JPH0520497B2 - - Google Patents
Info
- Publication number
- JPH0520497B2 JPH0520497B2 JP60203924A JP20392485A JPH0520497B2 JP H0520497 B2 JPH0520497 B2 JP H0520497B2 JP 60203924 A JP60203924 A JP 60203924A JP 20392485 A JP20392485 A JP 20392485A JP H0520497 B2 JPH0520497 B2 JP H0520497B2
- Authority
- JP
- Japan
- Prior art keywords
- build
- roll
- metal
- coating
- spraying
- 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 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000007751 thermal spraying Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000005530 etching Methods 0.000 claims 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910001208 Crucible steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment 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
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- 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
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
Description
（産業上の利用分野）
本発明は熱処理炉用ロールの、金属板、金属管
または金属棒等の被熱処理材を支持する面に、ス
ケールの付着を防止する耐ビルドアツプ性被覆を
形成する方法に関する。
（従来の技術）
熱処理炉用ロールは高温度下で熱処理する金属
板、金属管または金属棒（以後、被熱処理材）を
支持するので、ロール表面に被熱処理材の微粉や
その酸化物が付着、堆積するビルドアツプ現象が
発生する。ロール表面に発生したビルドアツプは
被熱処理材の表面に押疵をつけるなど品質に影響
を及ぼし、商品価値を著しく低下せしめる。
このため、従来よりロールへのビルドアツプ発
生防止のために、ロール材質の高級化、水冷方式
のロールの採用、セラミツクスや炭素材料スリー
ブの嵌合および各種のセラミツクスやサーメツト
材料を被覆する表面処理の適用などが提案されて
いる。その中で溶射法においてはAl2O3，ZrO2，
SiO2，WC，Cr3C2，TiCなどのセラミツクス材
料およびNi，Cr，Co，Moなどとのサーメツト
材料を被覆することが提唱されているが未だ耐ビ
ルドアツプ性については十分な効果は得られてい
ない。
また、Cr2O3（特開昭55−154522号公報）やCr2
O3−30〜70％Al2O3（特開昭60−2661号公報）は
鉄系金属とのぬれ性が悪く、また反応性が低いた
め耐ビルドアツプ性に優れた材料であることは公
知である。しかしCr2O3自体は熱的に不安定で、
特にAr−H2やN2−H2を作動ガスとするプラズ
マジエツトのような超高温下で、かつ還元性ガス
を含む雰囲気中ではCr2O3は酸素を放出して、
Cr2O3とCrの共晶組成となり、著しい場合Cr2O3
の量に対して１〜５重量％の金属CrがCr2O3を含
む被覆層の中に生成する。この金属Crが原因と
なりビルドアツプが発生し、プラズマ溶射法での
Cr2O3を含有する被覆による耐ビルドアツプ性の
向上は困難であつた。
（発明が解決しようとする問題点）
本発明の目的はCr2O3を含有する酸化物系溶射
用粉末材料を用いて熱処理炉用ロールの表面に耐
ビルドアツプ性の優れた被覆を溶射する方法を提
供しようとするものである。
（問題点を解決するための手段）
本発明は、Cr2O3を含有する酸化物系溶射用粉
末材料を熱処理炉用ロールの表面に溶射して、耐
ビルドアツプ性被覆を形成するにあたり、酸素含
有ガスを作動ガスとする被還元性プラズマジエツ
トによつて溶射し、金属Cr量が0.5wt％以下の溶
射被覆層を形成させることを特徴とする耐ビルド
アツプ性被覆の形成方法を要旨とする。
以下本発明について詳述する。
被覆層の緻密性と密着性の観点から、耐ビルド
アツプ性被覆の形成にあたつてはプラズマ溶射法
が適している。本発明者らはCr2O3からの金属Cr
の発生を低減するためには、プラズマ作動ガスを
酸素含有ガスとする非還元性プラズマジエツトが
有効であることを見出した。
その結果を表１に示す。具体的には純度99重量
％のCr2O3をO2−0.1〜99.9体積％Ar，O2−0.1〜
99.9体積％N2のような酸素含有ガスを作動ガス
とするプラズマジエツトによつて、溶射積層する
ことにより、被覆層中の、Cr2O3から発生する金
属Cr量を0.5重量％以下にすることが可能である。
しかし、耐ビルドアツプ性被覆として緻密かつ高
密着力の被覆を得るためにはプラズマジエツトの
保温、速さ、効率およびガスの安全性の観点から
O2ガスの比率をできる限り少なくする方が好ま
しく、さらに実用上O2の比率が0.1〜３体積％で
も目的は十分に達成される。尚、供試材および被
覆層中の金属Cr量は塩酸可溶Crを原子吸光分析
にて定量分析した。
次に本発明による被覆層についてのビルドアツ
プ試験の結果を表２に示す。このビルドアツプ試
験は溶射によつて被覆した50mm×30mm×５mmの２
枚の平板の間にビルドアツプ原料をのせて重ね合
せ、その上に荷重を加えて、ビルドアツプ原料と
２枚の平板がこすり合うような動きを与え雰囲気
をN2（95％）−H2（５％）に調整し、1000℃で５
時間加熱し、冷却後被覆の表面状態を観察した。
Cr2O3を含有する溶射用粉末材料の供試材は純
度99％Cr2O3および50％Cr2O3−50％Al2O3の混合
材料および固溶体材料の３種類を用いた。
以上の実験によりCr2O3を含有する上記３種類
の供試材では被覆層中の金属Cr量が低いほどビ
ルドアツプの発生量が小さい。また３種類の供試
材の内Cr2O3被覆はビルドアツプ試験の結果、皮
膜剥離を生じ、実用上使用できないと判断した。
以下実施例について説明する。
（実施例）
耐熱鋳鋼製ロール表面に表２に示すT.P.No.14
〜17の被覆を形成し、表面平滑度が100μm以下に
なるように研削し、熱処理炉用ロールとした。さ
らに従来品として耐熱鋳鋼製ロールを用意した。
上記５種類の熱処理炉用ロールを実際の鋼板熱
処理炉（温度800〜1050℃、N2−H2−H2Ｏ雰囲
気中）で3000時間使用した結果を表３に示す。
（発明の効果）
上記の実施例に示す如く、本発明に係る耐ビル
ドアツプ性被覆はロール寿命延長に貢献するもの
であるから、産業上裨益するところが極めて大で
ある。
(Industrial Application Field) The present invention relates to a method for forming a build-up resistant coating to prevent scale adhesion on the surface of a roll for a heat treatment furnace that supports a material to be heat treated such as a metal plate, metal tube or metal rod. . (Prior art) Since rolls for heat treatment furnaces support metal plates, metal tubes, or metal rods (hereinafter referred to as heat-treated materials) that are heat-treated at high temperatures, fine powder of the heat-treated materials and their oxides adhere to the roll surface. , a build-up phenomenon occurs. Build-up that occurs on the roll surface affects the quality of the heat-treated material by causing scratches on the surface, significantly reducing the product value. For this reason, in order to prevent build-up on rolls, conventional methods include using higher-grade roll materials, using water-cooled rolls, fitting ceramic or carbon material sleeves, and applying surface treatments to cover various ceramics and cermet materials. etc. have been proposed. Among them, Al 2 O 3 , ZrO 2 ,
Although it has been proposed to coat ceramic materials such as SiO 2 , WC, Cr 3 C 2 , TiC, and cermet materials with Ni, Cr, Co, Mo, etc., sufficient effects on build-up resistance have not yet been obtained. Not yet. In addition, Cr 2 O 3 (Japanese Patent Application Laid-open No. 154522/1983) and Cr 2
It is well known that O 3 -30 to 70% Al 2 O 3 (Japanese Unexamined Patent Publication No. 60-2661) is a material with excellent build-up resistance due to poor wettability with iron-based metals and low reactivity. It is. However, Cr 2 O 3 itself is thermally unstable;
In particular, under extremely high temperatures such as in a plasma jet using Ar-H 2 or N 2 -H 2 as a working gas, and in an atmosphere containing reducing gas, Cr 2 O 3 releases oxygen.
It becomes a eutectic composition of Cr 2 O 3 and Cr, and in significant cases Cr 2 O 3
1 to 5% by weight of metallic Cr is formed in the coating layer containing Cr 2 O 3 based on the amount of Cr. This metal Cr causes build-up, which causes the plasma spraying method to fail.
It has been difficult to improve the build-up resistance with a coating containing Cr 2 O 3 . (Problems to be Solved by the Invention) The purpose of the present invention is to provide a method for spraying a coating with excellent build-up resistance on the surface of a roll for a heat treatment furnace using an oxide thermal spraying powder material containing Cr 2 O 3. This is what we are trying to provide. (Means for Solving the Problems) The present invention provides a method for spraying an oxide-based thermal spraying powder material containing Cr 2 O 3 onto the surface of a roll for a heat treatment furnace to form a build-up resistant coating. The gist of the present invention is a method for forming a build-up resistant coating, which is characterized by forming a thermal sprayed coating layer with a metal Cr content of 0.5 wt% or less by thermal spraying using a reducible plasma jet using a containing gas as a working gas. . The present invention will be explained in detail below. From the viewpoint of the density and adhesion of the coating layer, plasma spraying is suitable for forming the build-up resistant coating. We have developed the metal Cr from Cr 2 O 3
It has been found that a non-reducing plasma jet using an oxygen-containing gas as the plasma working gas is effective in reducing the generation of . The results are shown in Table 1. Specifically, Cr 2 O 3 with a purity of 99% by weight is mixed with O 2 -0.1 to 99.9 volume% Ar, O 2 -0.1 to
The amount of metallic Cr generated from Cr 2 O 3 in the coating layer can be reduced to 0.5% by weight or less by laminating by thermal spraying using a plasma jet using an oxygen-containing gas such as 99.9% by volume N 2 as the working gas. It is possible to do so.
However, in order to obtain a dense and highly adhesive coating as a build-up resistant coating, it is necessary to take into consideration the heat retention, speed, efficiency, and gas safety of the plasma jet.
It is preferable to reduce the proportion of O 2 gas as much as possible, and in practice, the purpose can be sufficiently achieved even if the proportion of O 2 is 0.1 to 3% by volume. The amount of metal Cr in the sample material and coating layer was quantitatively analyzed by atomic absorption spectrometry of hydrochloric acid-soluble Cr. Next, Table 2 shows the results of the build-up test for the coating layer according to the present invention. This build-up test was conducted on two 50mm x 30mm x 5mm coated by thermal spraying.
Build-up raw materials are placed between two flat plates, stacked one on top of the other, and a load is applied on top of them to create a movement in which the build-up raw materials and the two flat plates rub against each other, creating an atmosphere of N 2 (95%) - H 2 (5 %) and 5 at 1000℃.
After heating for a period of time and cooling, the surface condition of the coating was observed. Three types of thermal spray powder materials containing Cr 2 O 3 were used: 99% pure Cr 2 O 3 , a mixed material of 50% Cr 2 O 3 -50% Al 2 O 3 , and a solid solution material. According to the above experiments, in the three types of test materials containing Cr 2 O 3 , the lower the amount of metal Cr in the coating layer, the smaller the amount of build-up occurs. Furthermore, among the three types of test materials, the Cr 2 O 3 coating caused peeling of the film as a result of the build-up test, and was judged to be unusable for practical use. Examples will be described below. (Example) TP No. 14 shown in Table 2 was placed on the surface of the heat-resistant cast steel roll.
A coating of ~17 was formed and ground to a surface smoothness of 100 μm or less to obtain a roll for a heat treatment furnace. Furthermore, we prepared a heat-resistant cast steel roll as a conventional product. Table 3 shows the results of using the five types of heat treatment furnace rolls described above in an actual steel plate heat treatment furnace (temperature 800 to 1050°C, N2 - H2 - H2O atmosphere) for 3000 hours. (Effects of the Invention) As shown in the above examples, the build-up resistant coating according to the present invention contributes to extending the life of the roll, and therefore has extremely great industrial benefits.
【表】【table】
【表】【table】
Claims (1)
熱処理炉用ロールの表面に溶射して、耐ビルドア
ツプ性被覆を形成するにあたり、酸素含有ガスを
作動ガスとする非環元性プラズマジエツトによつ
て溶射し、金属Cr量が0.5wt％以下の溶射被覆層
を形成させることを特徴とする耐ビルドアツプ性
被覆の形成方法。1 When spraying an oxide-based thermal spraying powder material containing Cr 2 O 3 onto the surface of a roll for a heat treatment furnace to form a build-up resistant coating, a non-cyclic plasma spray using an oxygen-containing gas as the working gas is used. 1. A method for forming a build-up resistant coating, which is characterized by forming a thermal sprayed coating layer with a metal Cr content of 0.5 wt% or less by thermal spraying using an etching method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203924A JPS6263664A (en) | 1985-09-14 | 1985-09-14 | Formation of build-up resistant coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203924A JPS6263664A (en) | 1985-09-14 | 1985-09-14 | Formation of build-up resistant coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6263664A JPS6263664A (en) | 1987-03-20 |
| JPH0520497B2 true JPH0520497B2 (en) | 1993-03-19 |
Family
ID=16481947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60203924A Granted JPS6263664A (en) | 1985-09-14 | 1985-09-14 | Formation of build-up resistant coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6263664A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3910145B2 (en) | 2003-01-06 | 2007-04-25 | 日本発条株式会社 | Thermal spray coating and method for producing the same |
-
1985
- 1985-09-14 JP JP60203924A patent/JPS6263664A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6263664A (en) | 1987-03-20 |
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