JPS6358793B2 - - Google Patents
Info
- Publication number
- JPS6358793B2 JPS6358793B2 JP59169373A JP16937384A JPS6358793B2 JP S6358793 B2 JPS6358793 B2 JP S6358793B2 JP 59169373 A JP59169373 A JP 59169373A JP 16937384 A JP16937384 A JP 16937384A JP S6358793 B2 JPS6358793 B2 JP S6358793B2
- Authority
- JP
- Japan
- Prior art keywords
- zrb
- sintered body
- refractory
- present
- molten metal
- 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
- 239000002184 metal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 4
- 239000011819 refractory material Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004901 spalling Methods 0.000 description 4
- 239000011449 brick Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- -1 ZrC Chemical class 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Ceramic Products (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は溶融金属の流量調節口特にスライデイ
ングノズル装置（摺動装置）に用いるのに最適な
プレートれんがなどの耐火物に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a refractory material such as a plate brick that is most suitable for use in a molten metal flow rate adjustment port, particularly a sliding nozzle device.
［従来の技術］
現在、溶鋼処理に主として用いられているこの
種の耐火物としてはAl2O3―Ｃ系、Al2O3―SiO2
系などであるが、溶鋼による溶損に十分耐えうる
ものには至つていない。このため本発明者らは先
にこの目的のために材質としてZrB2を用いるこ
とを提案し、それなりの改善された評価を得るに
至つた。[Prior art] At present, this type of refractories mainly used for processing molten steel include Al 2 O 3 -C series and Al 2 O 3 -SiO 2
However, it has not yet been developed that can sufficiently withstand corrosion damage caused by molten steel. For this reason, the present inventors have previously proposed the use of ZrB 2 as a material for this purpose, and have obtained a reasonably improved evaluation.
［発明の解決しようとする問題点］
確かにZrB2を用いる方法は有効であり、この
種のプレートの寿命を飛躍的に伸しうることが判
つているが、ZrB2はあまりにも耐蝕性が高いた
め、長時間使用すると、場合によつて閉塞を生ず
る欠点があることが判つて来た。この欠点は
ZrB2表面を鏡面に仕上げることで解決できるが、
これには多大のコストがかかり、汎用性を阻害す
ることにもなりかねない。又、ZrB2は耐スポー
ル性が必ずしも十分でなく（ΔT≒250℃）、この
ため十分に予熱してやることが必要でこのとき場
合により表面が１部酸化され酸化物層ができ、こ
れにより閉塞が加速されることも考えられるし場
合により熱スポールにより破損することもあるこ
とが分つた。[Problems to be solved by the invention] It is true that the method of using ZrB 2 is effective, and it has been found that it can dramatically extend the life of this type of plate, but ZrB 2 is too corrosion resistant. Due to their high price, it has been found that they have the disadvantage of sometimes causing blockages when used for long periods of time. This drawback is
This can be solved by finishing the ZrB 2 surface to a mirror finish, but
This requires a great deal of cost and may impede versatility. In addition, ZrB 2 does not necessarily have sufficient spall resistance (ΔT≒250°C), so it is necessary to preheat it sufficiently. At this time, part of the surface may be oxidized and an oxide layer is formed, which may prevent blockage. It has been found that it may be accelerated and in some cases may be damaged by thermal spalls.
［問題を解決するための手段］
本発明は上記問題点の解決として見い出された
ものであつてZrB2にBNを特定量添加した複合体
を形成することによつて熱的スポーリングに対す
る抵抗性を向上させ、同時に溶鋼接触面での溶融
金属に対する耐蝕性を適度に調整することを可能
にしたものである。[Means for Solving the Problems] The present invention was discovered as a solution to the above problems, and by forming a composite in which a specific amount of BN is added to ZrB 2 , resistance to thermal spalling can be improved. At the same time, it is possible to appropriately adjust the corrosion resistance against molten metal at the contact surface with molten steel.
即ち、本発明は流出する溶融金属と接触する表
面を特定組成のZrB2―BN系複合焼結体で形成せ
しめたことを特徴とする溶融金属流通用耐火物を
要旨とするものである。 That is, the gist of the present invention is a refractory for distributing molten metal, characterized in that the surface that comes into contact with flowing molten metal is formed of a ZrB 2 --BN composite sintered body having a specific composition.
摺動装置用のプレート煉瓦などの本発明流量調
節口用（流通用）耐火物は種々の形態のものが考
えられるが、少なくとも溶鋼等の溶融金属が通過
し、溶鋼等に接する表面特にプレート煉瓦のよう
に流通孔のあるものは流通孔の内表面即ち溶融金
属に面した表面が特定組成のZrB2―BN質となつ
ていることが必要であり、いいかえればそのよう
な表面の少なくとも一部が特定組成のZrB2―BN
質からなつていればそれなりに本発明の目的は達
成されるものである。 The refractory for the flow control port (for distribution) of the present invention, such as a plate brick for a sliding device, can be in various forms, but at least the surface through which molten metal such as molten steel passes and is in contact with the molten steel, especially the plate brick. For those with communication holes, as in the case of ZrB 2 -BN with a specific composition
The object of the present invention can be achieved to a certain extent if the quality is the same.
具体的に本発明によるZrB2―BN面（ZrB2―
BN含有層）の形成は大別して次の２つに分けら
れる。 Specifically, the ZrB 2 -BN surface (ZrB 2 -
The formation of the BN-containing layer can be roughly divided into the following two types.
１つは耐火物そのものを直接、大部分がZrB2
―BNからなるもの或はZrB2成分を均一に所定量
以上含むものとして得た一体成形体であり、他の
１つは主たる成形体そのものは通常別の材質（勿
論ZrB2―BN質でもよいが）でつくり、それらの
表面の少なくとも溶鋼流と接触する流路となる面
にZrB2―BN含有層を適当な手段で形成せしめた
層成体である。 One is directly the refractory itself, mostly ZrB 2
-It is an integrally molded body made of BN or that uniformly contains more than a predetermined amount of the two ZrB components, and the other one is the main molded body itself which is usually made of a different material (of course, ZrB 2 -BN may also be used). ), and a ZrB 2 -BN-containing layer is formed by an appropriate means on at least the surface that forms a flow path that contacts the molten steel flow.
これらについて、さらに説明するとまず前者と
しては次のようなものが好適に使用できる。 To explain these in more detail, the following can be suitably used as the former.
ZrB2―BN質焼結体
これはZrB2質及びBN質の粉末又は焼結により
ZrB2及びBNとなりうる原料と焼結材、還元材な
どの配合原料を成形後、通常還元雰囲気下で高温
高圧焼結することで得られる。 ZrB 2 - BN sintered body This is made by ZrB 2 and BN powder or sintering.
It is obtained by molding raw materials that can become ZrB 2 and BN, sintering material, reducing material, etc., and then sintering them at high temperature and high pressure in a reducing atmosphere.
例えば所定部分のZrB2質及びBN質の混合粉末
を有機質樹脂を結合材として予備成形し、これを
温度2000℃以上、圧力500Kg／cm2以上のホツトプ
レスして得られたものである。 For example, it is obtained by preforming a predetermined portion of a mixed powder of ZrB 2 and BN using an organic resin as a binder, and then hot pressing this at a temperature of 2000° C. or higher and a pressure of 500 kg/cm 2 or higher.
また、これらのZrB2―BN質成形体として、耐
火物の大きさ、形状等により一体物として得にく
いときは、分割した部分成形体として得、これを
少なくとも耐火物の最も必要な一部に又は組合せ
物として使用することも有効である。このZrB2
―BN質焼結体面の形成手段としての後者として
は、次のようなものが好適に使用できる。 In addition, when it is difficult to obtain these ZrB 2 -BN molded products as an integral product due to the size, shape, etc. of the refractory, it can be obtained as divided partial molded products, and this can be used to form at least the most necessary part of the refractory. Alternatively, it is also effective to use them as a combination. This ZrB 2
-As the latter method for forming the surface of the BN sintered body, the following can be suitably used.
即ち、成形体の表面に特定組成のZrB2―BN質
のペーストを塗布、吹付け等により被覆せしめ、
或いはZrB2―BN質懸濁溶液中に成形体を浸漬し
て成形体の気孔及び表面に該液を含浸、被覆せし
め、それぞれ乾燥焼成することで特定組成の
ZrB2―BN質層を形成することで得られる。さら
に強固な被覆を形成したいときにはプラズマコー
テイングも使用できる。 That is, a ZrB 2 -BN paste of a specific composition is coated on the surface of the molded body by spraying, etc.
Alternatively, a molded body is immersed in a ZrB 2 -BN suspension solution to impregnate and coat the pores and surface of the molded body with the liquid, and then dried and fired to obtain a specific composition.
ZrB 2 --obtained by forming a BN layer. Plasma coating can also be used if a stronger coating is desired.
尚、この後者の方法の場合にはこのZrB2―BN
層の形成をその必要な位置即ち、少なくとも溶鋼
流路で入口部分に近い表面にのみなしておくこと
も可能であり、目的によつては経済的であるが、
好ましくは成形体の全表面に適用しておくことで
ある。 In addition, in the case of this latter method, this ZrB 2 -BN
It is also possible to form the layer only at the necessary location, that is, at least on the surface near the inlet part of the molten steel flow path, which may be economical depending on the purpose.
Preferably, it is applied to the entire surface of the molded article.
これらのZrB2―BN又はZrB2―BN含有層にて
形成した耐火物のなかでも本発明の使用目的に最
も適したものは、耐蝕、耐摩耗などの耐久性の向
上においては最も実質的効果をもたらす高純度の
焼結体であり、一方実質的効果とコストを考慮す
ればプレート又はそのための成形体への塗布含浸
或いは吹付けなどで得たものである。 Among these refractories formed of ZrB 2 -BN or ZrB 2 -BN-containing layers, the one most suitable for the purpose of use of the present invention has the most substantial effect in improving durability such as corrosion resistance and abrasion resistance. It is a high-purity sintered body that provides a high-purity sintered body.On the other hand, in consideration of practical effects and cost, it is obtained by coating, impregnating, or spraying on a plate or a molded body therefor.
このような本発明耐火物において、ZrB2とBN
の焼結体としての配合割合は重量％で、前者が95
〜60％、後者が５〜40％であり、望ましくは前者
90〜70％、後者10〜30％である。 In such a refractory of the present invention, ZrB 2 and BN
The blending ratio as a sintered body is 95% by weight, and the former is 95% by weight.
~60%, the latter 5-40%, preferably the former
90-70%, the latter 10-30%.
これはBN成分が少なすぎると耐蝕性は十分で
あるが、この種用途としての耐スポール性が不十
分となるし、多すぎると耐スポール性は良いが耐
蝕性が十分でない問題が生ずるなどからである。 This is because if the BN content is too low, the corrosion resistance will be sufficient, but the spalling resistance will be insufficient for this type of use, and if it is too high, the problem will arise that the spalling resistance is good but the corrosion resistance is not sufficient. It is.
尚、本発明焼結体として、ZrB2及びBN成分以
外の成分としては可及的に少量であることを旨と
するが、本発明の目的、効果を実質的に損わない
範囲で含まれていても差支えなく、例えばZrB2
の一部をTiB2などの他の硼化物、ZrCなどの他
の炭化物等で置換することは可能である。尚、い
ずれにしろZrB2とBN成分の合量として90％以上
であることが望ましい。 In the sintered body of the present invention, components other than ZrB 2 and BN components are intended to be contained in as small a quantity as possible, but may not be included to the extent that the objects and effects of the present invention are not substantially impaired. For example, ZrB 2
It is possible to replace a part of with other borides such as TiB2 , other carbides such as ZrC, etc. In any case, it is desirable that the total amount of ZrB 2 and BN component is 90% or more.
［発明の効果］
以上の如く本発明は、ZrB2のもつ不十分な点
を、BNを添加することによつて補うことに成功
したものであつて溶融金属流通用耐火物として用
いた場合(1)閉塞の心配がなくなつた。(2)耐熱衝撃
による破損のキケンがなくなつた。(3)かつ、溶鋼
を4500T以上十分に通過させる耐蝕性を有してい
る。(4)予熱が不要又は、その温度が著しく低下で
きたなどのような効果を生じる優れたものであ
り、その実用的価値は多大である。[Effects of the Invention] As described above, the present invention has succeeded in compensating for the inadequacies of ZrB 2 by adding BN, and when used as a refractory for molten metal distribution ( 1) No more worries about blockages. (2) No more damage caused by thermal shock resistance. (3) It also has corrosion resistance that allows it to pass through 4500T or more of molten steel. (4) It is an excellent product that produces effects such as not requiring preheating or significantly lowering the temperature, and has great practical value.
本発明耐火物の最適な用途は従つて、摺動装置
として用いられる流通孔をもつスライデイングプ
レート状耐火物であり、また溶鋼等の連続鋳造用
ノズル等である。 Therefore, the optimum application of the refractory of the present invention is a sliding plate-like refractory having flow holes used as a sliding device, and a nozzle for continuous casting of molten steel, etc.
［実施例］
1μm以下に微粉砕したZrB2とBN粉を所定の割
合にてボールミル中に投入し、48時間混合粉砕す
る。混合粉砕された微粉は最大粒径で0.5μ以下で
ある。この混合粉を乾燥、解砕、及び必要に応じ
造粒する。これら解砕粉又は造粒粉を50mmφ×50
mmＨのプレス型中に充填し、ホツトプレスをかけ
る。ホツトプレス条件は300〜400Kg／cm2の加圧下
で2000℃にて１時間保持した。冷却後プレス型よ
り焼結体を取出した後に必要な大きさに加工（ダ
イヤモンド加工機及び放電加工機が利用された。）
し供試試料とした。[Example] ZrB 2 and BN powder finely pulverized to 1 μm or less were placed in a ball mill at a predetermined ratio, and mixed and pulverized for 48 hours. The mixed and pulverized fine powder has a maximum particle size of 0.5μ or less. This mixed powder is dried, crushed, and granulated if necessary. 50mmφ×50 of these crushed powder or granulated powder
Fill into a mmH press mold and hot press. The hot press condition was held at 2000° C. for 1 hour under a pressure of 300 to 400 kg/cm 2 . After cooling, the sintered body was removed from the press mold and processed into the required size (diamond processing machine and electric discharge machine were used).
This was used as a test sample.
このようにして得られた各種試料の耐スポーリ
ング性、耐蝕性及び曲げ強度の測定結果を第１
図、第２図及び第３図として示す。 The results of measuring the spalling resistance, corrosion resistance, and bending strength of the various samples obtained in this way were
2 and 3.
第１図：幅４mm×厚さ３mm×長さ36mmに切出した
焼結体を所定の温度に保つた炉に入れ30分
保持した後水中に落下急冷した。この試料
をJIS R1601に則り曲げ強度を測定し、曲
げ強度の低下する温度差ΔTとして表示し
たもの。Figure 1: A sintered body cut to a size of 4 mm wide x 3 mm thick x 36 mm long was placed in a furnace kept at a predetermined temperature for 30 minutes, and then dropped into water to rapidly cool it. The bending strength of this sample was measured in accordance with JIS R1601 and expressed as the temperature difference ΔT at which the bending strength decreased.
第２図：10×10×10mmの試料を鋼片とともにルツ
ボ中に入れ高周波誘導炉中で1500℃×１時
間溶解した。取出し後10mm寸法の減少を測
定し、これを２で除し侵蝕量とした。Figure 2: A 10 x 10 x 10 mm sample was placed in a crucible together with a steel piece and melted at 1500°C for 1 hour in a high frequency induction furnace. After removal, a 10 mm reduction in dimension was measured, and this was divided by 2 to determine the amount of erosion.
第３図：JIS R1601に則て測定した値を示す。Figure 3: Shows values measured in accordance with JIS R1601.
以上のような結果から得られた本発明に係る焼
結体（BN量10，20，30％）をタンデイシユノズ
ルに応用したところ、極めて安定した流量調節を
長時間維持することに成功した。 When the sintered body of the present invention (BN content 10, 20, 30%) obtained from the above results was applied to a tundish nozzle, it was possible to maintain extremely stable flow rate regulation for a long time. .
これに対しZrB2単味の焼結体では、スラグの
付着により閉塞が、またBN単味の焼結体ではノ
ズル径の拡がりがそれぞれ起ることが分り、流量
調節が困難となることが分つた。 On the other hand, in the case of a sintered body made only of ZrB 2 , blockage occurs due to the adhesion of slag, and in the case of a sintered body made only of BN, the nozzle diameter expands, making it difficult to control the flow rate. Ivy.
第１図は本発明耐火物のBN量とΔTの関係を
示す説明図。第２図は同様BN量と侵蝕量の関係
を示す説明図。第３図は同様BN量と曲げ強度の
関係を示す説明図である。
FIG. 1 is an explanatory diagram showing the relationship between the amount of BN and ΔT in the refractory of the present invention. FIG. 2 is an explanatory diagram showing the relationship between the amount of BN and the amount of erosion. FIG. 3 is an explanatory diagram similarly showing the relationship between the amount of BN and the bending strength.
Claims (1)
でZrB295〜60％、BN5〜40％からなる組成を有
するZrB2−BN系複合焼結体で形成せしめたこと
を特徴とする溶融金属流通用耐火物。 ２ 複合焼結体が重量％でZrB290〜70％、BN10
〜30％から成る組成を有する特許請求の範囲第１
項記載の耐火物。[Claims] 1. The surface in contact with the flowing molten metal is
A refractory for molten metal distribution, characterized in that it is formed of a ZrB 2 -BN composite sintered body having a composition of 95 to 60% ZrB 2 and 5 to 40% BN. 2 Composite sintered body contains ZrB 2 90-70% by weight, BN10
Claim 1 having a composition consisting of ~30%
Refractories listed in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59169373A JPS6148485A (en) | 1984-08-15 | 1984-08-15 | Refractories for flowing molten metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59169373A JPS6148485A (en) | 1984-08-15 | 1984-08-15 | Refractories for flowing molten metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6148485A JPS6148485A (en) | 1986-03-10 |
| JPS6358793B2 true JPS6358793B2 (en) | 1988-11-16 |
Family
ID=15885387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59169373A Granted JPS6148485A (en) | 1984-08-15 | 1984-08-15 | Refractories for flowing molten metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6148485A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06148359A (en) * | 1992-11-12 | 1994-05-27 | Teac Corp | Alarm clock |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6178541A (en) * | 1984-09-27 | 1986-04-22 | Mitsubishi Steel Mfg Co Ltd | Nozzle |
| JPH0822777B2 (en) * | 1989-02-14 | 1996-03-06 | 電気化学工業株式会社 | Molten metal resistant member |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58130166A (en) * | 1982-01-28 | 1983-08-03 | 株式会社小松製作所 | Cubic boron nitride sintered body and manufacture |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673118A (en) * | 1970-07-01 | 1972-06-27 | Union Carbide Corp | Composite article containing high purity hot pressed boron nitride |
-
1984
- 1984-08-15 JP JP59169373A patent/JPS6148485A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58130166A (en) * | 1982-01-28 | 1983-08-03 | 株式会社小松製作所 | Cubic boron nitride sintered body and manufacture |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06148359A (en) * | 1992-11-12 | 1994-05-27 | Teac Corp | Alarm clock |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6148485A (en) | 1986-03-10 |
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