WO2010111701A1 - Moules de carbone destinés à être utilisés dans la fabrication de pièces et moules en verre métallique massif - Google Patents

Moules de carbone destinés à être utilisés dans la fabrication de pièces et moules en verre métallique massif Download PDF

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Publication number
WO2010111701A1
WO2010111701A1 PCT/US2010/029049 US2010029049W WO2010111701A1 WO 2010111701 A1 WO2010111701 A1 WO 2010111701A1 US 2010029049 W US2010029049 W US 2010029049W WO 2010111701 A1 WO2010111701 A1 WO 2010111701A1
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WIPO (PCT)
Prior art keywords
bulk
mold
carbon
metallic glass
master shape
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PCT/US2010/029049
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English (en)
Inventor
Jan Schroers
Golden Kumar
Marc Madou
Rodrigo Martinez-Duarte
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Yale University
Regents Of The University Of California
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Priority to US13/260,537 priority Critical patent/US20120125071A1/en
Publication of WO2010111701A1 publication Critical patent/WO2010111701A1/fr

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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
    • C04B35/515—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
    • C04B35/52—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 carbon, e.g. graphite
    • C04B35/524—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 carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/006—Amorphous articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/007—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of moulds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0017—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor for the production of embossing, cutting or similar devices; for the production of casting means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape

Definitions

  • the current invention is directed to master molds and methods of fabricating bulk metallic glass molds and parts using inexpensive carbon master molds.
  • BMGs Bulk Metallic Glasses
  • MEMS micro-electromechanical-systems
  • NEMS nano-electro-mechanical-systems
  • precision surgery tools watch movement components
  • micro- nanomolds micro-scale applications
  • the BMGs can be thermoplastically formed like plastics.
  • Thermoplastic forming (TPF) takes place in the supercooled liquid region (SCLR) where the viscosity of BMG drops significantly allowing it to flow under small applied pressure.
  • SCLR supercooled liquid region
  • TPF of BMGs has been used for a wide range of applications including net-shape processing, extrusion, synthesis of amorphous metallic foams and blow molding. (See, e.g., Y.
  • TPF of BMGs has the potential to become an alternative to current metal forming techniques used in microforming such as electroplating.
  • a first advantage of TPF of BMGs stems from its Y2:01650
  • BMG molding can be carried out using complex alloys, which are intrinsically superior in strength, corrosion resistance and wear resistance compared to conventional electroplated metals. BMGs are also free of crystalline defects, which result in homogeneous and isotropic parts.
  • LIGA Lithography, Electroplating and Molding from the German /./thographie, Calvanoformung, /t ⁇ formung
  • silicon micromachining can be used to achieve desired mold structures, these techniques are extremely expensive. Additional drawbacks of the LIGA process are limited geometric complexity, inconsistent pattern transfer, and residual stresses in the metal product. Y2:01650
  • the current invention is directed to novel molds and methods for Bulk Metallic Glass (BMG) using carbon templates obtained from pyrolyzed polymeric materials.
  • BMG Bulk Metallic Glass
  • the method for molding the BMG includes patterning a master shape into a pyrolizable material, pyrolyzing the master shape into a carbon mold, thermoplastically forming the bulk-metallic glass material on the carbon mold to form a shaped bulk-metallic glass article.
  • the polymeric material should have the ability to substantially maintain its shape during pyrolysis and the carbon mold should be capable of withstanding the temperatures and pressures necessary to shape the bulk-metallic glass under thermoplastic forming conditions.
  • the molding is performed on a milli, micro or nanoscale.
  • the pyrolizable material is any material that can be pyrolized and can exhibit sufficient strength at molding temperatures such the BMG materials can be shaped.
  • the pyrolizable material is a polymeric material selected from the group consisting of photoresists and organic polymers, and preferably from one of the following SU-8, poly(methyl methacrylate) (PMMA), phenolic resins, polyfurfuryl alcohols, cellulose, polyvinyl chloride and polyimides.
  • the material is polymeric and the patterning includes one of the following processes stamping, casting, machining, CNC machining, electrical discharge machining (EDM), electrochemical machining (ECM), wet bulk machining, milling, ion beam milling), lithography, photolithography, X-ray lithography, Y2:01650
  • gray-scale lithography electron beam lithography (EBL), nanoimprint lithography (NIL) and focused-ion beam (FIB).
  • EBL electron beam lithography
  • NIL nanoimprint lithography
  • FIB focused-ion beam
  • the pyrolizable material may include 2D and 3D patterned biomaterials.
  • the technique further includes inserting a filter between the photolithographic light source and the polymeric material to prevent T-topping in the polymeric master shape.
  • the photolithographic pattern is preferably formed by a high- resolution chromium-on-quartz photomask patterned with an e-beam tool.
  • the master shape comprises a free-standing structure. In one such embodiment, the master shape is formed on a substrate, and the substrate layer in contact with the master shape and the material of the master shape have good coefficient of thermal expansion matching.
  • the substrate layer in contact with the master shape and the master shape are formed of the same material, and preferably the material is a polymeric material such as, for example, SU-8.
  • the substrate layer in contact with the master shape comprises a transparent polymeric film, and preferably the transparent polymeric film is selected from the group consisting of polyimide or polyester.
  • the master shape comprises undercuts and overlays.
  • the master shape is patterned using a process selected from multi-layer photolithography and grayscale lithography.
  • the material is disposed on a substrate during patterning, and the substrate is made from a material selected from the group consisting of silicon, silicon dioxide, silicon nitride, glass, quartz, polyethylene terephthalate, polyimide and the polymeric material. Y2:01650
  • the pyrolizable material is patterned such that the walls of said master shape have a positive slope.
  • the separating process consists of wet immersion, plasma ion etching, reactive ion etching, isotropic etching, mechanical scraping, thermal heating, sonication, and a combination thereof.
  • the bulk-metallic glass is selected from the group consisting of Zr-based, Ti-based, Fe-base, Ni-based and Co-based alloys.
  • the bulk-metallic glass has a supercooled liquid region ( ⁇ Tsc) of at least 3O 0 C.
  • thermoplastically forming includes one of net-shape processing, micro-replication, nano-replication, extrusion, and superplastic forming.
  • a further material the invention comprises shaping another material on the bulk-metallic glass article.
  • the bulk-metallic glass article is a mold
  • the further material is a polymer, metal or bulk-metallic glass having a molding temperature lower than that of the underlying bulk-metallic glass article.
  • the master structure may be only partially pyrolized and the unpyrolized material dissolved resulting in a porous carbon skeleton.
  • the porous carbon skeleton can be infiltrated with the BMG material or can be filled by thermoplastic forming the BMG such that composite materials or BMG foams may be formed.
  • the BMG need not be separated from the underlying carbon mold.
  • the carbon mold or BMG mold are used to form a new polymeric master shape and this new polymeric master shape is pyrolyzed such that the features of the polymeric master shape undergo isometric reduction in Y2:01650
  • this process is repeated until the feature sizes of the polymeric master shape have the desired dimensions.
  • the critical dimensions of the features of the polymeric master shape are less than 100 nm.
  • the invention is also directed to a mold for thermoplastically forming a bulk- metallic glass.
  • the mold comprises a carbonized master shape formed of a material capable of withstanding the temperatures and pressures necessary to shape the bulk-metallic glass under thermoplastic forming conditions.
  • the carbonized master shape is formed from a glass- like-carbon, and the glass-like-carbon is formed by carbonizing a polymeric material selected from the group of photoresists and organic polymers.
  • the master shape comprises undercuts and overlays.
  • the walls of the master shape have a positive slope.
  • the critical dimensions of the features of the carbonized polymeric master shape are less than 100 nm.
  • FIG. 1 provides a flowchart schematic of exemplary master mold fabrication and BMG molding techniques in accordance with the current invention.
  • FIG. 2 provides an image of a detail of a BMG part after plasma and sonication cleaning treatment.
  • FIG. 3 provides a schematic of a process for patterning a polymeric material in accordance with one embodiment of the current invention.
  • FIGs. 4A and 4B provide SEM reproductions comparing the wall roughness between the use of transparency (A) and e-beam patterned photomasks (B) in accordance with the current invention.
  • FIG. 5 provides a schematic of a process for patterning a polymeric material in accordance with another embodiment of the current invention incorporating an optical pathway between the light source and the polymeric film.
  • FIGs. 6A and 6B provide SEM reproductions of the T-topping effect (A) and its elimination by the use of a filter (B) in accordance with the current invention.
  • FIGs. 7A and 7B provide SEM reproductions of negative (A) and positive (B) slope walls on molds fabricated in accordance with the current invention.
  • FIG. 8 provides a series of schematics showing methods of obtaining different wall slopes using positive (A & B) and negative photoresists (C & D) in accordance with the current invention.
  • FIG. 9 provides schematics showing methods of fabricating holding substrates using a two-layer process in accordance with the current invention.
  • FIG. 10 provides schematics showing methods of fabricating free-standing structures using a grayscale lithography process in accordance with the current invention.
  • FIGs. 11 A to 11J provide SEM reproductions of an exemplary fabrication sequence in accordance with the current invention, where A and B show SU-8 molds with holes of 19 (A) and 38 um (B) and gaps of 17 (A) and 7 um (B) fabricated with photolithography on a Si substrate, C and D show carbon molds with holes of 33 (C) and
  • E and F show BMG parts after release from the carbon mold
  • G and H show Y2:01650
  • FIGs. 12A to 12C provide SEM reproductions of BMG parts formed using carbon molds in accordance with an exemplary embodiment of the current invention, where A is the carbon mold obtained from SU-8, and B and C show BMG parts formed in the mold of A by TPF using a Pt-based (B) and Zr-based (C) BMG (the dashed squared focus on the reproduction of fine features of the carbon molds on the BMG part).
  • A is the carbon mold obtained from SU-8
  • B and C show BMG parts formed in the mold of A by TPF using a Pt-based (B) and Zr-based (C) BMG (the dashed squared focus on the reproduction of fine features of the carbon molds on the BMG part).
  • FIGs. 14A to 14D provide SEM reproductions of original polymer molds and the final pyrolized carbon mold in accordance with the current invention using; (A) SU-8, (B) Kapton®,(C) Cirlex® and (D) Silicon as the substrate material.
  • FIGs. 15a and 15b provide images of SU-8 structures fabricated using grayscale lithography in accordance with an exemplary embodiment of the invention.
  • the current invention is directed to novel molds and methods for Bulk Metallic Glass (BMG) molding using carbon templates obtained from pyrolyzed materials that can be used in the shaping of BMGs by Thermoplastic Forming (TPF).
  • the invention employs a Carbon MEMS (C-MEMS) technique to derive molds of different geometries and dimensions. It has been discovered that the resultant carbon structures are stable at very high temperatures and have sufficient mechanical strength to be used as master molds for the thermoplastic forming of BMGs. (For additional details see, Y2:01650
  • BMGs Bulk Metallic Glasses
  • metal alloys which exhibit high strength, large elastic strain limit, and high corrosion resistance owing to their amorphous nature. They are isotropic, homogeneous, and free from any crystalline defects down to atomic scales.
  • Thermoplastic Forming is a shaping process that takes place in the supercooled liquid region (SCLR) of a BMG alloy where the viscosity of BMG drops significantly allowing it to flow under small applied pressure.
  • SCLR supercooled liquid region
  • ⁇ Tsc Supercooled Liquid Region
  • Tx the onset of crystallization
  • T 9 the onset of glass transition
  • Carbon-MicroElectroMechanical Systems (C-MEMS) and Carbon- NanoElectroMechnical Systems (C-NEMS):
  • C-MEMS Carbon-MicroElectroMechanical Systems
  • C-NEMS Carbon- NanoElectroMechnical Systems
  • a precursor such as, for example, a polymeric material.
  • the precursor may be a naturally occurring pattern, or may be a patternable material, such as, for example, a polymer or photoresist.
  • the polymeric material may be patterned using any known technique, for example using a combination of ultra violet (UV)/electron beam (EB) lithography.
  • UV ultra violet
  • EB electron beam
  • TPF of BMGs has been used for a wide range of applications including net-shape processing, extrusion, synthesis of amorphous metallic foams, superplastic forming of sheet material, synthesis of BMG composites and blow molding.
  • Thermoplastic forming takes place in the supercooled liquid region (SCLR) where the viscosity of BMG drops significantly allowing it to flow under small applied pressure.
  • SCLR supercooled liquid region
  • TPF of BMGs offers an economical technology to fabricate BMG parts and mold-inserts with excellent surface and mechanical properties.
  • C-MEMS carbon MEMS
  • C-NEMS NEMS structures with feature sizes ranging from millimeters down to few hundred nanometers can be synthesized by available fabrication techniques followed by pyrolysis.
  • the current invention describes novel master molds and novel methods for Bulk Metallic Glass (BMG) molding using carbon templates obtained from pyrolyzed materials, and preferably from polymeric materials. The following description details exemplary embodiments of the molds and molding methods of the current invention.
  • FIG 1. provides a schematic of an exemplary embodiment of the method for the mass production of high precision, high surface finish parts and molds utilizing TPF of BMG materials in accordance with the current invention.
  • a base material is formed into a desired master shape.
  • this master shape is converted into a carbon structure by pyrolysis.
  • the carbon pattern is then transferred to a BMG by thermoplastic forming process over the carbon mold in a third step.
  • the three dimensional BMG microparts can then be separated from the mold by a Y2:01650
  • the process of the current invention offers an alternate viable technology for precision net-shaping, micromolding, and fabrication of high-aspect ratio BMG structures compared to the expensive LIGA process, which requires a synchrotron source and can only be used for metals that can be electroplated, as shown in step four of FIG. 1
  • the BMG structures after release from the carbon mold, can also be used as precise molds or mold inserts to do further material processing.
  • the BMG structures may themselves be used as a hot embossing template for mass production of polymer parts, or even as a mold for other BMGs with different softening behaviors, i.e., with TPF molding temperatures lower than those required to shape the underlying BMG structure.
  • the BMG molds may be crystallized and used as a mold for the same BMG material. The good mechanical properties of BMGs make them excellent material for mold-inserts.
  • innumerable plastic or BMG copies can be mass-produced with high precision and a relatively low cost using injection molding or hot-embossing technique.
  • Step 1 Shaping the Master
  • step one of the process in accordance with the current invention requires that a material be formed into a desired master shape.
  • a material be formed into a desired master shape.
  • the specific embodiments discussed in this disclosure use a polymeric material, and more particularly, an SU-8 polymer that is shaped by a photolithographic technique, it should be understood that any material or Y2:01650
  • the current invention uses a polymeric material or photoresist such as, for example, SU-8 or poly(methyl methacrylate) (PMMA), or organic polymers, such as, for example, phenolic resins, polyfurfuryl alcohols, cellulose, polyvinyl chloride and polyimides.
  • a polymeric material or photoresist such as, for example, SU-8 or poly(methyl methacrylate) (PMMA)
  • organic polymers such as, for example, phenolic resins, polyfurfuryl alcohols, cellulose, polyvinyl chloride and polyimides.
  • any technique may be used to imprint the desire initial shape onto these materials, including, but not limited to, stamping, casting, machining (such as, CNC machining, electrical discharge machining (EDM), electrochemical machining (ECM), and wet bulk machining), milling (such as focused ion beam milling), lithography based techniques (such as photolithography or X-ray lithography), and Next-Generation Lithography (NGL) techniques (such as electron beam lithography (EBL), nanoimprint lithography (NIL) and focused-ion beam (FIB)).
  • stamping such as, CNC machining, electrical discharge machining (EDM), electrochemical machining (ECM), and wet bulk machining
  • milling such as focused ion beam milling
  • lithography based techniques such as photolithography or X-ray lithography
  • NNL Next-Generation Lithography
  • EBL electron beam lithography
  • NIL nanoimprint lithography
  • FIB focused-ion beam
  • the choice of technique and material is solely dictated by the cost, quality, complexity and final dimensions of the desired carbon mold, and thus the desired BMG part/mold.
  • the cost of obtaining carbon molds for BMGs can be controlled by using inexpensive polymers and patterning techniques such as casting, embossing or even CNC machining.
  • molds with nanometer dimensions could be implemented using NGL techniques, such as, for example, EBL, FIB and NIL.
  • NGL techniques such as, for example, EBL, FIB and NIL.
  • Different techniques could be explored depending on the desired dimension range.
  • Step 2 Conversion of the Master to a Carbon Mold
  • this conversion is the process by which solid residues with a high content of carbon are removed from the underlying patterned material, usually by pyrolysis, in an inert atmosphere.
  • pyrolysis the process by which solid residues with a high content of carbon are removed from the underlying patterned material, usually by pyrolysis, in an inert atmosphere.
  • carbonization is a complex process with many reactions taking place concurrently, including dehydrogenation, condensation, hydrogen transfer and isomerization.
  • pre-carbonization During pre-carbonization (T ⁇ 573 K) molecules of solvent and unreacted monomer are eliminated from the polymer matrix.
  • the carbonization step can be further divided into two stages. From 573 to 773 K, heteroatoms such as oxygen and halogens are eliminated causing a rapid loss of weight, but a minimal volume shrinkage, while a network of conjugated carbon systems is formed [i.e. carbon ribbons are formed). Hydrogen atoms start being eliminated towards the end of this stage.
  • the second stage of carbonization from 773 to 1473 K, completely eliminates hydrogen causing the carbon ribbons to move together.
  • the crumbling of this carbon network causes a significant loss of volume but a minimal change in weight.
  • permeability decreases and density, hardness, Young ' s modulus and electrical conductivity increase.
  • the final step, annealing is carried out at temperatures above 1473 K, to allow the gradual elimination of any structural defects and evolve further impurities.
  • the final pyrolysis temperature determines the degree of carbonization and the residual content of foreign elements. For instance, at T - 1200 K the carbon content of the residue exceeds a mass fraction of 90% in weight, whereas at T - 1600 K more than 99% carbon is found.
  • a typical carbon material obtained through pyrolysis of polymeric materials is glass-like carbon.
  • the properties of this material make it an ideal candidate for mold fabrication. It is impermeable to gases and extremely inert, with a remarkable resistance to chemical attack from strong acids such as nitric, sulfuric, hydrofluoric or chromic and other corrosive agents such as bromine. Moreover, its rates of oxidation in oxygen, carbon dioxide or water vapor are lower than those of any other carbon.
  • Glass- like carbon has a hardness of 6 to 7 on the Mohs ' scale, a value comparable to that of quartz.
  • One additional consequential advantage of using the method of the current invention to form the BMG parts and molds relates to the natural shrinkage that occurs during pyrolysis. It is well-known that during pyrolysis all materials undergo some shrinkage. Different degrees of shrinkage and carbon yield (the ratio of the weight of carbon to the weight of the original material) are obtained during carbonization depending on the precursor used. In the case of photoresists, for example, volume shrinkage varies from 50 to 90%. Although this shrinkage can cause deformation of the Y2:01650
  • one of the shaping techniques discussed above is used to pattern a polymer.
  • This patterned polymer structure is carbonized thereafter resulting in a carbon structure with features having a smaller critical dimension than its polymer precursor and possessing mechanical properties that would allow for its use as a mold/stamp to produce other polymer master shapes.
  • This phenomenon could then be exploited in a repeat fashion to obtain molds having features with ever-smaller critical dimensions.
  • the carbon mold is used to shape a BMG to fabricate a BMG part, foam, composite, or mold-insert.
  • the forming process used is a TPF forming process.
  • the ability to plastically form BMGs in their supercooled liquid region was recognized in the early days of metallic glass research and various terminologies are used, including superplastic forming, thermoplastic forming and hot-forming. (See, e.g., HJ. Leamy, et al., Metallurgical Transactions 3:699 (1972); CA. Pampillo & H.S. Chen, Materials Science and Engineering 13:181 -188 Y2:01650
  • TPF forming An alternative to TPF forming would be infiltration of a porous carbon mold. Such a process would allow for the production of foams and composite materials. In such an embodiment of the invention, the carbon mold would be only partially pyrolized. Y2:01650
  • the non-carbonized material could be dissolved or etched away, which would, in turn, lead to a porous carbon structure. Then a molten BMG could be infiltrated into the porous structure under pressure leading to BMG foams or carbon/BMG composites. In such an embodiment, the BMG material would not need to be separated from the underlying partially pyrolized carbon mold.
  • any suitable BMG material may be used with the carbon molds and molding methods of the instant invention so long as the material is capable of showing a glass transition in a Differential Scanning Calorimetry (DSC) scan at a forming temperature and under forming conditions compatible with the carbon molds described above.
  • DSC Differential Scanning Calorimetry
  • U.S. Pat. Nos. 5,288,344; 5,368,659; 5,618,359; 5,032,196; and 5,735,975, and WIPO Publication No. WO 2004/059019 each of which are incorporated by reference herein disclose families of BMGs having members with properties sufficient for use with the current invention, such as, for example, Zr-based, Ti-based, Mg-based, and Cu- based alloys.
  • compositions based on ferrous metals are compositions based on ferrous metals (Fe, Ni, Co). Examples of such compositions are disclosed in U.S. Pat. No. 6,325,868, (A. lnoue et. at., Appl. Phys. Lett., Volume 71 , p 464 (1997)), (Shen et. at., Mater. Trans., JIM, Volume 42, p 2136 (2001 )), and Japanese patent application 2000126277 (Publ. #0.2001303218 A), incorporated herein by reference. Finally, it is also possible to use bulk amorphous alloys comprising beneficial in-situ crystalline precipitates. One exemplary case is disclosed in (C. C.
  • the BMG materials used should be restricted to those highly processable BMGs with low viscosities and large supercooled liquid regions.
  • One method uses the size of the supercooled liquid region as a proxy for processablity. Under this measurement the feedstock of the BMG has a ⁇ Tsc (supercooled liquid region) of more than about 3O 0 C as determined by DSC Y2:01650
  • Another indirect measure of processability is the critical cooling rate of the material, namely, the rate at which the BMG material must be cooled to maintain its amorphous character. In this invention it is preferred that the BMG have a critical cooling rate of less than about 100°C/sec.
  • Yet another method is the formability characterization method, where the final diameter of a BMG of 0.1 cm 3 , when formed between two parallel platens under a load of 1000 Ib when heated through the supercooled liquid region, has a final diameter d>7 , more preferable d>10 and most preferable d> 12.
  • the BMG materials used in accordance with the current invention have viscosities below 10 8 Pascal-s, more preferably below 10 7 Pascal-s, and even more preferably below 10 6 Pascal-s.
  • preferred materials are those BMGs having a viscosity when heated to within the supercooled liquid temperature region such that a flow stress of less than about 3 MPa may be used to achieve overall lateral strains of at least 100% prior to crystallization.
  • Step 4 Release of the BMG Part/Mold from the Carbon Mold
  • the BMG part is released from the mold and the carbon mold either reused or discarded.
  • Any suitable method for demolding of the BMG parts may be used with the instant invention, such as, for example, sacrificing the mold by wet immersion, plasma or reactive ion etching, isotropic etching, mechanical scraping, thermal heating and sonication, or a Y2:01650
  • the bulk removal of carbon residues from formed BMG parts was implemented with a combination of Inductive Conductive Plasma/Reactive Ion Etching, (ICP/RIE), followed by a sonicated bath in acetone.
  • ICP/RIE Inductive Conductive Plasma/Reactive Ion Etching
  • FIG. 2 An SEM image of the detail of the surface of a BMG part cleaned in accordance with this method is provided in FIG. 2.
  • the final BMG part features only very small amounts of carbon residue on its walls.
  • it is believed such residues are mechanically interlocked and might be a direct consequence of the roughness of the walls of the part.
  • additional techniques can be used to facilitate the release of the BMG parts from the carbon mold, including, for example, the addition of a low-adhesiveness coatings such as polyester or PTFE to the carbon molds in order to facilitate the release of BMG parts after molding, the use of different polymer shaping processes or the use of positive slope mold features (an optional embodiment that will be discussed in greater detail below).
  • a low-adhesiveness coatings such as polyester or PTFE
  • the simplest setup shown schematically in FIG. 3, consists of a UV lamp illuminating the resist-coated substrate through a mask without any lenses between the two.
  • the purpose of the illumination systems is to deliver light with the proper intensity, directionality, spectral characteristics, and uniformity across the substrate, allowing a nearly perfect transfer or printing of the mask image onto the resist in the form of a Y2:01650
  • the first major step towards improving surface roughness of the mold walls is to use high quality masks. It is usually the case in research, especially when under economic restraints, to employ transparency masks for photolithography. These kinds of masks are plastic sheets that have been patterned (printed) with a high- resolution plotter and can be used directly to pattern photoresists.
  • T-topping Another phenomenon that can effect the quality of the molds is T-topping, which is an exaggerated negative slope at the top of the resist structure surface is (see, e.g., del Campo A. and Greiner C 1 J Micromech Microeng 17:R81 -R95 (2007), the disclosure of which is incorporated herein by reference), which can negatively impact photoresists such as SU-8, especially when deriving high aspect ratio structures.
  • the reason behind T-topping is the fact that photoresists strongly absorb certain light wavelengths. For example, SU-8 strongly absorbs light that has a wavelength of less than 350 nm. If using a broadband light source for exposure, as it is usually the case, Y2:01650
  • UV light shorter than 350 nm is strongly absorbed near the surface creating locally more acid that diffuses sideways along the top surface.
  • Selective filtration of the light source can be used to eliminate these undesirable wavelengths.
  • An easy and affordable way to accomplish this is to place a filter in between the light source and the mask, as shown schematically in FIG. 5.
  • suitable filters may be used in the polymeric patterning, such as, for example, by using a 50-100 ⁇ m layer of SU-8 or commercial high pass filters with cut-out wavelength of 360 nm are also available.
  • T-topping shown in FIG. 6A
  • FIG. 6B T-topping
  • FIG. 7A Another improvement to the process is obtained by constraining the wall slope of the patterned molds to greater than 90°, preferably (90-95°) to facilitate demolding.
  • the use of a mold featuring walls with positive slope facilitates the clean release of the part from the mold.
  • FIG. 8C and 8D As shown in these schematics, the result is a negative wall slope that resembles the one obtained by taking diffraction effects into account with positive photoresists (FIG. 8A). These diffusion effects are expected to be responsible for the negative slopes commonly seen in SU-8 walls (see, e.g., FIG. 6A). Accordingly, by implementing back-exposure through a transparent substrate (Fig. 8D), positive wall slopes on the final SU-8 mold can be obtained.
  • Another important refinement of the process includes the fabrication of carbon molds obtained from free-standing single polymeric material structures. Such development, besides reducing the process cost, eliminates stresses at the interface of different materials thus greatly improving carbon mold fidelity to the original designs.
  • traditional photolithography is usually conducted on rigid substrates such as silicon, quartz and glass.
  • CTE coefficient of thermal expansion
  • rigid substrates like silicon, quartz and glass have CTEs on the order of ( ⁇ 10 10 ⁇ 6 /K), which is significantly different from that of an exemplary polymeric material such as SU-8 (50-52 10 ⁇ 6 /K).
  • CTE matching is more profound in the instant invention where it is Y2:01650
  • the substrate material must either get carbonized together with the patterned polymer or get separated from the mold before carbonization, for instance by peeling the polymeric patterns from the substrate.
  • silicon, glass or quartz do not carbonize under a pyrolysis process and provide good adhesion to polymeric photoresists, such as SU-8.
  • the use of transparent films, such as PET provides a flexible substrate which enables the clean release of the polymeric mold from the film at the end of the polymer patterning process and before pyrolysis; a challenging fact when using glass or quartz. If the mold design features structures within structures, a mold for a nut or gear for example, and the goal is to obtain a free-standing polymeric part, a holding substrate must then be fabricated.
  • FIG. 9 Another advantage of the two-layer polymeric process described above (FIG. 9) is that it also allows for the creation of complex molds featuring undercuts and overhangs and can be expanded to n-layers. (For examples, of the complex parts possible using such a technique, see Example 5.)
  • This multi-layer process requires the individual processing of n-layers and the precise alignment of different masks, which might vary with layer, during exposure.
  • a multi-layer photolithographic technique to create such complex parts, the approach can be tedious and lengthy especially if high aspect ratio structures are being fabricated.
  • Alternatives to multi-layer photolithography, such as Grayscale Lithography may also be used with the current invention.
  • Grayscale lithography consists of the sequential exposure of different masks on the same layer and at the same exposure step, i.e., top or back-exposure, or a combination of both, as shown schematically in FIG. 10.
  • Another alternative Grayscale Lithography technique is the variation of light intensity across the SU-8 film to obtain topographies with two or more levels.
  • An affordable and easy way to achieve this is by employing the SF-100 Maskless Lithography System from Intelligent Micro Patterning, LLC.
  • the SF-100 systems are based on the Digital Micromirror Device (DMD) chip from Texas Instruments Inc. (Tl), and rely on the same spatial and temporal light modulation technology used in DLP (Digital Light Processing) projectors and HDTVs (high definition televisions).
  • DMD Digital Micromirror Device
  • Tl Texas Instruments Inc.
  • HDTVs high definition televisions
  • the current invention allows for the manufacture of high precision, high surface finish, and high strength BMG parts, foams, composites, and molds using carbon-based structures, on any desired size scale (milli-, micro- and/or nano-), that themselves are derived directly from easily formed master structures.
  • the use of carbon molds in accordance with the current invention allows for the fabrication of inexpensive parts with almost arbitrary lateral geometry and very high aspect ratios with heights on the millimeter range, which are expensive to obtain via conventional technologies such as silicon lithography or the LIGA process.
  • thermoplastic form BMGs on carbon molds offers a versatile technology for the fabrication of inexpensive BMG parts and molds.
  • process of the current invention enables the use of different materials and systems than those accessible by conventional mold fabrication processes such as LIGA.
  • the carbon molds can withstand high temperatures in the range where conventional polymer-based molds would deform;
  • the non-destructive detachability of the carbon molds means that the molds can be reused multiple times
  • the carbon molds can have high aspect ratios, and can be photolithographically defined down to nano-meter sized features. Y2:01650
  • an organic negative photoresist SU-8 2150 (Microchem) was used as carbon precursor.
  • Traditional photolithography was employed to fabricate SU-8 structures.
  • Materials employed as substrates for the photolithography process included: 1 ) 4 " Si wafer coated with a 5kA layer of SiCh (Noel Technologies), 2) 1.5 mm (0.0590 " ) thick Polyimide-based Cirlex ® , 3) 127 urn (0.005 " ) thick Polyimide (Kapton ® ) film, and 4) 70 urn thick Polyester film (Mc. Master-Carr).
  • a polymer film-holder apparatus was designed in-house and CNC-machined from a 1.78 mm (0.07 " ) thick aluminum sheet (Mc. Master-Carr).
  • Pyrolysis was conducted on a Thermco Mini-Brute MB-71 diffusion furnace featuring a quartz tube. Nitrogen (Praxair) gas was flowed at 2000 seem. AU pyrolysis processes were conducted at 900 0 C. Heating ramp was conducted in two steps. First ramp was from 0 to 300 0 C at 25 °C/min while second ramp was from 300 to 900 0 C at 12°C/min. Furnace was then held at 900 0 C for 1 hour. Cooling ramp was set to 2°C/min.
  • BMG molding was conducted using custom heating plates (top and bottom) installed on a load cell of an lnstron mechanical testing machine to allow a precise control of temperature and applied pressure during experiments. Carbon molds were heated to 430 0 C by the bottom heating plate while a piece of Zr-BMG, an alloy of Zr44TinCuioNiioBe25 also known as Viti b, was placed on the heated mold. After allowing 30 s to equilibrate the temperature of mold and Viti b, the applied load was increased to attain a preset pressure value of 10 MPa. The applied pressure was kept constant for varying time intervals depending on the mold type and features.
  • FIG. 11 Images from an exemplary fabrication sequence for two different BMG geometries are shown in FIG. 11.
  • S U -8 molds with holes of 19 (FIG. 11A) and 38 ⁇ m (FIG. 11 B) and gaps of 17 (FIG. 11A) and 7 ⁇ m (FIG. 11 B) were fabricated with photolithography on a Si substrate.
  • Finished BMG parts are shown in FIGs. 111 and 1 U.
  • the final BMG structure thickness is approximately 15 ⁇ m.
  • using the method and molds of the instant invention it is possible to transfer the underlying pattern with high-fidelity onto the final BMG part.
  • FIG. 12A shows an SEM image of the carbon mold with comb-type structures having spatial features ranging from 20 to 150 ⁇ m and having a depth of about 20 ⁇ m.
  • a Pt-based alloy was thermoplastically formed on the carbon mold at 275°C under 20 MPa.
  • FIG. 12B shows and SEM image of the Pt- based BMG part after releasing from the carbon mold of the instant invention.
  • FIG. 12C provides an SEM image of a Zr- based BMG part formed in the carbon molds of the instant invention. As marked by the dashed-boxes in FIGs. 12A to 12C, the TPF process replicates the wall roughness of the carbon molds on BMGs with excellent fidelity. This example also demonstrates that the molds of the instant invention may be used with different BMG materials. Y2:01650
  • FIG. 13A shows an SEM image of the carbon mold with comb-type structures having spatial features ranging from 20 to 150 ⁇ m and having a depth of about 20 ⁇ m.
  • a Zr-based alloy was thermoplastically formed on the carbon mold at 275°C under 20 MPa.
  • FIG. 13B shows and SEM image of the Zr-based BMG part after releasing from the carbon mold of the instant invention.
  • the Zr-based BMG was formed at 435°C and 20 MPa. In each case, the BMG was released from the carbon mold easily because of low thermal expansion of carbon molds.
  • Wall roughness present in the final BMG parts (dotted circle in FIG. 13B) is believed to be a direct cause of the mask used in the SU-8 photolithography process (a polymer sheet printed with a high definition photoplotter). Such conclusion was derived based on the images obtained in Example 4, below, where wall roughness can be seen as early in the process as in SU-8 molds. In the case of FIGs. 14B to 14D such roughness gets somewhat amplified after pyrolysis as shown in the respective carbon molds. However, as shown in FIG. 14A, the use of SU-8-only free-standing molds does not seem to amplify such roughness. These images do demonstrate that BMG molding is capable of replicating extremely tiny features present on the mold.
  • an important refinement to the process of the current invention includes the fabrication of carbon molds obtained from free-standing SU-8-only structures. Such development, besides reducing processing cost, eliminates stresses at the interface of different materials and greatly improves carbon mold fidelity to the original SU-8 designs. In this example, the formation of free-standing structures using three different substrates was examined.
  • FIG. 14 shows patterns exposed from similar blank disks on the mask and following the same process described above in Examples 1 to 3. The walls of the cylinder are intended to be vertical.
  • FIG. 14A the use of a SU-8 substrate gives the best results (FIG. 14A).
  • FIG. 14B Kapton ® film substrates
  • Cirlex ® a stack of polyimide films, gives the substrate a rigidity that negatively impacts wall vertically (FIG.
  • PET film was selected to be used as peel-off substrate. As mentioned before, the use of PET film allowed for Y2:01650
  • Polyester yielded the less adhesion of all of the materials used as substrates and greatly facilitated the peeling of SU-8 molds.
  • Polyimide and Cirlex ® were not meant to act as release layers, SU-8 molds could also be detached from them. However, such detachment proved to be more difficult than with polyester films and often led to only partial detachment and breakage of SU-8 molds. Detachment was not encountered at any degree on Si/SiO ⁇ substrates. It is important to note however, that PET film should be released after the developing step and not prior.
  • This invention teaches methods and molds that allow for the use of low cost carbon templates to obtain high quality BMG parts. These BMG parts may be the final product or may be used as a further mold for other materials.
  • the fabrication process demonstrated above represents an alternative to electroplating and LIGA.
  • the BMG molding can be carried out using complex alloys, which are intrinsically superior in strength, corrosion resistance and wear resistance compared to conventional electroplated metals. BMGs are also free of crystalline defects and as a consequence are homogeneous and isotropic.
  • the cost of carbon molds for BMGs can be even reduced further by exploring alternative polymers and patterning techniques such as casting, embossing or even CNC machining.
  • the invention will be used for manufacturing high precision, high surface finish, and high strength BMG parts and molds at lower costs departing from carbon-based mi LLi- , micro- and/or nano- structures.
  • This use of carbon molds allows the fabrication of inexpensive parts with almost arbitrary lateral geometry and very high aspect ratios with heights on the millimeter range, which are expensive to obtain via silicon lithography or LIGA process.
  • Possible applications include the use of lower cost BMG parts and molds in MEMS, NEMS, precision tools, precision molds, high precision microcomponents, non-silicon- based microfabrication technology, tool-making, mass production of polymer products, biomedical implants, watch movement components, surface patterning, nanoimprinting, and data storage.

Abstract

L'invention porte sur de nouveaux moules et procédés de moulage de verre métallique massif (VMM) à l'aide de matrices de carbone obtenues à partir de matières pyrolysées. Le procédé emploie la technique des systèmes micro-électro-mécaniques à base de carbone (C-MEMS) pour produire des moules de différentes géométries et dimensions. Les structures de carbone résultantes sont stables aux très hautes températures et ont une résistance mécanique suffisante pour être utilisées en tant que moules-maîtres pour le formage thermoplastique des VMM.
PCT/US2010/029049 2009-03-27 2010-03-29 Moules de carbone destinés à être utilisés dans la fabrication de pièces et moules en verre métallique massif WO2010111701A1 (fr)

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US8858868B2 (en) 2011-08-12 2014-10-14 Crucible Intellectual Property, Llc Temperature regulated vessel
US20150017479A1 (en) * 2012-01-30 2015-01-15 Chung-Ang University Industry-Academic Corporation Foundation Production method for glassy carbon mold
US9004151B2 (en) 2012-09-27 2015-04-14 Apple Inc. Temperature regulated melt crucible for cold chamber die casting
US9314839B2 (en) 2012-07-05 2016-04-19 Apple Inc. Cast core insert out of etchable material
WO2016058644A1 (fr) * 2014-10-16 2016-04-21 European Space Agency Procédé de fabrication de composants de verre métallique massif
US9346099B2 (en) 2012-10-15 2016-05-24 Crucible Intellectual Property, Llc Unevenly spaced induction coil for molten alloy containment
US9445459B2 (en) 2013-07-11 2016-09-13 Crucible Intellectual Property, Llc Slotted shot sleeve for induction melting of material
US9873151B2 (en) 2014-09-26 2018-01-23 Crucible Intellectual Property, Llc Horizontal skull melt shot sleeve
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US20150017479A1 (en) * 2012-01-30 2015-01-15 Chung-Ang University Industry-Academic Corporation Foundation Production method for glassy carbon mold
US9314839B2 (en) 2012-07-05 2016-04-19 Apple Inc. Cast core insert out of etchable material
US9004151B2 (en) 2012-09-27 2015-04-14 Apple Inc. Temperature regulated melt crucible for cold chamber die casting
US9004149B2 (en) 2012-09-27 2015-04-14 Apple Inc. Counter-gravity casting of hollow shapes
US9238266B2 (en) 2012-09-27 2016-01-19 Apple Inc. Cold chamber die casting with melt crucible under vacuum environment
US8701742B2 (en) 2012-09-27 2014-04-22 Apple Inc. Counter-gravity casting of hollow shapes
US8826968B2 (en) 2012-09-27 2014-09-09 Apple Inc. Cold chamber die casting with melt crucible under vacuum environment
US8813813B2 (en) 2012-09-28 2014-08-26 Apple Inc. Continuous amorphous feedstock skull melting
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US9445459B2 (en) 2013-07-11 2016-09-13 Crucible Intellectual Property, Llc Slotted shot sleeve for induction melting of material
US9925583B2 (en) 2013-07-11 2018-03-27 Crucible Intellectual Property, Llc Manifold collar for distributing fluid through a cold crucible
US10857592B2 (en) 2013-07-11 2020-12-08 Crucible Intellectual Property, LLC. Manifold collar for distributing fluid through a cold crucible
US9873151B2 (en) 2014-09-26 2018-01-23 Crucible Intellectual Property, Llc Horizontal skull melt shot sleeve
WO2016058644A1 (fr) * 2014-10-16 2016-04-21 European Space Agency Procédé de fabrication de composants de verre métallique massif
CN110227764A (zh) * 2019-06-11 2019-09-13 深圳大学 一种微模具的制备方法及微模具

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