CN104583429B - Al Nb B foundry alloy for crystal grain refinement - Google Patents

Al Nb B foundry alloy for crystal grain refinement Download PDF

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CN104583429B
CN104583429B CN201380043494.5A CN201380043494A CN104583429B CN 104583429 B CN104583429 B CN 104583429B CN 201380043494 A CN201380043494 A CN 201380043494A CN 104583429 B CN104583429 B CN 104583429B
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grain
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CN104583429A (en
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哈里巴比·内登德拉
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Brunel University London
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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
    • 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
    • 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
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium

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  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

The method of the foundry alloy of a kind of grain size prepared for refining bulk alloy, described method includes providing Al B alloy and adds the Nb of simple substance form to form the step of Al Nb B foundry alloy.Described Al B alloy can be prepared in the following manner: provides and has than the alloy of Al B of required higher Boron contents and diluted with pure aluminum.

Description

Al-Nb-B foundry alloy for crystal grain refinement
The application relates to preparation for the foundry alloy (also referred to as masterbatch alloy) of the grain size of fining metal alloy Method, and relate to the purposes of the grain refiner as metal alloy subsequently.Especially, it relates to refine aluminium-silicon The preparation of the foundry alloy of the grain size of alloy and (that comprise aluminium and that do not comprise aluminium two kinds) magnesium alloy.
One of production at metal alloy important goal is the grain size reducing end-product.This is referred to as " crystal grain Refine " and generally solved by adding so-called " grain refiner ", described grain refiner is considered as promoting metal The material of the inoculation of alloy crystal.Bring many benefits and right by the refinement of the crystal grain of inoculation in casting technique Improve mechanical performance and there is significant impact.Thin equi-axed crystal tissue give high yield strength, high toughness, good can Squeezing ground, being uniformly distributed and the microporosity in fine-scale of the second phase.This causes the machinability of improvement, good therewith Surface smoothness and the resistance (and other preferable performances various) to hot tear crack.
Applicant of the present invention have submitted international patent application no PCT/GB2012/050300 (excellent in the application First weigh after day and be disclosed as WO 2012/110788), its relate to refining (i) comprise the alloy of aluminium and at least 3%w/w silicon or (ii) comprising the method for the grain size of the alloy of magnesium, described method comprises the following steps:
A () adds enough niobiums and boron to form niobium dioxide or Al in described alloy3Nb or both, or
B () adds niobium dioxide in described alloy, or
C () adds Al in described alloy3Nb, or
(d) their any combination.
For manufacturing the industry of aluminium wrought alloy, add and there are 94 weight %Al-5 weight %Ti-1 weight %B The Al-Ti-B system grain refiner of the form of the foundry alloy of chemical composition is widespread practice.Foundry alloy adds to be avoided in casting Corrosivity KBF in technique4The use of salt.It is not recommended that add the boron of simple substance form, this is owing to the reality being dispersed in melt The difficulty trampled, this is the result by liquid Al or the character of Mg alloys wet that it is low.The interpolation of foundry alloy overcomes these Problem.
In WO 2012/110788, disclose: replacing salt to add, people can add in Al-Si system liquid alloy The niobium dioxide grain refiner of little Al-Nb-B foundry alloy sheet metal form is to obtain thin grain size.Add concentration Al-Nb-B alloy guarantees NbB2Dispersed in aluminum melt.
Especially, WO 2012/110788 discloses: melt the pure Al of business in electric furnace at temperature range 800-850 DEG C Ingot simultaneously keeps 2 hours.By 5 weight %NbB2(Nb and KBF4Mixture) add in melt to form NbB2Phase.In stirring simultaneously And after removing scum silica frost, cast liquid metal to mould, thus produce Al-Nb-B grain refiner foundry alloy.
In another example, WO 2012/110788 discloses: 900 DEG C fusing business Al-10Nb foundry alloys and Extremely pure Al is added to form Al-2Nb foundry alloy to dilute this alloy.Then in melt, 1 weight % boron is added to realize Al- The foundry alloy composition of 2Nb-B.
US 3,933,476 (Union Carbide Corporation) discloses utilization and adds titanium, aluminium and KBF4Use Method in aluminium grain refinement.
GB 1 244 082 (Kawecki Berylco Industries, Inc.) discloses for by silk or strips Alloying or crystal grain refinement composition add the method to major metal, and wherein said composition is by aluminium and boron, titanium or zirconium Plant or multiple composition.
According to the first aspect of the invention, the foundry alloy of a kind of grain size prepared for refining bulk alloy is provided Method, described method includes providing Al-B alloy and adds the Nb of simple substance form to form the step of Al-Nb-B foundry alloy.
The technological merit of the foundry alloy according to the present invention is: first, and it can not use corrosive salt such as KBF4Feelings Produce under condition；Second, add concentration Al-Nb-B alloy to ensure that uniformly dividing in the melt in opposite directions of Nb system in bulk alloy Dissipate；And the 3rd, its thinner grain size achieving in final alloy (in other words, which is the refinement of more effective crystal grain Agent).
In preferred embodiments, described Al-B alloy is prepared in the following manner: offer has higher than required The Al-B alloy of Boron contents and diluted with pure aluminum.For example, in order to prepare 97 weight %Al-2 weight %Nb-1 weights Amount % alloy, dilutes commercially available 95 weight %Al-5 weight %B alloys to produce 99 weight %Al-1 by adding fine aluminium Weight %B alloy.Add enough simple substance niobiums afterwards, until obtaining 97 required weight %Al-2 weight %Nb-1 weight %B Alloy.
According to the second aspect of the invention, provide a kind of by add as defined above foundry alloy and fining metal closes The method of the crystal grain of gold.In preferred embodiments, the metal alloy adding foundry alloy wherein is that (i) comprises at least 3% The Al-Si alloy of w/w silicon or (ii) magnesium alloy.
Masterbatch (also referred to as foundry alloy) can comprise the niobium of q.s and boron to be formed enough in final alloy product Niobium dioxide, thus when adding this foundry alloy to Al-Si or Mg alloy melt, it can be by the crystal grain of tissue of solidification Size refines.When representing the formula of alloy, generally omit the percetage by weight of high alloy component.Therefore, for adding to aluminium The masterbatch alloy of alloy can have a formula of Al-X weight %Nb-Y weight %B, and wherein X can be 0.01 to 99 and Y can Being 0.002 to 25, and the percetage by weight of al composition is the surplus making summation be 100.
It is now described with reference to the drawings multiple preferred embodiments of the present invention, in the accompanying drawings:
Typical microstructures feature in Fig. 1 Al-5B foundry alloy.Boride phase particle (AlB12) it is dark contrast.
Fig. 2: Al-4.05Nb-0.9B foundry alloy microscopic structure, shows NbB2Phase particle
Fig. 3 Al-2Nb-2B foundry alloy microscopic structure, shows NbB2Phase particle
Fig. 4 Al-2Nb-B foundry alloy microscopic structure, shows NbB2Phase particle
The photo on the surface of the corrosion of the macroscopic view of the cross section of Fig. 5 .Al-10Si mo(u)lding sample.The photo on the left side is Al- 10Si alloy, and the photo on the right is for adding Al-2Nb-2B to the sample of preparation after melt.
The light micrograph of the sample shown in Fig. 6: Fig. 5.A () & (b) is for Al-10Si, and (c) & (d) It is for the Al-10Si with Al-2Nb-2B interpolation.Can see thinner in there is the sample that Al-2Nb-2B adds Primary aluminium and thinner eutectic particle.
Fig. 7. it is not added with adding the photograph of the top surface of the A380 ingot bar of the liquid metal casting of Al-2Nb-B with (b) by (a) Piece.
Fig. 8. brilliant in the Al-10Si alloy blank and have without processing in the case that Al-2Nb-B foundry alloy adds The schematic diagram of the difference spatially of grain tissue.
Fig. 9. at the photograph and have without the Al-10Si alloy blank prepared in the case that Al-2Nb-B foundry alloy adds Piece.
Figure 10. the schematic diagram of the cross section of wedge shape mould.Tl, T2, T3 represent the position of thermocouple in mould.Also show The microscopic structure on surface in the corrosion of these three various locations.
Figure 11. it is not added with for (a) and the AM50 alloy of (b) interpolation Al-2Nb-B foundry alloy uses Hpdc technique system The microscopic structure of the cross section of standby tensile bar.
Figure 12. the sketch of the mould using in the experiment of embodiment 7.These sketches depict in these moulds The typical cooldown rate obtaining.As the thickness of cast structure body increases, cooldown rate reduces.
The cross section of the corrosion of the macroscopic view of Figure 13 alloy A wedge shape and cylinder sample: a) be not added with and b) add Al-2Nb-2B Foundry alloy.
Figure 14. the cross section of the corrosion of the macroscopic view of alloy B wedge shape and cylinder sample: a) be not added with and b) add Al-2Nb- 2B foundry alloy.
Figure 15. the cross section of the corrosion of the macroscopic view of alloy C wedge shape and cylinder sample: a) be not added with and b) add Al-2Nb- 2B foundry alloy.
Figure 16. (a) is not added with and (b) adds the foundry alloy with Al-2Nb-2B composition of the Nb being equivalent to 0.1 weight The microscopic structure of alloy D.Al-2Nb-2B adds the size having refined both grain structure Al crystal grain and eutectic Si pin significantly.
Figure 17. (a) is not added with adding the microscopic structure of the alloy E of Al-2Nb-2B foundry alloy with (b).For Al crystal grain and For the size of both eutectic Si pins, grain structure substantially refines.
Figure 18. the microscopic structure of the anodized of alloy F.The microscopic structure on the left side is for be not added with crystal grain thin Cylindrical die sample in the case of agent.The microscopic structure on the right with the addition of Al-2Nb-2B.
The cross section of the corrosion of the macroscopic view of Figure 19 alloy G wedge shape and cylinder sample: a) be not added with and b) add Al-2Nb-2B Foundry alloy.
Figure 20. comparison (a) the un-added alloy G of the microscopic structure of cylindrical cast samples.B () has Al-2Nb-2B The alloy G that foundry alloy adds.Compared with the large-scale arborescent structure seen in reference sample, Al-2Nb-2B foundry alloy form The interpolation of grain refiner creates the grain structure of very thin (～150 microns).It is thinner after Al-2Nb-2B adds The particle (dark contrast particle) of primary silicon size.
The processing of embodiment 1:Al-Nb-B foundry alloy
In the present embodiment, boron source is commercially available Al-5 weight %B foundry alloy.Nb is the form of elemental powders, it is thus achieved that Company Alfa Aesar under Johnson Matthey.Fig. 1 shows the microscopic structure of Al-B foundry alloy.Dark contrast is simultaneously And be the boride that spherical particle is aluminium.To there is this foundry alloy of desired content together with business pure Al ingot in electric furnace Melt at temperature range 800-850 DEG C and keep 2 hours, there is the concentration being suitable for listed in table 1.Use non-reacted pottery Porcelain rod stirring melt.We are introduced to the Nb metal dust of compacted form or discrete particle form in melt afterwards.Important It is to it should be noted that in the melt except NbB2The formation of phase, it is also possible to form (Al, Nb) B according to position chemical concentrations2、Al3Nb phase Field trash.By in melt casting to mould.The metal of casting is referred to as Al-Nb-B foundry alloy.Fig. 2,3 and 4 show various The microscopic structure of foundry alloy.These are molecular by the thin Nb system grain of distribution in Al matrix.
The application to Al-10Si alloy for the embodiment 2:Al-2Nb-2B foundry alloy
Al-10Si alloy is melted in electric furnace at 800 DEG C and keeps 2 hours.Reference is cast in taper die Product.Mould is preheated to 250 DEG C, and front in being poured onto taper die the temperature of melt is maintained at 740 DEG C.By fritter Al-2Nb-2B foundry alloy (is equivalent to 0.05 weight %NbB2, relative to the weight of Al in Al-10Si alloy) add to remaining In melt.After 15 minutes, by Melt Stirring about 1 minute and cast to taper die.Fig. 5 shows and is not added with and adds Al- The grain size of the Al-10Si alloy of 2Nb-1B foundry alloy.Obtained the crystal grain group of refinement by adding Al-Nb-B foundry alloy Knit.With all kinds foundry alloy, casting process is repeated to Al-Si, and show their corresponding grain sizes in Table 1.Card Real all foundry alloys with the composition shown in table 1 have refined the grain size of Al-Si alloy.Except thinner crystal grain is big Outside little, as shown in Fig. 6 (c) & (d), it was observed that thinner eutectic Si.
Foundry alloy composition in Al-10Si alloy for the table 1, pitch-based sphere and corresponding average crystal grain size
The application to A380 alloy for the embodiment 3:Al-2Nb-1B foundry alloy
The A380 alloy of 3Kg is melted in electric furnace at 750 DEG C and keeps 1 hour and cast to steel mold.Will Another batch of fusing of 3Kg, and by fritter Al-2Nb-BFemaleAlloy (is equivalent to 0.05 weight %NbB2, relative to A380 alloy Weight) add to melt.After 15 minutes, by Melt Stirring about 1 minute and cast to mould.Fig. 7 (a) shows this alloy Grain size, and Fig. 7 (b) display is added with the alloy of Al-Nb-B foundry alloy.The labor display Al-Nb-B of ingot bar is female Grain size is reduced to 0.4mm from 1cm by the interpolation of alloy.Also macroporosity is significantly reduced.
Embodiment 4: be added with the processing (simulation of direct cast-in chills method) of the Al-10Si blank of Al-2Nb-B
Prepare Al-10Si alloy melt with resistance furnace in graphite crucible.Melt temperature is maintained at 800 DEG C.By two ends Open cylindrical steel mould is placed in vertical tube furnace.The hot-zone of this stove is controlled by three-zone heating system with indulging along pipe Maintain uniform temperature to direction.It is maintained at 720 DEG C along the temperature of the axle of steel mold.The bottom of steel pipe Cu block is closed.Will Melt temperature is reduced to 740 DEG C and is poured onto melt in steel mold afterwards.Before toppling over melt, by having 4 l/ minutes Flow sparge pipe by Cu block cool down.It it is～5 seconds with the time that filling melt steel tube place spends.Cooling owing to being provided is Sparge pipe, melt starts solidification from bottom.After completing to topple over ten seconds, Cu block is removed and is placed directly within sparge pipe The bottom of Al-Si alloy graining block.As result, from melt, one direction extracts heat.In this experiment along longitudinal side To cooling condition similar to the cooling condition of horizontal direction in plant-scale direct cast-in chills method.Fig. 8 (a) display is passed through The schematic diagram of the blank that the method produces.Huge columnar grain tissue is formed in the melt.Fig. 8 (b) display is by being added with The schematic diagram of blank prepared by the melt with the NbB2 of Al-2Nb-B form interpolation of 0.05 weight %.After Al-Nb-B adds There is not columnar grain tissue and can be only seen thin equi-axed crystal tissue.Figure 9 illustrates with one direction solidification casting The surface of the corrosion of the macroscopic view of the cylinder blank made.Achieve the columnar growth being sought after by adding Al-Nb-B foundry alloy Elimination.
The application to magnesium (AM50) alloy for the embodiment 5:Al-2Nb-B foundry alloy
AM50 alloy is melted in electric furnace at 690 DEG C and keeps 2 hours.Use SF6+N2Admixture of gas is to protect Melt avoids oxidation.Relative to the weight of AM50, add the Al-2Nb-B foundry alloy of about 0.1 weight % to melt and Stir 1 minute with rod iron.Will be containing NbB2Melt be poured onto in wedge shape mould.For comparison purposes, also do not appoint What NbB2The experiment added.According to the thickness of casting, this wedge shape mould provides the cooldown rate of wide scope.At position T1 and point Cooldown rate between end, the scope of cooldown rate can be between 80 DEG C/s to 1000 DEG C/s.Two kinds of mo(u)lding samples are thrown Light chemical attack.Compare the microscopic structure at various position (T1, T2 and T3) place in Fig. 10.As shown in Figure 10, when When adding Al-2Nb-B to melt, it was observed that crystal grain refines.
Embodiment 6: be added with the Hpdc of magnesium (AMS0) alloy of Al-2Nb-B foundry alloy
Hpdc (HPDC) is the various large structure/assemblies producing for the application of automobile, electronics and building field Conventional process.It is a kind of mass production techniques.It provides higher cooldown rate and in the process of setting phase for melt Between obtain thinner grain structure.As described in example 5 above, AM50 alloy melt is prepared.By interpolation be not added with 0.1 weight % The melt charging of Al-2Nb-B to the shot sleeve (shot-sleeve) of high pressure die casting machine, then melt is injected to have In the permanent mold of stamping, and it is made to solidify afterwards under stress.Produce at least 15 foundry goods.Each cast structure body is by three Individual cylindrical bar and three flat bars compositions.Figure 11 shows the microscopic structure of the cross section of representative cylindrical sample.Because Cooldown rate during HPDC is～1000 DEG C/s, it is contemplated that form very thin grain structure.But, toppling over period, when When melt contacts with the cold wall of shot sleeve, occur on these walls heterogeneous nucleus and they grow in melt.At document In, these crystal are referred to as " premature coagulation crystal " (early solidified crystal, ESC).Measurement ESC a size of～ The size of 250 μm.When adding grain refiner, as shown in Figure 11 (b), the size of these crystal substantially reduce and Whole grain size in whole sample is it appear that be similar.Each carry out tension test at least 40 cylindrical samples. Statistically, when adding Al-2Nb-B, it was observed that percentage elongation improves 11%.
The application of the Al-Si alloy to various commercial source for the embodiment 7:Al-2Nb-2B foundry alloy
The alloy of the research being given in Table 2 the impact for carrying out Al-2Nb-2B foundry alloy forms.These alloys are (the alloy A) of nearly eutectic；Hypoeutectic alloy (alloy B-F) and hypereutectic (alloy G) business alloy.
The list of the alloy that table 2. is studied
Alloy Si Mg Mn Cu Ni Zn Fe
Alloy A 11-12 0.1 0.5 0.1 0.1 0.1 0.6
Alloy B 7.5-9.5 3 0.5 3.0 0.5 3 1.3
Alloy C 6.5-7.5 0.4 0.3 0.2 0.1 0.1 0.5
Alloy D 9.99 0.005 0.005 0.0017 0.0044 0.005 0.09
Alloy E 10.98 0.268 0.21 2.134 0.068 0.778 0.83
Alloy F 6.06 0.275 0.265 2.725 0.0257 0.305 0.356
Alloy G 13.0 0.4 0.5 0.7 1.5 0.1 1
Alloy is placed in clay-graphite crucible, melts, and before casting, be maintained at the processing temperature of 790 DEG C down to Few 1 hour.Now, it reference alloy standing is cooled to about 740 (± 3) DEG C and cast to the cylinder of preheating at 250 DEG C In shape mould and wedge shape copper mould.These moulds are steel mold and the copper wedge shape mould of 30mm diameter.In wedge shape mould, as can With what the sketch that is given at Figure 12 was seen, by this tectonic cycle period cooldown rate scope 2 DEG C/s to 150 DEG C/s it Between.
Crystal grain in the form adding (adding rate of 0.1 weight %Nb and 0.1 weight %B) with Al-2Nb-2B foundry alloy In the case that fining agent adds, melt is being maintained at 790 DEG C after 60 minutes, foundry alloy is added in melt and in order to New crystal grain refines and stands time of minimum 30 minutes dissolving inside melt, so that it is guaranteed that crystal grain refinement phase uniformly point Cloth.By polished surface is immersed in graph card (Tucker) solution (25ml H2O+15ml HF+15ml HNO3+45ml HCl) In 20 to 30 seconds, carry out the chemical attack for showing maceral.
Figure 13 shows corrosion transversal of the macroscopic view of the alloy A wedge shape shape sample being not added with and adding Al-2Nb-2B Face, there it can be seen that the alloy A not having grain refiner to add is characterised by the weight of the grain size of primary α-Al crystal grain The difference spatially wanted, because rising to almost 1mm (top of sample) in the range from from about 200 μm (most advanced and sophisticated).From figure 13b it is possible to note that the interpolation of foundry alloy significantly reduces average primary α-Al grain size and difference spatially, It is decreased to this latter between 100 μm and 200 μm.Similarly, final primary α-Al grain size is more unwise to cooldown rate Sense, and therefore, it can the work utilizing large-scale casting technique to obtain based on the alloy A with thin and uniform grain size Industry assembly.
Alloy A cylindrical sample grand being not added with and adding Al-2Nb-2B foundry alloy is also show in figure (right side) The cross section of the corrosion seen.It can be seen that as in the case of wedge shaped sample, the microscopic structure of reference material is come into being by thick α-Al crystal grain forms, and the difference spatially in terms of there is size.Especially, in terms of external diameter, grain size is thin, This is corresponding to the material with contacting dies solidification, and substantially increases afterwards, and final center in cylindrical sample is slightly Edge down low.The interpolation of foundry alloy causes thin primary α-Al crystal grain much and level.Alloy microscopic structure is also to cooldown rate Locally difference is less sensitive, and this is particularly important when manufacturing the cast article with different wall degree.
For other alloys whole listed in table 2, it was observed that similar refinement.Give in Figure 14 is to 20 macroscopic view or Microscopic structure.

Claims (8)

1. the method preparing the foundry alloy of grain size for refining bulk alloy, described method includes providing Al-B to close Gold and add the Nb of simple substance form to form the step of Al-Nb-B foundry alloy.
2. method according to claim 1, wherein prepares described Al-B alloy: provide and have than institute in the following manner Need the Al-B alloy of higher Boron contents and diluted with pure aluminum.
3. method according to claim 2, the wherein said Al-B alloy with higher Boron contents is Al-5B.
4. the foundry alloy obtaining by the method according to the aforementioned claim of any one.
5. one kind by adding the method that foundry alloy according to claim 4 carrys out the crystal grain of fining metal alloy.
6. method according to claim 5, wherein said metal alloy includes:
I () comprises the Al-Si alloy of at least 3%w/w silicon, or
(ii) magnesium alloy.
7. method according to claim 6, wherein said metal alloy is Mg-Al alloy.
8. method according to claim 6, wherein said metal alloy is the Al-Si alloy comprising 3 to 25 weight % silicon.
CN201380043494.5A 2012-08-16 2013-08-09 Al Nb B foundry alloy for crystal grain refinement Active CN104583429B (en)

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GBGB1214650.2A GB201214650D0 (en) 2012-08-16 2012-08-16 Master alloys for grain refining
GB1214650.2 2012-08-16
PCT/GB2013/052135 WO2014027184A1 (en) 2012-08-16 2013-08-09 Al-nb-b master alloy for grain refining

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GB201419715D0 (en) * 2014-11-05 2014-12-17 Univ Brunel Grain refiner for magnesium alloys
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CN106591637A (en) * 2017-01-21 2017-04-26 山东建筑大学 Aluminum-niobium-boron intermediate alloy and preparation method thereof
CN109022931B (en) * 2018-08-14 2020-02-21 南京云开合金有限公司 Aluminum-niobium-boron intermediate alloy, and preparation method and application thereof
CN109385542B (en) * 2018-09-17 2020-11-24 上海大学 Preparation method of aluminum-niobium-boron alloy rod for grain refinement
CN113122742A (en) * 2021-04-23 2021-07-16 东北大学 Preparation and use methods of Al-Nb-B intermediate alloy for grain refinement of aluminum/aluminum alloy
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CN115652120B (en) * 2022-12-28 2023-03-10 北京航空航天大学 Method for preparing aluminum-based alloy refined material by two-step method
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