EP0633948B1 - Alloying additive - Google Patents

Alloying additive Download PDF

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Publication number
EP0633948B1
EP0633948B1 EP94904291A EP94904291A EP0633948B1 EP 0633948 B1 EP0633948 B1 EP 0633948B1 EP 94904291 A EP94904291 A EP 94904291A EP 94904291 A EP94904291 A EP 94904291A EP 0633948 B1 EP0633948 B1 EP 0633948B1
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EP
European Patent Office
Prior art keywords
splat
melt
alloying
product
cooling surface
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
Application number
EP94904291A
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German (de)
English (en)
French (fr)
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EP0633948A1 (en
Inventor
Richard Charles Cameron Nixon
Stuart Ross Thistlethwaite
John Warren Wright
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
London and Scandinavian Metallurgical Co Ltd
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London and Scandinavian Metallurgical Co Ltd
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Publication of EP0633948A1 publication Critical patent/EP0633948A1/en
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    • 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

  • This invention relates to an alloying additive. More particulary it relates to a method of making an alloying additive of fine metallurgical structure.
  • our French Patent Specification No. 2133439 relates to aluminum-based alloying additives comprising a transition metal, normally titanium, and boron. Such alloying additives are added to aluminium-based melts to provide grain refinement.
  • the main active component of the alloying additive is boride particles, normally titanium diboride, TiB 2 .
  • the specification teaches subjecting the melt of the alloying material, as soon as possible after formation of the TiB 2 particles, to rapid cooling to form the solid alloy, thereby minimising the extent to which the TiB 2 particles can grow in size.
  • the preferred method of rapid cooling taught in FR 2133439 is casting into a mould of thermally conducting material such as copper, which is preferably water cooled.
  • a less preferred alternative suggested is a splat quenching process comprising atomising the melt to form droplets and projecting the molten droplets by means of a current of inert gas against a cooled smooth surface, so that the molten droplets are rapidly solidified by impact against the smooth surface without adhering to it.
  • the former method entails the danger that the rate of cooling will be insufficient, and also the moulded product will not be of suitable form for many applications.
  • the latter method is expensive to operate.
  • European Patent Specifications Nos. 0398449 A1 and 0421549 A1 disclose methods of producing strontium-aluminium alloying additives to be used as modifiers for aluminium-silicon alloys. They both make use of the knowledge that solidification of the melt at a relatively high rate of cooling will result in a fine metallurgical structure in the solidified alloying additive. In both cases the process for achieving the required rate of cooling involves atomisation of the melt. In EP 0398449 Al, the atomised droplets are quick-cooled to obtain solid particles which are subsequently processed to consolidate them. In EP 0421549 A1 the atomised particles are collected as solid material on a collecting surface. The atomisation process is expensive to operate, and in many cases requires steps, such as the provision of a special atmosphere, to guard against air contamination of the alloying material.
  • US Patent Specification No 4259270 describes an apparatus for treating alloys to give them a very fine structure to provide optimum properties in the treated alloy, such treatment requiring a very high solidification rate, for example one which is more than 10 5 °C per second. That specification mentions earlier attempts involving atomisation, either using a rotating perforated syphon or disintegrating the melt with a pressurised gas, and explains that the earlier proposals have produced unsatisfactory results, in particular because too many of the particles are insufficiently small to allow solidification to occur rapidly enough, and also because the melts tend to react adversely with the materials into which they come into contact.
  • the alloy is treated in an enclosed apparatus in which the alloy forms a self-consuming electrode, which melts and drops melt droplets onto a rotating counter electrode, where they are flung onto an internally cooled rotating conical plate, at which they are then rapidly cooled to form thin foils.
  • the process is normally carried out in an inert atmosphere and/or under reduced pressure.
  • an alloying additive of fine metallurgical structure comprising providing a melt of alloying material, providing cooling means comprising a cooling surface, applying one or more unatomised streams of the melt to the cooling surface to produce a splat product, and arranging the splat product into a dosage form suitable for making measured alloying additions.
  • the process of the invention provides a relatively inexpensive to operate process which is capable of reliably producing an alloying additive of fine metallurgical structure.
  • the splat product is comminuted, for example by granulation, as described later, before it is arranged into the dosage form suitable for making alloying additions.
  • the rate of cooling of the unatomised stream or streams by the cooling means is preferably from 20 to 1000 °C per second, most preferably from 50 to 500 °C per second.
  • a flow of cooling fluid such as air or water for example
  • the cooling means comprises thermally conductive material so as to facilitate the removal of heat from the alloying material on the cooling surface, and it desirably should also be such as readily to permit the release of the splat product from that surface; suitable materials are steel and copper, for example.
  • the techniques employed in the manufacture of amorphous metals can produce cooling rates of the order to 10 6 °C per second, but such techniques are relatively expensive to operate, and, if applied to a melt of alloying material, generally would not produce a worthwhile improvement in the fineness of the metallurgical structure of the alloying material, as compared with that achievable by the splat cooling used in the present invention.
  • the temperature of the alloying material when applied to the cooling surface will, of course, be above its solidus. It should preferably not be more than 200 °C above the liquidus.
  • the cooling means comprises a cooling surface which moves in an endless path.
  • a cooling means may comprise, for example, a rotating cylinder or recirculating belt having an external cooling surface.
  • the cooling surface is one which moves in an endless path, we have found that it is beneficial to cool it by applying a flow of cooling fluid, for example a water spray, to an internal surface of the cooling means, the internal surface being in thermal communication with the cooling surface.
  • the required thermal communication can be achieved by arranging that the cooling means comprises a suitable thermally conductive material such as steel or copper, for example. This arrangement can provide efficient, even removal of heat from the alloying material impinging on the cooling surface.
  • impurities in the melt are concentrated at an upper zone in the melt, and the unatomised stream or streams are fed to the cooling surface from below the said upper zone. That has the advantage that impurities in that zone are not included in the melt applied to the cooling surface.
  • the unatomised stream or streams can be fed from below the upper zone by underpouring from below it.
  • the melt is held in a metallurgical vessel and is released through one or more apertures in the vessel below the upper zone. We have found that it is advantageous to oscillate the melt so as to urge impurities in it to rise towards the upper zone.
  • the oscillation is preferably in a generally vertical plane.
  • the alloying material is a high melting one and impurities in the melt are not concentrated at an upper zone in the melt, it may be of benefit to feed the unatomised stream or streams to the cooling surface by pouring the melt from its surface, such as by lip pouring, for example.
  • this can be achieved by lip pouring from a vessel having castellations formed along the width of a surface over which the melt is to be poured.
  • the thickness of the splat product desirably should be from 0.1 to 5 mm, preferably less than 3 mm.
  • the width of the splat product is of less importance, and can conveniently be from 2 to 200 mm, for example. Its length can be unlimited, but generally will also be from 2 to 200 mm.
  • the splat product produced in the method of the invention can be arranged into a dosage form suitable for making measured alloying additions, for example:
  • the splat material in loose form which is employed has been produced by a process comprising comminuting the splat product.
  • the comminuted splat product has a mean maximum dimension of from 0.5 to 10 mm, more preferably from 1 to 5 mm.
  • the required comminution of the splat product can be achieved by means of a metallurgical granulation machine, which has rotating blades which can reduce the size of the splat product pieces to the required degree.
  • the alloying material used to produce the alloying additive in accordance with the method of the invention may be of any suitable kind.
  • it is an aluminium based material, where the alloying additive is to be used to make alloying additions to an aluminium-based melt.
  • aluminium-based alloying materials are:
  • Example 3 Where it is desired to make an alloying additive by the method of the invention such that the additive contains more than one alloying component, one can arrange that the original melt of alloying material contains all of the required alloying components, as illustrated in the following Example 3. However, we have found that in many circumstances the same object can be achieved with greater convenience by arranging that a splat product having a first composition is mixed with at least one additional splat product having a different composition to provide a mixed splat product for arranging into a dosage form in accordance with the invention. This is illustrated in the following Example 4.
  • the first and additional splat products are preferably comminuted as described above, either before or after they are mixed together.
  • the present invention also comprehends a method of making an alloying addition to an aluminium melt, comprising adding to the melt a dosage form which has been produced by a method in accordance with the invention.
  • Figures 1(a) and 1(b) are photographs at the same size as the original. The rest of the Figures are all photomicrographs at a magnification of 500.
  • Figures 1(a) and 1(b) are photographs at the same size as the original. The rest of the Figures are all photomicrographs at a magnification of 500.
  • Figures 1(a) and 1(b) are photographs at the same size as the original. The rest of the Figures are all photomicrographs at a magnification of 500.
  • a 300 kg melt of alloying material comprising 5 weight % titanium, 1 weight % boron balance aluminium of 99.7 weight % purity (5/1 TiBAl) was prepared by reacting potassium fluotitanate, K 2 TiF 6 , and potassium borofluoride, KBF 4 , with molten aluminium in an induction furnace.
  • the alloying material was then converted to a splat product in an apparatus comprising a tundish which was mounted vertically above cooling means comprising a water-cooled, standard cylindrical metallurgical packaging drum of 1 mm thick mild steel having a length of 880 mm and a diameter of 660 mm. It was mounted for rotation about its cylindrical axis, with the axis disposed horizontally, and was connected to a motor arranged to drive it at a rate of 30 r.p.m. The drum was openended, and was cooled by means of a spray bar which projected from the open end within the drum's interior so as to direct a spray of water to the interior of the drum, centred at approximately the 1 o'clock position.
  • a tundish which was mounted vertically above cooling means comprising a water-cooled, standard cylindrical metallurgical packaging drum of 1 mm thick mild steel having a length of 880 mm and a diameter of 660 mm. It was mounted for rotation about its cylindrical axis, with the axis
  • the tundish having a capacity of 10 kg of alloying material was arranged about 400 mm above the 12 o'clock position. It comprised a steel body of substantially V-section and extending over almost the whole of the axial length of the drum, and was lined internally with suitable refractory material.
  • the base of the "V" of the tundish included a horizontal internal floor section 50 mm wide which was provided with a line of 8 evenly spaced 6 mm diameter circular apertures to enable the contents of the tundish to exit in a line of streams which could be directed to the drum along its axial length at the 12 o'clock position.
  • the tundish was mounted so that it could be oscillated vertically, perpendicular to the axis of the drum, and was connected to an oscillator arranged to move it in that direction over a distance of 20 mm, at a rate of 100 oscillations per minute.
  • the splat producing apparatus had been prepared to receive the molten alloying material, by activating the drum drive motor and the oscillator, and supplying cooling water at a temperature of 15 °C at a rate of 100 kg per minute.
  • Molten alloying material at 850 °C was supplied to the tundish from the induction furnace continuously at a rate such as to keep it approximately three quarters full. The melt exited the holes in the base of the tundish, thus being underpoured.
  • the granulator used was a Blackfriars granulator, and comprised rotating blades for comminuting the splat product. It had been manufactured by Blackfriars Rotary Cutters Ltd., of Redhill, Surrey, England, and was designated as their 18 inch ASHD Rotary Cutter.
  • the comminuted splat product exiting the granulator had a mean maximum dimension of 3 mm.
  • a metallurgical briquetting apparatus comprising a hydraulic press for formation into dosage units.
  • the press cold compacted the comminuted splat product into the dosage units, each of which comprised a tablet in the form of a cylinder 90 mm in diameter and 25 mm long.
  • Each tablet weighed 300 g.
  • the tablets were used as a grain refiner alloying additive. They were added to molten aluminium of 99.7 weight % purity at an addition rate of 2 kg per tonne.
  • a sample of the treated melt was then solidified in accordance with a comparative test based on the AA TPl grain refiner test; the structure of the solidified sample is shown in Fig. 1(b); Fig. 1(a) shows the structure of an untreated sample of the aluminium.
  • a 300kg melt comprising 10 weight % strontium, balance aluminium of 99.7 weight % purity (10SrAl) was prepared by alloying 30 kg of strontium metal into a melt of 270 kg of molten aluminium in an induction furnace.
  • the alloying material was then converted to a splat product in the apparatus described in Example 1, under substantially the same conditions, with the exception that the temperature of the strontium-aluminium melt supplied to the splat casting apparatus was 870 °C.
  • the resulting splat product was then granulated and briquetted, as in Example 1, the comminuted splat product exiting the granulator having a mean maximum dimension of 3 mm, and the cylindrical briquetted tablets each being 90 mm in diameter x 25 mm in length, and weighing 300 g.
  • LM24 is a hypoeutectic aluminium-silicon alloy containing copper, and conforms to the specification, in weight %: 3.0 to 4.0 copper, 7.5 to 9.5 silicon, maximum 1.3 iron, maximum 3.0 zinc and maximum 0.5 manganese. Although this alloy is generally used in the un-modified state, it is an alloy which can be used to show modification particularly well.
  • Fig. 2(b) shows the structure of an untreated sample of the alloy.
  • a 300 kg melt of an alloying material comprising 10 weight % strontium, 1 weight % titanium, 0.2 weight % boron, balance aluminium of 99.7 weight % purity (10/1/0.2 SrTiBAl) was prepared by reacting the appropriate amounts of K 2 TiF 6 and KBF 4 with molten aluminium as in Example 1 and alloying 30 kg of strontium metal as in Example 2.
  • the alloying material was then converted to a splat product in the apparatus described in Example 1, under substantially the same conditions, with the exception that the temperature of the strontium-aluminium melt supplied to the splat casting apparatus was 870 °C.
  • the resulting splat product was then granulated and briquetted, as in Example 1, the comminuted splat product exiting the granulator having a mean maximum dimension of 3 mm, and the cylindrical briquetted tablets each being 90 mm in diameter x 25 mm in length, and weighing 300 g.
  • a melt of 5/1 TiBAl alloying material was prepared and converted to a splat product and then granulated, as described in Example 1, and a melt of 10SrAl was prepared and converted to a splat product and then granulated as described in Example 2.
  • Portions of the 5/1 TiBAl and 10SrAl splat products after comminution in the granulator were mixed in a weight ratio of 80 to 20, so that the resulting mixture was, in weight %: 4% titanium, 0.8% boron, 2% strontium, balance aluminium.
  • the resulting mixture was briquetted as described in Example 1 to produce cylindrical briquetted tablets, each being 90 mm in diameter x 25 mm in length, and weighing 300 g.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
EP94904291A 1993-01-29 1994-01-20 Alloying additive Expired - Lifetime EP0633948B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9301825 1993-01-29
GB9301825A GB2274656B (en) 1993-01-29 1993-01-29 Alloying additive
PCT/GB1994/000108 WO1994017217A1 (en) 1993-01-29 1994-01-20 Alloying additive

Publications (2)

Publication Number Publication Date
EP0633948A1 EP0633948A1 (en) 1995-01-18
EP0633948B1 true EP0633948B1 (en) 1999-06-09

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ID=10729549

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EP94904291A Expired - Lifetime EP0633948B1 (en) 1993-01-29 1994-01-20 Alloying additive

Country Status (9)

Country Link
EP (1) EP0633948B1 (no)
AU (1) AU674392B2 (no)
CA (1) CA2130819A1 (no)
DE (1) DE69418938T2 (no)
ES (1) ES2132375T3 (no)
GB (1) GB2274656B (no)
NO (1) NO305662B1 (no)
WO (1) WO1994017217A1 (no)
ZA (1) ZA94278B (no)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2299099A (en) * 1995-03-18 1996-09-25 Christopher Duncan Mayes Process for producing grain refining master alloys.
SE9604258D0 (sv) * 1996-11-21 1996-11-21 Hoeganaes Ab Iron Additive
ES2140300B1 (es) * 1997-05-09 2000-10-16 Bostlan Sa Aditivo para la introduccion de uno o mas metales en las aleaciones de aluminio.
US6024777A (en) * 1998-03-17 2000-02-15 Eramet Marietta Inc. Compacted steel powder alloying additive for aluminum melts, method of making and method of using
DE102006021772B4 (de) * 2006-05-10 2009-02-05 Siemens Ag Verfahren zur Herstellung von Kupfer-Chrom-Kontakten für Vakuumschalter und zugehörige Schaltkontakte
RU2518041C2 (ru) * 2012-07-05 2014-06-10 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Способ получения лигатуры алюминий-титан-цирконий

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259270A (en) * 1977-09-24 1981-03-31 Battelle-Institut E.V. Apparatus and method for the manufacture of splat foils from metallic melts

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
FR2133439A5 (en) * 1971-04-13 1972-11-24 London Scandinavian Metall Aluminium refining alloy - consisting of dispersion of fine transition metal diboride particles in aluminium
JPS5143011B2 (no) * 1972-02-14 1976-11-19
SE8702149L (sv) * 1987-05-22 1988-11-23 Baeckerud Innovation Ab Aluminiumfoerlegering
CA1331519C (en) * 1989-05-03 1994-08-23 Alcan International Limited Production of an aluminum grain refiner
NO902193L (no) * 1989-05-19 1990-11-20 Shell Int Research Fremgangsmaate for fremstilling av en aluminium/strontrium-legering.
GB8922487D0 (en) * 1989-10-05 1989-11-22 Shell Int Research Aluminium-strontium master alloy
US5091019A (en) * 1990-02-12 1992-02-25 Allied-Signal, Inc. Rapidly solidified aluminum lithium alloys having zirconium
JPH03267355A (ja) * 1990-03-15 1991-11-28 Sumitomo Electric Ind Ltd アルミニウム―クロミウム系合金およびその製法
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
ATE167239T1 (de) * 1992-02-15 1998-06-15 Santoku Metal Ind Legierungsblock für einen dauermagnet, anisotropes pulver für einen dauermagnet, verfahren zur herstellung eines solchen und dauermagneten

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259270A (en) * 1977-09-24 1981-03-31 Battelle-Institut E.V. Apparatus and method for the manufacture of splat foils from metallic melts

Also Published As

Publication number Publication date
DE69418938D1 (de) 1999-07-15
GB9301825D0 (en) 1993-03-17
CA2130819A1 (en) 1994-08-04
WO1994017217A1 (en) 1994-08-04
AU5841494A (en) 1994-08-15
GB2274656B (en) 1996-12-11
AU674392B2 (en) 1996-12-19
EP0633948A1 (en) 1995-01-18
ZA94278B (en) 1994-10-12
NO305662B1 (no) 1999-07-05
DE69418938T2 (de) 1999-09-30
ES2132375T3 (es) 1999-08-16
GB2274656A (en) 1994-08-03
NO943538L (no) 1994-09-23
NO943538D0 (no) 1994-09-23

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