JPH0229740B2 - MITSUCHAKUSEINISUGURETAYOSHASONOKEISEIHOHO - Google Patents
MITSUCHAKUSEINISUGURETAYOSHASONOKEISEIHOHOInfo
- Publication number
- JPH0229740B2 JPH0229740B2 JP15027181A JP15027181A JPH0229740B2 JP H0229740 B2 JPH0229740 B2 JP H0229740B2 JP 15027181 A JP15027181 A JP 15027181A JP 15027181 A JP15027181 A JP 15027181A JP H0229740 B2 JPH0229740 B2 JP H0229740B2
- Authority
- JP
- Japan
- Prior art keywords
- sprayed layer
- base material
- thermal
- spraying
- steel
- 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
Links
- 239000000463 material Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 9
- 238000007751 thermal spraying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- 239000011195 cermet Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000007750 plasma spraying Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
Description
本発明は、密着性のすぐれた溶射層の形成方法
に関する。
溶射法は、金属材料（基材）の耐食性、耐熱
性、あるいは耐摩耗性等を高める目的で、金属、
合金、セラミツク、サーメツト等の溶射材を、燃
料ガス、高周波発熱あるいはプラズマ炎などにて
半溶融状態に加熱し、その溶滴を噴射させ、高速
度で基材表面に衝突させることにより密着被覆さ
せる方法である。従つてこの溶射層は、衝突の際
偏平化した溶射材粒子が堆積したもので、粒子間
に小間隙が残留し、また粒子と基材表面との間に
は、化学的結合等を生ずることもあるが、通常は
基材表面の凹凸に粒子がくい込んだ機械的ないし
は物理的結合によつて密着している。
しかして、溶射層と基材表面との密着性は、溶
射条件により一様ではないが、例えば、プラズマ
溶射により形成した溶射層でも、その密着強度
は、200〜270Kg／cm2程度に過ぎないため、機械構
造材料、例えばロールのように大きな負荷が作用
する用途においては、溶射層の剥離を生じ易いと
いう問題がある。この対策として、例えば、基材
表面に予め下地処理としてNi、Mo、Co等の金属
を溶射して薄い金属材料を形成する方法、あるい
は、溶射後に加熱溶融させる方法などが用いられ
ている。しかしながら、これらの方法によつて
も、密着強度は300〜350Kg／cm程度となるに過ぎ
ず、機械構造材としての使用に十分耐え得るもの
は得がたい。
本発明は上記にかんがみてなされるものであ
り、金属基材表面に溶射層を被覆させたのち、こ
れを高真空中にて高温に加熱することにより、溶
射層の密着性を飛躍的に高めることに成功した。
以下、本発明方法について説明する。
本発明においては、まず常法により金属基材表
面に溶射層を形成する。その溶射方法は任意であ
り、火炎溶射、プラズマ溶射等を適宜用いてよ
い。
溶射材としては、目的・用途に応じ、Cr、Ni、
Moなどの金属、各種ステンレス鋼、Cr−Mo鋼、
Ni−Cr鋼などの合金鋼、各種金属の酸化物、炭
化物、窒化物、ホウ化物などのセラミツク、ある
いはセラミツクとNi、Coなどからなるサーメツ
ト等が用いられる。
金属基材としては、機械構造材として用いられ
る各種合金鋼、例えばCr−Ni鋼、Cr−Mo鋼、
Ni−Mo鋼、Ni−Cr−Mo鋼、などが挙げられ
る。
なお、溶射に先立つて、常法に従い、基材表面
の脱脂、および粗面化のためのシヨツトプラスト
あるいはグリツトプラストなどの前処理を行う。
常法により溶射層を形成したのち、高真空の雰
囲気中、高温に加熱する。この処理雰囲気とし
て、真空度10-1mmHg水素ガス雰囲気が好ましい。
また、その処理温度は、約1000℃以上であること
が望ましい。
上記高真空水素雰囲気中での高温加熱により、
溶射層および基材の表面が著しく活性化し、相互
の密着力は飛躍的に高められる。
また、この処理により、基材を構成する合金元
素、特にCr、Mnなどの溶射層への拡散浸透によ
つて溶射層との密着性が更に高められるととも
に、溶射層の粒子間小空隙の減少・緻密化を生
じ、溶射層の強度が高められる等、溶射層の性状
が改善される。
上記高真空・高温加熱処理時間は、例えば１〜
２時間程度でよく、処理を終えたのちは、炉外に
取出し、大気中で放冷してよく、冷却条件に特別
の制限は要しない。
かくして得られる溶射層と基材の密着強度は極
めて高く、大気雰囲気中で加熱を行なう従来の溶
融法で得られるものに比し、２倍もしくはそれ以
上にも達する。
次に実施例を挙げて本発明について具体的に説
明する。
実施例
粗面化処理したCr−Ni鋼基材（管材）に、溶
射材としてジルコニアとコバルトからなるサーメ
ツトを用い、常法によるプラズマ溶射を行なつて
外周面に層厚0.3mmの溶射層を形成し、ついで本
発明による高真空・高温加熱処理を施した。その
溶射条件および加熱処理条件は次のとおりであ
る。
〔〕 溶射条件
(1) 溶射装置：メテコ3M型プラズマ溶射装置
電流：500Amp
噴射ガス：Ｎ＋H2（Ｎ：H2＝100：15）
溶射距離：100mm
溶射材粉末流量：80ｇ／min
(2) 溶射材：ジルコニア80％＋コバルト20％
(3) 基材
材質：25％Cr−20％Ni鋼（JIS SCH22相
当）
寸法：直径160mm×肉厚20mm×長さ400mm
表面前処理：シヨツトブラスト（外周面粗
さ∇∇）
The present invention relates to a method for forming a thermally sprayed layer with excellent adhesion. Thermal spraying is a method to improve the corrosion resistance, heat resistance, or abrasion resistance of metal materials (base materials).
Thermal spray materials such as alloys, ceramics, and cermets are heated to a semi-molten state using fuel gas, high-frequency heating, or plasma flame, and the resulting droplets are sprayed and collided with the surface of the base material at high speed to form an adhesive coating. It's a method. Therefore, this thermal spray layer is a deposit of thermal spray material particles that were flattened during collision, leaving small gaps between the particles, and chemical bonds etc. may occur between the particles and the surface of the base material. Although there are some, the particles are usually stuck to each other through mechanical or physical bonding, where the particles are embedded in the irregularities on the surface of the base material. However, the adhesion between the sprayed layer and the surface of the base material is not uniform depending on the spraying conditions, but for example, even with a sprayed layer formed by plasma spraying, the adhesion strength is only about 200 to 270 kg/cm 2 . Therefore, in applications where large loads are applied to mechanical structural materials, such as rolls, there is a problem in that the thermal sprayed layer is likely to peel off. As a countermeasure against this problem, for example, a method is used in which a thin metal material is formed by spraying a metal such as Ni, Mo, or Co on the surface of the base material in advance as a base treatment, or a method in which the material is heated and melted after spraying. However, even with these methods, the adhesion strength is only about 300 to 350 kg/cm, and it is difficult to obtain a material that can be used as a mechanical structural material. The present invention has been made in view of the above, and the adhesion of the sprayed layer is dramatically improved by coating the surface of a metal base material with a sprayed layer and then heating it to a high temperature in a high vacuum. It was very successful. The method of the present invention will be explained below. In the present invention, first, a thermal spray layer is formed on the surface of a metal base material by a conventional method. The spraying method is arbitrary, and flame spraying, plasma spraying, etc. may be used as appropriate. Depending on the purpose and application, thermal spraying materials include Cr, Ni,
Metals such as Mo, various stainless steels, Cr-Mo steel,
Alloy steel such as Ni-Cr steel, ceramics such as oxides, carbides, nitrides, and borides of various metals, or cermets made of ceramics and Ni, Co, etc., are used. As the metal base material, various alloy steels used as machine structural materials, such as Cr-Ni steel, Cr-Mo steel,
Examples include Ni-Mo steel, Ni-Cr-Mo steel, and the like. Prior to thermal spraying, the surface of the base material is degreased and pretreated with shotplast or gritplast to roughen the surface according to a conventional method. After forming a sprayed layer by a conventional method, it is heated to a high temperature in a high vacuum atmosphere. The preferred atmosphere for this treatment is a hydrogen gas atmosphere with a degree of vacuum of 10 -1 mmHg.
Further, the processing temperature is desirably about 1000°C or higher. By high temperature heating in the above high vacuum hydrogen atmosphere,
The surfaces of the sprayed layer and the base material are significantly activated, and their mutual adhesion is dramatically increased. In addition, this treatment further improves the adhesion of the alloy elements constituting the base material, especially Cr and Mn, by diffusing into the sprayed layer, and reduces the small voids between particles in the sprayed layer.・Properties of the sprayed layer are improved, such as densification and increased strength of the sprayed layer. The above high vacuum/high temperature heat treatment time is, for example, 1~
It only takes about 2 hours, and after finishing the treatment, it can be taken out of the furnace and left to cool in the atmosphere, and no special restrictions are required on the cooling conditions. The adhesion strength between the sprayed layer and the base material thus obtained is extremely high, reaching twice or more than that obtained by conventional melting methods in which heating is performed in the air. Next, the present invention will be specifically explained with reference to Examples. Example: Using a cermet made of zirconia and cobalt as a thermal spraying material, plasma spraying was performed using a conventional method on a roughened Cr-Ni steel base material (pipe material) to form a sprayed layer with a thickness of 0.3 mm on the outer peripheral surface. It was then subjected to high vacuum and high temperature heat treatment according to the present invention. The thermal spraying conditions and heat treatment conditions are as follows. [] Thermal spraying conditions (1) Thermal spraying equipment: Metco 3M type plasma spraying equipment Current: 500Amp Injection gas: N + H 2 (N:H 2 = 100:15) Spraying distance: 100mm Spraying material powder flow rate: 80g/min (2) Thermal spraying Material: Zirconia 80% + Cobalt 20% (3) Base material Material: 25% Cr-20% Ni steel (JIS SCH22 equivalent) Dimensions: Diameter 160 mm x Wall thickness 20 mm x Length 400 mm Surface pretreatment: Shot blasting (outer periphery Surface roughness ∇∇)
【表】
上記処理後、それぞれについて溶射層と基材の
密着強度を測定した。その測定は、第１図に示す
ように、試験材１の回転下に（回転速度5RPM）、
その外周面に対応する湾曲部をもつた荷圧体２を
一定の荷重ｗで押圧せしめ、溶射層３の剥離発生
時の荷圧体２に加えられた荷重から密着強度を算
出した。
各供試材の測定結果を第２表に示す。[Table] After the above treatment, the adhesion strength between the sprayed layer and the base material was measured for each. The measurement was carried out under the rotation of the test material 1 (rotation speed 5 RPM), as shown in Figure 1.
A pressure body 2 having a curved portion corresponding to its outer peripheral surface was pressed with a constant load w, and the adhesion strength was calculated from the load applied to the pressure body 2 when the thermal sprayed layer 3 peeled off. Table 2 shows the measurement results for each sample material.
【表】
上記第２表から明らかなように、本発明により
得られる溶射層は、溶射のままのものに比し、約
2.5〜3.5倍以上の密着強度をもつ。
なお、第２図に溶射層における基材からの元素
移動状況を示す。同図〔〕は比較溶射層（溶射
のまま）、〔〕は本発明による溶射層（但し、熱
処理(B)）であり、いづれも溶射層を含む基材を断
面方向に切断し、研磨後、断面の外表面側をエネ
ルギー拡散型Ｘ線分析装置にて分析したものであ
る。
上記各図の比較から明らかなように、本発明に
よる溶射層には、その外側面へのCr、Mnの移動
が認められ、従来のものと著しく異なることがわ
かる。
以上のように、本発明により形成される溶射層
は基材との密着性にすぐれ、従来法による溶射層
の約２倍以上の密着強度を有するので、ロール、
機械部品、鉄骨、橋梁、その他各種機械構造用材
の用途においても、容易に剥離・損傷を生ずるこ
とがなく、長期間にわたり溶射層の耐食、耐熱、
あるいは耐摩耗性が保持され、安定した使用を保
証することができる。[Table] As is clear from Table 2 above, the thermal sprayed layer obtained by the present invention is approximately
It has 2.5 to 3.5 times more adhesion strength. Note that FIG. 2 shows the state of element transfer from the base material in the sprayed layer. In the same figure, [ ] is a comparison thermal sprayed layer (as sprayed), and [ ] is a thermal sprayed layer according to the present invention (heat treated (B)). , the outer surface side of the cross section was analyzed using an energy diffusion type X-ray analyzer. As is clear from the comparison of the above figures, it can be seen that the thermal sprayed layer according to the present invention has migration of Cr and Mn to its outer surface, and is significantly different from the conventional one. As described above, the thermal sprayed layer formed by the present invention has excellent adhesion to the base material, and has an adhesion strength about twice or more than that of the thermal sprayed layer formed by the conventional method.
In applications such as mechanical parts, steel frames, bridges, and various other mechanical structural materials, the sprayed layer will not easily peel off or be damaged, and will maintain the corrosion and heat resistance of the sprayed layer for a long period of time.
Alternatively, wear resistance can be maintained and stable use can be guaranteed.
第１図は溶射層密着性試験要領説明図、第２図
〔〕および〔〕は溶射層への基材元素移動状
況を示すＸ線分析による分析結果図である。
１：試験材、３：溶射層。
FIG. 1 is an explanatory diagram of the thermal sprayed layer adhesion test procedure, and FIGS. 2 [ ] and [ ] are analysis results obtained by X-ray analysis showing the migration of base material elements to the thermal sprayed layer. 1: Test material, 3: Sprayed layer.
Claims (1)
金、セラミツクまたはサーメツトを溶射したの
ち、真空度10-1mmHg以下の水素ガス中、温度
1000℃以上に加熱することを特徴とする密着性に
すぐれた溶射層の形成方法。1 After spraying metal, alloy, ceramic, or cermet as a thermal spraying material onto the surface of an alloy steel base material, the temperature is
A method for forming a sprayed layer with excellent adhesion, which involves heating to over 1000℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15027181A JPH0229740B2 (en) | 1981-09-22 | 1981-09-22 | MITSUCHAKUSEINISUGURETAYOSHASONOKEISEIHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15027181A JPH0229740B2 (en) | 1981-09-22 | 1981-09-22 | MITSUCHAKUSEINISUGURETAYOSHASONOKEISEIHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5852468A JPS5852468A (en) | 1983-03-28 |
| JPH0229740B2 true JPH0229740B2 (en) | 1990-07-02 |
Family
ID=15493295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15027181A Expired - Lifetime JPH0229740B2 (en) | 1981-09-22 | 1981-09-22 | MITSUCHAKUSEINISUGURETAYOSHASONOKEISEIHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0229740B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60215754A (en) * | 1984-04-11 | 1985-10-29 | Nippon Kokan Kk <Nkk> | Manufacturing method of high hardness sprayed layer |
| JPS6130657A (en) * | 1984-07-20 | 1986-02-12 | Nippon Carbon Co Ltd | Manufacture of silicon carbide-coated carbon article |
| JPH01242786A (en) * | 1988-03-23 | 1989-09-27 | Mitsubishi Heavy Ind Ltd | Sliding member and production thereof |
-
1981
- 1981-09-22 JP JP15027181A patent/JPH0229740B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5852468A (en) | 1983-03-28 |
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