EP3763842B1 - Verbundmaterial auf goldbasis - Google Patents

Verbundmaterial auf goldbasis Download PDF

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Publication number
EP3763842B1
EP3763842B1 EP19185638.4A EP19185638A EP3763842B1 EP 3763842 B1 EP3763842 B1 EP 3763842B1 EP 19185638 A EP19185638 A EP 19185638A EP 3763842 B1 EP3763842 B1 EP 3763842B1
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EP
European Patent Office
Prior art keywords
composite composition
advantageously
composite
epoxy resin
particles
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Active
Application number
EP19185638.4A
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English (en)
French (fr)
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EP3763842A1 (de
Inventor
Mickael CHABART
Lucie LE BRIS
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Richemont International SA
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Richemont International SA
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Priority to EP19185638.4A priority Critical patent/EP3763842B1/de
Publication of EP3763842A1 publication Critical patent/EP3763842A1/de
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0094—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with organic materials as the main non-metallic constituent, e.g. resin
    • 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
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • 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
    • 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
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • 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
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present invention relates to a composite composition and a composite material based on gold comprising conductive fillers, epoxy and fibers.
  • the field of use of the present invention relates in particular to the manufacture of timepieces, jewelery or jewellery.
  • Composites based on precious metals are commonly used in fields such as watchmaking or jewelry.
  • the properties sought may vary but are generally aesthetic and mechanical.
  • the document US 4,282,174 describes a material comprising metal particles and a thermoplastic polymer of the polyethylene, polystyrene, polymethyl methacrylate or nylon type.
  • a thermoplastic polymer of the polyethylene, polystyrene, polymethyl methacrylate or nylon type The presence of the thermoplastic polymer makes it possible to reduce the density of the composite material. In addition, this material has the advantage of being easily glued.
  • the document EP 2 668 305 discloses a material comprising 3-300 nm metal particles dispersed in an elastomeric silicone resin. Due to its shine and luster properties, this material is used in jewelry in particular.
  • EP 1 918 047 describes the preparation of a material comprising a metal and a thermoplastic polymer, by passage through an extruder. This treatment makes it possible to obtain a homogeneous material having elastic properties.
  • WO 2011/035446 describes a composite material comprising metal nanoparticles of core/shell type and a matrix formed by a polymer loaded with silicate or silica.
  • the purpose of the shell, or coating, of the nanoparticles is to prevent the reaction of the nanoparticles with the matrix during its polymerization.
  • This material has properties of hardness and mechanical resistance.
  • the document WO 2012/119647 describes a material comprising a precious metal and a boron-based ceramic matrix. This type of material has advantages, particularly in terms of hardness and electrical conduction. However, the ceramic matrix remains expensive and delicate to implement. Indeed, this material is prepared by infiltration of the metal at a pressure of 10 to 200 bars.
  • the Applicant has developed a composite material mainly based on gold, relatively light and not requiring a complex preparation process.
  • the present invention relates to a composite material comprising gold particles and an epoxy polymer matrix.
  • This material is electrically conductive, which makes it suitable for plating treatment and/or galvanic surface treatment.
  • the composite composition consists of these four types of components and a hardener. A person skilled in the art will know how to adjust the percentages by weight of the various constituents to reach 100%.
  • the particles may in particular be in the form of flakes or three-dimensional particles, for example spherical particles.
  • the size of the particles corresponds to the largest dimension of the particles, for example the diameter for spherical particles or the length for parallelepipedal or cylindrical or oval particles.
  • epoxy resin hardens by polymerization of monomers and/or prepolymers and/or by crosslinking. After hardening (curing) in the presence of a hardener, it provides hardness properties to the composite material.
  • the composite composition In the absence of hardener, the composite composition is in the form of a paste.
  • the percentages are expressed by weight relative to the weight of the composite composition, advantageously relative to the weight of the composite material, that is to say of the composite composition consisting of the four components above (particles of gold , titanium nitride, epoxy resin, fibers) and a hardener.
  • the dimensions (for example the size or the specific surface) of the particles can be measured according to the conventional techniques used by those skilled in the art, for example by laser granulometry (malvern).
  • the form factor can be determined, the density can also be determined as well as the specific surface by gas pycnometer or by BET, a technology based on Brunauer, Emmett and Teller theory.
  • Grain morphology can be determined by SEM (scanning electron microscopy) and chemical composition by EDX (energy dispersive spectrometry).
  • the gold particles represent at least 75% by weight of the composite composition, advantageously between 75% and 92%.
  • a composite composition or a composite material comprising 75% by weight of gold corresponds to an 18 carat composite.
  • a composite composition or a composite material comprising 92% by weight of gold corresponds to a 22 carat composite.
  • the percentages of the constituents are expressed, without distinction, relative to the weight of the composite composition or of the composite material. However, they advantageously correspond to the percentages of the constituents in the composite material.
  • the gold particles correspond to chemically pure gold particles, i.e. 24 carats. They are advantageously in the form of flakes or spherical particles or oval particles. They can in particular be obtained by chemical reduction of a gold salt or by atomization.
  • Gold flakes correspond to essentially two-dimensional gold particles.
  • the gold particles have a micrometric particle size.
  • the gold particles advantageously the powders of gold flakes, have a specific surface advantageously comprised between 0.22 m 2 /g and 0.35 m 2 /g, more advantageously between 0.26 m 2 /g and 0 .28 m 2 /g.
  • the particles advantageously spherical or parallelepipedal or cylindrical or oval, have an average size advantageously comprised between 1 ⁇ m and 60 ⁇ m, more advantageously between 1 ⁇ m and 50 ⁇ m.
  • size is meant the largest dimension of the particles, the length for oval particles or the diameter for spherical particles.
  • the flakes have an average size advantageously less than or equal to 650 micrometers ( ⁇ 650 ⁇ m), more advantageously between 1 micrometer and 3 micrometers.
  • ⁇ 650 ⁇ m micrometers
  • the size distribution of the gold particles is advantageously relatively narrow.
  • the particle size varies by less than 25%, preferably less than 15%, more preferably less than 10%, relative to the average particle size. These percentages correspond to the maximum difference in size between the largest particles and the smallest particles of gold in the composite composition.
  • the spherical gold particles have a distribution d50 equal to 21.34 ⁇ m and d90 equal to 34.48 ⁇ m.
  • 50%, by weight, of the spherical particles therefore have a size of less than 21.34 ⁇ m while 90%, by weight, of the spherical particles have a size of less than 34.48 ⁇ m.
  • the use of particles having a size of less than 600 nm generates a powder having too large a specific surface, which requires the addition of a larger quantity of resin to maintain a flowability allowing the shaping of the composite composition.
  • particles with a size of less than 600 nm do not make it possible to obtain a composite composition containing at least 75% by weight of gold particles and having satisfactory properties. This results in mechanical properties of the composite material that are markedly lower than those of the composite material according to the invention.
  • Gold particles having a size greater than 600 nm, in particular in the form of gold flakes have the advantage of allowing percolation of gold particles and therefore electrical conduction. This is in particular due to the form factor of the particles which, when it increases, causes the reduction of the percolation threshold and therefore a reduction in the quantity of particles required. This phenomenon is even more present when the gold particles are in the form of flakes, due to their flat shape and narrow size distribution.
  • Titanium Nitride (TiN) particles are electrically conductive fillers.
  • a portion of the gold powder can be replaced by titanium nitride powder in order to have, in the final composition, a proportion of gold greater than or equal to 75% by mass of gold and in order to keep the electrical conductivity of the material thus formed.
  • a proportion of 90% by mass of gold in the final material could be necessary for it to be electrically conductive.
  • Titanium nitride has the advantage of having a golden color, identical or close to that of gold. Titanium nitride powder, on the other hand, has a slightly greener color than gold powder. Also, titanium nitride is a ceramic. As such, titanium nitride provides hardness properties to the composite material, while having a low density, of the order of 5.24 g.cm ⁇ 3 .
  • the titanium nitride particles can advantageously be in powder form.
  • Their average size is advantageously between 0.10 ⁇ m and 3.00 ⁇ m, more advantageously between 1.00 ⁇ m and 3.00 ⁇ m.
  • the size of a particle corresponds to the most important dimension of the section of a particle (sectional view), for example the diameter for spherical particles.
  • the epoxy resin hardens by polymerization of monomers and/or prepolymers and/or by crosslinking in the presence of a hardener.
  • epoxy resin is colorless after curing. In other words, it does not modify the color of the gold particles.
  • the epoxy resin is advantageously poly(bisphenol A-co-epichlorohydrin), more advantageously the chemical compound having CAS number 25068-38-6.
  • the epoxy resin is advantageously crosslinked poly(bisphenol A-co-epichlorohydrin).
  • the epoxy resin may in particular correspond to a formulation marketed under the name Super Sap® CCR Epoxy Resin (from Entropy Resin), EPIKOTE TM Resin MGS LR 385 (from Hexion) or EPIKOTE TM Resin MGS L 235 (from Hexion).
  • the fibers are fibers made of an electrically conductive material, more advantageously carbon fibers, in particular carbon microfibers.
  • the carbon fibers are compatible with the various constituents of the composite material, they are easily integrated within the composite composition or the composite material.
  • the fibers represent between 0.5% and 6.0% by weight of the composite composition (or composite material), more preferably 1.0% and 4.0% by weight.
  • They have an average length advantageously between 100 micrometers and 500 micrometers, more advantageously between 200 micrometers and 250 micrometers.
  • the fibers have an average length of the order of 220 micrometers.
  • the composite composition can also comprise a hardener.
  • the composite material has a ratio, by weight, epoxy resin/hardener advantageously comprised between 100/30 and 100/50, more advantageously between 100/35 and 100/43.
  • the hardener may be a polyamine, advantageously a diamine, preferably polyoxypropylenediamine, advantageously the chemical compound having CAS number 9046-10-0.
  • the hardener may in particular correspond to a formulation marketed under the name Super Sap ® CCS Hardener (from Entropy Resin), Super Sap ® CCF Hardener (from Entropy Resin), EPIKURE TM MGS LH 385 (from Hexion), EPIKURE TM MGS LH 386 (from Hexion) or EPIKURE TM MGS LH 238 (from Hexion).
  • the composite material according to the invention is homogeneous. In other words, its components are evenly distributed within the composite material. Thus, the composite material does not include a concentration gradient of its components. It has a density advantageously between 4.00 g.cm -3 and 7.00 g.cm -3 , more advantageously between 5.00 g.cm -3 and 6.00 g.cm -3 ; the density of gold being equal to 19.30 g.cm -3 .
  • the composite material is in the form of a solid. As already indicated, it comprises a polymer matrix formed by the epoxy resin and the hardener, that is to say a three-dimensional network resulting from the polymerization and/or the crosslinking of the epoxy resin in the presence of the hardener.
  • the composite material advantageously consists of gold particles, titanium nitride particles, fibers and the polymer matrix formed by the epoxy resin and by the hardener. More specifically, the various constituents of the composite material are distributed homogeneously within the polymer matrix.
  • It can be in the form of a finished object or a preform. Thus, when it has been shaped prior to the hardening of the resin, it is a finished article. It can also be in the form of a preform which can be machined, for example a cylinder or a parallelepiped, in particular a block.
  • the composite material according to the invention is electrically conductive.
  • step a) without hardener
  • step b) with hardener
  • steps a) and b) can be carried out by simultaneous addition of all the components of the composite material.
  • the composite composition resulting from step a) is generally in the form of a paste.
  • this composite composition can be homogenized by passing it through a mill, advantageously a three-roll mill, also called a three-roll mill.
  • the formation of the composite composition, with or without a hardener, generally causes the incorporation of air bubbles into the paste.
  • the method can comprise a gas elimination step.
  • This step can advantageously be carried out using a centrifuge or a planetary centrifuge/mixer with a partial vacuum. It can be carried out before step b) and/or before step c) and/or simultaneously with step c).
  • step a) and/or b) The preparation of the composite composition (step a) and/or b)) and any treatments (homogenization and elimination of air) are advantageously carried out at a temperature of between 20°C and 25°C. However, the temperature may vary from step to step.
  • Step b) consists in introducing at least one epoxy resin hardener. As already indicated, this hardener allows the polymerization and/or crosslinking of the epoxy resin.
  • the composite composition can be homogenized by a propeller mixer or passage through a mill, advantageously a three-roll mill also called a three-roll mill.
  • step b) Once the composite composition of step b) has been obtained, it can be shaped.
  • the shaping is carried out according to conventional techniques, for example in a mould. It may be a mold making it possible to obtain a finished article or a preform which will subsequently be machined.
  • the mold is placed in a centrifuge, thus simultaneously ensuring the elimination of air and the shaping of the composite material.
  • the centrifugation is advantageously carried out at a temperature between 20°C and 50°C, more advantageously between 25°C and 35°C.
  • the increase in temperature makes it possible to fluidify the composite composition and accelerates the hardening of the epoxy resin.
  • the composite composition can be centrifuged before and/or after step b), that is to say before and/or after the addition of the hardener.
  • Hardening is, at least partially, carried out simultaneously with shaping. Indeed, a pre-hardening can be carried out during shaping. Pre-curing allows manipulation and completion of the curing of the composite material outside the shaping mold.
  • Another method consists in using a planetary mixer, advantageously with a partial vacuum to degas the composite composition which is in the form of a paste.
  • the hardening corresponds to the formation of a matrix polymer by reaction between the epoxy resin and the hardener.
  • step c) The hardening of step c) is advantageously carried out at a temperature between 20°C and 30°C, more advantageously between 25°C and 30°C. Under these conditions, the titanium nitride particles are not ceramized.
  • the present invention also relates to a shaped composite material or a preform that can be machined before forming a finished object.
  • It also relates to an article of watchmaking, jewelery or jewelery comprising the composite material having been hardened. It can be bracelets, earrings, pendants, necklaces, brooches, tie pins, hairpins, belt buckles, buttons, cufflinks, buckles belts, watch cases...
  • the gold particles are flakes having an average size of the order of 5.5 ⁇ m.
  • the titanium nitride particles have an average size between 0.10 micrometers and 3.00 micrometers.
  • the micro carbon fibers have an average length between 100 micrometers and 500 micrometers.
  • Table 1 summarizes the data relating to this composite material, the theoretical density of which is 5.5 g.cm -3 .
  • Table 1 composite material according to the invention gold glitter titanium nitride Carbon microfibers Epoxy resin + hardener Density (g.cm -3 ) 19.30 5.24 2.25 1.15 Percentage by weight 75.00 8.45 4.00 12.55 Volume percentage 21.36 8.87 9.77 60.00
  • This material being electrically conductive, it can then be covered with a plating.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Claims (15)

  1. Verbindung, nach Gewicht bezogen auf das Gewicht der Verbindung, bestehend aus:
    - mindestens 75,00 % Goldpartikel,
    - 2 % bis 10 % Titannitridpartikel
    - 5 % bis 15 % eines Epoxy-Harzes,
    - 0,5 % bis 6,0 % Fasern aus elektrisch leitendem Material, die Goldpartikel haben dabei eine Größe von über 600 nm.
  2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, dass die Verbindung zwischen 75,00 % und 92,00 % Goldpartikel enthält.
  3. Verbindung nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass die Verbindung zwischen 2% und 10%, vorteilhafterweise 6% und 10%, noch besser zwischen 8,00% und 9,00%, Titannitridpartikel enthält.
  4. Verbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Epoxyharz Poly(bisphenol A-co-epichlorohydrin) enthält, vorteilhafterweise die chemische Zusammensetzung mit der Nummer CAS 25068-38-6.
  5. Verbindung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es sich bei den Fasern um Kohlenstoffmikrofasern handelt, vorteilhafterweise Kohlenstoffmikrofasern mit einer durchschnittlichen Länge zwischen 100 Mikrometern und 500 Mikrometern, noch besser zwischen200 Mikrometern und 250 Mikrometern.
  6. Verbindung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Verbindung einen Härter enthält.
  7. Verbindung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Verbindung einen Härter enthält,
    dabei handelt es sich bei dem Härter um ein Polyamin, vorzugsweise ein Diamin, noch besser um Polyoxypropyendiamin.
  8. Verbindung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Verbindung einen Härter enthält und sie ein Verhältnis, nach Gewicht, Epoxyharz/ Härter zwischen 100/30 et 100/50, besser zwischen 100/35 und 100/43 aufweist.
  9. Verbindung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Verbindung zwischen 5 % und 15 % Epoxyharz und Härter enthält, vorteilhafterweise zwischen 10% und 15 %, noch besser zwischen 12 % und 13 %.
  10. Verbundmaterial bestehend aus der Verbindung nach einem der Ansprüche 6 bis 9, wobei das Epoxyharz und der Härter eine Polymermatrix bilden.
  11. Uhr- oder Schmuckartikel, die das Verbundmaterial nach Anspruch 10 enthalten.
  12. Herstellungsverfahren für ein Verbundmaterial, das die folgenden Schritte umfasst:
    a) Herstellung einer Verbindung, bestehend nach Gewicht aus:
    - mindestens 75,00 % Goldpartikel,
    - 2 % bis 10 % Titannitridpartikel ,
    - 5 % bis 15 % eines Epoxy-Harzes,
    - 0,5 % bis 6,0 % Fasern aus elektrisch leitendem Material, die Goldpartikel haben dabei eine Größe über 600 nm,
    b) Zugabe eines Härters in die Verbindung,
    c) Formung der Verbindung und Aushärtung des Epoxyharzes zur Bildung eines Verbundmaterials.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass es einen Schritt der Gasentfernung enthält, wobei dieser Schritt vorteilhafterweise mit einer Zentrifuge oder eines Planetenmischers mit partiellem Vakuum, vor Schritt b) und/ oder vor Schritt c) und/ oder gleichzeitig mit Schritt c) durchgeführt wird.
  14. Verfahren nach einem der Ansprüche 12 bis 13, dadurch gekennzeichnet, dass es einen Schritt der Homogenisierung mittels Durchgang durch einen Walzenbrecher enthält, dieser Schritt wird zwischen Schritt a) und Schritt b) und/oder zwischen Schritt b) und Schritt c) durchgeführt.
  15. Verfahren nach einem der Ansprüche 12 bis 14, dadurch gekennzeichnet, dass die Härtung des Schritts c) während einer Dauer zwischen 15 Minuten und 48 Stunden ausgeführt wird, vorteilhafterweise bei einer Temperatur zwischen 25°C und 30°C.
EP19185638.4A 2019-07-11 2019-07-11 Verbundmaterial auf goldbasis Active EP3763842B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19185638.4A EP3763842B1 (de) 2019-07-11 2019-07-11 Verbundmaterial auf goldbasis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19185638.4A EP3763842B1 (de) 2019-07-11 2019-07-11 Verbundmaterial auf goldbasis

Publications (2)

Publication Number Publication Date
EP3763842A1 EP3763842A1 (de) 2021-01-13
EP3763842B1 true EP3763842B1 (de) 2022-09-07

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1599399A (en) 1977-05-13 1981-09-30 Johnson Matthey Co Ltd Production of metallic articles
DE602007001180D1 (de) 2007-04-13 2009-07-09 Lorenzo Brunetti Verfahren zur Herstellung einer Legierung für Ziergegenstände und Legierung für Ziergegenstände, die insbesondere mit diesem Verfahren hergestellt werden kann
EP2305756A1 (de) 2009-09-22 2011-04-06 Rolex Sa Farbiges Verbundmaterial, das Nanopartikel enthält
AU2010333929A1 (en) * 2009-12-01 2012-05-24 Applied Nanostructured Solutions, Llc Metal matrix composite materials containing carbon nanotube-infused fiber materials and methods for production thereof
CH704429B1 (it) 2011-01-26 2016-03-31 Ecometal Sa Materiale composito per la realizzazione di articoli ornamentali e procedimento per la realizzazione di un articolo ornamentale.
EP2683841B1 (de) 2011-03-08 2019-10-30 Hublot Sa Verbundmaterial mit einem edelmetall, herstellungsverfahren und verwendung eines derartigen materials
TWI558826B (zh) * 2013-06-10 2016-11-21 蘋果公司 用於形成金金屬基質複合材料之方法及裝置

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