JPS636614B2 - - Google Patents
Info
- Publication number
- JPS636614B2 JPS636614B2 JP19914583A JP19914583A JPS636614B2 JP S636614 B2 JPS636614 B2 JP S636614B2 JP 19914583 A JP19914583 A JP 19914583A JP 19914583 A JP19914583 A JP 19914583A JP S636614 B2 JPS636614 B2 JP S636614B2
- Authority
- JP
- Japan
- Prior art keywords
- heat treatment
- carbon material
- roll
- porosity
- hearth
- 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
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003575 carbonaceous material Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 238000005087 graphitization Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000008119 colloidal silica Substances 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000976 Electrical steel Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/562—Details
- C21D9/563—Rolls; Drums; Roll arrangements
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
Description
（技術分野）
鋼板とくに電磁鋼板ストリツプの送行を案内す
る熱処理炉のハースロールに関し、この明細書に
述べる技術内容は、H2およびN2を主成分とし微
量のH2Oを含む900℃以上、それもとくに970℃
をこえる場合が含まれるような高温酸化性雰囲気
が選択される焼鈍条件下でも好適に使用できるよ
うにした、黒鉛質炭素材料からなる熱処理炉のハ
ースロールに関連し、鋼板ストリツプの熱処理の
属している技術の分野に位置している。
（従来技術とその問題点）
熱処理炉のハースロール用炭素材料としては、
出願人がさきに特開昭57−137419号公報で開示し
ているように黒鉛化度0.6以上で気孔率５〜15％、
シヨア硬度50〜100の黒鉛質炭素材料の押出成形
体が適する。すなわち発明者らは同号公報に掲げ
られた炭素材料からなるハースロールをその実施
例につき、以下の条件
温度900〜950℃、雰囲気組成H260〜65％、
H240〜35％、そして露点０〜30℃
において電磁鋼板ストリツプの熱処理炉にて実用
試験を行つたところ、ハースロールの損耗量は極
めて少なく鋼板にピツクアツプを発生することな
く、熱処理炉ハースロールの使用寿命が延伸され
ることが再確認された。
しかしながら、熱処理温度がときに970℃を越
えるような上記雰囲気下の焼鈍条件なかでも高露
点下では、ハースロールの損耗量が増大すること
が同時に判明した。
発明者らは、この原因を詳細にわたつて調査し
た結果の１例を第１図で示したように、上記の炭
素材料は、鉄粉との接触下の焼鈍条件のもとで高
温になるほど顕著に酸化減量が増大し、その挙動
を詳しく吟味したところ、化学的な消耗によるも
のと判断された。
すなわち上記実用試験における異常損耗は、熱
処理炉では常に鋼板と接触していることからFe
の触媒作用によつてハースロール炭素材料の酸化
が促進されたものと考えられる。
（発明の目的）
上記のような問題点についての有利な解決を与
えて熱処理炉の雰囲気条件の如何にかかわらず、
充分に高い酸化消耗抵抗性および耐ピツクアツプ
性をもつハースロールを与えることがこの発明の
目的である。
（発明の構成）
発明者らは、熱処理用ハースロールについての
上掲特開昭57−137419号公報による先行開発成果
においてなお未解決であつた上記の欠点を補うた
めに、検討と実験をあまた重ねて、次のような改
質手段の適合を見い出したものである。
すなわち、かさ比重1.75〜2.0、気孔率８〜17
％、シヨア硬度70以上、黒鉛化度0.6以上で平均
粒子径100μｍ以下の黒鉛質炭素材料のプレス成
形体よりなり、りん酸塩とコロイド状シリカを配
合した含浸剤のシリカ成分が当該炭素材料の表面
から少なくとも３mmにわたり浸透した表面封口層
をそなえ、酸化消耗抵抗性および耐ピツクアツプ
性に優れる熱処理炉のハースロール。
まずこの発明において黒鉛炭素材料の物性を限
定する理由は、次のとおりである。
かさ比重1.75〜2.0としたのは、次にのべる気
孔率の適正範囲を実現するために必要である。
気孔率は、一般的に低気孔率の場合に含浸処理
が困難であり、とくに８％未満では封口処理のた
めの含浸剤組成中とくに重要な（後述）シリカ成
分につき表面から３mm以上の浸透深さが確保され
ず、また17％を越るような炭素材料にあつては含
浸剤の浸透深さは十分であつても炭素材料の組織
自体が荒すぎて鉄粉凝集粒子の炭素材料への植込
みを防止しきれず鋼板に対するピツクアツプが解
消されないため気孔率８〜17％を必要とするので
ある。
シヨアー硬度70以上を限定するのは、機械的強
度を確保するためで、これ以下の硬度の材料では
ストリツプの荷重とくにストリツプエツヂによる
食い込みによるロールの減耗が増し、含浸効果が
早く失なわれるためであり、黒鉛化度0.6以上を
限定するのは、高温下の酸化損耗の防止効果を適
切に実現するためである。
また平均粒子径は、上記の気孔率およびシヨア
硬度を満足させるため100μｍ以下が必要である。
このような黒鉛質炭素材料は、一般的には静水
圧プレス法などで製造される極めてち密なもので
押出し成形では得られない。
次に含浸剤は、りん酸塩とコロイド状シリカを
配合したものであることが必要でこのうちりん酸
塩については、アルミニウム塩、マグネシウム塩
カルシウム塩および亜鉛塩の中から選ばれる１種
又は２種以上の混合液を用いることができ、また
コロイド状シリカとしては、超微粒子のもの例え
ば粒子径７〜９ｍμ程度が好適である。
第２図に、かさ比重1.94、気孔率10％、シヨア
硬度100、黒鉛化度は0.7で平均粒子径20μｍの黒
鉛質炭素材料を用意し、これにりん酸マグネシウ
ムとコロイド状シリカ（スノーテツクスＳ：商品
名 日産化学製）の混合液を含浸処理した材料の
表面から深さ方向の１mmごとにEPMAによつて
含浸成分濃度勾配を調べ、これと対応した各層に
おける酸化減量との関係を示した。
第２図より明らかなごとく表面から約５mmに至
るまではシリカ成分（Si）の含浸が検出され、そ
れに対応して炭素材料の酸化減量も低いが、表面
からの深さが５mmをこえるとシリカ成分が無含浸
の場合におけるレベルと変らないようになつて、
そこで急激に酸化減量率が急増している。なおシ
リカ成分と比べてりん酸塩成分（Ｐ，Mg）は十
分内部まで浸透し、従つてこれについては限定を
加える必要のないことがわかる。
ここでシリカ成分の含浸深さを３mm以上に限定
したのは、ハースロールの表面加工および熱処理
炉での機械的損耗量を考慮すると、気孔率８％の
下限では少なくとも３mm以上必要なためである。
（実施例）
次に実施例にもとづいて、さらに詳しく説明す
る。
熱処理温度1000℃、雰囲気組成H260％、H240
％、露点15℃において、各種炭素材料からなるハ
ースロール（ロール径150mmφ）を500時間実用試
験した結果を表１に示す。
(Technical field) Regarding the hearth roll of a heat treatment furnace that guides the feeding of steel sheets, especially electrical steel sheet strips , the technical contents described in this specification are as follows: Especially at 970℃
Related to hearth rolls for heat treatment furnaces made of graphitic carbon material, which can be suitably used under annealing conditions where high-temperature oxidizing atmospheres are selected, including cases where the temperature exceeds It is located in the field of technology. (Prior art and its problems) Carbon materials for hearth rolls in heat treatment furnaces include:
As previously disclosed by the applicant in JP-A-57-137419, the degree of graphitization is 0.6 or more, the porosity is 5 to 15%,
An extrusion molded body of graphite carbon material having a shore hardness of 50 to 100 is suitable. That is, the inventors developed the hearth roll made of carbon material disclosed in the same publication under the following conditions: temperature 900 to 950°C, atmosphere composition H 2 60 to 65%,
Practical tests were conducted in a heat treatment furnace for electrical steel strips at H 2 40 to 35% and dew points of 0 to 30°C, and the wear of the hearth rolls was extremely small and no pick-up occurred on the steel sheets. It has been reconfirmed that the service life of the product can be extended. However, it has also been found that the amount of wear on the hearth roll increases under high dew point annealing conditions under the above-mentioned atmosphere where the heat treatment temperature sometimes exceeds 970°C. The inventors conducted a detailed investigation into the cause of this problem, and as shown in Figure 1, one example of the results shows that the above-mentioned carbon material becomes less stable as the temperature increases under annealing conditions in contact with iron powder. Oxidation weight loss increased significantly, and upon closer examination of its behavior, it was determined that it was due to chemical consumption. In other words, the abnormal wear in the above practical test was due to the fact that Fe was constantly in contact with the steel plate in the heat treatment furnace.
It is thought that the oxidation of the hearth roll carbon material was promoted by the catalytic action of . (Objective of the Invention) To provide an advantageous solution to the above-mentioned problems, regardless of the atmospheric conditions of the heat treatment furnace.
It is an object of the invention to provide a hearth roll with sufficiently high oxidative wear resistance and pick-up resistance. (Structure of the Invention) The inventors have conducted numerous studies and experiments in order to compensate for the above-mentioned drawbacks that were still unresolved in the prior development results of the above-mentioned Japanese Patent Application Laid-Open No. 57-137419 regarding hearth rolls for heat treatment. In addition, we have found that the following modification means are suitable. That is, bulk specific gravity 1.75-2.0, porosity 8-17
%, Shore hardness of 70 or more, graphitization degree of 0.6 or more, and average particle size of 100 μm or less.The silica component of the impregnating agent containing phosphate and colloidal silica is A hearth roll for heat treatment furnaces that has a surface sealing layer that penetrates at least 3 mm from the surface and has excellent oxidation wear resistance and pick-up resistance. First, the reason for limiting the physical properties of the graphite carbon material in this invention is as follows. The bulk specific gravity of 1.75 to 2.0 is necessary to achieve the appropriate range of porosity described below. In general, when the porosity is low, impregnation treatment is difficult, especially when the porosity is less than 8%, the penetration depth of 3 mm or more from the surface is particularly important for the silica component (described later) in the impregnant composition for sealing treatment. In the case of carbon materials with a carbon content exceeding 17%, even if the penetration depth of the impregnant is sufficient, the structure of the carbon material itself is too rough and the iron powder agglomerated particles may not penetrate into the carbon material. A porosity of 8 to 17% is required because implantation cannot be completely prevented and pick-up against the steel plate cannot be eliminated. The reason why the Shore hardness is limited to 70 or more is to ensure mechanical strength; if the material has a hardness lower than this, the wear of the roll due to the load on the strip, especially the biting caused by the strip edge, will increase, and the impregnating effect will be lost quickly. The reason why the degree of graphitization is limited to 0.6 or more is to appropriately achieve the effect of preventing oxidative wear at high temperatures. Further, the average particle diameter needs to be 100 μm or less in order to satisfy the above-mentioned porosity and shore hardness. Such a graphitic carbon material is generally manufactured by a hydrostatic pressing method and is extremely dense and cannot be obtained by extrusion molding. Next, the impregnating agent must be a combination of phosphate and colloidal silica, and for phosphate, one or two selected from aluminum salts, magnesium salts, calcium salts, and zinc salts are required. A mixed solution of more than one species can be used, and as the colloidal silica, ultrafine particles, for example, particle diameters of about 7 to 9 mμ are suitable. In Figure 2, a graphite carbon material with a bulk specific gravity of 1.94, a porosity of 10%, a shore hardness of 100, a graphitization degree of 0.7, and an average particle size of 20 μm is prepared, and magnesium phosphate and colloidal silica (Snowtex S: The concentration gradient of the impregnated components was investigated using EPMA every 1 mm in the depth direction from the surface of the material impregnated with a mixed solution (trade name: Nissan Chemical), and the relationship between this and the corresponding oxidation loss in each layer was shown. As is clear from Figure 2, impregnation of silica component (Si) is detected up to about 5 mm from the surface, and the oxidation loss of the carbon material is correspondingly low, but when the depth from the surface exceeds 5 mm, silica component (Si) impregnation is detected. The level of ingredients is no different from that in the case of no impregnation,
Therefore, the oxidation loss rate rapidly increases. It should be noted that, compared to the silica component, the phosphate component (P, Mg) penetrates into the interior sufficiently, so it is understood that there is no need to limit this. Here, the impregnation depth of the silica component was limited to 3 mm or more because, considering the surface treatment of the hearth roll and the amount of mechanical wear in the heat treatment furnace, at least 3 mm or more is required at the lower limit of porosity of 8%. . (Example) Next, a more detailed explanation will be given based on an example. Heat treatment temperature 1000℃, atmosphere composition H2 60%, H2 40
Table 1 shows the results of a practical test of hearth rolls (roll diameter 150 mmφ) made of various carbon materials for 500 hours at a dew point of 15°C.
【表】
実施例１〜８においてはロールの損耗量が極め
て少なく、またロール面への鉄粉凝集粒子の植込
みも全く認められなかつた。
これに対して比較例１，２および５においては
ロール面への鉄粉凝集粒子の植込みこそ認められ
ないが、ロールの損耗量は著しい。
一方比較例３，４においては、ロールの損耗量
は少ないものの、鉄粉凝集粒子のロール面への植
込みは防止されなかつた。
（発明の効果）
このようにこの発明の炭素材料は、すぐれた酸
化消耗抵抗性とロール面への鉄粉凝集粒子の植込
み防止を実現し、したがつて鋼板表面にピツクア
ツプなどのきずを発生させることなく熱処理ロー
ルとして有利に使用できることがわかる。[Table] In Examples 1 to 8, the amount of roll wear was extremely small, and no iron powder agglomerated particles were observed to be embedded in the roll surface. On the other hand, in Comparative Examples 1, 2, and 5, no iron powder agglomerated particles were observed on the roll surface, but the amount of roll wear was significant. On the other hand, in Comparative Examples 3 and 4, although the amount of roll wear was small, implantation of iron powder agglomerated particles into the roll surface was not prevented. (Effects of the Invention) As described above, the carbon material of the present invention achieves excellent oxidation wear resistance and prevents iron powder agglomerated particles from implanting on the roll surface, thereby preventing scratches such as pick-ups from occurring on the surface of the steel sheet. It can be seen that it can be advantageously used as a heat treatment roll without any heat treatment.
第１図は、かさ比重1.87、気孔率10％、シヨア
硬度80、黒鉛化度0.85で平均粒子径50μｍの炭素
材料を湿H2中（dp.50℃）で焼鈍温度を変えたと
きの酸化減量の推移を示したグラフ、第２図はか
さ比重1.94、気孔率10％、シヨア硬度100、黒鉛
化度0.7で平均粒子径20μｍの炭素材料にりん酸マ
グネシウムとスノーテツクス−Ｓの混合液を含浸
処理した材料の表面から１mmごとにEPMAによ
つて含浸成分の濃度勾配とそれに対応した各層に
おける酸化減量との関係を示したグラフである。
Figure 1 shows the oxidation of a carbon material with a bulk specific gravity of 1.87, a porosity of 10%, a shore hardness of 80, a degree of graphitization of 0.85, and an average particle size of 50 μm in wet H 2 (dp. 50°C) at varying annealing temperatures. A graph showing the change in weight loss, Figure 2 shows a carbon material with a bulk specific gravity of 1.94, porosity of 10%, Shore hardness of 100, degree of graphitization of 0.7, and an average particle diameter of 20 μm, impregnated with a mixed solution of magnesium phosphate and Snowtex-S. It is a graph showing the relationship between the concentration gradient of the impregnated component and the corresponding oxidation loss in each layer measured by EPMA every 1 mm from the surface of the treated material.
Claims (1)
900℃以上の雰囲気ガスを用いる、熱処理炉のハ
ースロールであつて、かさ比重1.75〜2.0、気孔
率８〜17％、シヨア硬度70以上、黒鉛化度0.6以
上で平均粒子径100μｍ以下の黒鉛質炭素材料の
プレス成形体よりなり、りん酸塩とコロイド状シ
リカを配合した含浸剤のシリカ成分が当該炭素材
料の表面から少なくとも３mmにわたり浸透した表
面封口層をそなえ、酸化消耗抵抗性および耐ピツ
クアツプ性に優れる、熱処理炉のハースロール。1 Mainly composed of H 2 and N 2 and contains a trace amount of H 2 O
A hearth roll for a heat treatment furnace that uses atmospheric gas at 900℃ or higher, and is graphite with a bulk specific gravity of 1.75 to 2.0, a porosity of 8 to 17%, a shore hardness of 70 or higher, a degree of graphitization of 0.6 or higher, and an average particle size of 100 μm or lower. It is made of a press-molded carbon material, and has a surface sealing layer in which the silica component of the impregnating agent containing phosphate and colloidal silica penetrates at least 3 mm from the surface of the carbon material, and has oxidative wear resistance and pick-up resistance. Hearth rolls for heat treatment furnaces with excellent properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19914583A JPS6092427A (en) | 1983-10-26 | 1983-10-26 | Hearth roll for heat treatment furnace with superior resistance to consumption due to oxidation and superior pickup resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19914583A JPS6092427A (en) | 1983-10-26 | 1983-10-26 | Hearth roll for heat treatment furnace with superior resistance to consumption due to oxidation and superior pickup resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6092427A JPS6092427A (en) | 1985-05-24 |
| JPS636614B2 true JPS636614B2 (en) | 1988-02-10 |
Family
ID=16402892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19914583A Granted JPS6092427A (en) | 1983-10-26 | 1983-10-26 | Hearth roll for heat treatment furnace with superior resistance to consumption due to oxidation and superior pickup resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6092427A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056193C (en) * | 1994-08-22 | 2000-09-06 | 山东省生建八三厂特种耐火材料厂 | Graphite sleeve of furnace bed roller and metal infiltration method, and special equipment for it |
| KR100419060B1 (en) * | 1999-12-24 | 2004-02-14 | 재단법인 포항산업과학연구원 | A method of preparing silica sleeve for hearth roll by sol-gel process |
| KR100461738B1 (en) * | 1999-12-24 | 2004-12-13 | 주식회사 포스코 | A method of inhibiting crystallization of silica sleeve for hearth roll |
| JP4779372B2 (en) * | 2005-01-31 | 2011-09-28 | Ｊｆｅスチール株式会社 | Carbon roll, steel sheet manufacturing apparatus and manufacturing method |
| JP7047239B1 (en) * | 2021-03-08 | 2022-04-05 | 株式会社レイホー製作所 | Manufacturing method of graphite material |
-
1983
- 1983-10-26 JP JP19914583A patent/JPS6092427A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6092427A (en) | 1985-05-24 |
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