JP4422424B2 - Cast-in-composite and method for producing the same - Google Patents

Description

【００１８】
結果として、TiB₂単体より、総合的に硬度が高く、かつ耐欠損性の指標である破壊靭性に優れ、ハンドリング性や焼結性に優れたセラミックス固溶体が存在することを見出した。特に、Ti_1-XMe_XB₂(ここで、MeはV、Nb、Ta、Cr及びMoの少なくとも1種、0.02≦ｘ≦0.60)の組成である金属ホウ化物固溶体セラミックスに平均0.20μm以上2μm以下の炭化珪素焼結体破砕粉を0.5質量%以上10質量%以下含む金属ホウ化物固溶体セラミックス焼結体は、従来の高Cr鋼やサイアロンセラミックス製ライナーに比べて、耐摩耗性を高めつつ、チッピングや割れ等の耐欠損性を著しく改善できる。
【００１９】
2ホウ化バナジウム(VB₂)、2ホウ化ニオブ(NbB₂)、2ホウ化タンタル(TaB₂)、2ホウ化クロム(CrB₂)、2ホウ化モリブデン(MoB₂)から選ばれる少なくとも1種の金属ホウ化物を2ホウ化チタン(TiB₂)に固溶させると、TiB₂単体に比べ、硬度や破壊靭性値が総合的に上昇する。しかしながら、Ti_1-XMe_XB₂(Me=V、Nb、Ta、Cr及びMoの少なくとも1種)と表わした場合のxが0.02より小さい場合には、TiB₂への固溶効果が乏しくなり、十分な高硬度化が図れず、一方、xが0.60を越える場合にも、幾つかの機械的な特性が低下する。前記粒子分散炭化珪素質セラミックス中の固溶体粒子の平均粒径は1〜10μmであることが望ましい。より好ましくは3〜5μmである。該平均粒径が1μmより小さいと、靭性への寄与が得られ難く、一方、10μmより大きいと、硬さや破壊靭性値の低下を招く。
【００２０】
さらに、前記Ti-Zr-B系又はTi-Hf-B系の一方又は双方の固溶体粒子分散炭化珪素質焼結体、又は、Ti_1-XMe_XB₂(ここで、MeはV、Nb、Ta、Cr及びMoの少なくとも1種、0.02≦ｘ≦0.60)の組成である金属ホウ化物固溶体セラミックスの相対密度は、理論密度に対して95%以上であることが望ましい。相対密度が95%未満では、粒子分散による焼結体への残留応力の付与が不充分になり、破壊靭性の向上効果が見られないことがある。
【００２１】
一方、ホウ化チタン粉末(TiB₂)、及び2ホウ化バナジウム(VB₂)、2ホウ化ニオブ(NbB₂)、2ホウ化タンタル(TaB₂)、2ホウ化クロム(CrB₂)、2ホウ化モリブデン(MoB₂)から選ばれる少なくとも1種の金属ホウ化物は、粉砕に要する費用が高額で、かつ、平均2μm以下の微粉末では表面酸化層の影響が大きく、焼結性や焼結体の物性を著しく低下させるため、成形及び焼結工程の直前に、粉砕及び整粒工程が必要となる。その際に、炭化珪素の混合容器と混合用メディアを用い、粉砕、整粒、並びに混合工程で混入する粒径が、平均0.20μm以上2μm以下の微細な炭化珪素焼結体破砕粉を0.5〜10質量%含有させることが有効であり、より好ましくは2〜4質量%である。添加量の制御法としては、混合メディアである炭化珪素ボール径、ミル回転数や混合時間によって、再現よく行うことが可能である。この炭化珪素焼結体からの微細な破砕粉は、硬質かつ耐酸化性のある高融点化合物であり、焼結後にホウ化チタン焼結体中に分散粒子として残留し、焼結体全体の硬度や破壊靭性値を向上させる作用を有する。ホウ化チタンと炭化珪素との熱膨張差やヤング率の相違等により、非常に微細な状態で分散した炭化珪素の近傍に残留応力が発生し、焼結体の破壊に際して破壊エネルギーを分散させる作用を有し、靭性を著しく向上させ、耐摩耗性も向上させる効果もある。
【００２２】
靭性の向上は、耐欠損性に効果があり、セラミックスの標準的な靭性の比較評価が可能なSEPB法(JIS R 1607)による破壊靭性値で5MPa・m^1/2以上の高靭性を有することが好適である。また、耐摩耗性の指標であるビッカース硬度は、ダイヤモンド圧子を用い、押込み荷重98Nで2.4×10⁴MPa以上で摩耗が抑制される。
【００２３】
さらに、2ホウ化バナジウム、2ホウ化ニオブ、2ホウ化タンタル、2ホウ化クロム、2ホウ化モリブデンから選ばれる少なくとも1種の金属ホウ化物粉末を2〜60モル%、混合時に不可避的に混入する非常に微細なミル容器内壁並びに混合メディアの炭化珪素セラミックス破砕粉、及び残部2ホウ化チタンからなる混合粉末を、焼結した焼結体の密度は、理論密度に比して95%以上であることが望ましい。理論密度比95%未満では、硬さや破壊靭性の向上効果が十分とは言い切れない。
【００２４】
ここで、Ti-Me-Ｂ系の固溶体粒子(Me=V、Nb、Ta、Cr及びMoの少なくとも1種)は、各種金属ホウ化物を個々に添加する以外に、例えば、複合ホウ化物粒子として添加したり、TiB₂にVC、NbC等の金属炭化物として所定量を混合しても、焼結時の反応により複合ホウ化物を形成することが可能である。また、Ti-Me-Ｂ系の固溶体粒子(Me=V、Nb、Ta、Cr及びMoの少なくとも1種)の緻密化を促進するために、焼結助剤として機能する炭化ホウ素、ホウ素含有有機物を添加することが望ましい。焼結助剤としては、炭化ホウ素、金属ホウ素とカーボンブラックの混合粉体や有機質炭素等の側鎖にホウ素を有する各種前駆体材料、等を用いることができる。焼結助剤である炭化ホウ素の添加量は、Ti-Me-B系の固溶体粒子の純度や粒径によって最適値が異なるものの、マトリックス粉体100質量部に対し、炭化ホウ素換算で0.1〜2.0質量部が好ましい。
【００２５】
焼結性の向上を目的として添加する焼結助剤の炭化ホウ素粉末は、焼結前に均一分散させることが有効である。
【００２６】
本発明の金属ホウ化物固溶体セラミックスの焼結設備は、特に限定するものではなく、前記2ホウ化バナジウム、2ホウ化ニオブ、2ホウ化タンタル、2ホウ化クロム、2ホウ化モリブデンから選ばれる少なくとも1種の金属ホウ化物粉末を2〜60モル%、混合する際に混合容器や混合メディアから混入する微細な炭化珪素破砕粉、及び残部2ホウ化チタンからなる混合粉末を、公知の各種焼結設備を用いることにより製造できる。
【００２７】
焼結方法としては、特に限定するものではなく、例えば真空焼結法、無加圧焼結法、ガス圧焼結法、ホットプレス焼結法、熱間静水圧プレス焼結法、等の各種焼結法を単独でも用いることができ、さらにこれらの焼結法を複数組み合せても良い。中でも、1.3×10^-2Pa以下の高真空下、1700〜2200℃の温度にて、4時間以上保持を行うと緻密な焼結体が得られ易い。十分な緻密化を図るために、アルゴン雰囲気下、100〜200MPaで、1650〜2150℃の温度にて2時間以上保持の熱間静水圧加圧処理する二次焼結を行うことが好ましい。
【００２８】
一次の焼結条件としては、1.3×10^-2Pa以下の高真空度では緻密化が進行し易く、同時に安定した物性が得られ易い。また、焼結温度が1700℃未満では、緻密な焼結体が得られず、十分な硬さを付与することが困難となり、かつ高靭性の焼結体とすることができない。一方、焼結温度が2200℃を越える高温では、破砕粉として混入した炭化珪素が昇華、分解するため、焼結体が得られない。また、保持時間が4時間未満では、焼結反応による緻密化が十分には起こらないため、目的とする焼結体の特性が得られない。
【００２９】
二次の焼結条件として熱間静水圧プレス焼結を行う場合は、1650℃未満では、緻密化の効果が十分に得られない。一方、2150℃を越える高温では、マトリックス粒子が異常成長するため、焼結体の特性が低下する恐れがある。また、保持時間が2時間未満では、緻密化が十分に進行しない。また、一次焼結時の最高温度と二次焼結の最高温度は50℃の差を設けて、二次焼結時を低くすることが好ましい。異常粒成長が起こらず、比較的短時間の処理により緻密化が促進されるので、焼結工程の歩留りが向上し、HIP装置への負担も軽減される。
【００３０】
高炉内部で用いられる各種耐磨耗部材、製鉄用焼結ラインのクラッシングガイドのストーンボックス、製鉄用コークス炉のバケットライナー、原料部門のコンベアシュート等の大型部材等のライナーの表層材料として、該セラミックス材を耐摩耗金属中に鋳ぐるんだ複合体を製造する場合、該セラミックス材と耐摩耗金属材の熱膨張率との差を少なくすることや抜け落ちが生じ難い形状を該セラミックスに附与することが有効である。鋼材の熱膨張率は、インコネル等の超低熱膨張鋼を除けば、概ね6〜11×10^-6/K(室温〜800℃)の範囲内である。該セラミックスは概ね4〜8×10^-6/K(室温〜800℃)の範囲内であり、熱膨張率が比較的小さい高Ni鋼、高Ni合金系グレン鋳鉄に加え、耐磨耗に優れるマルテン系高クロム鋳鉄、マルテン系ハイス鋼等が好ましい。
【００３１】
該粒子分散炭化珪素質セラミックス及び粒子分散炭化珪素質セラミックス形状に関しても、例えば、ライナーの摺動部からライナー背面に向かって、徐々に裾を広げる形状や欠落防止の嵌め込み構造化などの組み合わせを行うことが可能であり、鋳ぐるみ複合体のメリットは安価な製造プロセスに限らず、鋳ぐるまれるセラミックス形状の選択が自由な点にある。該セラミックスの鋳ぐるみ粒サイズが長軸で3mm以上20mm以下、短軸で1mm以上10mm以下の範囲内で平均粒径を有する分布が好ましい。鋳ぐるみ複合体を施工する部位に応じて、粒形状や粒サイズの選定が有効であり、鋳ぐるみ層の肉厚及び肉厚変化を有する施工部位にも対応することが可能である。サイズとしては1mm未満の平均粒径では、セラミックス複合による耐磨耗性向上効果が乏しく、平均粒径が20mm超では、複合体の均質性に欠け、複合体全体としての耐磨耗性の低下に繋がるため、好適ではない。鋳ぐるみ方法に関し、特に限定するものではなく、複数孔からの注入を行う際にエアー抜き孔も適宜設定する等の施工で対応可能である。
【００３２】
本発明の鋳ぐるみ複合体を用いれば、製鉄用高炉のホッパーやベルから供給落下される鉄鉱石やコークスを高炉内部に分配する旋回シュート、ベルロッドウエアリング、ムーバブルアーマーライナー、鉱石受け金物に加え、製鉄用焼結ラインのクラッシングガイドに用いられるストーンボックス、製鉄用コークス炉バケットライナー、原料部門コンベアシュート等の大型部材の耐摩耗性を高めることが可能になる。長寿命化による資材費の圧縮に加え、直接摺動する部材の他にも、背面に位置する短時間の休止を除き、連続操業中には交換不能な部材の破損を防ぎ、安定操業や高炉自体の炉命延長にも効果を発現することが期待される。
【００３３】
コスト面でも該セラミックス材の形状を変更することにより、容易に高肉厚化や大面積化に対応できる鋳ぐるみ法が有効に作用する。該鋳ぐるみ複合体をライナーに被覆する際には、最も負荷が大きく、摩耗が激しい部位にのみ使用しても構わない。
【００３４】
【実施例】
次に、本発明の実施例を比較例と共に説明する。
【００３５】
(実施例1〜10)
炭化珪素(SiC)粉末 (平均粒径0.8μm)、
2ホウ化チタン(TiB₂)粉末 (平均粒径4.2μm)、
2ホウ化バナジウム(VB₂)粉末 (平均粒径5.5μm)、
2ホウ化ニオブ(NbB₂)粉末 (平均粒径4.8μm)、
2ホウ化タンタル(TaB₂)粉末 (平均粒径5.5μm)、
2ホウ化クロム(CrB₂)粉末 (平均粒径4.5μm)、
2ホウ化モリブデン(MoB₂)粉末 (平均粒径5.8μm)、
炭化ニオブ(NbC)粉末 (平均粒径5.0μm)、
炭化バナジウム(VC)粉末 (平均粒径5.5μm)、
炭化タンタル(TaC)粉末 (平均粒径4.5μm)、
炭化ホウ素(B₄C)粉末 (平均粒径0.8μm)、
を第2表に示す所定量(質量%)添加し、分散媒としてアセトン又はエタノールを用い、炭化珪素セラミックスを内貼りしたボールミルにφ5mmの炭化珪素セラミックスボールを混合メディアとして用い、48時間混練した。アセトン又はエタノールの添加量は、投入したセラミックス粉末100gに対し80gの割合とした。
【００３６】
次いで、得られた混合粉末を成形後、焼結した。成形条件としては、冷間静水圧による加圧150MPaとし、φ20mm×厚さ20mmに成形した。これを素地加工し、φ10〜15mm×厚さ15mmの2種、凹凸円盤形状の成形体を得た。焼結条件としては、3.0×10^-2Pa中にて、第2表中に示す温度で8時間保持の真空焼結を行った。必要に応じ、その後の二次焼結として、同じく第2表中に示す温度、圧力のArガス雰囲気中にて、3時間保持の熱間静水圧加圧(HIP)処理を行った。物性評価用に同条件にて製造した焼結体(50mm×50mm×厚さ10mm)の平板からJIS試験片を研削加工し、機械的性質として、硬さは押込荷重98Nにてビッカース硬さとして測定した。破壊靭性についてはJIS R 1607のSEPB法により室温にて破壊靭性値K_ICを測定した。焼結体密度は、アルキメデス法により相対密度として測定した。また、X線回折法を用いて、混合前の原料粉末段階での各粉末のX線回折ピークをそれぞれ測定し、混合・成形し、焼結後の焼結体のX線回折ピークと照合したところ、TIB₂中にV、Nb、Ta、Cr、Moがそれぞれ固溶し、結晶格子のずれが生じていることを確認した。さらに、破砕混入した炭化珪素(SiC)についても、X線回折で同定され、混入量についてはボールミルとφ5mm炭化珪素ボールの摩耗量から求められ、本実施例では、いずれも原料投入量に対し、2〜4質量部の混入量であった。得られた各焼結体の諸特性を焼結体密度と共に第3表に示す。
【００３７】
高Ni系グレン鋳鉄に、それぞれのセラミックスを体積割合が40%で鋳ぐるみ、落重試験による耐久性を評価した。落重試験は、セラミックス固溶体を厚さ1mmのカーボンシートを挿入した鋼材(SS400)に装着(端部を機械止め)し、質量3kgの鋼球(SS400)を10cm刻みに高さを上げながら実施した。最大200cmまでの試験後、各供試材の損傷有無、チッピングの深さ、及びヒビ割れの深さを蛍光探傷法及び断面研磨面の光学顕微鏡観察により評価した。
【００３８】
(比較例11〜15)
比較例11〜15は、それぞれ高Ni系グレン鋳鉄の場合(比較例11)、高Ni系グレン鋳鉄にφ3〜5mmの分布を有する超硬(WC-6%Co)粒子を鋳ぐるんだライナーを用いた場合(比較例12)、通常のサイアロンセラミックスを用いた場合(比較例13)の各比較例である。比較例14は、一般市販のボロン-カーボン系炭化珪素セラミックス単体(純度97質量%)、比較例15は、一般市販の2ホウ化チタンセラミックス単体(純度92質量%)の焼結体である。これらを併せて第2表及び第3表の比較例の欄に示す。また、これら比較例11〜15も実施例1〜10と同様の条件で落重試験を行った。
【００３９】
【表２】

【００４０】
【表３】

【００４１】
第3表に示すように、落重試験高さが僅か50cmにおいて、比較例11〜12では、非可逆的なヘコミが生じ、50cm超に高さを増すにつれ、ヘコミが増大した。本発明の実施例1〜10によるものは、落重試験の最大高さが何れも150cm以上と、比較例の13〜15の120cm以下に比べ高く、併せてヒビ割れやチッピング等の欠損も少ない傾向が確認された。また、ヤング率について、表中には記載しなかったが、2ホウ化チタン単体の550GPaに比べ、本発明の実施例は470〜530GPa僅かながら低下しており、耐機械的衝撃性の向上の一因と考えることも可能である。したがって、機械的特性並びに落重試験のいずれも本発明の材質が総合的に良好な結果を得ることができた。
【００４２】
【発明の効果】
以上述べたように、本発明のTi-Zr-B系又はTi-Hf-B系の一方又は双方の固溶体粒子を分散した炭化珪素を焼結した粒子分散炭化珪素質焼結体、又は、Ti_1-XMe_XB₂(ここで、MeはV、Nb、Ta、Cr及びMoの少なくとも1種、0.02≦ｘ≦0.60)の組成である金属ホウ化物固溶体セラミックスの一方又は両方を、耐磨耗金属で鋳ぐるんだ複合体は、硬度や破壊靭性値に代表される機械的安定性に優れ、落重試験で高い耐久性を有する。
【００４３】
高炉内で塊状装入物の落下衝突による負荷の大きな各種部材の表層部のライナー、製鉄用焼結ラインのクラッシングガイドで用いられるストーンボックス、製鉄用コークス炉のバケットライナー、原料部門コンベアシュート等の大型ライナー部材に加え、熱延工程や冷延工程で用いられる各種搬送ロールやサイドロール等の大型ロール部材に本発明のTi-Zr-B系の固溶体粒子又はTi-Hf-B系の固溶体粒子の一方又は双方を分散した炭化珪素を焼結した粒子分散炭化珪素質焼結体、又は、Ti_1-XMe_XB₂(ここで、MeはV、Nb、Ta、Cr及びMoの少なくとも1種、0.02≦ｘ≦0.50)の組成である金属ホウ化物固溶体セラミックスの一方又は両方を耐磨耗金属で鋳ぐるんでなる複合体を使用すれば、鉄鋼製造設備の長寿命化による資材費圧縮と高炉、焼結炉、コークス炉等の安定操業による生産性向上に伴う製造コスト低減に寄与すること大である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cast ceramic material that is excellent in wear resistance and fracture resistance and can easily cope with an increase in area, and a method for manufacturing the same.
[0002]
[Prior art]
Usually, when distributing blast furnace charges such as iron ore, lime, and coke to the furnace center, various cantilever chute members are used. However, these various chute members have a remarkable wear rate due to impact caused by dropping of the charge and sliding during contact flow, and a structure in which a liner for protecting these members is embedded in the surface layer portion of the member. Has been. So far, as disclosed in Patent Document 1, the surface coating portion (= liner) used for these various members is manufactured with cast-in materials of high Cr steel or high Cr steel + carbide (WC) particles. However, the wear situation has not been improved sufficiently due to the collision depending on the physical properties of the charge, the falling speed, the size of the lump, and the like. In particular, the surface layer liners of various members are worn violently due to contact and collision of the charged material, so the lifespan varies depending on the site, but it is said to be 1 to 2 years at the longest. It is necessary to carry out maintenance, and for that reason, the maintenance and maintenance costs are soaring.
[0003]
[Patent Document 1]
JP 11-131114 A
[0004]
[Problems to be solved by the invention]
Therefore, development of materials such as liners using materials that improve wear resistance and service life has been desired. Accordingly, the present invention provides a surface layer liner for various members to be loaded with blast furnace charges such as iron ore, lime, coke, etc., a stone box used in a crushing guide for a steel making sintering line, and iron making coke. In addition to liners used for large parts such as furnace bucket liners and conveyor chutes in the raw material department, wear resistance and service life of large roll members such as various transport rolls and side rolls used in hot rolling and cold rolling processes It is an object of the present invention to provide a composite in which a ceramic material that is improved and can be coped with by an inexpensive manufacturing process even in a large area is cast in wear-resistant metal and a method for manufacturing the same.
[0005]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have intensively studied the characteristics of various ceramic sintered bodies, combinations with various wear-resistant metals, and the characteristics of cast-in composites. It has been found that when a cast-in composite using ceramics is used, it has excellent properties as a material such as various liners used in an iron making process and the like, and the present invention has been completed.
[0006]
That is, the present invention
(1) Ti-Zr-B system or Ti-HfParticle dispersed silicon carbide ceramics obtained by sintering silicon carbide in which one or both solid solution particles of -B system are dispersed, or Ti_1-XMe_XB₂(Where Me is at least one of V, Nb, Ta, Cr and Mo, 0.02 ≦ x ≦ 0.60). One or both of the metal boride solid solution ceramics is cast with an abrasion resistant metal. The particle-dispersed silicon carbide ceramic and the metal boride solid solution ceramic have an average thermal expansion coefficient.7.4~9.8× 10^-6/ K (room temperature to 800 ° C.), and the wear resistant metal has an average coefficient of thermal expansion.7.4~9.8× 10^-6/ K (room temperature to 800 ° C.) high-Ni steel and high-Ni alloy-based Glen cast iron,
(2) The particle size of the particle-dispersed silicon carbide ceramic or metal boride solid solution ceramic has a distribution in which the average particle size is 3 mm to 20 mm in the major axis and 1 mm to 10 mm in the minor axis (1) Cast-in-the-line composite for liners,
(3) In the cast-in composite for a liner formed by casting particle-dispersed silicon carbide ceramics obtained by sintering silicon carbide in which the Ti-Zr-B-based solid solution particles dispersed in (1) are dispersed, the Ti- The composition of the Zr-B solid solution particles is Ti_1-xZr_xB₂(0.0 ≦ x ≦ 0.20) a cast-in composite for a liner,
(4) In the cast-in composite for a liner formed by casting particle-dispersed silicon carbide ceramics obtained by sintering silicon carbide in which the Ti-Hf-B-based solid solution particles dispersed in (1) are dispersed, the Ti- The composition of the Hf-B solid solution particles is Ti_1-xHf_xB₂(0.0 ≦ x ≦ 0.20) a cast-in composite for a liner,
(5) Ti-Zr-B system or Ti- described in (1)HfA cast-for-combination composite for a liner formed by casting particle-dispersed silicon carbide ceramics obtained by sintering silicon carbide in which one or both solid solution particles of B type are dispersed, wherein the solid solution particles in the particle-dispersed silicon carbide ceramics Cast-in-line composite for liners having an average particle size of 1 to 10 μm,
(6) Ti-Zr-B system or Ti- described in (1)HfIn a cast-for-combination composite for a liner formed by casting particle-dispersed silicon carbide ceramics obtained by sintering silicon carbide in which one or both solid solution particles of -B system are dispersed, the volume fraction of the solid solution particles is 20 to 70 % Cast-in-line composite for liners,
(7) Ti-Zr-B system or Ti- described in (1)HfIn a cast-for-combination composite for a liner formed by casting particle-dispersed silicon carbide ceramics obtained by sintering silicon carbide in which one or both solid solution particles of -B system are dispersed, the relative density of the particle-dispersed silicon carbide ceramics is Cast-in-line composite for liner, which is 95% or more,
(8) Ti-Zr-B system or Ti- described in (1)HfIn a cast-for-combination composite for a liner formed by casting a particle-dispersed silicon carbide ceramic obtained by sintering silicon carbide in which one or both solid solution particles of -B system are dispersed, the solid solution particles are carbonized as composite boride particles. Add to silicon or TiB₂And ZrB₂, ZrC, HfB₂, A cast-in composite for a liner formed by mixing a predetermined amount of one or more types of HfC with silicon carbide, a sintering temperature of 1850 to 2200 ° C., and a holding time of 3 hours or more, and a reaction during sintering;
(9) A cast-out composite for a liner formed by casting the metal boride solid solution ceramics according to (1), wherein the metal boride solid solution ceramics has a theoretical density ratio of 95% or more; 4 × 10⁴Vickers hardness above 5 MPa, 5 MPa · m^1/2Cast-in-line composite for liners having the above fracture toughness values,
(10) TiB₂VB for powder₂, NbB₂, TaB₂, CrB₂And MoB₂2 to 60 mol% of at least one metal boride powder selected from 1 and a mixed powder to which a sintering aid is added, 1.3 × 10^-2Sintering is performed at a temperature of 1700-2200 ° C. for 4 hours or more in a high vacuum of Pa or less or in an argon atmosphere, and the obtained metal boride solid solution ceramic is cast in a wear-resistant metal by 30% or more by volume. A method for producing a cast-in-combustion composite, wherein the wear resistant metal has an average coefficient of thermal expansion.7.4~9.8× 10^-6/ K (room temperature to 800 ° C.) high-Ni steel and high-Ni alloy-based grain cast iron production method of a cast-in composite for a liner that is at least one kind,
(11) Ti-Zr-B system or Ti-HfA particle-dispersed silicon carbide ceramics obtained by sintering silicon carbide in which one or both solid solution particles of -B series are dispersed or a metal boride solid solution ceramics described in (10) is further added at 1650 at 100 to 200 MPa in an argon atmosphere. A method for producing a cast-in-hole composite that is subjected to hot isostatic pressing at a temperature of ˜2150 ° C. for 2 hours or more and then cast into a wear-resistant metal, wherein the wear-resistant metal has an average thermal expansion Rate is7.4~9.8× 10^-6/ K (room temperature to 800 ° C.) is a method for producing a cast composite for a liner, characterized in that it is at least one of high-Ni steel and high-Ni alloy-based grain cast iron in the range of room temperature to 800 ° C.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0008]
As a result of earnest analysis of the wear situation of the liners arranged on the surface layers of various chute members used when distributing the blast furnace charge such as iron ore, lime, coke, etc. inside the blast furnace, It has been found that when the charge collides in the form of a lump, the surface layer in contact with the material having inferior hardness easily wears and breaks down and wears out.
[0009]
This wear and chipping were particularly noticeable when the hardness and fracture toughness of the liner material arranged on the surface layer of various members were low. Therefore, in order to stably use the liners arranged on the surface layer portions of various members for a long period of time, it is necessary to simultaneously improve the wear resistance and fracture resistance. For that purpose, the hardness is high and at the same time high. In addition to using tough ceramic materials, it is indispensable to develop a cast-in method that can be applied in an inexpensive manufacturing process for increasing the area and increasing the wall thickness.
[0010]
As wear-resistant metals, C is 1.2 to 2.6% by mass, 0.5Cr + 2Mo + W eutectic carbide is 9 to 23% by mass in terms of Mo, V carbide is 5 to 8% by mass, and the total amount of Mn and Ni Is 0.5 to 2.0 mass%, Co is 0 to 9 mass%, the metal composed of the balance Fe and inevitable impurities, as well as martensitic high chromium cast iron, high Ni alloy based Glen cast iron, martensitic high-speed steel, etc. In order to further improve the wear resistance, it is possible to increase the amount of each component other than Fe. However, it is effective to reduce C addition as much as possible for rough skin of the sliding surface.
[0011]
Since known silicon carbide ceramics alone are inferior in fracture toughness, it is effective to disperse particles selected on the basis of the following criteria in silicon carbide. Dispersed Ti-Zr-B or Ti-Hf-B due to differences in thermal expansion or Young's modulus between one or both solid solution particles of silicon carbide and Ti-Zr-B or Ti-Hf-B Residual stress is generated in the vicinity of one or both solid solution particles of the system, and when the sintered body is broken, the fracture energy is dispersed, the toughness is remarkably improved, and the wear resistance is also improved. is there. One or both solid solution particles of this Ti-Zr-B system or Ti-Hf-B system are hard and oxidation-resistant high melting point compounds of the hcp structure, and after sintering, in the silicon carbide sintered body It remains as dispersed particles and has the effect of improving the hardness and fracture toughness of the entire sintered body.
[0012]
The composition of each Ti-Zr-B or Ti-Hf-B solid solution particle is Ti_1-xZr_xB₂, Ti_1-xHf_xB₂The range of x is preferably 0.02 to 0.20, more preferably 0.02 to 0.10. TiB₂ZrB₂Or HfB₂When TiB is dissolved, TiB₂Hardness and fracture toughness values increase compared to simple substances. However, when x is less than 0.02, Zr, Hf TiB₂However, if x exceeds 0.20, the coefficient of thermal expansion of the matrix is somewhat different from that of silicon carbide, and it becomes dense during sintering. It becomes difficult, and it becomes easy to become a sintered compact with a low relative density, and there exists a high possibility that fracture toughness will fall. The volume fraction in the particle-dispersed silicon carbide ceramics of one or both of the solid solution particles of the Ti-Zr-B system or Ti-Hf-B system is preferably 20 to 70%. If the volume fraction is less than 20%, it will be difficult to contribute to the improvement of hardness and toughness.On the other hand, if it exceeds 70%, the residual stress due to particle dispersion becomes excessive, resulting in a decrease in fracture toughness and a decrease in fracture resistance. To do.
[0013]
The method for producing a particle-dispersed silicon carbide sintered body obtained by sintering silicon carbide in which one or both solid solution particles of Ti-Zr-B system or Ti-Hf-B system are dispersed is not particularly limited. After adding or mixing a predetermined amount of solid solution particles of Ti-Zr-B or Ti-Hf-B and / or a sintering aid as required, the silicon powder is molded. Can be manufactured. Here, one or both of the solid solution particles of the Ti-Zr-B system or the Ti-Hf-B system are added as composite boride particles, for example, TiB₂And ZrB₂, ZrC, HfB₂A predetermined amount of one or more kinds of HfC may be mixed with silicon carbide, and a composite boride may be formed by a reaction during sintering.
[0014]
In addition, silicon carbide is a substance having a strong covalent bond and is often difficult to sinter alone. Therefore, it is desirable to add a sintering aid for densification. As the sintering aid, boron carbide, metal boron, various carbon materials such as carbon black and organic carbon, aluminum nitride, aluminum oxide, rare earth oxide, and the like can be used. The addition amount of the sintering aid needs to vary depending on the purity and particle size of the silicon carbide powder, but with respect to 100 parts by mass of silicon carbide, 0.1 to 2.0 parts by mass of boron carbide, 0.5 to 2.5 parts by mass of carbon, Etc. are preferred.
[0015]
The sintering method is not particularly limited. For example, various sintering methods such as a pressureless sintering method, a gas pressure sintering method, a hot isostatic pressing method, and a hot press sintering method are used. Further, a plurality of these sintering methods may be combined. When the pressureless sintering method is performed in a vacuum or in an inert gas flow, a dense sintered body is easily obtained. In the case of producing a large thick shape, it is preferable to perform hot isostatic pressing in an inert gas atmosphere after pressureless sintering in order to achieve sufficient densification. As sintering conditions, it is desirable that the sintering temperature is 1850 to 2200 ° C. and the holding time is 3 hours or more. If it is less than 1850 ° C., a dense sintered body cannot be obtained, and it becomes difficult to generate sufficient residual stress in the vicinity of the solid solution particles, so that a high toughness sintered body cannot be obtained. On the other hand, at a high temperature exceeding 2200 ° C., the silicon carbide in the matrix sublimates and decomposes, so that a sintered body cannot be obtained. In addition, when the holding time is less than 3 hours, composite boride particles are not sufficiently generated by the sintering reaction, so that the effect of dispersing the particles of the sintered body cannot be obtained.
[0016]
In addition, in order to improve both the properties of hardness and fracture toughness at the same time, the unit cell, space group, and structural type are hexagonal, D from various metal boride ceramics known for their high hardness.¹ _6h-P6 /_mmm, AlB₂Select a combination that is exactly the same for the mold and very close to the lattice constant (Table 1), and after confirming by X-ray diffraction pattern that each forms a solid solution, ceramic sintered bodies were sequentially produced, Its characteristics were evaluated.
[0017]
[Table 1]

[0018]
As a result, TiB₂The present inventors have found that there is a ceramic solid solution that is generally higher in hardness than the simple substance, excellent in fracture toughness, which is an index of fracture resistance, and excellent in handling properties and sintering properties. In particular, Ti_1-XMe_XB₂(Where Me is at least one of V, Nb, Ta, Cr, and Mo, 0.02 ≦ x ≦ 0.60) and a metal boride solid solution ceramic with an average of 0.20 μm or more and 2 μm or less of silicon carbide sintered body crushed powder Compared to conventional high-Cr steel and sialon ceramic liners, metal boride solid solution ceramic sintered bodies containing 0.5 mass% or more and 10 mass% or less of metal have improved wear resistance and chip resistance such as chipping and cracking. It can be remarkably improved.
[0019]
2 Vanadium boride (VB₂), Niobium diboride (NbB₂), Tantalum boride (TaB)₂), Chromium diboride (CrB₂), Molybdenum diboride (MoB)₂At least one metal boride selected from titanium diboride (TiB₂) To dissolve in TiB₂Compared to simple substance, hardness and fracture toughness value increase comprehensively. However, Ti_1-XMe_XB₂When x is smaller than 0.02 when expressed as (Me = V, Nb, Ta, Cr and Mo), TiB₂The solid solution effect becomes poor, and sufficient hardness cannot be achieved. On the other hand, even when x exceeds 0.60, some mechanical properties deteriorate. The average particle size of the solid solution particles in the particle-dispersed silicon carbide ceramic is preferably 1 to 10 μm. More preferably, it is 3-5 micrometers. When the average particle size is less than 1 μm, it is difficult to obtain a contribution to toughness, while when it is greater than 10 μm, the hardness and fracture toughness value are reduced.
[0020]
Furthermore, one or both of the Ti-Zr-B system and Ti-Hf-B system solid solution particle dispersed silicon carbide sintered body, or Ti_1-XMe_XB₂(Where Me is at least one of V, Nb, Ta, Cr and Mo, 0.02 ≦ x ≦ 0.60), the relative density of the metal boride solid solution ceramics is 95% or more of the theoretical density It is desirable. When the relative density is less than 95%, residual stress is not sufficiently applied to the sintered body due to particle dispersion, and the effect of improving fracture toughness may not be observed.
[0021]
Meanwhile, titanium boride powder (TiB₂), And vanadium diboride (VB₂), Niobium diboride (NbB₂), Tantalum boride (TaB)₂), Chromium diboride (CrB₂), Molybdenum diboride (MoB)₂At least one metal boride selected from (1) has a high cost for pulverization, and a fine powder with an average of 2 μm or less has a large effect on the surface oxide layer, which significantly reduces the sinterability and physical properties of the sintered body. Therefore, a pulverization and sizing step is required immediately before the forming and sintering steps. At that time, using a silicon carbide mixing container and a mixing medium, the particle size mixed in the pulverization, sizing, and mixing steps is 0.5 to 2 μm. It is effective to contain 10% by mass, more preferably 2 to 4% by mass. The addition amount can be controlled with good reproducibility according to the silicon carbide ball diameter, the mill rotation speed, and the mixing time, which are mixed media. The fine crushed powder from this silicon carbide sintered body is a high melting point compound that is hard and has oxidation resistance, and remains as dispersed particles in the titanium boride sintered body after sintering. And has the effect of improving the fracture toughness value. Residual stress is generated in the vicinity of silicon carbide dispersed in a very fine state due to differences in thermal expansion and Young's modulus between titanium boride and silicon carbide. Has the effect of significantly improving toughness and improving wear resistance.
[0022]
The improvement in toughness has an effect on fracture resistance, and the fracture toughness value by the SEPB method (JIS R 1607), which allows comparative evaluation of standard toughness of ceramics, is 5 MPa · m.^1/2It is preferable to have the above high toughness. The Vickers hardness, which is an index of wear resistance, is 2.4 × 10 at an indentation load of 98 N using a diamond indenter.^FourWear is suppressed above MPa.
[0023]
Furthermore, 2 to 60 mol% of at least one metal boride powder selected from vanadium diboride, niobium diboride, tantalum diboride, chromium diboride and molybdenum diboride is mixed unavoidably when mixed. The density of the sintered body obtained by sintering a very fine mill container inner wall, mixed powder of silicon carbide ceramic pulverized powder of the mixed media, and the remaining titanium diboride is 95% or more compared to the theoretical density. It is desirable to be. If the theoretical density ratio is less than 95%, it cannot be said that the effect of improving hardness and fracture toughness is sufficient.
[0024]
Here, Ti-Me-B-based solid solution particles (Me = V, Nb, Ta, Cr, and Mo) can be used as, for example, composite boride particles in addition to adding various metal borides individually. Add TiB₂Even if a predetermined amount is mixed as a metal carbide such as VC or NbC, a composite boride can be formed by a reaction during sintering. Also, boron carbide and boron-containing organic substances that function as sintering aids to promote densification of Ti-Me-B solid solution particles (Me = V, Nb, Ta, Cr, and Mo). It is desirable to add. As the sintering aid, boron carbide, mixed powder of metal boron and carbon black, various precursor materials having boron in the side chain such as organic carbon, and the like can be used. Although the optimum amount of boron carbide as a sintering aid varies depending on the purity and particle size of the Ti-Me-B solid solution particles, it is 0.1 to 2.0 in terms of boron carbide with respect to 100 parts by mass of the matrix powder. Part by mass is preferred.
[0025]
It is effective to uniformly disperse the boron carbide powder as a sintering aid added for the purpose of improving the sinterability before sintering.
[0026]
The sintering facility for the metal boride solid solution ceramics of the present invention is not particularly limited, and is at least selected from the vanadium diboride, niobium diboride, tantalum diboride, chromium diboride, and molybdenum diboride. 2 to 60 mol% of one type of metal boride powder, fine silicon carbide crushed powder mixed from mixing container or mixing media when mixing, and mixed powder consisting of the remainder titanium diboride, various known sintering It can be manufactured by using equipment.
[0027]
The sintering method is not particularly limited. For example, various methods such as vacuum sintering, pressureless sintering, gas pressure sintering, hot press sintering, hot isostatic pressing, etc. Sintering methods can be used alone, and a plurality of these sintering methods may be combined. Above all, 1.3 × 10^-2When held at a temperature of 1700-2200 ° C. for 4 hours or more under a high vacuum of Pa or lower, a dense sintered body can be easily obtained. In order to achieve sufficient densification, it is preferable to perform secondary sintering in a hot isostatic pressing process that is maintained at a temperature of 1650 to 2150 ° C. for 2 hours or more at 100 to 200 MPa in an argon atmosphere.
[0028]
As primary sintering conditions, 1.3 × 10^-2When the degree of vacuum is less than Pa, densification tends to proceed, and at the same time, stable physical properties are easily obtained. On the other hand, if the sintering temperature is less than 1700 ° C., a dense sintered body cannot be obtained, it becomes difficult to impart sufficient hardness, and a high toughness sintered body cannot be obtained. On the other hand, when the sintering temperature exceeds 2200 ° C., silicon carbide mixed as crushed powder is sublimated and decomposed, so that a sintered body cannot be obtained. In addition, if the holding time is less than 4 hours, densification due to the sintering reaction does not occur sufficiently, so that the desired characteristics of the sintered body cannot be obtained.
[0029]
When hot isostatic pressing is performed as a secondary sintering condition, the effect of densification cannot be sufficiently obtained at a temperature lower than 1650 ° C. On the other hand, when the temperature exceeds 2150 ° C., the matrix particles grow abnormally, which may deteriorate the characteristics of the sintered body. Further, if the holding time is less than 2 hours, the densification does not proceed sufficiently. In addition, it is preferable that the maximum temperature during the primary sintering and the maximum temperature during the secondary sintering be set at a difference of 50 ° C. to reduce the time during the secondary sintering. Abnormal grain growth does not occur and densification is promoted by a relatively short processing time, so that the yield of the sintering process is improved and the burden on the HIP apparatus is reduced.
[0030]
As the surface layer material of liners such as various wear-resistant members used in the blast furnace, stone box of crushing guide for iron making sintering line, bucket liner for iron making coke oven, conveyor chute in raw material department, etc. When producing a composite in which a ceramic material is cast in wear-resistant metal, the ceramic is given a shape that reduces the difference between the thermal expansion coefficient of the ceramic material and the wear-resistant metal material and does not easily fall off. It is effective to do. The coefficient of thermal expansion of steel is generally 6 to 11 x 10 except for ultra-low thermal expansion steel such as Inconel.^-6/ K (room temperature to 800 ° C.). The ceramic is roughly 4-8 × 10^-6In addition to high-Ni steel and high-Ni alloy-based Glen cast iron with a relatively low coefficient of thermal expansion within the range of / K (room temperature to 800 ° C), marten-based high-chromium cast iron, martens-based high-speed steel, etc. with excellent wear resistance Is preferred.
[0031]
Regarding the shape of the particle-dispersed silicon carbide ceramic and the particle-dispersed silicon carbide ceramic, for example, combinations such as a shape that gradually widens the bottom from the sliding portion of the liner toward the back of the liner and a structure for fitting to prevent missing are performed. Therefore, the merit of the cast-in composite is not limited to an inexpensive manufacturing process, but the ceramic shape to be cast can be freely selected. A distribution having an average particle size within the range of 3 mm to 20 mm in the major axis and 1 mm to 10 mm in the minor axis is preferable. Selection of the grain shape and grain size is effective according to the part where the cast-in composite is constructed, and it is possible to cope with the construction part having the thickness and thickness change of the cast-in layer. When the average particle size is less than 1 mm, the effect of improving the wear resistance by the ceramic composite is poor, and when the average particle size exceeds 20 mm, the composite lacks homogeneity and the overall wear resistance decreases. Therefore, it is not preferable. The cast-in method is not particularly limited, and can be handled by construction such as appropriately setting air vent holes when injecting from a plurality of holes.
[0032]
Using the cast-in composite of the present invention, in addition to the turning chute, bell rod wear ring, movable armor liner, ore receiving material that distributes the iron ore and coke supplied and dropped from the hopper and bell of the blast furnace for iron making to the inside of the blast furnace. It becomes possible to improve the wear resistance of large members such as a stone box used for a crushing guide of a sintering line for iron making, a coke oven bucket liner for iron making, a material department conveyor chute, and the like. In addition to reducing material costs by extending the service life, in addition to the members that slide directly, except for a brief pause on the back, it prevents damage to non-replaceable members during continuous operation, stable operation and blast furnace It is expected that it will be effective in extending its own reactor life.
[0033]
In terms of cost, a cast-in method that can easily cope with an increase in thickness and area is effective by changing the shape of the ceramic material. When the cast-in-composite is coated on the liner, it may be used only in a portion where the load is greatest and the wear is severe.
[0034]
【Example】
Next, examples of the present invention will be described together with comparative examples.
[0035]
(Examples 1 to 10)
Silicon carbide (SiC) powder (average particle size 0.8μm),
Titanium boride (TiB₂) Powder (average particle size 4.2μm),
2 Vanadium boride (VB₂) Powder (average particle size 5.5μm),
2 Niobium boride (NbB₂) Powder (average particle size 4.8μm),
2 Tantalum boride (TaB₂) Powder (average particle size 5.5μm),
2 Chromium boride (CrB₂) Powder (average particle size 4.5μm),
2 Molybdenum boride (MoB₂) Powder (average particle size 5.8μm),
Niobium carbide (NbC) powder (average particle size 5.0 μm),
Vanadium carbide (VC) powder (average particle size 5.5μm),
Tantalum carbide (TaC) powder (average particle size 4.5μm),
Boron carbide (B_FourC) Powder (average particle size 0.8μm),
Was added in a predetermined amount (mass%) shown in Table 2, and acetone or ethanol was used as a dispersion medium, and a silicon carbide ceramic ball having a diameter of 5 mm was used as a mixing medium in a ball mill in which silicon carbide ceramics were adhered, and kneaded for 48 hours. The amount of acetone or ethanol added was 80 g with respect to 100 g of the ceramic powder charged.
[0036]
Next, the obtained mixed powder was molded and then sintered. The molding conditions were a pressure of 150 MPa by cold isostatic pressure, and a molding of φ20 mm × thickness 20 mm. This was subjected to a base processing to obtain two types of shaped bodies having a concavo-convex disk shape of φ10 to 15 mm × thickness 15 mm. As sintering conditions, 3.0 × 10^-2Vacuum sintering was performed in Pa at a temperature shown in Table 2 for 8 hours. If necessary, as the subsequent secondary sintering, a hot isostatic pressing (HIP) treatment for 3 hours was performed in an Ar gas atmosphere having the same temperature and pressure as shown in Table 2. JIS test specimens were ground from a flat plate of sintered body (50mm x 50mm x thickness 10mm) manufactured under the same conditions for the evaluation of physical properties. The mechanical properties were determined as Vickers hardness with an indentation load of 98N. It was measured. With regard to fracture toughness, the fracture toughness value K at room temperature according to the SEPB method of JIS R 1607_{I c}Was measured. The sintered body density was measured as a relative density by the Archimedes method. Also, using the X-ray diffraction method, the X-ray diffraction peak of each powder at the raw material powder stage before mixing was measured, mixed, molded, and collated with the X-ray diffraction peak of the sintered body after sintering TIB₂It was confirmed that V, Nb, Ta, Cr, and Mo were dissolved therein, and the crystal lattice was displaced. Furthermore, silicon carbide (SiC) mixed and crushed is also identified by X-ray diffraction, and the mixing amount is obtained from the wear amount of the ball mill and φ5 mm silicon carbide ball. The mixing amount was 2 to 4 parts by mass. Table 3 shows various characteristics of the obtained sintered bodies together with the sintered body density.
[0037]
High Ni-based Glen cast iron was cast into each ceramic at a volume ratio of 40%, and durability was evaluated by drop weight test. The drop weight test was performed by attaching a solid ceramic solution to a steel material (SS400) with a carbon sheet with a thickness of 1 mm inserted (machined at the end) and increasing the height of a 3 kg steel ball (SS400) in 10 cm increments. did. After the test up to a maximum of 200 cm, the presence or absence of damage, the chipping depth, and the crack depth of each test material were evaluated by fluorescent flaw detection and observation of the cross-section polished surface with an optical microscope.
[0038]
(Comparative Examples 11-15)
Comparative Examples 11-15 are high Ni-based Glen cast iron (Comparative Example 11), high-Ni-based Glen cast iron liners with cast carbide (WC-6% Co) particles having a distribution of φ3-5mm These are comparative examples in the case of using (Comparative Example 12) and in the case of using ordinary sialon ceramics (Comparative Example 13). Comparative Example 14 is a sintered body of a general commercially available boron-carbon-based silicon carbide ceramics simple substance (purity 97 mass%), and Comparative Example 15 is a general commercially available titanium diboride ceramic simple substance (purity 92 mass%). These are also shown in the comparative example column of Tables 2 and 3. In addition, in these Comparative Examples 11 to 15, a drop weight test was performed under the same conditions as in Examples 1 to 10.
[0039]
[Table 2]

[0040]
[Table 3]

[0041]
As shown in Table 3, irreversible dents occurred in Comparative Examples 11-12 when the drop test height was only 50 cm, and the dents increased as the height increased above 50 cm. According to Examples 1 to 10 of the present invention, the maximum height of the drop weight test is 150 cm or more, which is higher than 120 cm or less of 13 to 15 of the comparative example, and there are also few defects such as cracks and chipping. A trend was confirmed. In addition, although the Young's modulus was not described in the table, compared with 550 GPa of titanium diboride alone, the example of the present invention slightly decreased by 470 to 530 GPa, and improved mechanical impact resistance. It can also be considered as a factor. Therefore, both the mechanical properties and drop weight test were able to obtain comprehensively good results with the material of the present invention.
[0042]
【The invention's effect】
As described above, the particle-dispersed silicon carbide sintered body obtained by sintering silicon carbide in which one or both solid solution particles of the Ti-Zr-B system or Ti-Hf-B system of the present invention are dispersed, or Ti_1-XMe_XB₂(Here, Me is at least one of V, Nb, Ta, Cr and Mo, 0.02 ≦ x ≦ 0.60). One or both of the metal boride solid solution ceramics is cast with an abrasion resistant metal. The composite is excellent in mechanical stability typified by hardness and fracture toughness, and has high durability in a drop weight test.
[0043]
The liner of the surface layer of various parts that are heavily loaded due to the drop impact of the bulk charge in the blast furnace, the stone box used in the crushing guide of the sintering line for iron making, the bucket liner of the coke oven for iron making, the conveyor chutes of the raw material department, etc. Ti-Zr-B solid solution particles or Ti-Hf-B solid solution particles of the present invention for large roll members such as various transport rolls and side rolls used in the hot rolling process and cold rolling process Particle-dispersed silicon carbide sintered body obtained by sintering silicon carbide in which one or both of particles are dispersed, or Ti_1-XMe_XB₂(Where Me is at least one of V, Nb, Ta, Cr and Mo, 0.02 ≦ x ≦ 0.50). A composite formed by casting one or both of metal boride solid solution ceramics with wear-resistant metal. If the body is used, it contributes to the reduction of the manufacturing cost accompanying the improvement of the productivity by the stable operation of the blast furnace, the sintering furnace, the coke oven, etc. by reducing the material cost by extending the life of the steel manufacturing equipment.

Claims (11)

Particle-dispersed silicon carbide ceramics obtained by sintering silicon carbide in which solid solution particles of one or both of Ti-Zr-B and Ti- Hf -B are dispersed, or Ti _1-X Me _X B ₂ (where, Me is a casting formed by casting one or both of metal boride solid solution ceramics having a composition of at least one of V, Nb, Ta, Cr and Mo, 0.02 ≦ x ≦ 0.60) with a wear-resistant metal. A gurgurumi complex,
The particle-dispersed silicon carbide ceramics and metal boride solid solution ceramics have an average coefficient of thermal expansion in the range of 7.4 to 9.8 × 10 ⁻⁶ / K (room temperature to 800 ° C.),
The wear-resistant metal is at least one of high Ni steel and high Ni alloy-based grain cast iron having an average coefficient of thermal expansion in the range of 7.4 to 9.8 × 10 ⁻⁶ / K (room temperature to 800 ° C.). A cast-in-the-complex for a liner, characterized in that   2. The liner according to claim 1, wherein a cast-out grain size of the particle-dispersed silicon carbide ceramic or metal boride solid solution ceramic has a distribution having an average particle size of 3 mm to 20 mm in the major axis and 1 mm to 10 mm in the minor axis. Cast-out composite 2. A cast-in-composite for a liner made by casting a particle-dispersed silicon carbide-based ceramic obtained by sintering silicon carbide in which Ti-Zr-B-based solid solution particles are dispersed according to claim 1, wherein the Ti-Zr-B A cast-out composite for a liner in which the composition of the solid solution particles of the system is Ti _1-x Zr _x B ₂ (0.01 ≦ x ≦ 0.20). In the cast-in composite for a liner formed by casting a particle-dispersed silicon carbide ceramic obtained by sintering silicon carbide in which the Ti-Hf-B-based solid solution particles according to claim 1 are dispersed,
The Ti-Hf-B based composition of the solid solution particles _{is, Ti 1-x Hf x B} 2 (0.01 ≦ x ≦ 0.20) in which insert casting composite for liner. A casting for a liner made by casting a particle-dispersed silicon carbide ceramic obtained by sintering silicon carbide in which one or both solid solution particles of the Ti-Zr-B system or Ti- Hf -B system according to claim 1 are dispersed. In the Gurumi complex,
A cast-in composite for a liner in which the average particle size of solid solution particles in the particle-dispersed silicon carbide ceramic is 1 to 10 μm. A casting for a liner made by casting a particle-dispersed silicon carbide ceramic obtained by sintering silicon carbide in which one or both solid solution particles of the Ti-Zr-B system or Ti- Hf -B system according to claim 1 are dispersed. In the Gurumi complex,
A cast-in composite for a liner, wherein the volume fraction of the solid solution particles is 20 to 70%. A casting for a liner made by casting a particle-dispersed silicon carbide ceramic obtained by sintering silicon carbide in which one or both solid solution particles of the Ti-Zr-B system or Ti- Hf -B system according to claim 1 are dispersed. In the Gurumi complex,
A cast-in composite for a liner in which the relative density of the particle-dispersed silicon carbide ceramic is 95% or more. A casting for a liner made by casting a particle-dispersed silicon carbide ceramic obtained by sintering silicon carbide in which one or both solid solution particles of the Ti-Zr-B system or Ti- Hf -B system according to claim 1 are dispersed. In the Gurumi complex,
The solid solution particles are added to silicon carbide as composite boride particles, or a predetermined amount of TiB ₂ and one or more of ZrB ₂ , ZrC, HfB ₂ , and HfC is mixed with silicon carbide, and the sintering temperature is 1850 to A cast-in composite for a liner formed by a reaction during sintering at 2200 ° C. and a holding time of 3 hours or more. A cast-for-combination composite for a liner formed by casting the metal boride solid solution ceramics according to claim 1,
A cast-out composite for a liner in which the metal boride solid solution ceramic has a Vickers hardness of 2.4 × 10 ⁴ MPa or more and a fracture toughness value of 5 MPa · m ^1/2 or more at a theoretical density ratio of 95% or more. TiB ₂ powder _to, VB _2, NbB _2, TaB 2, CrB ₂ and MoB 2 to 60 mol% of at least one metal boride powder is selected from _2, and the mixed powder was added sintering aid, Sintering is performed at a temperature of 1700-2200 ° C. for 4 hours or more under a high vacuum of 1.3 × 10 ⁻² Pa or less or in an argon atmosphere, and the obtained metal boride solid solution ceramic is vol% in the wear resistant metal. 30% or more of the cast-in-comb complex manufacturing method,
The wear-resistant metal is at least one of high Ni steel and high Ni alloy-based grain cast iron having an average coefficient of thermal expansion in the range of 7.4 to 9.8 × 10 ⁻⁶ / K (room temperature to 800 ° C.). A method for producing a cast-in composite for a liner. A particle-dispersed silicon carbide ceramic obtained by sintering silicon carbide in which one or both solid solution particles of Ti-Zr-B system or Ti- Hf -B system are dispersed, or a metal boride solid solution ceramic according to claim 10, In an argon atmosphere, a method for producing a cast-gold composite that is hot isostatically pressed at a temperature of 1650 to 2150 ° C. for 2 hours or more at 100 to 200 MPa, and cast in wear-resistant metal,
The wear-resistant metal is at least one of high Ni steel and high Ni alloy-based grain cast iron having an average coefficient of thermal expansion in the range of 7.4 to 9.8 × 10 ⁻⁶ / K (room temperature to 800 ° C.). A method for producing a cast-in-combination composite for a liner, which is characterized in that