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WO2010115919A1 - Procédé de fabrication de corps creux renfermant des particules pouvant se déplacer librement - Google Patents

Procédé de fabrication de corps creux renfermant des particules pouvant se déplacer librement Download PDF

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Publication number
WO2010115919A1
WO2010115919A1 PCT/EP2010/054580 EP2010054580W WO2010115919A1 WO 2010115919 A1 WO2010115919 A1 WO 2010115919A1 EP 2010054580 W EP2010054580 W EP 2010054580W WO 2010115919 A1 WO2010115919 A1 WO 2010115919A1
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WO
WIPO (PCT)
Prior art keywords
particles
cores
coated
polymer
dispersed
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/EP2010/054580
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German (de)
English (en)
Inventor
Ingo Bellin
Julien Courtois
Jan Kurt Walter Sandler
Klaus Hahn
Christoffer Kieburg
Norbert Wagner
Ketan Joshi
Alexander Traut
Bernd Kieback
Günther STEPHANI
Ulrike Jehring
Peter Quadbeck
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO2010115919A1 publication Critical patent/WO2010115919A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G10—MUSICAL INSTRUMENTS; ACOUSTICS
    • G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
    • G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/162—Selection of materials
    • G10K11/165—Particles in a matrix

Definitions

  • the invention relates to a method for producing hollow bodies with enclosed in the hollow body, freely moving particles.
  • hollow bodies with trapped, freely movable particles serve as sound-absorbing structures, in particular for applications in which structure-borne noise occurs and requires damping.
  • a coating formed from at least two individual layers formed one above the other is applied to a core of an organic substance.
  • solid particles of a substance are contained, which are formed from a material having a higher sintering temperature than particles of a material which are contained in a further applied layer.
  • a heat treatment is carried out, in which first the organic constituents are expelled, the pulverulent particles of the layer, which are formed directly on the core, are released, and the powdery particles of the outer layer are sintered into a shell.
  • the hollow structural elements are used as a loose bed or, after sintering by gluing, soldering or sintering material fit together to form bodies.
  • DE-A 2342948 discloses a method for producing hollow bodies consisting of a cavity enclosing a shell of a ceramic material. For this purpose, moldings of a combustible or heat-decomposable organic material are coated with a green ceramic powder and a binder, and then the coated moldings are heated to 200 to 2000 ° C. to burn or decompose the organic material and burn the binder or decomposes or merges into its own ceramic bond and the ceramic material sinters.
  • EP-A 300 543 describes a method for producing metallic or ceramic hollow spheres by applying a solid layer to a substantially spherical particle of foamed polymer and pyrolyzing the coated polymer core.
  • the particles of foamed polymer preferably of expanded polystyrene, are treated with agitation with an aqueous suspension containing dissolved or suspended binder and metallic and / or ceramic powder particles, the coated and dried particles at 400 to 500 0 C pyrolyzed with movement and at Temperatures of 900 to 1500 0 C sintered under motion.
  • the invention is therefore based on the object to provide a method for producing hollow bodies with trapped, freely movable particles, which is easier to carry out and allows the more convenient production of moldings from interconnected hollow bodies.
  • the object is achieved by a method for producing hollow bodies with freely movable particles enclosed in the hollow body, in which cores of essentially closed-cell polymer foam particles in which particles are dispersed, with a composition containing a sinterable material and a binder coated and the coated cores subjected to a heat treatment in which the polymer and the binder are expelled and the sinterable material sintered into a closed shell.
  • the process according to the invention starts from cores of essentially closed-cell polymer foam particles in which particles are dispersed.
  • substantially closed-cell means that more than 70%, preferably more than 80% of the cells of the individual foam particles are closed-celled (determined, for example, according to ASTM D 2856-87, Method C).
  • the closed-cell polymer foam particles are suitable for coating with the sinterable material and a binder-containing composition due to their liquid-impermeable property.
  • the bulk density p (in g / l) of the cores and the weight fraction x of the dispersed particles satisfy the weight of the cores of the inequality:
  • the weight proportion x of the dispersed particles in the weight of the cores is preferably 0.10 to 0.80, in particular 0.40 to 0.70.
  • the cores are substantially spherical.
  • the cores generally have a diameter (or a length in the direction of the largest spatial extent in the case of non-spherical cores) of 0.5 to 30 mm, in particular 1 to 10 mm.
  • Substantially closed cell polymer foam particles in which particles are dispersed are obtainable, for example, by first preparing an expandable thermoplastic polymer granule by blending an organic blowing agent and filler particles into a polymer melt and granulating the melt. The expandable, thermoplastic polymer granules can then be foamed by means of hot air or steam into foam particles. Such a method is described for example in DE 10 358 786 A1, to which reference is made in full.
  • Suitable polymers include thermoplastic polymers, such as, for example, styrene polymers, polyamides (PA), polyolefins, such as polypropylene (PP), polyethylene (PE) or polyethylene-propylene copolymers, polyacrylates, such as polymethylmethacrylate (PMMA), polycarbonate (PC ), Polyesters, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof. Styrene polymers are particularly preferably used.
  • styrene polymers polyamides (PA), polyolefins, such as polypropylene (PP), polyethylene (PE) or polyethylene-propylene copolymers, polyacrylates, such as polymethylmethacrylate (PMMA), polycarbonate (PC ), Polyesters, such as polyethylene terephthalate (PET) or polybutylene
  • styrene polymers glassy polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or impact polystyrene (A-IPS), styrene- ⁇ -methstyrene copolymers, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN) Acrylonitrile-styrene-acrylic ester (ASA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS), ⁇ -methylstyrene-acrylonitrile (AMSAN) polymers or mixtures thereof or with polyphenylene ether (PPE) used.
  • GPPS glassy polystyrene
  • HIPS impact polystyrene
  • A-IPS anionically polymerized polystyren
  • the blowing agent-containing polymer melt usually contains one or more blowing agents in a homogeneous distribution in a proportion of 2 to 10 wt .-%, preferably 3 to 7 wt .-%, based on the melt.
  • Suitable blowing agents are physical blowing agents, such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane.
  • Expandable styrene polymer pellets (EPS) suitable according to the invention generally have bulk densities of from 590 to 1200 g / l (before foaming), depending on the nature and content of the dispersed particles.
  • the density of the dispersed particles used in the present invention is generally from 1,000 to 20,000 g / l.
  • the particles generally have a higher sintering temperature than the sinterable material, for. B. a higher by at least 100 K sintering temperature.
  • the particles are selected from inorganic materials, e.g. A carbide such as silicon carbide or boron carbide; a nitride, silicon nitride, aluminum nitride, boron nitride or titanium nitride; Silicide and / or aluminide.
  • a carbide such as silicon carbide or boron carbide
  • Silicide and / or aluminide e.g.
  • a carbide such as silicon carbide or boron carbide
  • Particularly preferred particles are oxides, such as Al 2 O 3 (in all modifications, in particular as corundum, boehmite, AIO (OH) or as aluminum hydroxide), ZrO 2 , Y 2 O 3, MgO, ZnO, CdO, SiO 2 , TiO 2 , CeO 2 , Fe 2 O 3 , Fe 3 O 4 , BaTiO 3 , CuO, NiO, CoO, Co 3 O 4 .
  • oxides such as Al 2 O 3 (in all modifications, in particular as corundum, boehmite, AIO (OH) or as aluminum hydroxide), ZrO 2 , Y 2 O 3, MgO, ZnO, CdO, SiO 2 , TiO 2 , CeO 2 , Fe 2 O 3 , Fe 3 O 4 , BaTiO 3 , CuO, NiO, CoO, Co 3 O 4 .
  • These may be, for example, particles which are usually used for the production of glass (eg borosilicate glass, soda lime glass or silica glass), glass ceramics or ceramics (eg based on the oxides SiO 2 , BeO, Al 2 O 3 , ZrO 2 or MgO or the corresponding mixed oxides), or non-oxide ceramics such as silicon nitride, silicon carbide, boron nitride nitrides such as BN, AIN, Si 3 N 4 and Ti 3 N 4 , or boron carbide). It can also be particles that serve as fillers or pigments. Technically important fillers are z. B.
  • glass eg borosilicate glass, soda lime glass or silica glass
  • glass ceramics or ceramics eg based on the oxides SiO 2 , BeO, Al 2 O 3 , ZrO 2 or MgO or the corresponding mixed oxides
  • non-oxide ceramics such as silicon nitrid
  • fillers based on SiO 2 such as quartz, cristobalite, tripolite, novaculite, kieselguhr, silica, fumed silicas, precipitated silicas and silica gels, silicates, such as talc, pyrophyllite, kaolin, mica, muscovite, phlogopite, vermiculite, Wollastonite and perlite, aluminas and titania.
  • Particularly preferred materials for the particles are ZrO 2 , Al 2 O 3 , TiO 2 and SiO 2 or mixtures thereof.
  • the mean size of the dispersed particles is 5 nm to 500 ⁇ m, in particular 0.1 to 50 ⁇ m (measured by analytical ultracentrifuge or dynamic light scattering).
  • dispensing aids may be included.
  • examples are oligomeric polyethylene oxide having an average molecular weight of 200 to 600, stearic acid, stearic acid amide, hydroxystearic acid, fatty alcohols, fatty alcohol sulfonates and block copolymers of ethylene oxide and propylene oxide, and also polyisobutylene.
  • the cores are coated with a composition containing a sinterable material and a binder. The coating of sinterable material and binder can be applied to the cores in various ways.
  • the sinterable material with the binder in the form of a suspension and covers the cores with this suspension for example in a mixer, fluidized bed reactor or granulation.
  • the cores are expediently introduced into a fluidized-bed reactor.
  • the dispersion of the sinterable material in the solution or dispersion of the binder is introduced into the fluidized bed.
  • the temperature of the fluidizing gas is z. B. between 70 and 120 0 C. layer application and drying are generally completed in a period of 5 to 60 minutes.
  • the cores may first be uniformly sprayed with the liquid binder and then powdered on the sinterable material and, if the desired layer thickness is not reached in a single operation, this operation is repeated until the desired coating thickness is obtained.
  • the coated cores are then dried.
  • Suitable sinterable material are metal powders and ceramic powders. It is also conceivable to mix the metal or ceramic powders.
  • the sinterable ceramics may include, for example, nitride, oxide and silicate ceramics and carbides.
  • sinterable ceramic powders are oxidic ceramic powders such as Al 2 O 3, ZrO 2, Y 2 O 3, as well as non-oxide ceramic powders such as SiC or SisISU.
  • the sinterable material is a metal powder.
  • metals which are in powder form are aluminum, iron, in particular iron carbonyl powder, cobalt, copper, nickel, silicon, titanium and tungsten.
  • powdered metal alloys for example, high or low alloyed steels and Metallle- alloys based on aluminum, iron, titanium, copper, nickel, cobalt or tungsten, such. As bronze, to call. Both powder of already finished alloys and the powder mixtures of the individual alloy components can be used.
  • the metal powder, metal alloy powder and Carbonylmetallpulver can also be used in a mixture.
  • carbonyl iron powder is preferable.
  • Carbonyl iron powder is an iron powder produced by thermal decomposition of iron carbonyl compounds. In order to maintain flowability and to prevent agglomeration, it may be coated, for example, with SiC 2 O.
  • the corrosion inhibitor used may preferably be iron phosphide powder.
  • the binder is generally present as a solution or dispersion, preferably in an aqueous medium. As the binder, a variety of polymers can be used.
  • polymers or copolymers from the group of vinyl ester polymers such as polyvinyl acetate, copolymers of vinyl acetate / ethylene, vinyl acetate / ethylene / vinyl chloride, vinyl acetate / acrylic ester, vinyl acetate / maleic di-n-butyl ester, vinyl acetate / vinyl laurate, vinyl acetate / acrylate; partially saponified polyvinyl acetate, polyvinyl alcohol; polybutyral; Polyamides, such as polyvinylpyrrolidone; Polyacrylates, copolymer of styrene / acrylate; Celluloseester; Phenolic resins, amino resins such as urea resins or melamine resins; and epoxy resins used. Simple tests can be used to determine which binder is the most suitable considering the selected powder material and the pyrolysis and sintering conditions given.
  • polyvinyl alcohols and cellulose esters are suitable.
  • the individual cores coated in this way can be subjected to heat treatment as such or cohesively bonded coated cores before the heat treatment in order to obtain shaped bodies.
  • the cores can z. B. are glued together.
  • the bonding can z. Example, by moistening the coated cores with a solvent that dissolves the binder, and then brings the cores together in the desired arrangement.
  • it is possible to provide self-supporting sound-insulating structures which also have a certain degree of mechanical strength and, within certain limits, achieve load-bearing properties.
  • partitions, door elements or floors of vehicles can be obtained in this form with hollow bodies according to the invention.
  • the polymer of the cores and the binder of the coating are expelled.
  • the sinterable material is sintered into a closed shell.
  • the term "expelling" is intended to include upstream decomposition and / or pyrolysis operations.
  • the heat treatment can be carried out in a single-stage or multistage process. Taking into account the binder according to the type and amount and sufficient layer thickness, the dried solid layers have sufficient strength, so that the coated cores can be subjected to a pyrolytic decomposition process, without the shell loses its shape.
  • the binder of the solid layer volatilizes and leaves behind a self-supporting hollow sphere with a porous shell structure.
  • the pyrolysis of the coated foam particles can be carried out in air, inert gas or under reducing conditions, depending on the type of powder used.
  • the heating time to a temperature of about 500 ° C. is up to 3 hours and depends on the type and composition of the polymer used.
  • the pyrolytic treatment which serves both to remove the coated polymer core and to at least partially remove the organic binder, is followed by a sintering process.
  • This sintering process at a temperature of 900 to 1500 0 C is in an oven, for. B. rotary kiln, Krähl- or belt furnace made.
  • the atmosphere in the kiln aggregate can be matched to the powder material used for coating. It can therefore be used in a vacuum, under oxidizing or reducing conditions and under inert gas.
  • inert powders can be easily removed mechanically or chemically from the hollow bodies after the sintering process. They can also act as a supporting shell for the actual hollow sphere during the pyrolysis and sintering process, in particular when the wall thickness of the hollow body is very thin or the actual hollow body powder layer does not yet have sufficient green strength after pyrolysis.
  • Suitable inert powders, depending on the hollow body material are e.g. Carbon, aluminum hydroxide or chalk.
  • the pyrolysis and the sintering process can also be carried out without constant movement of the coated foam particles.
  • the coated foam particles are introduced into a mold with perforated walls and by the action of heat energy (eg about 100 0 C) and optionally by mechanical pressure, the foam particles are "re-foamed", with stronger mold filling and compaction and bonding takes place , After cooling, the mold contents can be removed and handled as a dimensionally stable body. That is, the molded article of good "green strength" can be pyrolyzed without loss of its shape and then sintered.
  • heat energy eg about 100 0 C
  • mechanical pressure optionally by mechanical pressure
  • hollow bodies can also be deformed after the heat treatment, if, for example, a solid combination of structural elements to a sound-absorbing lightweight component is desired.
  • the hollow bodies can form a sound-absorbing structure in the form of a loose bed.
  • hollow bodies produced according to the invention can also be disposed within a Matrix, which is possible, for example, with a suitable hardenable plastic, such as an epoxy resin, or a relatively low-melting metal.
  • the green spheres thus produced were then subjected to a heat treatment under a protective gas atmosphere with a maximum sintering temperature of 1 120 0 C.
  • the organic components were expelled and the spherical shells were consolidated by sintering.
  • the aluminum oxide particles were freely movable in the dense spherical shell.
  • the balls were usable as damping elements.
  • Green spheres which were obtained according to Example 1, were bonded to form bodies by means of an aqueous ethanol solution.
  • the moldings were subjected to a heat treatment as described in Example 1.
  • the aluminum oxide particles were freely movable in the hollow structural elements.
  • the moldings were usable as damping elements.
  • the green spheres thus produced were then subjected to a heat treatment under a protective gas atmosphere with a maximum sintering temperature of 1 120 0 C. Due to the high proportion of the polymer to be pyrolyzed, a mechanical rupture of the coating occurred.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Acoustics & Sound (AREA)
  • Multimedia (AREA)
  • Powder Metallurgy (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de fabrication de corps creux renfermant des particules pouvant se déplacer librement. Le procédé consiste à revêtir des noyaux composés de particules de mousse polymère à cellules essentiellement fermées, dans lesquelles des particules sont dispersées, au moyen d'une composition contenant un matériau frittable et un liant. Les noyaux revêtus sont soumis à un traitement thermique au cours duquel le polymère et le liant sont expulsés et le matériau frittable est fritté sous forme de coquille fermée.
PCT/EP2010/054580 2009-04-07 2010-04-07 Procédé de fabrication de corps creux renfermant des particules pouvant se déplacer librement Ceased WO2010115919A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09157551 2009-04-07
EP09157551.4 2009-04-07

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WO2010115919A1 true WO2010115919A1 (fr) 2010-10-14

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2636658A3 (fr) * 2012-03-07 2014-05-07 Manfred Jaeckel Procédé de fabrication d'un corps céramique à pores ouverts
US9080259B2 (en) 2009-06-30 2015-07-14 Basf Se Polyamide fibers with dyeable particles and production thereof
US9181136B2 (en) 2010-01-19 2015-11-10 Basf Se Method for producing hollow bodies having enclosed freely displaceable particles
US11179694B2 (en) 2017-09-11 2021-11-23 Basf Se Method of forming porous metal oxide microspheres
US11185835B2 (en) 2017-09-11 2021-11-30 Basf Se Method of forming porous metal oxide microspheres using polydisperse polymer nanospheres

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2342948A1 (de) 1973-08-25 1975-03-27 Rauschert Kg P Verfahren zur herstellung von keramikmaterialhohlkoerpern und deren verwendung
EP0300543A1 (fr) 1987-07-22 1989-01-25 Norddeutsche Affinerie Ag Procédé de fabrication de sphères creuses métalliques ou céramiques
DE10358786A1 (de) 2003-12-12 2005-07-14 Basf Ag Partikelschaumformteile aus expandierbaren, Füllstoff enthaltenden Polymergranulaten
DE102004003507A1 (de) 2004-01-16 2005-08-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Schallabsorbierende Struktur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2342948A1 (de) 1973-08-25 1975-03-27 Rauschert Kg P Verfahren zur herstellung von keramikmaterialhohlkoerpern und deren verwendung
EP0300543A1 (fr) 1987-07-22 1989-01-25 Norddeutsche Affinerie Ag Procédé de fabrication de sphères creuses métalliques ou céramiques
DE10358786A1 (de) 2003-12-12 2005-07-14 Basf Ag Partikelschaumformteile aus expandierbaren, Füllstoff enthaltenden Polymergranulaten
DE102004003507A1 (de) 2004-01-16 2005-08-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Schallabsorbierende Struktur

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9080259B2 (en) 2009-06-30 2015-07-14 Basf Se Polyamide fibers with dyeable particles and production thereof
US9181136B2 (en) 2010-01-19 2015-11-10 Basf Se Method for producing hollow bodies having enclosed freely displaceable particles
EP2636658A3 (fr) * 2012-03-07 2014-05-07 Manfred Jaeckel Procédé de fabrication d'un corps céramique à pores ouverts
US11179694B2 (en) 2017-09-11 2021-11-23 Basf Se Method of forming porous metal oxide microspheres
US11185835B2 (en) 2017-09-11 2021-11-30 Basf Se Method of forming porous metal oxide microspheres using polydisperse polymer nanospheres
US11471849B2 (en) 2017-09-11 2022-10-18 President And Fellows Of Harvard College Porous metal oxide microspheres with varying pore sizes
US11517871B2 (en) 2017-09-11 2022-12-06 President And Fellows Of Harvard College Porous metal oxide microspheres

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