチタン
材とジルコニウム材とで各種のものを使用できるのであ
る。Therefore, in the present invention, it is not necessary to cover the entire surface of the titanium material, and various combinations of titanium and zirconium materials can be used.
次に実施例により本発明をさらに説明する。Next, the present invention will be further explained by examples.
実施例
第１表に示すＪＩＳ １種の工業用純チタン板（８ｍｍ
Ｘ １ｏｏｏｏ＋ｍ Ｘ １０１０００ＩＩＩに通常の
プラズマ溶射機ヲ用いて、はぼ１０−’Ｔｏｒｒの真空
下でジルコニウムの溶射を行った。溶射材料には工業用
純度の純ジルコニウム粉末（粒径０．ＩＩ程度）を用い
た。また比較材としては同じ条件でアルミニウム溶射し
たチタン板を用いた。Example JIS 1 type industrial pure titanium plate (8 mm) shown in Table 1
Zirconium was thermally sprayed using a conventional plasma spraying machine under a vacuum of about 10-' Torr. Pure zirconium powder of industrial purity (particle size of about 0.II) was used as the thermal spraying material. A titanium plate sprayed with aluminum under the same conditions was used as a comparison material.
このときの溶射条件は次の通りであった。The thermal spraying conditions at this time were as follows.
プラズマ溶射条件：
プラズマ電圧ニア０（Ｖ）
電流 ＝４００〜６００ （Ａ）
使用ガス ： 純アルゴン（純度９９．９９％）溶
射距離 ：１００〜２００ （ｍｍ）雰囲気 ：
高真空（１０”” Ｔｏｒｒ）ジルコニウム供給速度
−〇、１〜１ ｋｇ／ｈ溶射速度 ： １０〜３０
ｍ／＋ｅｉｎ次いで、表面被覆率を変えてこのように
両面に溶射した一連のチタン板を３０ Ｘ ３０ （＋
ｍ）に切断し、腐食試験を行った。試験条件は、４５％
硝酸（沸騰）中に４８時間浸漬し、試験後、腐食減量を
測定した。腐食減量は最初の重量（Ｗｏ）に対する減少
重量の割合をもって表わす（Ｗ／Ｗｏ Ｘ １００％）
。結果を添付図面にグラフで示す。ジルコニウムを溶射
したチタンは、被覆率５％程度から高耐食性を示しはじ
める。これに対してアルミニウムを溶射したチタンでは
効果がほとんどない。Plasma spraying conditions: Plasma voltage near 0 (V) Current = 400-600 (A) Gas used: Pure argon (99.99% purity) Spraying distance: 100-200 (mm) Atmosphere:
High vacuum (10”” Torr) Zirconium supply rate - 〇, 1~1 kg/h Spraying rate: 10~30
m/+ein Then, a series of titanium plates sprayed on both sides in this way with varying surface coverage were 30 x 30 (+
m) and subjected to a corrosion test. The test conditions are 45%
It was immersed in nitric acid (boiling) for 48 hours, and the corrosion loss was measured after the test. Corrosion weight loss is expressed as the ratio of reduced weight to initial weight (Wo) (W/Wo x 100%)
. The results are shown graphically in the accompanying drawings. Titanium sprayed with zirconium begins to show high corrosion resistance at a coverage of about 5%. On the other hand, titanium sprayed with aluminum has almost no effect.
ジルコニウム２容射したチタンでは、このように表面を
完全に被覆せずとも十分有効な耐食性を発揮することが
わかり、チタン材の用途拡大が図れ（発明の効果）
以上説明してきたように、本発明によれば、ジルコニウ
ムの溶射という比較的簡便な手段でもってチタン材、特
に純チタン材の耐食性が著しく高められ、その適用範囲
が拡大されるなど、本発明の効果には大きいものがある
。It has been found that titanium coated with zirconium 2 exhibits sufficient corrosion resistance even without completely covering the surface, and the use of titanium materials can be expanded (effects of the invention). According to the invention, the corrosion resistance of titanium materials, especially pure titanium materials, is significantly improved by the relatively simple method of thermal spraying of zirconium, and the range of application thereof is expanded, and the effects of the present invention are significant.
第１図は、チタン材表面の溶射面の模式的説明図； 第２図は、その一部拡大図；および 第３図は、実施例の結果を示すグラフである。 FIG. 1 is a schematic explanatory diagram of the sprayed surface of the titanium material surface; Figure 2 is a partially enlarged view; and FIG. 3 is a graph showing the results of the example.
Claims (2)
食性チタン材。(1) Highly corrosion-resistant titanium material made by spraying zirconium onto the surface of titanium material.
覆してなる、特許請求の範囲第１項記載の高耐食性チタ
ン材。(2) The highly corrosion-resistant titanium material according to claim 1, wherein 5% or more of the surface of the titanium material is coated with thermally sprayed zirconium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13143585A JPS61291958A (en) | 1985-06-17 | 1985-06-17 | Titanium material having high corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13143585A JPS61291958A (en) | 1985-06-17 | 1985-06-17 | Titanium material having high corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61291958A true JPS61291958A (en) | 1986-12-22 |
Family
ID=15057894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13143585A Pending JPS61291958A (en) | 1985-06-17 | 1985-06-17 | Titanium material having high corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61291958A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63204680A (en) * | 1987-02-20 | 1988-08-24 | Toshiba Corp | Blower fin for excimer laser |
| JPS63204681A (en) * | 1987-02-20 | 1988-08-24 | Toshiba Corp | Heat exchanger fin for excimer laser |
-
1985
- 1985-06-17 JP JP13143585A patent/JPS61291958A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63204680A (en) * | 1987-02-20 | 1988-08-24 | Toshiba Corp | Blower fin for excimer laser |
| JPS63204681A (en) * | 1987-02-20 | 1988-08-24 | Toshiba Corp | Heat exchanger fin for excimer laser |
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