WO2014075194A1 - Additives for improving the castability of aluminum-boron carbide composite material - Google Patents

Additives for improving the castability of aluminum-boron carbide composite material Download PDF

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Publication number
WO2014075194A1
WO2014075194A1 PCT/CA2013/050881 CA2013050881W WO2014075194A1 WO 2014075194 A1 WO2014075194 A1 WO 2014075194A1 CA 2013050881 W CA2013050881 W CA 2013050881W WO 2014075194 A1 WO2014075194 A1 WO 2014075194A1
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WO
WIPO (PCT)
Prior art keywords
composite material
additive
cast
concentration
respect
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.)
Ceased
Application number
PCT/CA2013/050881
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English (en)
French (fr)
Inventor
Joseph Langlais
Neivi Andrade
Jean-Alain Laurin
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.)
Rio Tinto Alcan International Ltd
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Alcan International Ltd Canada
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Alcan International Ltd Canada filed Critical Alcan International Ltd Canada
Priority to EP13854766.6A priority Critical patent/EP2919932B1/en
Priority to AU2013344742A priority patent/AU2013344742C1/en
Priority to CN201380055557.9A priority patent/CN104755194A/zh
Priority to US14/443,964 priority patent/US20150275338A1/en
Priority to CA2890771A priority patent/CA2890771A1/en
Priority to JP2015542126A priority patent/JP6245267B2/ja
Priority to KR1020157010756A priority patent/KR102014330B1/ko
Publication of WO2014075194A1 publication Critical patent/WO2014075194A1/en
Anticipated expiration legal-status Critical
Priority to US16/456,793 priority patent/US20200002792A1/en
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • C22C32/0057Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides based on B4C
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C9/00Moulds or cores; Moulding processes
    • B22C9/22Moulds for peculiarly-shaped castings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00Casting in, on, or around objects which form part of the product
    • B22D19/14Casting in, on, or around objects which form part of the product the objects being filamentary or particulate in form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D2/00Arrangement of indicating or measuring devices, e.g. for temperature or viscosity of the fused mass
    • B22D2/008Arrangement of indicating or measuring devices, e.g. for temperature or viscosity of the fused mass for the viscosity of the molten metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002Castings of light metals
    • B22D21/007Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00Special casting characterised by the nature of the product
    • B22D25/06Special casting characterised by the nature of the product by its physical properties
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • C22C1/1068Making hard metals based on borides, carbides, nitrides, oxides or silicides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/04Light metals
    • C22C49/06Aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments

Definitions

  • the present invention relates to cast aluminum/boron carbide composite metal matrix material having products obtained from a peritectic reaction to increase their fluidity prior to casting.
  • the reaction products are obtained by using additives capable of undergoing a perictectic reaction with the boron of the boron carbide.
  • titanium can be added.
  • reaction products are formed near the interface of the B 4 C particles and the aluminum matrix which "poison" the B 4 C particles.
  • the reaction products are taught to shield the B 4 C particles from the aluminum.
  • the present disclosure provides a cast composite material comprising aluminum, products of a peritectic reaction between an additive and boron as well as dispersed boron carbide particles.
  • the presence of the products of the peritectic reaction maintains the fluidity of the molten composite material, prior to casting, and facilitate castability and shaping of the composite material.
  • the present disclosure provides a cast composite material comprising (i) aluminum, (ii) products of a peritectic reaction between an additive and boron, (iii) dispersed boron carbide particles and (iv) optionally titanium.
  • the additive is selected from the group consisting of chromium, molybdenum, vanadium, niobium, zirconium, strontium, scandium, and any combination thereof.
  • a sample of the composite material has a fluidity, after having been heated, prior to casting, to a temperature of about 700°C for about 120 minutes, corresponding to a cast length of at least 100 mm when measured using a mold having a groove for containing the sample, the groove having a width of about 33 mm, a height of between about 6.5 mm and about 4.0 mm and being downwardly inclined, from an horizontal axis, of about 10°.
  • the cast length of the sample is at least 190 mm.
  • the cast composite material is submitted to holding during a holding time and to casting during a casting time and wherein the holding time and the casting time amounts to 120 minutes.
  • the products of the peritectic reaction are provided by combining a molten aluminum or a molten aluminum alloy with the additive capable of undergoing the peritectic reaction (prior to the incorporation of boron carbide particles).
  • the additive is selected from the group consisting of zirconium, strontium, scandium and any combination thereof.
  • the additive is scandium.
  • the additive is strontium.
  • the additive is zirconium.
  • the concentration (v/v) of the dispersed boron carbide particles is between 4% and 40% with respect to the total volume of the cast composite material.
  • the concentration (w/w) of the additive can be between 0.47% and 8.00% with respect to the total weight of the cast composite material and optionally, the composite material can further comprise titanium at a concentration (w/w) between 0.50% and 4.00% with respect to the total weight of the cast composite material.
  • the concentration (v/v) of the dispersed boron carbide particles is between 4.5% and 18.9% with respect to the total volume of the cast composite material.
  • the concentration (w/w) of the additive can be between 0.38% and 4.00% with respect to the total weight of the cast composite material and, optionally, the cast composite material further comprises titanium at a concentration (w/w) between 0.40% and 2.00% with respect to the total weight of the cast composite material.
  • the concentration (v/v) of the dispersed boron carbide particles is between 19.0% and 28.0% with respect to the total volume of the cast composite material.
  • the concentration (w/w) of the additive can be between 1.68% and 6.00% with respect to the total weight of the cast composite material and, optionally, the cast composite material can further comprise titanium at a concentration (w/w) between 1.80% and 3.00% with respect to the total weight of the cast composite material.
  • the concentration (v/v) of the dispersed boron carbide particles is between 25.0% and 28.0% or between 28.0% and 33.0% with respect to the total volume of the cast composite material.
  • the concentration (w/w) of the additive can be between 0.94% and 4.00% with respect to the total weight of the cast composite material and, optionally, the cast composite material can further comprise titanium at a concentration (w/w) between 1.00% and 2.00% with respect to the total weight of the cast composite material.
  • the present disclosure provides a method of preparing a cast composite material.
  • the method comprises (a) combining (i) a molten aluminum alloy comprising an additive capable of undergoing a peritectic reaction with boron with (ii) a source of boron carbide particles so as to provide a molten composite material comprising products of the peritectic reaction between the additive and boron and dispersed boron carbide particles and (b) casting the molten composite so as to form the cast composite material.
  • the additive is selected from the group consisting of chromium, molybdenum, vanadium, niobium, zirconium, strontium, scandium, and any combination thereof.
  • a sample of the composite material has a fluidity, after having been heated, prior to casting, to a temperature of about 700°C for about 120 minutes, corresponding to a cast length of at least 100 mm when measured using a mold having a groove for containing the sample, the groove having a width of about 33 mm, a height of between about 6.5 mm and about 4.0 mm and being downwardly inclined, from an horizontal axis, of about 10°.
  • the cast length is at least 190 mm.
  • the method further comprises, prior to step (b), holding the molten composite material during a holding time and casting the molten composite during a casting time, wherein the holding time and the casting time amounts to 120 minutes.
  • the method further comprises, prior to step (a), providing the molten aluminum alloy by combining a molten aluminum or a molten aluminum alloy with the additive capable of undergoing the peritectic reaction.
  • step (a) providing the molten aluminum alloy by combining a molten aluminum or a molten aluminum alloy with the additive capable of undergoing the peritectic reaction.
  • the present disclosure provides a method of improving the casting and/or shaping properties of a molten composite material comprising aluminum, products of a peritectic reaction between an additive and boron, and dispersed boron carbide particles.
  • the method comprises combining (i) a molten aluminum alloy comprising the additive capable of undergoing a peritectic reaction with boron with (ii) a source of boron carbide particles so as to provide a molten composite material.
  • the additive is selected from the group consisting of chromium, molybdenum, vanadium, niobium, zirconium, strontium, scandium, and any combination thereof.
  • a sample of the composite material has a fluidity, after having been heated, prior to casting, to a temperature of about 700°C for about 120 minutes, corresponding to a cast length of at least 100 mm when measured using a mold having a groove for containing the sample, the groove having a width of about 33 mm, a height of between about 6.5 mm and about 4.0 mm and being downwardly inclined, from an horizontal axis, of about 10°.
  • the type of additives that can be used, the concentration of the additives, the concentration of the boron carbide particles, the optional presence of titanium in the composite material have been described above and do apply herein.
  • the present disclosure provides a method of facilitating shaping of a molten composite material of a molten composite material comprising aluminum, products of a peritectic reaction between an additive and boron, and dispersed boron carbide particles.
  • the method comprises combining (i) a molten aluminum alloy comprising the additive capable of undergoing a peritectic reaction with boron with (ii) a source of boron carbide particles so as to provide a molten composite material.
  • the additive is selected from the group consisting of chromium, molybdenum, vanadium, niobium, zirconium, strontium, scandium, and any combination thereof.
  • the type of additives that can be used, the concentration of the additives, the concentration of the boron carbide particles, the optional presence of titanium in the composite material have been described above and do apply herein.
  • Figure 1 shows the loss of fluidity of molten aluminum mixture containing different lots of B 4 C powder.
  • Results are shown as fluidity (as measured as a cast length (in mm) of sample measured using a K-mold) in function of holding time in the furnace (in min) for various lots (A to E) of B 4 C powders (30% v/v) added to molten aluminum at an initial temperature of 735°C.
  • Results are shown for lot A containing 3.5% w/w Ti ( ⁇ ), lot B containing 3.5% w/w Ti ( ⁇ ), lot C containing 3.5% w/w Ti (A), lot D containing 3.0% w/w Ti ( ⁇ ) and lot E containing 2.0 % Ti w/w
  • Figure 2 illustrates an embodiment of a K-mold that can be used for determining the cast length of the composite material.
  • A Schematic side elevation view of the lower inclined portion 10 of the K-mold.
  • B Schematic top elevation view of the groove-containing portion 40 of the K-mold.
  • C Schematic cross-sectional view of the groove-containing portion 50 of the K-mold.
  • B 4 C powder of exceptional quality.
  • High quality B 4 C powders have a good granulometric distribution and have a minimum of fine powder-like particles. Generally, only such B 4 C powder may be incorporated in high amounts into the metal matrix.
  • B 4 C powder is not of such good quality, significant losses of fluidity during the holding time of the molten metal, i.e. prior to casting, can be observed.
  • increasing the holding temperature of the molten metal does not compensate for this loss of fluidity because this can favor the reaction between the aluminum and the B 4 C powder thereby further increasing the viscosity (loss of fluidity). In such circumstances, the molten metal behaves as a thixotropic material.
  • Figure 1 shows the loss of fluidity during the holding time of a molten composite, prior to casting.
  • a certain fluidity is required for a certain amount of time for allowing the shaping/casting of the AI-B 4 C mixture.
  • the curves shown in Figure 1 show that the B 4 C powder used in the preparation of the composite material increased the viscosity of the material and failed to meet the fluidity required in industrial settings for subsequent steps (shaping for example), even in the presence of titanium.
  • a cast AI-B 4 C composite material comprising aluminum, products of a peritectic reaction and dispersed boron carbide particles.
  • the composite material is obtained by first combining aluminum (or an aluminum alloy) with an additive (or a combination of additives) capable of undergoing a peritectic reaction with the boron of the boron carbide particles and ultimately provide products of such peritectic reaction in the aluminum or the aluminum alloy. Once the additive has been included in the aluminum (or in the aluminum alloy), boron carbide particles are combined with the aluminum (or the aluminum alloy), thereby causing the peritectic reaction between the additive and the boron.
  • the use of the additive in the aluminum/aluminum alloy (and, ultimately the presence of peritectic reaction products in the composite material) has been shown useful for maintaining the fluidity of the molten composite and as such imparts good castability to a molten composite material.
  • the use of the additive inhibits or slows down the formation of reaction products occurring during holding of the molten composite (such as, for example, the reaction products occurring between Al and B 4 C or between Al and B 4 C).
  • the additives can be used to limit the use of titanium in such composite materials without altering substantially their fluidity.
  • This maintenance in fluidity of the molten composite material can allow for the lengthening of the holding time of the molten mixture in the furnace, for using a lower grade of B 4 C source as well as for facilitating shaping and/or casting of the resulting metal matrix composite(s).
  • the composite material Prior to being casted, the composite material is in a molten state and has a fluidity.
  • the molten composite material has, prior to casting, a fluidity which permits casting in an industrial setting.
  • Such mold currently used and known in the art, measures the length of a sample of the composite material before it solidifies. The length measured with a K-mold is referred to as a cast length.
  • a K-mold that can be used to determine the fluidity of a sample of a molten composite material is shown in Figure 2.
  • a K-mold is usually composed of two engageable portions, a lower inclined portion 010 (as shown in Figure 2A) and a groove-containing portion 040 (as shown in Figures 2B and 2C).
  • the inclined portion 010 is engaged with the groove-containing portion 040.
  • the sample is allowed to cast along the inclined portion 010 and within the groove 040 until it sets.
  • the length covered by the sample is a measure of fluidity and refers to a cast length.
  • the lower inclined portion is usually monolithic and comprises a plane 015 having a smooth surface and being downwardly inclined from an horizontal axis 020 by an angle 030 of about 10°.
  • the plane 015 is for contacting directly the external sides 055 of the groove-containing portion 040 (shown on Figures 2B and 2C) and for providing an angle to the groove of about 10°.
  • the groove-containing portion 040 is a partially hollowed structure defining an enclosable groove 050 for containing the sample of the molten composite (Figure 2B). As shown on Figure 2B, the groove-containing portion has external sides 055 for contacting directly the plane 015 of the inclined portion 010. In the embodiment shown in Figure 2B, the groove 050 contains two different sections: sections 060 and sections 070 (defining a protuberance). In some embodiments, the K-mold comprises at least four sections 070 (e.g., four protuberances) located at a distance of 93 mm, 130 mm, 168 mm and 205 mm from the start of the mold (e.g., the position at which the sample starts contacting the inclined plane 015).
  • Figure 2C shows an enlarged of the enclosable groove 050.
  • the sections 060 have a similar height 061 of about 6.5 mm.
  • the height 061 is constant between the length defined by the external walls 055.
  • the height 061 is measured with respect to the axis 080 defined by the inclined plane 015 (when the groove-containing portion 040 is engaged with the inclined portion 010).
  • the sections 070 also have a similar height 071 of about 4 mm.
  • the height 071 is constant between the length defined by the external walls 055.
  • the height is measured with respect to the axis 080 defined by the inclined plane 015 (when the groove-containing portion 040 is engaged on the inclined portion 010).
  • the cast composite material has a fluidity, preferably prior to casting, corresponding to a cast sample length of at least 100 mm, at least 120 mm, at least 140 mm, at least 160 mm, at least 180 mm, at least 190 mm or at least 200 mm.
  • the sample used for determining the fluidity of the composite material can be heated at a temperature of about 700°C and for about 120 min to reproduce the industrial casting settings.
  • the present disclosure also provides a method of manufacturing a cast composite material.
  • a molten aluminum alloy also referred to as an aluminum-base matrix alloy
  • the additive or a combination of additives capable of undergoing the peritectic reaction
  • a source of boron carbide to provide a molten composite.
  • the fluidity of the molten composite can be maintained at acceptable industrial levels for a longer period of time when compared to a similar molten composite which lacks the additive.
  • the aluminum or the aluminum alloy used is provided in a molten form.
  • the aluminum or the aluminum alloy is preferably heated to its melting temperature prior to its combination with the B 4 C particles.
  • the aluminum alloy comprises (in embodiments consists essentially of and, in further embodiments, consists of) an additive capable of undergoing the peritectic reaction, the remainder being essentially aluminum or an aluminum alloy.
  • Unavoidable or inevitable impurities can also be present in the alloy (for a total of impurities of at most 0.15% w/w).
  • Exemplary aluminum alloys include, but are not limited to, alloys from the 1 1xx series and from the 6xxx series.
  • Ti can be included in the aluminum or the aluminum alloy. In an alternative embodiment, if Ti is present in the aluminum or the molten aluminum alloy, it is considered to be a trace element (e.g. its concentration does not exceed the concentration of inevitable impurities).
  • the composite material comprises between 4% and 40% (v/v) of B 4 C particles and the molarity of the additive (or the combination of additives) in the composite material is between 0.01044 and 0.08351.
  • the combined molarity of the additive (or the combination of additives) and Ti is between 0.01044 and 0.08351.
  • the concentration of the additive in the composite material can be between 0.47% to 15.32%, 0.47% to 8.00%, 0.90% to 8.00%, 0.95% to 8.00%, 1.00% to 8.00% or 1.10% to 8.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the combined concentration of the additive and Ti in the composite can be between 0.47% to 15.32%, 0.47% to 8.00%, 0.90% to 8.00%, 0.95% to 8.00%, 1.00% to 8.00% or 1.10% to 8.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the composite material comprises between 4.5% and 18.9% (v/v) of B 4 C particles and the molarity of the additive (or the combination of additives) in the composite material is between 0.00835 and 0.04175.
  • the combined molarity of the additive (or the combination of additives) and Ti is between 0.00835 and 0.04175.
  • the concentration of the additive in the composite material can be between 0.38% to 7.68%, 0.38% to 4.00%, 0.90% to 4.00%, 0.95% to 4.00%, 1.00% to 4.00% or 1.10% to 4.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the combined concentration of the additive and Ti in the composite can be between 0.38% to 7.68%, 0.38% to 4.00%, 0.90% to 4.00%, 0.90% to 4.00%, 1.00% to 4.00% or 1.10% to 4.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the composite material comprises between 19% and 28% (v/v) of B 4 C particles and the molarity of the additive (or the combination of additives) in the composite material is between 0.03758 and 0.06263.
  • the combined molarity of the additive (or the combination of additives) and Ti is between 0.03758 and 0.06263.
  • the concentration of the additive in the composite material can be between 1.69% to 1 1.51 % or 1.69% to 6.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the combined concentration of the additive and Ti in the composite can be between 1.69% to 1 1.51 % or 1.69% to 6.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the composite material comprises between 25% and 28% (v/v) or between 28% and 33% (v/v) of B 4 C particles and the molarity of the additive (or the combination of additives) in the composite material is between 0.02088 and 0.04175.
  • the combined molarity of the additive (or the combination of additives) and Ti is between 0.02088 and 0.04175.
  • the concentration of the additive in the composite material can be between 0.94% to 7.68%, 0.94% to 4.00%, 0.95% to 4.00%, 1.00% to 4.00% or 1.10% to 4.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the combined concentration of the additive and Ti in the composite can be between 0.94% to 7.68%, 0.94% to 4.00%, 0.95% to 4.00%, 1.00% to 4.00% or 1.10% to 4.00% with respect to the total weight of the composite material (comprising the B 4 C particles).
  • the concentration of the additive is to be understood to include all forms of the additives (including soluble additive, excess additive that comes out of solution as intermetallics or refractory compounds, as well additive included in a B- containing peritectic reaction product).
  • the additive capable of causing the formation of a peritectic reaction's product can be added in any convenient form, including master alloy (for example an AI-10% additive master alloy) or as additive-containing granules or powders.
  • the additive as a form of a powder to wrought alloys (including AAlxxx, AA2xxx, AA3xxx, AA4xxx or AA6xxx) or casting alloys (including AA2xx or AA3xx).
  • the titanium concentration or molarity given in the foregoing description represent titanium in all forms (including soluble Ti, excess Ti coming out of solution as intermetallics or refractory compounds, as well Ti-B compounds).
  • the titanium can be added in any convenient form, including master alloy (for example an AI-10% Ti master alloy) or as titanium containing granules or powders. In some embodiments, it may be advisable to use an AAIxxx alloy containing titanium in the aluminum alloy.
  • a titanium as an aluminum alloy such as, for example, wrought alloys (including AA2xxx, AA3xxx, AA4xxx or AA6xxx), or casting alloys (including AA2xx or AA3xx).
  • the additive capable of causing the formation of a peritectic reaction's product can be zirconium and the aluminum alloy can comprises or contains zirconium.
  • the composite material does not comprise Ti (if present, Ti is considered to be a trace element).
  • Ti can be present in the composite material.
  • zirconium can be provided at a concentration of between about 0.95 to about 7.61 , between about 1.00 to about 7.61 or between about 1.10 to about 7.61 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • Ti when present, it can be provided at a concentration of between about 0.50 to about 4.00, between about 0.90 to about 4.00, between about 0.95 to about 4.00, between about 1.00 to about 4.00 or between about 1.10 to about 4.00 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • zirconium in a composite material comprising between 4.5% and 18.9% (v/v) of B 4 C particles, zirconium can be provided at a concentration of between about 0.76 to about 3.81 , between about 0.90 to about 3.81 , between about 0.95 to about 3.81 , between about 1.00 to about 3.81 or between about 1.10 to about 3.81 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • Ti when it is present, it can be provided at a concentration of between about 0.40 to about 2.00, between about 0.90 to about 2.00, between about 0.95 to about 2.00, between about 1.00 to about 2.00 or between about 1.10 to about 2.00 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weigh.
  • zirconium in a composite material comprising between 19% and 28% (v/v) of B 4 C particles, zirconium can be provided at a concentration of between about 3.43 to about 5.71 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • Ti when it is present, it can be provided at a concentration of between about 1.80 to about 3.00 weight percentage with respect of the composite material's (comprising the B 4 C particles) total weight.
  • zirconium can be provided at a concentration of between about 1.90 to about 3.81 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • titanium when Ti is present, it can be provided at whereas titanium can be provided at a concentration between about 1.00 to about 2.00 or between about 1.10 to about 2.00 weight percentage with respect of the composite material's (comprising the B 4 C particles) total weight.
  • zirconium concentrations given in the foregoing description represent zirconium in all forms (including soluble Zr, excess Zr coming out of solution as intermetallics or refractory compounds, as well Zr-B compounds).
  • the zirconium can be added in any convenient form, including master alloy (for example an AI-10% Zr master alloy) or as zirconium containing granules or powders. In some embodiments, it may be advisable to use an AAlxxx alloy containing zirconium in the aluminum alloy.
  • a zirconium as an aluminum alloy such as, for example, wrought alloys (including AA2xxx, AA3xxx, AA4xxx or AA6xxx), or casting alloys (including AA2xx or AA3xx).
  • the additive capable of causing the formation of a peritectic reaction's product can be strontium and the aluminum alloy can comprises or contains strontium in combination with titanium.
  • strontium can be provided at a concentration of between about 0.91 to about 7.32, between about 0.95 to about 7.32, between about 1.00 to about 7.32 or between about 1.10 to about 7.32 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight
  • titanium can be provided at a concentration of between about 0.50 to about 4.00, between about 0.90 to about 4.00, between about 0.95 to about 4.00, between about 1.00 to about 4.00 or between about 1.10 to about 4.00 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • strontium can be provided at a concentration of between about 0.73 to about 3.66, between about 0.90 to about 3.66, between about 0.95 to about 3.66, between about 1.00 to about 3.66 or between about 1.10 to about 3.66 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight
  • titanium can be provided at a concentration of between about 0.40 to about 2.00, between about 0.90 to about 2.00, between about 0.95 to about 2.00, between about 1.00 to about 2.00 or between about 1.10 to about 2.00 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • strontium can be provided at a concentration of between about 3.29 to about 5.49 weight percentage with respect to the composite material (comprising the B 4 C particles) total weight, whereas titanium can be provided at a concentration between about 1.80 to about 3.00 weight percentage with respect of the composite material's (comprising the B 4 C particles) total weight.
  • strontium can be provided at a concentration of between about 1.83 to about 3.66 weight percentage with respect to the composite material (comprising the B 4 C particles) total weight
  • titanium can be provided at a concentration between about 1.00 to about 2.00 or between about 1.10 to about 2.00 weight percentage with respect of the composite material's (comprising the B 4 C particles) total weight.
  • strontium concentrations given in the foregoing description represent strontium in all forms (including soluble Sr, excess Sr coming out of solution as intermetallics or refractory compounds, as well Sr-B compounds).
  • the strontium can be added in any convenient form, including master alloy (for example an AI-10% Sr master alloy) or as strontium containing granules or powders. In some embodiments, it may be advisable to use an AAIxxx alloy containing strontium in the aluminum alloy.
  • a strontium as an aluminum alloy such as, for example, wrought alloys (including AA2xxx, AA3xxx, AA4xxx or AA6xxx), or casting alloys (including AA2xx or AA3xx).
  • the additive capable of causing the formation of a peritectic reaction's product can be scandium and the aluminum alloy can comprises or contains scandium in combination with titanium.
  • scandium can be provided at a concentration of between about 0.47 to about 3.75, between about 0.90 to about 3.75, between about 1.00 to about 3.75 or between about 1.10 to about 3.75 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight
  • titanium can be provided at a concentration between about 0.50 to about 4.00, between about 0.90 to about 4.00, between about 0.95 to about 4.00, between about 1.00 to about 4.00 or between about 1.10 to about 4.00 with respect to the composite material's (comprising the B 4 C particles) total weight.
  • scandium can be provided at a concentration of between about 0.38 to about 1.88, between about 0.90 to about 1.88, between about 1.00 to about 1.88 or between about 1.10 to about 1.88 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight
  • titanium can be provided at a concentration of between about 0.40 to about 2.00, between about 0.90 to about 2.00, between about 0.95 to about 2.00, between about 1.00 to about 2.00 or between about 1.10 to about 2.00 weight percentage with respect to the composite material's (comprising the B 4 C particles) total weight.
  • scandium can be provided at a concentration of between about 1.69 to about 2.82 weight percentage with respect to the composite material (comprising the B 4 C particles) total weight
  • titanium can be provided at a concentration between about 1.80 to about 3.00 weight percentage with respect of the composite material's (comprising the B 4 C particles) total weight.
  • scandium can be provided at a concentration of between about 0.94 to about 1.88, between about 1.00 to about 1.88 or between about 1.10 to about 3.88 weight percentage with respect to the composite material (comprising the B 4 C particles) total weight
  • titanium can be provided at a concentration between about 1 .00 to about 2.00 or between about 1 .10 to about 2.00 weight percentage with respect of the composite material's (comprising the B 4 C particles) total weight.
  • the scandium concentrations given in the foregoing description represent scandium in all forms (including soluble Sc, excess Sc coming out of solution as intermetallics or refractory compounds, as well Sc-B compounds).
  • the scandium can be added in any convenient form, including master alloy (for example an AI-10% Sc master alloy) or as scandium containing granules or powders. In some embodiments, it may be advisable to use an AAIxxx alloy containing scandium in the aluminum alloy.
  • a scandium as an aluminum alloy such as, for example, wrought alloys (including AA2xxx, AA3xxx, AA4xxx or AA6xxx), or casting alloys (including AA2xx or AA3xx).
  • the additive can be used in the methods described herein to form reaction products with B having an enthalpy of formation which is more negative than the one associated to AIB 2 .
  • B having an enthalpy of formation which is more negative than the one associated to AIB 2 .
  • the reaction product could be a compound such as (Ti,V)B 2 .
  • the formation of such reaction products would stop or reduce the reaction between the aluminum melt containing titanium and the B 4 C particles.
  • the present disclosure thus provides for the addition of additive capable of causing the formation of a peritectic reaction's products as inhibitors of the reaction between the aluminum melt and the B 4 C particles to maintain the fluidity of the composite until the composite is shaped, preferably cast.
  • the additive includes, but is not limited to chromium (Cr), molybdenum (Mo), vanadium (V), niobium (Nb), hafnium (Hf), zirconium (Zr), strontium (Sr), scandium (Sc), tantalum (Ta), tungsten (W) as well as any combination thereof.
  • the additive includes, but is not limited to (Mo), vanadium (V), niobium (Nb), hafnium (Hf), zirconium (Zr), strontium (Sr), scandium (Sc) as well as any combination thereof.
  • the additive includes, but is not limited to zirconium (Zr), strontium (Sr), scandium (Sc) as well as any combination thereof.
  • the additive comprises or consists of Cr.
  • the additive comprises or consists of Mo.
  • the additive comprises or consists of V.
  • the additive comprises or consists of Nb.
  • the additive comprises or consists of Ta.
  • the additive comprises or consists of W.
  • the additive comprises or consists of Hf.
  • the additive comprises or consists of Zr.
  • the additive comprises or consists of Sr.
  • the additive comprises or consists of Sc. In one embodiment, the additive comprises or consists of a combination of Zr and Sc. In another embodiment, the additive comprises or consists of a combination of Zr and Sr. In yet another embodiment, the additive comprises or consists of a combination of Sr and Sc. In yet another embodiment, the additive comprises or consists of a combination of Zr, Sr and Sc.
  • the additive(s), an optionally titanium is (are) added to molten aluminum or to a molten aluminum or a molten aluminum alloy.
  • an aluminum alloy containing titanium can used. In such embodiment, it is not necessary to add the titanium and the additive (or a combination of additives) in a specific order to the aluminum or aluminum alloy.
  • the titanium is first added to the molten aluminum/alloy and then the additive(s) is (are) added.
  • the additive(s) is (are) first added to the molten aluminum/alloy and then the titanium is added.
  • the titanium and the additive(s) are added simultaneously to the molten aluminum/alloy.
  • the molten aluminum alloy is combined with a source of boron carbide (a boron carbide powder (such as a free-flowing powder) for example) to provide a molten composite material comprising dispersed boron carbide particles.
  • a source of boron carbide a boron carbide powder (such as a free-flowing powder) for example
  • the aluminum alloy supplied with the additive and optionally titanium
  • the boron carbide particles are in a solid form and are at least partially in association with the products of the peritectic reaction.
  • the mixing/stirring be carried out in a manner that allows the appropriate wetting of the B 4 C particles in the composite material.
  • the molten composite material due to the presence of the products of the peritectic reaction products, has a fluidity amenable for casting in an industrial setting.
  • Fluidity can be determined by various ways as known by those skilled in the art. In one example, fluidity is measured with a viscometer. In another example, fluidity is assessed by measuring the length of a cast sample in a mold. In order to do so, it is possible to add a quantity of B 4 C powder inside a reactor (capacity of about 35 kg for example) that contains liquid aluminum-based mixture at a specific temperature (about 700°C for example) to which a vacuum is applied.
  • Samples of the mixture of molten metal and B 4 C powder can be obtained at a fixed interval (for example, every 20 minutes) using a step-mold and having a predetermined length.
  • a K- mold step-mold can be used. Fluidity is quantified as the distance achieved/covered by the resulting mixture before its solidification.
  • the K-mold can be a graphite- coated stainless steel step-mould having a sample-receiving chamber or groove having a width of 33 mm (and, in some embodiments, a maximal length of 315 mm) and being inclined at an angle of about 10°.
  • a molten composite material achieving a distance of 100 mm after 120 minutes of holding time in the K-mold described above is considered as having a fair fluidity for direct chilled casting.
  • a molten composite material achieving a distance of 190 mm after 120 minutes of holding time in the K-mold described above is considered as having an excellent fluidity for direct chilled casting.
  • the fluidity of the composite material is 190 mm or more after 120 min.
  • the fluidity of the composite material is of 200 mm or more after 120 minutes.
  • the fluidity of the molten composite is at least 100 mm when measured at a temperature of about 700°C after a holding time of 120 min.
  • the fluidity of the composite material is at least 105 mm, 1 10 mm, 1 15 mm, 120 mm, 125 mm, 130 mm, 135 mm, 140 mm, 145 mm, 150 mm, 155 mm, 160 mm, 165 mm, 170 mm, 175 mm, 180 mm, 181 mm, 182 mm, 183 mm, 184 mm, 185 mm, 186 mm, 187 mm, 188 mm, 189 mm, 190 mm, 191 mm, 192 mm, 193 mm, 194 mm, 195 mm, 196 mm, 197 mm, 198 mm, 199 mm or 200 mm when measured at a temperature of about 700°C after a holding time of 120 min.
  • the fluidity of the molten composite can vary upon holding time and holding temperature.
  • the fluidity of the composite material is not measured upon the mixture of the aluminum alloy and the boron carbide particles, but after the peritectic reaction products have been formed or even molten composite material is held at a specific temperature (e.g. , holding temperature) and for a specific amount of time (e.g. , holding time).
  • the composite material is held at a specific temperature for allowing the material to remain in a molten state.
  • the composite material is held at a minimal holding temperature of equal to or higher than about 660°C, 670°C, 680°C, 690°C, 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C or 800°C.
  • the composite material is held at a maximal holding temperature equal to or lower than about 800°C, 790°C, 780°C, 770°C, 760°C, 750°C, 740°C, 730°C, 720°C, 710°C, 700°C, 690°C, 680°C, 670°C or 660°C.
  • the composite material is held at a temperature ranging between the minimal holding temperature as defined above and the maximal holding temperature as defined above.
  • the composite material is held for a minimal holding time of equal to or higher than about 20 min, 30 min, 40, min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min , 1 10 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min or 200 min.
  • the composite material is held for a maximal holding time equal to or lower than about 200 min, 190 min, 180 min, 170 min, 160 min, 150 min, 140 min, 130 min, 120 min, 1 10 min, 100 min, 90 min, 80 min, 70 min, 60 min, 50 min, 40 min 30 min or 20 min.
  • the specific holding time ranges between the minimal holding time as defined above and the maximal holding time as defined above. In some embodiments, it is contemplated to cast the composite material during a specific casting time.
  • the composite material is casted for a minimal casting time of equal to or higher than about 20 min, 30 min, 40, min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min ,1 10 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min or 200 min.
  • the composite material is casted for a maximal casting time equal to or lower than about 200 min, 190 min, 180 min, 170 min, 160 min, 150 min, 140 min, 130 min, 120 min, 1 10 min, 100 min, 90 min, 80 min, 70 min, 60 min, 50 min, 40 min 30 min or 20 min.
  • the specific castung time ranges between the minimal casting time as defined above and the maximal casting time as defined above.
  • the molten composite is amenable any form of casting (including DC casting of billets or slabs), casting of ingots for future remelting and casting as well as casting into shapes using any convenient form of shape casting.
  • the cast composite can be further processed and is well adapted for further operations such as (a) remelting and casting a shape, (b) extrusion and (c) rolling or (d) forging.
  • the method described herein may be used for the preparation of any shaped aluminum boron carbide composite material, particularly those containing high levels of B 4 C.
  • a lower-grade B 4 C powder in the presence of additive, can be used without altering significantly the fluidity of the molten AI-Ti-B 4 C composite.
  • a primary aluminum metal alloy (AA1100) was melted in a reactor at a temperature of 765°C. Ti was added and then Sr was added. Thereafter, B 4 C particles were injected into the melt. The final concentrations of Ti and Sr were both 1.65 wt%. The final concentration of the B 4 C particles was 28 vol %.
  • a primary aluminum metal alloy (AA1 100) was melted in a reactor at a temperature of 765°C. Zr was added. Thereafter, B 4 C particles were injected into the melt. The final concentration of Zr was 3.8 wt%. The final concentration of the B 4 C particles was 19 vol %.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Mold Materials And Core Materials (AREA)
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PCT/CA2013/050881 2012-11-19 2013-11-19 Additives for improving the castability of aluminum-boron carbide composite material Ceased WO2014075194A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP13854766.6A EP2919932B1 (en) 2012-11-19 2013-11-19 Method of preparing a cast aluminium composite material
AU2013344742A AU2013344742C1 (en) 2012-11-19 2013-11-19 Additives for improving the castability of aluminum-boron carbide composite material
CN201380055557.9A CN104755194A (zh) 2012-11-19 2013-11-19 用于改善铝-碳化硼复合材料的可铸性的添加剂
US14/443,964 US20150275338A1 (en) 2012-11-19 2013-11-19 Additives for improving the castability of aluminum-boron carbide composite material
CA2890771A CA2890771A1 (en) 2012-11-19 2013-11-19 Additives for improving the castability of aluminum-boron carbide composite material
JP2015542126A JP6245267B2 (ja) 2012-11-19 2013-11-19 アルミニウム−炭化ホウ素複合材料の可鍛性を向上させるための添加剤
KR1020157010756A KR102014330B1 (ko) 2012-11-19 2013-11-19 알루미늄-붕소 카바이드 복합 물질의 주조성을 증대시키기 위한 첨가물
US16/456,793 US20200002792A1 (en) 2012-11-19 2019-06-28 Additives for improving the castability of aluminum-boron carbide composite material

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US201261727949P 2012-11-19 2012-11-19
US61/727,949 2012-11-19

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US16/456,793 Continuation US20200002792A1 (en) 2012-11-19 2019-06-28 Additives for improving the castability of aluminum-boron carbide composite material

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EP2919932B1 (en) 2022-03-23
CN111575522A (zh) 2020-08-25
EP2919932A4 (en) 2016-06-15
KR20150101443A (ko) 2015-09-03
CA2890771A1 (en) 2014-05-22
AU2013344742C1 (en) 2017-10-19
AU2013344742A1 (en) 2015-05-14
JP2016502604A (ja) 2016-01-28
AU2013344742A8 (en) 2015-05-21
CN104755194A (zh) 2015-07-01
US20150275338A1 (en) 2015-10-01
JP6245267B2 (ja) 2017-12-13
AU2013344742B2 (en) 2017-03-30
KR102014330B1 (ko) 2019-08-26
EP2919932A1 (en) 2015-09-23
US20200002792A1 (en) 2020-01-02

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