JP6375958B2 - Sliding nozzle plate for Ca-treated steel - Google Patents
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本発明は、溶鋼の流量を制御するスライディングノズル装置に用いられるプレートに関する。 The present invention relates to a plate used in a sliding nozzle device for controlling the flow rate of molten steel.
スライディングノズルプレートは内孔を持つ２枚乃至は３枚のプレートから構成され、摺動により孔の重なり度合いを変化させることで取鍋やタンディッシュなどの溶融金属容器から排出される溶鋼の流量を制御する装置である。プレートの面間からの溶鋼漏洩を防止するためスライディングノズルプレートは拘束条件下で、面圧が付加された状態で使用される。 The sliding nozzle plate is composed of two or three plates with inner holes, and the flow rate of molten steel discharged from a molten metal container such as a ladle or tundish is changed by changing the overlapping degree of the holes by sliding. It is a device to control. In order to prevent molten steel leakage from between the surfaces of the plate, the sliding nozzle plate is used under restraint conditions and with surface pressure applied.
このことから、スライディングノズルプレートには、拘束条件での使用が可能な機械的強度、溶鋼成分や介在物等に対する耐食性、摺動面が受ける摩擦に対する耐摩耗性、溶鋼受鋼時の急激な熱衝撃に対する耐スポーリング性などの特性が要求される。 For this reason, the sliding nozzle plate has mechanical strength that can be used under restraint conditions, corrosion resistance to molten steel components and inclusions, wear resistance to friction received by the sliding surface, and rapid heat when receiving molten steel. Characteristics such as spalling resistance against impact are required.
このような理由から、スライディングノズルプレートにはＡｌ２Ｏ３−Ｃ質耐火物が広く使用されている。 For these reasons, Al 2 O 3 —C refractories are widely used for sliding nozzle plates.
ところで、操業中の浸漬ノズルへのＡｌ２Ｏ３介在物付着に伴うノズル閉塞の防止や、圧延時鋼片の傷の原因となる硬質のＡｌ２Ｏ３系介在物の無害化を目的として溶鋼中にＣａを添加する処理（Ｃａ処理）を行う鋼種がある。通常、Ｃａ処理は二次精錬後の溶鋼に対してＣａ濃度１０〜３０ ｐｐｍ程度となるようにＣａＳｉワイヤもしくはＣａＳｉ粉体の形態でＣａを添加することで行われている。Ｃａ処理鋼は、非Ｃａ処理鋼に比較して、耐火物の損耗が著しく大きくなる。この理由は、溶鋼中のＣａが耐火物中のＡｌ２Ｏ３と反応し、溶鋼の温度よりも融点が低いＣａＯ−Ａｌ２Ｏ３−ＳｉＯ２系化合物が生成されることにより、耐火物が損耗（溶損）するためであると考えられている。その結果、Ｃａ処理鋼において、Ｃａが耐火物の損耗に与える影響は、無視できないほどに大きくなる。 By the way, molten steel is used for the purpose of preventing nozzle clogging due to adhesion of Al 2 O 3 inclusions to the immersion nozzle during operation and detoxifying hard Al 2 O 3 inclusions that cause damage to the steel pieces during rolling. There are steel types that perform a process of adding Ca therein (Ca process). Usually, Ca treatment is performed by adding Ca in the form of CaSi wire or CaSi powder so that the Ca concentration is about 10 to 30 ppm with respect to the molten steel after the secondary refining. The Ca-treated steel has significantly increased wear of the refractory compared to the non-Ca-treated steel. The reason for this is that Ca in the molten steel reacts with Al 2 O 3 in the refractory, and a CaO—Al 2 O 3 —SiO 2 based compound having a melting point lower than the temperature of the molten steel is generated. This is considered to be due to wear (melting damage). As a result, in Ca-treated steel, the influence of Ca on the wear of the refractory is so great that it cannot be ignored.
その対策として、特許文献１には耐火物骨材をＡｌ２Ｏ３骨材ではなくＣａ処理鋼中のＣａと反応しても低融点層を生成しにくいＺｒＯ２骨材に置換したＺｒＯ２−Ｃ系材質の採用が提案され、Ｃａ処理鋼による溶損量の低減が認められている。 As a countermeasure, ZrO 2 in Patent Document 1 is replaced with refractory aggregate the Al 2 O 3 also react with Ca in the Ca-treated steels rather than aggregate produces a low melting point layer hard ZrO 2 aggregates - Adoption of a C-based material has been proposed, and a reduction in the amount of erosion caused by Ca-treated steel is recognized.
また、Ａｌ２Ｏ３骨材に替えてＣａＯと低融点相を生成しにくいＭｇＯ骨材を用いたＭｇＯ−Ｃ材質についても検討がなされている。例えば、特許文献２ではＭｇＯ骨材の使用により、耐食性を高めるとともに金属Ａｌと炭素原料を添加することで耐面荒れ性の両立を図った材質を開示している。
In addition, MgO—C materials using MgO aggregates that hardly generate CaO and a low melting point phase instead of Al 2 O 3 aggregates have been studied. For example,
上記のように、スライディングノズルプレートの耐ＣａＯ性を改善するため、Ａｌ２Ｏ３−Ｃ中のＡｌ２Ｏ３骨材をＺｒＯ２骨材やＭｇＯ骨材に置換した従来技術があるが、其々別の課題がある。 As described above, in order to improve the CaO resistance of the sliding nozzle plate, there is a conventional technique in which Al 2 O 3 aggregate in Al 2 O 3 -C is replaced with ZrO 2 aggregate or MgO aggregate. There are different challenges.
ＺｒＯ２−Ｃ質はＣａと低融点相を生成しないという点でＣａ処理鋼に対する耐用の向上が見られたものの、ＺｒＯ２のかさ密度の大きさからスライディングノズルプレートの重量が大きくなり作業性が悪くなるという問題があった。 Although ZrO 2 -C material has improved durability against Ca-treated steel in that it does not form a low melting point phase with Ca, the weight of the sliding nozzle plate increases due to the bulk density of ZrO 2 , and workability is improved. There was a problem of getting worse.
ＭｇＯ−Ｃ質ではＭｇＯの持つ高い熱膨張率のため、受鋼時の耐熱衝撃性に難があり、頻繁に割れが生じるため使用回数が限られるという課題があった。 The MgO—C material has a problem that the thermal expansion coefficient of MgO is difficult, and the thermal shock resistance at the time of receiving steel is difficult, and cracks frequently occur, so the number of uses is limited.
本発明の目的はスライディングノズルプレートに要求される耐熱衝撃性、耐摩耗性、機械的強度が適正にバランス化されており、耐火物の溶損を拡大させるＣａ処理鋼に対しても高い耐食性を有するスライディングノズルプレートを提供することにある。 The object of the present invention is to properly balance the thermal shock resistance, wear resistance, and mechanical strength required for a sliding nozzle plate, and to provide high corrosion resistance even to Ca-treated steel that expands the refractory erosion. It is to provide a sliding nozzle plate having the same.
上記の課題を解決するために、本発明は以下の構成を要旨とする。
（１）耐火物骨材が、ＣＡ６骨材と、Ａｌ２Ｏ３骨材とＡｌ２Ｏ３−ＺｒＯ２骨材の少なくともいずれか一方とを含有し、前記ＣＡ６骨材が、前記耐火物骨材の３〜３０質量％であることを特徴とするＣａ処理鋼用スライディングノズルプレート。
（２）前記ＣＡ６骨材が、８０質量％以上のヒボナイト鉱物からなることを特徴とする（１）に記載のＣａ処理鋼用スライディングノズルプレート。
（３）前記ＣＡ６骨材の気孔率が、１０％以下であることを特徴とする（１）又は（２）に記載のＣａ処理鋼用スライディングノズルプレート。
In order to solve the above-described problems, the present invention has the following configuration.
(1) refractory aggregate, and CA6 aggregate, contain and at least one of Al 2 O 3 aggregate and Al 2 O 3 -
(2) The sliding nozzle plate for Ca-treated steel according to (1), wherein the CA6 aggregate is composed of 80% by mass or more of a hibonite mineral.
(3) The sliding nozzle plate for Ca-treated steel according to (1) or (2), wherein the porosity of the CA6 aggregate is 10% or less.
高温下で空孔の生じやすい耐火物骨材に替えて、酸化物として安定で気相化しにくいＣＡ６骨材を適用することにより、実使用下においても耐火物が空孔を生じず緻密に保たれる。これにより浸食作用の強いＣａＯ−Ａｌ２Ｏ３−ＳｉＯ２系化合物とスライディングノズル材質との反応界面積を最小限に抑えることができ、耐溶損性を向上させることが可能となる。さらに、本発明は、耐熱衝撃性、耐摩耗性、及び機械的強度も適正にバランス化されている。 In place of refractory aggregates that are prone to vacancies at high temperatures, the use of CA6 aggregates that are stable and difficult to vaporize as oxides ensures that refractories do not form vacancies even under actual use. Be drunk. As a result, the reaction interface area between the CaO—Al 2 O 3 —SiO 2 -based compound having a strong erosion action and the sliding nozzle material can be minimized, and the resistance to erosion can be improved. Furthermore, the present invention also has an appropriate balance of thermal shock resistance, wear resistance, and mechanical strength.
以下に添付図面を参照しながら、本発明の好適な実施の形態について詳細に説明する。 Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
本発明で耐火物骨材、例えばＡｌ２Ｏ３骨材とは、主成分がＡｌ２Ｏ３であって不可避的不純物を含み、通常の耐火物用原料として用いるものである。また、本発明の対象とするスライディングノズルプレートは、耐火物骨材以外にバインダーや、酸化防止、強度向上を目的とした金属や炭化物がマトリックス部を構成している。 In the present invention, a refractory aggregate, such as an Al 2 O 3 aggregate, is mainly used as a raw material for a refractory, containing Al 2 O 3 as a main component and containing inevitable impurities. In addition to the refractory aggregate, the sliding nozzle plate that is the subject of the present invention comprises a matrix portion of a binder, a metal or carbide for the purpose of preventing oxidation and improving strength.
上述のように、Ｃａ処理鋼による耐火物損耗は、マトリックス部および骨材部に存在するＡｌ２Ｏ３とＣａ処理鋼中のＣａＯ含有介在物との反応による低融点化が一つの要因である。しかし、実際にＣａ処理鋼に対して使用したアルミナカーボン質プレートを調査すると、非Ｃａ処理鋼に対して使用した場合には見られない顕著な空隙が観察された。さらにその空隙部分にはＣａＯ含有相が浸潤している様子が確認された。 As described above, the refractory wear due to the Ca-treated steel is caused by the low melting point due to the reaction between Al 2 O 3 present in the matrix part and the aggregate part and the CaO-containing inclusions in the Ca-treated steel. . However, when the alumina carbonaceous plate actually used for the Ca-treated steel was investigated, remarkable voids that were not seen when used for the non-Ca-treated steel were observed. Further, it was confirmed that the CaO-containing phase was infiltrated into the void portion.
そこで空隙生成について熱力学的に検討を実施した。耐火物中の各種酸化物と炭素との反応は以下の式（化１）〜（化４）で表わされる。また、（化１）〜（化４）で示す反応式におけるギブスの自由エネルギー変化ΔＧ０は、温度をＴとすると、それぞれ以下の数式（数１）〜（数４）で表される。
１／２Ｃ＋１／２Ａｌ２Ｏ３＝ＡｌＯ（ｇ）＋１／２ＣＯ（ｇ） （化１）
２Ｃ＋Ａｌ２Ｏ３＝Ａｌ２Ｏ（ｇ）＋２ＣＯ（ｇ） （化２）
Ｃ＋ＺｒＯ２＝ＺｒＯ（ｇ）＋ＣＯ（ｇ） （化３）
Ｃ＋ＳｉＯ２＝ＳｉＯ（ｇ）＋ＣＯ（ｇ） （化４）
Therefore, the void formation was studied thermodynamically. The reaction between various oxides and carbon in the refractory is represented by the following formulas (Chemical Formula 1) to (Chemical Formula 4). Also, Gibbs free energy change ΔG 0 in the reaction formulas shown in (Chemical Formula 1) to (Chemical Formula 4) is expressed by the following formulas (Formula 1) to (Formula 4), where T is the temperature.
1 / 2C + 1 / 2Al 2 O 3 = AlO (g) + 1 / 2CO (g)
2C + Al 2 O 3 = Al 2 O (g) + 2CO (g)
C + ZrO 2 = ZrO (g) + CO (g)
C + SiO 2 = SiO (g) + CO (g)
図１に（数１）〜（数４）をもとに１６００℃における酸素分圧と酸化物ガス分圧との関係を示す。低酸素分圧では、ＳｉＯ２やＡｌ２Ｏ３から生成される酸化物ガスの分圧が高いことが分かる。すなわち、従来のスライディングノズルプレートに使用されていた酸化物は、高温化（即ち低酸素分圧下）において分解しやすいといえる。 FIG. 1 shows the relationship between the oxygen partial pressure and the oxide gas partial pressure at 1600 ° C. based on (Equation 1) to (Equation 4). It can be seen that at a low oxygen partial pressure, the partial pressure of the oxide gas generated from SiO 2 or Al 2 O 3 is high. That is, it can be said that the oxide used in the conventional sliding nozzle plate is easily decomposed at a high temperature (that is, under a low oxygen partial pressure).
すなわち、高温下における酸化物の分解により骨材まわりに空隙が生じることで、耐火物を浸食させる溶融酸化物が浸透しやすい環境になることが考察された。こうして発明者は、Ｃａ処理鋼においては骨材とＣとの反応により生じる耐火物組織中の空隙が耐火物を浸食させる促進要因であることを知見した。すなわち、気相生成反応の抑制により耐火物組織の空隙生成を防止することで総合的な耐食性向上が図れると考えた。 That is, it was considered that a void is generated around the aggregate due to the decomposition of the oxide at a high temperature, so that the molten oxide that erodes the refractory easily penetrates. Thus, the inventor has found that in the Ca-treated steel, voids in the refractory structure generated by the reaction between the aggregate and C are an accelerating factor for eroding the refractory. That is, it was thought that the overall corrosion resistance could be improved by preventing the formation of voids in the refractory structure by suppressing the gas phase formation reaction.
そこでＣａに対して耐食性を向上させるためには、低酸素分圧でも酸化物として安定で分解しにくい骨材が必要である。ＣａＯ含有骨材は酸化物として非常に安定であるが、たとえばドロマイト（ドロマイト：ＣａＣＯ３−ＭｇＣＯ３）は消化に伴う粉化の問題があり、またＣａＺｒＯ３は加熱時にＺｒＯ２の脱安定化に伴う骨材の分解が生じるため物理的にも過酷な環境で用いられるスライディングノズルプレート材質には不適当である。 Therefore, in order to improve the corrosion resistance with respect to Ca, an aggregate which is stable as an oxide and hardly decomposes even at a low oxygen partial pressure is required. Although CaO-containing aggregates are very stable as an oxide, for example dolomite (dolomite: CaCO 3 -MgCO 3) has a problem of powder of accompanying digestion also CaZrO 3 to destabilization of ZrO 2 upon heating Since the accompanying aggregate decomposition occurs, it is unsuitable for a sliding nozzle plate material used in physically severe environments.
ところで、従来、カルシウムヘキサアルミネート（ＣＡ６）骨材はＡｌ２Ｏ３骨材よりも低融点であるため、化学的耐食性の要求される耐火物への適用は試みられてこなかった。単体での耐食性としてはＡｌ２Ｏ３骨材やＡｌ２Ｏ３−ＺｒＯ２骨材よりも劣るものの、ＣＡ６骨材は消化や加熱による分解反応が生じず安定に使用できるとともに、気相生成反応を生じにくい骨材である。すなわちスライディングノズルプレート耐火物用として用いることで耐食性の向上が可能であると考え、本発明を成すに至った。
By the way, conventionally, calcium hexaaluminate (CA6) aggregate has a lower melting point than Al 2 O 3 aggregate, so that it has not been tried to be applied to a refractory requiring chemical corrosion resistance. Although inferior to Al 2 O 3 aggregate and Al 2 O 3 -
そこで本発明は、耐火物骨材としてＡｌ２Ｏ３骨材又はＡｌ２Ｏ３−ＺｒＯ２骨材の少なくとも一方と、ＣＡ６骨材とを使用するＣａ処理鋼用スライディングノズルプレートを提供する。 Therefore, the present invention provides a sliding nozzle plate for Ca-treated steel using at least one of Al 2 O 3 aggregate or Al 2 O 3 —ZrO 2 aggregate as a refractory aggregate and CA6 aggregate.
ＣＡ６骨材の配合量は質量比で３〜３０質量％であることを推奨する。ＣＡ６骨材の配合量が３質量％より小さい場合には耐火物骨材とＣとの反応による気相生成を抑制する効果が小さく、耐用の向上が見込めない。一方、ＣＡ６骨材が３０質量％より多い場合には、気相生成は抑制できるものの、ＣＡ６骨材そのものとＣａＯ−Ａｌ２Ｏ３−ＳｉＯ２系介在物との反応による低融点化が進行し耐用の向上が見込めない。 It is recommended that the blending amount of CA6 aggregate is 3 to 30% by mass. When the blending amount of the CA6 aggregate is smaller than 3% by mass, the effect of suppressing the gas phase generation due to the reaction between the refractory aggregate and C is small, and the improvement in durability cannot be expected. On the other hand, when the amount of CA6 aggregate is more than 30% by mass, although vapor phase generation can be suppressed, the melting point is lowered by the reaction between the CA6 aggregate itself and the CaO—Al 2 O 3 —SiO 2 inclusion. Cannot be expected to improve durability.
ＣＡ６骨材以外の耐火物骨材としては、Ａｌ２Ｏ３−ＺｒＯ２骨材又はＡｌ２Ｏ３骨材の少なくとも一方を用いる。Ａｌ２Ｏ３−ＺｒＯ２骨材は、ＣａＯ−Ａｌ２Ｏ３−ＳｉＯ２系介在物と低融点相を生成しにくい原料種として含有することが望ましいことから、本発明は、より好ましくは両骨材を用いることを推奨する。全骨材に占めるＡｌ２Ｏ３−ＺｒＯ２骨材の配合量が３０質量％より少量な場合にはＣａＯ−Ａｌ２Ｏ３−ＳｉＯ２系介在物に対する耐食性向上の寄与が小さい。しかし、Ａｌ２Ｏ３−ＺｒＯ２骨材量が６７質量％より多量となると価格が高価になるだけでなく、その重量の大きさから作業性に難が生じうる。 As the refractory aggregate other than the CA6 aggregate, at least one of Al 2 O 3 —ZrO 2 aggregate and Al 2 O 3 aggregate is used. Since it is desirable that the Al 2 O 3 —ZrO 2 aggregate contains a CaO—Al 2 O 3 —SiO 2 inclusion and a low-melting-point phase as a raw material species, the present invention is more preferably both It is recommended to use aggregate. When the blending amount of Al 2 O 3 —ZrO 2 aggregate in the total aggregate is less than 30% by mass, the contribution of improving corrosion resistance to CaO—Al 2 O 3 —SiO 2 inclusions is small. However, if the amount of the Al 2 O 3 —ZrO 2 aggregate is greater than 67% by mass, not only the price becomes expensive, but also the workability may be difficult due to the size of the weight.
一方、Ａｌ２Ｏ３骨材の配合量を６７質量％以上とするとＣａ処理鋼中のＣａＯ−Ａｌ２Ｏ３−ＳｉＯ２系介在物との反応による低融点化が進行し耐用の低下を招く。そのため、耐食性、価格、重量のバランスに優れたスライディングノズルプレートの骨材としてはＣＡ６骨材、Ａｌ２Ｏ３−ＺｒＯ２骨材、Ａｌ２Ｏ３骨材からなることが最も好ましい。なお、Ａｌ２Ｏ３−ＺｒＯ２、Ａｌ２Ｏ３は、従来よりスライディングノズルプレートに用いられた耐火物でよい。 On the other hand, when the blending amount of the Al 2 O 3 aggregate is 67% by mass or more, the melting point is lowered due to the reaction with the CaO—Al 2 O 3 —SiO 2 inclusions in the Ca-treated steel, and the durability is lowered. . Therefore, the aggregate of the sliding nozzle plate having an excellent balance of corrosion resistance, price, and weight is most preferably composed of CA6 aggregate, Al 2 O 3 —ZrO 2 aggregate, and Al 2 O 3 aggregate. Al 2 O 3 —ZrO 2 and Al 2 O 3 may be refractories conventionally used for sliding nozzle plates.
また本発明では、ＣＡ６骨材は８０質量％以上のヒボナイト鉱物からなることが望ましい。ヒボナイト鉱物の定量はリートベルト法を用いる。このヒボナイト鉱物が８０質量％未満ではＣＡ６骨材による気孔生成抑制効果が小さく、耐食性向上への寄与が小さい。 In the present invention, it is desirable that the CA6 aggregate is composed of 80% by mass or more of a hibonite mineral. Rietveld method is used for quantitative determination of the hibonite mineral. When this hibonite mineral is less than 80% by mass, the effect of suppressing pore formation by CA6 aggregate is small, and the contribution to improving corrosion resistance is small.
さらに本発明では、ＣＡ６骨材の気孔率は１０％以下であることが望ましい。気孔率はＪＩＳ Ｒ ２２０５により測定を行う。骨材の気孔率が１０％より大きい場合には、骨材の気孔へＣａＯ−Ａｌ２Ｏ３−ＳｉＯ２系介在物の浸潤が生じやすくなるため、耐食性の向上への寄与が小さくなる。 Furthermore, in the present invention, the porosity of CA6 aggregate is preferably 10% or less. The porosity is measured according to JIS R 2205. When the porosity of the aggregate is larger than 10%, CaO—Al 2 O 3 —SiO 2 inclusions tend to be infiltrated into the pores of the aggregate, so that the contribution to the improvement of the corrosion resistance becomes small.
本発明のＣａ処理鋼用スライディングノズルプレートは、上記ＣＡ６骨材と、少なくともＡｌ２Ｏ３骨材又はＡｌ２Ｏ３−ＺｒＯ２骨材とを耐火物骨材にして、バインダーとしてフェノールレジン等を添加した配合物を混練し、フリクションでスライディングノズル形状に成形し、１２００℃程度で焼成した後、タール含浸処理を施すことにより作製される。骨材の種類、配合量以外は、従来と同様の方法によって製造可能である。 The sliding nozzle plate for Ca-treated steel according to the present invention uses the above-mentioned CA6 aggregate and at least Al 2 O 3 aggregate or Al 2 O 3 —ZrO 2 aggregate as a refractory aggregate, and a phenol resin or the like as a binder. The added compound is kneaded, formed into a sliding nozzle shape by friction, fired at about 1200 ° C., and then subjected to tar impregnation treatment. Except for the type and blending amount of the aggregate, it can be produced by the same method as in the prior art.
表１〜６に本発明の実施例、表７、８に比較例を一覧する。 Tables 1 to 6 list examples of the present invention, and Tables 7 and 8 list comparative examples.
（実施例１〜２８）
表１〜６に記載の、気孔率、ヒボナイト含有量のＣＡ６骨材と、少なくともＡｌ２Ｏ３骨材又はＡｌ２Ｏ３−ＺｒＯ２骨材とを所定量配合し、バインダーとしてフェノールレジンを外掛けで５質量％添加した配合物を混練し、フリクションでスライディングノズルプレート形状に成形し、１２００℃で焼成した後、ピッチ含浸処理を施した。
(Examples 1 to 28)
A predetermined amount of a CA6 aggregate having a porosity and a hibonite content described in Tables 1 to 6 and at least Al 2 O 3 aggregate or Al 2 O 3 —ZrO 2 aggregate is blended, and a phenol resin is used as a binder. The blend added at 5% by mass was kneaded, formed into a sliding nozzle plate shape by friction, fired at 1200 ° C., and then subjected to pitch impregnation treatment.
（比較例１〜７）
比較のために、Ａｌ２Ｏ３骨材、Ａｌ２Ｏ３−ＺｒＯ２骨材、ＣＡ６骨材を用いて表５、６に記載のように配合し、バインダーとしてフェノールレジンを外掛けで５質量％添加した配合物を混練し、フリクションでスライディングノズルプレート形状に成形し、１２００℃で焼成した後、タール含浸処理を施した。
(Comparative Examples 1-7)
For comparison, Al 2 O 3 aggregate, Al 2 O 3 —ZrO 2 aggregate, and CA6 aggregate are used as shown in Tables 5 and 6, and 5 mass of phenol resin as a binder is used as a binder. % Of the added compound was kneaded, formed into a sliding nozzle plate shape by friction, baked at 1200 ° C., and then subjected to tar impregnation treatment.
実施例、比較例で作製したスライディングノズルプレートについて、かさ密度、見掛気孔率、曲げ強度、耐熱衝撃性、耐摩耗性、浸食性を評価した。かさ密度および見掛気孔率は煮沸法（ＪＩＳ Ｒ ２２０５）により測定を行った。ＣＡ６骨材の置換量が増えるに従い、かさ密度は小さくなる傾向が見られた。特に気孔率が１５％のＣＡ６骨材を適用した、実施例１〜１０でその傾向が顕著であった。見掛気孔率についてはＣＡ６骨材の置換量が増えるに従い、増加する傾向が見られ、気孔率が１５％であるＣＡ６骨材を適用した実施例１〜１５でその傾向が顕著であった。しかし本発明の適用範囲内においての見掛気孔率は耐用性に影響しなかった。 The sliding nozzle plates produced in the examples and comparative examples were evaluated for bulk density, apparent porosity, bending strength, thermal shock resistance, wear resistance, and erosion resistance. The bulk density and the apparent porosity were measured by a boiling method (JIS R 2205). As the replacement amount of CA6 aggregate increased, the bulk density tended to decrease. In particular, the tendency was remarkable in Examples 1 to 10 in which CA6 aggregate having a porosity of 15% was applied. The apparent porosity tends to increase as the replacement amount of the CA6 aggregate increases, and this tendency is remarkable in Examples 1 to 15 in which the CA6 aggregate having a porosity of 15% is applied. However, the apparent porosity within the scope of the present invention did not affect the durability.
曲げ強度は３点曲げ試験法（ＪＩＳ Ｒ ２２１３−１９７８）により測定を行った。曲げ強度は骨材の種類、置換量に依らずいずれも２８ＭＰａ前後の値をとっており、ＣＡ６骨材に置換してもスライディングノズルプレートに求められる強度を維持することが可能であった。 The bending strength was measured by a three-point bending test method (JIS R 2213-1978). The bending strength was about 28 MPa regardless of the type of aggregate and the amount of replacement, and it was possible to maintain the strength required for the sliding nozzle plate even when replaced with CA6 aggregate.
耐熱衝撃性の評価は１６００℃に維持した溶鋼中に４０ｍｍ×４０ｍｍ×１６０ｍｍに加工した試験サンプルを５分間浸漬させた後、引き上げ５分間空冷するサイクルを５回行い、試験後のサンプルの断面の亀裂発生の程度により評価を行った。比較例１を基準に亀裂量が同等程度であれば○と、比較例１より亀裂発生量が小さいものを◎で表記した。一方、比較例１より亀裂発生量が大きいものを△で表記した。Ａｌ２Ｏ３−ＺｒＯ２骨材の量が多い場合に耐熱衝撃性は良好になる傾向が見られた。ＣＡ６骨材の量に依らず耐熱衝撃性は比較例１と同等か、比較例１よりも良好な結果であり、スライディングノズルプレートに求められる耐熱衝撃性を維持することが可能であった。 Evaluation of thermal shock resistance was performed by immersing a test sample processed to 40 mm × 40 mm × 160 mm in molten steel maintained at 1600 ° C. for 5 minutes and then pulling it up for 5 minutes and air-cooling it 5 times. Evaluation was made according to the degree of cracking. If the amount of cracks is about the same with reference to Comparative Example 1, the symbol “◯” indicates that the amount of crack generation is smaller than that of Comparative Example 1, and “◎” indicates that. On the other hand, the case where the crack generation amount is larger than that of Comparative Example 1 is indicated by Δ. When the amount of the Al 2 O 3 —ZrO 2 aggregate is large, the thermal shock resistance tends to be good. Regardless of the amount of CA6 aggregate, the thermal shock resistance was the same as or better than Comparative Example 1, and the thermal shock resistance required for the sliding nozzle plate could be maintained.
耐摩耗性の評価は熱間摩耗試験法（ＪＩＳ Ｒ ２２５２−２）により行った。１００ｍｍ×１００ｍｍ×１０ｍｍの形状の試験片を用いた。試験温度は８００℃とした。摩耗材であるＳｉＣ粒を吹付け、摩耗量を測定した。比較例１を基準に摩耗量が同等程度であれば○と、比較例１より摩耗量が小さいものを◎で表記した。一方、比較例１より摩耗量が大きいものを△で表記した。Ａｌ２Ｏ３−ＺｒＯ２骨材の量が多い場合に耐摩耗性は良好になる傾向が見られた。一方、ＣＡ６骨材の量に依らず耐摩耗性は比較例１と同等か、比較例１よりも良好な結果であり、スライディングノズルプレートに求められる耐摩耗性を維持することが可能であった。 The wear resistance was evaluated by a hot wear test method (JIS R2252-2). A test piece having a shape of 100 mm × 100 mm × 10 mm was used. The test temperature was 800 ° C. SiC particles as a wear material were sprayed to measure the amount of wear. If the amount of wear was approximately the same as that of Comparative Example 1, it was marked with ◯, and the amount with less wear than Comparative Example 1 was marked with ◎. On the other hand, those having a larger amount of wear than Comparative Example 1 are indicated by Δ. When the amount of the Al 2 O 3 —ZrO 2 aggregate is large, the wear resistance tends to be good. On the other hand, regardless of the amount of CA6 aggregate, the wear resistance is equal to or better than Comparative Example 1, and it was possible to maintain the wear resistance required for the sliding nozzle plate. .
浸食試験ではＣａ処理鋼を模擬した鋼を高周波誘導加熱炉により１６００℃に加熱した後、直径２０ｍｍ、高さ１２０ｍｍの円筒形状の試験サンプルを浸漬させ１時間保持した。その後、気相と溶鋼の界面における試験サンプルの直径の変化量をノギスにて測定した。表１〜４に、比較例１における直径変化量を基準として、実施例１〜２８、比較例２〜８の寸法変化を百分率にて表わした。 In the erosion test, a steel simulating Ca-treated steel was heated to 1600 ° C. by a high-frequency induction heating furnace, and then a cylindrical test sample having a diameter of 20 mm and a height of 120 mm was immersed and held for 1 hour. Then, the amount of change in the diameter of the test sample at the interface between the gas phase and the molten steel was measured with calipers. In Tables 1 to 4, the dimensional changes of Examples 1 to 28 and Comparative Examples 2 to 8 are expressed as percentages based on the diameter change amount in Comparative Example 1.
浸食試験の結果を見ると、ＣＡ６骨材の量を４０質量％とした比較例２、３、４のいずれの場合も比較例１と比べ耐食性が低下する結果であった。また、すべての骨材をＡｌ２Ｏ３骨材とした比較例５の場合には比較例１と比べ耐食性が低下する結果となった。一方、ＣＡ６骨材量が５、１５、２５質量％のいずれの実施例においても比較例１より耐食性が向上する結果となった。更に、ＣＡ６骨材の置換量が５質量％である実施例１、６、１１を比較するとＣＡ６骨材中のヒボナイト含有量が多いほど、またＣＡ６骨材の気孔率が小さいほど耐食性が向上する結果となった。この傾向はＣＡ６骨材の置換量を１５質量％、２５質量％にした場合にも同様であった。 Looking at the results of the erosion test, the results of Comparative Examples 2, 3, and 4 in which the amount of CA6 aggregate was 40 mass% were lower than those of Comparative Example 1. Moreover, all the aggregate in the case of Comparative Example 5 in which the Al 2 O 3 aggregate resulted in reduced corrosion resistance as compared with Comparative Example 1. On the other hand, in any of Examples in which the amount of CA6 aggregate was 5, 15, and 25% by mass, the corrosion resistance was improved as compared with Comparative Example 1. Furthermore, when Examples 1, 6, and 11 in which the replacement amount of CA6 aggregate is 5% by mass are compared, the corrosion resistance improves as the content of hibonite in CA6 aggregate increases and the porosity of CA6 aggregate decreases. As a result. This tendency was the same when the replacement amount of CA6 aggregate was 15% by mass and 25% by mass.
以上の実施例、比較例の結果から、３０〜６７質量％のＡｌ２Ｏ３骨材と、３０〜６７質量％のＡｌ２Ｏ３−ＺｒＯ２骨材と、３〜３０質量％のＣＡ６骨材とからなるスライディングノズルプレートがＣａ処理鋼に対してより好ましい耐食性を有し、ＣＡ６骨材中のヒボナイト含有量を８０質量％以上、ＣＡ６骨材の気孔率を１０％以下とすることで更に高い耐食性を得られた。
From the results of the above Examples and Comparative Examples, 30 to 67% by mass of Al 2 O 3 aggregate, 30 to 67% by mass of Al 2 O 3 —ZrO 2 aggregate, and 3 to 30% by mass of CA6 bone. The sliding nozzle plate made of the material has more preferable corrosion resistance with respect to the Ca-treated steel, and further, the hibonite content in the CA6 aggregate is 80% by mass or more, and the porosity of the CA6 aggregate is 10% or less. High corrosion resistance was obtained.
以上、添付図面を参照しながら本発明の好適な実施形態について詳細に説明したが、本発明はかかる例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、これらについても、当然に本発明の技術的範囲に属するものと了解される。
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.
Claims (3)
前記ＣＡ６骨材が、前記耐火物骨材の３〜３０質量％であることを特徴とするＣａ処理鋼用スライディングノズルプレート。 The refractory aggregate contains CA6 aggregate, Al 2 O 3 aggregate and at least one of Al 2 O 3 —ZrO 2 aggregate,
The sliding nozzle plate for Ca-treated steel, wherein the CA6 aggregate is 3 to 30% by mass of the refractory aggregate.
The sliding nozzle plate for Ca-treated steel according to claim 1 or 2, wherein the porosity of the CA6 aggregate is 10% or less.
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