JP2669928B2 - Underlayer plasma spray coating - Google Patents
Underlayer plasma spray coatingInfo
- Publication number
- JP2669928B2 JP2669928B2 JP2250979A JP25097990A JP2669928B2 JP 2669928 B2 JP2669928 B2 JP 2669928B2 JP 2250979 A JP2250979 A JP 2250979A JP 25097990 A JP25097990 A JP 25097990A JP 2669928 B2 JP2669928 B2 JP 2669928B2
- Authority
- JP
- Japan
- Prior art keywords
- underlayer
- plasma sprayed
- plasma
- sprayed film
- film
- 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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- Coating By Spraying Or Casting (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明はセラミックスプラズマ溶射膜の下地溶射膜
に係り、特に高温かつ弱酸化性の雰囲気で使用される信
頼性に優れるプラズマ溶射膜に関する。Description: TECHNICAL FIELD The present invention relates to a base sprayed film of a ceramics plasma sprayed film, and more particularly to a plasma sprayed film which is used in a high temperature and weakly oxidizing atmosphere and has excellent reliability.
従来、ジェットタービン等のブレードの耐酸化，耐食
性向上のため、ジルコニア等のセラミックスを保護膜と
して、溶射等の方法で被覆することは広く行われてい
る。また、その場合、基板金属との密着性確保のため、
Ni−CrもしくはNi−Cr−Al−Ｙ合金の下地用プラズマ溶
射膜を施すこともよく行われる。Conventionally, in order to improve oxidation resistance and corrosion resistance of a blade of a jet turbine or the like, coating with a method such as thermal spraying using ceramics such as zirconia as a protective film has been widely performed. Also, in that case, in order to ensure adhesion with the substrate metal,
A Ni-Cr or Ni-Cr-Al-Y alloy underlayer plasma spray coating is often applied.
このような用途のひとつとしては、例えば、ヘリウム
ガスを冷却材、黒鉛を減速材として用いる原子炉である
高温ガス炉における、各種構造金属材料と黒鉛の相互反
応を抑制する手段とての用途がある。特に、炉内温度計
測用シース型熱電対の保護コーティングとして、ジルコ
ニアプラズマ溶射膜の適用が有用である。As one of such applications, for example, in a high temperature gas reactor which is a nuclear reactor using helium gas as a coolant and graphite as a moderator, there is an application as a means for suppressing interaction between various structural metal materials and graphite. is there. In particular, it is useful to apply a zirconia plasma sprayed film as a protective coating for the sheath type thermocouple for measuring the temperature inside the furnace.
上記高温ガス炉内のように環境が不活性ガスのヘリウ
ムである場合には、酸化性が弱いので下地金属としてNi
−Cr−Al−Ｙ系合金が用いられる。Ni−Cr−Al−Ｙ系合
金は、弱酸化性の雰囲気においてAl系の緻密な酸化膜を
形成し下地用プラズマ溶射膜の強度が低下せず、ジルコ
ニア保護膜の密着性は一般に良好である。When the environment is helium, which is an inert gas, such as in the high temperature gas furnace, Ni is used as the base metal because the oxidizing property is weak.
A -Cr-Al-Y-based alloy is used. Ni-Cr-Al-Y-based alloys form a dense Al-based oxide film in a weakly oxidizing atmosphere, the strength of the underlying plasma sprayed film does not decrease, and the adhesion of the zirconia protective film is generally good. .
しかしながらこのようなプラズマ溶射膜においては、
劣化がおこり、ジルコニア保護膜の密着性が失われる場
合があることがわかった。However, in such a plasma spray coating,
It has been found that deterioration may occur and the adhesion of the zirconia protective film may be lost.
例えば、加工金属にナイクロシル（Nibal（バラン
ス）,Cr14％,Si1.4％），下地用プラズマ溶射膜にNi−C
r−Al−Ｙ合金（Niバランス,Cr22％,Al10％,Y1.4％）を
用いてジルコニア保護膜を形成し、純ヘリウムガス中に
おいて1200℃の温度で3000h放置すると、ジルコニア保
護膜が剥離する。For example, Nicrosil (Nibal (balance), Cr14%, Si1.4%) for processed metal, Ni-C for underlayer plasma spray coating.
When a zirconia protective film is formed using r-Al-Y alloy (Ni balance, Cr22%, Al10%, Y1.4%), and left in pure helium gas at a temperature of 1200 ° C for 3000 hours, the zirconia protective film peels off. To do.
この発明は上述の点に鑑みてなされ、その目的は、Ni
−Cr−Al−Ｙ系合金の組成を調整することにより、セラ
ミックス保護膜の密着性に優れる下地用のプラズマ溶射
膜を提供することにある。The present invention has been made in view of the above points, and an object thereof is Ni
An object of the present invention is to provide a plasma sprayed film for an underlayer having excellent adhesion to a ceramic protective film by adjusting the composition of a —Cr—Al—Y-based alloy.
本発明者は下地用プラズマ溶射膜劣化の理由について
鋭意研究を重ねた結果、下地用プラズマ溶射膜中にボイ
ドが発生していること、そしてこのボイドが成長するに
つれジルコニア保護膜が加工金属から剥離していくこと
を見出し、このボイド発生のメカニズムを推定するに至
った。As a result of intensive studies on the reason for the deterioration of the plasma sprayed film for the underlayer, the present inventor has found that a void is generated in the plasma sprayed film for the underlayer, and the zirconia protective film is peeled from the processed metal as the void grows. We have found that we are going to do so, and have come to presume the mechanism of this void generation.
上述の目的はこの発明によれば、ナイクロシル（Niバ
ランス,Cr14％,Si1.4％）からなる加工金属にセラミッ
クスをプラズマ溶射する際に、予め加工金属に形成され
るNi−Cr−Alベース合金からなる下地用プラズマ溶射膜
であって、そのCr含有量が15％以下であるものとするこ
とにより達成される。According to the present invention, the above-mentioned object is a Ni-Cr-Al base alloy which is preliminarily formed on the processed metal when plasma-spraying ceramics onto the processed metal made of nicrosil (Ni balance, Cr 14%, Si 1.4%). And a Cr plasma content of 15% or less.
第６図は従来のNi−Cr−Al−Ｙ合金系下地用プラズマ
溶射膜２内に発生成長したボイド４を示す模式断面図で
ある。これは、加工金属としてナイクロシル（Niバラン
ス,Cr14％,Si1.4％），下地用プラズマ溶射膜としてNi
−Cr−Al−Ｙ合金（Niバランス,Cr22％,Al10％,Y1.4
％），保護膜としてジルコニアを用いて大気圧プラズマ
溶射を行い、純ヘリウムガス中において1200℃の温度で
3000h放置して得られた。ボイドは初めナイクロシルと
下地溶射膜の境界付近に発生し、次第に成長する。FIG. 6 is a schematic cross-sectional view showing a void 4 generated and grown in a conventional Ni-Cr-Al-Y alloy-based underlayer plasma spray coating 2. This is Nicrosil (Ni balance, Cr14%, Si1.4%) as the processing metal, and Ni as the plasma spray coating for the underlayer.
-Cr-Al-Y alloy (Ni balance, Cr22%, Al10%, Y1.4
%), Atmospheric pressure plasma spraying was performed using zirconia as the protective film, and the temperature was 1200 ° C in pure helium gas.
It was obtained by leaving it for 3000 hours. Voids initially appear near the boundary between nicrosil and the thermal spray coating, and gradually grow.
第２図は第６図の試験と同様な条件下におけるボイド
寸法の時間依存性を示す線図である。時間とともにボイ
ド寸法は増大する。FIG. 2 is a diagram showing the time dependence of void size under the same conditions as the test of FIG. The void size increases with time.
第３図は第６図の試験と同様な条件下で時間500hにお
けるボイド寸法の温度依存性を示す線図である。1000℃
でのボイドの成長足度は1200℃における成長速度の約1/
3である。1000℃で１年間使用するとボイドの大きさ
は、約40μｍに成長する。FIG. 3 is a diagram showing the temperature dependence of the void size at a time of 500 hours under the same conditions as in the test of FIG. 1000 ° C
The growth rate of voids at about 1/100 of the growth rate at 1200 ℃
Is 3. When used at 1000 ° C for 1 year, the size of void grows to about 40 μm.
第４図は第６図の試験と同様な条件下における下地用
プラズマ溶射膜の初期状態を示す断面図である。酸化ア
ルミニウム（内部酸化物）の粒子５が生成していること
がわかる。これは溶射施工に起因するものである。酸化
アルミニウムはこれに伴って５〜10μｍのミクロな間隙
を生じさせる。FIG. 4 is a sectional view showing an initial state of the underlayer plasma sprayed film under the same conditions as in the test of FIG. It can be seen that particles 5 of aluminum oxide (internal oxide) are generated. This is due to thermal spraying construction. Aluminum oxide causes microscopic gaps of 5 to 10 μm along with this.
第５図はCrの濃度分布につき加熱試験前（特性線51）
と加熱試験後（特性線52）の分布を対比して示す線図で
ある。加熱によりCrが下地用プラズマ溶射膜より加工金
属へ拡散していることがわかる。Fig. 5 shows the Cr concentration distribution before the heating test (characteristic line 51).
FIG. 5 is a diagram showing the distribution after the heating test (characteristic line 52) in contrast. It can be seen that Cr is diffused into the processed metal from the plasma sprayed film for the undercoat by heating.
さらに図示しないがボイドの内壁は酸化アルミニウム
膜であり、加熱後においてはボイドの内壁以外ではAlは
殆ど存在しないことがわかった。Further, although not shown, the inner wall of the void was an aluminum oxide film, and it was found that Al hardly existed after heating except the inner wall of the void.
これらの事実はボイドが次に述べるようなメカニズム
によって発生し、成長していくものであることを示して
いる。即ちNi−Cr−Al−Ｙからなる下地用プラズマ溶射
膜には溶射施工時のアルミナ系内部酸化物に起因してミ
クロな間鋤が発生しているが、高温に加熱すると、前記
間隙表面にAlが拡散して酸化アルミニウム膜が成長す
る。同時にCr含有量の差異によりNi−Cr−Al−Ｙの下地
用プラズマ溶射膜よりナイクロシルへCrが拡散する。こ
のとき前記酸化アルミニウム膜はCr拡散をさまたげるの
で、酸化アルミニウム膜のナイクロシル側にはCrが供給
されることがなく、ボイドが成長するものと推定され
る。These facts indicate that voids are generated and grow by the mechanism described below. That is, the base plasma sprayed film made of Ni-Cr-Al-Y has micro-plows due to the alumina-based internal oxide at the time of thermal spraying. Al diffuses and an aluminum oxide film grows. At the same time, due to the difference in Cr content, Cr diffuses from the Ni-Cr-Al-Y underlayer plasma sprayed film to Nicrosil. At this time, since the aluminum oxide film blocks Cr diffusion, Cr is not supplied to the nicrosil side of the aluminum oxide film, and it is presumed that voids grow.
下地用プラズマ溶射膜のCr含有量を15％以下とするこ
とにより下地用プラズマ溶射膜から加工金属へのCrの拡
散がなくなる。By setting the Cr content of the underlayer plasma sprayed film to 15% or less, the diffusion of Cr from the underlayer plasma sprayed film into the processed metal is eliminated.
さらに、減圧下で溶射した下地用プラズマ溶射膜にお
いては、膜中にボイド発生の核となるミクロな間隙が少
なくなり、より好適なプラズマ溶射膜が得られる。また
下地用プラズマ溶射膜にAl表面酸化膜が形成される。Furthermore, in the plasma sprayed film for the underlayer sprayed under reduced pressure, the microscopic gaps that become nuclei for void generation in the film are reduced, and a more suitable plasma sprayed film can be obtained. Further, an Al surface oxide film is formed on the base plasma sprayed film.
加工金属がナイクロシルの場合は下地用プラズマ溶射
膜のCr含有量が15重量％以下となっても、弱酸化性の雰
囲気においてはAlが腐蝕防止の効果を持つので、Cr含有
量が低くても下地用プラズマ溶射膜として使用すること
ができる。When the processed metal is nicrosil, even if the Cr content of the underlayer plasma sprayed film is 15% by weight or less, Al has the effect of preventing corrosion in a weakly oxidizing atmosphere, so even if the Cr content is low. It can be used as a plasma spray coating for a base.
次にこの発明の実施例について説明する。 Next, an embodiment of the present invention will be described.
加工金属として、シース型熱電対（素線材質/Nタイ
プ，絶縁材材質／マグネシア，シース材質／ナイクロシ
ル）の表面に、ジルコニア保護膜を被覆したものを用
い、温度1200℃，純Heガス中に3000h放置した。この場
合の下地用プラズマ溶射膜の化学組成，施工法は以下の
通りである。As the processed metal, a sheath type thermocouple (element wire material / N type, insulation material / magnesia, sheath material / nicrosil) coated with a zirconia protective film was used at a temperature of 1200 ° C and in pure He gas. I left it for 3000 hours. In this case, the chemical composition of the base plasma sprayed coating and the construction method are as follows.
加熱試験後の下地用プラズマ溶射膜の断面の観察結果
によれば、従来の下地用プラズマ溶射膜であるの試験
片では、下地用プラズマ溶射膜中にボイドの発生が多数
認められジルコニア保護膜も部分的に剥離したが、それ
ぞれの対策を施した，の試験片ではボイドの発生は
認められなかった。また、減圧プラズマ溶射で溶射した
の試験片では第１図に示すように緻密なAl表面酸化膜
６が面状に形成された内部酸化が抑制されるため、ボイ
ド寸法は15μｍ程度に抑制されたものの、ボイドの発生
は認められる。 According to the observation result of the cross section of the underlayer plasma sprayed film after the heating test, in the test piece of the conventional underlayer plasma sprayed film, many voids were observed in the underlayer plasma sprayed film, and the zirconia protective film was also observed. Although the pieces were partially peeled off, no void was found in the test pieces to which the respective measures were taken. Further, in the test piece sprayed by the low pressure plasma spraying, as shown in FIG. 1, since the dense Al surface oxide film 6 formed in a plane shape was suppressed from internal oxidation, the void size was suppressed to about 15 μm. However, the occurrence of voids is recognized.
次に加工金属として、シース型熱電対（素線材質/Nタ
イプ，絶縁材材質／マグネシア，シース材質／ナイクロ
シル）の表面に、ジルコニア保護膜を被覆したものを用
い、温度1200℃，純Heガス中に3000h放置した。この場
合の下地用プラズマ溶射膜の化学組成，施工法は以下の
通りである。Next, as the processing metal, use a sheath type thermocouple (element wire material / N type, insulating material / magnesia, sheath material / nicrosil) with a zirconia protective film coated on it, temperature 1200 ° C, pure He gas It was left inside for 3000 hours. In this case, the chemical composition of the base plasma sprayed coating and the construction method are as follows.
加熱試験の結果、ナイクロシルよりCr含有量が小さい
，ではボイドの発生は認められず、でもボイドは
約15μｍで実用上問題とならない程度であったが、で
は約30μｍのボイドが発生し、若干の剥離も認められ
た。 As a result of the heating test, when the Cr content was smaller than that of nicrocil, no void was observed, but the void was about 15 μm, which was not a problem in practical use, but about 30 μm of void was generated, Peeling was also observed.
この発明は、ナイクロシル（Niバランス,Cr14％,Si1.
4％）からなる加工金属にセラミックスをプラズマ溶射
する際に、予め加工金属に形成されるNi−Cr−Alベース
合金からなる下地用プラズマ溶射膜であって、そのCr含
有量が15％以下であるものとしたので下地用プラズマ溶
射膜から加工金属へのCrの拡散がなくなり、ボイドの成
長が抑えられ、高温かつ弱酸化性の雰囲気で使用したと
きに密着性に優れるプラズマ溶射膜が得られる。This invention is Nicrosil (Ni balance, Cr14%, Si1.
4%) when plasma-spraying ceramics to a processed metal, it is an underlayer plasma sprayed film made of a Ni-Cr-Al base alloy that is previously formed on the processed metal, and its Cr content is 15% or less. As a result, the diffusion of Cr from the base plasma sprayed film to the processed metal is eliminated, the growth of voids is suppressed, and a plasma sprayed film with excellent adhesion is obtained when used in a high temperature and weakly oxidizing atmosphere. .
第１図は下地用溶射膜のCr含有量が22％の場合のプラズ
マ溶射膜を示す断面図、第２図は、従来のプラズマ溶射
膜につきボイド寸法を時間依存性を示す線図、第３図は
従来のプラズマ溶射膜につきボイド寸法の温度依存性を
示す線図、第４図は従来のプラズマ溶射膜につき初期状
態を示す断面図、第５図は従来のプラズマ溶射膜のCrの
濃度分布につき加熱試験前（特性線51）と加熱試験後
（特性線52）の分布を対比して示す線図、第６図は従来
のプラズマ溶射膜内のボイドを示す断面図である。 1:ジルコニア保護膜、2:下地用プラズマ溶射膜、3:加工
金属、4:ボイド、5:内部酸化膜、6:Al表面酸化膜。FIG. 1 is a cross-sectional view showing the plasma sprayed film when the Cr content of the undercoating sprayed film is 22%, and FIG. 2 is a diagram showing the time dependence of the void size of the conventional plasma sprayed film. The figure is a diagram showing the temperature dependence of the void size for the conventional plasma sprayed film, Fig. 4 is a cross-sectional view showing the initial state of the conventional plasma sprayed film, and Fig. 5 is the Cr concentration distribution of the conventional plasma sprayed film. FIG. 6 is a diagram showing the distribution before the heating test (characteristic line 51) and the distribution after the heating test (characteristic line 52) in contrast, and FIG. 6 is a sectional view showing the voids in the conventional plasma sprayed film. 1: zirconia protective film, 2: plasma sprayed film for base, 3: processed metal, 4: void, 5: internal oxide film, 6: Al surface oxide film.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山田 政治 茨城県那珂郡東海村白方字白根２番地の ４ 日本原子力研究所東海研究所内 (72)発明者 川上 春雄 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 木村 秀雄 大阪府高槻市三島江１丁目５番24号 山 里産業株式会社高槻工場内 (72)発明者 藤田 信一 大阪府高槻市三島江１丁目５番24号 山 里産業株式会社高槻工場内 (56)参考文献 特開 昭53−33931（ＪＰ，Ａ) 特開 昭58−87273（ＪＰ，Ａ) 特開 昭62−211389（ＪＰ，Ａ) 特開 昭62−211390（ＪＰ，Ａ) 特開 昭62−205223（ＪＰ，Ａ) 特開 昭59−208425（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Political inventor Yamada politics 2 Shirane, Shikata, Tokai-mura, Naka-gun, Ibaraki Prefecture 4 Tokai Research Institute, Japan Atomic Energy Research Institute (72) Haruo Kawakami Arata Tanabe, Kawasaki-ku, Kanagawa Prefecture No. 1-1 No. 1 Fuji Electric Co., Ltd. (72) Hideo Kimura 1-5-24 Mishimae, Takatsuki-shi, Osaka Prefecture In-house Takatsuki Plant, Yamasato Sangyo Co., Ltd. (72) Shinichi Fujita Mishima, Takatsuki-shi, Osaka Prefecture E 1-chome 5-24 Yamasato Sangyo Co., Ltd. Takatsuki factory (56) Reference JP-A-53-33931 (JP, A) JP-A-58-87273 (JP, A) JP-A-62-212389 (JP) , A) JP 62-211390 (JP, A) JP 62-205223 (JP, A) JP 59-208425 (JP, A)
Claims (1)
％）からなる加工金属にセラミックスをプラズマ溶射す
る際に、予め加工金属に形成されるNi−Cr−Alベース合
金からなる下地用プラズマ溶射膜であって、そのCr含有
量が15％以下であることを特徴とする下地用プラズマ溶
射膜。1. Nicrosil (Ni balance, Cr14%, Si1.4
%) Is a base plasma sprayed film made of a Ni-Cr-Al base alloy which is previously formed on the processed metal when plasma spraying the ceramics to the processed metal composed of 15% or less, and the Cr content is 15% or less. A plasma sprayed film for a base, which is characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2250979A JP2669928B2 (en) | 1990-09-20 | 1990-09-20 | Underlayer plasma spray coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2250979A JP2669928B2 (en) | 1990-09-20 | 1990-09-20 | Underlayer plasma spray coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04131363A JPH04131363A (en) | 1992-05-06 |
| JP2669928B2 true JP2669928B2 (en) | 1997-10-29 |
Family
ID=17215871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2250979A Expired - Lifetime JP2669928B2 (en) | 1990-09-20 | 1990-09-20 | Underlayer plasma spray coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2669928B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993008315A1 (en) * | 1991-10-18 | 1993-04-29 | Harold Leroy Harford | A method of producing a wear-resistant coating |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4095003A (en) * | 1976-09-09 | 1978-06-13 | Union Carbide Corporation | Duplex coating for thermal and corrosion protection |
| DE2842848C2 (en) * | 1977-10-17 | 1987-02-26 | United Technologies Corp., Hartford, Conn. | Material for covering objects |
| JPS5887273A (en) * | 1981-11-18 | 1983-05-25 | Hitachi Ltd | Parts having ceramic coated layer and their production |
| JPS62211389A (en) * | 1986-03-12 | 1987-09-17 | Hitachi Ltd | Ceramic coated turbo charger and its production |
| JPS62211390A (en) * | 1986-03-12 | 1987-09-17 | Hitachi Ltd | Ceramic coated heat resistant member and its production |
-
1990
- 1990-09-20 JP JP2250979A patent/JP2669928B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04131363A (en) | 1992-05-06 |
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