JP6279068B2 - 鋼の鋳造用耐火物,及びスライディングノズル装置用のプレート,並びに鋼の鋳造用耐火物の製造方法 - Google Patents
鋼の鋳造用耐火物,及びスライディングノズル装置用のプレート,並びに鋼の鋳造用耐火物の製造方法 Download PDFInfo
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- JP6279068B2 JP6279068B2 JP2016505261A JP2016505261A JP6279068B2 JP 6279068 B2 JP6279068 B2 JP 6279068B2 JP 2016505261 A JP2016505261 A JP 2016505261A JP 2016505261 A JP2016505261 A JP 2016505261A JP 6279068 B2 JP6279068 B2 JP 6279068B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 37
- 239000010959 steel Substances 0.000 title claims description 37
- 239000011819 refractory material Substances 0.000 title claims description 35
- 238000005266 casting Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 126
- 229910052751 metal Inorganic materials 0.000 claims description 97
- 239000002184 metal Substances 0.000 claims description 97
- 229910052782 aluminium Inorganic materials 0.000 claims description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 239000004927 clay Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 10
- 229910000676 Si alloy Inorganic materials 0.000 claims description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 48
- 230000035939 shock Effects 0.000 description 43
- 230000007797 corrosion Effects 0.000 description 41
- 238000005260 corrosion Methods 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 230000006378 damage Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000000280 densification Methods 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 9
- 235000012245 magnesium oxide Nutrition 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 230000029087 digestion Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011800 void material Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010443 kyanite Substances 0.000 description 1
- 229910052850 kyanite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- B22—CASTING; POWDER METALLURGY
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- B22C9/00—Moulds or cores; Moulding processes
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- B22D11/10—Supplying or treating molten metal
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- B22D41/14—Closures
- B22D41/22—Closures sliding-gate type, i.e. having a fixed plate and a movable plate in sliding contact with each other for selective registry of their openings
- B22D41/28—Plates therefor
- B22D41/30—Manufacturing or repairing thereof
- B22D41/32—Manufacturing or repairing thereof characterised by the materials used therefor
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Description
0.31×Al≦(P−4)/D ・・・式1 (請求項1)
2.前記金属酸化物が,Al2O3,SiO2,ZrO2,MgO,TiO2から選択する1又は複数の成分を含み,前記残部の総量を100質量%とするときに,前記成分の合計が95質量%以上である,前記1に記載の鋼の鋳造用耐火物。(請求項2)
3.金属シリコンを0.5質量%以上4質量%以下含有する,前記1又は前記2に記載の耐火物。(請求項3)
4.金属アルミニウムの含有量が6質量%以上15質量%以下である,前記1又は前記2に記載の耐火物。(請求項4)
5.一部又は全部が前記1から前記4のいずれかに記載の鋼の鋳造用耐火物から構成された,スライディングノズル装置用のプレート。(請求項5)
6.アルミニウムを含有する金属を含み,残部がAl2O3,SiO2,ZrO2,MgO,TiO2から選択する1又は複数の成分を含む金属酸化物を含む耐火材料からなる混合された粉体に,熱硬化性樹脂を1質量%以上7質量%以下添加し混練して成形用坏土を作製する工程と,前記成形用坏土を加圧成形する工程と,熱処理する工程をと含む,前記1から前記4のいずれかに記載の鋼の鋳造用耐火物の製造方法であって,
前記熱処理後の耐火物中の金属アルミニウム含有量を4質量%以上15質量%以下とし,前記式1を満たすように見掛気孔率を調整することを特徴とする,鋼の鋳造用耐火物の製造方法。(請求項6)
7.前記の混合された粉体中に含まれるアルミニウムを含有する金属は,最大長が140μm以下の鱗片状,粒径140μm以下の粒子状,又は横断面の最大径が200μm以下かつ最大長さが5mm以下の繊維状から選択する1又は複数の形態の金属アルミニウム単体からなる原料に由来する,前記6に記載の鋼の鋳造用耐火物の製造方法。(請求項7)
8.前記の混合された粉体中に含まれるアルミニウムを含有する金属の一部又は全部が,金属アルミニウムを含む合金からなる原料に由来する,前記6に記載の鋼の鋳造用耐火物の製造方法。(請求項8)
9.前記の金属アルミニウムを含む合金は,アルミニウム−マグネシウム合金又はアルミニウム−シリコン合金である,前記8に記載の鋼の鋳造用耐火物の製造方法。(請求項9)
2Al+3CO → Al2O3+3C ・・・式2
4Al+4CO → Al4O4C+3C ・・・式3
4Al+3C → Al4C3 ・・・式4
ΔV={1×(Al/100)}/2.7×{(1.35+1.15+0)/3}
・・・式5
となり,これを整理すると
ΔV=0.31×(Al/100) ・・・式6
となる。
Vp=(1/D)×{(P−4)/100} ・・・式7
ΔV≦Vp ・・・式8
0.31×(Al/100)≦(1/D)×{(P−4)/100} ・・・式9
0.31×Al≦(P−4)/D ・・・式1
(1)坏土の成形時に成形圧力を増減させて,構成原料間の接触点を減じて又は接触距離等を変化させてその充填度合いを調整する,
(2)坏土の粒度構成を,最密充填の理論曲線から所要量ずらして,構成原料間の接触点は維持した上で構成原料間の空隙を増減させる。
実施例Aは,本発明の金属アルミニウム(Al)量,フリーの炭素(F.C.)量での,前記の式1との関係を調査した結果を示す。
実施例Bは,金属アルミニウム含有量の影響を調査した結果である。表2に試料構成と結果を示す。
実施例Cは,フリーの炭素含有量の影響を調査した結果である。表3に試料構成と結果を示す。
実施例Dは,金属アルミニウム,フリーの炭素以外(残部)の構成物の種類による影響を調査した結果である。表4に試料構成と結果を示す。
実施例Eは,金属シリコンの有無及びその含有量の影響を調査した結果である。消化試験は,温度を40℃,湿度を90℃に保った恒温槽に試料を放置し,30日経過後の試料の重量と前記処理前の重量の重量変化率で評価する方法により,経験上一般的な操業条件で標準的又は下限程度と考えられる耐消化性を備えた実施例29の重量変化率を基準とし,それと同程度以下の場合を「○」で表示し,それより高いものの,通常の操業条件で少なくとも1回の使用が可能と考えられる程度の場合を「△」として表示した。
実施例Fは,熱処理温度が大きく異なる場合の例示である。表6に試料構成と結果を示す。
実施例Gは,坏土中に含有する金属Al(熱処理後の残存Al量ではない)の一部又は全部をアルミニウム−マグネシウム合金(実施例35〜実施例41),又はアルミニウム−シリコン合金(実施例42〜実施例44)に置換した例を示す。
実施例Hは,本発明の耐火物を鋼の連続鋳造に用いられるスライディングノズル装置に使用するプレートとして使用した結果を示す。
Claims (9)
- フリーの炭素を1質量%以上10質量%以下,金属アルミニウムを4質量%以上15質量%以下含有し,残部が金属酸化物を含む耐火材料からなる鋼の鋳造用耐火物であって,
当該耐火物内の金属アルミニウム含有量をAl質量%,見掛気孔率をP%,かさ比重をDとするときに,式1を満たすことを特徴とする,鋼の鋳造用耐火物。
0.31×Al≦(P−4)/D ・・・式1 - 前記金属酸化物が,Al2O3,SiO2,ZrO2,MgO,TiO2から選択する1又は複数の成分を含み,前記残部の総量を100質量%とするときに,前記成分の合計が95質量%以上である,請求項1に記載の鋼の鋳造用耐火物。
- 金属シリコンを0.5質量%以上4質量%以下含有する,請求項1又は請求項2に記載の鋼の鋳造用耐火物。
- 金属アルミニウムの含有量が6質量%以上15質量%以下である,請求項1又は請求項2に記載の鋼の鋳造用耐火物。
- 一部又は全部が請求項1から請求項4のいずれかに記載の鋼の鋳造用耐火物から構成された,スライディングノズル装置用のプレート。
- アルミニウムを含有する金属を含み,残部がAl2O3,SiO2,ZrO2,MgO,TiO2から選択する1又は複数の成分を含む金属酸化物を含む耐火材料からなる混合された粉体に,熱硬化性樹脂を1質量%以上7質量%以下添加し混練して成形用坏土を作製する工程と,前記成形用坏土を加圧成形する工程と,熱処理する工程をと含む,請求項1から請求項4のいずれかに記載の鋼の鋳造用耐火物の製造方法であって,
前記熱処理後の耐火物中の金属アルミニウム含有量を4質量%以上15質量%以下とし,前記式1を満たすように見掛気孔率を調整することを特徴とする,鋼の鋳造用耐火物の製造方法。 - 前記の混合された粉体中に含まれるアルミニウムを含有する金属は,最大長が140μm以下の鱗片状,粒径140μm以下の粒子状,又は横断面の最大径が200μm以下かつ最大長さが5mm以下の繊維状から選択する1又は複数の形態の金属アルミニウム単体からなる原料に由来する,請求項6に記載の鋼の鋳造用耐火物の製造方法。
- 前記の混合された粉体中に含まれるアルミニウムを含有する金属の一部又は全部が,金属アルミニウムを含む合金からなる原料に由来する,請求項6に記載の鋼の鋳造用耐火物の製造方法。
- 前記の金属アルミニウムを含む合金は,アルミニウム−マグネシウム合金又はアルミニウム−シリコン合金である,請求項8に記載の鋼の鋳造用耐火物の製造方法。
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