EP1144337A2 - Materiaux lies par reaction a base de nitrure de silicium et leur procede de fabrication - Google Patents

Materiaux lies par reaction a base de nitrure de silicium et leur procede de fabrication

Info

Publication number
EP1144337A2
EP1144337A2 EP99969908A EP99969908A EP1144337A2 EP 1144337 A2 EP1144337 A2 EP 1144337A2 EP 99969908 A EP99969908 A EP 99969908A EP 99969908 A EP99969908 A EP 99969908A EP 1144337 A2 EP1144337 A2 EP 1144337A2
Authority
EP
European Patent Office
Prior art keywords
silicon
oxidation
materials
silicon nitride
compounds
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Withdrawn
Application number
EP99969908A
Other languages
German (de)
English (en)
Inventor
Lothar SCHÖNFELDER
Gerhard WÖTTING
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.)
Kyocera Fineceramics Precision GmbH
Original Assignee
Cfi Ceramics For Industry & Co KG GmbH
CFI CERAMICS FOR INDUSTRY 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 Cfi Ceramics For Industry & Co KG GmbH, CFI CERAMICS FOR INDUSTRY GmbH filed Critical Cfi Ceramics For Industry & Co KG GmbH
Publication of EP1144337A2 publication Critical patent/EP1144337A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/591—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/589—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/593—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by pressure sintering
    • C04B35/5935—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by pressure sintering obtained by gas pressure sintering

Definitions

  • the invention relates to reaction-bound silicon-containing materials and a method for their production.
  • reaction-bonded silicon nitride In the group of silicon-containing materials, reaction-bonded silicon nitride (RBSN) is of technical importance. RBSN is made from silicon powder in the reaction bond process by reaction with nitrogen-containing reaction gases. This reaction produces a porous silicon nitride (Si 3 N 4 ) material which, depending on the shaping process used for the silicon powder, still has a porosity of 15 to 30%. Because of this relatively high porosity, the use of this material in the area of high temperatures and especially under simultaneous oxidizing conditions is severely restricted. The oxidation of the reaction-bound silicon nitride leads to severe losses in the mechanical properties of the material. The reaction-bound silicon nitride material is, however, of importance for that due to the inexpensive silicon raw materials that can be used and easy processing, which can advantageously be carried out in the so-called green state or after pre-nitriding
  • the object of the present invention is therefore to develop materials based on silicon nitride with improved properties.
  • the focus is on the mechanical properties, the density or porosity and the behavior under oxidizing conditions at high temperatures. This is intended to significantly improve the application behavior and the area of application for corresponding materials.
  • Microstructure composed of ⁇ -SiC and ⁇ - and ⁇ -Si 3 N 4 in addition to an open porosity of> 7.9%.
  • This structure is described as an interwoven texture with no chemical bond or solid solution with micro vacancies between SiC and Si 3 N 4 , which differs fundamentally from conventional SiC-Si 3 N 4 composite materials.
  • a disadvantage of the composite system described is that only very special organic silicone polymers can be used for its production. The use of simple polysilanes or polysiloxanes is not possible.
  • the object of the present invention is achieved by reaction-bound materials which contain silicon nitride (Si 3 N 4 ), silicon carbide (SiC) and silicon oxynitride (Si 2 N 2 O) as well as any remaining unreacted silicon as the X-ray-detectable crystalline phases, and which contain a unreacted silicon can be produced in which mixtures of silicon, organic silicon compounds and silicon nitride or moldings from these mixtures are thermally treated in a nitrogen-containing gas atmosphere.
  • the organosilicon compounds are pyrolyzed in the presence of silicon and silicon nitride and nitrided in the subsequent step.
  • the starting substances are preferably in powder form. Powder qualities with average grain sizes ⁇ 10 ⁇ m are advantageously used as silicon powder. Powder qualities with average grain sizes ⁇ 3 ⁇ m are advantageously suitable as silicon nitride powder.
  • Polysilanes or polycarbosilanes or copolymers of these compounds are used.
  • these compounds can include carbon, nitrogen, hydrogen and / or oxygen and other heteroatoms such as Contain boron, titanium, zirconium, phosphorus or aluminum.
  • the organic silicon compounds used have the function of a binder.
  • molded articles can be produced from the raw material mixture using the known methods, for example cold pressing, hot pressing, isostatic pressing, injection molding or extrusion.
  • they are broken down into ceramic phases and reactants by pyrolysis in an inert atmosphere and are thus included in the structure of the material.
  • the organic silicon compounds are pyrolyzed, and in the subsequent nitridation step a complex course of the reaction results, on the one hand the nitridation of the silicon powder and on the other hand the reaction of the pyrolysis products of the organosilicon
  • Compounds comprises a multi-phase material, which contains silicon nitride (Si 3 N 4 ), silicon carbide (SiC) and silicon oxynitride (Si 2 N 2 O), as well as any remaining unreacted Si as the crystalline phases which can be detected by X-ray.
  • the material according to the invention thus clearly differs from the material disclosed in DE 30 45 010 C2 with regard to the phase inventory which can be detected by X-ray analysis.
  • the process according to the invention is advantageously carried out in such a way that the free silicon is converted almost completely, i.e. practically no free silicon can be detected in the material according to the invention by X-ray diffraction, which is the case at contents of ⁇ 1% by weight.
  • silicon nitride powder is added to the starting mixture of silicon powder and organosilicon compounds. This addition above all improves the oxidation resistance of the material at high temperatures. As shown in the examples below goes, these materials have significantly improved mechanical properties after an oxidation treatment compared to those which are made from silicon nitride-free mixtures.
  • Oxidation treatment means this temperature change places a greater strain on the material.
  • These cyclical loads also simulate real operating conditions, such as B. when using ceramic components for combustion chamber linings and crucibles.
  • the nitridation products according to the invention Compared to the pure RBSN material, produced by nitridation of silicon powder, the nitridation products according to the invention, starting from mixtures of silicon powder, silicon nitride powder and organosilicon compounds, have significantly improved properties under oxidizing conditions. This is especially true for the room temperature flexural strength after an oxidizing treatment. In addition, these materials have significantly improved mechanical properties at high temperatures both before and after an oxidation treatment. Corresponding measurements are listed in Table 2.
  • Table 2 shows that the reaction-bound material based on Si 3 N 4 according to the invention after an oxidation treatment in air at 1400 ° C., 100 h, statically or cyclically at intervals of 10 h, for example a flexural strength at room temperature of more than 40% of the flexural strength before oxidation. It preferably even has> 80% of the bending strength before the oxidation.
  • the open porosity of the material is of crucial importance for the oxidation of the RBSN.
  • the open porosity is associated with a high inner surface, the reaction of which with oxygen leads to damage to the material structure as a result of SiO 2 formation.
  • a key figure for the degree of oxidation is the weight increase normalized to the sample surface, given in mg / cm 2 .
  • RBSN has a relatively high oxidation-related weight gain and is associated with a strong oxidation-related decrease in strength.
  • the materials according to the invention are characterized by significantly lower open porosities, which are typically below 13% by volume. Compared to the prior art for reaction-bonded silicon-containing materials, the change in weight due to oxidation for the materials according to the invention is significantly reduced and thus the drop in strength is also significantly less. Because of these outstanding properties, the materials according to the invention are suitable for high-temperature applications, in particular under oxidizing conditions such as in turbines and combustion chambers.
  • the materials according to the invention are produced from mixtures of silicon, silicon nitride and an organic silicon compound, the proportion of individual mixture components can vary within a comparatively wide range.
  • the starting mixture can contain 15-90% by weight of silicon, 5 to 60% by weight of silicon nitride and 5 to 60% by weight of the organic silicon compound, preferably polysiloxane and / or polycarbosilane and / or copolymers of these compounds , contain.
  • Si contents below 15% by weight and Si 3 N 4 contents above 60% by weight lead to the fact that the porosity reduction resulting from the nitriding of Si to Si 3 N 4 is no longer sufficient to produce a material with an open To obtain porosity ⁇ 13 vol%.
  • Si contents> 90% by weight allow only low concentrations of Si 3 N 4 powder and the organic silicon compound, which means that the desired phase inventory, which is responsible for the positive properties of the material, no longer occurs. This also justifies the specified lower limits of> 5% by weight for the Si 3 N 4 powder and the organic silicon compound.
  • the upper limit for the organic silicon compound is set at 60% by weight. Even higher levels would lead to high shrinkage values and an undesirably high open porosity during pyrolysis.
  • the organic silicon compounds used can additionally contain heteroatoms, such as B, Ti, P, Zr and / or Al, which after pyrolysis of the organic silicon compound react with matrix constituents or the gas atmosphere to give the corresponding oxides, carbides, nitrides and / or carbonitrides.
  • heteroatoms such as B, Ti, P, Zr and / or Al
  • the increases in volume usually associated with these reactions promote the achievement of the low open porosity of the material according to the invention of ⁇ 13% by volume.
  • these new formations enable the setting of very specific properties, e.g. regarding the electrical and / or tribological
  • metals or metallic compounds with a catalytic effect on the nitridation reaction can advantageously be added to the raw material mixtures.
  • metals or metallic compounds with a catalytic effect on the nitridation reaction can advantageously be added to the raw material mixtures.
  • Molybdenum, manganese or iron in powder form and concentrations ⁇ 5% by weight have proven to be favorable for the catalysis of the nitridation reaction.
  • Components which bring about a reinforcement of the materials in the form of fibers, as short or long fibers, whiskers, platelets or particles can furthermore advantageously be introduced into the raw material mixtures according to the invention.
  • post-infiltrations with the organic silicon compound and additional ones can be carried out
  • Examples 1b, 1c and 3 show a typical process for producing the materials according to the invention.
  • the material is advantageously produced by intensively mixing Si powder with an average particle size ⁇ 10 ⁇ m and Si 3 N 4 powder with an average particle size ⁇ 3 ⁇ m, the organic silicon compound and optionally other of the additives described by wet and / or dry grinding become.
  • Si powder with average particle sizes> 10 ⁇ m lead to long nitriding times and the risk that unreacted silicon remains in the material in a concentration greater than 1% by weight.
  • Si 3 N 4 powders with average particle sizes> 3 ⁇ m can already lead to material inhomogeneities and reduce the mechanical properties and oxidation resistance.
  • the shaping is carried out by the customary methods or also by hot pressing, the thermal crosslinking of the polymer, the pyrolysis of the organic silicon compound under inert gas and the nitriding.
  • This takes place for the raw material mixtures according to the invention or shaped bodies produced therefrom in a nitrogen-containing gas atmosphere.
  • the reaction gas can additionally contain hydrogen and / or ammonia gas.
  • the nitridation reaction can take place either under normal pressure or under elevated gas pressure, preferably from 1 to 100 bar.
  • the maximum temperatures for this nitridation reaction are advantageously from 1300 to 1600 ° C.
  • the temperature-time curve for the nitriding reaction has to be adapted to the respective specific conditions, such as furnace size and component volume.
  • the basic composition is preferably already prepared in an organic medium in which the organic
  • Silicon compound is soluble.
  • isopropanol, butanol, ethoxylethanol or xylene can be suitable as solvents.
  • the ratio of the solids to the organic medium is to be adjusted so that a viscosity suitable for the further processing of the suspension is present.
  • Further processing can be carried out according to the known fiber coating and winding process, polygons for flat laminate panels, pipes or more complex parts being wound according to the winding cores used. Laminates are then stacked and meshed, and finished parts are meshed directly with regard to the target geometry.
  • the crosslinking follows, possibly after an intermediate processing, the pyrolysis and nitridation, as already described.
  • the materials and components according to the invention are suitable for corresponding operating conditions, such as turbines and combustion chambers, and for processing metallic melts.
  • operating conditions such as turbines and combustion chambers
  • metallic melts such as metallic melts.
  • the polymer was crosslinked at 250 ° C., the pyrolysis at 900 ° C. in an inert gas atmosphere.
  • the molded articles are nitrided in a nitrogen atmosphere.
  • the samples were heated up to 1450 ° C, with a total process time of 74 hours.
  • Silicon powder (900 g), methylpolysiloxane (500 g), qualities as in Example la, and 600 g of silicon nitride powder with an average grain size of 0.5 ⁇ m, BET specific surface area 13.8 m 2 / g were as in Example la mixed and processed.
  • Example 1b The mixture was prepared as in Example 1b, the nitriding of the test specimens was carried out in a nitrogen atmosphere up to 1450 ° C., with an entire sample duration of 130 hours.
  • material samples according to Example 1c were further investigated with regard to their cyclic and isothermal oxidation behavior between 1400 ° C. and 1500 ° C. up to 1000 hours of aging.
  • the properties of the nitrided or oxidized samples determined in this way are summarized in Table 2.
  • the materials according to Examples 1b and 1c have Si 3 N 4 , SiC and Si 2 N 2 O as crystalline phases.
  • the Si content is below the detection limit of ⁇ 1%, the shrinkage during production is well below 5% and the open porosity ⁇ 13% by volume.
  • silicon powder was used without further additives and, as in Example 1a, nitrided to form reaction-linked silicon nitride (RBS R).
  • RBS R reaction-linked silicon nitride
  • a cyclical temperature-time profile also exposed the materials to a change in temperature.
  • the holding time at 1400 ° C was 10 hours per cycle, a total of 10 cycles were run through.
  • An oxidation cycle was carried out with the following temperature-time control:
  • Double ring bending strength sample dimensions: diameter approx. 50 mm, height approx. 4 mm, load ring radius 8 mm, support ring radius 16 mm
  • 4-point bending strength sample dimensions: 3 x 4 x 45 mm, supports 40/20 mm
  • cyclic oxidation 1400 ° C 100 hd) mercury buoyancy method
  • mercury pressure porosimetry f) based on room temperature bending strength before the oxidation treatment
  • test specimen dimensions 3 x 4 x 45 mm supports: 40/20 mm
  • Double ring bending strength sample dimensions: diameter 50 mm, height 4 mm, load ring radius 8 mm, support ring radius 16 mm b) mercury pressure porosimetry c) mercury buoyancy method
  • the materials resulting from the variation of the starting compositions all have an open porosity ⁇ 13% by volume.
  • Si 3 N 4 , SiC and Si 2 N 2 O phases were determined by X-ray diffraction in different ratios, the residual silicon content is below the detection limit of ⁇ 1%, the shrinkage occurring during production is clearly below 5% .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne des matériaux liés par réaction à base de nitrure de silicium, qui contiennent comme phases cristallines du nitrure de silicium (Si3N4), du carbure de silicium (SiC) et de l'oxynitrure de silicium (Si2N2O), possèdent une teneur en phase silicium ≤ 1 % et présentent de très bonnes propriétés mécaniques et un comportement très stable dans des conditions oxydantes à des températures élevées. L'invention concerne également un procédé pour la fabrication de ces matériaux à partir d'un mélange de silicium, de nitrure de silicium et de composés de silicium organiques (de préférence des polysiloxanes et/ou des polycarbosilanes) par traitement thermique de ce mélange en atmosphère azotée, de sorte que les composés de silicium organiques sont pyrolysés et nitrurés en présence du silicium. L'invention concerne d'autre part l'utilisation de ces matériaux pour la fabrication de pièces céramiques.
EP99969908A 1998-12-03 1999-12-01 Materiaux lies par reaction a base de nitrure de silicium et leur procede de fabrication Withdrawn EP1144337A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1998155811 DE19855811A1 (de) 1998-12-03 1998-12-03 Reaktionsgebundene Werkstoffe auf Basis von Siliciumnitrid und Verfahren zu deren Herstellung
DE19855811 1998-12-03
PCT/EP1999/009341 WO2000032537A2 (fr) 1998-12-03 1999-12-01 Materiaux lies par reaction a base de nitrure de silicium et leur procede de fabrication

Publications (1)

Publication Number Publication Date
EP1144337A2 true EP1144337A2 (fr) 2001-10-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99969908A Withdrawn EP1144337A2 (fr) 1998-12-03 1999-12-01 Materiaux lies par reaction a base de nitrure de silicium et leur procede de fabrication

Country Status (4)

Country Link
EP (1) EP1144337A2 (fr)
AU (1) AU3148600A (fr)
DE (1) DE19855811A1 (fr)
WO (1) WO2000032537A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10060221A1 (de) 2000-12-04 2002-06-13 Cfi Ceramics For Industry Gmbh Substrat auf Basis von Siliciumnitrid für Halbleiter-Bauelemente
DE10203473A1 (de) 2002-01-25 2003-07-31 Skf Ab Verfahren zur Herstellung keramischer Lagerbauteile
CN100453508C (zh) * 2006-06-14 2009-01-21 中国科学院理化技术研究所 化学激励燃烧合成氮化硅/碳化硅复合粉体的方法
HUE036751T2 (hu) 2008-06-13 2018-07-30 Saint Gobain Ceramics Térfogatváltozásnak ellenálló szilícium-oxinitrid vagy szilícium-oxinitrid és szilícium-nitrid-kötött szilícium-karbid tûzálló termék
RU2651861C1 (ru) * 2016-11-03 2018-04-24 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский авиационный институт (национальный исследовательский университет)" Способ получения изделий на основе нитрида кремния

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2650083A1 (de) * 1976-10-30 1978-05-03 Daimler Benz Ag Verfahren zum herstellen von werkstuecken aus siliziumnitrid
DE2803658A1 (de) * 1977-01-27 1978-08-10 Kyoto Ceramic Verfahren zur herstellung von dichten, gesinterten siliciumcarbidkoerpern aus polycarbosilan
JPS6031799B2 (ja) * 1979-11-30 1985-07-24 黒崎窯業株式会社 ＳｉＣ−Ｓｉ↓３Ｎ↓４系複合耐熱セラミツクス材料及びその製造方法
US5190709A (en) * 1989-06-29 1993-03-02 Hercules Incorporated Reaction injection molding of ceramics using a ceramic precursor as a binder
DE4318974C2 (de) * 1993-06-08 1995-04-27 Fraunhofer Ges Forschung Verfahren zur Herstellung von Formkörpern

Non-Patent Citations (1)

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Title
See references of WO0032537A3 *

Also Published As

Publication number Publication date
DE19855811A1 (de) 2000-06-08
WO2000032537A2 (fr) 2000-06-08
WO2000032537A3 (fr) 2000-10-05
AU3148600A (en) 2000-06-19

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