WO2016064430A1 - Ceramic preform and method - Google Patents

Ceramic preform and method Download PDF

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Publication number
WO2016064430A1
WO2016064430A1 PCT/US2014/064624 US2014064624W WO2016064430A1 WO 2016064430 A1 WO2016064430 A1 WO 2016064430A1 US 2014064624 W US2014064624 W US 2014064624W WO 2016064430 A1 WO2016064430 A1 WO 2016064430A1
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WO
WIPO (PCT)
Prior art keywords
ceramic
preform
reinforcing fibers
ceramic preform
matrix composite
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/US2014/064624
Other languages
English (en)
French (fr)
Inventor
Dan T. Moore
Evelyn M. Deliso
Joseph B. Richey
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.)
Intellectual Property Holding Co
Intellectual Property Holdings LLC
Original Assignee
Intellectual Property Holding Co
Intellectual Property Holdings LLC
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 Intellectual Property Holding Co, Intellectual Property Holdings LLC filed Critical Intellectual Property Holding Co
Priority to EP14904605.4A priority Critical patent/EP3209471A4/en
Priority to CN201480084224.3A priority patent/CN107000249A/zh
Priority to JP2017540539A priority patent/JP6672319B2/ja
Publication of WO2016064430A1 publication Critical patent/WO2016064430A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/0081—Casting in, on, or around objects which form part of the product pretreatment of the insert, e.g. for enhancing the bonding between insert and surrounding cast metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/02—Casting in, on, or around objects which form part of the product for making reinforced articles
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/515—Other specific metals
    • C04B41/5155—Aluminium
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/06—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/06—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
    • C22C47/062—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element from wires or filaments only
    • C22C47/068—Aligning wires
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/08—Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
    • C22C47/12—Infiltration or casting under mechanical pressure
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/04—Light metals
    • C22C49/06—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D65/00—Parts or details
    • F16D65/02—Braking members; Mounting thereof
    • F16D65/12—Discs; Drums for disc brakes
    • F16D65/125—Discs; Drums for disc brakes characterised by the material used for the disc body
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D65/00—Parts or details
    • F16D65/02—Braking members; Mounting thereof
    • F16D65/12—Discs; Drums for disc brakes
    • F16D65/125—Discs; Drums for disc brakes characterised by the material used for the disc body
    • F16D65/126—Discs; Drums for disc brakes characterised by the material used for the disc body the material being of low mechanical strength, e.g. carbon, beryllium; Torque transmitting members therefor
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00362—Friction materials, e.g. used as brake linings, anti-skid materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00905—Uses not provided for elsewhere in C04B2111/00 as preforms
    • C04B2111/00913—Uses not provided for elsewhere in C04B2111/00 as preforms as ceramic preforms for the fabrication of metal matrix comp, e.g. cermets
    • C04B2111/00931—Coated or infiltrated preforms, e.g. with molten metal
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/522—Oxidic
    • C04B2235/5228—Silica and alumina, including aluminosilicates, e.g. mullite
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5264—Fibers characterised by the diameter of the fibers
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D65/00—Parts or details
    • F16D65/02—Braking members; Mounting thereof
    • F16D2065/13—Parts or details of discs or drums
    • F16D2065/134—Connection
    • F16D2065/1384—Connection to wheel hub

Definitions

  • a metal matrix composite is generally made by incorporating a reinforcing material into a metal matrix.
  • a MMC may comprise a ceramic preform that is infiltrated with a metal.
  • a MMC generally has properties and physical characteristics different from metal that may be desirable depending on the application.
  • Other methods for manufacturing MMC's for brake rotors are hampered by the high manufacturing and material cost of the product and inferior performance of the reinforced brake rotor at high temperature. There is also a need for a ceramic preform with increased strength to withstand handling for metal infiltration.
  • Vehicles may include drum brakes and/or disc brakes.
  • a drum brake generally comprises a rotating drum-shaped part called a brake drum. Shoes or pads of the drum brake press against the interior surface of the brake drum to cause friction, thereby generating heat, and reduce the rotation of the brake drum.
  • a disc brake generally comprises a rotating brake disc or rotor. Calipers having brake pads that squeeze the exterior and interior of the brake disc to cause friction and reduce the rotation of the brake disc.
  • the present application discloses a ceramic preform, a method of making a ceramic preform, a MMC comprising a ceramic preform, and a method of making a MMC.
  • the method of making a ceramic preform comprises the steps of detangling a mass of reinforcing fibers to separate the
  • the ceramic compound comprises separated strands of reinforcing fibers, ceramic particles, a fugitive porosity generating component, starch, low temperature organic binder, colloidal silica, and water.
  • the ceramic preform comprises a ceramic compound formed as either a disc or a ring for use in a brake disc metal matrix composite.
  • the ceramic compound comprises between about 41 Wt% and about 47 Wt% ceramic particles; between about 9 Wt% and about 15 Wt% alkaline earth aluminosilicate reinforcing fibers having a diameter greater than 3.5 microns; between about 4.5 Wt% and about 5.5 Wt% fugitive porosity generating component; between about 3 Wt% and about 4 Wt% starch; between about 1 .5 Wt% and about 2 Wt% low temperature organic binder; between about 4.5 Wt% and about 1 1 Wt% colloidal silica; and between about 17 Wt% and about 38 Wt% water.
  • the metal matrix composite comprises the ceramic preform infiltrated with a molten high temperature performance aluminum alloy to form the brake disc metal matrix composite.
  • the method of making the metal matrix composite comprises the steps of heating the ceramic preform to a preheat
  • the preheat temperature of the ceramic preform is greater than the temperature of the molten metal.
  • Figure 1 illustrates a method of making a ceramic preform according to an embodiment of the present application.
  • Figure 2 illustrates a method of making a ceramic compound according to an embodiment of the present application.
  • Figures 3A and 3B are top and side cross sectional views, respectively, of a ceramic preform blank from which a ceramic preform ring can be cut according to an embodiment of the present application.
  • Figures 4A and 4B are top and side cross sectional views, respectively, of a ceramic preform according to an embodiment of the present application.
  • Figure 5A is a top view of a metal matrix composite brake disc according to an embodiment of the present application.
  • Figure 5B is a side cross sectional view of the metal matrix composite brake disc of Figure 5A.
  • Figure 6A is a top view of a metal matrix composite brake disc according to an embodiment of the present application.
  • Figure 6B is a side cross sectional view of the metal matrix composite brake disc of Figure 6A.
  • the present application discloses a ceramic preform, a method of making a ceramic preform, a MMC comprising a ceramic preform, and a method of making a MMC.
  • the MMC of the present application is generally less dense, lighter, stronger at higher temperatures and provides a higher wear resistance than certain metal, non- composite materials used for brake drums and brake discs.
  • an aluminum MMC of the present application generally has greater wear resistance and stiffness (i.e., resistance to deformation) than cast iron. As such, the MMC of the present application is useful in applications where high wear resistance, light weight, and strength is beneficial.
  • the MMC of the present application may be formed as a brake drum, brake disc or rotor, or any component thereof for a vehicle.
  • the ceramic preform of the present application may be infiltrated with a metal, such as, for example, aluminum alloys and certain special high temperature aluminum alloys, magnesium, titanium, or copper, and form at least a portion of a brake drum or brake disc.
  • the MMC of the present application generally forms at least a portion of the braking surface of the brake drum or brake disc.
  • the braking surface for the brake drum is generally located on the interior surface of the brake drum that contacts the shoes or pads of the drum brake.
  • the braking surface for the disc brake is generally located on the surfaces of the brake disc that contact the brake pads.
  • the brake drum and brake disc of the present application may be used for virtually any vehicle, including but not limited to, aircraft, trucks, trains, vans, cars, military vehicles, construction vehicles, motorcycles, hybrid vehicles, SUVs, ATVs, and XUVs.
  • the MMC of the present application may be formed as a variety of other items, such as, for example, bearings, pistons, cylinder liners, piston rings, connecting rods, aerospace components, armor, or the like.
  • the MMC brake drums and brake discs of the present application generally have greater wear resistance and less weight than a conventional cast iron brake drums or brake discs.
  • One exemplary method of making a MMC brake drum or brake disc is to insert a ceramic preform of the present application into a direct squeeze-casting machine. Molten metal (e.g., aluminum) is then squeezed under high pressure when the mold halves are closed. The molten metal will infiltrate the porous and/or absorbent ceramic preform and fill the die to produce the MMC brake drum, disc or rotor.
  • molten metal e.g., aluminum
  • One difficulty found in conventional MMC brake drum or disc manufacturing processes is developing a preform with enough strength such that it doesn't break during the handling process, the machining process or when the high pressure molten metal is injected filling the preform and the die.
  • the methods and apparatuses for forming a ceramic preform described in the present application produce a part that is stronger and more dimensionally stable than ceramic preforms made by conventional processes.
  • the ceramic preform of the present application comprises a ceramic compound that has been kneaded, stamped, rolled and formed into a solid disc or a ring-shaped preform.
  • the metal matrix composite of the present application comprises a ceramic preform formed in the shape of a ring.
  • the metal matrix composite may be formed as a brake disc or brake drum and the ceramic preform may form at least a portion of a braking surface of the brake disc.
  • the method of making a ceramic preform results in a porous ceramic preform with a porosity between about 60% and 65% and improved strength for handling of the preform during metal infiltration.
  • the high temperature aluminum alloy is introduced into the preform by direct squeeze-casting.
  • the preform infiltrated portion of the brake rotor makes up the surface of the brake rotor that is compressed by the brake pads on the calipers to stop the vehicle.
  • Figure 1 illustrates an exemplary method 100 of making a ceramic preform according to an embodiment of the present application.
  • the method 100 comprises the steps of fiber detangling; preparation of the ceramic compound; pressing, rolling, and forming the ceramic compound; drying; heat treatment for binder burnout; and heat treatment for inorganic binder setting or sintering of the ceramic compound. These steps are described in greater detail below.
  • the ceramic compound used to make the ceramic preform of the present application may comprise ceramic particles, reinforcing fiber, a fugitive porosity- generating component, starch, organic low temperature binder, colloidal silica suspension, and water. Table 1 below shows typical weight percentages for the components of exemplary ceramic compounds of the present application.
  • the ceramic particles of the compound typically provide the ceramic preform with wear resistance and hardness.
  • the ceramic particles may comprise a variety of materials, such as, for example, silicon carbide, alumina, boron carbide, or combinations or mixtures thereof. In certain embodiments, the ceramic particles comprise 360 grit silicon carbide particles.
  • the reinforcing fiber or whisker of the ceramic compound may include short or long fibers and may comprise a variety of materials, such as, for example, carbon, silicon carbide, metallic, or ceramic fibers, whiskers, or chopped filaments.
  • the carbon fiber may be in the form of chopped carbon tape or carbon nanotubes.
  • the reinforcing fiber of the ceramic compound is an alkaline earth aluminosilicate fiber, such as, for example, those fibers labeled Fiber D and E in Table 2 below.
  • the reinforcing fiber of the ceramic compound may be prepared prior to introducing the fiber into the batch of ceramic compound components (see, e.g., Fiber Detangling step in Figure 1 ).
  • the fiber may be prepared prior to introducing the fiber into the batch.
  • the alkaline earth aluminosilicate refractory fiber is spun from melted high purity mineral ores (e.g., melted in an electric arc furnace).
  • the fiber is often received from the manufacturer interlocked together in clumps (e.g., a clumped matted ball of refractory fiber) and including shot glass beads left over from the melt spinning process.
  • the alkaline earth aluminosilicate fibers used in the compound of the present application may also be of a compositional family that is high in calcia (CaO) and magnesia (MgO) and may not contain shot when received from the manufacturer.
  • the diameters of alkaline earth glass fibers are generally larger than 3.5 microns which is approximately the diameter of typical aluminosilicate glass fibers (see, e.g., Fiber A of Table 2 below).
  • Alkaline earth aluminosilicate glass fibers are also commercially available at cost effective prices making the total cost of the methods described herein commercially attractive.
  • the composition and fiber diameter of several exemplary reinforcing fibers is shown in Table 2 below.
  • the formulations in columns labeled Fiber D and Fiber E of Table 2 are alkaline earth aluminosilicate fibers as discussed above.
  • Table 2 Exemplary Ceramic Fiber Chemical Compositions, wt%
  • the ceramic preform In order for the ceramic preform to be infiltrated with molten metal, it is advantageous to have highly interconnected porosity which creates a continuous pathway for the flow of molten metal.
  • the fugitive porosity-generating component of the ceramic compound permits the ceramic preform to have a highly interconnected porosity.
  • the porosity-generating component is a carbonaceous material that will burnout of the molded ceramic article during heat treatment (see, e.g., Binder Burnout and Sintering steps in Figure 1 ).
  • Exemplary carbonaceous materials include, but are not limited to, graphite, carbon black, graphene or organic materials with a high carbon content such as, for example, walnut shell flour, pecan shell flour, rice hulls, and saw dust.
  • the low temperature organic binder of the ceramic preform compound is methyl cellulose. When methyl cellulose is used, it is generally heat activated. Further, other binders that may be used including, but not limited to, guar gum and Xanthum gum. After molding of the ceramic compound and exposure to a temperature between, for example, about 49 and 60 degrees C (or between about 120 and 140 degrees F), the ceramic preform develops green strength which maintains its shape during handling.
  • the colloidal silica solution of the ceramic compound is generally flocced with a starch, such as, for example, a cationic corn starch, to provide a high
  • the colloidal silica solution includes colloidal silica particles having a negative surface charge.
  • a cationic starch is positively charged such that there is electrostatic attraction for flocculation to occur.
  • This flocced bonding system is used to bond the refractory fibers and particles of the ceramic compound and contributes to the green strength of the ceramic preform.
  • the effects of the flocculation are noticeable with a highly loaded ceramic body and a minimum amount of water present (e.g., between about 15 and 30%).
  • adding a first water amount followed by adding a second water amount with the colloidal silica solution may contribute to the effectiveness of the flocced bonding system.
  • Figure 1 illustrates a method 100 of preparing a preform compound according to an embodiment of the present application.
  • the method 100 begins with a pretreatment step of the fiber that results in detangling of the fiber.
  • a liquid dispersion of bulk fibrous ceramic materials may be separated and de- tangled into individual fibers for introduction into the ceramic compound.
  • alkaline earth aluminosilicate fibers are received from the manufacturer in a tangled and agglomerated mass.
  • One exemplary method of separating the tangled alkaline earth aluminosilicate fibers into the individual fibers involves first placing a given quantity into a vessel and adding an aqueous solution comprised of distilled water and an alkylolamino amide additive at a 1 .0 to 2.5 vol% concentration. The fiber material and solution within the vessel are held in a
  • the contents of the vessel are then gently stirred over a minimum period, for example 18 hours.
  • the additive solution is then decanted or poured off from the vessel leaving the treated fiber material on the bottom and sides of the vessel.
  • the fiber is then washed with water to remove any residual additive solution.
  • the vessel may be backfilled with water such that the settled out ceramic fibers become re-dispersed in the water and not caked on the bottom of the vessel.
  • the washing procedure is performed generally at least five times giving adequate time, typically one hour, for the ceramic fibers to settle out so that the wash water can be decanted without the loss of suspended fibers.
  • Water is added to wet the fiber in an amount needed for a first water addition to the batch (e.g., between about 14 wt% and about 27 wt% of the batch composition) so that it can be added to the other batch constituents as an aqueous washed dispersed fiber suspension.
  • Figure 2 illustrates the steps in the method for preparing the ceramic compound.
  • dry powders such as, for example, the silicon carbide particles, burnout material, starch and organic binder
  • the silicon carbide particles are dry mixed with the walnut shell flour, starch, and methyl cellulose in a tumble mixer or other suitable mixer for a period of time (e.g., approximately 30 minutes).
  • a US Stoneware Roller Mill, Model 755, with an enclosed cylindrical container may be used for this dry tumbling step.
  • the addition of water to the mixture is generally divided into two parts, the first water addition and a second water addition.
  • the first water addition e.g., between about 14 wt% and about 27 wt% of the batch composition
  • a mixer e.g., Hobart Mixer
  • the mixture is mixed for a period of time (e.g., approximately 20 minutes) with a paddle mixer blade. This amount of wet mixing time generally insures that the starch is completely wetted out in the batch.
  • a certain amount of water e.g., between about 3.5 wt% and about 9 wt% of the batch composition
  • a period of time e.g., approximately 1 -2 minutes.
  • the blade on the mixer is changed from a paddle blade to a dough hook.
  • the ceramic compound is mixed for approximately 1 minute with the dough hook kneading the batch.
  • a commercially available equipment such as a kneader/extruder available from Charles Ross & Sons, Inc. can be used to work the batch and to extrude the ceramic compound in a continuous ribbon of desired thickness that is then transported on a conveyor belt for a continuous forming operation.
  • the ceramic compound may be molded to form a brake drum or brake disc preform using a process which generally includes pressing, rolling, and forming the compound as illustrated in Figure 1 .
  • a commercial available kneader/extruder can be used to work the batch and to extrude a cylindrical part that is about 6 inches in diameter.
  • the 6-inch diameter cylindrical part is extruded onto a conveyor belt which moves the extruded part to the pressing step. Pressing increases the diameter and reduces thickness of the ceramic compound, for example from a diameter of approximately 6 inches to a diameter of approximately 10 inches and a height of about one inch.
  • the next step in the method for forming a brake drum or brake disc preform is to roll the ceramic compound.
  • the rolling step removes air pockets from the ceramic compound and contributes to the uniformity of the material.
  • the rolling process further increases the diameter and reduces the height of the ceramic compound, for example to a diameter of approximately 14 inches and a height of about 0.5 inches.
  • the ceramic compound is formed (e.g., by stamping or cutting) into a shape for use in a MMC brake drum or brake disc.
  • a stamp or die is used to form the ceramic compound into a cylindrical, disc, or ring shape.
  • the ceramic compound may be formed as a disc for use as brake disc or rotor preform.
  • Figures 3A and 3B illustrate a disc shaped ceramic compound 300 according to an embodiment of the present application.
  • the disc shaped ceramic preform 300 was made by forming a disc shape of the required dimensions from a ceramic compound.
  • the outer diameter (OD) of the disc shaped preform 300 is between about 9 inches and about 16 inches and the height (H) is between about 1/8 inch and about 2 inches after the compound has been pressed, rolled and stamped.
  • the ceramic compound may also be formed as a ring for use as a brake disc or rotor preform.
  • a stamp or die may be used to stamp or cut a ring- shaped preform from the ceramic compound.
  • Figures 4A and 4B illustrate a ring shaped ceramic compound 400 according to an embodiment of the present application.
  • the ring shaped ceramic preform 400 was made by forming a ring shape of the required dimensions from a ceramic compound.
  • the outer diameter (OD) of the ring shaped preform 300 is between about 9 inches and about 16 inches; the inner diameter (ID) is between about 5 inches and about 12.5 inches; and the height (H) is between about 1/8 inch and about 2 inches.
  • the dimensions of the stamped preforms are generally greater than the desired dimensions by a certain amount (e.g., 2%-4% greater) to make possible the final dimensions needed for the brake drum or brake disc or rotor preform, which is to be infiltrated with molten metal to form the MMC.
  • the over-sized dimensions of the stamped preforms allow for shrinkage of the ceramic compound during further processing steps and machining of the preform to the desired dimensions for metal infiltration of the preform.
  • the ceramic preform goes through the further processing steps of drying, binder burnout, and heat treatment.
  • the ceramic preform is generally dried in the drying oven at a certain temperature (e.g., about 60 degrees C or about 140 degrees F) for a period of time.
  • the length of the oven drying time will often vary based on the water content of the ceramic preform and the size of the part.
  • a ceramic preform is generally considered dry when the weight loss is between about 20 wt% and about 35 wt% due to the removal of water from the part.
  • a low temperature heat treatment is conducted to remove the organics or volatile components from the ceramic preform.
  • these organics include the walnut shell flour, the starch, and the methyl cellulose.
  • the low temperature heat treatment cycle is generally an approximately 1 hour ramp to a certain temperature (e.g., about 260 degrees C or about 500 degrees F) with an approximately two hour hold at about the same temperature.
  • Sintering is a high temperature heat treatment conducted to seal the ceramic bond created by the colloidal silica.
  • the high temperature heat treatment generally has a hold at a certain temperature (e.g., about 985 degrees C or about 1800 degrees F) for approximately two hours.
  • the colloidal silica particles remain in the ceramic preform and the ceramic preform comprises silicon carbide particles, refractory fiber and the silicate bond between the silicon carbide particles and the refractory fibers.
  • the burnout materials, starch, and methyl cellulose are all removed from the porous ceramic preform body after the low and high temperature heat treatments.
  • the ceramic preform can be cut to shape and/or machined to achieve final dimensional requirements for accepting a ceramic preform into a brake drum or disc brake rotor high pressure die-casting mold.
  • a disc shaped ceramic preform was made by stamping a shape of the required dimensions from the ceramic compound.
  • the ceramic compound formulation was made by combining 43.2 wt.% Silicon Carbide 360 grit particles (Washington Mills Carborex 360), 8.6 wt.% alkaline earth aluminosilicate refractory fiber, 7 vol% fiber (Fibrox Technology LP Fibrox 300D), 4.9% walnut shell flour - 100 mesh (Echo-Shell, Inc.), 3.3 wt% flaked cationic corn starch (Wesbond Westar +3), 1 .6 wt% hydroxypropyl methyl cellulose (Dow Chemical MethocelTM A4M), 24.1 wt% of first water addition, 4.1 wt% of second water addition and 10.1 wt% colloidal silica solutions (Wesbond Bindzil® 1440).
  • the concentration of fiber in this ceramic compound is 7 vol%.
  • the fiber detangling of the alkaline earth aluminosilicate fiber was accomplished using an aqueous mixture of 2.105 wt% of an alkylolamino amide (Altana Disperbyk-109) in distilled water.
  • a disc shaped ceramic preform was made by stamping a shape of the required dimensions from the ceramic compound.
  • the ceramic was made by combining 41 .5 wt.% Silicon Carbide 360 grit particles (Washington Mills Carborex 360), 1 1 .8 wt.% alkaline earth aluminosilicate refractory fiber, 10 vol% fiber (Lapinus Rockseal® RS480-Roxul®1000), 4.9% walnut shell flour - 100 mesh (Echo-Shell, Inc.) 3.3 wt% flaked cationic corn starch (Wesbond Westar +3), 1 .7 wt% hydroxypropyl methyl cellulose (Dow Chemical MethocelTM A4M), 23.8 wt% of first water addition, 4.0 wt% of second water addition and 9.0 wt% colloidal silica solutions (Wesbond Bindzil® 1440).
  • the ceramic compound was kneaded, pressed, rolled and stamped for form a preform that was approximately 14 inches in diameter and approximately 1 ⁇ 2 inch thick.
  • the ceramic part was dried, fired for binder burnout, and sintered.
  • the resulting finished part had a weight of approximately 1256 gm and it measured 14.3 inches in diameter and 0.564 inch thick.
  • the composition of the final part was 72.9 wt% silicon carbide, 20.7 wt% alkaline earth aluminosilicate fiber and 6.4 wt% silicate binder.
  • the ceramic preform of the present application may be infiltrated with a metal, such as, for example, aluminum, magnesium, titanium, or copper, to form a MMC of the present application.
  • a metal such as, for example, aluminum, magnesium, titanium, or copper
  • the ceramic preform may be introduced into a die-casting mold for infiltration of metals that are capable of being die cast, such as, for example, aluminum, magnesium, or copper, to form a MMC of the present application.
  • Certain high temperature performance aluminum alloys may be used for infiltration. High temperature performance aluminum alloys have improved elevated temperature tensile and creep properties when compared to 356 or A356 die-casting alloys. These high temperature performance aluminum alloys are often used for common rail diesel cylinder heads.
  • the compositional family is the aluminum/silicon/copper alloys
  • the high temperature performance aluminum alloy comprises
  • a die cast mold generally includes two die parts: a first die part, the lower part or cope, that is generally stationary and coupled to a non-moving platen of the die casting machine and a second die part, the upper part or drag, that is movable relative to the first die part and is generally coupled to a movable platen of the die casting machine.
  • a mold cavity that receives the injected molten metal.
  • the mold cavity is representative of the final product shape with calculated shrink factored in and draft added to aid in part release. In certain embodiments, the amount of shrinkage is between about .07 % and about 2.19%.
  • the cavity also generally includes a nesting area that accepts and locates the ceramic preform within the mold cavity.
  • the molten metal is introduced from above the preform while the two die parts are open.
  • the pre-heated ceramic preform is placed within the mold cavity of the drag portion of the mold.
  • the molten metal is introduced on top of the preform.
  • the two die parts, cope and drag, are closed applying pressure to the part being infiltrated.
  • Molten metal infiltrates the preform during the squeezing process.
  • the preform is generally at a temperature that is higher than the molten metal during the squeeze casting process. If the molten metal hits a preform of a lower temperature than the metal, the metal freezes in contact with the surface of the preform and does not infiltrate.
  • the die parts are typically machined from tool steel with various
  • Heating and cooling circuits may also be added throughout the die parts to aid in attaining and retaining optimum temperatures for the casting process. These circuits may use various fluids to transfer temperatures into or out of predetermined areas of the die and are typically placed close to the mold cavity but do not enter the cavity.
  • the ceramic preform is placed within the mold cavity of the die cast mold.
  • the ceramic preform may be preheated to a certain temperature prior to introduction into the mold cavity.
  • the ceramic preform may be preheated to a temperature that is above the temperature of the molten metal that is being injected into the mold cavity (e.g., aluminum).
  • the ceramic preform is heated to at least 50 degrees F above the temperature of the molten metal that is being injected into the mold cavity. In other embodiments, the ceramic preform is heated to at least 100 degrees F above the temperature of the molten metal that is being injected into the mold cavity.
  • Molten metal is injected into the mold cavity at a low velocity and infiltrates the porous body of the ceramic preform.
  • the velocity of the molten metal is such that the ceramic preform does not deform during injection of the molten metal.
  • the molten metal infiltrates substantially through the entire wall thickness. Further, in certain embodiments, the molten metal infiltrates substantially through a ceramic preform having a wall thickness of 2 inches or less.
  • a 4X4 inch preform was infiltrated with molten metal to form an AI-MMC.
  • the 4X4 inch preform made by the methods described herein and containing 7 vol% Fiber E from Table 2 (Fibrox Fiber) and silicon carbide particles was infiltrated with a high temperature performance aluminum die-casting alloy.
  • the preform temperature was about 1500 °F and the metal temperature was about 1420 °F.
  • the composition of the alloy was 6.83% silicon, 0.125% iron, 3.46% copper, 0.0082% manganese, 0.344% magnesium, 0.129% titanium, 0.1 14% zirconium, 0.1 14% vanadium and a balance of aluminum.
  • the pressure exerted during the squeeze casting on the sample was 12,570 pounds per square inch with a dwell time of 9 seconds.
  • the preform sample was completely infiltrated with metal. The sharp corners of the preform edges of the infiltrated sample were maintained indicating that there was no deformation of the preform during the squeeze casting.
  • Microstructure development of the high temperature alloy was developed with a solution heat treatment at 941 °F (505°C) for five hours followed by a water quench. Subsequently, the preform sat at room temperature in air for 24 hours before an aging heat treatment at 392°F (200°C) for five hours.
  • FIGS 5A and 5B illustrate a MMC brake disc 500 according to an embodiment the present application.
  • the MMC brake disc 500 is formed using a ring shaped ceramic preform 502 having approximately the same shape as the MMC brake disc.
  • Each ceramic preform was infiltrated with a metal (e.g., aluminum) to form the MMC brake disc 500, such as during a direct squeeze die casting process as discussed herein.
  • the ceramic preform 502 and MMC brake disc 500 may be a variety of sizes and shapes for a variety of different vehicles.
  • the MMC brake disc 500 is between about 9 inches and about 16 inches in diameter and between about 1/8 and about 2 inches thick.
  • FIGs 6A and 6B illustrate a MMC brake disc 600 according to an embodiment of the present application.
  • the MMC brake disc comprises a vented and finned brake disc design having a raised center portion or hat 604 and a channel 606 that facilitates cooling of the disc brakes.
  • the MMC brake disc 600 has two reinforced ceramic surfaces formed using two ring shaped ceramic preforms 602 having approximately the same shape as the MMC brake disc. These ceramic surfaces are engaged by the brake calipers for stopping the vehicle. Each ceramic preform 602 was infiltrated with a metal (e.g., aluminum) to form the MMC brake disc 600, such as during a die casting process as discussed herein.
  • a metal e.g., aluminum
  • the ceramic preforms 602 and MMC brake disc 600 may be a variety of sizes and shapes for a variety of different vehicles.
  • the MMC brake disc 600 is between about 9 inches and about 16 inches in diameter and between about 1 inch and about 2.0 inches thick.
  • the strength of the ceramic preform facilitates the handling that is required to prepare the ceramic preform for placement in the die-casting mold.
  • the ceramic preform disclosed herein have improved strength over similar type preforms made using a different forming method.
  • the ceramic preform formulation was made by combining 43.2 wt.% Silicon Carbide 360 grit particles; 8.6 wt.% Fiber D, an alkaline earth aluminosilicate refractory fiber with a fiber diameter of approximately 5.5 micron; 4.9% walnut shell flour - 100 mesh; 3.3 wt% flaked cationic corn starch 1 .6 wt%
  • hydroxypropyl methyl cellulose 24.1 wt% of first water addition; 4.1 wt% of second water addition; and 10.1 wt% colloidal silica solutions.
  • concentration of fiber in this ceramic compound is 7 vol%.
  • the fiber detangling of the alkaline earth aluminosilicate fiber was accomplished using an aqueous mixture of 2.105 wt% of an alkylolamino amide in distilled water.
  • the ceramic preform formulation was made by combining 43.2 wt.% Silicon Carbide 360 grit particles; 8.6 wt.% Fiber E, an alkaline earth aluminosilicate refractory fiber with a fiber diameter of 5-6 microns by population; 4.9% walnut shell flour - 100 mesh; 3.3 wt% flaked cationic corn starch; 1 .6 wt% hydroxypropyl methyl cellulose; 24.1 wt% of first water addition; 4.1 wt% of second water addition; and 10.1 wt% colloidal silica solutions.
  • the concentration of fiber in this ceramic compound is 7 vol%.
  • the fiber detangling of the alkaline earth aluminosilicate fiber was accomplished using an aqueous mixture of 2.0 wt% of an alkylolamino amide in distilled water.
  • the ceramic preform formulation was made by combining 41 .5 wt.% Silicon Carbide 360 grit particles; 1 1 .8 wt.% Fiber D, an alkaline earth aluminosilicate refractory fiber with a fiber diameter of approximately 5.5 micron; 4.9% walnut shell flour - 100 mesh; 3.3 wt% flaked cationic corn starch; 1 .7 wt%
  • the concentration of fiber in this ceramic compound is 10 vol%.
  • the fiber detangling of the alkaline earth aluminosilicate fiber was accomplished using an aqueous mixture of 2.0 wt% of an alkylolamino amide in distilled water.
  • the ceramic preform formulation was made by combining 41 .5 wt.% Silicon Carbide 360 grit particles; 1 1 .8 wt.% Fiber E, an alkaline earth aluminosilicate refractory fiber with a fiber diameter of 5-6 microns by population; 4.9% walnut shell flour - 100 mesh; 3.3 wt% flaked cationic corn starch; 1 .7 wt%
  • the concentration of fiber in this ceramic compound is 10 vol%.
  • the fiber detangling of the alkaline earth aluminosilicate fiber was accomplished using an aqueous mixture of 2.0 wt% of an alkylolamino amide in distilled water.
  • Preform 1 was a ceramic preform made by combining 47.63 wt% Silicon Carbide 360 grit particles; 9.53 wt% hammermilled and sieved Fiber A, an
  • aluminosilicate refractory fiber with a fiber diameter of 3.5 micron; 5.4 wt% walnut shell flour -100 mesh; 3.63 wt% flaked cationic corn starch; 1 .77 wt% hydroxypropyl methyl cellulose; 1 1 .3 wt.% of first water addition; 9.64 wt% of second water addition; and 1 1 .1 wt% colloidal silica solution.
  • the process for preparing the fiber for introduction into the batch included the steps of hammermilling and sieving the fiber received from the manufacturer. After hammermilling, the fiber included less shot and consisted of clumps that were less than about 6 mm in length.
  • the fiber clumps were then pressed to further break down the clumps.
  • the pressed fiber was then screened (e.g., through a 500 micron wire mesh screen) to remove loose shot (e.g., shot having a diameter greater than 500 microns).
  • the fiber left on top of the screen was then added to the batch of ceramic compound components.
  • the fiber added to the batch after this pre- treatment was in the form of small clumps of fiber that were not fully detangled.
  • Table 3 below shows the bulk density and porosity as measured by ASTM C830 and the compressive strength as measured by ASTM C133 for the five ceramic preforms 1 -5.
  • the compressive strength is measured parallel and perpendicular to the pressing direction of the ceramic preform.
  • the formulations made by the methods disclosed herein and using Fiber D and Fiber E i.e., Preforms 2-5) have increased strength by approximately as much as a factor of four over the formulation using Fiber A.
  • Preforms 2-5 are stronger than Preform 1 due to the well dispersed fibers within the ceramic formulation of Preforms 2-5 having larger fiber diameters than Preform 1 (5-6 microns vs. 3.5 microns).
  • the individually separated larger diameter fibers in Preforms 2-5 is able to create an interlocking structure between the fiber and silicon carbide particles that is very strong. This interlocking strong network is held together by a silicate bond.
  • the pre-treatment of Fiber A is laborious, costly and wasteful as half of the received fiber is used as a raw material in the ceramic formulation.
  • Fiber A includes 50 wt% useable fiber and 50 wt% shot.
  • Shot is unacceptable in a ceramic preform used for a brake disc or rotor, or a brake drum, because when a shot particle is on the braking surface the braking event may be compromised.
  • the aqueous detangling process for the fiber using an alkykolamino amide additive incorporated into the processing of Preforms 2-5 is simple, lends itself to a scaleable manufacturing process, and is cost effective.

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US9714686B2 (en) 2017-07-25
US20160108980A1 (en) 2016-04-21
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