EP1654404A1 - Procede de production electrophoretique de structures ceramiques - Google Patents

Procede de production electrophoretique de structures ceramiques

Info

Publication number
EP1654404A1
EP1654404A1 EP04741370A EP04741370A EP1654404A1 EP 1654404 A1 EP1654404 A1 EP 1654404A1 EP 04741370 A EP04741370 A EP 04741370A EP 04741370 A EP04741370 A EP 04741370A EP 1654404 A1 EP1654404 A1 EP 1654404A1
Authority
EP
European Patent Office
Prior art keywords
ceramic
electrodes
particle size
suspension
structures according
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.)
Granted
Application number
EP04741370A
Other languages
German (de)
English (en)
Other versions
EP1654404B1 (fr
Inventor
Jürgen HAUSSELT
Melanie Dauscher
Holger Von Both
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Karlsruher Institut fuer Technologie KIT
Original Assignee
Forschungszentrum Karlsruhe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Forschungszentrum Karlsruhe GmbH filed Critical Forschungszentrum Karlsruhe GmbH
Publication of EP1654404A1 publication Critical patent/EP1654404A1/fr
Application granted granted Critical
Publication of EP1654404B1 publication Critical patent/EP1654404B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material

Definitions

  • the invention relates to a method for producing ceramic structures (such as layers, filters or microstructures) and to ceramic structures and gradient structures produced using this method.
  • Ceramic (micro) structures, ceramic coatings and two-dimensional structures such as plates, substrates or filters are gaining in importance for many areas of technology. This applies both to so-called structural ceramics such as Al 2 O 3 , ZrO, mullite, SiC, Si3 4 as well as to functional ceramics such as BaTi0 3 or PZT (lead zirconate titanate) and to so-called bioceramics such as hydroxylapatite Ca (OH ) (P0 4 ) 3 , but also for mineral glasses.
  • dry pressing, powder technology injection molding, hot molding, slip molding, film casting, electrophoretic deposition from powder suspensions and other processes with subsequent sintering are used as production processes.
  • feedstocks are used for the shaping, which consist of ceramic powders and binders, dispersants and lubricants to improve the processability.
  • feedstocks consist of ceramic powders and binders, dispersants and lubricants to improve the processability.
  • additives are only added to the powders in parts by volume of a few percent.
  • injection molding, hot molding, slip casting and film casting use far higher volumes of binders, dispersants, lubricants, polymers, waxes and
  • Suspension liquids such as water and alcohol are added.
  • the powder proportions are 30 to 70 percent by volume.
  • the volume fractions of the ceramic powder can be in the range from approx. 5 to 50%.
  • powders are used which are present as so-called monomodal powders in a relatively broad distribution, which often follow normal distributions, logarithmic normal distributions or so-called Rosin-Rammler distributions. In some cases, powders are also used, which are in the form of complex multimodal distributions.
  • the roughness of the resulting parts and layers as well as their pore size and sometimes their structure after sintering are influenced by the particle size distribution.
  • the rough proportions of the powders used determine the surface roughness.
  • the pore size distribution for example of filter membranes, also correlates with the particle size: the coarser the powder particles, the larger the resulting pores. Therefore, in the conventional manufacturing processes, for example, to achieve particularly smooth layers or microstructures or to achieve a very fine pore size, only particles below a certain size, such as. B. 500 nm can be used.
  • the powders first have to be fractionated and classified in a complicated way, for example by sieving or air screening, and only the desired powder fraction should be introduced into the feedstock before the production of the starting feedstock.
  • the method according to the invention is based on the combination of electrophoretic deposition and sedimentation due to gravity or centrifugal forces.
  • the electrophoretic deposition of ceramic particles from particle suspensions is known as a process for the production of ceramic layers (Heavens, SN: Electrophoretic Deposition as a Processing Route for Ceramics; in Binner, J. (Ed.), Advanced Ceramics Processing and Technology, Vol. 1, Noyes Publ., Park Ridge, NJ, USA). More recently, attempts have been made to use this technique to realize ceramic microstructures (Both, H. von; Haußelt, J.: l st In tern. Conf. On Elektrophoretic Deposition, Banff, Canada, 2002). For this purpose, by applying an electric field between two electrodes immersed in the powder suspension, a particle stream of charged particles is moved to one of the two electrodes and deposited there.
  • AI 2 O 3 , Zr ⁇ 2, S1O 2 depends on the dispersant and binder additives, but that there may also be a slight dependence on the particle size. Depending on the system, different, but in all cases small, dependencies of the migration speed on the particle size can be observed.
  • Particle size distribution can be separated.
  • a field is superimposed on the electric field, which brings about a particle velocity that is largely independent of particle size in the direction of the electric field, and causes a particle velocity that is dependent on particle size.
  • Particle size-dependent sedimentation is suitable for this either in a constant, location-independent gravitational field (gravity sedimentation) or in a variable and location-dependent gravitational field (centrifugation).
  • the rate of descent v is proportional to r 2 at constant viscosity ⁇ . Even if due to particle shapes in usually deviate from the spherical shape, and at high concentrated
  • a critical particle size r c results for each electric field strength E and for each acceleration b in the gravitational field, at which the effects of both fields cancel and the particle floats. All particles with r> r c move in the direction of the gravitational field, all particles with r ⁇ r c move in the direction of the electrical field.
  • E and the acceleration b for example by varying the speed in a centrifuge
  • largely freely selectable fractions of the particle size distribution originally present can thus be deposited on an electrically conductive substrate.
  • the angle between the directions of the electric field and the gravitational field is chosen such that a velocity component that is dependent on the particle size can be added or subtracted from the velocity distribution in the electric field that is largely independent of particle size.
  • variation of the electric field strength and the angle between the two field directions can ensure that the fine fraction of a particle size distribution is preferably deposited on an electrode.
  • the electrical and the gravitational fields are preferably arranged parallel to one another, ie the electrodes are essentially perpendicular to the direction of the gravitational field (eg horizontally in the gravitational field).
  • a fraction of the suspended particles is deposited in the gravitational field on the upper electrode.
  • the fraction deposited in the form of a ceramic structure is generally distinguished by the fact that its particle size distribution differs from the particle size distribution of the suspension, which is not the case in conventional electrophoresis. Since the finer particles are preferably deposited, the particle size distribution of the ceramic structure has lower values than the particle size distribution of the suspension.
  • the particle size distribution to be separated can be influenced in that not only the absolute amount, but also the point in time at which the electric field from the
  • Gravity sedimentation is superimposed, is freely chosen.
  • the desired limit of the separated size fraction can be set.
  • a particularly preferred embodiment of the invention results from the superimposition of an electric field which is variable in its absolute amount with a gravitational field which is variable in its absolute amount, as is represented in particular by centrifugation, in which centrifugal forces (centrifugal forces) occur.
  • the resulting gravitational field is directed outwards with respect to the axis of rotation of the centrifuge.
  • the fine fraction of the suspension in the form of a ceramic layer is deposited according to the invention on the inner electrode in this arrangement.
  • a further influence on the particle size distribution to be separated can be achieved by not only choosing the absolute amounts of the electrical field and the gravitational field of the centrifugal acceleration over a wide range, but also freely choosing the times at which both fields are switched on and / or off .
  • the present invention is also applicable to suspensions (dispersions) which consist of particles of different compositions. If such particle mixtures differ in their specific electrical charge, their electrophoretic mobilities and their electrophoretic deposition rates are different. If such particle mixtures differ in their density, then their sedimentation speeds are different in the gravitational or centrifugal force field, because in both cases the sedimentation speed according to equation 2 is proportional to the difference between the density of the particles and the density of the liquid of the suspension.
  • the superimposition of an electric field with a gravitational field consequently permits extensive influence on the deposition conditions in the case of particle mixtures which differ not only in their size, but also in their surface charge and / or in their density.
  • the method according to the invention can also be used to separate those particle mixtures which do not differ in their particle size, but do differ in their surface charge and / or their density.
  • the method according to the invention can thus be used to produce ceramic structures with a multiple or continuous variation of the electric field and / or (in the case of centrifugation) of the gravitational field in a deposition process without changing the powder suspension, which structures have a gradient in relation to their composition and / or have pore depth.
  • Ceramic gradient structures of this type are suitable, for example, as filter membranes.
  • the method according to the invention is suitable not only for the production of layers in which the particle size distribution or, if several different powders are present, the composition can be varied within wide limits, but also for Separation of suspensions with a wider range of variation compared to pure sedimentation or centrifugation processes.
  • An Al 2 O 3 layer was produced by superimposing electrophoresis deposition and gravity sedimentation.
  • the counter electrode and substrate were arranged horizontally, ie both surfaces of the pair of electrodes were aligned perpendicular to the direction of the gravitational field.
  • the roughness depth was optically examined with the aid of a surface measuring device (FRT Microglider).
  • FRT Microglider a surface measuring device
  • an additional layer was also produced, in the deposition of which the sedimentation was suppressed in accordance with the prior art by stirring the suspension and the electrodes were arranged vertically.
  • the electrode gap was 13 mm. There were four profiles in each examined a ceramic layer. The mean is given. There was a significant reduction in the roughness depth with superimposed sedimentation, which was determined in each case in accordance with DIN 4678 or ISO 4287.
  • Overlaying electrophoresis deposition and gravity sedimentation were used to produce Al 2 ⁇ 3 layers using different field strengths.
  • the counter electrode and substrate were arranged horizontally to one another.
  • the roughness depth was optically examined using a surface measuring device (FRT microglider).
  • the layers were deposited from this suspension under the following conditions:
  • An SiO 2 layer was produced by superimposing electrophoresis deposition and gravity sedimentation.
  • the counter electrode and substrate were arranged horizontally.
  • the roughness depth was optically examined with the help of a surface measuring device (FRT Microglider).
  • FRT Microglider a surface measuring device
  • an additional layer was also produced, in the deposition of which the sedimentation was suppressed in accordance with the prior art by stirring the suspension and the electrodes were arranged vertically.
  • There was an ethanolisc e Si0 2 suspension (dso 15 microns) with 5 volume percent solids and a dispersant content of 2 mass percent based on the mass of the powder.
  • the layers were deposited from this suspension under the following conditions:
  • the electrode distance was 13 mm.
  • Four profiles in each layer were examined. The mean is given. There was a significant reduction in the roughness depth with overlaid sedimentation, which was determined in accordance with DIN 4678 and ISO 4287.
  • an Al 2 O 3 layer was produced by means of electrophoresis and superimposed gravity sedimentation.
  • the electrodes were arranged horizontally. Electrophoretic deposition was carried out on the upper electrode.
  • the particle size distribution in the suspension and in the layer was determined optically with a laser granulometer.
  • an ethanolic Al 2 O 3 suspension with 30 volume percent solids content and a dispersant content of 2 mass percent based on the mass of the powder was prepared. The layers were deposited from this suspension under the following conditions:
  • the particle size distribution in the suspension before the deposition, during and after the deposition and in the deposited layer after redispersion in pure ethanol was examined in each case.
  • a PZT layer (lead zirconate titanate layer) was produced by superimposing electrophoresis deposition and gravity sedimentation.
  • the counter electrode and substrate were arranged horizontally.
  • a surface measuring device FRT Microglider
  • an additional layer was also produced, in the deposition of which the sedimentation was suppressed in accordance with the prior art by stirring the suspension and the electrodes were arranged vertically.
  • the electrode gap was 13 mm.
  • Four profiles in each layer were examined. The mean is given. There was a significant reduction in the roughness depth with overlaid sedimentation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Electrostatic Separation (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé pour produire des structures et structures à gradient d'indice céramiques présentant des valeurs de distribution granulométrique au moins partiellement inférieures à celles de la suspension à partir de laquelle elles sont produites. Le procédé selon l'invention consiste : à préparer une suspension contenant des particules céramiques entre une paire d'électrodes, puis ; à appliquer un champ électrique à la paire d'électrodes, tandis que les surfaces des électrodes de ladite paire d'électrodes sont disposées perpendiculairement à une composante d'un champ gravitationnel. Selon l'invention, une fraction des particules se dépose, sous la forme d'une structure céramique, sur l'électrode de la paire d'électrodes qui se trouve en amont du champ, par rapport à ladite composante du champ gravitationnel.
EP04741370.3A 2003-08-16 2004-08-05 Procédé de production électrophorétique de structures céramiques Not-in-force EP1654404B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10337688A DE10337688B3 (de) 2003-08-16 2003-08-16 Verfahren zur Herstellung von keramischen Strukturen und nach diesem Verfahren hergestellte keramische Strukturen
PCT/EP2004/008768 WO2005019505A1 (fr) 2003-08-16 2004-08-05 Procede de production electrophoretique de structures ceramiques

Publications (2)

Publication Number Publication Date
EP1654404A1 true EP1654404A1 (fr) 2006-05-10
EP1654404B1 EP1654404B1 (fr) 2013-10-09

Family

ID=34201583

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04741370.3A Not-in-force EP1654404B1 (fr) 2003-08-16 2004-08-05 Procédé de production électrophorétique de structures céramiques

Country Status (5)

Country Link
US (1) US20070221500A1 (fr)
EP (1) EP1654404B1 (fr)
JP (1) JP2007502912A (fr)
DE (1) DE10337688B3 (fr)
WO (1) WO2005019505A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030012985A1 (en) 1998-08-03 2003-01-16 Mcalister Roy E. Pressure energy conversion systems
DE102008036661A1 (de) 2008-08-06 2010-02-11 Forschungszentrum Karlsruhe Gmbh Verfahren zur Herstellung von oxidischer Zahnkeramik
US8329219B2 (en) * 2009-12-22 2012-12-11 Cook Biotech Incorporated Methods for producing ECM-based biomaterials
US9377105B2 (en) 2013-03-12 2016-06-28 Mcalister Technologies, Llc Insert kits for multi-stage compressors and associated systems, processes and methods
US8838367B1 (en) 2013-03-12 2014-09-16 Mcalister Technologies, Llc Rotational sensor and controller
WO2014144581A1 (fr) 2013-03-15 2014-09-18 Mcalister Technologies, Llc Moteur à combustion interne et systèmes et procédés associés
US9255560B2 (en) 2013-03-15 2016-02-09 Mcalister Technologies, Llc Regenerative intensifier and associated systems and methods

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3023910A (en) * 1957-01-24 1962-03-06 Shirley E Schless Support for sliding shelves
US3791577A (en) * 1972-08-08 1974-02-12 J Lacher Centrifuge and rotating discharge means therefor
US3929596A (en) * 1972-10-02 1975-12-30 Toyo Kogyo Co Electrodeposition of wear resistant and oil retentive nickel coatings and article having such a coating
US4026780A (en) * 1976-04-05 1977-05-31 Rca Corporation Method and apparatus for cataphoretic deposition
US4459327A (en) * 1979-08-24 1984-07-10 Kennecott Corporation Method for the production of copper-boron carbide composite
CA2007501A1 (fr) * 1989-02-01 1990-08-01 Jau-Ho Jean Procede d'electrodeposition de revetements protecteurs de metaux precieux pour electrophorese
DE10013092C2 (de) * 2000-03-17 2002-01-24 Haenel & Co Altstaetten Lagerregal
CA2418138A1 (fr) * 2003-01-29 2004-07-29 Eugenia Kumacheva Methode de culture de cristaux colloidaux sur des surfaces texturees

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005019505A1 *

Also Published As

Publication number Publication date
DE10337688B3 (de) 2005-03-17
EP1654404B1 (fr) 2013-10-09
US20070221500A1 (en) 2007-09-27
JP2007502912A (ja) 2007-02-15
WO2005019505A1 (fr) 2005-03-03

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