JP2756587B2 - Method of forming alumina film - Google Patents
Method of forming alumina filmInfo
- Publication number
- JP2756587B2 JP2756587B2 JP18091789A JP18091789A JP2756587B2 JP 2756587 B2 JP2756587 B2 JP 2756587B2 JP 18091789 A JP18091789 A JP 18091789A JP 18091789 A JP18091789 A JP 18091789A JP 2756587 B2 JP2756587 B2 JP 2756587B2
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- Japan
- Prior art keywords
- alumina
- film
- dispersion
- hours
- temperature
- 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.)
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、酸化皮膜を有する金属の表面に、アルミナ
皮膜を形成する方法に関し、主として耐摩耗性の要求さ
れる分野において使用されるものである。Description: TECHNICAL FIELD The present invention relates to a method for forming an alumina film on a surface of a metal having an oxide film, and is mainly used in a field requiring abrasion resistance. is there.
金属表面にアルミナ皮膜を形成する方法に関してこれ
までいくつか提案されているが、これ等は触媒用のγ−
アルミナに関するものである。There have been several proposals for a method for forming an alumina film on a metal surface.
It relates to alumina.
特公昭59−35659号公報には、ニッケル表面にアルミ
ニウム等の含有化合物の懸濁液を塗布または浸漬した
後、高温酸化処理した後で還元処理することからなるニ
ッケル触媒の製造方法が記載されている。該公報の実施
例１では酢酸アルミニウムのエチルアルコール懸濁液が
使用されていて、付着量はAl2O3として0.0016g/cm3と少
量である。JP-B-59-35659 describes a method for producing a nickel catalyst, which comprises applying or dipping a suspension of a compound containing aluminum or the like on a nickel surface, subjecting the suspension to a high-temperature oxidation treatment and then a reduction treatment. I have. In Example 1 of this publication, a suspension of aluminum acetate in ethyl alcohol is used, and the amount of adhesion is as small as 0.0016 g / cm 3 as Al 2 O 3 .
特開昭56−152965号公報には酸化物ウィスカーでカバ
ーされた面を水性アルミナゲルで濡らす工程、その面に
さらに水性アルミナゲルに懸濁したマクロアルミナ粒子
よりなる材料を塗布する工程を包含するコーティング方
法が記載されている。JP-A-56-152965 includes a step of wetting a surface covered with oxide whiskers with aqueous alumina gel and a step of further applying a material comprising macro-alumina particles suspended in aqueous alumina gel to the surface. A coating method is described.
マイクロアルミナ粒子はγ−アルミナであって、コー
ティング皮膜はγ−アルミナである。The micro-alumina particles are γ-alumina, and the coating film is γ-alumina.
特開昭62−7875号公報には平均粒子径0.7〜３μｍの
酸化物の水性スラリーを使用するコーティング方法が記
載されている。焼成により得られた皮膜は活性アルミナ
である。JP-A-62-27875 describes a coating method using an aqueous slurry of an oxide having an average particle diameter of 0.7 to 3 μm. The coating obtained by firing is activated alumina.
上記の引例はいずれも触媒用の酸化皮膜であって、剥
落しない程度の付着強度を有しておればよい。しかるに
耐摩耗性の用途には高い硬度を有し強固に付着した厚膜
を形成する必要がある。そのためにはα−アルミナの緻
密焼結体が望ましい。Each of the above references is an oxide film for a catalyst, and has only to have an adhesive strength that does not peel off. However, for wear-resistant applications, it is necessary to form a thick film having high hardness and firmly attached. For this purpose, a dense sintered body of α-alumina is desirable.
一般にα−アルミナの緻密焼結体を得るには1600〜18
00℃の焼成が必要で、サブミクロンの微粒のα−アルミ
ナを使用する場合でも1400℃を要する。この領域の高温
では金属母体の結晶成長が著しく、そのために強度の低
下をもたらす。したがって約1300℃以下の焼成によって
緻密な組織を与えるα−アルミナの皮膜形成方法を見出
すことが課題であった。Generally, to obtain a dense sintered body of α-alumina, 1600 to 18
Firing at 00 ° C is required, and 1400 ° C is required even when submicron α-alumina is used. At a high temperature in this region, the crystal growth of the metal matrix is remarkable, which results in a decrease in strength. Therefore, it was an issue to find a method of forming a film of α-alumina which gives a dense structure by firing at about 1300 ° C. or less.
かかる現状に鑑み、本発明者等は低温度で焼成して緻
密焼結体を得るためのα−アルミナの条件について鋭意
検討した結果、特定の粒径を有するα−アルミナのコロ
イド分散液を塗布することによって良好な皮膜が形成で
きることを見出し、本発明を完成させるに至った。In view of this situation, the present inventors have conducted intensive studies on the conditions of α-alumina for firing at a low temperature to obtain a dense sintered body, and as a result, applied a colloidal dispersion of α-alumina having a specific particle size. The present inventors have found that a good film can be formed by performing the method, and have completed the present invention.
すなわち、本発明は表面に主としてアルミナからなる
酸化皮膜を有する金属の表面に、粒径0.2μｍ以下のα
−アルミナのコロイド分散液を被覆した後、乾燥し焼成
することを特徴とするアルミナ皮膜の形成方法を提供す
るものである。That is, according to the present invention, the surface of a metal having an oxide film mainly composed of alumina
-A method for forming an alumina film, comprising coating a colloidal dispersion of alumina, followed by drying and firing.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において皮覆液として使用するコロイド分散液
は、懸濁液のなかでも粒径の微細なコロイド粒子が液体
中に分散したものを称し、その際のコロイド粒子の粒径
が0.2μｍ以下の範囲のものであるため、容易に沈降し
ないものである。The colloid dispersion used as the skin covering liquid in the present invention refers to a suspension in which fine colloid particles having a small particle diameter are dispersed in a liquid, and the particle diameter of the colloid particles at that time is 0.2 μm or less. Because it is in the range, it does not settle easily.
本発明で使用するα−アルミナはその製造方法につい
て何ら限定されるものではない。The α-alumina used in the present invention is not limited at all in the production method.
水酸化アルミニウム、硝酸アルミニウム、硫酸アルミ
ニウム、硫酸アルミニウムアンモニウム、アンモニウム
ドーソナイト等を焼成してα−アルミナとし、凝集粒を
粉砕するのが一般的な方法である。It is a general method to bake aluminum hydroxide, aluminum nitrate, aluminum sulfate, aluminum ammonium sulfate, ammonium dawsonite, etc. to form α-alumina, and pulverize the aggregated particles.
コロイド分散液中のα−アルミナの粒径は0.2μｍ以
下、好ましくは0.1μｍのものが使用できる。粒径が0.2
μｍを越えると緻密な焼結体を与える焼結温度が高くな
り好ましくない。0.01μｍ未満のものは製造が難しく、
実際的でない。The particle size of α-alumina in the colloidal dispersion may be 0.2 μm or less, preferably 0.1 μm. Particle size 0.2
If it exceeds μm, the sintering temperature for providing a dense sintered body is undesirably high. Those with less than 0.01 μm are difficult to manufacture,
Impractical.
α−アルミナの粒径を0.2μｍ以下にするためには、
分散後に自然沈降または遠心沈降をおこない、大きな粒
子を除去することが好ましい。この方法によれば大粒径
の夾雑物を容易に除去することができる。In order to reduce the particle size of α-alumina to 0.2 μm or less,
It is preferable to perform natural sedimentation or centrifugal sedimentation after dispersion to remove large particles. According to this method, impurities having a large particle diameter can be easily removed.
α−アルミナのコロイド分散液の調製は、分散媒中に
α−アルミナの微粒子を投入して撹拌する周知の方法が
採用できる。For preparing the colloidal dispersion of α-alumina, a known method in which α-alumina fine particles are charged into a dispersion medium and stirred may be employed.
分散媒は水、アルコール、ケトン等揮散し易いものが
使用でき、これらの中でも水がより好ましい。As the dispersion medium, water, alcohol, ketone and the like which can be easily vaporized can be used, and among these, water is more preferable.
本発明に用いるコロイド分散液中に凝集粒の解膠のた
めの分散剤、液の粘度を調製するための増粘剤等を添加
してもよい。A dispersant for peptizing aggregates, a thickener for adjusting the viscosity of the liquid, and the like may be added to the colloidal dispersion used in the present invention.
分散剤としてはポリカルボン酸類の塩等のアニオン性
界面活性剤が好適である。またpH2〜３に調製して分散
することもでき、この場合塩酸、硝酸等の酸が使用でき
る。As a dispersant, an anionic surfactant such as a salt of a polycarboxylic acid is suitable. It is also possible to adjust the pH to 2 to 3 and disperse it. In this case, an acid such as hydrochloric acid or nitric acid can be used.
増粘剤としてはポリオキシエチレン、ポリアクリルア
ミド等が好適である。Polyoxyethylene, polyacrylamide and the like are suitable as the thickener.
また撹拌、混合の工程において超音波を作用させた
り、ホモジナイザー、乳化機等を使用することもでき
る。In addition, ultrasonic waves can be applied in the steps of stirring and mixing, and a homogenizer, an emulsifier, and the like can be used.
コロイド分散液中のα−アルミナの濃度は特に限定さ
れないが、好ましくは５〜20重量％であり、所望する皮
膜の厚さによって選択すればよい。The concentration of α-alumina in the colloidal dispersion is not particularly limited, but is preferably 5 to 20% by weight, and may be selected depending on the desired film thickness.
本発明により得られたコロイド分散液を基体に被覆す
る方法としては塗布法、噴霧法、浸漬法等通常の方法が
採用できる。As a method of coating the colloidal dispersion obtained by the present invention on a substrate, a usual method such as a coating method, a spraying method, and a dipping method can be adopted.
本発明において用いられる金属は、高温酸化処理によ
って主としてアルミナの皮膜を表面に形成するものであ
って、約1300℃の後処理によって母材強度が低下しない
ものが用いられる。たとえばFe−Cr−Al、Ni−Cr−Al、
Co−Cr−Al等の金属が例示できる。これ等に希土類元素
等を添加して酸化皮膜の性状を改善したものも含まれ
る。The metal used in the present invention is one that mainly forms an alumina film on the surface by high-temperature oxidation treatment, and that does not lower the base material strength by the post-treatment at about 1300 ° C. For example, Fe-Cr-Al, Ni-Cr-Al,
Metals such as Co-Cr-Al can be exemplified. These include those in which the properties of an oxide film are improved by adding a rare earth element or the like.
基体に被覆されたコロイド分散液は、乾燥されさらに
焼成される。The colloidal dispersion coated on the substrate is dried and fired.
焼成条件は使用する分散媒および分散剤の消失温度、
基体の耐熱温度、α−アルミナの焼結温度を考慮して決
定すればよい。具体的には焼成温度は1100〜1300℃であ
り、より好ましくは1100〜1250℃である。焼成温度が11
00℃より低い場合はα−アルミナの焼結が不十分であ
り、1300℃より高い場合は金属の強度を低下させるおそ
れがあるので好ましくない。焼成時間はα−アルミナの
焼結に必要な十分な時間を選択すればよく、通常0.5〜
６時間である。The firing conditions are the dissipating temperature of the dispersant and dispersant used,
The temperature may be determined in consideration of the heat resistance temperature of the base and the sintering temperature of α-alumina. Specifically, the firing temperature is from 1100 to 1300 ° C, more preferably from 1100 to 1250 ° C. Firing temperature 11
If the temperature is lower than 00 ° C., the sintering of α-alumina is insufficient, and if it is higher than 1300 ° C., the strength of the metal may be reduced, which is not preferable. The sintering time may be selected to be a sufficient time necessary for sintering α-alumina.
6 hours.
以下、本発明を実施例により説明するが、本発明はこ
れ等に限定されるものではない。Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
なお実施例において用いる「％」は「重量％」を意味
する。“%” Used in the examples means “% by weight”.
実施例１ α−アルミナ（住友化学工業（株）製、AKP−50、粒
径0.1〜0.3μｍ）を振動ミルで２時間処理し、分散剤と
してポリカルボン酸アンモニウム（サンノプコ（株）
製、SN−EX5468、30％液）をα−アルミナ100部に対し
て２部を含む20％水性スラリーとし、湿式ボールミル処
理を48時間行った。その後遠心分離機にて3000rpmで35
分処理して0.15μｍ以上の粒子を沈降させ、上澄液をさ
らに4200rpmで２時間40分処理して粒子をほとんどすべ
て沈降させた。Example 1 α-alumina (AKP-50, manufactured by Sumitomo Chemical Co., Ltd., particle size: 0.1 to 0.3 μm) was treated with a vibration mill for 2 hours, and ammonium polycarboxylate (San Nopco Co., Ltd.) was used as a dispersant.
(SN-EX5468, 30% solution) was used as a 20% aqueous slurry containing 2 parts of α-alumina in 100 parts, and wet ball milling was performed for 48 hours. Then, centrifuge at 3000rpm for 35
The particles were sedimented to settle particles of 0.15 μm or more, and the supernatant was further treated at 4200 rpm for 2 hours and 40 minutes to settle almost all the particles.
上澄液を除き、上記と同濃度の分散液の中に沈降物を
入れ、超音波分散処理を２時間することによって10％の
α−アルミナコロイド分散液を得た。The supernatant was removed, and the sediment was placed in the dispersion having the same concentration as above, and subjected to ultrasonic dispersion treatment for 2 hours to obtain a 10% α-alumina colloid dispersion.
一方、次の組成のFe−Cr−Al合金を常法にしたがって
作成した。On the other hand, an Fe-Cr-Al alloy having the following composition was prepared according to a conventional method.
Cr:30％、Al:3.2％、Mo:2.0％、Zr:0.2％、 Si:0.15％、C:0.004％、N:0.007％、0:0.001％、 Fe:残部 この合金を酸素中1250℃で３時間処理し、酸化物皮膜
を形成させた。酸化物皮膜の厚みは20μｍで組成は以下
のとおりであった。Cr: 30%, Al: 3.2%, Mo: 2.0%, Zr: 0.2%, Si: 0.15%, C: 0.004%, N: 0.007%, 0: 0.001%, Fe: balance This alloy is placed in oxygen at 1250 ° C. For 3 hours to form an oxide film. The thickness of the oxide film was 20 μm, and the composition was as follows.
Al2O3:90モル％、ZrO2:5モル％、 Fe2O3:3モル％、Cr2O3:2モル％、 この合金（15×30×4mm）の表面に上記のα−アルミ
ナコロイド分散液を塗布し、乾燥後1250℃で２時間焼成
した。表面には膜厚60μｍのα−アルミナの緻密な皮膜
が形成されていた。Al 2 O 3 : 90 mol%, ZrO 2 : 5 mol%, Fe 2 O 3 : 3 mol%, Cr 2 O 3 : 2 mol%, The surface of this alloy (15 × 30 × 4 mm) An alumina colloid dispersion was applied, dried and calcined at 1250 ° C. for 2 hours. A dense film of α-alumina having a thickness of 60 μm was formed on the surface.
実施例２ 実施例１において、合金組織をZr:0.2％の代わりにY:
0.3％にした以外は実施例１と同様にして合金を作成
し、酸素中1250℃で３時間処理して、酸化物皮膜を形成
させた。酸化物皮膜の厚みは20μｍで組成は以下のとお
りであった。Example 2 In Example 1, the alloy structure was changed to Y: instead of Zr: 0.2%.
An alloy was prepared in the same manner as in Example 1 except that the content was changed to 0.3%. The alloy was treated in oxygen at 1250 ° C. for 3 hours to form an oxide film. The thickness of the oxide film was 20 μm, and the composition was as follows.
Al2O3:99モル％、Fe2O3＋Cr2O3:1モル％ この合金（15×30×4mm）の表面に実施例１と同様に
α−アルミナコロイド分散液を塗布し、乾燥後1250℃で
２時間焼成した。Al 2 O 3 : 99 mol%, Fe 2 O 3 + Cr 2 O 3 : 1 mol% An α-alumina colloidal dispersion is applied to the surface of this alloy (15 × 30 × 4 mm) in the same manner as in Example 1 and dried. Thereafter, it was baked at 1250 ° C. for 2 hours.
表面には膜厚60μｍのα−アルミナの緻密な皮膜が形成
された。A dense film of α-alumina having a thickness of 60 μm was formed on the surface.
比較例１ α−アルミナ（前出AKP−50）を粉砕処理せずに使用
して分散液を調製し、その他は実施例１と同様の処理を
行った。1250℃で２時間焼成した結果皮膜は軟らかく、
α−アルミナの緻密な焼成基板（1600℃焼成体）によっ
て容易に削りとることができた。Comparative Example 1 A dispersion was prepared using α-alumina (AKP-50 described above) without pulverization, and the same treatment as in Example 1 was performed except for the above. As a result of baking at 1250 ° C for 2 hours, the film is soft,
It could be easily scraped off by a dense fired substrate of α-alumina (fired body at 1600 ° C.).
比較例２ 比較例１において、焼成温度1400℃で２時間焼成した
結果、皮膜は硬いものであったが、金属の粒成長が見ら
れ、強度低下をもたらした。Comparative Example 2 In Comparative Example 1, as a result of baking for 2 hours at a baking temperature of 1400 ° C., the film was hard, but metal grain growth was observed, resulting in a decrease in strength.
本発明によって、金属表面に形成されたα−アルミナ
皮膜は金属の酸化皮膜との密着性がよく、かつ膜厚が大
で硬度が高いので耐摩耗性の用途にきわめて望ましいも
のである。The α-alumina film formed on the metal surface according to the present invention is highly desirable for wear-resistant applications because it has good adhesion to the metal oxide film, and has a large film thickness and high hardness.
Claims (1)
を有する金属の表面に、粒径0.2μｍ以下のα−アルミ
ナのコロイド分散液を被覆した後、乾燥し焼成すること
を特徴とするアルミナ皮膜の形成方法。1. A method for forming an alumina film, comprising: coating a metal having an oxide film mainly composed of alumina on the surface with a colloidal dispersion of α-alumina having a particle size of 0.2 μm or less, drying and firing. Forming method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18091789A JP2756587B2 (en) | 1989-07-12 | 1989-07-12 | Method of forming alumina film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18091789A JP2756587B2 (en) | 1989-07-12 | 1989-07-12 | Method of forming alumina film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0344478A JPH0344478A (en) | 1991-02-26 |
| JP2756587B2 true JP2756587B2 (en) | 1998-05-25 |
Family
ID=16091541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18091789A Expired - Lifetime JP2756587B2 (en) | 1989-07-12 | 1989-07-12 | Method of forming alumina film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2756587B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4848815B2 (en) * | 2006-03-31 | 2011-12-28 | 大日本印刷株式会社 | Method for producing corundum laminate |
| JP5739189B2 (en) * | 2011-02-24 | 2015-06-24 | 三菱マテリアル株式会社 | Method for producing surface-coated cutting tool with excellent wear resistance |
| JP6364195B2 (en) * | 2014-01-30 | 2018-07-25 | 三菱マテリアル株式会社 | Surface-coated cutting tool with excellent chipping resistance in high-speed intermittent cutting |
-
1989
- 1989-07-12 JP JP18091789A patent/JP2756587B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0344478A (en) | 1991-02-26 |
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