JPS6239234B2 - - Google Patents
Info
- Publication number
- JPS6239234B2 JPS6239234B2 JP14441983A JP14441983A JPS6239234B2 JP S6239234 B2 JPS6239234 B2 JP S6239234B2 JP 14441983 A JP14441983 A JP 14441983A JP 14441983 A JP14441983 A JP 14441983A JP S6239234 B2 JPS6239234 B2 JP S6239234B2
- Authority
- JP
- Japan
- Prior art keywords
- boron nitride
- stainless steel
- weight
- alloy
- vacuum
- 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
- 229910052582 BN Inorganic materials 0.000 claims description 26
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 8
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 nitric acid Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は高真空容器用、特に超高真空容器用に
好適な材料及びその製造方法に関する。
従来、真空容器用材料としては通常ステンレス
鋼が用いられている。ステンレス鋼はその表面に
気体が付着し易く、超高真空にするためには容器
全体を150〜200℃、場合によつて約500℃にまで
加熱する必要があり、かつ超高真空に達するまで
に長時間を必要とする欠点があつた。
そのため、容器材料の表面に気体の付着に対し
て不活性になるような表面処理を行う必要があ
る。窒化ボロンは気体の付着に対して不活性な性
質を有するが、これを従来技術である化学的気相
蒸着法により表面に被覆しようとすると、材料を
1000〜2000℃という非常に高い温度に加熱しなけ
ればならなく、その操作も面倒である欠点があ
る。
本発明はこのような欠点がなく、比較的低温
で、且つ容易に窒化ボロン皮膜を析出し得られ、
表面を気体の付着に対して不活性なものとした高
真空容器用材料及びその製造方法を提供するにあ
る。
本発明者は前記目的を達成すべく鋭意研究の結
果、Ni6〜26重量％、Cr16〜26重量％、残部Feか
らなるオーステナイト系ステンレス鋼の成分に、
N0.1〜0.3重量％、B0.005〜0.02重量％及び
Ce0.001〜0.1重量％を含有させた合金を真空中で
700〜900℃に加熱すると、合金内部から表面に窒
化ボロンが析出して均一な皮膜が形成し得られ、
これにより合金表面を気体の付着に対し不活性に
なし得られることを究明し得た。この知見に基づ
いて本発明を完成した。
本発明の要旨は、
(3) Ni6〜26重量％、Cr16〜26重量％、残部Feか
らなるオーステナイト系ステンレス鋼成分に、
N0.1〜0.3重量％、B0.005〜0.02重量％及び
Ce0.001〜0.1重量％を含有させた合金の表面に
窒化ボロンを加熱析出させたものからなる高真
空容器用材料。
(2) Ni6〜26重量％、Cr16〜26重量％、残部Feか
らなるオーステナイト系ステンレス鋼成分に、
N0.1〜0.3重量％、B0.005〜0.02重量％及び
Ce0.001〜0.1重量％を含有させた合金を、真空
中で700〜900℃に加熱して、その表面に窒化ボ
ロンを析出させることを特徴とする高真空容器
用材料の製造方法。にある。
本発明において使用するオーステナイト系ステ
ンレス鋼の成分は、Ni6〜26％以下％は重量％を
表わす、Cr16〜26％、残部Feからなるものであ
る。Crが16％未満では硝酸のような酸化性酸に
侵され、Crが26％を超えると塩酸や硫酸などの
非酸化性酸に非常に侵され易くなる。またNiが
６％未満では非酸化性酸には耐えられなくなり、
26％を超えても耐酸化性は殆んど向上しない。従
つて、最も耐食性があり、かつ経済性の点から
Ni6〜26％、Crが16〜26％であることが必要であ
る。
なお、この成分中に不純物としてチタンが含ま
れていると、真空中での加熱によりチタン炭化物
が表面に析出して窒化ボロンの析出が困難となる
ので、チタンが含まれていてはいけない。
これらの鋼成分に添加するＮ、Ｂは表面に析出
する窒化ボロンの原料でありCeは均一に窒化ボ
ロンを析出させる作用をする。Ｎ、Ｂ及びCeの
添加量（重量％）は、それぞれ、0.1％〜0.3％、
0.005〜0.02％、0.001〜0.1％であることが必要で
ある。窒化ボロンが表面に析出するためには、ス
テンレス鋼内部に窒化ボロンが析出していなくて
はならない。ステンレス鋼内部に窒化ボロンが析
出する条件は、Ｎが0.1％以上、Ｂが0.005％以上
ステンレス鋼中に含まれることである。鋼中に通
常、不純物として含まれる硫黄は窒化ボロンの析
出を防害し、窒化ボロンを均一に析出し得なくす
る。硫黄をステンレス鋼中で不活性にするために
は、Ceの硫化物をステンレス鋼内部に析出させ
る必要がある。ステンレス鋼内部にCeの硫化物
が析出するためにはCeが0.001％以上ステンレス
鋼中に含まれなければならない。Ｎが0.3％、Ｂ
が0.02％、Ceが0.1％を越えると、加工性が悪く
なる。表面に窒化ボロンを析出させるには、
10-5Pa以下、好ましくは10-6Pa、10-7Paの真空中
で700〜900℃に加熱する。これにより合金内部か
ら表面に窒化ボロンが析出して皮膜が形成され
る。900℃を越えるとCeの硫化物は鋼中で分解
し、Ceの効果が失われ、硫黄が窒化ボロンの析
出を妨害する。
本発明の窒化ボロン皮膜により被覆された合金
を用いた真空容器は、窒化ボロンが気体の付着に
対して不活性なため、容器全体を気体を脱着させ
るために加熱する必要はなく、また短時間で超高
真空に達し得られる。
また、合金表面に窒化ボロン皮膜を形成させる
に際し、高価な蒸着装置を必要とせず、真空中で
の加熱により容易に得られ、しかも合金内部から
表面に窒化ボロン皮膜を析出させるため、複雑な
形状のもので、極めて均一に皮膜を形成し得られ
る。また、使用中に窒化ボロン皮膜が破損しても
外部からの加熱だけで再び該皮膜を析出させるこ
とによつて補修し得られる等、優れた効果を奏し
得られる。
実施例 １〜２
SUS304ステンレス鋼成分に、Ｎを0.17％、Ｂ
を0.008％、及びCeを0.004％添加した合金（以
下、SUS304―NBCe(1)合金と言う）、及び
SUS304ステンレス鋼に、Ｎを0.23％、Ｂを0.016
％、及びCeを0.083％添加した合金（以下、
SUS304―NBCe(2)合金と言う）、及びSUS304ス
テンレス鋼成分にＮを0.16％、Ｂを0.01％添加し
た合金（以下SUS304―NB合金と言う）を使用し
た。これらの合金の組成は表１の通りである。
これらの合金を真空中（10-6Pa）で700℃以上
に加熱したところ、両方の合金とも合金内部から
表面に窒化ボロンが析出し皮膜を形成した。しか
し、SUS304―NBの表面上に析出した窒化ボロン
皮膜は表２に示すように不均一であつたが、
SUS304―NBCe(1)、及びSUS304―NBCe(2)の表
面上に析出したそれは均一であつた。
The present invention relates to a material suitable for high vacuum containers, particularly ultrahigh vacuum containers, and a method for manufacturing the same. Conventionally, stainless steel has been commonly used as a material for vacuum containers. Gas easily adheres to the surface of stainless steel, and in order to create an ultra-high vacuum, it is necessary to heat the entire container to 150 to 200°C, in some cases up to approximately 500°C, and it is necessary to heat the entire container to a temperature of 150 to 200°C, and in some cases it is necessary to heat the entire container to about 500°C. The disadvantage was that it required a long time. Therefore, it is necessary to perform a surface treatment on the surface of the container material to make it inactive against gas adhesion. Boron nitride has the property of being inert to gas adhesion, but when attempting to coat it on a surface using the conventional chemical vapor deposition method, the material is
It has the disadvantage that it must be heated to a very high temperature of 1000 to 2000°C, and the operation is troublesome. The present invention does not have such drawbacks and can easily deposit a boron nitride film at a relatively low temperature.
An object of the present invention is to provide a material for a high vacuum container whose surface is inert to gas adhesion, and a method for producing the same. As a result of intensive research to achieve the above object, the present inventor found that the composition of austenitic stainless steel consisting of 6 to 26% by weight of Ni, 16 to 26% by weight of Cr, and the balance Fe,
N0.1~0.3wt%, B0.005~0.02wt% and
An alloy containing 0.001 to 0.1% by weight of Ce is prepared in a vacuum.
When heated to 700-900℃, boron nitride precipitates from inside the alloy to the surface, forming a uniform film.
It has been found that this makes the alloy surface inert to gas adhesion. The present invention was completed based on this knowledge. The gist of the present invention is that (3) an austenitic stainless steel component consisting of 6 to 26% by weight of Ni, 16 to 26% by weight of Cr, and the balance Fe;
N0.1~0.3wt%, B0.005~0.02wt% and
A material for high vacuum containers made of boron nitride deposited on the surface of an alloy containing 0.001 to 0.1% by weight of Ce. (2) Austenitic stainless steel composition consisting of 6 to 26% Ni, 16 to 26% Cr, and the balance Fe,
N0.1~0.3wt%, B0.005~0.02wt% and
A method for producing a material for a high vacuum container, which comprises heating an alloy containing 0.001 to 0.1% by weight of Ce to 700 to 900°C in vacuum to precipitate boron nitride on its surface. It is in. The composition of the austenitic stainless steel used in the present invention is 6 to 26% Ni, % represents weight %, 16 to 26% Cr, and the balance is Fe. If the Cr content is less than 16%, it will be attacked by oxidizing acids such as nitric acid, and if the Cr content exceeds 26%, it will be highly susceptible to non-oxidizing acids such as hydrochloric acid and sulfuric acid. Also, if Ni is less than 6%, it will not be able to withstand non-oxidizing acids,
Even if it exceeds 26%, oxidation resistance hardly improves. Therefore, it is the most corrosion resistant and economical
It is necessary that Ni be 6 to 26% and Cr be 16 to 26%. Note that if this component contains titanium as an impurity, titanium carbide will precipitate on the surface by heating in vacuum, making it difficult to precipitate boron nitride, so titanium must not be included. N and B added to these steel components are raw materials for boron nitride that precipitates on the surface, and Ce acts to uniformly precipitate boron nitride. The amount of N, B, and Ce added (weight%) is 0.1% to 0.3%, respectively.
It is necessary to be 0.005-0.02%, 0.001-0.1%. In order for boron nitride to precipitate on the surface, boron nitride must be precipitated inside the stainless steel. The conditions for boron nitride to precipitate inside the stainless steel are that the stainless steel contains 0.1% or more of N and 0.005% or more of B. Sulfur, which is normally contained as an impurity in steel, prevents the precipitation of boron nitride and makes it impossible to uniformly precipitate boron nitride. In order to make sulfur inert in stainless steel, it is necessary to precipitate Ce sulfide inside the stainless steel. In order for Ce sulfide to precipitate inside stainless steel, Ce must be contained in the stainless steel at 0.001% or more. N is 0.3%, B
When Ce exceeds 0.02% and 0.1%, workability deteriorates. To deposit boron nitride on the surface,
It is heated to 700 to 900°C in a vacuum of 10 -5 Pa or less, preferably 10 -6 Pa or 10 -7 Pa. As a result, boron nitride is deposited from the inside of the alloy onto the surface to form a film. When the temperature exceeds 900℃, Ce sulfide decomposes in the steel, the effect of Ce is lost, and sulfur interferes with the precipitation of boron nitride. In a vacuum container using an alloy coated with the boron nitride film of the present invention, since boron nitride is inert to gas adhesion, there is no need to heat the entire container to desorb gas, and there is no need to heat the entire container for a short time. can reach ultra-high vacuum. In addition, when forming a boron nitride film on the alloy surface, there is no need for expensive vapor deposition equipment, and it can be easily obtained by heating in a vacuum.Moreover, since the boron nitride film is deposited from the inside of the alloy onto the surface, complex shapes can be formed. It is possible to form an extremely uniform film. In addition, even if the boron nitride film is damaged during use, it can be repaired by depositing the film again simply by applying external heat, providing excellent effects. Examples 1-2 SUS304 stainless steel ingredients, 0.17% N, B
An alloy containing 0.008% of Ce and 0.004% of Ce (hereinafter referred to as SUS304-NBCe(1) alloy), and
SUS304 stainless steel, 0.23% N, 0.016 B
%, and an alloy with 0.083% Ce added (hereinafter referred to as
SUS304-NBCe(2) alloy) and an alloy containing SUS304 stainless steel with 0.16% N and 0.01% B added (hereinafter referred to as SUS304-NB alloy) were used. The compositions of these alloys are shown in Table 1. When these alloys were heated to over 700°C in a vacuum (10 -6 Pa), boron nitride precipitated from inside the alloy to the surface of both alloys, forming a film. However, the boron nitride film deposited on the surface of SUS304-NB was non-uniform as shown in Table 2;
The deposits on the surfaces of SUS304-NBCe (1) and SUS304-NBCe (2) were uniform.
【表】
これらの表面に窒化ボロンを析出させた合金及
びSUS304の各々に空気を触れさせた後、表面に
付着した気体の量を測定した結果は表２に示す通
りであつた。[Table] Table 2 shows the results of measuring the amount of gas adhering to the surfaces of the alloy and SUS304 on which boron nitride was precipitated after exposing them to air.
Claims (1)
らなるオーステナイト系ステンレス鋼成分に、
N0.1〜0.3重量％、B0.005〜0.02重量％及び
Ce0.001〜0.1重量％を含有させた合金の表面に窒
化ボロンを加熱析出させたものからなる高真空容
器用材料。 ２ Ni6〜26重量％、Cr16〜26重量％、残部Feか
らなるオーステナイト系ステンレス鋼成分に、
N0.1〜0.3重量％、B0.005〜0.02重量％及び
Ce0.001〜0.1重量％を含有させた合金を、真空中
で700〜900℃に加熱して、その表面に窒化ボロン
を析出させることを特徴とする高真空容器用材料
の製造方法。[Claims] 1. An austenitic stainless steel component consisting of 6 to 26% by weight of Ni, 16 to 26% by weight of Cr, and the balance Fe,
N0.1~0.3wt%, B0.005~0.02wt% and
A material for high vacuum containers made of boron nitride deposited on the surface of an alloy containing 0.001 to 0.1% by weight of Ce. 2 Austenitic stainless steel composition consisting of 6 to 26% Ni, 16 to 26% Cr, and the balance Fe,
N0.1~0.3wt%, B0.005~0.02wt% and
A method for producing a material for a high vacuum container, which comprises heating an alloy containing 0.001 to 0.1% by weight of Ce to 700 to 900°C in vacuum to precipitate boron nitride on its surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14441983A JPS6036648A (en) | 1983-08-09 | 1983-08-09 | Material for high vacuum vessel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14441983A JPS6036648A (en) | 1983-08-09 | 1983-08-09 | Material for high vacuum vessel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6036648A JPS6036648A (en) | 1985-02-25 |
| JPS6239234B2 true JPS6239234B2 (en) | 1987-08-21 |
Family
ID=15361734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14441983A Granted JPS6036648A (en) | 1983-08-09 | 1983-08-09 | Material for high vacuum vessel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6036648A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994029492A1 (en) * | 1993-06-15 | 1994-12-22 | Tadahiro Ohmi | Member or part of superhigh-purity gas supply system |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711063B2 (en) * | 1986-12-16 | 1995-02-08 | 日本鋼管株式会社 | Manufacturing method of austenitic stainless steel |
| US5192409A (en) * | 1990-03-09 | 1993-03-09 | National Research Institute For Metals | Method of sputtering a mixture of hexagonal boron nitride and stainless steel onto a steel vessel and heating the film so as to precipitate the boron nitride onto the film surface |
| US5478524A (en) * | 1992-08-24 | 1995-12-26 | Nissan Motor Co., Ltd. | Super high vacuum vessel |
-
1983
- 1983-08-09 JP JP14441983A patent/JPS6036648A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994029492A1 (en) * | 1993-06-15 | 1994-12-22 | Tadahiro Ohmi | Member or part of superhigh-purity gas supply system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6036648A (en) | 1985-02-25 |
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