EP1242641B1 - Verfahren zur herstellung einer aluminium-titan-bor-vorlegierung als kornfeinungsmittel - Google Patents
Verfahren zur herstellung einer aluminium-titan-bor-vorlegierung als kornfeinungsmittel Download PDFInfo
- Publication number
- EP1242641B1 EP1242641B1 EP00983193A EP00983193A EP1242641B1 EP 1242641 B1 EP1242641 B1 EP 1242641B1 EP 00983193 A EP00983193 A EP 00983193A EP 00983193 A EP00983193 A EP 00983193A EP 1242641 B1 EP1242641 B1 EP 1242641B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- prealloy
- melt
- particles
- al3ti
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 aluminum-titanium-boron Chemical compound 0.000 title claims abstract 3
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000007858 starting material Substances 0.000 claims abstract description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims abstract 9
- 229910033181 TiB2 Inorganic materials 0.000 claims abstract 9
- 239000010936 titanium Substances 0.000 claims description 36
- 238000007670 refining Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000009749 continuous casting Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 239000000274 aluminium melt Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000000956 alloy Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000005266 casting Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 3
- 229910018575 Al—Ti Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition 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
- 230000035784 germination Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
Definitions
- the invention relates to a method for producing a grain refining agent according to the preamble of claim 1.
- EP-A-0396389 describes a process for the continuous production of a Al-Ti-B grain refining alloy discloses, in which Ti and B-containing starting materials added to a molten aluminum reaction zone are, the melt being stirred in the reaction zone. A mixture the alloy formed becomes continuous together with the reaction products fed to a cleaning zone in which the slag with reaction products is collected on the surface of the melt and removed. The grain refining alloy formed is continuously removed from the cleaning station led to a casting station, in which the melt continuously is cast in one strand.
- the cast strand can either directly have the desired strand or wire thickness, or it can be further Processing by rolling or extrusion to the desired grain refining material are processed.
- the TiB 2 particles in the Al-Ti-B grain refining agents known today have a strong tendency to form agglomerates. This results in a reduced effect of the grain refining agent. Further disadvantages result from agglomerates and inclusions, which can lead to errors in the end product. Examples include gray lines, holes, material separations and stringers.
- agglomerates occur preferentially on low-melting salts such as KF and NaCl as well as on oxide skins and can thereby further increase. As such, the agglomerates are "soft", can force themselves through filters and as such end up in a cast strand.
- the invention is therefore based on the object of providing a process for producing an Al-Ti-B grain refining agent with which the formation of agglomerates of TiB 2 particles can be largely prevented and existing agglomerates can be deagglomerated.
- cavitation ie the formation of bubbles
- the implosion of which generates shock waves leads to the deagglomeration of agglomerated TiB 2 particles.
- the latter methods include, for example, ultrasound treatment and vibration using a magnetostrictive resonator.
- the grain refining agent produced by the process according to the invention brings about an improved and more homogeneous effect of the refining agent, particularly in the case of grain refinement of casting formats made of aluminum alloys, by a more homogeneous distribution of the individual TiB 2 particles, a better coating of the TiB 2 particles with Al 3 Ti phase and one Reduction or dispersion of any salts and oxide inclusions still present in the grain refining agent.
- the master alloy is preferably set in motion before the liquidus temperature of the Al 3 Ti phase is undershot.
- the effect of the grain refining agent produced according to the invention is shown by the fact that the individual, approximately 0.5 to 5 ⁇ m large TiB 2 particles have an excellent germination effect as a result of a coating formed from a thin Al 3 Ti layer and the particles are isolated and not as agglomerates act so that a comparable grain refinement can be achieved with a considerably smaller amount of grain refining agent than with grain refining agents according to the prior art.
- the liquidus temperature of the Al 3 Ti phase is dropped below prematurely. This is especially the case when a master alloy with a high Ti content and a correspondingly higher liquidus temperature is produced or when a master alloy that has already solidified is assumed.
- By heating the melt again above the liquidus temperature already precipitated Al 3 Ti particles can be completely dissolved again. This process typically takes 5 to 60 minutes, depending on the size of the Al 3 Ti particles.
- the Ultrasonic movement of the melt with a frequency of 10 to 50 kHz generated.
- the second cooling rate is preferably greater than 2 ° C./sec, in particular greater than 5 ° C / sec.
- the master alloy melt can be cast into any format. However, preference is given to casting by vertical or horizontal continuous casting continuously produced strand. This strand can either already in the format of the rod or Cast wire material or in a further operation by rolling or presses to be processed into bar or wire material. Vertically cast, large-sized strands are mainly processed by extrusion. Horizontal continuous casting of formats is preferred relatively small diameter because this process is continuous Manufacturing allowed. The horizontally cast continuous casting formats are preferably by rolling to the desired bar or wire material processed.
- a master alloy produced using the method according to the invention has a composition whose total titanium content exceeds the stoichiometric ratio of TiB 2 .
- a preferred alloy used contains titanium and boron in a weight ratio of 5: 2 to 10: 1.
- the process is suitable for producing master alloys with 0.15 to 20% by weight of titanium and 0.01 to 4% by weight of boron, it has proven to be advantageous if the master alloy contains 0.3 to 5, preferably 0.5 to 2,% by weight. % Ti and 0.02 to 1, preferably 0.05 to 0.5 wt .-% B contains.
- the method according to the invention is particularly suitable for production of grain refining agents for the grain refining of aluminum and aluminum alloys.
- FIG. 1 This is schematic in the Al-Ti equilibrium diagram shown in FIG. 1 Process flow shown for the production of an Al-Ti-B master alloy drawn in for grain refinement of aluminum alloys.
- the illustration A of the alloy phases to the left of the 0.5% Ti line shows the processes during the preparation of an already solidified master alloy, the illustration B to the right of the 0.5% Ti line shows the processes during the solidification of the master alloy.
- the master alloy melt contains TiB 2 particles in partially agglomerated form. Even before the liquidus temperature T L Al3Ti is undershot and shortly before the solidus temperature T s v of the pre-alloy of the Al 3 Ti phase is reached, the partially agglomerated TiB 2 particles are deagglomerated by a strong melt movement using ultrasound treatment at a frequency of, for example, 25 kHz and distributed homogeneously. Simultaneous controlled cooling with a first cooling rate v 1 of, for example, 0.5 ° C./sec, causes the deposition of a thin layer of the Al 3 Ti phase on the parallel surfaces of the TiB 2 particles and at the same time the formation of coarse-grained Al 3 Ti particles prevented.
- a first cooling rate v 1 of, for example, 0.5 ° C./sec
- a system 10 shown in FIG. 2 for producing an Al-Ti-B master alloy for grain refining of aluminum alloys comprises a reaction vessel 12 with an inlet channel 14 in its upper region and an outlet channel 16 in its lower region.
- the reaction vessel 12 is surrounded by an induction motor 18 as an electromagnetic stirring device, with which the aluminum melt 20 located in the reaction vessel 12 is stirred vigorously to form a vortex 22.
- Salts containing Ti and B, such as K 2 TiF 6 and KBF 4 are guided in the direction of arrow 24 into the vortex 22, which draws the salts into the aluminum melt 20.
- the aluminum melt 20 with the reaction products is shown below through the outlet duct 16 via a further inlet duct 26 into the upper one Area of an aftertreatment boiler 28 out.
- Another electromagnetic Stirring device 30 in the lower area of the aftertreatment boiler 28 leads to a lower turbulent zone 32 and an upper calm Zone 34.
- the slag 36 formed by reaction products is over the removal opening 38 is removed from the aftertreatment boiler 28.
- the cleaned aluminum melt 20 with the elements titanium and boron contained therein is fed as a pre-alloy in the lower region of the aftertreatment boiler 28 via a casting trough 38 to a mold, not shown in the drawing, of a horizontal continuous casting machine.
- Two ultrasonic transmitters 40, 42 are arranged in the region of the casting trough 38, the sonotrodes 44, 46 of which immerse in the melt.
- An induction heater 48 arranged below the casting trough 38 serves to heat the melt if its temperature should have already dropped below the liquidus temperature T L Al3Ti of the Al 3 Ti phase when the melt flows from the aftertreatment boiler 28 into the casting trough 38.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Continuous Casting (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
- Fig. 1 einen Ausschnitt aus dem Al-Ti-Gleichgewichtsdiagramm;
- Fig. 2 einen Querschnitt durch eine Anlage zur Herstellung einer Al-Ti-B-Vorlegierung.
Claims (12)
- Verfahren zur Herstellung eines Kornfeinungsmittels auf der Basis einer Aluminium-Titan-Bor-Vorlegierung durch Einbringen von Ti- und B-haltigen Ausgangsmaterialien in eine Aluminiumschmelze unter Bildung von TiB2-Partikeln, bei welchem Verfahren die TiB2-Partikel als Keime für die unterhalb der Liquidustemperatur (TL Al3Ti) der Al3Ti-Phase entstehende Al3Ti-Phase wirken und die Oberfläche der TiB2-Partikel zumindest teilweise mit einem Überzug aus Al3Ti bedeckt werden, und Erstarrenlassen dieser Vorlegierungsschmelze,
dadurch gekennzeichnet, dass
die Vorlegierung zwischen der Liquidustemperatur (TL Al3Ti) der Al3Ti-Phase und der Solidustemperatur (Ts v) der Vorlegierung zur Dispergierung der TiB2-Partikel in der Schmelze zur Erzeugung von Kavitation durch Vibrieren mit einer Frequenz von 50 Hz bis 50 kHz in Bewegung versetzt, gleichzeitig mit einer ersten Abkühlungsgeschwindigkeit (v1) und nachfolgend mit einer gegenüber der ersten Abkühlungsgeschwindigkeit (v1) höheren Abkühlungsgeschwindigkeit (v2) mit mehr als 1°C/sec unter die Solidustemperatur (TS V) der Vorlegierung abgekühlt wird. - Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Vorlegierung vor dem Unterschreiten der Liquidustemperatur (TL Al3Ti) der Al3Ti-Phase in Bewegung versetzt wird.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass bei vorzeitigem Unterschreiten der Liquidustemperatur (TL Al3Ti) bzw. bei bereits erfolgter Erstarrung die Vorlegierung bis zum vollständigen Lösen bereits ausgeschiedener Al3Ti-Partikel in der Schmelze über die Liquidustemperatur ((TL Al3Ti) aufgeheizt wird.
- Verfahren nach einem der Ansprüche 1 bis 3, gekennzeichnet, dass die Bewegung der Schmelze mittels eines magnetostriktiven Resonators oder mittels Ultraschall Resonators erzeugt wird.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die zweite Abkühlungsgeschwindigkeit (v2) grösser ist als 2°C/sec, insbesondere grösser als 5°C/sec.
- Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Vorlegierungsschmelze zu einem Strang vergossen wird.
- Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass ein kontinuierlicher Strang, vorzugsweise durch Horizontalstranggiessen, hergestellt wird.
- Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass der Strang weiter zu Kornfeinungsstangen oder -draht gezogen wird.
- Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Vorlegierung eine Zusammensetzung aufweist, deren Gesamtgehalt an Titan das stöchiometrische Verhältnis von TiB2 übersteigt.
- Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Vorlegierung Ti und B im Gewichtsverhältnis 5:2 bis 10:1 enthält.
- Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Vorlegierung 0.05 bis 20, vorzugsweise 0.1 bis 5, insbesondere 0.5 bis 2 Gew.-% Ti und 0.01 bis 4, vorzugsweise 0.02 bis 1, insbesondere 0.05 bis 0.5 Gew.-% B enthält.
- Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass aus der Vorlegierung Kornfeinungsmittel für die Kornfeinung von Aluminium und Aluminiumlegierungen hergestellt werden.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00983193A EP1242641B1 (de) | 1999-12-10 | 2000-11-30 | Verfahren zur herstellung einer aluminium-titan-bor-vorlegierung als kornfeinungsmittel |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP99811137 | 1999-12-10 | ||
| EP99811137A EP1114875A1 (de) | 1999-12-10 | 1999-12-10 | Verfahren zur Herstellung einer Aluminium-Titan-Bor-Vorlegierung als Kornfeinungsmittel |
| EP00983193A EP1242641B1 (de) | 1999-12-10 | 2000-11-30 | Verfahren zur herstellung einer aluminium-titan-bor-vorlegierung als kornfeinungsmittel |
| PCT/EP2000/012015 WO2001042521A1 (de) | 1999-12-10 | 2000-11-30 | Verfahren zur herstellung einer aluminium-titan-bor-vorlegierung als kornfeinungsmittel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1242641A1 EP1242641A1 (de) | 2002-09-25 |
| EP1242641B1 true EP1242641B1 (de) | 2004-02-18 |
Family
ID=8243179
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99811137A Withdrawn EP1114875A1 (de) | 1999-12-10 | 1999-12-10 | Verfahren zur Herstellung einer Aluminium-Titan-Bor-Vorlegierung als Kornfeinungsmittel |
| EP00983193A Expired - Lifetime EP1242641B1 (de) | 1999-12-10 | 2000-11-30 | Verfahren zur herstellung einer aluminium-titan-bor-vorlegierung als kornfeinungsmittel |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99811137A Withdrawn EP1114875A1 (de) | 1999-12-10 | 1999-12-10 | Verfahren zur Herstellung einer Aluminium-Titan-Bor-Vorlegierung als Kornfeinungsmittel |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20030075020A1 (de) |
| EP (2) | EP1114875A1 (de) |
| CA (1) | CA2394485A1 (de) |
| DE (1) | DE50005366D1 (de) |
| WO (1) | WO2001042521A1 (de) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TR200504376A2 (tr) * | 2005-11-02 | 2008-05-21 | T�B�Tak-T�Rk�Ye B�L�Msel Ve Tekn�K Ara�Tirma Kurumu | Tane küçültücü ön alaşım üretmek için bir proses |
| CN101768708B (zh) * | 2010-02-05 | 2012-05-23 | 深圳市新星轻合金材料股份有限公司 | 通过控制压缩比来控制铝钛硼合金晶粒细化能力的变化量的方法 |
| CN105671350A (zh) * | 2015-03-19 | 2016-06-15 | 中信戴卡股份有限公司 | 一种铝合金细化剂、其制备方法及用途 |
| EP3162460A1 (de) | 2015-11-02 | 2017-05-03 | Mubea Performance Wheels GmbH | Leichtmetallgussbauteil und verfahren zum herstellen eines leichtmetallgussbauteils |
| RU2625375C2 (ru) * | 2015-12-03 | 2017-07-13 | Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) | Способ получения композиционных сплавов и установка для его осуществления |
| CN107377914A (zh) * | 2017-08-04 | 2017-11-24 | 江西金世纪特种焊接材料有限公司 | 一种铝合金焊接材料熔炼连铸设备 |
| FR3082763A1 (fr) * | 2018-06-25 | 2019-12-27 | C-Tec Constellium Technology Center | Procede de fabrication d une piece en alliage d aluminium |
| CN109371277A (zh) * | 2018-12-11 | 2019-02-22 | 徐州宁铝业科技有限公司 | 一种用于铝合金熔炼的精炼剂及制备方法 |
| CN110157935B (zh) * | 2019-06-28 | 2021-05-07 | 上海大学 | 铸造铝硅合金用Al-V-B细化剂、其制备方法及应用 |
| CN110195168B (zh) * | 2019-07-12 | 2021-01-01 | 东北大学 | 一种铝-钛-硼细化剂板的制备工艺 |
| CN114959348B (zh) * | 2022-06-09 | 2023-12-05 | 上海大学 | 一种高分散度Al-xMB2细化剂的制备方法和应用方法 |
| CN115558821B (zh) * | 2022-12-06 | 2023-03-10 | 北京航空航天大学 | 一种实现TiB2尺寸可控的Al-Ti-B细化剂制备方法 |
| CN115976373B (zh) * | 2022-12-30 | 2024-09-06 | 中山瑞泰铝业有限公司 | 一种铝合金材料的加工工艺及其应用 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE349331B (de) * | 1970-04-28 | 1972-09-25 | Svenska Aluminiumkompaniet Ab | |
| US4612073A (en) * | 1984-08-02 | 1986-09-16 | Cabot Corporation | Aluminum grain refiner containing duplex crystals |
| US5230754A (en) * | 1991-03-04 | 1993-07-27 | Kb Alloys, Inc. | Aluminum master alloys containing strontium, boron, and silicon for grain refining and modifying aluminum alloys |
-
1999
- 1999-12-10 EP EP99811137A patent/EP1114875A1/de not_active Withdrawn
-
2000
- 2000-11-30 WO PCT/EP2000/012015 patent/WO2001042521A1/de not_active Ceased
- 2000-11-30 EP EP00983193A patent/EP1242641B1/de not_active Expired - Lifetime
- 2000-11-30 CA CA002394485A patent/CA2394485A1/en not_active Abandoned
- 2000-11-30 DE DE50005366T patent/DE50005366D1/de not_active Expired - Fee Related
- 2000-11-30 US US10/148,659 patent/US20030075020A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001042521A1 (de) | 2001-06-14 |
| EP1114875A1 (de) | 2001-07-11 |
| US20030075020A1 (en) | 2003-04-24 |
| WO2001042521A8 (de) | 2001-07-12 |
| CA2394485A1 (en) | 2001-06-14 |
| EP1242641A1 (de) | 2002-09-25 |
| DE50005366D1 (de) | 2004-03-25 |
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