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
  • C22C1/03—Making non-ferrous alloys by melting using master alloys

Definitions

• This invention relates to an alloying additive. More partculaiy 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, norm ⁇ dly titanium diboride, TiT ⁇ .
• the specification teaches subjecting the melt of the alloying material, as soon as possible after formation of the TiB2 particles, to rapid cooling to form the solid alloy, thereby minimising the extent to which the TiB2 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, ⁇ o 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 Al and 0421549 Al 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.
• EP 0398449 Al the atomised droplets are quick-cooled to obtain solid particles which are subsequently processed to consolidate them.
• EP 0421549 Al the atomised particles are collected as solid materi.al on a collecting surface.
• 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 substantially 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 atomised 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 rate of cooling within tho.se ranges it is generally necessary to apply a flow of cooling fluid, such as air or water for example, in thermal communication with the .alloying material applied to the cooling surface.
• 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" °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 metaUurgical 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:
• Splat material in loose form is packaged into unit quantities.
• the unit quantities are relatively small, for example, 250 g, 500 g or 1 kg
• the alloying addition can be made by adding the required number of packaged unit quantities directly to the melt.
• the unit quantities of splat material are conveniently packed into suitable packages that can release the splat material, for example by being melted or burnt away when the package is added to the melt to which the alloying addition is to be made.
• suitable combustible packaging materials are plastics such as a chlorine-free, low melt, low density polyethylene.
• An alternative approach in cases where packaged unit quantities are to be added directly to the melt to be alloyed is to package the splat material in material which can add a useful component to the melt which is being alloyed; aluminium foil is an example of such a packaging material which would be appropriate in many instances.
• the packaged unit quantities may be substantially larger than as described above, e.g. 10 kg or more. In such cases it may be convenient to add the splat material to the melt which is to be alloyed by means of suitable dosing apparatus such as injection apparatus.
• Splat material in loose form is compressed into unit quantities. There are several possibilities for this:
• the splat material in loose form is formed into suitable self-supporting unit bodies by means of any of the various kinds of briquetting apparatus known in the art. If desired, any suitable binders or other desired additives may be added to the splat material before briquetting.
• the briquetted product may be of any suitable form, for example cylinders, pucks, pillows, lumps or cubes. We prefer cylinders between 50 and 200 mm in diameter and between 5 and 200 mm in height. Suitable unit weights of the briquetted products are 100 g, 250 g, 500 g or 1 kg, for example.
• the shapes produced are somewhat larger, e.g. 5 kg, 10 kg or 25 kg.
• the bulk shapes may be waffle plates or ingots, for example. They may be added directly to the melt which is to be aHoyed. Alternatively, they may be extruded to an elongated form, such as rod or wire, for example, which is suitable for continuous feeding to the melt which is to be alloyed. A rod of about 9 mm diameter is a preferred form.
• Splat material in loose form is cold extruded through a die to an elongated form, rod or wire for example, suitable for continuous feeding to a melt. Again rod of about 9 mm diameter is preferred.
• a suitable cold extrusion process is known as the Conform process; see the paper by J. A. Padre "The continuous extrusion of wire and sections from non-ferrous metal powders by the CONFORM process", presented at the International Powder Metallurgy Conference, Washington, U.S.A., on 24th June 1980.
• 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 aUoying 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:
• a modifier comprising strontium.
• Such alloying materials are suitable for making alloying additions to hypoeutectic and eutectic aluminium-silicon alloy melts for the purpose of improving the crystal structure of the aluminium-silicon eutectic crystals when the alloy solidifies.
• the preferred such alloy is a strontium-aluminium alloy containing strontium in the range from 3 to 30 weight % , preferably from 8 to 20 weight %, more preferably about 10 weight %. Because of the fine metallurgical structure of strontium-.aluminium alloying additives produced by the method of the invention, it is possible to produce the aUoying additions in rod form, even at higher strontium levels than can be formed to rod from strontium-aluminium alloys produced by more conventional methods.
• the strontium-aluminium modifier may additionally comprise titanium, and boron; such an alloying addition can be added to hypoeutectic aluminium-silicon melts to produce grain refinement of the aluminium component as well as modification of the aluminium-silicon component of the solidified aluminium-silicon alloy.
• Such an alloying addition may comprise, in weight % : 5% to 25% strontium, 0.5% to 12% titanium, 0.1% to 2% boron.
• Three preferred compositions comprise in weight %: (a) about 10% strontium, about 1 % titanium and about 0.2% boron; (b) about 10% strontium, about 5% titanium and about 1% boron; and (c) about 5% strontium, about 10% titanium and about 1 % boron. 2.
• a grain refiner may additionally comprise titanium, and boron; such an alloying addition can be added to hypoeutectic aluminium-silicon melts to produce grain refinement of the aluminium component as well as modification of the aluminium-silicon component of the
• Grain refiners for adding to aluminium-based melts may comprise titanium; they usuaUy comprise boron as well as titanium. When produced by the method of the invention their activity can be enhanced as a result of the improvement in the fineness of the metaUurgical structure. The rate of dissolution may also be enhanced. With those comprising boron as weU as titanium, this is especiaUy the case when the melt of the aUoying material is appUed to the cooling surface within a short time of the beginning of the co-existence of the boron and the titanium in the melt.
• FR 2133439 describes techniques which can readUy be adapted to the method of the present invention whereby it wiU be possible to minimise the length of that time period. Examples of suitable compositions of aluminium-based grain refiners which can be produced by the method of the invention are those comprising, in addition to the aluminium, in weight %:
• Such additives generally comprise aluminium and boron, and are added to aluminium melts to precipitate out conductivity-impairing impurities such as vanadium. When produced by the method of the invention, they can have an improved rate of dissolution and rate of precipitating out of the conductivity-impairing impurities.
• the preferred such aUoy is a boron-aluminium aUoy comprising boron in the range from 3 to 10 weight % , preferably about 4 weight % .
• An alloying additive for adding an alloying metal can be employed to add an aUoying metal such as zirconium, manganese, copper, vanadium, iron or chromium, for example, to an aluminium-based melt. When produced by the method of the invention their rate of dissolution may be enhanced.
• Preferred compositions for such aUoying additives are:
• zirconium-aluminium comprising zirconium in the range from 5 to 30 weight % , preferably about 15 weight % ;
• manganese-aluminium comprising manganese in the range from 5 to 40 weight %, preferably about 20 weight %;
• copper-aluminium comprising copper in the range from 20 to 60 weight %, preferably about 50 weight %;
• vanadium-aluminium comprising vanadium in the range from 5 to 30 weight %, preferably about 10 weight %;
• iron-aluminium comprising iron in the range from 5 to 40 weight % , preferably about 20 weight %;
• chromium-aluminium comprising chromium in the range from 5 to 40 weight % , preferably about 20 weight % .
• aUoying additive by the method of the invention such that the additive contains more than one aUoying component
• the original melt of aUoying material contains aU of the required aUoying components
• 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.
• 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 aUoying 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.
• FIGS. 1(a) and 1(b) are photographs at the same size as the original. The rest of the Figures are aU photomicrographs at a magnification of 500.
• Fig. 1(a) shows the structure of untreated aluminium metal as used in Example 1.
• Fig. 1(b) shows the structure of aluminium metal after being grain refined with the grain refiner aUoying briquettes produced in accordance with Example 1.
• Fig. 2(a) shows the structure of untreated LM24 aUoy as used in Examples 2 to 4.
• Fig. 1(a) shows the structure of untreated aluminium metal as used in Example 1.
• FIG. 2(b) shows the structure of LM24 aUoy after being modified with modifier aUoying briquettes produced in accordance with Example 2.
• Fig. 3 shows the structure of LM24 .aUoy alter being modified and gram refined with modifier and grain refiner aUoying briquettes produced in accordance with
• Example 3 shows the structure of LM24 aUoy after being modified and grain refined with modifier and grain refiner aUoying briquettes produced in accordance with
• a 300 kg melt of aUoying material comprising 5 weight % titanium, 1 weight % boron balance aluminium of 99.7 weight % purity (5/1 TiBAl) was prepared by reacting potassium fluotitanate, and potassium borofluoride, KBF4, with molten aluminium in an induction furnace.
• the aUoying 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 metaUurgical packaging drum of 1 mm thick ⁇ tild 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 horizontaUy, and was connected to a motor arranged to drive it at a rate of 30 r.p.m. The drum was open-ended, 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 metaUurgical packaging drum of 1 mm thick ⁇ tild steel having a length of 880 mm and a diameter of 660 mm. It was
• the tundish having a capacity of 10 kg of aUoying material was arranged about 400 mm above the 12 o'clock position. It comprised a steel body of substantiaUy V-section and extending over almost the whole of the axial length of the drum, and was lined internaUy 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 verticaUy, perpendicular to the axis of the drum, and was connected to .an osciUator arranged to move it in that direction over a distance of 20 mm, at a rate of 100 oscUlations per minute.
• the splat producing apparatus had been prepared to receive the molten alloying material, by activating the drum drive motor and the osciUator, and supplying cooling water at a temperature of 15 °C at a rate of 100 kg per minute.
• Molten aUoying material at 850 °C was suppUed to the tundish from the induction furnace continuously at a rate such as to keep it approximately three quarters fuU. 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 RedhiU, 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 metaUurgical briquetting apparatus comprising a hydrauhc 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 cyUnder 90 mm in diameter and 25 mm long.
• Each tablet weighed 300 g.
• the tablets were used as a grain refiner aUoying 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 TP1 grain refiner test; the structure of the soUdified sample is shown in Fig. 1(b); Fig. 1(a) shows the structure of an untreated sample of the aluminium. Exa ple 2
• a 300kg melt comprising 10 weight % strontium, balance aluminium of 99.7 weight % purity (lOSrAl) was prepared by aUoying 30 kg of strontium metal into a melt of 270 kg of molten aluminium in an induction furnace.
• the aUoying material was then converted to a splat product in the apparatus described in Example 1, under substantiaUy 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-siUcon aUoy 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 maj mum 0.5 manganese.
• this aUoy is generaUy used in the un-modified state, it is an aUoy which can be used to show modification particul ⁇ irly weU.
• Fig. 2(b) shows the structure of an untreated sample of the aUoy.
• a 300 kg melt of an aUoying 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 ⁇ TiFg and KBF 4 with molten aluminium as in Example 1 and aUoying 30 kg of strontium metal as in Example 2.
• the aUoying material was then converted to a splat product in the apparatus described in Example 1, under substantiaUy 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 aUoying material was prepared and converted to a splat product and then granulated, as described in Example 1, and a melt of lOSrAl was prepared and converted to a splat product and then granulated as described in Example 2.
• Portions of the 5/1 TiBAl and lOSrAl 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)

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• 1993
  • 1993-01-29 GB GB9301825A patent/GB2274656B/en not_active Expired - Fee Related
• 1994
  • 1994-01-14 ZA ZA94278A patent/ZA94278B/xx unknown
  • 1994-01-20 EP EP94904291A patent/EP0633948B1/de not_active Expired - Lifetime
  • 1994-01-20 ES ES94904291T patent/ES2132375T3/es not_active Expired - Lifetime
  • 1994-01-20 CA CA002130819A patent/CA2130819A1/en not_active Abandoned
  • 1994-01-20 AU AU58414/94A patent/AU674392B2/en not_active Ceased
  • 1994-01-20 WO PCT/GB1994/000108 patent/WO1994017217A1/en active IP Right Grant
  • 1994-01-20 DE DE69418938T patent/DE69418938T2/de not_active Expired - Fee Related
  • 1994-09-23 NO NO943538A patent/NO305662B1/no not_active IP Right Cessation

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