JPH02156060A - Surface treatment of metallic material - Google Patents
Surface treatment of metallic materialInfo
- Publication number
- JPH02156060A JPH02156060A JP63309422A JP30942288A JPH02156060A JP H02156060 A JPH02156060 A JP H02156060A JP 63309422 A JP63309422 A JP 63309422A JP 30942288 A JP30942288 A JP 30942288A JP H02156060 A JPH02156060 A JP H02156060A
- Authority
- JP
- Japan
- Prior art keywords
- metallic material
- thermal
- alloy
- spraying
- sprayed
- 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.)
- Granted
Links
- 239000007769 metal material Substances 0.000 title claims abstract description 20
- 238000004381 surface treatment Methods 0.000 title claims description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000002485 combustion reaction Methods 0.000 claims abstract description 5
- 238000004880 explosion Methods 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 25
- 238000005507 spraying Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 238000007751 thermal spraying Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 29
- 239000007789 gas Substances 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 4
- 229910003470 tongbaite Inorganic materials 0.000 abstract description 3
- 150000001247 metal acetylides Chemical class 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 238000010285 flame spraying Methods 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 229910020639 Co-Al Inorganic materials 0.000 abstract 1
- 229910020675 Co—Al Inorganic materials 0.000 abstract 1
- 229910003310 Ni-Al Inorganic materials 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 7
- 239000011651 chromium Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002360 explosive Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000007750 plasma spraying Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 241000616862 Belliella Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical group [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010283 detonation spraying Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は金属材料の表面処理方法に関し、さらに詳しく
はガスの爆発または燃焼等の高エネルギーを利用する高
エネルギーガス溶射法による金属材料の表面処理方法に
関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for surface treatment of metal materials, and more particularly, the present invention relates to a method for surface treatment of metal materials, and more specifically, a method for treating the surface of metal materials by a high-energy gas spraying method that utilizes high energy such as gas explosion or combustion. Regarding processing method.
石炭焚ボイラの伝熱管、バー６ナインベラやバーナチッ
プ等の部品、ガスタービンやディーゼルエンジン等の部
品などにおいては、約５００℃〜１０００℃の高温での
耐熱性、燃焼ガスにる高温腐食、燃焼灰の衝突による摩
耗、部材同士の摺動による摩耗などが大きな問題となる
。これらの問題に対処し、材料の耐熱性、耐蝕性および
耐摩耗性を向上させるため、これらの緒特性に優れた材
料を金属材料（母材）表面に溶射する方法が用いられて
いる。Parts such as heat transfer tubes for coal-fired boilers, bar 6 nine bellas, burner tips, and parts for gas turbines and diesel engines have heat resistance at high temperatures of approximately 500°C to 1000°C, high temperature corrosion due to combustion gas, and combustion resistance. Abrasion due to collision of ash and abrasion due to sliding of parts become major problems. In order to deal with these problems and improve the heat resistance, corrosion resistance, and wear resistance of materials, a method is used in which a material having excellent these properties is thermally sprayed onto the surface of a metal material (base material).
溶射材料としては、耐熱性、耐蝕性および耐摩耗性に優
れる必要があり、メタル系、サーメット系、酸化物セラ
ミックス系などが用いられている。Thermal spray materials must have excellent heat resistance, corrosion resistance, and wear resistance, and metal-based, cermet-based, oxide ceramic-based, etc. are used.
これらのうちＡｌ！Ｏ，、ＺｒＯ，、Ｃｒ、Ｏ。Among these, Al! O,, ZrO,, Cr, O.
等の酸化物系セラミックス粉末が好ましく用いられ、特
にＡｌ２ｚＯｙ粉末が最も廉価な粉末であるため広く使
用されている。Oxide-based ceramic powders such as the following are preferably used, and in particular, Al2zOy powder is widely used because it is the cheapest powder.
酸化物系セラミックスの溶射皮膜の性能には、前記耐熱
性、耐蝕性および耐摩耗性の他、母材との密着強度およ
び皮膜中の気孔の有無が重要な因子となる。すなわち、
密着力が低いと、使用中の加熱および冷却の繰返しによ
って生じる熱応力で皮膜が容易に剥離し、また皮膜中に
気孔が多いと、その気孔を通じて燃焼ガスが侵入して母
材を腐食する。In addition to the heat resistance, corrosion resistance, and abrasion resistance mentioned above, the adhesion strength with the base material and the presence or absence of pores in the coating are important factors for the performance of the thermal spray coating of oxide ceramics. That is,
If the adhesion is low, the film will easily peel off due to thermal stress caused by repeated heating and cooling during use, and if there are many pores in the film, combustion gas will enter through the pores and corrode the base material.
溶射皮膜の密着力低下および気孔生成の主な原因は、母
材表面に衝突する溶射粒子の可塑性（特に未溶融粒子）
不足と、粒子速度不足による圧着力不足にある。従って
、密着力向上および皮膜の無気孔化を図るためには、（
イ）粒子速度を速くして母材への衝突エネルギーを高く
すること、（ロ）溶射粒子を溶融または半溶融状態にす
ることが必要でなる。The main cause of reduced adhesion and pore formation in thermal sprayed coatings is the plasticity of thermal spray particles (especially unmelted particles) that collide with the base material surface.
This is due to insufficient pressing force due to insufficient particle speed. Therefore, in order to improve adhesion and make the film pore-free, (
(b) It is necessary to increase the particle velocity to increase the energy of collision with the base material, and (b) it is necessary to bring the thermal spray particles into a molten or semi-molten state.
溶射方法としては、（１）プラズマ溶射法、（２）高エ
ネルギー溶射法（酸素−アセチレンの爆発エネルギーを
利用した爆発溶射法、超音速強化ガス溶射法等）が利用
されている。As thermal spraying methods, (1) plasma spraying, and (2) high-energy thermal spraying (explosive thermal spraying using the explosive energy of oxygen-acetylene, supersonic enhanced gas thermal spraying, etc.) are used.
前記プラズマ溶射法の場合は、被溶射物表面に到達する
際の粒子速度が例えばＬｏｏｍ／ｓであるため、粒子の
母材に対する圧着力が不足し、また形成した皮膜の気孔
が通常数％〜士数％となり、良好な耐摩耗性が得られな
い。In the case of the above-mentioned plasma spraying method, since the particle velocity when reaching the surface of the sprayed object is, for example, Loom/s, the pressure force of the particles against the base material is insufficient, and the pores of the formed film are usually several to several percent. %, and good wear resistance cannot be obtained.
皮膜を緻密化して気孔を少なくする方法として、プラズ
マ溶射後に皮膜表面をレーザ等の高密度エネルギー源で
加熱溶融させる方法や加熱しながら静水圧を付加する方
法（ＨＩ Ｐ処理）があるが、これらの方法は装置等の
設備および施工に多額の費用がかかり、エネルギーや圧
力の制御が複雑であるなどの問題がある。Methods for making the film denser and reducing pores include heating and melting the film surface with a high-density energy source such as a laser after plasma spraying, and applying hydrostatic pressure while heating (HIP treatment). This method requires a large amount of equipment and construction costs, and has problems such as complicated energy and pressure control.
一方、高エネルギー溶射法の場合は、粒子速度がマツハ
２〜３と高粒子速度が得られるため、粒子の母材に対す
る圧着力が大きく、また溶射皮膜中の気孔を少なくして
粒子間の結合力を大きくすることができるため、充分な
耐摩耗性を得ることができる。しかし、咳高エネルギー
溶射では、高温で使用する場合には酸化物皮膜と被溶射
物との熱膨張差による熱応力によって剥離し易い欠点が
ある。On the other hand, in the case of high-energy thermal spraying, a high particle velocity of Matsuha 2 to 3 can be obtained, so the pressure of the particles against the base material is large, and the pores in the sprayed coating are reduced to form bonds between particles. Since the force can be increased, sufficient wear resistance can be obtained. However, high-energy thermal spraying has the disadvantage that when used at high temperatures, it tends to peel off due to thermal stress caused by the difference in thermal expansion between the oxide film and the object to be sprayed.
この問題を解決する方法として、第１層として被溶射金
属との結合性に優れた低融点のＮ１−ＡＥやＮｉ−Ｃｒ
等のメタル粉末を溶射し、その後に酸化物を溶射する方
法があるが、高エネルギー溶射法の場合は、前記メタル
粉末が完全溶融状態で被溶射物表面に衝突するため、母
材への食い込みが不充分となり、母材と皮膜との密着力
が低下する。さらにこの解決法として、特開昭６１−２
９６０３０号公報に示されるように、例えばニクロムと
炭化クロムの複合粉末による第１層を形成し、その後に
酸化物粉末による皮膜を形成する方法があるが、この方
法で得られる溶射皮膜でも耐熱温度は７００℃程度であ
り、温度がこれ以上高くなると第１層と第２層の間で剥
離が生じる問題がある。As a way to solve this problem, the first layer is made of N1-AE or Ni-Cr, which has a low melting point and has excellent bonding properties with the metal to be sprayed.
There is a method of spraying a metal powder such as, and then spraying an oxide, but in the case of high-energy spraying, the metal powder collides with the surface of the object to be sprayed in a completely molten state, so it may bite into the base material. becomes insufficient, and the adhesion between the base material and the film decreases. Furthermore, as a solution to this problem, JP-A-61-2
As shown in Publication No. 96030, for example, there is a method of forming a first layer of composite powder of nichrome and chromium carbide, and then forming a film of oxide powder, but even the thermal sprayed film obtained by this method has a high heat resistance temperature. is approximately 700° C., and if the temperature is higher than this, there is a problem that peeling occurs between the first layer and the second layer.
本発明の目的は、前記従来技術の問題点を解決し、被溶
射物との密着力に優れた高エネルギーガス溶射法による
金属材料の表面処理方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art described above and to provide a method for surface treatment of metal materials using a high-energy gas spraying method that has excellent adhesion to the object to be sprayed.
本発明は、ガスの爆発または燃焼による高エネルギーガ
スを利用してアルミナ酸化物からなる溶射皮膜を金属材
料表面に形成する表面処理方法において、前記金属材料
表面に、高融点で高硬度の物質とアルミニウムを含む合
金とからなる混合物を溶射して第１層溶射皮膜を形成し
、次にこの被膜にアルミナ酸化物を溶射して多層溶射被
膜を形成した後、該多層溶射被膜を酸化性雰囲気中で８
００℃〜１０００℃の温度で加熱することを特徴とする
。The present invention provides a surface treatment method for forming a thermally sprayed coating made of alumina oxide on the surface of a metal material using high-energy gas generated by gas explosion or combustion, in which a substance having a high melting point and high hardness is applied to the surface of the metal material. A first layer thermal sprayed coating is formed by thermal spraying a mixture consisting of an alloy containing aluminum, and then alumina oxide is thermally sprayed on this coating to form a multilayer thermal sprayed coating, and then the multilayer thermal sprayed coating is placed in an oxidizing atmosphere. At 8
It is characterized by heating at a temperature of 00°C to 1000°C.
本発明に用いられる高融点で高硬度の物質としては、２
０００ ”Ｃ〜３０００℃のガス温度において、未溶融
または半溶融で硬さを有する状態となる物質であれば特
に限定されず、例えばＷＣｌＣｒ ３ Ｃｚ 、Ｔ ｉ
Ｃ等の金属炭化物の他、金属酸化物や金属窒化物など
が用いられる。The high melting point and high hardness substance used in the present invention includes 2
The material is not particularly limited as long as it is unmolten or semi-molten and has hardness at a gas temperature of 000"C to 3000"C, for example, WClCr3Cz, Ti
In addition to metal carbides such as C, metal oxides and metal nitrides are used.
本発明に用いられるアルミニウムを含む合金としては、
アルミニウムを含み、高エネルギーガス溶射によって完
全に溶融する合金であれば特に限定はされないが、合金
中に１〜１０重量％のアルミニウムを含有し、かつＦｅ
、Ｃｒ、ＮｉおよびＣｏの少なくとも１種の元素を含有
する合金が好ましい。合金中のアルミニウム含有量が１
重量％未満では、溶射後の熱処理によって生成するアル
ミナ酸化物量が少ないため充分な密着力が得られず、ま
た１０重量％を超えると、Ｎｆ、ＡＩｌ、Ｃｒ、Ａ、ｌ
、ＦｅＡｌ、等の脆い金属化合物が生成し、また粉末の
融点が極端に低下するため、粉末が母材へ飛行中に過度
に酸素を溶解し、酸化物の多い皮膜となることがある。The aluminum-containing alloy used in the present invention includes:
There is no particular limitation as long as the alloy contains aluminum and can be completely melted by high-energy gas spraying, but alloys containing 1 to 10% by weight of aluminum and Fe
, Cr, Ni and Co are preferred. Aluminum content in the alloy is 1
If it is less than 10% by weight, sufficient adhesion cannot be obtained because the amount of alumina oxide produced by the heat treatment after thermal spraying is small, and if it exceeds 10% by weight, Nf, Al, Cr, A, L
, FeAl, etc. are formed, and the melting point of the powder is extremely lowered, so that the powder may dissolve too much oxygen during flight to the base material, resulting in a film with a large amount of oxide.
前記アルミニウムを含む合金には、Ｙ等の希土類元素を
、例えば合金中に０．１〜１重景％程度添加することが
できる。この希土類元素の添加によってアルミナ酸化物
と第１層皮膜との密着力がより強固となるため、より苛
酷な環境で使用する場合に添加するのが効果的である。In the alloy containing aluminum, a rare earth element such as Y can be added to the alloy, for example, in an amount of about 0.1 to 1%. Since the addition of this rare earth element strengthens the adhesion between the alumina oxide and the first layer film, it is effective to add it when used in a harsher environment.
本発明における多層溶射被膜は、酸化性雰囲気中で８０
０℃〜１０００℃の温度で加熱される。The multilayer thermal sprayed coating in the present invention has a temperature of 80% in an oxidizing atmosphere.
It is heated at a temperature of 0°C to 1000°C.
該処理温度が８００℃未満では、１０〜２０時間の熱処
理時間で密着性に充分な作用をするアルミナ酸化物が生
成せず、また１０００℃を超えると、高融点で高硬度の
物質、例えばクロム炭化物の変態等が生じる。If the treatment temperature is less than 800°C, alumina oxide, which has a sufficient effect on adhesion, will not be produced even after a heat treatment time of 10 to 20 hours, and if it exceeds 1000°C, a material with a high melting point and high hardness, such as chromium, will not be produced. Carbide transformation etc. occur.
第１図は、本発明の方法で表面処理された金属材料の断
面図、第２図は、第１図のＡ部拡大図、第３図は、第１
図のＢ部の拡大図である。図において、母材１の表面に
は溶射被膜２、すなわち、初層溶射被膜２ａおよび表層
溶射被膜２ｂが形成されている。また前記初層溶射皮膜
２ａは、高融点で高硬度の物質（炭化物）３と、アルミ
ニウムを含む合金（メタル）４との混合物で形成されて
いる。ｖＡ混合物が母材１に溶射されると、炭化物３の
粒子が未溶融または半溶融かつ硬さを存する状態で母材
１表面に衝突し、投錨効果によって第２図に示すように
母材面に食い込む、またメタル４は完全溶融状態で高い
濡れ性を有するため、母材へ移行中に炭化物３を包む状
態となり、炭化物の分解を防止するとともに、衝突エネ
ルギーを増加させ、炭化物粒子にも母材の凹凸面にもよ
く密着する。従って、母材１と初層溶射被膜２ａの密着
力が向上し、高温下で長時間使用しても剥離することが
ない。FIG. 1 is a cross-sectional view of a metal material surface-treated by the method of the present invention, FIG. 2 is an enlarged view of part A in FIG. 1, and FIG.
It is an enlarged view of part B of the figure. In the figure, a thermal spray coating 2, that is, an initial thermal spray coating 2a and a surface spray coating 2b, are formed on the surface of a base material 1. The initial thermal spray coating 2a is formed of a mixture of a substance (carbide) 3 with a high melting point and high hardness and an alloy (metal) 4 containing aluminum. When the vA mixture is thermally sprayed onto the base material 1, the particles of carbide 3 collide with the surface of the base material 1 in an unmolten or semi-molten and hard state, and due to the anchoring effect, the surface of the base material 1 is fixed as shown in Fig. 2. Also, since metal 4 has high wettability in a completely molten state, it wraps around carbide 3 during transfer to the base metal, preventing decomposition of the carbide, increasing collision energy, and causing carbide particles to also absorb into the matrix. Adheres well to uneven surfaces of materials. Therefore, the adhesion between the base material 1 and the first sprayed coating 2a is improved, and the coating does not peel off even when used for a long time at high temperatures.
さらに前記初層溶射皮膜２ａと表面溶射皮膜２ｂの接触
部（Ｂ部）では、溶射後に行なう酸化性雰囲気中の熱処
理によって、初層溶射被膜２ａに含まれるアルミニウム
が、第３図に示すように初層溶射被膜２ａ表面全体に微
細なアルミナ酸化物５となって優先的に析出する。この
微細なアルミナ酸化ｆ＃Ｊ５が初層溶射被膜２ａと表層
溶射皮膜２ｂを強固に結びつける糊の役目をするため、
初層溶射被膜２ａと表層溶射被膜２ｂの境界の密着力が
向上する。この微細なアルミナ酸化物５を初層溶射被膜
２ａ表面に優先的に生成させるには、熱処理雰囲気中の
酸素分圧をできるだけ小さくする必要があるが、前記初
層溶射被膜２ａは、緻密な表層溶射皮膜２ｂを介して雰
囲気ガスと接触しており、初層溶射層２ａの酸素分圧は
大気中雰囲気でも充分低く、アルミニウムが優先的に酸
化されることになる。Furthermore, at the contact area (part B) between the initial thermal sprayed coating 2a and the surface thermal sprayed coating 2b, the aluminum contained in the initial thermal sprayed coating 2a is removed by heat treatment in an oxidizing atmosphere after thermal spraying, as shown in FIG. Fine alumina oxide 5 is preferentially deposited over the entire surface of the first thermal sprayed coating 2a. Because this fine alumina oxide f#J5 acts as a glue that firmly binds the initial sprayed coating 2a and the surface sprayed coating 2b,
The adhesion of the boundary between the initial sprayed coating 2a and the surface sprayed coating 2b is improved. In order to generate this fine alumina oxide 5 preferentially on the surface of the first sprayed coating 2a, it is necessary to reduce the oxygen partial pressure in the heat treatment atmosphere as much as possible. The initial thermal sprayed layer 2a is in contact with atmospheric gas through the thermal sprayed coating 2b, and the oxygen partial pressure in the initial thermal sprayed layer 2a is sufficiently low even in the air, so that aluminum is preferentially oxidized.
なお、本発明においては、熱衝撃が激しい環境に通用す
る場合には、溶射皮膜を３層とし、初層溶射被膜２ａと
表層溶射被膜２ｂの間に、中間層として初層溶射層用粉
末と表層溶射層用粉末の混合物による皮膜を形成するこ
とができる。このようにすると溶射皮膜２中の熱膨脹係
数が被膜厚方向に連続的に変化するようになるのでより
長寿命化を図ることができる。In addition, in the present invention, when applicable to an environment with severe thermal shock, the thermal sprayed coating is formed into three layers, and a powder for the initial thermal sprayed layer is provided as an intermediate layer between the initial thermal sprayed coating 2a and the surface thermal sprayed coating 2b. A coating can be formed using a mixture of powders for the surface thermal spray layer. In this way, the coefficient of thermal expansion in the thermal spray coating 2 changes continuously in the direction of the coating thickness, so that a longer life can be achieved.
以下、本発明を実施例により詳しく説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
なお、実施例で使用した溶射方法は不連続型爆発溶射法
である。この溶射法は、円筒型状のガン内の後部に送給
された燃焼ガスと酸素ガスとの混合ガスをスバーグブラ
グで点火爆発して内部に供給されている粉末粒子を瞬間
的に高温に加熱し、ガンの先端から２〜３マツハの高速
で噴射させ、該噴射を不連続的に繰返す方法である。こ
のときのガス温度は２０００〜３０００℃である。The thermal spraying method used in the examples is a discontinuous explosive thermal spraying method. This thermal spraying method involves igniting and exploding a mixture of combustion gas and oxygen gas fed into the rear part of a cylindrical gun using a Sberg Blag to instantaneously heat the powder particles supplied inside to a high temperature. This is a method in which the gun is injected from the tip of the gun at a high speed of 2 to 3 meters, and the injection is repeated discontinuously. The gas temperature at this time is 2000 to 3000°C.
実施例１
まず母材の表面をショツトブラスト処理を行なった後、
不連続爆発溶射によって、クロム炭化物Ｃｒ、、Ｃｚ
７５重量％と、アルミニウムを含む金属（Ｎ ｔ ：
８０重量％、Ｃｒ：１７重量％、Ａ２：３重量％）２５
重量％との混合粉末を溶射し、初Ｎ溶射皮膜２ａを形成
させ、次にアルミナ酸化物粉末を上記と同じ方法で溶射
して表層溶射皮膜２ｂを形成させ、大気雰囲気中で１０
００″Ｃで２４時間熱処理を行なった。Example 1 First, after shot blasting the surface of the base material,
By discontinuous detonation spraying, chromium carbide Cr,,Cz
75% by weight and metals containing aluminum (N t :
80% by weight, Cr: 17% by weight, A2: 3% by weight) 25
% by weight to form an initial N sprayed coating 2a, and then sprayed alumina oxide powder in the same manner as above to form a surface sprayed coating 2b.
Heat treatment was performed at 00''C for 24 hours.
その際の混合粉末およびアルミナ酸化物粉末の溶射条件
は以下のとおりである。The thermal spraying conditions for the mixed powder and alumina oxide powder at that time were as follows.
酸素流ｉｔ ：３５１／ｍｉｎ
アセチレン流量：３０１／ｍｉｎ
溶射粉末供給量：１０■／ ｓ ｅ ｃ形成された溶射
皮膜について、５００“Ｃ１７００℃および９００℃の
それぞれの温度から室温への加熱冷却試験を１０回行な
い、試験後に皮膜が剥離したかどうかを調べることによ
って母材と皮膜間の密着力を評価した。その結果を第１
表に示す。Oxygen flow rate: 351/min Acetylene flow rate: 301/min Thermal spray powder supply rate: 10/sec The formed thermal spray coating was subjected to heating and cooling tests from 500°C to room temperature from 1700°C and 900°C. The adhesion between the base material and the film was evaluated by checking whether the film had peeled off after the test.
Shown in the table.
比較例１
実施例１において、１０００ ’Ｃで熱処理を行わなか
った以外は実施例１と同様にして溶射被膜を形成させ、
その密着力を評価した。その結果を第１表に示した。Comparative Example 1 A thermal spray coating was formed in the same manner as in Example 1 except that the heat treatment at 1000'C was not performed,
The adhesion was evaluated. The results are shown in Table 1.
比較例２および３ 実施例１において、溶射被膜材料としてＡ１．。Comparative examples 2 and 3 In Example 1, A1. .
０、のみを用いてそれぞれ爆発溶射（比較例２）および
大気中プラズマ溶射（比較例３）を行い、かつｌ ００
０ ”Ｃで熱処理を行わなかった以外は実施例１と同様
にして溶射被膜を形成させ、その密着力を評価した。そ
の結果を第１表に示した。Explosive spraying (Comparative Example 2) and atmospheric plasma spraying (Comparative Example 3) were carried out using only l 00, and l 00
A thermally sprayed coating was formed in the same manner as in Example 1, except that no heat treatment was performed at 0''C, and its adhesion was evaluated.The results are shown in Table 1.
以下余白
第
表
以上の結果から、本発明の方法によって作製した皮膜は
５００“Ｃ，７００℃および９００℃それぞれの試験温
度での加熱・冷却の繰返し試験において剥離が発生せず
、砥めて良好な密着性を有していることが示された。From the results shown in the table below, the film produced by the method of the present invention did not peel off in repeated heating and cooling tests at test temperatures of 500"C, 700°C and 900°C, and was polished well. It was shown that it had good adhesion.
本発明の方法によれば、母材と溶射被膜層の境界および
溶射皮膜層間の境界が高い密着力を有するため、高温で
の長時間の使用や急熱・急冷の繰返し使用によっても溶
射被膜が剥離することがない。したがって、耐蝕性、耐
熱性および耐摩耗性を要する製品の耐用年数を飛躍的に
向上させることができる。According to the method of the present invention, the boundaries between the base material and the sprayed coating layer and the boundaries between the sprayed coating layers have high adhesion, so the thermal sprayed coating will remain intact even after long periods of use at high temperatures or repeated use of rapid heating and cooling. Will not peel off. Therefore, the service life of products requiring corrosion resistance, heat resistance, and wear resistance can be dramatically improved.
第１図は、本発明の方法で得られた表面処理された金属
材料の断面図、第２図は、第１図のＡ部拡大図、第３図
は、第１図のＢ部の拡大図である。
ｌ・・・母材、２・・・溶射被膜、２ａ・・・初層溶射
被膜、２ｂ・・・表層溶射被膜、３・・・高融点で高硬
度の物質、４・・・アルミニウムを含む合金、５・・・
熱処理で生成したアルミナ酸化物。
出願人 バブコック日立株式会社
代理人 弁理士 川 北 武 長
：母材
：溶射皮膜
：初層溶射皮膜
：表層溶射皮膜
第
３：高融点で高硬度の一物質
４ニアルミニウムを含む合金
第
：熱処理で生成した
アルミナ酸化物Figure 1 is a cross-sectional view of the surface-treated metal material obtained by the method of the present invention, Figure 2 is an enlarged view of part A in Figure 1, and Figure 3 is an enlarged view of part B in Figure 1. It is a diagram. l...Base material, 2...Thermal spray coating, 2a...First layer spray coating, 2b...Surface spray coating, 3...High melting point and high hardness substance, 4...Contains aluminum Alloy, 5...
Alumina oxide produced by heat treatment. Applicant Babcock-Hitachi Co., Ltd. Representative Patent Attorney Takeshi Kawakita: Base material: Thermal sprayed coating: Initial thermal sprayed coating: Surface sprayed coating No. 3: Alloy containing 4 aluminum, a substance with high melting point and high hardness No. 3: By heat treatment Alumina oxide produced
Claims (2)
利用してアルミナ酸化物からなる溶射皮膜を金属材料表
面に形成する表面処理方法において、前記金属材料表面
に、高融点で高硬度の物質とアルミニウムを含む合金と
からなる混合物を溶射して第１層溶射皮膜を形成し、次
にこの被膜にアルミナ酸化物を溶射して多層溶射被膜を
形成した後、該多層溶射被膜を酸化性雰囲気中で８００
℃〜１０００℃の温度で加熱することを特徴とする金属
材料の表面処理方法。(1) In a surface treatment method in which a thermal spray coating made of alumina oxide is formed on the surface of a metal material using high-energy gas generated by gas explosion or combustion, a substance with a high melting point and high hardness and aluminum are coated on the surface of the metal material. A first layer thermal sprayed coating is formed by thermal spraying a mixture consisting of an alloy containing 800
A method for surface treatment of a metal material, characterized by heating at a temperature of 1000°C to 1000°C.
ルミニウムを含有し、かつＦｅ、Ｃｒ、ＮｉおよびＣｏ
の少なくとも１種の元素を含有することを特徴とする請
求項（１）記載の金属材料の表面処理方法。(2) The alloy containing aluminum contains 1 to 10% by weight of aluminum and contains Fe, Cr, Ni and Co.
The method for surface treatment of a metal material according to claim 1, characterized in that the method contains at least one element of the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63309422A JP2770967B2 (en) | 1988-12-07 | 1988-12-07 | Surface treatment method for metal materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63309422A JP2770967B2 (en) | 1988-12-07 | 1988-12-07 | Surface treatment method for metal materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02156060A true JPH02156060A (en) | 1990-06-15 |
| JP2770967B2 JP2770967B2 (en) | 1998-07-02 |
Family
ID=17992815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63309422A Expired - Fee Related JP2770967B2 (en) | 1988-12-07 | 1988-12-07 | Surface treatment method for metal materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2770967B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63149364A (en) * | 1986-12-12 | 1988-06-22 | Babcock Hitachi Kk | High-energy gas thermal spraying method |
| JPS63166954A (en) * | 1986-12-27 | 1988-07-11 | Toshiba Corp | Method for forming ceramic member |
| JPS63255352A (en) * | 1987-04-10 | 1988-10-21 | Kawasaki Steel Corp | Coated roll for conveying high-temperature steel sheet |
-
1988
- 1988-12-07 JP JP63309422A patent/JP2770967B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63149364A (en) * | 1986-12-12 | 1988-06-22 | Babcock Hitachi Kk | High-energy gas thermal spraying method |
| JPS63166954A (en) * | 1986-12-27 | 1988-07-11 | Toshiba Corp | Method for forming ceramic member |
| JPS63255352A (en) * | 1987-04-10 | 1988-10-21 | Kawasaki Steel Corp | Coated roll for conveying high-temperature steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2770967B2 (en) | 1998-07-02 |
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