JP2008532772A - Method for continuous casting of metals with improved mechanical strength and products obtained by this method - Google Patents
Method for continuous casting of metals with improved mechanical strength and products obtained by this method Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000009749 continuous casting Methods 0.000 title claims abstract description 21
- 150000002739 metals Chemical class 0.000 title 1
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 239000000919 ceramic Substances 0.000 claims abstract description 27
- 239000011343 solid material Substances 0.000 claims abstract description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 44
- 239000010959 steel Substances 0.000 claims description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010079 rubber tapping Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005551 mechanical alloying Methods 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910021332 silicide Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 229910002065 alloy metal Inorganic materials 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 229910001338 liquidmetal Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910001563 bainite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/108—Feeding additives, powders, or the like
Abstract
本発明は注入取鍋またはタンディッシュと連続鋳造鋳型との間に配置されたノズル内の中空ジェットの形での金属の連続鋳造のための方法に関し、前記ノズルがその上方部に、ノズル入口に到達する液体金属の少なくとも一部をそれが鋳型に入る前にノズルの内壁に向けて偏向することができる分配部材を含む。前記方法は中空ジェットの内部容積中に微粉固体材料を注入することを含み、微粉固体材料が２００ｎｍ未満、好ましくは１００ｎｍ未満の特徴的寸法の工業用セラミックナノ粒子を含むことを特徴とする。
【選択図】 なしThe present invention relates to a method for continuous casting of metal in the form of a hollow jet in a nozzle arranged between a pouring ladle or tundish and a continuous casting mold, said nozzle being at its upper part, at the nozzle inlet. It includes a dispensing member capable of deflecting at least a portion of the reaching liquid metal towards the inner wall of the nozzle before it enters the mold. Said method comprises injecting a finely divided solid material into the internal volume of the hollow jet, characterized in that the finely divided solid material comprises industrial ceramic nanoparticles with a characteristic dimension of less than 200 nm, preferably less than 100 nm.
[Selection figure] None
Description
本発明は溶融金属、特に鋼の連続鋳造のための新規な方法に関し、その方法は、その化学組成がより大きな機械的強度を与えるために元素の添加により変性されるように、積層、連続焼なまし等のような続く熱機械的処理前に、スラブ、ビレット、ワイヤー等のような中間製品を得ることを可能とする。 The present invention relates to a novel process for continuous casting of molten metal, in particular steel, which is laminated, continuously fired so that its chemical composition is modified by the addition of elements to give greater mechanical strength. It makes it possible to obtain intermediate products such as slabs, billets, wires etc. before subsequent thermomechanical treatment such as annealing.
以下の説明は鋼の連続鋳造に対して特に言及する。しかし、この選択は例示にすぎず、本発明の如何なる限定も伴わない。 The following description refers specifically to continuous casting of steel. However, this selection is exemplary only and does not involve any limitation of the present invention.
本発明はまた、本方法により得られた改善された機械的特徴を有する製品に関する。 The invention also relates to a product having improved mechanical characteristics obtained by the method.
鋼の連続鋳造技術は周知である。それは本質的に、溶融金属を取鍋からまたはタンディッシュから底端部で開放している“連続鋳造鋳型”と呼ばれる冷却された銅または銅合金型中に供給すること、及びこの開口から部分的に凝固した連続シートの形の鋳塊を引出すことからなる。 Steel continuous casting techniques are well known. It essentially feeds molten metal from a ladle or from a tundish into a cooled copper or copper alloy mold called a “continuous casting mold” that is open at the bottom end and partly from this opening. And drawing ingots in the form of continuous sheets solidified.
一般的に、溶融鋼は少なくとも一つのノズル、すなわちタンディッシュと鋳型との間に配置された一般的に管状の要素により鋳型中に供給される。ノズルの底端部は通常、ノズルの軸上または側面上に設けられた一つまたは二つの出口開口を備えており、かつ鋳型に存在する溶融鋼がないレベルの下に出現する。 Generally, the molten steel is fed into the mold by at least one nozzle, i.e. a generally tubular element arranged between the tundish and the mold. The bottom end of the nozzle usually has one or two outlet openings provided on the axis or side of the nozzle and appears below a level where there is no molten steel present in the mold.
タンディッシュから来る熱過ぎる溶融鋼の改善された冷却を達成することを意図されたノズルの開発もまた知られている。この目的はその鋼の鋳型中への流入時にペーストの形で鋼を得ることである。これらのノズルは特に、水冷銅管または偏向体またはドームを備えた熱交換器を含むことができる。水冷銅管または偏向体またはドームは過熱鋼をノズルの壁に沿って薄層でしたたり落とすよう強制する目的を持ち、それは熱交換面積を著しく増やすことができる。導管の冷却は鋼からの過剰熱の除去を確実とし、鋼をその鋳型中への流入時にペーストに変える固体部分の出現を起こす。導管内への加圧下の保護ガス、例えばアルゴンの導入は溶融鋼の酸化またはアルミナの形成及びノズルの詰まりを導く溶融鋼を通るいかなる空気流も防ぐ過負荷を起こす。特許ＥＰ−Ｂ−２６９１８０に記載されたこの技術は中空ジェットによるまたはＨＪＮすなわち中空ジェットノズルによる鋳造と呼ばれる。 The development of nozzles intended to achieve improved cooling of overheated molten steel coming from the tundish is also known. The purpose is to obtain the steel in the form of a paste when it flows into the mold. These nozzles can in particular include water-cooled copper tubes or heat exchangers with deflectors or domes. Water-cooled copper tubes or deflectors or domes have the purpose of forcing the superheated steel into a thin layer or drop along the nozzle wall, which can significantly increase the heat exchange area. Conduit cooling ensures the removal of excess heat from the steel and causes the appearance of a solid part that turns the steel into a paste as it flows into the mold. The introduction of a protective gas, such as argon, under pressure into the conduit causes an overload that prevents any air flow through the molten steel leading to oxidation of the molten steel or alumina formation and nozzle clogging. This technique described in patent EP-B-269180 is called casting by hollow jet or by HJN or hollow jet nozzle.
特許ＥＰ−Ｂ−６０５３７９に記載された別の開発は空気のいかなる流入も防ぐために大気圧に関してわずかに高い圧力のベクトルとして非酸化性ガスを使用することによる微粉金属材料の幾らかの量の中空ジェット中への注入に関する。場合に依存して、その目的は新しい凝固種を作ることによる凝固構造の改善または鋼の基本的化学組成の変性を得ることである。 Another development described in the patent EP-B-605379 is that some amount of fine metal material hollow by using a non-oxidizing gas as a slightly higher pressure vector with respect to atmospheric pressure to prevent any inflow of air. Regarding injection into a jet. Depending on the case, the aim is to improve the solidification structure or to modify the basic chemical composition of the steel by creating a new solidification seed.
特許ＢＥ−Ａ−１０１２０３７に記載のように、回転ジェットを持つ連続鋳造ノズルもまた知られており、それはその上方部に分配装置またはドームを持つ垂直導管から構成され、この分配装置またはドームの機能はまた、ノズルに流入する金属を前記導管の内部表面に向けて偏向することであり、それはノズル軸に関して星パターンで配置されかつ水平に関して傾斜した三本の腕を含む。これらの腕は内壁に沿ってらせん状回転運動を溶融鋼に与えるような形状をしている。溶融鋼はそのときノズルの二つの側面出口を通して同じ流れを持つ従来のノズルで得られる速度より有意に低い速度で出て行き、それは引き出される鋳塊の品質を改善する（より少ない混在物及びより少ない気泡）。 A continuous casting nozzle with a rotating jet is also known, as described in patent BE-A-1012037, which consists of a vertical conduit with a distributor or dome above it, the function of this distributor or dome. Is also to deflect the metal flowing into the nozzle towards the inner surface of the conduit, which comprises three arms arranged in a star pattern with respect to the nozzle axis and inclined with respect to the horizontal. These arms are shaped to impart a helical rotational motion to the molten steel along the inner wall. The molten steel then exits at a speed significantly lower than that obtained with a conventional nozzle having the same flow through the two side outlets of the nozzle, which improves the quality of the drawn ingot (less mixture and less Fewer bubbles).
混合された化学薬品または二成分組成を持つ鋼系製品の連続鋳造はまた、長い製品及び平坦な製品の両者で極めて多数の特別の用途で大きな興味を起こした（例えば積層製品の亜鉛メッキへの適合性を改善するためのスラブの表面のケイ素レベルの低減；包晶鋼の鋳造流れを改善するためにそれらの表面での炭素含量の変更；例えば表面での大きな強度及びコア内の高い延性のような厚さに沿って機械的性質が変わる製品の鋳造など）。二成分という用語は研究される製品のその位置に依存して変わる、例えばコアと比べて表皮が異なる鋼の化学組成を持つ製品を言う。この要求に合致するように、本出願人は国際特許出願ＷＯ−Ａ−０２／３０５９８で、溶融鋼を二つの流れ、内部流と外部流、二つの物理的に十分に分離された領域に分離するように設計された、上部にドームを持つ分配装置を含む連続鋳造ノズルを提案した。ドームの下で内部領域中にガス、液体または微粉固体材料（典型的には１００ミクロンより大きい粒子寸法を持つ粉末）を注入するための手段は基本鋼、すなわち外部領域の鋳造体の化学組成と異なる化学組成を持つ鋼の形成を可能とする。 Continuous casting of steel products with mixed chemicals or binary compositions has also generated great interest in a large number of special applications, both long and flat products (eg to galvanization of laminated products). Reducing the silicon level of the surface of the slab to improve compatibility; changing the carbon content at their surface to improve the casting flow of peritectic steel; for example, high strength at the surface and high ductility in the core Such as casting of products whose mechanical properties vary along the thickness). The term binary refers to a product with a chemical composition of steel that varies depending on the location of the product being studied, for example, the skin is different from the core. To meet this requirement, the Applicant has separated the molten steel into two streams, an internal flow and an external flow, and two physically well separated regions, in international patent application WO-A-02 / 30598. A continuous casting nozzle was proposed that included a dispensing device with a dome on top, designed to do this. Means for injecting a gas, liquid, or finely divided solid material (powder with a particle size typically greater than 100 microns) under the dome into the inner region are based on the chemical composition of the base steel, ie the outer region casting. Allows formation of steels with different chemical compositions.
加えて、例えば鋼のミクロ組織（マルテンサイト、ベイナイト等）によるまたは内因性析出による鋼の機械的特徴を改善することを目的とした伝統的な熱機械的処理は、最終的に得られた鋼の構造が製品の熱的後処理（例えば溶接、亜鉛メッキ等）により悪影響を受けるかもしれないという欠点を持つことが知られている。従って、少なくとも幾つかの場合で、製品が受けるかもしれないいずれかの続く処理を通して安定な構造、従って機械的性質を持つ製品を直接鋳造することができることが望ましいであろう。 In addition, traditional thermomechanical treatment aimed at improving the mechanical characteristics of the steel, for example by the microstructure of the steel (martensite, bainite, etc.) or by intrinsic precipitation, Is known to have the disadvantage that it may be adversely affected by thermal post-treatment of the product (eg welding, galvanizing, etc.). Thus, in at least some cases, it would be desirable to be able to directly cast a product with a stable structure and thus mechanical properties through any subsequent processing that the product may undergo.
本発明は、従来技術の欠点を克服することを可能とする解決策を提供することを目的とする。 The present invention aims to provide a solution that makes it possible to overcome the drawbacks of the prior art.
本発明は特に、積層前に鋼に大きな機械的強度を与えるのに適応した変性された化学組成のスラブまたはビレットを製造可能とする連続鋳造法を提供することを目的とする。 In particular, the present invention aims to provide a continuous casting process that makes it possible to produce a modified chemical composition slab or billet adapted to give the steel a high mechanical strength prior to lamination.
本発明は、鋳造に続いての熱機械的処理及び／または積層工程に関して安定化された構造及び／または均質な化学組成の鋼を得ることを目的とする。 It is an object of the present invention to obtain a steel with a stabilized structure and / or a homogeneous chemical composition with respect to the thermomechanical treatment and / or lamination process following casting.
本発明の一つの特別な目的は、微粉セラミック粒子を連続鋳造ノズルを通して注入するために中空ジェット技術を利用することである。 One particular object of the present invention is to utilize hollow jet technology to inject fine ceramic particles through a continuous casting nozzle.
本発明の第一目的は、取鍋またはタンディッシュと連続鋳造鋳型との間に配置されたノズル内の中空ジェットの形での金属の連続鋳造のための方法に関し、前記ノズルがその上方部に、ノズルの入口に到達する溶融金属の少なくとも一部をそれが鋳型に入る前にノズルの内壁に向けて偏向することができる分配装置を含み、前記方法が微粉固体材料の中空ジェットの内部容積内への注入を含むものにおいて、微粉固体材料が２００ｎｍ未満、好ましくは１００ｎｍ未満の特徴的寸法の工業用セラミックのナノ粒子を含むことを特徴とする。 The first object of the invention relates to a method for continuous casting of metal in the form of a hollow jet in a nozzle arranged between a ladle or tundish and a continuous casting mold, said nozzle being above it. A dispensing device capable of deflecting at least a portion of the molten metal reaching the inlet of the nozzle towards the inner wall of the nozzle before it enters the mold, said method being in the internal volume of a hollow jet of finely divided solid material In which the finely divided solid material comprises industrial ceramic nanoparticles with a characteristic dimension of less than 200 nm, preferably less than 100 nm.
有利には、工業用セラミックのナノ粒子は酸化物、窒化物、炭化物、ホウ化物、ケイ化物及び／またはそれらの複合体のナノ粒子を含む。 Advantageously, the industrial ceramic nanoparticles comprise oxide, nitride, carbide, boride, silicide and / or composite nanoparticles thereof.
酸化物は好ましくはＡｌ２Ｏ３，ＴｉＯ２，ＳｉＯ２，ＭｇＯ，ＺｒＯ２またはＹ２Ｏ３である。 The oxide is preferably Al 2 O 3 , TiO 2 , SiO 2 , MgO, ZrO 2 or Y 2 O 3 .
更なる利点としてナノ粒子の寸法は１０〜１００ｎｍである。 As a further advantage, the size of the nanoparticles is 10-100 nm.
更に、本発明によれば、溶融金属中に混入されるナノ粒子の量は鋳造金属の重量で５重量％より少ないかまたは５重量％に等しく、好ましくは０．１〜１重量％である。 Furthermore, according to the present invention, the amount of nanoparticles incorporated in the molten metal is less than or equal to 5% by weight of the cast metal, preferably 0.1-1% by weight.
本発明の好適実施態様によれば、ノズルの中空ジェットの内部容積中へ注入されるセラミックナノ粒子は非酸化性ガス、好ましくはアルゴン中に懸濁されており、前記ガスは大気圧に関してわずかに高い圧力にあり、最大でも鋳造金属の鋳型中への流入時の鋳造金属の静圧に等しい。 According to a preferred embodiment of the present invention, the ceramic nanoparticles injected into the interior volume of the hollow jet of the nozzle are suspended in a non-oxidizing gas, preferably argon, said gas being slightly in relation to atmospheric pressure. It is at a high pressure and is at most equal to the static pressure of the cast metal as it flows into the mold.
本発明の別の好適実施態様によれば、セラミックナノ粒子はウォームスクリューのような機械的運搬装置によりノズルの中空ジェットの内部容積中に注入される。 According to another preferred embodiment of the invention, the ceramic nanoparticles are injected into the internal volume of the nozzle's hollow jet by a mechanical conveying device such as a worm screw.
特別な利点として、ナノ粒子はノズル中へのそれらの注入の前に本質的に１０〜１０００ミクロン、好ましくは１００〜２００ミクロンの寸法のミクロ粒子に集塊される。 As a particular advantage, the nanoparticles are agglomerated into microparticles of dimensions essentially 10 to 1000 microns, preferably 100 to 200 microns, prior to their injection into the nozzle.
更に有利には、ナノ粒子のノズル中への注入の前に、ナノ粒子は鋳造金属と同じ金属または異なる金属から作られた金属マトリックスにおいて集塊される。 More advantageously, prior to injection of the nanoparticles into the nozzle, the nanoparticles are agglomerated in a metal matrix made of the same metal as the cast metal or a different metal.
鋳造金属は好ましくは溶融鋼であり、金属マトリックスは鉄マトリックスであり、または金属マトリックスは鉄以外の合金金属を含む。 The cast metal is preferably molten steel, the metal matrix is an iron matrix, or the metal matrix comprises an alloy metal other than iron.
更なる利点として、ナノ粒子の集塊はセラミックナノ粒子をマイクロメーターの鉄粒子、すなわち１０ミクロンを越えかつ好ましくは２０ミクロン未満の寸法の鉄粒子と混合することにより得られる。 As a further advantage, the agglomeration of nanoparticles is obtained by mixing ceramic nanoparticles with micrometer iron particles, ie iron particles with a size of more than 10 microns and preferably less than 20 microns.
第一の好適方法によれば、前記混合物はスラリー中の予備混合、続いての乾燥、粉砕、静水圧プレス成形及び更なる粉砕により製造される。 According to a first preferred method, the mixture is prepared by premixing in a slurry followed by drying, grinding, isostatic pressing and further grinding.
第二の好適方法によれば、前記混合物は、セラミックを鉄マトリックス中に混入するように“機械的合金化”の高エネルギータッピングにより製造される。 According to a second preferred method, the mixture is produced by high energy tapping of “mechanical alloying” so that the ceramic is incorporated into the iron matrix.
第一の有利な実施態様によれば、使用される中空ジェットノズルは回転ジェット形式のものであり、すなわちそれはその上方部にドームを有する分配装置を持つ垂直導管を含み、その機能はノズルに入る溶融金属を前記導管の内部表面に向けて偏向することであり、それはノズルの軸に関して星パターンで対称的に配置されかつ水平に関して傾斜された一連の腕を含み、前記腕はノズルの内壁に沿って溶融鋼に対しらせん状回転運動を与えるように配置されている。 According to a first advantageous embodiment, the hollow jet nozzle used is of the rotary jet type, i.e. it comprises a vertical conduit with a distributor having a dome above it, whose function enters the nozzle Deflecting molten metal towards the inner surface of the conduit, which comprises a series of arms arranged symmetrically in a star pattern with respect to the axis of the nozzle and inclined with respect to the horizontal, said arms being along the inner wall of the nozzle And arranged to give a helical rotational motion to the molten steel.
別の有利な実施態様によれば、使用される中空ジェットノズルはその上方部に、溶融金属を二つの流れ、内部流と外部流に、二つの物理的に十分に分離された領域に分離するように設計されたドームを有する分配装置を含み、ドームの下の内部領域内へのセラミックナノ粒子の注入は基本金属、すなわち外部領域内の鋳造体の化学組成と異なる化学組成を持つ金属の形成を可能とする。 According to another advantageous embodiment, the hollow jet nozzle used at its upper part separates the molten metal into two streams, an internal stream and an external stream, in two physically well separated regions. Injecting ceramic nanoparticles into the inner region under the dome includes forming a base metal, that is, a metal having a chemical composition different from the chemical composition of the casting in the outer region. Is possible.
これに代えて、セラミックナノ粒子の注入はノズルの外部領域内で実行されることができる。 Alternatively, ceramic nanoparticle injection can be performed in the external region of the nozzle.
本発明の第二目的は、高い機械的強度を持ち、鋳塊の鋳造後にその連続鋳造鋳型から出るときに連続シートの形を取り、特に上述の方法により得られたかつ鋳塊の少なくとも一部分に均質に分配された工業用セラミックを１重量％未満含む、金属、好ましくは鋼に関する。 The second object of the present invention is that it has a high mechanical strength and takes the form of a continuous sheet as it leaves the continuous casting mold after casting of the ingot, in particular obtained by the above-described method and at least partly of the ingot. It relates to a metal, preferably steel, containing less than 1% by weight of a homogeneously distributed industrial ceramic.
本発明が基本とする思想は、続く熱処理（単数または複数）のために劣化しない安定な性質を鋼に与えるセラミック粒子の微細分散により硬化された鋼を開発することである。 The idea on which the present invention is based is to develop a steel hardened by fine dispersion of ceramic particles that gives the steel stable properties that do not deteriorate due to subsequent heat treatment (s).
一例として、鋼の連続鋳造の場合が考えられるであろう。 As an example, the case of continuous casting of steel may be considered.
従って、標準的な基本鋼を鋳造することが提案され、この標準基本鋼には要求により希望の強度特性を得るのに必要な一定量の粒子が添加される。利点として、溶融金属への粒子の添加は連続鋳造ノズルのレベルで直接的に実行される。というのも一般的に使用されかつ上記される実施態様では連続鋳造ノズルは一般的に、ノズルを通過する溶融金属の少なくとも一部分内に合金元素または酸化物を挿入するための手段を含むからである。 Therefore, it is proposed to cast a standard base steel, to which a certain amount of particles necessary to obtain the desired strength properties is added as required. As an advantage, the addition of particles to the molten metal is carried out directly at the level of the continuous casting nozzle. This is because, in the embodiment generally used and described above, a continuous casting nozzle generally includes means for inserting an alloying element or oxide into at least a portion of the molten metal that passes through the nozzle. .
本発明によれば、添加される粒子はセラミック粒子である。当業者は工業用または産業用セラミックが非金属及び無機である製造された材料の種類に関することを知っている。それらは二つの主要な群：酸化物（例えばＡｌ２Ｏ３，ＴｉＯ２，ＳｉＯ２，ＭｇＯ，ＺｒＯ２，Ｙ２Ｏ３等）及び非酸化物（窒化物、炭化物、ホウ化物、ケイ化物等）に分類される。更に、本発明の条件のためには、セラミック粒子は次の操作的限定に従わねばならない：それらはナノメートル寸法、典型的には１０−１００ナノメートル（１ｎｍ＝１０−９ｍ）であり、溶融鋼中に混入した後にそれらは本質的に鋳造製品の全区域を通して均質的に分配されていること。粒子の“寸法”はここでは粒子の最大寸法を意味する。含有物のための粒子のナノメートル寸法の性質は実際に製品の強化に欠くことができない。対照的に、マイクロメートルの包含物は製品をより弱くする欠陥、すなわち不均質領域を構成する。 According to the invention, the added particles are ceramic particles. Those skilled in the art know that industrial or industrial ceramics relate to the types of materials produced that are non-metallic and inorganic. They are in two main groups: oxides (eg Al 2 O 3 , TiO 2 , SiO 2 , MgO, ZrO 2 , Y 2 O 3 etc.) and non-oxides (nitrides, carbides, borides, silicides, etc.) )are categorized. Furthermore, for the conditions of the present invention, the ceramic particles must obey the following operational limitations: they are nanometer dimensions, typically 10-100 nanometers (1 nm = 10 −9 m), After mixing in the molten steel, they are essentially homogeneously distributed throughout the entire area of the cast product. The “dimension” of a particle here means the largest dimension of the particle. The nanometer dimensional nature of the particles for inclusion is actually essential for product enhancement. In contrast, micrometer inclusions constitute defects that make the product weaker, i.e., inhomogeneous regions.
溶融鋼に添加されるナノ粒子の量は最大１重量％である。 The amount of nanoparticles added to the molten steel is a maximum of 1% by weight.
溶融鋼中の粒子の湿潤性は粒子の選択のために最も重要な判断基準であり、この技術的問題の解決は本発明の核心である。溶融鋼中のナノ粒子の均質な分配は欠くことができず、それは溶融鋼の表面に注入された粉末の拘束を排除する。 The wettability of particles in molten steel is the most important criterion for the selection of particles, and the solution to this technical problem is the core of the present invention. A homogeneous distribution of the nanoparticles in the molten steel is essential, which eliminates the constraint of the powder injected on the surface of the molten steel.
本発明によれば、粒子は有利にはＨＪＮノズルを通して注入されることができるように１００−２００μｍの寸法まで集塊されることができる。 According to the invention, the particles can advantageously be agglomerated to a size of 100-200 μm so that they can be injected through an HJN nozzle.
溶融鋼中の粒子の湿潤性を改善するために、ナノメートルのセラミック粒子は特徴的な最終寸法が１００−２００μｍである複合体を得るために鉄または金属マトリックスにおいて集塊されることができる。鉄または金属マトリックスは溶融鋼中の粒子の分散を助ける。この複合体を得るために、ナノメーターのセラミック粒子はマイクロメーターの鉄粒子（その寸法は例えば１０から２０ミクロンである）と混合して使用される。この混合物は次のいずれかにより製造される：
− スラリー中に混合し、次いで乾燥、粉砕、静水圧プレス成形及び次いで再粉砕する；
− セラミックが鉄マトリックス中に混入されることを確実にするために高エネルギータッピング（機械的合金化）する。
タッピングは元素を第一元素とは異なる一つまたは幾つかの元素から形成された組合せと接触させて元素上に力を働かせることによりそれを組合せ中に導入することからなる操作である。
In order to improve the wettability of the particles in the molten steel, the nanometer ceramic particles can be agglomerated in an iron or metal matrix to obtain a composite with a characteristic final dimension of 100-200 μm. The iron or metal matrix helps disperse the particles in the molten steel. To obtain this composite, nanometer ceramic particles are used in admixture with micrometer iron particles (whose dimensions are, for example, 10 to 20 microns). This mixture is made by either:
-Mixing into the slurry, then drying, grinding, isostatic pressing and then re-grinding;
-High energy tapping (mechanical alloying) to ensure that the ceramic is incorporated into the iron matrix.
Tapping is an operation that consists of bringing an element into contact with a combination formed from one or several elements different from the first element and applying force on the element.
有利には、これらの複合体はガス状雰囲気下でＨＪＮノズル中に注入される（特許ＥＰ−Ｂ−６０５３７９参照）。ノズル中に発生する強い乱流はかくして溶融鋼中への粒子の混入を可能とする。 Advantageously, these composites are injected into the HJN nozzle under a gaseous atmosphere (see patent EP-B-605379). The strong turbulence generated in the nozzle thus makes it possible to mix particles into the molten steel.
Claims (18)
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| BE2005/0139 | 2005-03-16 | ||
| BE2005/0139A BE1016550A3 (en) | 2005-03-16 | 2005-03-16 | Process for casting continuous metal mechanical resistance and improved product obtained by the process. |
| PCT/BE2006/000003 WO2006096942A1 (en) | 2005-03-16 | 2006-01-19 | Method for continuous casting of a metal with improved mechanical strength and product obtained by said method |
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| JP2015514585A (en) * | 2012-03-28 | 2015-05-21 | アルセロルミタル・インベステイガシオン・イ・デサロジヨ・エセ・エレ | Metal continuous casting process |
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| BE1017392A3 (en) | 2006-12-12 | 2008-08-05 | Ct Rech Metallurgiques Asbl | HOLLOW JET BUSHET FOR CONTINUOUS STEEL CASTING. |
| EP2047926A1 (en) | 2007-10-10 | 2009-04-15 | Ugine & Alz France | Method of manufacturing stainless steels comprising fine carbonitrides, and product obtained from this method |
| KR101269451B1 (en) * | 2011-06-27 | 2013-05-30 | 연세대학교 산학협력단 | Oxygen atoms-dispersed metal-based composite material and method for manufacturing the same |
| CN103243194B (en) * | 2013-05-31 | 2015-01-21 | 安徽工业大学 | Method for optimizing steel structure by adding nano particles into steel liquid |
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| DE10253577B4 (en) * | 2002-11-15 | 2011-05-19 | Ab Skf | Process for producing a dispersion-hardened iron material |
| US7235118B2 (en) * | 2003-04-16 | 2007-06-26 | National Research Council Of Canada | Process for agglomeration and densification of nanometer sized particles |
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| JPH0768346A (en) * | 1990-01-04 | 1995-03-14 | Pechiney Rech | Method and device for continuous casting of composite material having metal matrix reinforced by particle of heat resisting ceramic material |
| JPH07207381A (en) * | 1992-09-01 | 1995-08-08 | Inoue Akihisa | Production of particle reinforced composite material |
| JPH09104944A (en) * | 1995-10-05 | 1997-04-22 | Nippon Steel Corp | Slab for fire resistant rolled shape steel and production of fire resistant rolled shape steel using the same as stock |
| JP2000505040A (en) * | 1996-11-18 | 2000-04-25 | ユニバーシティー オブ コネクチカット | Nanostructured oxides and hydroxides and methods for their synthesis |
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| BE1016550A3 (en) | 2007-01-09 |
| JP4906840B2 (en) | 2012-03-28 |
| US20090266506A1 (en) | 2009-10-29 |
| ATE485906T1 (en) | 2010-11-15 |
| DE602006017811D1 (en) | 2010-12-09 |
| KR20070110368A (en) | 2007-11-16 |
| ES2351886T3 (en) | 2011-02-11 |
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