JPH0468385B2 - - Google Patents
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- Publication number
- JPH0468385B2 JPH0468385B2 JP60045899A JP4589985A JPH0468385B2 JP H0468385 B2 JPH0468385 B2 JP H0468385B2 JP 60045899 A JP60045899 A JP 60045899A JP 4589985 A JP4589985 A JP 4589985A JP H0468385 B2 JPH0468385 B2 JP H0468385B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- treated
- article
- sputtering
- tin
- 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 - Lifetime
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- Physical Vapour Deposition (AREA)
Description
（産業上の利用分野）
本発明は、TiN被覆ステンレス鋼の製法、特
にTiNを被処理物品表面に生成させた反応性ス
パツタ法によるTiN被覆ステンレス鋼物品の製
法に関する。
（従来の技術）
機能性材料としてのセラミツクスのコーテイン
グ膜はそのすぐれた特性から今後とも多くの分野
で多くの用途が期待されている。しかし、セラミ
ツクスのコーテイングといつてもその種類は実に
多くそれぞれれについて特性が異なるように、そ
の製法も区々であつてそれぞれ特有の方法で製造
されているのが現状である。
例えば、TiNコーテイング膜は、耐摩耗性お
よび耐食性材料として、あるいは黄金色を呈する
材料としてそのすぐれた特性から、今日、核融合
炉の材料としての用途ばかりでなく、その他広範
囲の用途開発に多くの努力がなされているところ
であるが、そのTiNのコーテイング法は通常コ
ーテイングすべきTi，Ｎをもとに外部源から供
給しながら被処理物品をスパツタ処理するのであ
つて、例えば従来の反応性スパツタ法によれば、
N2含有雰囲気中でTiをターゲツト材料としてス
パツタ処理を行つている。
（発明が解決すべき問題点）
このように、反応性スパツタ法によりTiNコ
ーテイング膜を生成させる従来法にあつては、
Tiターゲツト材を使用するとともにN2を雰囲気
から供給するため、特に雰囲気調整が難しく、ス
パツタ処理時にも絶えず雰囲気中のN2含有量を
一定範囲に調整しなければならないなど、操作上
の問題も多かつた。
よつて、本発明が本質的に目的とするのは、上
述のように外部からＮを供給する必要のない
TiNセラミツクコーテイング被膜形成法、特に
雰囲気調整を容易なものとした、処理操作の簡便
な反応性スパツタ法によるTiNセラミツクコー
テイング被膜形成法を提供することである。
さらに、本発明の別の具体的目的は、反応性ス
パツタ法によるTiN被覆、特にTiN被覆を備え
たステンレス鋼物品の製法を提供することであ
る。
（問題点を解決するための手段）
本発明者は反応性スパツタ法によるTiNセラ
ミツクコーテイング法について種々研究を続けて
いたところステンレス鋼を処理する場合には、雰
囲気からのN2の供給は必要ではなく、むしろ鋼
中のＮとTiスパツタ処理による析出Tiとを利用
することにより、すぐれた特性の表面層が形成さ
れることを見い出して本発明を完成した。
よつて、本発明の要旨とするところは、広義に
は、内部Ｎ源を利用した金属窒化物被覆ステンレ
ス鋼の製法であり、より特定的には、被処理物品
をステンレス鋼から構成するとともに窒素源とし
て該ステンレス鋼中の窒素を利用すべく前記被処
理物品をTiコーテイング処理し、次いで加熱処
理してステンレス鋼中のＮとコーテイング処理し
たTiとを反応せしめ、被処理物品表面にTiNセ
ラミツクコーテイング層を形成することを特徴と
する、TiNセラミツクコーテイング被覆ステン
レス鋼物品の製法である。Tiに代えて、Nb，Ta
等を用いた場合それぞれに対応する金属窒化物被
覆が得られる。
また、本発明は、その１つの態様にあつては、
被処理物品をステンレス鋼から構成するとともに
窒素源として該ステンレス鋼中の窒素を利用すべ
く実質上窒素を含まない雰囲気下で前記被処理物
品をTiスパツタ処理し、次いで加熱処理するこ
とを特徴とする、反応性スパツタ法によるTiN
被覆ステンレス鋼物品の製法である。
なお、「Tuコーテイング処理」とはスパツタ
法、化学めつき、真空蒸着法などの適宜手段で被
処理物品表面にTiを被覆する処理方法であつて、
後続の加熱処理によりTiが被処理物品表面に拡
散し得るTi含有被膜を設ける処理一般を包含す
る。また、「Tiスパツタ処理」とは、Tiをスパツ
タさせて被処理物品表面に析出させるスパツタ処
理方法であつて、ターゲツト材料としてTiを利
用し、これに加速イオンを衝突させてスパツタを
発生させ、これを陰極近傍に置いた被処理物品表
面上に析出させる処理法である。
ここに、被処理物品を構成するステンレス鋼は
Ｎ含有量が0.05％以上、好ましくは0.20％以上含
有するものであつて、一般にはオーステナイト系
ステンレス鋼である。
本発明において、スパツタ法でTiコーテイン
グ処理を行う場合、従来のスパツタ法と異なり、
Tiのみが被処理物品表面にスパツタ処理で蒸着
されるだけであるため、その後、雰囲気からの影
響のないArなどの不活性ガス雰囲気、または真
空下で適宜温度で加熱処理し、表面に蒸着した
Tiを内部に拡散させるとともに、同時に、鋼中
のＮをその表面部分に拡散させ、両者を化合させ
て該表面部分にTiNを形成させる必要がある。
好適態様にあつて、かかる加熱処理は900〜1100
℃で３分間ないし１時間行われる。加熱温度が
1100℃を超えると母材であるステンレス鋼の機械
的特性の劣化が生じることがあり注意を要す。
（作用）
添付図面により本発明をさらに説明すると、第
１図は反応性高周波スパツタ装置１０の概略説明
図である。
図中、Ti板のターゲツト１１を上部に、被処
理物品であるステンレス鋼の基板金属１２を下部
に設置し、全体を真空容器１３内に収容し、外部
電源１４からの高周波電界により、図示例では
Ar供給源１５から上記真空容器１３内に供給さ
れるアルゴンイオンを用いてTiをスパツタさせ、
金属基板上にTiを析出させる。図中、符号１６，
１７，１８および１９はそれぞれコンデンサ、磁
石、真空計およびシヤツターである。高純度コー
テイング膜を作るためには基板材料にほぼ−
500V程度の負のバイアス電圧を印加する必要が
ある。また、ターゲツト材料のTi表面は、不純
物除去のためには約10分間程度前処理としてスパ
ツタ清浄化処理を行つてもよい。
一般に、第１図に示すような装置では真空度は
１×10-7〜３×10-7トール、印加電圧は2KVであ
る。このときのTi析出速度はほぼ200Å／minで
ある。
このようにして得られたTi被膜は、次いで、
図示しない真空炉などで所定温度に加熱し、Ｎお
よびTiの拡散処理を行い、TiNセラミツクコー
テング被膜を生成させる。
次に本発明を実施例に関連させてさらに説明す
る。
実施例
第１表に鋼組成を示すオーステナイト系ステン
レス鋼を表面清浄化したのち第１図に示す装置を
使い、実質上N2を含有しないArガス雰囲気中で
反応性スパツタ処理した。このときの処理条件は
次の通りであつた。
アルゴンガス圧力 ：４×10-2Torr
全圧力 ：４×10-2Torr
バイアス電圧 ：−200V
放電時の電圧、電流：2KV、0.22A
生成膜厚 ：1000Å
次いで、かくして得られたTiスパツタ処理済
のステンレス鋼を加熱処理した。このとき加熱温
度および加熱時間を次のようにそれぞれ変えてそ
のときの鋼中窒素の拡散挙動をスパツタエツチン
グ法により調べた。
加熱温度： 600〜1000℃
加熱時間： 15〜60分間
(Field of Industrial Application) The present invention relates to a method for manufacturing TiN-coated stainless steel, and particularly to a method for manufacturing TiN-coated stainless steel articles by a reactive sputtering method in which TiN is generated on the surface of the article to be treated. (Prior Art) Ceramic coating films as functional materials are expected to be used in many fields in the future due to their excellent properties. However, just as there are many types of ceramic coatings, each with different characteristics, the current state of affairs is that their manufacturing methods also vary, and each is manufactured using its own unique method. For example, TiN coating film is currently being used not only as a material for nuclear fusion reactors but also for the development of a wide range of other applications due to its excellent properties as a wear-resistant and corrosion-resistant material and as a material exhibiting a golden color. Efforts are being made to coat the TiN, but the TiN coating method usually sputters the article while supplying the Ti and N to be coated from an external source, such as the conventional reactive sputtering method. According to
Sputtering is performed using Ti as a target material in an N2 - containing atmosphere. (Problems to be solved by the invention) As described above, in the conventional method of producing a TiN coating film by the reactive sputtering method,
Because Ti target material is used and N 2 is supplied from the atmosphere, it is particularly difficult to adjust the atmosphere, and there are operational problems such as the need to constantly adjust the N 2 content in the atmosphere to a certain range during sputtering processing. It was a lot. Therefore, the essential objective of the present invention is to eliminate the need to supply N from the outside as described above.
It is an object of the present invention to provide a method for forming a TiN ceramic coating film, particularly a method for forming a TiN ceramic coating film using a reactive sputtering method that facilitates atmosphere adjustment and has simple processing operations. Furthermore, another specific object of the present invention is to provide a method for producing a TiN coating, in particular a stainless steel article provided with a TiN coating, by reactive sputtering. (Means for Solving the Problems) The inventor of the present invention has been conducting various research on TiN ceramic coating method using reactive sputtering method, and found that it is not necessary to supply N2 from the atmosphere when treating stainless steel. Rather, the present invention was completed based on the discovery that a surface layer with excellent properties could be formed by utilizing N in the steel and Ti precipitated by Ti sputtering treatment. Therefore, the gist of the present invention, in a broad sense, is a method for producing metal nitride-coated stainless steel using an internal N source, and more specifically, the gist of the present invention is a method for producing metal nitride-coated stainless steel using an internal N source. The article to be treated is coated with Ti to utilize the nitrogen in the stainless steel as a source, and then heat treated to cause the N in the stainless steel to react with the coated Ti to form a TiN ceramic coating on the surface of the article to be treated. A method for producing a stainless steel article coated with a TiN ceramic coating, characterized by forming a layer. Instead of Ti, Nb, Ta
etc., corresponding metal nitride coatings are obtained. Further, in one aspect of the present invention,
The article to be treated is made of stainless steel, and the article to be treated is subjected to a Ti sputtering treatment in an atmosphere substantially free of nitrogen in order to utilize the nitrogen in the stainless steel as a nitrogen source, and then subjected to a heat treatment. TiN by reactive sputtering method
A method for manufacturing coated stainless steel articles. Note that "Tu coating treatment" is a treatment method in which the surface of the article to be treated is coated with Ti using an appropriate method such as sputtering, chemical plating, or vacuum evaporation.
It includes a general process in which a Ti-containing film is provided in which Ti can be diffused onto the surface of an article to be treated by a subsequent heat treatment. In addition, "Ti sputtering treatment" is a sputtering treatment method in which Ti is spattered and deposited on the surface of the object to be treated.Ti is used as a target material, and accelerated ions are collided with it to generate spatter. This is a treatment method in which this is deposited on the surface of an article to be treated placed near the cathode. The stainless steel constituting the article to be treated has an N content of 0.05% or more, preferably 0.20% or more, and is generally an austenitic stainless steel. In the present invention, when performing Ti coating treatment using the sputtering method, unlike the conventional sputtering method,
Since only Ti is deposited on the surface of the object to be treated by sputtering, it is then heat-treated at an appropriate temperature in an inert gas atmosphere such as Ar, which is not affected by the atmosphere, or under vacuum, and then deposited on the surface.
It is necessary to diffuse Ti into the interior and, at the same time, to diffuse N in the steel to the surface portion of the steel, and to combine the two to form TiN on the surface portion.
In a preferred embodiment, such heat treatment is performed at a temperature of 900 to 1100
C. for 3 minutes to 1 hour. heating temperature
If the temperature exceeds 1100℃, the mechanical properties of the base material stainless steel may deteriorate, so care must be taken. (Operation) To further explain the present invention with reference to the accompanying drawings, FIG. 1 is a schematic explanatory diagram of a reactive high frequency sputtering device 10. In the figure, a target 11 made of a Ti plate is placed at the top, a substrate metal 12 made of stainless steel, which is an article to be processed, is placed at the bottom, and the entire body is housed in a vacuum container 13. Well then
sputtering Ti using argon ions supplied into the vacuum container 13 from the Ar supply source 15;
Deposit Ti on a metal substrate. In the figure, numerals 16,
17, 18 and 19 are a capacitor, a magnet, a vacuum gauge and a shutter, respectively. In order to make a high-purity coating film, the substrate material must be approximately -
It is necessary to apply a negative bias voltage of about 500V. Further, the Ti surface of the target material may be subjected to spatter cleaning treatment as a pretreatment for about 10 minutes to remove impurities. Generally, in the apparatus shown in FIG. 1, the degree of vacuum is 1.times.10.sup. -7 to 3.times.10.sup. -7 Torr, and the applied voltage is 2 KV. The Ti precipitation rate at this time is approximately 200 Å/min. The Ti coating thus obtained is then
It is heated to a predetermined temperature in a vacuum furnace (not shown), and N and Ti are diffused to form a TiN ceramic coating. Next, the present invention will be further explained in connection with examples. Example After surface cleaning of austenitic stainless steel whose steel composition is shown in Table 1, it was subjected to reactive sputtering treatment in an Ar gas atmosphere substantially free of N 2 using the apparatus shown in FIG. The processing conditions at this time were as follows. Argon gas pressure: 4×10 -2 Torr Total pressure: 4×10 -2 Torr Bias voltage: -200V Voltage and current during discharge: 2KV, 0.22A Thickness of film produced: 1000Å Next, the Ti spatter treated thus obtained heat treated stainless steel. At this time, the heating temperature and heating time were changed as follows, and the diffusion behavior of nitrogen in the steel was investigated using the sputter etching method. Heating temperature: 600~1000℃ Heating time: 15~60 minutes
【表】
第２図は、第１表の鋼番号１のものについて
Tiスパツタ処理後、真空下で1000℃で30分間加
熱処理したときのセラミツクコーテイング被膜の
スパツタエツチング法による元素分析例である。
特に最表面部にTiN被膜が形成されているのが
分かる。色調は金色であつた。
第３図ａは鋼番号２の試料についての加熱処理
を始める前のTiスパツタ処理ままの元素分析例
であり、第３図ｂは1000℃、15分間加熱処理した
ときの元素分析例である。
第３図ａからは、被処理物品表面はほとんどス
パツタされたTiにより覆われているのが分かる。
Ｎは表面部にはほとんど検出されない。なお、図
中、横軸は時間（分）がとつてあるが、これはス
パツタエツチング法により元素分析を行つている
ためであり、表面からの深さと比例関係にあり、
ほぼ100分間が1500Åに相当する。
第３図ｂになると鋼中のN2の表面部への拡散
そしてTiの内部への拡散がすすみ、表面被膜層
は第２図の場合と同様に実質上TiNから構成さ
れているのが分かる。第２図に示したＮ含有量の
少ない鋼番号１のものに比較し、極めて短時間で
TiNが表面形成されたことを示している。しか
も、このとき被処理物品表面は金色を呈してい
た。装飾的用途にも十分適用できるほど鮮明な色
調が得られた。
以上においては、反応性スパツタ法を利用した
場合について述べたが、この他、化学的な方法や
真空蒸着法等によりTiを表面にコーテイングし、
その後の加熱処理により、ステンレス鋼内部から
の拡散N2により表面にTiNを形成させることも
可能である。
また、Tiに限らずＮと結合性を有するNb，Zr
あるいは他の金属をコーテイング源として、上述
の方法により、該金属の窒化物コーテイングを形
成することも可能であり、本発明の応用対象、利
用分野は極めて広く工業的な価値は極めて大と云
える。[Table] Figure 2 is for steel number 1 in Table 1.
This is an example of elemental analysis by sputter etching of a ceramic coating film that was heat treated at 1000°C for 30 minutes under vacuum after Ti sputter treatment.
In particular, it can be seen that a TiN film is formed on the outermost surface. The color was golden. FIG. 3a is an example of elemental analysis of a sample of steel No. 2 as it was treated with Ti sputtering before heat treatment was started, and FIG. 3b is an example of elemental analysis after heat treatment at 1000° C. for 15 minutes. From FIG. 3a, it can be seen that the surface of the article to be treated is almost entirely covered with sputtered Ti.
Almost no N is detected on the surface. In the figure, time (minutes) is plotted on the horizontal axis, but this is because the elemental analysis is performed using the sputter etching method, which is proportional to the depth from the surface.
Approximately 100 minutes corresponds to 1500 Å. In Figure 3b, it can be seen that the diffusion of N 2 to the surface and Ti in the steel progresses, and the surface coating layer is essentially composed of TiN, as in the case of Figure 2. . Compared to steel No. 1 with low N content shown in Figure 2, it takes a very short time to
This shows that TiN was formed on the surface. Moreover, at this time, the surface of the article to be treated had a golden color. The color tone was sufficiently vivid to be applicable for decorative purposes. In the above, we have described the case where the reactive sputtering method is used, but in addition to this, Ti can be coated on the surface by chemical methods, vacuum evaporation methods, etc.
Through subsequent heat treatment, it is also possible to form TiN on the surface due to N2 diffusion from inside the stainless steel. In addition to Ti, Nb, Zr, which has bonding properties with N,
Alternatively, it is also possible to form a nitride coating of another metal by the above-described method using another metal as the coating source, and the present invention can be applied to a wide range of fields and has extremely large industrial value. .
第１図は、本発明に係る反応性スパツタ処理を
行うための装置の模式図；第２図は、通常のステ
ンレス鋼を本発明によりTiスパツタ処理してか
ら1000℃で30分間加熱したときの被覆層の元素分
析例を示すグラフ；および第３図ａおよび第３図
ｂは、Ｎ含有量を高めたステンレス鋼のそれぞれ
Tiスパツタ処理直後の、および1000℃で15分間
の加熱処理を経たときの元素分析例を示すグラフ
である。
１０：反応性高周波スパツタ装置、１１：ター
ゲツト、１２：基板金属、１３：真空容器、１
４：外部電源、１５：Ar供給源。
Figure 1 is a schematic diagram of an apparatus for performing reactive sputtering treatment according to the present invention; Figure 2 is a schematic diagram of an apparatus for performing reactive sputtering treatment according to the present invention; Figure 2 is a diagram showing the results of ordinary stainless steel treated with Ti sputtering according to the present invention and then heated at 1000°C for 30 minutes. Graphs showing examples of elemental analysis of coating layers; and Figures 3a and 3b are graphs showing examples of elemental analysis of coating layers, respectively, of stainless steel with increased N content.
2 is a graph showing an example of elemental analysis immediately after Ti sputtering treatment and after heat treatment at 1000° C. for 15 minutes. 10: Reactive high frequency sputtering device, 11: Target, 12: Substrate metal, 13: Vacuum vessel, 1
4: External power supply, 15: Ar supply source.
Claims (1)
もに窒素源として該ステンレス鋼中の窒素を利用
すべく前記被処理物品をTiコーテイング処理し、
次いで加熱処理してステンレス鋼中のＮとコーテ
イング処理したTiとを反応せしめ、被処理物品
表面にTiNセラミツクコーテイング層を形成す
ることを特徴とする、TiNセラミツクコーテイ
ング被覆ステンレス鋼物品の製法。 ２ 被処理物品を構成するステンレス鋼がオース
テナイト系ステンレス鋼であつて、反応性スパツ
タ法により実質上窒素を含まない雰囲気下で前記
被処理物品をTiスパツタ処理し、次いでTiスパ
ツタ処理後900〜1100℃の温度で３分間〜１時間
加熱処理する、特許請求の範囲第１項記載の方
法。 ３ 被処理物品を構成する前記ステンレス鋼のＮ
含有量が0.05％以上である、特許請求の範囲第１
項または第２項記載の方法。[Claims] 1. The article to be treated is made of stainless steel, and the article to be treated is subjected to a Ti coating treatment in order to utilize nitrogen in the stainless steel as a nitrogen source,
A method for producing a stainless steel article coated with a TiN ceramic coating, the method comprising: then heating the stainless steel to cause N in the stainless steel to react with the coated Ti to form a TiN ceramic coating layer on the surface of the article. 2. The stainless steel constituting the article to be treated is an austenitic stainless steel, and the article to be treated is treated with Ti sputtering in an atmosphere substantially free of nitrogen by a reactive sputtering method, and then after the Ti sputtering treatment, a temperature of 900 to 1100 The method according to claim 1, wherein the heat treatment is performed at a temperature of 3 minutes to 1 hour. 3 N of the stainless steel constituting the article to be treated
Claim 1, in which the content is 0.05% or more
or the method described in paragraph 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4589985A JPS61204367A (en) | 1985-03-08 | 1985-03-08 | Production of tin coated stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4589985A JPS61204367A (en) | 1985-03-08 | 1985-03-08 | Production of tin coated stainless steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61204367A JPS61204367A (en) | 1986-09-10 |
| JPH0468385B2 true JPH0468385B2 (en) | 1992-11-02 |
Family
ID=12732088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4589985A Granted JPS61204367A (en) | 1985-03-08 | 1985-03-08 | Production of tin coated stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61204367A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2762619B1 (en) * | 1997-04-24 | 1999-07-02 | Univ Nantes | PROCESS FOR FORMING A NITRIDE LAYER, PARTICULARLY A BORON NITRIDE, ON THE SURFACE OF A SUBSTRATE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5613510A (en) * | 1979-07-16 | 1981-02-09 | Tdk Corp | Magnetic head and its manufacture |
-
1985
- 1985-03-08 JP JP4589985A patent/JPS61204367A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61204367A (en) | 1986-09-10 |
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