EP2519480A2 - Graphite-containing moulded body and method for the production thereof - Google Patents
Graphite-containing moulded body and method for the production thereofInfo
- Publication number
- EP2519480A2 EP2519480A2 EP10803462A EP10803462A EP2519480A2 EP 2519480 A2 EP2519480 A2 EP 2519480A2 EP 10803462 A EP10803462 A EP 10803462A EP 10803462 A EP10803462 A EP 10803462A EP 2519480 A2 EP2519480 A2 EP 2519480A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- additive
- graphite
- shaped body
- mixture
- inorganic
- 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.)
- Withdrawn
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 111
- 239000010439 graphite Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000000654 additive Substances 0.000 claims abstract description 92
- 230000000996 additive effect Effects 0.000 claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000006259 organic additive Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 31
- 239000001307 helium Substances 0.000 claims description 19
- 229910052734 helium Inorganic materials 0.000 claims description 19
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 19
- 239000011888 foil Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229910021382 natural graphite Inorganic materials 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- 238000005056 compaction Methods 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 150000005130 benzoxazines Chemical class 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 238000004049 embossing Methods 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 238000007688 edging Methods 0.000 claims 1
- 238000000691 measurement method Methods 0.000 claims 1
- 238000003856 thermoforming Methods 0.000 claims 1
- 238000003466 welding Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 description 34
- 239000007788 liquid Substances 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000037396 body weight Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052580 B4C Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—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
- C04B35/536—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 based on expanded graphite or complexed graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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
- C04B35/528—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 carbonaceous particles with or without other non-organic components
- C04B35/532—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 carbonaceous particles with or without other non-organic components containing a carbonisable binder
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63496—Bituminous materials, e.g. tar, pitch
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- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
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- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
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- C04B37/021—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles in a direct manner, e.g. direct copper bonding [DCB]
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/46—Graphite
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
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Definitions
- the present invention relates to a graphite-containing molded body, which is particularly suitable for use as a seal, as a building material, such as wall or ceiling paneling, as a bipolar plate, for example, for a redox flow cell, as a heat exchanger plate or as a heat exchanger tube, and a Process for its preparation.
- Seals such as gaskets, which are used for example in chemical apparatus construction, must meet a variety of requirements. In particular, they must have a low permeability to liquids and gases, in particular, as in the case of gaskets, in the plane of the gasket. Apart from that, they must be characterized by high tensile strength, high transverse strength, good thermal conductivity, good adaptability and good dry sliding properties. For a variety of applications also a high temperature resistance and a good resistance to aggressive chemicals are essential.
- a disadvantage of such materials produced by liquid impregnation is that the impregnating agent, in particular in the depth direction or z-direction of the material, is distributed unevenly.
- the impregnating agent in particular in the depth direction or z-direction of the material, is distributed unevenly.
- the inner region of the material impregnated between the surface regions has no or only a comparatively low or uneven degree of impregnation.
- the profile of requirements for molded articles designed for other applications may include high tensile strength, high electrical conductivity or low electrical resistance and low contact resistance.
- Examples of such shaped bodies are in particular bipolar plates, which are used in fuel cells, in redox flow cells or in lead-acid batteries. Identical or at least similar requirement profiles are also required for shaped bodies which are used, for example, as a heat exchanger plate or as a heat exchanger tube.
- Molded body is formed to produce a seal.
- properties of sealing materials produced in this way are better than those of liquid-impregnated sealing materials, the sum of the properties of these materials is still in need of improvement in some applications.
- this object is achieved by providing a graphite-containing molded article which is obtainable by a process in which graphite particles with at least one solid additive to a mixture containing at least one inorganic additive, a mixture of at least one inorganic additive and at least one organic additive contains more than 10 wt .-% organic additive, are mixed and the mixture thus obtained is then compressed, wherein the at least one additive used has a determined according to ISO 13320 average particle diameter (d 5 o) between 1 and 500 ⁇ .
- This solution is based on the surprising finding that a molded article based on graphite and graphite with a specific particle size which is obtainable in this way not only has a high degree of infiltration of pore-containing additive, but also that the pore-sealing additive over all three dimensions and in particular in the depth direction of the shaped body, ie in the z-direction of the shaped body, is homogeneously distributed.
- the shaped body has the same properties in all three dimensions and in particular also in the plane of the shaped body, that is to say in the xy direction or the plane in which the shaped body has its longest extent, and in particular also in the xy Direction by a high tensile strength, high strength in the z-direction, high thermal conductivity, a good dry sliding property, high temperature resistance, good chemical resistance, high density and in particular surface sealing against liquids and gases and by a high stability, namely especially even with a low surface pressure of the molding.
- the homogeneous distribution of the additive or additives over all three dimensions namely in particular ensures that the additive is present not only in the near-surface regions of the molding, but in particular also in the located between the near-surface areas inner or central region of the molding. Thereby, it is prevented that the molded article has high impermeability only in its surface areas but can diffuse gases or liquids in the interior of the molded article. Rather, a high impermeability in all dimensions and therefore in particular a high surface density is achieved by the homogeneous distribution of additives in the interior of the molded body.
- the moldings of the invention are fast, easy and inexpensive to produce, especially by a continuous process in which, for example, a graphite particles containing gas stream continuously a solid and preferably dry additive, for example via a Conveyor screw is added and mixed with it and this mixture is then continuously passed through a roller in which the mixture is compacted.
- the shaped body according to the invention is obtained by a process in which graphite particles are first mixed with at least one solid additive to form a mixture, before the resulting mixture is subsequently compacted.
- the at least one additive used has a mean particle diameter (d 5 o) between 1 and 500 ⁇
- all additives used have a corresponding mean particle diameter (d 5 o) determined by the measuring methods specified in ISO 13320.
- particles based on all known graphites as graphite starting material, for example particles of natural graphite or of synthetic graphite.
- Expanded graphite is understood to mean graphite that is expanded by a factor of 80 or more in the plane perpendicular to the hexagonal carbon layers compared to natural graphite, for example.
- expanded graphite is distinguished by outstanding formability and good toothability, which is why it is particularly suitable for producing the shaped bodies according to the invention.
- Due to its likewise high porosity, expanded graphite can also be mixed very well with additive particles having a correspondingly small particle diameter and, due to the degree of expansion, easily compacted or compacted.
- graphite such as natural graphite is usually mixed with an intercalation compound such as nitric acid or sulfuric acid and heat-treated at an elevated temperature of, for example, 600 to 1,200 ° C.
- expanded graphite is used which has been produced from natural graphite having a mean particle diameter (d 5 o) of at least 149 ⁇ m and preferably of at least 180 ⁇ , determined in accordance with the measuring method and sieve set specified in DIN 66165.
- particles of expanded graphite which has an expansion of 10 to 1 .400, preferably from 20 to 700 and particularly preferably from 60 to 100.
- These graphite particles can be mixed and compacted particularly well with particulate additives.
- the average diameter (d 5 o) of the graphite particles is determined in accordance with the measuring method and sieve set specified in DIN 66165.
- the mixture to be compressed contains 50 to 99 wt .-%, preferably 75 to 97 wt .-% and particularly preferably 80 to 95 wt .-% graphite particles and preferably corresponding particles of expanded graphite.
- the molded body at a surface pressure of 20 MPa using helium as a gas (40 bar pressure) a according to DIN EN 13555 as measured at room temperature impermeability of less than 10 "1 mg / (s' m), preferably less than 10 "2 mg / (sm), and more preferably less than 10 " 3 mg / (sm).
- the present invention comprises three basic embodiments, namely, first, a graphite-containing shaped body, which contains only inorganic additive in addition to graphite, second, a graphite-containing molding body, which contains only organic additive in addition to graphite, in an amount of more than 10 wt .-%, and third, a graphite-containing molded body, which contains both inorganic additive and organic additive in addition to graphite.
- this or the mixture to be compressed contains preferably 1 to 50 wt .-%, particularly preferably 2 to 20 wt .-% and most preferably 3 to 10 wt .-% of one or more inorganic additives.
- an inorganic additive which has a melting temperature of at most 1 .800 ° C., preferably between 50 and 1 000 ° C.
- the at least one inorganic additive has a glass transition temperature of at most 1, 800 ° C., preferably between 50 and 1 000 ° C., and particularly preferably between 100 and 650 ° C.
- the at least one inorganic additive has a sintering temperature between 50 and 950 ° C., and preferably between 100 and 600 ° C.
- the shaped body can also contain fillers in addition to the graphite and the inorganic additive, but this does not required and not preferred. Therefore, the molded article according to the invention according to this embodiment preferably consists of the aforementioned amount of inorganic additive and balance graphite.
- the inorganic additive may be any inorganic material. Good results are obtained, in particular, if the inorganic additive is at least one glass former and / or at least one precursor of a glass former. With such materials, a high permeability of the molding for liquid and gaseous substances is achieved, in particular at comparatively high temperatures of, for example, 250 ° C. to 600 ° C.
- the at least one glass former and / or the at least one precursor of a glass former is a compound selected from the group consisting of phosphates, silicates, aluminosilicates, boron oxides, borates and any mixtures of two or more of the aforementioned compounds.
- a phosphate is used as glass former, because this can be distributed well throughout the cross section of the molding.
- particularly suitable phosphates are those selected from the group consisting of ammonium dihydrogen phosphate, polyphosphate, hydrogen phosphate, calcium phosphates and aluminum phosphates.
- the inorganic additive is preferably selected in terms of its chemical nature and amount used so that the molding is impermeable in a temperature range between 250 and 600 ° C and in particular in a temperature range between 300 and 550 ° C, being impermeable in the context of the present invention is understood that the molding at a surface pressure of 32 MPa preferably after the TA-air after a removal for 48 hours at 300 ° C or preferably after a storage for 48 hours at 400 ° C, a leakage rate of less than 1 x 10 "4 mbarl / s ' m (1, 1 bar, helium) in development of the inventive concept it is proposed that the inorganic additive and the inorganic additives a particular according to the ISO 13320 average particle diameter in the mixture to be compacted (d 5 o) ⁇ of 0.5 to 300 and preferably from 1 to 50 ⁇ have. Further, it is in that the molded article containing only an inorganic additive according to this embodiment has a density of at least 0.7 g g
- the molding according to the invention contains only organic additive, but no inorganic additive.
- the mixture or the molding to be compacted is more than 10 to 50% by weight, preferably 10 to 25% Wt .-% and particularly preferably 10 to 20 wt .-% of one or more organic additives.
- a molded article with a very high tensile strength and with a high impermeability is obtained, in particular in the z-direction of the molded article.
- the addition of a comparatively large amount of organic additive facilitates shaping and results in better
- the shaped body in this embodiment can also contain fillers in addition to the graphite and the organic additive, but this is not necessary and also not preferred. Therefore, according to this embodiment, the shaped article according to the invention preferably consists of the abovementioned amount of organic additive and remainder of graphite.
- any organic material can be used as the organic additive.
- the organic additive is a polymer selected from the group consisting of thermoplastics, thermosets, elastomers and any mixtures thereof. With such materials, especially at comparatively low temperatures of, for example, -100 ° C. to 300 ° C., a high impermeability of the molding for liquid and gaseous substances is achieved.
- Examples of corresponding polymers are silicone resins, polyolefins, epoxy resins, phenolic resins, melamine resins, urea resins, polyester resins, polyetheretherketones, benzoxazines, polyurethanes, nitrile rubbers, such as acrylonitrile-butadiene-styrene rubber, polyamides, polyimides, polysulfones, polyvinyl chloride and fluoropolymers, such as polyvinylidene fluoride , Ethylene-tetrafluoroethylene copolymers, polytetrafluoroethylene and mixtures or copolymers of two or more of the aforementioned compounds.
- the organic additive or the organic additives are exclusively fluorine-free polymers.
- this has surprisingly resulted in the balance of all the required properties, such as high tensile strength, high transverse strength, high thermal conductivity, good dry slip properties. shank, high temperature resistance, good chemical resistance and high impermeability to liquids and gases, proved to be particularly advantageous.
- fluorine-free polymers are polymers selected from the group consisting of silicone resins, polyolefins, epoxy resins, phenolic resins, melamine resins, urea resins, polyester resins, polyetheretherketones, benzoxazines, polyurethanes, nitrile rubbers, polyamides, polyimides, polysulfones and any mixtures or copolymers of two or more of the aforementioned compounds.
- particularly suitable polyols are polyethylene and polypropylene, acrylonitrile-butadiene-styrene rubber is particularly suitable as the nitrile rubber.
- silicone resins better sealing and in particular a significantly better surface density is achieved compared to the addition of fluoropolymers.
- the organic additive is preferably selected such that the shaped body is impermeable in a temperature range between -100 and 300 ° C. and in particular in a temperature range between -20 and 250 ° C. and very particularly at room temperature
- Impermeable in the context of the present invention is understood that the molding at a surface pressure of 20 MPa with helium gas (40 bar internal pressure) according to DIN EN 13555 measured in the aforementioned temperature ranges impermeability of less than 10 "1 mg / (s ' m), preferably of less than 10 "2 mg / (sm), and more preferably less than 10 " 3 mg / (sm).
- the molding in a temperature range between -100 and 300 ° C and INS special in a temperature range between -20 and 250 ° C at a surface pressure of 20 MPa with helium as gas (1 bar helium test gas internal pressure) in a measuring apparatus based on the DIN 28090-1 at room temperature in accordance with DIN 28090-1 in measured the aforementioned temperature ranges impermeability in the z-direction of less than 10 "1 mg / (s' m 2), preferably of less than 10" 2 mg / (sm 2), and more preferably of less than 10 "3 mg / ( sm 2 ).
- the graphite-containing molded body Due to the addition of organic additive, it is easily possible to provide the graphite-containing molded body in such a way that it has a tensile strength of from 10 to 35 MPa, and preferably from 15 to 25 MPa, measured according to DIN ISO 1924-2.
- the or- ganic additive or organic additives a particular according to the ISO 13320 average particle diameter in the to be compacted mixture (d 5 o) ⁇ from 1 to 150, preferably ⁇ 2-30 and particularly preferably from 3 to 10 ⁇ have.
- the molded article containing only organic additive according to this embodiment has a density of at least 1.0 g / cm 3 , preferably a density of 1.2 to 1.8 g / cm 3 and particularly preferably a density of 1, 4 to 1.7 g / cm 3 .
- the molding according to the invention contains organic additive and inorganic additive.
- a particular advantage of this embodiment is that, due to the combination of organic additive and inorganic additive, a high impermeability of the shaped body to liquids and gases over a very broad temperature range from comparatively very low to comparatively high temperatures is reached.
- This can be achieved, for example, by selecting an inorganic additive and an organic additive, the inorganic additive decomposing at one in the range of the temperature and in particular just below the temperature at which the organic additive decomposes, for example by pyrolysis, combustion or a decomposition reaction is, begins, for example, initiated by a sintering or melting process to contribute to a densification of the molding and thus take over the role of the organic additive at a higher temperature.
- the mixture to be compacted or molded 1 to 25 wt .-% inorganic additive and 1 to 25 wt .-% organic additive and preferably 3 to 20 wt .-% inorganic additive and 5 to 15 wt .-% organic additive.
- the shaped body in this embodiment in addition to the graphite, the inorganic additive and the organic additive still fillers, but this is not necessary and not preferred. Therefore, according to this embodiment, the shaped article according to the invention preferably consists of the abovementioned amount of organic additive, inorganic additive and remainder graphite.
- Particularly suitable inorganic additives and organic additives are those already mentioned above for the other two particularly preferred embodiments of the present invention. Particularly with the combination of glass-forming agent as inorganic additive and silicone resin as organic additive, particularly good results are achieved, above all with regard to an excellent surface density.
- the inorganic and Organic additives on the above-mentioned for the other two particularly preferred embodiments average particle diameter.
- the organic additive and the inorganic additive are preferably selected with regard to their chemical nature and amounts used such that the shaped body is impermeable in a temperature range between -100 and 600 ° C. and in particular in a temperature range between -20 and 550 ° C.
- the shaped body at a surface pressure of 20 MPa with helium gas (40 bar internal pressure) in a temperature range between -100 ° C and 600 ° C and preferably between -20 ° C and 550 ° C determined according to DIN EN 13555 impermeability less than 10 "2 mg / (sm), and more preferably less than 10 " 3 mg / (sm).
- helium gas 40 bar internal pressure
- the molding containing both organic and inorganic additive according to this embodiment have a density of at least 0.7 g / cm 3 and preferably a density of 1, 0 to 1, 8 g / cm 3 .
- the shaped body is formed at least substantially flat, for example as a plate, tape or foil.
- shaped bodies of essentially flat design are also understood as meaning specially shaped articles, such as, for example, sealing rings.
- specially shaped articles such as, for example, sealing rings.
- the advantage of a high surface density can be used particularly well.
- this can be provided with a two- or three-dimensionally structured reinforcement.
- structured sheets such as spits.
- a further subject of the present invention is a process for the production of a previously described shaped body which comprises the following steps:
- the process according to the invention is preferably carried out continuously so as to produce the shaped bodies according to the invention rapidly, simply and inexpensively.
- the continuous process management can be carried out, for example, in a pipeline system in which the mixing according to process step a) is carried out so that a graphite particle-containing gas stream, a solid additive is supplied for example via a screw conveyor and the thus obtained, mixed, graphite particles and additive containing gas stream for compacting according to the method step b) is guided by a roller.
- a graphite particle-containing gas stream a solid additive is supplied for example via a screw conveyor and the thus obtained, mixed, graphite particles and additive containing gas stream for compacting according to the method step b) is guided by a roller.
- no mixing is carried out in a static or dynamic stirring device for more than 5 minutes, in particular for more than 20 minutes and in particular for more than 1 hour, prior to compacting.
- the mixture containing graphite particles and additive is melted and / or sintered during compaction or after compaction according to method step b).
- this can further increase the impermeability of the molding to liquids and gases.
- the fusion of the graphite particles with the additive particles is improved by such melting or sintering, and further pores are closed and contact points are created by the then thin-fluid additive.
- a separate shaping step can take place, in which the shaped body is formed, for example, by forming, profiling, joining, Hot pressing, Thermoumfornnen, edge, deep drawing, embossing or punching is formed.
- the shaping step can advantageously take place before a final compression step.
- pre-compaction can be carried out before deformation, for example by compression.
- the shaped body can be heated in a mold, whereby certain profiles, shapes, waves and / or embossments are generated.
- the additive stabilizes these forms and prevents the reformation known from conventional graphite films.
- the mechanical load capacity generated by the present invention allows for the first time to apply such methods.
- the present invention relates to the use of a previously described graphite molded body as a sealing element, as bipolar plate of a fuel cell, a redox flow battery, as a heat conducting foil, as a molded part in the construction sector, in particular wall cladding, ceiling cladding or heat conduction, as a current conductor in lead-acid batteries or in corresponding hybrid systems, as foil or fin in PCM graphite stores, as lining material, as contacting element, as electrode material for battery systems, as heat distribution element, as surface heater, as material for winding graphite tubes with weldability of the individual layers, as stuffing box, as packages for chemical columns, as a heat exchanger plate or as a heat exchanger tube.
- the shaped body is preferably in the form of a foil or plate with a thickness of 0.02 to 1.5 mm, particularly preferably with a thickness of 0.2 to 1 mm and completely particularly preferably formed with a thickness of 0.5 to 0.8 mm.
- Thicker plates can be produced, for example, by pressing, gluing, hot-bonding of two individual shaped bodies. This is possible with or without printing and by using adhesives, adhesion promoters or by the additive present in the molding. The direct weldability of two shaped bodies is particularly preferred.
- a felt which preferably contains graphite and / or carbon and particularly preferably graphite and / or carbon fibers.
- the connection can be made for example by gluing.
- a conductive adhesive may be used, such as an adhesive filled with silver particles, carbon particles or graphite particles.
- Such a compound can also be made by melting or by sintering with a plastic, in particular a polymer described above for the organic additive. In the simplest case, therefore, a felt is thermally bonded to a molding according to the invention without further materials.
- the density of the felt is preferably 0.01 to 0.2 g / cm 3 .
- the specific electrical resistance, measured in the felt plane is preferably between 0.5 and 15 ohm mm and the specific electrical resistance measured perpendicular to the felt plane, preferably between 2 and 20 ohm mm. These values refer to a compression of the felt of 20 to 30%. With stronger or weaker compression, the specific electrical resistance is correspondingly lower or higher.
- the specific surface of the felt is preferably between 0.2 and 300 m 2 / g.
- the molded article according to the invention as a molded part in the construction sector, in particular as wall cladding, ceiling cladding or réelleleitplatte, it has proven to be advantageous to provide the molded body plastically deformable and, for example, in the form of a plate, so that the molding at the installation simply to predetermined Contours of walls or ceilings, such as edges, bends, corners, friezes and the like, can be molded. Subsequently, the plate can then be finally consolidated at the installation site, for example by heating the still plastically deformable plate in the installed state.
- the shaped body according to the invention can be used before or after a complete curing or before or after a melting and / or sintering of the additive.
- the shaped body after a partial curing, melting and / or sintering of the additive, wherein the final curing, melting and / or sintering of the additive takes place, for example, when used at the operating temperature.
- a high density of the molded body occurs only in the course of use. This has the advantage that in the mold, the moldability to achieve a better adaptation of the molding is possible, for example, to tightly connected parts.
- a further subject matter of the present invention is the use of a previously described graphite-containing shaped body in a method for connecting the shaped body to another shaped body, wherein the other shaped body is, for example, a graphite foil, a metal foil, a metal sheet, a metal foil. tallblock, a textile fabric, preferably a felt body, or may be a previously described molding.
- the bonding of the shaped body takes place without additional adhesive.
- Such an adhesive is dispensable in the use according to the invention because the organic additive contained in the shaped body acts as a binder and thus allows the two bodies to be welded together.
- Figure 1 is a graphite-containing molded body according to the prior art
- FIG. 2 shows a graphite-containing molded body according to an embodiment of the present invention.
- FIG. 1 shows a schematic cross section of a graphite-shaped molded body 1 according to the prior art which is designed as a plate.
- This shaped body 1 contains pressed, expanded graphite 2 and a liquid binder 3, wherein the binder 3 has subsequently been introduced into the shaped body 1 by liquid or melt impregnation from the side surfaces of the shaped body 1. Due to the incorporation of the binder 3 by liquid or melt impregnation this is only unevenly and especially superficially penetrated into the molded body 1, which is why especially between the surface areas lying inner region, such as lying in the oval, dashed border area 4, little binder Contains 3 or is almost binder-free.
- the characteristics of the Shaped body 1, in particular the mechanical strength and the impermeability, of the molded body 1, especially in the depth direction or z-direction, the inner region of the shaped body 1 lying between the surface regions having a poorer impermeability and poorer mechanical properties than the surface areas of the shaped body 1 has.
- the molded body 5 according to the present invention shown in FIG. 2 consists of particles 6 of expanded graphite, which are configured worm-shaped or concertina-shaped in a known manner, as well as of additive particles 7.
- the additive particles 7 are uniformly distributed in the shaped body 5 according to the invention in all dimensions of the shaped body 5, and in particular also in the inner area of the shaped body 5 lying between the surface areas.
- the graphite particles 6 were first homogeneously mixed with the solid additive particles 7 before the mixture thus produced was compacted and shaped into the desired shape.
- Expanded graphite having a bulk density of 3.5 g / l was treated with a silicone resin powder, namely Silres MK from Wacker Chemie AG in Burghausen, Germany, to form an 80% by weight expanded graphite and 20% by weight silicone rubber. mixture containing resin powder and then mixed in a container for 1 minute.
- a silicone resin powder namely Silres MK from Wacker Chemie AG in Burghausen, Germany
- the mixture thus obtained was then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and taken as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the pre-compact was compressed with a press to the desired film thickness of 1 mm and the resulting doped film was conditioned at 180 ° C for 60 minutes to melt the plastic.
- Comparative Example 1 According to the method described for Example 1, two graphite foils were produced, except that only expanded graphite and no additive were used for their production.
- the additive improves the impermeability.
- the addition of additive achieves a certain level of tightness even at significantly lower surface pressures.
- the mixture thus obtained was then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and taken as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the pre-compacts were compressed with a press to the desired film thickness of 1 mm and the resulting doped film was conditioned at 180 ° C for 60 minutes.
- a graphite foil was produced according to the procedures described for Examples 2 and 3, except that exclusively expanded graphite and no additive were used for their production.
- the leakage rate was measured according to DIN 28090-1 with nitrogen as the test gas and 32 MPa surface pressure based on a basis weight of the molded body of 2,000 g / m 2 .
- Expanded graphite with a bulk density of 3.5 g / l was admixed with ammonium dihydrogen phosphate (NHH 2 PO 4 ) for Examples 4 and 5 and ammonium hydrogenphosphate (NH) 2 HPO 4 for Examples 6 and 7 as inorganic filler 95 wt .-% expanded graphite and 5 wt .-% inorganic filler containing mixtures added, which were then mixed in a container for 1 minute.
- ammonium dihydrogen phosphate (NHH 2 PO 4 ) for Examples 4 and 5
- ammonium hydrogenphosphate (NH) 2 HPO 4 ammonium hydrogenphosphate
- the mixtures thus obtained were then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and removed as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the preform was compressed with a press to the desired film thickness of 1 mm and the resulting doped films were at different conditions, which are summarized in the following Table 3, conditioned.
- the leakage rate was measured according to DIN 28090-1 with nitrogen as the test gas and 32 MPa surface pressure based on a basis weight of the molded article of 2,000 g / m 2 .
- Comparative Example 3 A graphite foil was produced according to the methods described for Examples 4 to 7, except that exclusively expanded graphite and no additive were used for their production.
- the leakage rate was measured according to DIN 28090-1 with nitrogen as the test gas and 32 MPa surface pressure based on a basis weight of the molded body of 2,000 g / m 2 .
- Example 8 Expanded graphite having a bulk density of 3.5 g / l was mixed with a polypropylene powder, namely with Licocene PP 2602 Clariant, Germany, to a 80 wt .-% expanded graphite and 20 wt .-% polypropylene polymer powder mixture and then in a container for 1 minute mixed.
- a polypropylene powder namely with Licocene PP 2602 Clariant, Germany
- the mixture thus obtained was then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and taken as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the pre-compact was compressed with a press to the desired film thickness of 0.6 mm and the resulting doped film was removed at 180 ° C for 60 minutes to melt the plastic.
- the impermeability of the molding in the z-direction at a surface pressure of 20 MPa with helium as gas (1 bar helium test gas internal pressure) in a measuring apparatus based on DIN 28090-1 at room temperature was determined.
- the tensile strength of the graphite-containing molded body was determined according to DIN ISO 1924-2. The values obtained are summarized in Table 4 below.
- Comparative Example 4 According to the method described for Example 8, a molded article was produced in the form of graphite foils, except that exclusively expanded graphite and no additive were used in the production.
- the impermeability of the shaped body in the z-direction at a surface pressure of 20 MPa with helium as gas (1 bar helium test gas internal pressure) was determined a measuring apparatus based on DIN 28090-1 determined at room temperature.
- the tensile strength of the graphite-containing molded body was determined according to DIN ISO 1924-2. The values obtained are summarized in Table 4 below.
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Abstract
The invention relates to a graphite-containing moulded body (5) which can be obtained by a method in which graphite particles (6) are mixed with at least one solid additive (7) to form a mixture which comprises at least one inorganic additive, a mixture consisting of an inorganic additive and an organic additive or more than 10 wt.% of an organic additive and the thus obtained mixture is subsequently compressed. Said at least one additive (1) which is used comprises particles having an average diameter (d50) of between 1 and 500 μm, determined in accordance with the ISO 13320 standard.
Description
Graphithaltiger Formkörper und Verfahren zu seiner Herstellung Graphite-containing molding and process for its preparation
Die vorliegende Erfindung betrifft einen graphithaltigen Formkörper, welcher insbesondere für den Einsatz als Dichtung, als Baustoff, wie Wand- bzw. Deckenverkleidung, als Bipolarplatte, beispielsweise für eine Redox-Flow-Zelle, als Wärme- tauscherplatte oder als Wärmetauscherrohr geeignet ist, sowie ein Verfahren zu seiner Herstellung. The present invention relates to a graphite-containing molded body, which is particularly suitable for use as a seal, as a building material, such as wall or ceiling paneling, as a bipolar plate, for example, for a redox flow cell, as a heat exchanger plate or as a heat exchanger tube, and a Process for its preparation.
Dichtungen, wie Flachdichtungen, welche beispielsweise im chemischen Apparatebau eingesetzt werden, müssen eine Vielzahl von Anforderungen erfüllen. Insbesondere müssen diese eine niedrige Permeabilität für Flüssigkeiten und Gase aufweisen, und zwar insbesondere, wie im Fall von Flachdichtungen, in der Ebene der Dichtung. Abgesehen davon müssen sich diese durch eine hohe Zugfestigkeit, durch eine hohe Querfestigkeit, durch eine gute Wärmeleitfähigkeit, durch eine gute Anpassungsfähigkeit und durch gute Trockengleiteigenschaften auszeichnen. Für eine Vielzahl von Anwendungen sind ferner eine hohe Temperaturbeständigkeit sowie eine gute Beständigkeit gegen aggressive Chemikalien unabdingbar. Seals, such as gaskets, which are used for example in chemical apparatus construction, must meet a variety of requirements. In particular, they must have a low permeability to liquids and gases, in particular, as in the case of gaskets, in the plane of the gasket. Apart from that, they must be characterized by high tensile strength, high transverse strength, good thermal conductivity, good adaptability and good dry sliding properties. For a variety of applications also a high temperature resistance and a good resistance to aggressive chemicals are essential.
Aufgrund der hohen Temperaturbeständigkeit insbesondere zwischen -200 °C und +400 °C, der hervorragenden Dimensionsstabilität unter thermischer Belastung, der guten Chemikalienbeständigkeit und der hohen Rückfederung von Graphit werden derartige Dichtungen häufig aus Graphit hergestellt. Um die Dichtigkeit von Graphit zu erhöhen, ist es bereits vorgeschlagen worden, als Dichtungsmaterial flüssigimprägnierten Graphit einzusetzen, also Graphit, dessen Poren zumindest teilweise durch Flüssigimprägnierung bzw. Schmelzimprägnierung mit einem geeigneten Imprägniermittel geschlossen worden sind. Als Imprägniermittel werden beispielweise lösemittelfreie Harze eingesetzt, wobei hier der Graphitgehalt des Dichtungsmaterials herkömmlicherweise 90 Gew.-% oder mehr beträgt. Durch
die Imprägnierung kann neben der Dichtigkeit zudem sowohl die Handhabung als auch die Kratzbeständigkeit des Materials verbessert werden. Due to the high temperature resistance especially between -200 ° C and +400 ° C, the excellent dimensional stability under thermal stress, the good chemical resistance and the high springback of graphite, such seals are often made of graphite. In order to increase the density of graphite, it has already been proposed to use liquid-impregnated graphite as the sealing material, ie graphite whose pores have at least partially been closed by liquid impregnation or melt impregnation with a suitable impregnating agent. As impregnating agents, for example, solvent-free resins are used, in which case the graphite content of the sealing material is conventionally 90% by weight or more. By In addition to the impermeability, the impregnation can also improve both the handling and the scratch resistance of the material.
Ein Nachteil solcher durch Flüssigimprägnierung hergestellter Materialien ist es jedoch, dass das Imprägniermittel, insbesondere in der Tiefenrichtung bzw. z- Richtung des Materials, ungleichmäßig verteilt ist. Während mithin in den Oberflächenbereichen des Materials ein hoher Imprägniergrad und eine vergleichsweise homogene Imprägnierung erreicht werden, weist der zwischen den Oberflächenbereichen liegende innere Bereich des so imprägnierten Materials keinen oder nur einen vergleichsweise niedrigen bzw. ungleichmäßigen Imprägniergrad auf. Dadurch weist eine aus einem solchen Material hergestellte Dichtung zwar in ihren Oberflächenbereichen durch die Oberflächenimprägnierung eine vergleichsweise hohe Impermeabilität für Flüssigkeiten und Gase auf; allerdings ist diese in dem zwischen den Oberflächenbereichen liegenden zentralen Bereich vergleichsweise permeabel, weswegen diese Dichtungen insbesondere für die Verwendung als Flachdichtungen nur bedingt geeignet sind. A disadvantage of such materials produced by liquid impregnation, however, is that the impregnating agent, in particular in the depth direction or z-direction of the material, is distributed unevenly. Thus, while a high degree of impregnation and a comparatively homogeneous impregnation are achieved in the surface regions of the material, the inner region of the material impregnated between the surface regions has no or only a comparatively low or uneven degree of impregnation. As a result, a seal made of such a material, although in their surface areas by the surface impregnation on a comparatively high impermeability to liquids and gases; However, this is relatively permeable in the lying between the surface areas central region, which is why these seals are particularly suitable for use as flat gaskets only conditionally.
Ein ähnliches Problem tritt auch bei Bauplatten, wie Wandverkleidungsplatten oder Wärmeleitplatten, auf Basis von Graphit auf. Um solchen Platten eine ausreichend hohe Festigkeit, eine ausreichend hohe Steifigkeit sowie eine ausreichend hohe Abriebsfestigkeit zu verleihen, damit diese den bei ihrer bestimmungsgemäßen Verwendung auftretenden mechanischen Belastungen standhalten können, werden diese üblicherweise ebenfalls durch Flüssigimprägnierung mit einem Bindemittel auf Basis von Harz oder Thermoplast imprägniert. Auch hier wird nur in den Oberflächenbereichen des Materials ein hoher Imprägniergrad und eine vergleichsweise homogene Imprägnierung erreicht, nicht jedoch in dem zwischen den Oberflächenbereichen liegenden inneren Bereich, weswegen diese Platten eine über ihren Querschnitt ungleichmäßige Steifigkeit und Stabilität aufweisen und die Querfestigkeit dieser Platten sehr stark variiert.
Ferner kann das Anforderungsprofil für für andere Anwendungen konzipierte Formkörper, wie beispielsweise für Bipolarplatten, Stromableiter und Elektroden- materialien, eine hohe Zugfestigkeit, eine hohe elektrische Leitfähigkeit bzw. einen niedrigen elektrischen Widerstand sowie einen geringen Kontaktwiderstand um- fassen. Beispiele für solche Formkörper sind im Speziellen Bipolarplatten, welche in Brennstoffzellen, in Redox-Flow-Zellen oder in Blei-Säure-Batterien eingesetzt werden. Gleiche oder zumindest ähnliche Anforderungsprofile werden auch für Formkörper gefordert, welche beispielsweise als Wärmetauscherplatte oder als Wärmetauscherrohr eingesetzt werden. A similar problem also occurs with structural panels, such as wall cladding panels or heat conducting panels, based on graphite. In order to give such plates a sufficiently high strength, a sufficiently high rigidity and a sufficiently high abrasion resistance, so that they can withstand the mechanical stresses occurring during their intended use, they are usually also impregnated by liquid impregnation with a binder based on resin or thermoplastic. Again, a high degree of impregnation and a comparatively homogeneous impregnation is achieved only in the surface regions of the material, but not in the lying between the surface regions inner region, which is why these plates have a non-uniform stiffness and stability over their cross-section and the transverse strength of these plates varies greatly , Furthermore, the profile of requirements for molded articles designed for other applications, such as, for example, bipolar plates, current conductors and electrode materials, may include high tensile strength, high electrical conductivity or low electrical resistance and low contact resistance. Examples of such shaped bodies are in particular bipolar plates, which are used in fuel cells, in redox flow cells or in lead-acid batteries. Identical or at least similar requirement profiles are also required for shaped bodies which are used, for example, as a heat exchanger plate or as a heat exchanger tube.
Zur Überwindung wenigstens einen Teils der vorgenannten Probleme sind bereits Materialien beispielsweise zur Verwendung als Dichtungen auf Basis von Graphit vorgeschlagen worden, welche hergestellt werden, indem zum Verschließen der Poren des Graphits Graphit und ein festes Ethylen-Tetrafluorethylen-Copolymer miteinander vermischt werden, bevor aus der so hergestellten Mischung einIn order to overcome at least a part of the aforementioned problems, there have been proposed, for example, materials for use as graphite-based gaskets, which are prepared by mixing graphite and a solid ethylene-tetrafluoroethylene copolymer together to close the pores of the graphite, before leaving so prepared mixture
Formkörper zur Herstellung einer Dichtung geformt wird. Obwohl die Eigenschaften so hergestellter Dichtungsmaterialien besser als die von flüssigimprägnierten Dichtungsmaterialien sind, ist die Summe der Eigenschaften dieser Materialien für manche Anwendungen noch verbesserungsbedürftig. Molded body is formed to produce a seal. Although the properties of sealing materials produced in this way are better than those of liquid-impregnated sealing materials, the sum of the properties of these materials is still in need of improvement in some applications.
Aufgabe der vorliegenden Erfindung ist es daher, einen graphithaltigen Formkörper bereitzustellen, welcher nicht nur eine hohe Zugfestigkeit, eine hohe Querfestigkeit, eine hohe Wärmeleitfähigkeit, eine gute Trockengleiteigenschaft, eine hohe Temperaturbeständigkeit sowie eine gute Chemikalienbeständigkeit aufweist, sondern welcher sich über einen breiten Temperaturbereich und/oder bei einer geringen Flächenpressung insbesondere durch eine besonders hohe Impermeabi- lität gegenüber Flüssigkeiten und Gasen, und zwar in Abhängigkeit von der konkreten Anwendung insbesondere in der Ebene, d.h. in der x-y-Richtung der Dichtung, und/oder, wie dies beispielsweise für die Verwendung als Bipolarplatte oder Wärmetauscher wichtig ist, senkrecht zu der Ebene, d.h. in der z-Richtung, durch
einen geringen Abrieb sowie durch einen geringen elektrischen Widerstand, aber dennoch durch eine gute Flexibilität auszeichnet, und, welcher einfach und kostengünstig hergestellt werden kann. Erfindungsgemäß wird diese Aufgabe durch die Bereitstellung eines graphithaltigen Formkörpers gelöst, welcher durch ein Verfahren erhältlich ist, bei dem Graphitpartikel mit wenigstens einem festen Additiv zu einer Mischung, welche wenigstens ein anorganisches Additiv, eine Mischung aus wenigstens einem anorganischen Additiv und wenigstens einem organischen Additiv oder mehr als 10 Gew.-% organisches Additiv enthält, vermischt werden und die so erhaltene Mischung anschließend verdichtet wird, wobei das eingesetzte wenigstens eine Additiv einen gemäß der ISO 13320 bestimmten mittleren Partikeldurchmesser (d5o) zwischen 1 und 500 μιτι aufweist. Diese Lösung basiert auf der überraschenden Erkenntnis, dass ein so erhältlicher Formkörper auf Basis von Graphit und Graphit mit einer spezifischen Partikelgröße nicht nur einen hohen Infiltrationsgrad an Poren verschließendem Additiv aufweist, sondern dass das Poren verschließende Additiv zudem über alle drei Dimensionen und insbesondere in der Tiefenrichtung des Formkörpers, also in der z-Richtung des Formkörpers, homogen verteilt ist. Aus diesem Grund weist der Formkörper in allen drei Dimensionen und insbesondere auch in der Ebene des Formkörpers, also in der x-y-Richtung bzw. der Ebene, in welcher der Formkörper seine längste Ausdehnung besitzt, gleiche Eigenschaften auf und zeichnet sich insbesondere auch in der x-y-Richtung durch eine hohe Zugfestigkeit, eine hohe Festigkeit in z-Richtung, eine hohe Wärmeleitfähigkeit, eine gute Trockengleiteigenschaft, eine hohe Temperaturbeständigkeit, eine gute Chemikalienbeständigkeit, eine hohe Dichtigkeit und insbesondere Flächendichtigkeit gegenüber Flüssigkeiten und Gasen sowie durch eine hohe Stabilität aus, und zwar insbesondere auch bei einer geringen Flächenpressung des Formkörpers. Aufgrund der homo- genen Verteilung des Additivs bzw. der Additive über alle drei Dimensionen wird
nämlich insbesondere erreicht, dass das Additiv nicht nur in den oberflächennahen Bereichen des Formkörpers vorliegt, sondern insbesondere auch in dem zwischen den oberflächennahen Bereichen befindlichen inneren bzw. zentralen Bereich des Formkörpers. Dadurch wird es verhindert, dass der Formkörper nur in seinen Oberflächenbereichen eine hohe Impermeabilität aufweist, aber in dem Inneren des Formkörpers Gase oder Flüssigkeiten diffundieren können. Vielmehr wird durch die homogene Additivverteilung auch in dem Inneren des Formkörpers eine hohe Impermeabilität in allen Dimensionen und daher auch insbesondere eine hohe Flächendichtigkeit erreicht. It is therefore an object of the present invention to provide a graphite-containing molded article which not only has high tensile strength, high transverse strength, high thermal conductivity, good dry sliding property, high temperature resistance and good resistance to chemicals but which can be spread over a broad temperature range and / or or with a low surface pressure, in particular by a particularly high impermeability to liquids and gases, depending on the specific application, in particular in the plane, ie in the xy direction of the seal, and / or, as for example for use as a bipolar plate or heat exchanger is important, perpendicular to the plane, ie in the z-direction, through a low abrasion and by a low electrical resistance, but still characterized by a good flexibility, and which can be easily and inexpensively manufactured. According to the invention, this object is achieved by providing a graphite-containing molded article which is obtainable by a process in which graphite particles with at least one solid additive to a mixture containing at least one inorganic additive, a mixture of at least one inorganic additive and at least one organic additive contains more than 10 wt .-% organic additive, are mixed and the mixture thus obtained is then compressed, wherein the at least one additive used has a determined according to ISO 13320 average particle diameter (d 5 o) between 1 and 500 μιτι. This solution is based on the surprising finding that a molded article based on graphite and graphite with a specific particle size which is obtainable in this way not only has a high degree of infiltration of pore-containing additive, but also that the pore-sealing additive over all three dimensions and in particular in the depth direction of the shaped body, ie in the z-direction of the shaped body, is homogeneously distributed. For this reason, the shaped body has the same properties in all three dimensions and in particular also in the plane of the shaped body, that is to say in the xy direction or the plane in which the shaped body has its longest extent, and in particular also in the xy Direction by a high tensile strength, high strength in the z-direction, high thermal conductivity, a good dry sliding property, high temperature resistance, good chemical resistance, high density and in particular surface sealing against liquids and gases and by a high stability, namely especially even with a low surface pressure of the molding. Due to the homogeneous distribution of the additive or additives over all three dimensions namely in particular ensures that the additive is present not only in the near-surface regions of the molding, but in particular also in the located between the near-surface areas inner or central region of the molding. Thereby, it is prevented that the molded article has high impermeability only in its surface areas but can diffuse gases or liquids in the interior of the molded article. Rather, a high impermeability in all dimensions and therefore in particular a high surface density is achieved by the homogeneous distribution of additives in the interior of the molded body.
Im weiteren besondere Vorteil gegenüber den aus dem Stand der Technik bekannten Formkörpern sind die erfindungsgemäßen Formkörper schnell, einfach und kostengünstig herstellbar, und zwar insbesondere auch durch ein kontinuierliches Verfahren, bei dem beispielsweise einem Graphitpartikeln enthaltendem Gasstrom kontinuierlich ein festes und vorzugsweise trockenes Additiv beispielsweise über eine Förderschnecke zugegeben und damit vermischt wird und diese Mischung dann kontinuierlich durch eine Walze geführt wird, in welcher die Mischung verdichtet wird. Wie dargelegt, wird der erfindungsgemäße Formkörper durch ein Verfahren erhalten, bei dem Graphitpartikel zunächst mit wenigstens einem festen Additiv zu einer Mischung vermischt werden, bevor die so erhaltene Mischung anschließend verdichtet wird. Darunter wird im Rahmen der vorliegenden Patentanmeldung verstanden, dass im Gegensatz zu einer Flüssig- bzw. Schmelzimprägnierung bis zu der Verdichtung der Mischung weder die Graphitpartikel noch das Additiv noch die Graphitpartikel und Additiv enthaltende Mischung geschmolzen oder gesintert werden. In a further particular advantage over the known from the prior art moldings, the moldings of the invention are fast, easy and inexpensive to produce, especially by a continuous process in which, for example, a graphite particles containing gas stream continuously a solid and preferably dry additive, for example via a Conveyor screw is added and mixed with it and this mixture is then continuously passed through a roller in which the mixture is compacted. As stated, the shaped body according to the invention is obtained by a process in which graphite particles are first mixed with at least one solid additive to form a mixture, before the resulting mixture is subsequently compacted. For the purposes of the present patent application, this means that, in contrast to a liquid or melt impregnation up to the compression of the mixture, neither the graphite particles nor the additive nor the mixture containing graphite particles and additive are melted or sintered.
Mit der Spezifizierung, dass das eingesetzte wenigstens eine Additiv einen mittle- ren Partikeldurchmesser (d5o) zwischen 1 und 500 μιτι aufweist, ist gemeint, dass
alle eingesetzten Additive einen entsprechenden, mit dem in der ISO 13320 spezifizierten Messverfahren bestimmten mittleren Partikeldurchmesser (d5o) aufweisen. Grundsätzlich können als Graphitausgangsmaterial Partikel auf Basis aller bekannten Graphite eingesetzt werden, also beispielsweise Partikel aus Naturgraphit oder aus synthetischem Graphit. By specifying that the at least one additive used has a mean particle diameter (d 5 o) between 1 and 500 μιτι, it is meant that all additives used have a corresponding mean particle diameter (d 5 o) determined by the measuring methods specified in ISO 13320. In principle, it is possible to use particles based on all known graphites as graphite starting material, for example particles of natural graphite or of synthetic graphite.
Allerdings wird es gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung vorgeschlagen, als Graphitpartikel Partikel aus expandiertem Graphit einzusetzen. Unter expandiertem Graphit wird Graphit verstanden, der im Vergleich zu natürlichem Graphit in der Ebene senkrecht zu den hexagona- len Kohlenstoffschichten beispielsweise um den Faktor 80 oder mehr expandiert ist. Aufgrund dieser Expansion zeichnet sich expandierter Graphit durch eine her- vorragende Formbarkeit und eine gute Verzahnbarkeit aus, weswegen dieser zur Herstellung der erfindungsgemäßen Formkörper besonders geeignet ist. Aufgrund seiner ebenfalls hohen Porosität lässt sich expandierter Graphit zudem sehr gute mit Additivpartikeln mit einem entsprechend kleinen Partikeldurchmesser vermischen und aufgrund des Expansionsgrades leicht verdichten bzw. kompaktieren. Zur Herstellung von expandiertem Graphit mit einer wurmförmigen Struktur wird üblicherweise Graphit, wie Naturgraphit, mit einer Interkalationsverbindung, wie beispielsweise Salpetersäure oder Schwefelsäure, vermischt und bei einer erhöhten Temperatur von beispielswiese 600 bis 1 .200 °C wärmebehandelt. Vorzugsweise wird expandierter Graphit eingesetzt, welcher aus Naturgraphit mit einem gemäß dem in der DIN 66165 spezifizierten Messverfahren und Siebsatz bestimmten mittleren Partikeldurchmesser (d5o) von wenigstens 149 μιτι und bevorzugt von wenigstens 180 μιτι hergestellt worden ist.
Besonders gute Ergebnisse werden bei dieser Ausführungsform insbesondere mit Partikeln aus expandiertem Graphit erhalten, welcher einen Expansionsgrad von 10 bis 1 .400, vorzugsweise von 20 bis 700 und besonders bevorzugt von 60 bis 100 aufweist. However, it is proposed according to a particularly preferred embodiment of the present invention to use particles of expanded graphite as the graphite particles. Expanded graphite is understood to mean graphite that is expanded by a factor of 80 or more in the plane perpendicular to the hexagonal carbon layers compared to natural graphite, for example. As a result of this expansion, expanded graphite is distinguished by outstanding formability and good toothability, which is why it is particularly suitable for producing the shaped bodies according to the invention. Due to its likewise high porosity, expanded graphite can also be mixed very well with additive particles having a correspondingly small particle diameter and, due to the degree of expansion, easily compacted or compacted. For producing expanded graphite having a vermiform structure, graphite such as natural graphite is usually mixed with an intercalation compound such as nitric acid or sulfuric acid and heat-treated at an elevated temperature of, for example, 600 to 1,200 ° C. Preferably, expanded graphite is used which has been produced from natural graphite having a mean particle diameter (d 5 o) of at least 149 μm and preferably of at least 180 μιτι, determined in accordance with the measuring method and sieve set specified in DIN 66165. Particularly good results are obtained in this embodiment, in particular with particles of expanded graphite, which has an expansion of 10 to 1 .400, preferably from 20 to 700 and particularly preferably from 60 to 100.
Dies entspricht im Wesentlichen expandiertem Graphit mit einem Schüttgewicht von 0,5 bis 95 g/l, vorzugsweise von 1 bis 25 g/l und besonders bevorzugt von 2 bis 10 g/l. In Weiterbildung des Erfindungsgedankens wird es vorgeschlagen, Graphitpartikel und insbesondere Partikel aus expandiertem Graphit mit einem mittleren Partikeldurchmesser (d5o) von 150 bis 3.500 μιτι, vorzugsweise von 250 bis 2.000 μιτι und besonders bevorzugt von 500 bis 1 .500 μιτι einzusetzen. Diese Graphitpartikel lassen sich besonders gut mit partikelförmigen Additiven vermischen und verdich- ten. Dabei wird der mittlere Durchmesser (d5o) der Graphitpartikel gemäß dem in der DIN 66165 spezifizierten Messverfahren und Siebsatz bestimmt. This essentially corresponds to expanded graphite having a bulk density of from 0.5 to 95 g / l, preferably from 1 to 25 g / l and particularly preferably from 2 to 10 g / l. In a further development of the inventive concept, it is proposed to use graphite particles and in particular particles of expanded graphite having a mean particle diameter (d 5 o) of 150 to 3,500 μιτι, preferably from 250 to 2,000 μιτι and more preferably from 500 to 1, 500 μιτι. These graphite particles can be mixed and compacted particularly well with particulate additives. The average diameter (d 5 o) of the graphite particles is determined in accordance with the measuring method and sieve set specified in DIN 66165.
Vorzugsweise enthält die zu verdichtende Mischung 50 bis 99 Gew.-%, bevorzugt 75 bis 97 Gew.-% und besonders bevorzugt 80 bis 95 Gew.-% Graphitpartikel und bevorzugt entsprechende Partikel aus expandiertem Graphit. Preferably, the mixture to be compressed contains 50 to 99 wt .-%, preferably 75 to 97 wt .-% and particularly preferably 80 to 95 wt .-% graphite particles and preferably corresponding particles of expanded graphite.
Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung weist der Formkörper bei einer Flächenpressung von 20 MPa mit Helium als Gas (40 bar Innendruck) eine gemäß der DIN EN 13555 bei Raumtemperatur gemessene Impermeabilität von weniger als 10"1 mg/(s'm), bevorzugt von weniger als 10"2 mg/(s m) und besonders bevorzugt von weniger als 10"3 mg/(s m) auf. According to a particularly preferred embodiment of the present invention, the molded body at a surface pressure of 20 MPa using helium as a gas (40 bar pressure) a according to DIN EN 13555 as measured at room temperature impermeability of less than 10 "1 mg / (s' m), preferably less than 10 "2 mg / (sm), and more preferably less than 10 " 3 mg / (sm).
Wie dargelegt, umfasst die vorliegende Erfindung drei grundsätzliche Ausführungsformen, nämlich erstens einen graphithaltigen Formkörper, welcher neben Graphit nur anorganisches Additiv enthält, zweitens einen graphithaltigen Form-
körper, welcher neben Graphit nur organisches Additiv, und zwar in einer Menge von mehr als 10 Gew.-%, enthält, und drittens einen graphithaltigen Formkörper, welcher neben Graphit sowohl anorganisches Additiv als auch organisches Additiv enthält. As stated, the present invention comprises three basic embodiments, namely, first, a graphite-containing shaped body, which contains only inorganic additive in addition to graphite, second, a graphite-containing molding body, which contains only organic additive in addition to graphite, in an amount of more than 10 wt .-%, and third, a graphite-containing molded body, which contains both inorganic additive and organic additive in addition to graphite.
In der erstgenannten Ausführungsform, bei welcher der graphithaltige Formkörper nur anorganisches Additiv, aber kein organisches Additiv enthält, enthält dieser bzw. die zu verdichtende Mischung vorzugsweise 1 bis 50 Gew.-%, besonders bevorzugt 2 bis 20 Gew.-% und ganz besonders bevorzugt 3 bis 10 Gew.-% eines oder mehrerer anorganischer Additive. Dadurch wird nicht nur eine hohe Imper- meabilität erreicht, sondern insbesondere auch eine gute Oxidationsbeständigkeit bis 500 °C sowie eine hohe Zugfestigkeit und insgesamt eine exzellente mechanische Stabilität des Formkörpers. In Weiterbildung des Erfindungsgedankens wird es vorgeschlagen, ein anorganisches Additiv einzusetzen, welches eine Schmelztemperatur von maximal 1 .800 °C, bevorzugt zwischen 50 und 1 .000 °C und besonders bevorzugt zwischen 100 und 650 °C aufweist. Gute Ergebnisse werden insbesondere auch erreicht, wenn das wenigstens eine anorganische Additiv eine Glasübergangstemperatur von maximal 1 .800 °C, bevorzugt zwischen 50 und 1 .000 °C und besonders bevorzugt zwischen 100 und 650 °C aufweist. Gemäß einer weiteren bevorzugten Variante der vorliegenden Ausführungsform weist das wenigstens eine anorganische Additiv eine Sintertemperatur zwischen 50 und 950 °C und bevorzugt zwischen 100 und 600 °C auf. In the first-mentioned embodiment, in which the graphite-containing molding contains only inorganic additive, but no organic additive, this or the mixture to be compressed contains preferably 1 to 50 wt .-%, particularly preferably 2 to 20 wt .-% and most preferably 3 to 10 wt .-% of one or more inorganic additives. As a result, not only is a high impermeability achieved, but in particular also a good oxidation resistance up to 500 ° C and a high tensile strength and overall excellent mechanical stability of the molded body. In a further development of the inventive idea, it is proposed to use an inorganic additive which has a melting temperature of at most 1 .800 ° C., preferably between 50 and 1 000 ° C. and particularly preferably between 100 and 650 ° C. Good results are also achieved in particular when the at least one inorganic additive has a glass transition temperature of at most 1, 800 ° C., preferably between 50 and 1 000 ° C., and particularly preferably between 100 and 650 ° C. According to a further preferred variant of the present embodiment, the at least one inorganic additive has a sintering temperature between 50 and 950 ° C., and preferably between 100 and 600 ° C.
Grundsätzlich kann der Formkörper bei dieser Ausführungsform neben dem Gra- phit und dem anorganischen Additiv noch Füllstoffe enthalten, was jedoch nicht
erforderlich und auch nicht bevorzugt ist. Daher besteht der erfindungsgemäße Formkörper gemäß dieser Ausführungsform bevorzugt aus der vorgenannte Menge anorganischem Additiv und Rest Graphit. Bei dem anorganischen Additiv kann es sich um jedes beliebige anorganische Material handeln. Gute Ergebnisse werden insbesondere erhalten, wenn das anorganische Additiv wenigstens ein Glasbildner und/oder wenigstens eine Vorstufe eines Glasbildners ist. Mit solchen Materialien wird insbesondere bei vergleichsweise hohen Temperaturen von beispielsweise 250 °C bis 600 °C eine hohe Im- permeabilität des Formkörpers für flüssige und gasförmige Substanzen erreicht. In principle, in this embodiment, the shaped body can also contain fillers in addition to the graphite and the inorganic additive, but this does not required and not preferred. Therefore, the molded article according to the invention according to this embodiment preferably consists of the aforementioned amount of inorganic additive and balance graphite. The inorganic additive may be any inorganic material. Good results are obtained, in particular, if the inorganic additive is at least one glass former and / or at least one precursor of a glass former. With such materials, a high permeability of the molding for liquid and gaseous substances is achieved, in particular at comparatively high temperatures of, for example, 250 ° C. to 600 ° C.
Gute Ergebnisse diesbezüglich werden insbesondere erreicht, wenn der wenigstens eine Glasbildner und/oder die wenigstens eine Vorstufe eines Glasbildners eine Verbindung ist, welche aus der Gruppe ausgewählt ist, welche aus Phospha- ten, Silicaten, Aluminosilicaten, Boroxiden, Boraten und beliebigen Mischungen von zwei oder mehr der vorgenannten Verbindungen besteht. Good results in this respect are particularly achieved when the at least one glass former and / or the at least one precursor of a glass former is a compound selected from the group consisting of phosphates, silicates, aluminosilicates, boron oxides, borates and any mixtures of two or more of the aforementioned compounds.
Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung wird als Glasbildner ein Phosphat eingesetzt, weil sich dieses gut im gesam- ten Querschnitt des Formkörpers verteilen lässt. Beispiele für besonders geeignete Phosphate sind solche, welche aus der Gruppe ausgewählt sind, welche aus Ammoniumdihydrogenphosphat, Polyphosphat, Hydrogenphosphat, Calcium- phosphaten und Aluminiumphosphaten besteht. Mithin wird das anorganische Additiv hinsichtlich seiner chemischen Natur und eingesetzten Menge bevorzugt so ausgewählt, dass der Formkörper in einem Temperaturbereich zwischen 250 und 600 °C und insbesondere in einem Temperaturbereich zwischen 300 und 550 °C impermeabel ist, wobei unter impermeabel im Sinne der vorliegenden Erfindung verstanden wird, dass der Formkörper bei einer Flächenpressung von 32 MPa vorzugsweise eine nach der TA-Luft nach
einer Auslagerung für 48 Stunden bei 300 °C oder bevorzugt nach einer Auslagerung für 48 Stunden bei 400 °C eine Leckagerate von weniger als 1 x 10"4 mbarl/s'm (1 ,1 bar, Helium) aufweist. In Weiterbildung des Erfindungsgedankens wird es vorgeschlagen, dass das anorganische Additiv bzw. die anorganischen Additive in der zu verdichtenden Mischung einen gemäß der ISO 13320 bestimmten mittleren Partikeldurchmesser (d5o) von 0,5 bis 300 μιτι und vorzugsweise von 1 bis 50 μιτι aufweisen. Ferner ist es bevorzugt, dass der nur anorganisches Additiv enthaltende Formkörper gemäß dieser Ausführungsform eine Dichte von wenigstens 0,7 g/cm3 und bevorzugt eine Dichte von 1 ,0 bis 1 ,4 g/cm3 aufweist. According to a particularly preferred embodiment of the present invention, a phosphate is used as glass former, because this can be distributed well throughout the cross section of the molding. Examples of particularly suitable phosphates are those selected from the group consisting of ammonium dihydrogen phosphate, polyphosphate, hydrogen phosphate, calcium phosphates and aluminum phosphates. Thus, the inorganic additive is preferably selected in terms of its chemical nature and amount used so that the molding is impermeable in a temperature range between 250 and 600 ° C and in particular in a temperature range between 300 and 550 ° C, being impermeable in the context of the present invention is understood that the molding at a surface pressure of 32 MPa preferably after the TA-air after a removal for 48 hours at 300 ° C or preferably after a storage for 48 hours at 400 ° C, a leakage rate of less than 1 x 10 "4 mbarl / s ' m (1, 1 bar, helium) in development of the inventive concept it is proposed that the inorganic additive and the inorganic additives a particular according to the ISO 13320 average particle diameter in the mixture to be compacted (d 5 o) μιτι of 0.5 to 300 and preferably from 1 to 50 μιτι have. Further, it is in that the molded article containing only an inorganic additive according to this embodiment has a density of at least 0.7 g / cm 3 and preferably a density of from 1.0 to 1.4 g / cm 3 .
Gemäß einer zweiten ganz besonders bevorzugten Ausführungsform der vorlie- genden Erfindung enthält der erfindungsgemäße Formkörper nur organisches Additiv, aber kein anorganisches Additiv. Gute Ergebnisse insbesondere im Hinblick auf eine gewünschte Impermeabilität, aber auch im Hinblick auf eine hohe Zugfestigkeit und mechanische Stabilität werden insbesondere erreicht, wenn die zu verdichtende Mischung bzw. der Formkörper mehr als 10 bis 50 Gew.-%, be- vorzugt 10 bis 25 Gew.-% und besonders bevorzugt 10 bis 20 Gew.-% eines oder mehrerer organischer Additive enthält. Durch den Zusatz von mehr als 10 Gew.-% organischem Additiv wird ein Formkörper mit einer sehr hohen Zugfestigkeit und mit einer hohen Impermeabilität insbesondere in der z-Richtung des Formkörpers erhalten. Abgesehen davon erleichtert der Zusatz einer vergleichsweise großen Menge organischem Additiv die Formgebung und führt zu einer besseren According to a second very particularly preferred embodiment of the present invention, the molding according to the invention contains only organic additive, but no inorganic additive. Good results, in particular with regard to a desired impermeability, but also with regard to a high tensile strength and mechanical stability, are achieved, in particular, if the mixture or the molding to be compacted is more than 10 to 50% by weight, preferably 10 to 25% Wt .-% and particularly preferably 10 to 20 wt .-% of one or more organic additives. By adding more than 10% by weight of organic additive, a molded article with a very high tensile strength and with a high impermeability is obtained, in particular in the z-direction of the molded article. Besides, the addition of a comparatively large amount of organic additive facilitates shaping and results in better
Verschweißbarkeit des Formkörpers mit beispielsweise einem anderen erfindungsgemäßen Formkörper, mit einer Graphitfolie, Metallfolie, einem Metallblech oder einem Metallblock oder mit einem textilen Flächengebilde, wie beispielsweise mit einem Filz. Zudem wird dadurch eine bessere Gleitreibung sowie eine höhere
Querfestigkeit als bei dem Zusatz geringerer Mengen organischem Additiv erreicht. Weldability of the molded article with, for example, another shaped article according to the invention, with a graphite foil, metal foil, a metal sheet or a metal block or with a textile fabric, such as for example with a felt. In addition, a better sliding friction and a higher Transverse strength achieved as the addition of lesser amounts of organic additive.
Grundsätzlich kann der Formkörper bei dieser Ausführungsform neben dem Gra- phit und dem organischen Additiv noch Füllstoffe enthalten, was jedoch nicht erforderlich und auch nicht bevorzugt ist. Daher besteht der erfindungsgemäße Formkörper gemäß dieser Ausführungsform bevorzugt aus der vorgenannte Menge organischem Additiv und Rest Graphit. Grundsätzlich kann als organisches Additiv jedes beliebige organische Material eingesetzt werden. Gute Ergebnisse werden insbesondere erhalten, wenn das organische Additiv ein Polymer ausgewählt aus der Gruppe bestehend aus Thermoplasten, Duroplasten, Elastomeren und beliebigen Mischungen hiervon ist. Mit solchen Materialien wird insbesondere bei vergleichsweise niedrigen Temperatu- ren von beispielsweise -100 °C bis 300 °C eine hohe Impermeabilität des Formkörpers für flüssige und gasförmige Substanzen erreicht. In principle, the shaped body in this embodiment can also contain fillers in addition to the graphite and the organic additive, but this is not necessary and also not preferred. Therefore, according to this embodiment, the shaped article according to the invention preferably consists of the abovementioned amount of organic additive and remainder of graphite. In principle, any organic material can be used as the organic additive. In particular, good results are obtained when the organic additive is a polymer selected from the group consisting of thermoplastics, thermosets, elastomers and any mixtures thereof. With such materials, especially at comparatively low temperatures of, for example, -100 ° C. to 300 ° C., a high impermeability of the molding for liquid and gaseous substances is achieved.
Beispiele für entsprechende Polymere sind Siliconharze, Polyolefine, Epoxidharze, Phenolharze, Melaminharze, Harnstoffharze, Polyesterharze, Polyetheretherketo- ne, Benzoxazine, Polyurethane, Nitrilkautschuke, wie Acrylnitril-Butadien-Styrol- Kautschuk, Polyamide, Polyimide, Polysulfone, Polyvinylchlorid und Fluorpolymere, wie Polyvinylidenfluorid, Ethylen-Tetrafluorethylen-Copolymere, Polytetrafluor- ethylen und Mischungen oder Copolymere von zwei oder mehr der vorgenannten Verbindungen. Examples of corresponding polymers are silicone resins, polyolefins, epoxy resins, phenolic resins, melamine resins, urea resins, polyester resins, polyetheretherketones, benzoxazines, polyurethanes, nitrile rubbers, such as acrylonitrile-butadiene-styrene rubber, polyamides, polyimides, polysulfones, polyvinyl chloride and fluoropolymers, such as polyvinylidene fluoride , Ethylene-tetrafluoroethylene copolymers, polytetrafluoroethylene and mixtures or copolymers of two or more of the aforementioned compounds.
Gemäß einer ganz besonders bevorzugten Variante dieser Ausführungsform ist das organische Additiv bzw. sind die organischen Additive ausschließlich fluorfreie Polymere. Dies hat sich im Rahmen der vorliegenden Erfindung überraschenderweise für die Ausgewogenheit aller erforderlicher Eigenschaften, wie hohe Zugfes- tigkeit, hohe Querfestigkeit, hohe Wärmeleitfähigkeit, gute Trockengleiteigen-
schaft, hohe Temperaturbeständigkeit, gute Chemikalienbeständigkeit und hohe Impermeabilität gegenüber Flüssigkeiten und Gasen, als besonders vorteilhaft erwiesen. Beispiele für entsprechende, fluorfreie Polymere sind Polymere ausgewählt aus der Gruppe bestehend aus Siliconharzen, Polyolefinen, Epoxidharzen, Phenolharzen, Melaminharzen, Harnstoffharzen, Polyesterharzen, Polyetheretherketonen, Benzoxazinen, Polyurethanen, Nitrilkautschuken, Polyamiden, Polyimiden, Poly- sulfonen und beliebigen Mischungen oder Copolymeren von zwei oder mehr der vorgenannten Verbindungen. Während Beispiele für besonders geeignete Polyole- fine Polyethylen und Polypropylen sind, ist als Nitrilkautschuk insbesondere Acryl- nitril-Butadien-Styrol-Kautschuk geeignet. Insbesondere durch den Zusatz von Siliconharzen wird im Vergleich zu dem Zusatz von Fluorpolymeren eine bessere Dichtigkeit und insbesondere eine signifikant bessere Flächendichtigkeit erreicht. According to a very particularly preferred variant of this embodiment, the organic additive or the organic additives are exclusively fluorine-free polymers. In the context of the present invention, this has surprisingly resulted in the balance of all the required properties, such as high tensile strength, high transverse strength, high thermal conductivity, good dry slip properties. shank, high temperature resistance, good chemical resistance and high impermeability to liquids and gases, proved to be particularly advantageous. Examples of corresponding fluorine-free polymers are polymers selected from the group consisting of silicone resins, polyolefins, epoxy resins, phenolic resins, melamine resins, urea resins, polyester resins, polyetheretherketones, benzoxazines, polyurethanes, nitrile rubbers, polyamides, polyimides, polysulfones and any mixtures or copolymers of two or more of the aforementioned compounds. While examples of particularly suitable polyols are polyethylene and polypropylene, acrylonitrile-butadiene-styrene rubber is particularly suitable as the nitrile rubber. In particular, by the addition of silicone resins better sealing and in particular a significantly better surface density is achieved compared to the addition of fluoropolymers.
Folglich wird das organische Additiv hinsichtlich seiner chemischen Natur und eingesetzten Menge bevorzugt so ausgewählt, dass der Formkörper in einem Temperaturbereich zwischen -100 und 300 °C und insbesondere in einem Temperaturbereich zwischen -20 und 250 °C und ganz insbesondere bei Raumtempera- tur impermeabel ist, wobei unter impermeabel im Sinne der vorliegenden Erfindung verstanden wird, dass der Formkörper bei einer Flächenpressung von 20 MPa mit Helium als Gas (40 bar Innendruck) eine gemäß der DIN EN 13555 in den vorgenannten Temperaturbereichen gemessene Impermeabilität von weniger als 10"1 mg/(s'm), bevorzugt von weniger als 10"2 mg/(s m) und besonders bevor- zugt von weniger als 10"3 mg/(s m) aufweist. Consequently, with regard to its chemical nature and amount used, the organic additive is preferably selected such that the shaped body is impermeable in a temperature range between -100 and 300 ° C. and in particular in a temperature range between -20 and 250 ° C. and very particularly at room temperature , Impermeable in the context of the present invention is understood that the molding at a surface pressure of 20 MPa with helium gas (40 bar internal pressure) according to DIN EN 13555 measured in the aforementioned temperature ranges impermeability of less than 10 "1 mg / (s ' m), preferably of less than 10 "2 mg / (sm), and more preferably less than 10 " 3 mg / (sm).
Insbesondere Formkörper, welche für Anwendungen, wie beispielsweise als Bipolarplatten oder als Wärmetauscherplatten konzipiert werden, bei denen vor allem eine hohe Impermeabilität in der z-Richtung erforderlich ist, ist es bevorzugt, dass der Formkörper in einem Temperaturbereich zwischen -100 und 300 °C und ins-
besondere in einem Temperaturbereich zwischen -20 und 250 °C bei einer Flächenpressung von 20 MPa mit Helium als Gas (1 bar Helium Prüfgassinnendruck) in einer Messapparatur in Anlehnung an die DIN 28090-1 bei Raumtemperatur eine in Anlehnung an die DIN 28090-1 in den vorgenannten Temperaturbereichen gemessene Impermeabilität in der z-Richtung von weniger als 10"1 mg/(s'm2), bevorzugt von weniger als 10"2 mg/(s m2) und besonders bevorzugt von weniger als 10"3 mg/(s m2) aufweist. In particular moldings, which are designed for applications such as bipolar plates or as heat exchanger plates, where especially a high impermeability in the z-direction is required, it is preferred that the molding in a temperature range between -100 and 300 ° C and INS special in a temperature range between -20 and 250 ° C at a surface pressure of 20 MPa with helium as gas (1 bar helium test gas internal pressure) in a measuring apparatus based on the DIN 28090-1 at room temperature in accordance with DIN 28090-1 in measured the aforementioned temperature ranges impermeability in the z-direction of less than 10 "1 mg / (s' m 2), preferably of less than 10" 2 mg / (sm 2), and more preferably of less than 10 "3 mg / ( sm 2 ).
Aufgrund des Zusatzes an organischem Additiv ist es leicht möglich, den graphit- haltigen Formkörper so vorzusehen, dass dieser eine gemäß der DIN ISO 1924-2 gemessene Zugfestigkeit von 10 bis 35 MPa und bevorzugt von 15 bis 25 MPa aufweist. Due to the addition of organic additive, it is easily possible to provide the graphite-containing molded body in such a way that it has a tensile strength of from 10 to 35 MPa, and preferably from 15 to 25 MPa, measured according to DIN ISO 1924-2.
In Weiterbildung des Erfindungsgedankens wird es vorgeschlagen, dass das or- ganische Additiv bzw. die organischen Additive in der zu verdichtenden Mischung einen gemäß der ISO 13320 bestimmten mittleren Partikeldurchmesser (d5o) von 1 bis 150 μιτι, vorzugsweise von 2 bis 30 μιτι und besonders bevorzugt von 3 bis 10 μιτι aufweisen. Ferner ist es bevorzugt, dass der nur organisches Additiv enthaltende Formkörper gemäß dieser Ausführungsform eine Dichte von wenigstens 1 ,0 g/cm3, bevorzugt eine Dichte von 1 ,2 bis 1 ,8 g/cm3 und besonders bevorzugt eine Dichte von 1 ,4 bis 1 ,7 g/cm3 aufweist. Gemäß einer dritten ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung enthält der erfindungsgemäße Formkörper organisches Additiv und anorganisches Additiv. Ein besonderer Vorteil dieser Ausführungsform ist es, dass durch die Kombination aus organischem Additiv und anorganischem Additiv eine hohe Impermeabilität des Formkörpers gegenüber Flüssigkeiten und Gasen über einen sehr breiten Temperaturbereich von vergleichsweise sehr niedrigen bis
vergleichsweise sehr hohen Temperaturen erreicht wird. Dies kann beispielsweise dadurch erreicht werden, dass ein anorganisches Additiv und ein organisches Additiv ausgewählt werden, wobei sich das anorganische Additiv bei einer im Bereich der Temperatur und insbesondere knapp unterhalb der Temperatur, bei welcher das organische Additiv beispielsweise durch Pyrolyse, Verbrennung oder eine Zersetzungsreaktion zersetzt wird, beginnt, beispielsweise initiiert durch einen Sinter- oder Schmelzvorgang zu einer Verdichtung des Formkörpers beizutragen und so bei einer höheren Temperatur die Rolle des organischen Additivs zu übernehmen. In a further development of the inventive concept it is proposed that the or- ganic additive or organic additives a particular according to the ISO 13320 average particle diameter in the to be compacted mixture (d 5 o) μιτι from 1 to 150, preferably μιτι 2-30 and particularly preferably from 3 to 10 μιτι have. Further, it is preferable that the molded article containing only organic additive according to this embodiment has a density of at least 1.0 g / cm 3 , preferably a density of 1.2 to 1.8 g / cm 3 and particularly preferably a density of 1, 4 to 1.7 g / cm 3 . According to a third very particularly preferred embodiment of the present invention, the molding according to the invention contains organic additive and inorganic additive. A particular advantage of this embodiment is that, due to the combination of organic additive and inorganic additive, a high impermeability of the shaped body to liquids and gases over a very broad temperature range from comparatively very low to comparatively high temperatures is reached. This can be achieved, for example, by selecting an inorganic additive and an organic additive, the inorganic additive decomposing at one in the range of the temperature and in particular just below the temperature at which the organic additive decomposes, for example by pyrolysis, combustion or a decomposition reaction is, begins, for example, initiated by a sintering or melting process to contribute to a densification of the molding and thus take over the role of the organic additive at a higher temperature.
Um diesbezüglich besonders gute Ergebnisse zu erreichen, wird es in Weiterbildung des Erfindungsgedankens vorgeschlagen, dass die zu verdichtende Mischung bzw. der Formkörper 1 bis 25 Gew.-% anorganisches Additiv und 1 bis 25 Gew.-% organisches Additiv und bevorzugt 3 bis 20 Gew.-% anorganisches Addi- tiv und 5 bis 15 Gew.-% organisches Additiv enthält. In order to achieve particularly good results in this regard, it is proposed in development of the invention that the mixture to be compacted or molded 1 to 25 wt .-% inorganic additive and 1 to 25 wt .-% organic additive and preferably 3 to 20 wt .-% inorganic additive and 5 to 15 wt .-% organic additive.
Grundsätzlich kann der Formkörper bei dieser Ausführungsform neben dem Graphit, dem anorganischen Additiv und dem organischen Additiv noch Füllstoffe enthalten, was jedoch nicht erforderlich und auch nicht bevorzugt ist. Daher be- steht der erfindungsgemäße Formkörper gemäß dieser Ausführungsform bevorzugt aus der vorgenannte Menge organischem Additiv, anorganischem Additiv und Rest Graphit. In principle, the shaped body in this embodiment, in addition to the graphite, the inorganic additive and the organic additive still fillers, but this is not necessary and not preferred. Therefore, according to this embodiment, the shaped article according to the invention preferably consists of the abovementioned amount of organic additive, inorganic additive and remainder graphite.
Als anorganische Additive und als organische Additive eignen sich insbesondere die vorstehend bereits für die beiden anderen ganz besonders bevorzugten Ausführungsformen der vorliegenden Erfindung genannten. Insbesondere mit der Kombination Glasbildner als anorganisches Additiv und Siliconharz als organisches Additiv werden vor allem im Hinblick auf eine exzellente Flächendichtigkeit besonders gute Ergebnisse erreicht. Vorzugsweise weisen die anorganischen und
organischen Additive die vorstehend für die beiden anderen ganz besonders bevorzugten Ausführungsformen genannten mittleren Partikeldurchmesser auf. Particularly suitable inorganic additives and organic additives are those already mentioned above for the other two particularly preferred embodiments of the present invention. Particularly with the combination of glass-forming agent as inorganic additive and silicone resin as organic additive, particularly good results are achieved, above all with regard to an excellent surface density. Preferably, the inorganic and Organic additives on the above-mentioned for the other two particularly preferred embodiments, average particle diameter.
Bevorzugt werden das organische Additiv und das anorganische Additiv hinsicht- lieh ihrer chemischen Natur und eingesetzten Mengen so ausgewählt, dass der Formkörper in einem Temperaturbereich zwischen -100 und 600 °C und insbesondere in einem Temperaturbereich zwischen -20 und 550 °C impermeabel ist, wobei unter impermeabel im Sinne der vorliegenden Erfindung verstanden wird, dass der Formkörper bei einer Flächenpressung von 20 MPa mit Helium als Gas (40 bar Innendruck) eine gemäß der DIN EN 13555 in einem Temperaturbereich von -100 bis 300 °C gemessene Impermeabilität von weniger als 10"1 mg/(s'm) aufweist und der Formkörper bei einer Flächenpressung von 32 MPa eine nach der TA-Luft in einem Temperaturbereich von 300 bis 600 °C nach einer Auslagerung für 48 Stunden gemessene Leckagerate von weniger als 1 x 10"4 mbarl/s'm (1 ,1 bar, Helium) aufweist. Vorzugsweise weist der Formkörper bei einer Flächenpressung von 20 MPa mit Helium als Gas (40 bar Innendruck) in einem Temperaturbereich zwischen -100°C und 600°C und bevorzugt zwischen -20°C und 550°C eine gemäß der DIN EN 13555 bestimmte Impermeabilität von weniger als 10"2 mg/(s m) und besonders bevorzugt von weniger als 10"3 mg/(s m) auf. The organic additive and the inorganic additive are preferably selected with regard to their chemical nature and amounts used such that the shaped body is impermeable in a temperature range between -100 and 600 ° C. and in particular in a temperature range between -20 and 550 ° C. Under impermeable in the sense of the present invention is understood that the shaped body at a surface pressure of 20 MPa with helium gas (40 bar internal pressure) according to DIN EN 13555 in a temperature range of -100 to 300 ° C measured impermeability of less than 10 "1 mg / (s ' m) and the shaped body at a surface pressure of 32 MPa a measured after the TA air in a temperature range of 300 to 600 ° C after aging for 48 hours leakage rate of less than 1 x 10 " 4 mbarl / s ' m (1, 1 bar, helium). Preferably, the shaped body at a surface pressure of 20 MPa with helium gas (40 bar internal pressure) in a temperature range between -100 ° C and 600 ° C and preferably between -20 ° C and 550 ° C determined according to DIN EN 13555 impermeability less than 10 "2 mg / (sm), and more preferably less than 10 " 3 mg / (sm).
In Weiterbildung des Erfindungsgedankens wird es vorgeschlagen, dass der sowohl organisches als auch anorganisches Additiv enthaltende Formkörper gemäß dieser Ausführungsform eine Dichte von wenigstens 0,7 g/cm3 und bevorzugt eine Dichte von 1 ,0 bis 1 ,8 g/cm3 aufweist. In a further development of the inventive concept, it is proposed that the molding containing both organic and inorganic additive according to this embodiment have a density of at least 0.7 g / cm 3 and preferably a density of 1, 0 to 1, 8 g / cm 3 .
Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung ist der Formkörper zumindest im Wesentlichen flächig ausgebildet, und zwar beispielsweise als Platte, Band oder Folie. Unter im Wesentlichen flächig ausgebildeter Formkörper werden im Rahmen der vorliegenden Erfindung auch speziell aus- geformte Formkörper, wie beispielsweise Dichtungsringe, verstanden. Für flächig
ausgebildete Formkörper lässt sich der Vorteil einer hohen Flächendichtigkeit besonders gut nutzen. According to a further preferred embodiment of the present invention, the shaped body is formed at least substantially flat, for example as a plate, tape or foil. In the context of the present invention, shaped bodies of essentially flat design are also understood as meaning specially shaped articles, such as, for example, sealing rings. For flat formed moldings, the advantage of a high surface density can be used particularly well.
Um die mechanische Stabilität des Formköpers zu erhöhen, kann dieser mit einer zwei- oder dreidimensional strukturierten Verstärkung versehen sein. Für diesen Zweck eigen sich insbesondere strukturierte Bleche, wie beispielsweise Spießbleche. In order to increase the mechanical stability of the molded body, this can be provided with a two- or three-dimensionally structured reinforcement. For this purpose, in particular structured sheets, such as spits.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines zuvor beschriebenen Formkörpers, welches die nachfolgenden Schritte umfasst: A further subject of the present invention is a process for the production of a previously described shaped body which comprises the following steps:
Vermischen von Graphitpartikeln mit wenigstens einem festen Additiv zu einer Mischung, welche wenigstens ein anorganisches Additiv, eine Mischung aus wenigstens einem anorganischen Additiv und wenigstens einem organischen Additiv oder mehr als 10 Gew.-% organisches Additiv enthält, wobei das eingesetzte wenigstens eine Additiv einen gemäß der ISO 13320 bestimmten mittleren Partikeldurchmesser (d5o) zwischen 1 und 500 μιτι aufweist, sowie Mixing of graphite particles with at least one solid additive to a mixture containing at least one inorganic additive, a mixture of at least one inorganic additive and at least one organic additive or more than 10 wt .-% organic additive, wherein the at least one additive used according to the ISO 13320 certain average particle diameter (d 5 o) between 1 and 500 μιτι has, and
Verdichten der in dem Verfahrensschritt a) erhaltenen Mischung. Compacting the mixture obtained in process step a).
Vorzugsweise wird das erfindungsgemäße Verfahren kontinuierlich durchgeführt, um so die erfindungsgemäßen Formkörper schnell, einfach und kostengünstig herzustellen. The process according to the invention is preferably carried out continuously so as to produce the shaped bodies according to the invention rapidly, simply and inexpensively.
Die kontinuierliche Verfahrensführung kann beispielsweise in einem Rohrleitungssystem durchgeführt werden, in dem das Vermischen gemäß dem Verfahrensschritt a) so durchgeführt wird, dass einem Graphitpartikel enthaltendem Gasstrom ein festes Additiv beispielsweise über eine Förderschnecke zugeführt wird und der
so erhaltene, vermischte, Graphitpartikel und Additiv enthaltende Gasstrom zum Verdichten gemäß dem Verfahrensschritt b) durch eine Walze geführt wird. So lassen sich nicht nur die Graphitpartikel und das Additiv schnell und einfach miteinander vermischen, sondern insbesondere schonend, d.h. ohne größere me- chanische Beanspruchung, vermischen, so dass ein Zerkleinern, wie Zermahlen, der Feststoffpartikel bei dem Vermischen, wie dies bei dem Vermischen in einem statischen oder dynamischen Rührer für mehrere Minuten oder gar Stunden zwangsläufig auftritt, vermieden wird. Dadurch werden die vorstehenden vorteilhaften Eigenschaften der erfindungsgemäßen Formkörper, vor allem eine hohe Zugfestigkeit sowie eine hohe Querfestigkeit, begünstigt. The continuous process management can be carried out, for example, in a pipeline system in which the mixing according to process step a) is carried out so that a graphite particle-containing gas stream, a solid additive is supplied for example via a screw conveyor and the thus obtained, mixed, graphite particles and additive containing gas stream for compacting according to the method step b) is guided by a roller. Thus, not only can the graphite particles and the additive be mixed with one another quickly and easily, but also in particular gently, ie without greater mechanical stress, mixed, so that comminution, such as grinding, of the solid particles during mixing, as in the mixing in A static or dynamic stirrer inevitably occurs for several minutes or even hours, is avoided. As a result, the above advantageous properties of the moldings of the invention, especially a high tensile strength and a high transverse strength, favors.
Bei dem erfindungsgemäßen Verfahren wird mithin vor dem Verdichten kein Vermischen in einer statischen oder dynamischen Rühreinrichtung für mehr als 5 Minuten, vor allem für mehr als 20 Minuten und insbesondere für mehr als 1 Stun- de durchgeführt. Thus, in the method according to the invention, no mixing is carried out in a static or dynamic stirring device for more than 5 minutes, in particular for more than 20 minutes and in particular for more than 1 hour, prior to compacting.
Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung wird die Graphitpartikel und Additiv enthaltende Mischung bei dem Verdichten oder nach dem Verdichten gemäß dem Verfahrensschritt b) geschmolzen und/oder gesintert. Im Rahmen der vorliegenden Erfindung wurde überraschenderweise festgestellt, dass dadurch die Impermeabilität des Formkörpers gegenüber Flüssigkeiten und Gasen weiter gesteigert werden kann. Ohne an eine Theorie gebunden werden zu wollen, wird es erachtet, dass durch ein solches Schmelzen bzw. Sintern die Verbindung der Graphitpartikel mit den Additivpartikeln ver- bessert wird und durch das dann dünnflüssige Additiv weitere Poren geschlossen und Kontaktpunkte erzeugt werden. According to another preferred embodiment of the present invention, the mixture containing graphite particles and additive is melted and / or sintered during compaction or after compaction according to method step b). In the context of the present invention, it has surprisingly been found that this can further increase the impermeability of the molding to liquids and gases. Without wishing to be bound by theory, it is considered that the fusion of the graphite particles with the additive particles is improved by such melting or sintering, and further pores are closed and contact points are created by the then thin-fluid additive.
Zur endgültigen Formgebung kann ein separater Formgebungsschritt erfolgen, bei welchem der Formkörper beispielsweise durch Umformen, Profilieren, Fügen,
Heißpressen, Thermoumfornnen, Umkanten, Tiefziehen, Prägen oder Stanzen ausgebildet wird. For the final shaping, a separate shaping step can take place, in which the shaped body is formed, for example, by forming, profiling, joining, Hot pressing, Thermoumfornnen, edge, deep drawing, embossing or punching is formed.
Dabei kann der Formgebungsschritt vorteilhafterweise vor einem endgültigen Verdichtungsschritt erfolgen. Beispielsweise kann es bei dem Einsatz des Formkörpers als Dichtung vorteilhaft sein, den Formkörper durch ein Einklemmen zwischen zwei abzudichtende Teile zu verformen und anschließend endgültig zu verdichten, beispielsweise durch Temperaturanwendung. Eine Vorverdichtung kann jedoch schon vor dem Verformen durchgeführt werden, beispielsweise durch ein Verpressen. In this case, the shaping step can advantageously take place before a final compression step. For example, it may be advantageous in the use of the molding as a seal to deform the molded body by pinching between two parts to be sealed and then finally compact, for example by applying temperature. However, pre-compaction can be carried out before deformation, for example by compression.
Außerdem kann der Formkörper in einer Pressform erhitzt werden, wodurch bestimmte Profile, Formen, Wellen und/oder Prägungen erzeugt werden. Das Additiv stabilisiert diese Formen und verhindert das von herkömmlichen Graphitfolien bekannte Rückverformen. Die durch die vorliegende Erfindung erzeugte mechanische Belastbarkeit erlaubt es erstmalig, solche Verfahren anzuwenden. In addition, the shaped body can be heated in a mold, whereby certain profiles, shapes, waves and / or embossments are generated. The additive stabilizes these forms and prevents the reformation known from conventional graphite films. The mechanical load capacity generated by the present invention allows for the first time to apply such methods.
Schließlich betrifft die vorliegende Erfindung die Verwendung eines zuvor beschriebenen graphithaltigen Formkörpers als Dichtungselement, als Bipolarplatte einer Brennstoffzelle, einer Redox-Flow-Batterie, als Wärmeleitfolie, als Formteil im Baubereich, insbesondere Wandverkleidung, Deckenverkleidung oder Wärmeleitplatte, als Stromableiter in Blei-Säure-Batterien oder in entsprechenden Hybridsystemen, als Folie oder Finne in PCM-Graphit-Speichern, als Auskleidungsmaterial, als Kontaktierungselement, als Elektrodenmaterial für Batteriesysteme, als Wärmeverteilungselement, als Flächenheizer, als Material zum Wickeln von Graphitrohren mit Verschweißbarkeit der einzelnen Lagen, als Stopfbuchspackung, als Packungen für chemische Kolonnen, als Wärmetauscherplatte oder als Wärmetauscherrohr.
Für die erfindungsgemäße Verwendung des Formkörpers als Bipolarplatte in einer Redox-Flow-Batterie ist der Formkörper vorzugsweise als Folie oder Platte mit einer Dicke von 0,02 bis 1 ,5 mm, besonders bevorzugt mit einer Dicke von 0,2 bis 1 mm und ganz besonders bevorzugt mit einer Dicke von 0,5 bis 0,8 mm ausge- bildet. Dickere Platten können beispielsweise durch Verpressen, Verkleben, Heißkleben von zwei einzelnen Formkörpern hergestellt werden. Dies ist mit oder ohne Druck und durch Verwendung von Klebstoffen, Haftvermittlern oder durch das in dem Formkörper vorliegende Additiv möglich. Dabei ist die direkte Verschweiß- barkeit zweier Formkörper besonders bevorzugt. Finally, the present invention relates to the use of a previously described graphite molded body as a sealing element, as bipolar plate of a fuel cell, a redox flow battery, as a heat conducting foil, as a molded part in the construction sector, in particular wall cladding, ceiling cladding or heat conduction, as a current conductor in lead-acid batteries or in corresponding hybrid systems, as foil or fin in PCM graphite stores, as lining material, as contacting element, as electrode material for battery systems, as heat distribution element, as surface heater, as material for winding graphite tubes with weldability of the individual layers, as stuffing box, as packages for chemical columns, as a heat exchanger plate or as a heat exchanger tube. For the inventive use of the shaped body as a bipolar plate in a redox flow battery, the shaped body is preferably in the form of a foil or plate with a thickness of 0.02 to 1.5 mm, particularly preferably with a thickness of 0.2 to 1 mm and completely particularly preferably formed with a thickness of 0.5 to 0.8 mm. Thicker plates can be produced, for example, by pressing, gluing, hot-bonding of two individual shaped bodies. This is possible with or without printing and by using adhesives, adhesion promoters or by the additive present in the molding. The direct weldability of two shaped bodies is particularly preferred.
Bei der erfindungsgemäßen Verwendung des Formkörpers als Bipolarplatte kann es besonders vorteilhaft sein, den erfindungsgemäßen Formkörper mit einem Filz, der vorzugsweise Graphit und/oder Kohlenstoff und besonders bevorzugt Graphit- und/oder Kohlenstofffasern enthält, zu verbinden. Dabei kann die Verbindung beispielsweise durch Verklebung erfolgen. Insbesondere kann ein leitfähiger Klebstoff verwendet werden, wie etwa ein mit Silberpartikeln, Kohlenstoffpartikeln oder Graphitpartikeln gefüllter Klebstoff. Eine solche Verbindung kann auch durch Aufschmelzen oder durch Sintern mit einem Kunststoff, insbesondere einem vorstehend für das organische Additiv beschriebenen Polymer, erfolgen. Im einfachsten Fall wird also ein Filz thermisch mit einem erfindungsgemäßen Formkörper ohne weitere Materialien verbunden. When using the shaped body according to the invention as a bipolar plate, it can be particularly advantageous to bond the shaped body according to the invention with a felt, which preferably contains graphite and / or carbon and particularly preferably graphite and / or carbon fibers. The connection can be made for example by gluing. In particular, a conductive adhesive may be used, such as an adhesive filled with silver particles, carbon particles or graphite particles. Such a compound can also be made by melting or by sintering with a plastic, in particular a polymer described above for the organic additive. In the simplest case, therefore, a felt is thermally bonded to a molding according to the invention without further materials.
Bei der vorstehend beschriebenen Ausführungsform beträgt die Dichte des Filzes vorzugsweise 0,01 bis 0,2 g/cm3. Dabei liegt der spezifische elektrische Wider- stand, in der Filzebene gemessen, bevorzugt zwischen 0,5 und 15 Ohm mm und der spezifische elektrische Widerstand, senkrecht zu der Filzebene gemessen, bevorzugt zwischen 2 und 20 Ohm mm. Diese Werte beziehen sich auf eine Kompression des Filzes von 20 bis 30 %. Bei stärkerer bzw. schwächerer Kompression ist der spezifische elektrische Widerstand entsprechend niedriger bzw. höher. Die
spezifische Oberfläche des Filzes beträgt vorzugsweise zwischen 0,2 und 300 m2/g. In the embodiment described above, the density of the felt is preferably 0.01 to 0.2 g / cm 3 . In this case, the specific electrical resistance, measured in the felt plane, is preferably between 0.5 and 15 ohm mm and the specific electrical resistance measured perpendicular to the felt plane, preferably between 2 and 20 ohm mm. These values refer to a compression of the felt of 20 to 30%. With stronger or weaker compression, the specific electrical resistance is correspondingly lower or higher. The specific surface of the felt is preferably between 0.2 and 300 m 2 / g.
Vor allem bei der erfindungsgemäßen Verwendung des Formkörpers als Formteil im Baubereich, insbesondere als Wandverkleidung, Deckenverkleidung oder Wärmeleitplatte, hat es sich als vorteilhaft erwiesen, den Formkörper plastisch verformbar und beispielsweise in der Form einer Platte vorzusehen, so dass der Formkörper am Einbauort einfach an vorgegebene Konturen von Wänden oder Decken, beispielsweise Kanten, Krümmungen, Ecken, Friesen und dergleichen, angeformt werden kann. Anschließend kann die Platte dann am Einbauort, beispielsweise durch Erhitzen der noch plastisch verformbaren Platte im eingebauten Zustand, endverfestigt werden. Especially when using the molded article according to the invention as a molded part in the construction sector, in particular as wall cladding, ceiling cladding or Wärmeleitplatte, it has proven to be advantageous to provide the molded body plastically deformable and, for example, in the form of a plate, so that the molding at the installation simply to predetermined Contours of walls or ceilings, such as edges, bends, corners, friezes and the like, can be molded. Subsequently, the plate can then be finally consolidated at the installation site, for example by heating the still plastically deformable plate in the installed state.
Grundsätzlich kann der erfindungsgemäße Formkörper vor oder nach einer voll- ständigen Aushärtung oder vor oder nach einem Aufschmelzen und/oder Sintern des Additivs verwendet werden. In principle, the shaped body according to the invention can be used before or after a complete curing or before or after a melting and / or sintering of the additive.
Alternativ dazu ist es auch möglich, den Formkörper nach einem teilweisen Aushärten, Aufschmelzen und/oder Sintern des Additivs zu verwenden, wobei das endgültige Aushärten, Aufschmelzen und/oder Sintern des Additivs beispielsweise bei der Verwendung bei der Betriebstemperatur erfolgt. Bei dieser Ausführungsform tritt beispielsweise eine hohe Dichtigkeit des Formkörpers erst im Laufe des Einsatzes ein. Dies hat den Vorteil, dass bei dem Einbau die Formbarkeit zur Erzielung einer besseren Anpassung des Formkörpers beispielsweise an dicht zu verbindende Teile möglich ist. Alternatively, it is also possible to use the shaped body after a partial curing, melting and / or sintering of the additive, wherein the final curing, melting and / or sintering of the additive takes place, for example, when used at the operating temperature. In this embodiment, for example, a high density of the molded body occurs only in the course of use. This has the advantage that in the mold, the moldability to achieve a better adaptation of the molding is possible, for example, to tightly connected parts.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung eines zuvor beschriebenen graphithaltigen Formkörpers in einem Verfahren zum Verbinden des Formkörpers mit einem anderen Formkörper, wobei der andere Form- körper beispielsweise eine Graphitfolie, eine Metallfolie, ein Metallblech, ein Me-
tallblock, ein textiles Flächengebilde, bevorzugt ein Filzkörper, oder auch ein zuvor beschriebener Formkörper sein kann. Dabei findet das Verbinden der Formkörper ohne zusätzlichen Klebstoff statt. Ein solcher Klebstoff ist bei der erfindungsge- mäßen Verwendung entbehrlich, weil das in dem Formkörper enthaltene organi- sehe Additiv als Bindemittel wirkt und so eine Verschweißung der beiden Körper zulässt. A further subject matter of the present invention is the use of a previously described graphite-containing shaped body in a method for connecting the shaped body to another shaped body, wherein the other shaped body is, for example, a graphite foil, a metal foil, a metal sheet, a metal foil. tallblock, a textile fabric, preferably a felt body, or may be a previously described molding. In this case, the bonding of the shaped body takes place without additional adhesive. Such an adhesive is dispensable in the use according to the invention because the organic additive contained in the shaped body acts as a binder and thus allows the two bodies to be welded together.
Nachfolgend wird die vorliegende Erfindung rein beispielhaft anhand vorteilhafter Ausführungsformen und unter Bezugnahme auf die beigefügten Zeichnungen beschrieben. Hereinafter, the present invention will be described purely by way of example with reference to advantageous embodiments and with reference to the accompanying drawings.
Dabei zeigen: Showing:
Figur 1 einen graphithaltigen Formkörper gemäß dem Stand der Technik und Figure 1 is a graphite-containing molded body according to the prior art and
Figur 2 einen graphithaltigen Formkörper gemäß einem Ausführungsbeispiel der vorliegenden Erfindung. In der Figur 1 ist ein schematischer Querschnitt eines als Platte ausgebildeten graphithaltigen Formkörpers 1 gemäß dem Stand der Technik dargestellt. Dieser Formkörper 1 enthält verpressten, expandierten Graphit 2 und ein flüssiges Bindemittel 3, wobei das Bindemittel 3 nachträglich durch Flüssig- oder Schmelzimprägnierung von den Seitenflächen des Formkörpers 1 in den Formkörper 1 ein- gebracht worden ist. Aufgrund des Einbringens des Bindemittels 3 durch Flüssigoder Schmelzimprägnierung ist dieses nur ungleichmäßig und vor allem oberflächlich in den Formkörper 1 eingedrungen, weswegen vor allem der zwischen den Oberflächenbereichen liegende innere Bereich, wie beispielsweise der in der ovalen, gestrichelten Umrandung liegende Bereich 4, nur wenig Bindemittel 3 enthält bzw. nahezu bindemittelfrei ist. Aufgrund dessen variieren die Eigenschaften des
Formkörpers 1 , insbesondere die mechanische Festigkeit und die Dichtigkeit, des Formkörpers 1 vor allem in der Tiefenrichtung bzw. z-Richtung, wobei der zwischen den Oberflächenbereichen liegende innere Bereich des Formkörpers 1 eine schlechtere Dichtigkeit und schlechtere mechanische Eigenschaften als die Ober- flächenbereiche des Formkörpers 1 aufweist. 2 shows a graphite-containing molded body according to an embodiment of the present invention. FIG. 1 shows a schematic cross section of a graphite-shaped molded body 1 according to the prior art which is designed as a plate. This shaped body 1 contains pressed, expanded graphite 2 and a liquid binder 3, wherein the binder 3 has subsequently been introduced into the shaped body 1 by liquid or melt impregnation from the side surfaces of the shaped body 1. Due to the incorporation of the binder 3 by liquid or melt impregnation this is only unevenly and especially superficially penetrated into the molded body 1, which is why especially between the surface areas lying inner region, such as lying in the oval, dashed border area 4, little binder Contains 3 or is almost binder-free. Because of this, the characteristics of the Shaped body 1, in particular the mechanical strength and the impermeability, of the molded body 1, especially in the depth direction or z-direction, the inner region of the shaped body 1 lying between the surface regions having a poorer impermeability and poorer mechanical properties than the surface areas of the shaped body 1 has.
Der in der Figur 2 dargestellte Formkörper 5 gemäß der vorliegenden Erfindung besteht aus Partikeln 6 aus expandiertem Graphit, welche in bekannter Weise wurm- oder ziehharmonikaförmig ausgestaltet sind, sowie aus Additivpartikeln 7. Im Unterschied zu dem in der Figur 1 gezeigten Formkörper 1 gemäß dem Stand der Technik sind die Additivpartikel 7 in dem erfindungsgemäßen Formkörper 5 in allen Dimensionen des Formkörpers 5 gleichmäßig verteilt, und zwar insbesondere auch in dem zwischen den Oberflächenbereichen liegenden inneren Bereich des Formkörpers 5. The molded body 5 according to the present invention shown in FIG. 2 consists of particles 6 of expanded graphite, which are configured worm-shaped or concertina-shaped in a known manner, as well as of additive particles 7. In contrast to the molded body 1 according to the prior art shown in FIG In the art, the additive particles 7 are uniformly distributed in the shaped body 5 according to the invention in all dimensions of the shaped body 5, and in particular also in the inner area of the shaped body 5 lying between the surface areas.
Zur Herstellung des in der Figur 2 dargestellten erfindungsgemäßen Formkörpers 5 wurden zunächst die Graphitpartikel 6 mit den festen Additivpartikeln 7 homogen vermischt, bevor die so hergestellte Mischung verdichtet und zu der gewünschten Form geformt wurde. To produce the shaped body 5 according to the invention shown in FIG. 2, the graphite particles 6 were first homogeneously mixed with the solid additive particles 7 before the mixture thus produced was compacted and shaped into the desired shape.
Nachfolgend wird die vorliegende Erfindung anhand von diese erläuternden, diese aber nicht einschränkenden Beispielen weiter beschrieben. Hereinafter, the present invention will be further described by way of these illustrative but nonlimiting examples.
Beispiele Examples
Beispiel 1 example 1
Expandierter Graphit mit einem Schüttgewicht von 3,5 g/l wurde mit einem Siliconharzpulver, nämlich Silres MK der Firma Wacker Chemie AG in Burghausen, Deutschland, zu einer 80 Gew.-% expandierten Graphit und 20 Gew.-% Silicon-
harzpulver enthaltenden Mischung versetzt und anschließend in einem Behälter für 1 Minute vermischt. Expanded graphite having a bulk density of 3.5 g / l was treated with a silicone resin powder, namely Silres MK from Wacker Chemie AG in Burghausen, Germany, to form an 80% by weight expanded graphite and 20% by weight silicone rubber. mixture containing resin powder and then mixed in a container for 1 minute.
Die so erhaltene Mischung wurde dann in ein Stahlrohr mit 90 mm Durchmesser überführt, mit einem Druckkolben durch das eigene Körpergewicht verpresst und als Vorpressling mit einer Dichte von ca. 0,07 g/cm3 entnommen. Anschließend wurde der Vorpressling mit einer Presse auf die gewünschte Folienstärke von 1 mm komprimiert und die so entstandene dotierte Folie wurde bei 180°C für 60 Minuten konditioniert, um den Kunststoff aufzuschmelzen. The mixture thus obtained was then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and taken as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the pre-compact was compressed with a press to the desired film thickness of 1 mm and the resulting doped film was conditioned at 180 ° C for 60 minutes to melt the plastic.
Zwei dieser Folien wurden mit einem Spießblech mit einer Dicke von 0,1 mm verpresst und es wurde die Leckagerate dieses Formkörpers gemäß der DIN EN 13555 mit Helium als Prüfgas (40 bar Innendruck) bestimmt. In der untenstehenden Tabelle 1 sind die bestimmten Flächenpressungen angegeben, welche benötigt werden, um eine bestimmte Leckageklasse zu erreichen. Two of these films were pressed with a spit plate with a thickness of 0.1 mm and it was the leakage rate of this molding according to DIN EN 13555 with helium as the test gas (40 bar internal pressure) determined. Table 1 below gives the specific surface pressures needed to achieve a particular leakage class.
Vergleichsbeispiel 1 Gemäß dem für das Beispiel 1 beschriebenen Verfahren wurden zwei Graphitfolien hergestellt, ausgenommen, dass zu deren Herstellung ausschließlich expandierter Graphit und kein Additiv eingesetzt wurde. Comparative Example 1 According to the method described for Example 1, two graphite foils were produced, except that only expanded graphite and no additive were used for their production.
Zwei dieser Folien wurden mit einem Spießblech mit einer Dicke von 0,1 mm ver- presst und es wurde die Leckagerate dieses Formkörpers gemäß der DIN EN 13555 mit Helium als Prüfgas (40 bar Innendruck) bestimmt. Two of these films were pressed with a spit plate having a thickness of 0.1 mm and the leakage rate of this shaped article was determined according to DIN EN 13555 with helium as test gas (40 bar internal pressure).
Die erhaltenen Werte sind in der nachfolgenden Tabelle 1 zusammengefasst.
Tabelle 1 The values obtained are summarized in Table 1 below. Table 1
Es ist deutlich zu erkennen, dass durch das Additiv die Impermeabilität verbessert wird. Durch den Zusatz von Additiv wird schon bei deutlich niedrigeren Flächenpressungen ein bestimmtes Dichtigkeitsniveau erreicht. It can be clearly seen that the additive improves the impermeability. The addition of additive achieves a certain level of tightness even at significantly lower surface pressures.
Beispiele 2 und 3 Expandierter Graphit mit einem Schüttgewicht von 3,5 g/l wurde mit einem anorganischem Füllstoff, nämlich Ammoniumdihydrogenphosphat (NH H2PO4) in dem Beispiel 2 und Borcarbid (B C) in dem Beispiel 3, zu einer 90 Gew.-% expandierten Graphit und 10 Gew.-% anorganischen Füllstoff enthaltenden Mischung versetzt und anschließend in einem Behälter für 1 Minute vermischt. EXAMPLES 2 and 3 Expanded graphite having a bulk density of 3.5 g / l was mixed with an inorganic filler, namely ammonium dihydrogen phosphate (NHH 2 PO 4 ) in Example 2 and boron carbide (BC) in Example 3 to give 90 wt. -% expanded graphite and 10 wt .-% inorganic filler containing mixture and then mixed in a container for 1 minute.
Die so erhaltene Mischung wurde dann in ein Stahlrohr mit 90 mm Durchmesser überführt, mit einem Druckkolben durch das eigene Körpergewicht verpresst und als Vorpressling mit einer Dichte von ca. 0,07 g/cm3 entnommen. Anschließend wurde der Vorpresslinge mit einer Presse auf die gewünschte Folienstärke von 1 mm komprimiert und die so entstandene dotierte Folie wurde bei 180°C für 60 Minuten konditioniert. The mixture thus obtained was then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and taken as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the pre-compacts were compressed with a press to the desired film thickness of 1 mm and the resulting doped film was conditioned at 180 ° C for 60 minutes.
Für beide Proben wurde die Leckagerate nach DIN 28090-1 mit Stickstoff als Prüfgas und 32 MPa Flächenpressung bezogen auf ein Flächengewicht des Formkörpers von 2.000 g/m2 gemessen.
Die erhaltenen Werte sind in der nachfolgenden Tabelle 2 zusammengefasst. For both samples, the leakage rate was measured according to DIN 28090-1 with nitrogen as test gas and 32 MPa surface pressure based on a basis weight of the molded body of 2,000 g / m 2 . The values obtained are summarized in Table 2 below.
Verqleichsbeispiel 2 Comparative Example 2
Gemäß den für die Beispiele 2 und 3 beschriebenen Verfahren wurde eine Graphitfolie hergestellt, ausgenommen, dass zu deren Herstellung ausschließlich expandierter Graphit und kein Additiv eingesetzt wurde. A graphite foil was produced according to the procedures described for Examples 2 and 3, except that exclusively expanded graphite and no additive were used for their production.
Für die Probe wurde die Leckagerate nach DIN 28090-1 mit Stickstoff als Prüfgas und 32 MPa Flächenpressung bezogen auf ein Flächengewicht des Formkörpers von 2.000 g/m2 gemessen. For the sample, the leakage rate was measured according to DIN 28090-1 with nitrogen as the test gas and 32 MPa surface pressure based on a basis weight of the molded body of 2,000 g / m 2 .
Die erhaltenen Werte sind in der nachfolgenden Tabelle 2 zusammengefasst. The values obtained are summarized in Table 2 below.
Tabelle 2 Table 2
VBsp.: Vergleichsbeispiel VBsp .: comparative example
Bsp.: Beispiel Example: example
Aus den in der Tabelle 2 wiedergegebenen Werten lässt sich deutlich erkennen, dass durch den Zusatz des anorganischen Additivs die Leckagerate des Formköpers beträchtlich verringert wird. Zudem wird nach Ausbildung des nun im ganzen
Folienverbund vorliegenden glasartigen Netzwerkes die Druckfestigkeit positiv beeinflusst. From the values shown in Table 2 it can be clearly seen that the addition of the inorganic additive considerably reduces the leakage rate of the molded article. In addition, after training the now in the whole Foil composite present glassy network positively influences the compressive strength.
Beispiele 4 bis 7 Examples 4 to 7
Expandierter Graphit mit einem Schüttgewicht von 3,5 g/l wurde mit Ammoniumdi- hydrogenphosphat (NH H2PO4) für die Beispiele 4 und 5 und Ammoniumhydro- genphosphat (NH )2HPO4für die Beispiele 6 und 7 als anorganischem Füllstoff zu 95 Gew.-% expandierten Graphit und 5 Gew.-% anorganischen Füllstoff enthal- tenden Mischungen versetzt, welche anschließend in einem Behälter für 1 Minute vermischt wurden. Expanded graphite with a bulk density of 3.5 g / l was admixed with ammonium dihydrogen phosphate (NHH 2 PO 4 ) for Examples 4 and 5 and ammonium hydrogenphosphate (NH) 2 HPO 4 for Examples 6 and 7 as inorganic filler 95 wt .-% expanded graphite and 5 wt .-% inorganic filler containing mixtures added, which were then mixed in a container for 1 minute.
Die so erhaltene Mischungen wurde dann in ein Stahlrohr mit 90 mm Durchmesser überführt, mit einem Druckkolben durch das eigene Körpergewicht verpresst und als Vorpressling mit einer Dichte von ca. 0,07 g/cm3 entnommen. Anschließend wurde die Vorpressling mit einer Presse auf die gewünschte Folienstärke von 1 mm komprimiert und die so entstandene dotierten Folien wurden bei verschiedenen Bedingungen, welche in der nachfolgenden Tabelle 3 zusammenge- fasst sind, konditioniert. The mixtures thus obtained were then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and removed as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the preform was compressed with a press to the desired film thickness of 1 mm and the resulting doped films were at different conditions, which are summarized in the following Table 3, conditioned.
Für alle Proben wurde die Leckagerate nach DIN 28090-1 mit Stickstoff als Prüfgas und 32 MPa Flächenpressung bezogen auf ein Flächengewicht des Formkörpers von 2.000 g/m2 gemessen. For all samples, the leakage rate was measured according to DIN 28090-1 with nitrogen as the test gas and 32 MPa surface pressure based on a basis weight of the molded article of 2,000 g / m 2 .
Die erhaltenen Werte sind in der nachfolgenden Tabelle 3 zusammengefasst. The values obtained are summarized in Table 3 below.
Verqleichsbeispiel 3
Gemäß den für die Beispiele 4 bis 7 beschriebenen Verfahren wurde eine Graphitfolie hergestellt, ausgenommen, dass zu deren Herstellung ausschließlich expandierter Graphit und kein Additiv eingesetzt wurde. Für die Probe wurde die Leckagerate nach DIN 28090-1 mit Stickstoff als Prüfgas und 32 MPa Flächenpressung bezogen auf ein Flächengewicht des Formkörpers von 2.000 g/m2 gemessen. Comparative Example 3 A graphite foil was produced according to the methods described for Examples 4 to 7, except that exclusively expanded graphite and no additive were used for their production. For the sample, the leakage rate was measured according to DIN 28090-1 with nitrogen as the test gas and 32 MPa surface pressure based on a basis weight of the molded body of 2,000 g / m 2 .
Die erhaltenen Werte sind in der nachfolgenden Tabelle 3 zusammengefasst. The values obtained are summarized in Table 3 below.
Tabelle 3 Table 3
Bsp.: Beispiel Example: example
Aus den in der Tabelle 3 wiedergegebenen Werten lässt sich deutlich erkennen, dass durch den Zusatz des anorganischen Additivs die Leckagerate des Formköpers beträchtlich verringert wird und diese durch die Art der Konditionierung zusätzlich beeinflusst werden kann. From the values shown in Table 3 it can be clearly seen that the addition of the inorganic additive considerably reduces the leakage rate of the molded article and that this can additionally be influenced by the type of conditioning.
Beispiel 8
Expandierter Graphit mit einem Schüttgewicht von 3,5 g/l wurde mit einem Polypropylenpulver, nämlich mit Licocene PP 2602 der Firma Clariant, Deutschland, zu einer 80 Gew.-% expandierten Graphit und 20 Gew.-% Polypropylenpolymerpulver enthaltenden Mischung versetzt und anschließend in einem Behälter für 1 Minute vermischt. Example 8 Expanded graphite having a bulk density of 3.5 g / l was mixed with a polypropylene powder, namely with Licocene PP 2602 Clariant, Germany, to a 80 wt .-% expanded graphite and 20 wt .-% polypropylene polymer powder mixture and then in a container for 1 minute mixed.
Die so erhaltene Mischung wurde dann in ein Stahlrohr mit 90 mm Durchmesser überführt, mit einem Druckkolben durch das eigene Körpergewicht verpresst und als Vorpressling mit einer Dichte von ca. 0,07 g/cm3 entnommen. Anschließend wurde der Vorpressling mit einer Presse auf die gewünschte Folienstärke von 0,6 mm komprimiert und die so entstandene dotierte Folie wurde bei 180°C für 60 Minuten ausgelagert, um den Kunststoff aufzuschmelzen. The mixture thus obtained was then transferred to a steel tube of 90 mm diameter, pressed with a pressure piston by its own body weight and taken as a pre-compact with a density of about 0.07 g / cm 3 . Subsequently, the pre-compact was compressed with a press to the desired film thickness of 0.6 mm and the resulting doped film was removed at 180 ° C for 60 minutes to melt the plastic.
Es wurde die Impermeabilität des Formkörpers in z-Richtung bei einer Flächen- pressung von 20 MPa mit Helium als Gas (1 bar Helium Prüfgassinnendruck) in einer Messapparatur in Anlehnung an die DIN 28090-1 bei Raumtemperatur bestimmt. Zudem wurde die Zugfestigkeit des graphithaltigen Formkörper gemäß der DIN ISO 1924-2 bestimmt. Die erhaltenen Werte sind in der nachfolgenden Tabelle 4 zusammengefasst. The impermeability of the molding in the z-direction at a surface pressure of 20 MPa with helium as gas (1 bar helium test gas internal pressure) in a measuring apparatus based on DIN 28090-1 at room temperature was determined. In addition, the tensile strength of the graphite-containing molded body was determined according to DIN ISO 1924-2. The values obtained are summarized in Table 4 below.
Verqleichsbeispiel 4 Gemäß dem für das Beispiel 8 beschriebenen Verfahren wurde ein Formkörper in Form einer Graphitfolien hergestellt, ausgenommen, dass bei der Herstellung ausschließlich expandierter Graphit und kein Additiv eingesetzt wurde. Comparative Example 4 According to the method described for Example 8, a molded article was produced in the form of graphite foils, except that exclusively expanded graphite and no additive were used in the production.
Es wurde die Impermeabilität des Formkörpers in z-Richtung bei einer Flächen- pressung von 20 MPa mit Helium als Gas (1 bar Helium Prüfgassinnendruck) in
einer Messapparatur in Anlehnung an die DIN 28090-1 bei Raumtemperatur bestimmt. Zudem wurde die Zugfestigkeit des graphithaltigen Formkörper gemäß der DIN ISO 1924-2 bestimmt. Die erhaltenen Werte sind in der nachfolgenden Tabelle 4 zusammengefasst. The impermeability of the shaped body in the z-direction at a surface pressure of 20 MPa with helium as gas (1 bar helium test gas internal pressure) was determined a measuring apparatus based on DIN 28090-1 determined at room temperature. In addition, the tensile strength of the graphite-containing molded body was determined according to DIN ISO 1924-2. The values obtained are summarized in Table 4 below.
Tabelle 4 Table 4
VBsp.: Vergleichsbeispiel VBsp .: comparative example
Bsp.: Beispiel Example: example
Es ist deutlich zu erkennen, dass durch den Zusatz des organischen Additivs in eine Graphitfolie deren Impermeabilitat insbesondere auch in der z-Richtung verbessert wird und auch die Zugfestigkeit im Vergleich zu einem additivfreien graphithaltigen Formkörpers deutlich gesteigert werden kann.
It can be clearly seen that the addition of the organic additive to a graphite foil improves its impermeability, in particular also in the z-direction, and also that the tensile strength can be significantly increased compared to an additive-free graphite-containing shaped body.
Bezugszeichenliste LIST OF REFERENCE NUMBERS
1 Formkörper gemäß dem Stand der Technik1 shaped body according to the prior art
2 (expandierter) Graphit 2 (expanded) graphite
3 Bindemittel 3 binders
4 Bereich des Formkörpers 4 area of the molding
5 Formkörper gemäß der vorliegenden Erfindung 6 Partikel aus (expandiertem) Graphit 5 Moldings According to the Present Invention 6 Particles of (expanded) graphite
7 Additivpartikel
7 additive particles
Claims
Graphithaltiger Formkörper (5) erhältlich durch ein Verfahren, bei dem Graphitpartikel (6) mit wenigstens einem festen Additiv (7) zu einer Mischung, welche wenigstens ein anorganisches Additiv (7), eine Mischung aus wenigstens einem anorganischen Additiv (7) und wenigstens einem organischen Additiv (7) oder mehr als 10 Gew.-% organisches Additiv (7) enthält, vermischt werden und die so erhaltene Mischung anschließend verdichtet wird, wobei das eingesetzte wenigstens eine Additiv (7) einen gemäß der ISO 13320 bestimmten mittleren Partikeldurchmesser (d5o) zwischen 1 und 500 μιτι aufweist. Graphite-containing shaped body (5) obtainable by a process in which graphite particles (6) with at least one solid additive (7) to a mixture, which at least one inorganic additive (7), a mixture of at least one inorganic additive (7) and at least one organic additive (7) or more than 10% by weight of organic additive (7), and the mixture thus obtained is subsequently compressed, the at least one additive (7) used having an average particle diameter determined according to ISO 13320 (i.e. 5 o) between 1 and 500 μιτι has.
Formkörper (5) nach Anspruch 1 , Shaped body (5) according to claim 1,
dadurch gekennzeichnet, dass characterized in that
die Graphitpartikel (6), das wenigstens eine feste Additiv (7) und die daraus hergestellte Mischung vordem Verdichten nicht geschmolzen und nicht gesintert werden. the graphite particles (6), the at least one solid additive (7) and the mixture produced therefrom are not melted prior to compaction and are not sintered.
Formkörper (5) nach Anspruch 1 oder 2, Shaped body (5) according to claim 1 or 2,
dadurch gekennzeichnet, dass characterized in that
als Graphitpartikel (6) Partikel aus expandiertem Graphit (6) eingesetzt werden, welcher bevorzugt aus Naturgraphit mit einem gemäß dem in der DIN 66165 spezifizierten Messverfahren und Siebsatz bestimmten mittleren Partikeldurchmesser (d5o) von wenigstens 149 μιτι und bevorzugt von wenigstens 180 μιτι hergestellt worden ist. as graphite particles (6) particles of expanded graphite (6) are used, which preferably made of natural graphite with a specified in the DIN 66165 measurement method and sieve set mean particle diameter (d 5 o) of at least 149 μιτι and preferably of at least 180 μιτι produced has been.
4. Formkörper (5) nach Anspruch 3, 4. molded body (5) according to claim 3,
dadurch gekennzeichnet, dass die Partikel aus expandiertem Graphit (6) ein Schüttgewicht von 0,5 bis 95 g/l, vorzugsweise von 1 bis 25 g/l und besonders bevorzugt von 2 bis 10 g/l aufweisen. characterized in that the particles of expanded graphite (6) have a bulk density of 0.5 to 95 g / l, preferably from 1 to 25 g / l and particularly preferably from 2 to 10 g / l.
Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Shaped body (5) according to at least one of the preceding claims, characterized in that
dieser bei einer Flächenpressung von 20 MPa mit Helium als Gas (40 bar Innendruck) eine gemäß der DIN EN 13555 bei Raumtemperatur gemessene Impermeabilität von weniger als 10"1 mg/(s'm), bevorzugt von weniger als 10"2 mg/(s m) und besonders bevorzugt von weniger als 10"3 mg/(s m) aufweist. this at a surface pressure of 20 MPa using helium as a gas (40 bar internal pressure), measured according to DIN EN 13555 at room temperature impermeability of less than 10 "1 mg / (s' m), preferably less than 10" 2 mg / ( sm) and more preferably less than 10 -3 mg / (sm).
Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Shaped body (5) according to at least one of the preceding claims, characterized in that
dieser bei einer Flächenpressung von 20 MPa mit Helium als Gas (1 bar Helium Prüfgassinnendruck) in einer Messapparatur in Anlehnung an die DIN 28090-1 bei Raumtemperatur eine gemessene Impermeabilität in der z-Richtung von weniger als 10-1 mg/(s m2), bevorzugt von weniger als 10-2 mg/(s m2) und besonders bevorzugt von weniger als 10-3 mg/(s m2) aufweist. this at a surface pressure of 20 MPa with helium as gas (1 bar helium test gas internal pressure) in a measuring apparatus based on DIN 28090-1 at room temperature a measured impermeability in the z-direction of less than 10-1 mg / (sm 2 ) , preferably less than 10-2 mg / (sm 2 ), and more preferably less than 10-3 mg / (sm 2 ).
Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Shaped body (5) according to at least one of the preceding claims, characterized in that
die zu verdichtende Mischung 1 bis 50 Gew.-%, bevorzugt 2 bis 20 Gew.-% und besonders bevorzugt 3 bis 10 Gew.-% eines oder mehrerer anorganischer Additive (7) enthält. the mixture to be compacted contains 1 to 50% by weight, preferably 2 to 20% by weight and more preferably 3 to 10% by weight of one or more inorganic additives (7).
Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das wenigstens eine anorganische Additiv eine Schmelztemperatur und/oder Glasübergangstemperatur von maximal 1.800 °C, bevorzugt zwischen 50 und 1.000 °C und besonders bevorzugt zwischen 100 und 650 °C aufweist. Shaped body (5) according to at least one of the preceding claims, characterized in that the at least one inorganic additive has a melting temperature and / or glass transition temperature of at most 1,800 ° C., preferably between 50 and 1,000 ° C. and particularly preferably between 100 and 650 ° C.
9. Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass 9. Shaped body (5) according to at least one of the preceding claims, characterized in that
die zu verdichtende Mischung mehr als 10 bis 50 Gew.-%, bevorzugt 10 bis 25 Gew.-% und besonders bevorzugt 10 bis 20 Gew.-% eines oder mehrerer organischer Additive (7) enthält. the mixture to be compressed more than 10 to 50 wt .-%, preferably 10 to 25 wt .-% and particularly preferably 10 to 20 wt .-% of one or more organic additives (7).
10. Formkörper (5) nach Anspruch 9, 10. shaped body (5) according to claim 9,
dadurch gekennzeichnet, dass characterized in that
die zu verdichtende Mischung als organisches Additiv (7) nur fluorfreie(s) Polymer(e) enthält. the mixture to be compressed contains as organic additive (7) only fluorine-free polymer (s).
11. Formkörper (5) nach Anspruch 9 oder 10, 11. molded body (5) according to claim 9 or 10,
dadurch gekennzeichnet, dass characterized in that
die zu verdichtende Mischung als organisches Additiv (7) wenigstens ein Polymer ausgewählt aus der Gruppe bestehend aus Siliconharzen, Polyole- finen, bevorzugt Polyethylen oder Polypropylen, Epoxidharzen, Phenolharzen, Melaminharzen, Harnstoffharzen, Polyesterharzen, Polyetheretherke- tonen, Benzoxazinen, Polyurethanen, Nitrilkautschuken, bevorzugt Acryl- nitril-Butadien-Styrol-Kautschuk, Polyamiden, Polyimiden, Polysulfonen und beliebigen Mischungen oder Copolymeren von zwei oder mehr der vorgenannten Verbindungen enthält. the mixture to be compressed as organic additive (7) at least one polymer selected from the group consisting of silicone resins, polyolefins, preferably polyethylene or polypropylene, epoxy resins, phenolic resins, melamine resins, urea resins, polyester resins, polyetheretherketones, benzoxazines, polyurethanes, nitrile rubbers, preferably acrylonitrile-butadiene-styrene rubber, polyamides, polyimides, polysulfones and any mixtures or copolymers of two or more of the aforementioned compounds.
12. Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass organische(s) Additiv(e) (7) mit einem gemäß der ISO 13320 bestimmten mittleren Partikeldurchmesser (d5o) von 1 bis 150 μιτι, vorzugsweise von 2 bis 30 μιτι und besonders bevorzugt von 3 bis 10 μιτι eingesetzt 12. Shaped body (5) according to at least one of the preceding claims, characterized in that organic (s) additive (s) (7) with a determined according to ISO 13320 average particle diameter (d 5 o) of 1 to 150 μιτι, preferably from 2 to 30 μιτι and particularly preferably from 3 to 10 μιτι used
wird/werden. will be.
13. Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass 13. Shaped body (5) according to at least one of the preceding claims, characterized in that
die zu verdichtende Mischung wenigstens ein anorganisches Additiv (7) und wenigstens ein organisches Additiv (7) enthält. the mixture to be compressed contains at least one inorganic additive (7) and at least one organic additive (7).
14. Formkörper (5) nach Anspruch 13, 14. molded body (5) according to claim 13,
dadurch gekennzeichnet, dass characterized in that
dieser bei einer Flächenpressung von 20 MPa mit Helium als Gas (40 bar Innendruck) eine gemäß der DIN EN 13555 in einem Temperaturbereich von -100 bis 300 °C gemessene Impermeabilität von weniger als 10"1 mg/(s'm) aufweist und der Formkörper bei einer Flächenpressung von 32 MPa eine nach der TA-Luft in einem Temperaturbereich von 300 bis 600 °C nach einer Auslagerung für 48 Stunden gemessene Leckagerate von weniger als 1 x 10-4 mbarl/(s'm) (1,1 bar, Helium) aufweist. at a surface pressure of 20 MPa with helium as the gas (40 bar internal pressure), this has an impermeability of less than 10 -1 mg / (s ' m) measured according to DIN EN 13555 in a temperature range of -100 to 300 ° C and Shaped body at a surface pressure of 32 MPa a measured after the TA-air in a temperature range of 300 to 600 ° C after aging for 48 hours leakage rate of less than 1 x 10-4 mbarl / (s ' m) (1.1 bar , Helium).
15. Formkörper (5) nach zumindest einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass 15. Shaped body (5) according to at least one of the preceding claims, characterized in that
dieser nur anorganisches Additiv enthält und eine Dichte von 0,7 bis 1 ,4 g/cm3 aufweist, dieser nur organisches Additiv enthält und eine Dichte von 1 ,0 bis 1 ,8 g/cm3 aufweist oder dieser anorganisches und organisches Additiv enthält und eine Dichte von 0,7 bis 1,8 g/cm3 aufweist. contains only inorganic additive and has a density of 0.7 to 1, 4 g / cm 3 , this contains only organic additive and has a density of 1, 0 to 1, 8 g / cm 3 or contains this inorganic and organic additive and has a density of 0.7 to 1.8 g / cm 3 .
16. Verfahren zur Herstellung eines Formkörpers (5) nach zumindest einem der vorhergehenden Ansprüche, welches die nachfolgenden Schritte umfasst: a) Vermischen von Graphitpartikeln (6) mit wenigstens einem festen Additiv (7) zu einer Mischung, welche wenigstens ein anorganisches Additiv (7), eine Mischung aus wenigstens einem anorganischen Additiv (7) und wenigstens einem organischen Additiv (7) oder mehr als 10 Gew.-% organisches Additiv (7) enthält, wobei das eingesetzte wenigstens eine Additiv (7) einen gemäß der ISO 13320 bestimmten mittleren Partikeldurchmesser (d5o) zwischen 1 und 500 μιτι aufweist, sowie 16. A process for producing a shaped body (5) according to at least one of the preceding claims, which comprises the following steps: a) mixing of graphite particles (6) with at least one solid additive (7) to a mixture comprising at least one inorganic additive (7), a mixture of at least one inorganic additive (7) and at least one organic additive (7) or more Contains 10 wt .-% organic additive (7), wherein the at least one additive used (7) has a determined according to ISO 13320 average particle diameter (d 5 o) between 1 and 500 μιτι, and
b) Verdichten der in dem Schritt a) erhaltenen Mischung. b) compacting the mixture obtained in step a).
17. Verfahren nach Anspruch 16, 17. The method according to claim 16,
dadurch g e k e n n z e i c h n e t, dass By doing so, that is
dieses zusätzlich einen Formgebungsschritt umfasst, bei welchem der Formkörper (5) durch Umformen, Profilieren, Heißpressen, Thermoumfor- men, Umkanten, Tiefziehen, Prägen oder Stanzen ausgebildet wird. this additionally comprises a shaping step, in which the shaped body (5) is formed by forming, profiling, hot pressing, thermoforming, edging, deep drawing, embossing or stamping.
18. Verwendung eines graphithaltigen Formkörpers (5) nach zumindest einem der Ansprüche 1 bis 15 als Dichtungselement, als Bipolarplatte einer Brennstoffzelle, bevorzugt einer Redox-Flow-Batterie, als Wärmeleitfolie, als Formteil im Baubereich, insbesondere Wandverkleidung, Deckenverkleidung oder Wärmeleitplatte, als Stromableiter in Blei-Säure-Batterien o- der entsprechenden Hybridsystemen, als Folie oder Finne in PCM-Graphit- Speichern, als Auskleidungsmaterial, als Kontaktierungselement, als Elektrodenmaterial für Batteriesysteme, als Wärmeverteilungselement, als Flächenheizer, als Material zum Wickeln von Graphitrohren mit Verschweiß- barkeit der einzelnen Lagen, als Stopfbuchspackung, als Packungen für chemische Kolonnen, als Wärmetauscherplatte oder als Wärmetauscherrohr. Verwendung eines graphithaltigen Formkörpers (5) nach zumindest einem der Ansprüche 1 bis 15 in einem Verfahren zum Verbinden des Formkörpers (5) mit einem anderen Formkörper, insbesondere durch Verschweißen, wobei der andere Formkörper ein Formkörper nach einem der Ansprüche 1 bis 15, eine Graphitfolie, eine Metallfolie, ein Metallblech, ein Metallblock oder ein textiles Flächengebilde, bevorzugt ein Filzkörper, ist. 18. Use of a graphite-containing molded body (5) according to at least one of claims 1 to 15 as a sealing element, as a bipolar plate of a fuel cell, preferably a redox flow battery, as a heat conducting foil, as a molded part in the construction sector, in particular wall cladding, ceiling cladding or heat conduction, as a current conductor in lead-acid batteries o- of the corresponding hybrid systems, as a film or fin in PCM graphite stores, as a lining material, as a contacting element, as electrode material for battery systems, as a heat distribution element, as a surface heater, as a material for winding graphite tubes with weldability the individual layers, as stuffing box, as packages for chemical columns, as a heat exchanger plate or as a heat exchanger tube. Use of a graphite-containing shaped body (5) according to at least one of claims 1 to 15 in a method for joining the shaped body (5) to another shaped body, in particular by welding, wherein the other shaped body is a shaped body according to one of claims 1 to 15, a graphite foil , a metal foil, a metal sheet, a metal block or a textile fabric, preferably a felt body, is.
Applications Claiming Priority (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009055442A DE102009055442A1 (en) | 2009-12-31 | 2009-12-31 | Graphite-containing plate comprises a solidified mixture of largely uniformly distributed graphite particles and plastic particles, where the graphite particles and plastic particles are distributed homogeneously into the mixture |
DE102009055440A DE102009055440A1 (en) | 2009-12-31 | 2009-12-31 | Ceiling- or wall element for use as composite material for attachment to ceiling or wall, particularly thermally active concrete wall or concrete ceiling, is regulated over frame with base, in which heating- or cooling register is arranged |
DE102009055441A DE102009055441A1 (en) | 2009-12-31 | 2009-12-31 | Device for controlling temperature in room of building, has thermally coupled pipes embedded in plate, which contains expanded graphite, where plate is thermal-contacted with surface area of structural element |
DE102009055443A DE102009055443A1 (en) | 2009-12-31 | 2009-12-31 | Ceiling or wall element |
DE200910055444 DE102009055444A1 (en) | 2009-12-31 | 2009-12-31 | Graphite-containing mold body for use as e.g. gasket in chemical plant, is manufactured by mixing fixed additives with graphite particles and compacting, where particles comprises expanded natural graphite and/or synthetic graphite |
DE201010002000 DE102010002000A1 (en) | 2010-02-16 | 2010-02-16 | Heat sink and electrical energy storage |
DE201010002434 DE102010002434B4 (en) | 2010-02-26 | 2010-02-26 | Temperature System |
DE102010002989A DE102010002989A1 (en) | 2010-03-17 | 2010-03-17 | Material composition, its production and use |
DE102010041085 | 2010-09-20 | ||
DE102010041822A DE102010041822A1 (en) | 2010-09-30 | 2010-09-30 | Thermosolares cladding element |
US12/915,340 US20120107662A1 (en) | 2010-10-29 | 2010-10-29 | Thermal management matrix |
PCT/EP2010/070976 WO2011080336A2 (en) | 2009-12-31 | 2010-12-31 | Graphite-containing moulded body and method for the production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2519480A2 true EP2519480A2 (en) | 2012-11-07 |
Family
ID=43755122
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10803103A Withdrawn EP2519576A1 (en) | 2009-12-31 | 2010-12-31 | Graphite-containing plate and method for producing a graphite-containing plate |
EP10803462A Withdrawn EP2519480A2 (en) | 2009-12-31 | 2010-12-31 | Graphite-containing moulded body and method for the production thereof |
EP10798152.4A Active EP2519479B1 (en) | 2009-12-31 | 2010-12-31 | Layered composite material for use in a redox flow battery |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10803103A Withdrawn EP2519576A1 (en) | 2009-12-31 | 2010-12-31 | Graphite-containing plate and method for producing a graphite-containing plate |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10798152.4A Active EP2519479B1 (en) | 2009-12-31 | 2010-12-31 | Layered composite material for use in a redox flow battery |
Country Status (8)
Country | Link |
---|---|
US (1) | US20130040194A1 (en) |
EP (3) | EP2519576A1 (en) |
JP (2) | JP2013527964A (en) |
KR (2) | KR20120110151A (en) |
CA (3) | CA2786134A1 (en) |
ES (1) | ES2641013T3 (en) |
SG (1) | SG182294A1 (en) |
WO (3) | WO2011080334A2 (en) |
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DE102012024753A1 (en) | 2012-12-19 | 2014-06-26 | Eisenhuth Gmbh & Co. Kg | Frame with integrated bipolar plate for electrochemical reactors, consists of electrically conductive bipolar plate(s) of thermoformable carbon-polymer composite material with thermoplastic polymer providing liquid-tight connection |
JP2015138692A (en) * | 2014-01-23 | 2015-07-30 | 東洋紡株式会社 | integrated carbon electrode |
KR101580405B1 (en) * | 2014-08-14 | 2015-12-28 | 일도에프엔씨(주) | Unified Bipolar plate with flow frame for redox flow battery |
CN107108228B (en) * | 2014-11-25 | 2020-05-12 | 东洋炭素株式会社 | Expanded graphite sheet and battery using the same |
KR102000658B1 (en) * | 2015-08-21 | 2019-07-16 | 롯데케미칼 주식회사 | Preparation method of electrode for redox flow battery comprising the same, and redox flow battery |
KR101693438B1 (en) * | 2015-09-15 | 2017-01-05 | 한국해양대학교 산학협력단 | Binder for electrode of the bioelectrochemical cell, and method for manufacturing the same |
JPWO2017204351A1 (en) * | 2016-05-26 | 2019-03-28 | 東洋炭素株式会社 | Composite and method of producing composite |
CN105968706A (en) * | 2016-07-11 | 2016-09-28 | 南通星球石墨设备有限公司 | Graphite pipe |
CN106848346B (en) * | 2017-03-06 | 2019-07-26 | 昆山知氢信息科技有限公司 | Flow battery bipolar plates and preparation method thereof |
CN109096693A (en) * | 2018-07-10 | 2018-12-28 | 天长市优信电器设备有限公司 | A kind of tear-resistant electric automobile charger shell |
DE102021203265B3 (en) | 2021-03-31 | 2022-09-22 | Sgl Carbon Se | separator plate |
EP4163090A1 (en) | 2021-10-08 | 2023-04-12 | Branson Ultraschall Niederlassung der Emerson Technologies GmbH & Co. oHG | Through transmission connecting device, connecting method using the device as well as connection structure |
KR102653132B1 (en) | 2021-11-11 | 2024-04-02 | 금성테크 주식회사 | Recycled Graphite extrusion-molded bodies and manufacturing method therefor |
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Also Published As
Publication number | Publication date |
---|---|
WO2011080336A3 (en) | 2011-10-20 |
WO2011080334A2 (en) | 2011-07-07 |
KR20120110151A (en) | 2012-10-09 |
US20130040194A1 (en) | 2013-02-14 |
EP2519576A1 (en) | 2012-11-07 |
ES2641013T3 (en) | 2017-11-07 |
SG182294A1 (en) | 2012-08-30 |
CA2786134A1 (en) | 2011-07-07 |
WO2011080336A2 (en) | 2011-07-07 |
WO2011080334A3 (en) | 2011-10-20 |
WO2011080339A1 (en) | 2011-07-07 |
JP2013527964A (en) | 2013-07-04 |
EP2519479A2 (en) | 2012-11-07 |
CA2786143A1 (en) | 2011-07-07 |
KR20120112676A (en) | 2012-10-11 |
EP2519479B1 (en) | 2017-08-23 |
JP2013516374A (en) | 2013-05-13 |
CA2786180A1 (en) | 2011-07-07 |
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