EP1570116B1 - Verbundwerkstoff aus einer metallmatrix und talk - Google Patents

Verbundwerkstoff aus einer metallmatrix und talk Download PDF

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Publication number
EP1570116B1
EP1570116B1 EP03815090A EP03815090A EP1570116B1 EP 1570116 B1 EP1570116 B1 EP 1570116B1 EP 03815090 A EP03815090 A EP 03815090A EP 03815090 A EP03815090 A EP 03815090A EP 1570116 B1 EP1570116 B1 EP 1570116B1
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EP
European Patent Office
Prior art keywords
talc
composite material
metal matrix
talc particles
coating
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.)
Expired - Lifetime
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EP03815090A
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English (en)
French (fr)
Other versions
EP1570116A2 (de
Inventor
François Martin
Jean-Pierre Bonino
Patrice Bacchin
Stéphane VAILLANT
Eric Ferrage
William Vautrin
Philippe Barthes
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Centre National de la Recherche Scientifique CNRS
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Centre National de la Recherche Scientifique CNRS
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Publication of EP1570116A2 publication Critical patent/EP1570116A2/de
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Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31703—Next to cellulosic

Definitions

  • the invention relates to a composite material, its use as a lubricating metal coating, and a method for its preparation.
  • a so-called “electroless” coding process on a substrate is a process of incorporating particles during the process of growth of a catalyzed oxidation-reduction metal or alloy.
  • An electrochemical coding method involves incorporating particles during the process of growing a metal or alloy onto a substrate to be coated from an electrolyte in an electrolysis cell.
  • Ni-BN h coatings are described by Mr. Pushpavanam, et al., ((Metal Finishing, June 1995 )] and composite coatings of nickel loaded with MOS 2 are described by Yu-Chi Chang, et al., [Electrochimica Acta, vol. 43, Issues 3-4, 1998, p. 315-324 ]. In both cases, the coatings can be obtained electrochemically. However, boron nitrides have very low chemical resistance in acidic and basic medium.
  • the object of the present invention is to provide a material which has the properties of hardness and wear resistance conventionally required for mechanical parts in contact and displacement relative to each other in a mechanical assembly, and lubricant properties stable at high temperatures, for example of the order of 800 ° C. This is why the present invention relates to a composite material, its use as a self-lubricating coating of a substrate, and a process for its preparation.
  • the composite material according to the invention consists of a metal matrix in which are distributed talc particles in sheets. It is characterized in that the talc particles carry on their surface a compound derived from cellulose, fixed by replacing all or part of the hydroxyl groups.
  • the metal matrix may consist of a metal chosen from Fe, Co, Ni, Mn, Cr, Cu, W, Mo, Zn, Au, Ag, Pb, Sn, by an intermetallic compound or an alloy of several metals chosen from said metals, or an alloy of one or more of said metals with a metalloid.
  • Composite materials whose matrix is nickel, a metal alloy of nickel with other metals, or a nickel alloy with a metalloid (for example NiP) are particularly interesting.
  • the unmodified talc is a magnesium silicate having the formula Mg 3 Si 4 O 10 (OH) 2 which is part of the family of phyllosilicates and is in the form of a stack of sheets.
  • the elemental sheet has a thickness of 0.9 nm. It loses its constitution water around 800 ° C and decomposes around 950 ° C. The properties it gives to a composite material are therefore stable up to 950 ° C.
  • the presence of modified talc particles in the composite material according to the invention can be determined using various analytical technique.
  • Scanning Electron Microscopy (SEM) images show that the treated talc has on the surface groups derived from micron-sized cellulose.
  • X-ray energy scattering scanning electron microscopy (MEB-EDX) analyzes after Au metallization, low voltage SEM, or electron spectroscopy for chemical analysis (ESCA) yield amounts of C, which show the presence of an organic compound on the surface.
  • X-ray diffraction thanks to the use of multi-element detectors and the reduction of the size of the analysis spot (10 to 100 ⁇ 2 ), confirms the existence of cellulose derivatives on the surface of talc, the size of the spot and the size of the cellulose derivative groups on the talc being substantially identical.
  • the diffuse reflectance Fourier Transform Infrared spectrometry shows the presence of talc-specific vibration bands as well as vibration bands specific to the carbon-bonded groups of the cellulose derivative, the positions of the respective vibration bands being different.
  • RAMAN point laser
  • the coating of the talc particles with a cellulose derivative in the composite material of the invention can also be demonstrated by the micro-PIXE (particle-induced X-ray emission) technique which allows a chemical analysis of the micrometer order, and by the EXAFS technique (X-ray absorption by the fine structure) which allows the determination of the ligands of the probed atom and the inter-atomic distances around the ligand up to 6 nm.
  • micro-PIXE particle-induced X-ray emission
  • EXAFS X-ray absorption by the fine structure
  • talc which is a relatively soft material, into the metal matrix, does not modify the properties of hardness and abrasion resistance inherent in the material constituting said matrix.
  • the composite material according to the invention can advantageously be used as a coating on a substrate.
  • a coating constituted by a composite material according to the invention may be deposited electrolytically on the substrate to be treated.
  • the method of depositing on a substrate a coating constituted by the composite material according to the invention consists in performing an electrolytic deposition using a solution of precursors of the metal matrix of the coating. It is characterized in that the precursor solution further contains suspended talc particles, said talc particles having been previously surface-modified by irreversible adsorption of a cellulose-derived compound by replacing all or part of the hydroxyl groups .
  • the deposition process is carried out chemically, by contacting the surface of the substrate to be coated with the solution containing the precursors of the metal matrix, the modified talc particles, and a compound acting as a catalyst for the oxidation reduction of the precursors of the metal matrix of the coating.
  • the deposition process is carried out electrochemically in an electrochemical cell in which said substrate to be coated constitutes the cathode and the electrolyte is a precursor solution of the metal matrix of the coating further containing the modified talc particles.
  • CMC carboxymethylcellulose
  • guar guar
  • CMC is a cellulose ether resulting from the reaction of alkali-cellulose and sodium monoacetate. Part of the hydroxyl groups of the cellulose are replaced by carboxymethyl groups of sodium (-CH 2 COONa).
  • the respective formulas of the recurring unit of the cellulose and the repeating unit of the CMC are shown below.
  • CMC may have different degrees of substitution.
  • the degree of substitution DS is 3 in theory. In practice, the DS is well below 3.
  • Commercial CMCs have DSs ranging from 0.6 to 0.95. Dissolution of the CMC in water causes ionization of the carboxymethylcellulose groups, giving the CMC macromolecule a negative charge. When an aqueous solution contains a weakly substituted, more hydrophobic CMC, it has a thixotropic character. When an aqueous solution contains a strongly substituted CMC, it has a pseudoplastic nature.
  • the viscosity of the aqueous medium in which the CMC is dissolved depends on the length of the CMC macromolecule, i.e. the number of anhydroglucose units and the critical micelle concentration.
  • Commercial CMCs can cover a fairly wide range of viscosity (10 to 9000 mPa.s) depending on the length of the chain and the concentration.
  • a guar is a cellulosic compound in which certain hydroxyl groups (-OH) of a cellulosic ring are substituted by hydroxyglucose groups. In this case the possibility of substitution on a given chain length is much lower than in the case of the CMC. The degrees of substitution of guar are close to 0.1.
  • the formula for the recurrent unit of guar is shown below.
  • the inventors have finally found that the preliminary modification of the talc particles using a Cellulosic compound in which at least a portion of the OH groups are substituted overcomes these problems.
  • the talc particles preferably have an average size of less than 15 ⁇ m.
  • the precursors of the metal matrix are chosen from ionic compounds, complexed or non-complexed, reducible in solution by chemical means or by electron addition.
  • ionic compounds such as chlorides, sulphates and sulphamates, as well as complexes such as citrates and acetates.
  • the precursor solution further contains one or more compounds for adjusting the pH to the desired value, as well as the modified talc particles.
  • the electrolyte is a solution containing at least one nickel salt selected from nickel sulfate and nickel chloride, a pH regulating agent and a supporting electrolyte.
  • a particularly preferred pH regulator is boric acid; at pH 4.5, it forms a complex with nickel by releasing H + and thus balances the reduction of H + ions at the cathode.
  • a supporting electrolyte mention may be made, for example, of sodium sulphate, magnesium sulphate and sodium bromide.
  • an electrolyte containing at least one nickel salt selected from nickel sulfate and chloride, a pH regulating agent, a phosphorus precursor and a supporting electrolyte containing at least one nickel salt selected from nickel sulfate and chloride, a pH regulating agent, a phosphorus precursor and a supporting electrolyte.
  • H 3 PO 3 is advantageously chosen phosphorus precursor.
  • the pH regulator may be chosen from H 3 PO 4 and H 3 BO 3 , H 3 PO 4 being particularly preferred.
  • a supporting electrolyte mention may be made, for example, of sodium sulphate, magnesium sulphate and sodium bromide.
  • a coating comprising a zinc-nickel matrix is deposited electrochemically, it is possible to use basic or acidic electrolytes containing at least one nickel salt chosen from nickel sulphate and chloride, at least one zinc oxide or a zinc salt such as zinc chloride, an amine complexing agent, and a supporting electrolyte such as, for example, KCl.
  • the process is carried out under the usual conditions of electrochemical deposition.
  • the duration of the electrolysis depends in particular on the desired thickness for the coating.
  • the temperature in the electrochemical cell is advantageously between 0 ° C. and 90 ° C. and the current density applied to the cell is between 0.1 and 10 A.dm -2 .
  • An electrochemical cell is preferably used in which the anode is of the soluble anode type, consisting of the metal to be deposited.
  • the substrate may be constituted by an intrinsically conductive material (for example a metal or an alloy) used in solid state or in the form of a coating on any support.
  • the substrate may further consist of an insulating or semiconductor material (for example a polymer or a ceramic) whose surface to be treated has been rendered conductive by a preliminary metallization step.
  • the mechanical properties of the composite coatings were tested with a pion-disk tribometer in which the pin (which constitutes the antagonist body) is a 100C6 steel ball having a hardness of 1000 Hv.
  • the pin which constitutes the antagonist body
  • the pin is a 100C6 steel ball having a hardness of 1000 Hv.
  • the adhesion of nickel to the steel is manifested by a high coefficient of friction and a high wear rate of the steel ball.
  • the disc used consists of a nickel-talc composite material according to the invention, the coefficient of friction and the wear rate are greatly reduced.
  • Modified talc particles were prepared using 3 samples of carboxymethylcellulose (CMC), the characteristics of which (degree of substitution which causes the charge, and viscosity which depends on the chain length) are given in the table below. below.
  • CMC carboxymethylcellulose
  • Reference Degree of substitution Viscosity 21901 0.78 15-50 mPa.s ( sol at 4% by mass ) 21900 0.79 500-2500 mPa.s ( sol at 4% by mass ) 21903 0.92 700-1500 mPa.s ( sol at 1% by mass )
  • Nickel / talc composite coating
  • the coating was prepared in an electrochemical cell consisting of a 4 cm 2 nickel anode and a 1.762 cm 2 copper cathode on which the deposition is carried out.
  • the deposition is carried out by maintaining the electrolyte at a temperature of 55 ° C. under a current density of 2.5 A.dm -2 for a duration of 1h30.
  • Scanning electron microscopy (SEM) analysis of the resulting coating shows that the talc sheets incorporated in the metal matrix are perpendicular to the surface of the substrate.
  • the qualitative chemical analysis by EDX of the surface of the composite coating reveals the characteristic peaks of the carbon present on the particles.
  • Infrared spectrometry analysis in diffuse reflection shows the vibration bands of the cellulosic groups of the CMC and talc-specific bands.
  • Deposition is performed by maintaining the electrolyte at a temperature of 80 ° C for a period of 45 min.
  • the SEM analysis of the resulting coating shows the presence of the talc sheets incorporated in the metal matrix
  • the qualitative chemical analysis by EDX of the surface of the composite coating makes appear the characteristic peaks of the carbon present on the particles.
  • the presence of this in the form of cellulosic groups characteristic of the CMC is confirmed by the diffuse reflection infrared spectrometry analysis.
  • the deposition is carried out by maintaining the electrolyte at a temperature of 55 ° C. under a current density of 5 A.dm -2 , for a duration of 12 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Sliding-Contact Bearings (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Glass Compositions (AREA)

Claims (14)

  1. Verbundmaterial, umfassend eine Metallmatrix, in der lamellare Talkteilchen verteilt sind, dadurch gekennzeichnet, dass die Talkteilchen auf ihrer Oberfläche eine von Cellulose abgeleitete Verbindung aufweisen, die durch Ersetzen aller oder eines Teils der Hydroxylgruppen gebunden ist.
  2. Verbundmaterial nach Anspruch 1, dadurch gekennzeichnet, dass die Metallmatrix aus einem aus Fe, Co, Ni, Mn, Cr, Cu, W, Mo, Zn, Au, Ag, Pb, Sn ausgewählten Metall, einer intermetallischen Verbindung oder einer Legierung mehrerer der zuvor angeführten Metalle ausgewähltem Metall oder einer Legierung eines oder mehrerer dieser Metalle mit einem Nichtmetall besteht.
  3. Verbundmaterial nach Anspruch 2, dadurch gekennzeichnet, dass die Metallmatrix aus Nickel, einer Nickelmetalllegierung mit anderen Metallen oder einer Legierung von Nickel mit einem Nichtmetall besteht.
  4. Verbundmaterial nach Anspruch 1, dadurch gekennzeichnet, dass die Talkteilchen eine mittlere Größe von weniger als 15 µm aufweisen.
  5. Substrat mit einer Schmiermittelbeschichtung darauf, dadurch gekennzeichnet, dass die Beschichtung aus einem Verbundmaterial nach einem der Ansprüche 1 bis 4 besteht.
  6. Substrat nach Anspruch 5, dadurch gekennzeichnet, dass es aus einem eigenleitfähigen Material besteht.
  7. Substrat nach Anspruch 5, dadurch gekennzeichnet, dass es aus einem Isoliermaterial oder Halbleitermaterial besteht, dessen zu behandelnde Oberfläche durch einen vorherigen Metallisierungsschritt leitfähig gemacht wurde.
  8. Verfahren zur Abscheidung einer Beschichtung aus einem Verbundmaterial, das eine Metallmatrix umfasst, in der lamellare Talkteilchen verteilt sind, auf einem Substrat, darin bestehend, dass eine elektrolytische Abscheidung unter Einsatz einer Vorläuferlösung der Metallmatrix der Beschichtung durchgeführt wird, dadurch gekennzeichnet, dass die Vorläuferlösung weiters suspendierte Talkteilchen enthält, wobei diese Talkteilchen zuvor durch irreversible Adsorption einer von Cellulose abgeleiteten Verbindung durch Ersetzen aller oder eines Teils der Hydroxylgruppen oberflächemodifiziert wurden.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass dieses auf chemischem Weg durch Kontaktieren der zu beschichtenden Substratoberfläche mit der Lösung, die die Vorläufer der Metallmatrix, die modifizierten Talkteilchen sowie eine als Katalysator wirkende Verbindung für die Redoxreaktion der Vorläufer der Metallmatrix der Beschichtung enthält.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass dieses auf elektrochemischem Weg in einer elektrochemischen Zelle umgesetzt wird, in der das zu beschichtende Substrat die Kathode bildet und der Elektrolyt eine Lösung der Vorläufer der Metallmatrix der Beschichtung ist, die weiters die modifizierten Talkteilchen enthält.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die Anode der elektrochemischen Zelle aus einem Metall besteht, das die Matrix bildet.
  12. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die von Cellulose abgeleitete Verbindung aus Carboxymethylcellulose (CMC) und Guargummi ausgewählt ist.
  13. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die Vorläufer der Metallmatrix aus ionischen, komplexierten oder nicht komplexierten Verbindungen ausgewählt ist, die in Lösung auf chemischem Weg oder durch Zufuhr von Elektronen reduzierbar sind.
  14. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die Behandlung der Talkteilchen mit der von Cellulose abgeleiteten Verbindung (CAV) folgende Schritte umfasst:
    - Herstellung einer wässrigen CAV-Stammlösung (20 bis 80 g/l);
    - Herstellung einer Paste aus entmineralisiertem Wasser (100 ml), Talk (50-150 g) und CAV (2-10 g), die aus der CAV-Stammlösung eingeführt wird, mittels Homogenisierung durch mechanisches Rühren (10-20 min);
    - vollständiges Verdampfen der wässrigen Phase der Paste in einem Trockenschrank (50-90 °C) bis zum Erhalt eines entwässerten Feststoffs;
    - Deagglomeration des entwässerten Feststoffs, um behandelte Talkteilchen zu erhalten, die eine Granulometrie aufweisen, die jener des ursprünglichen Talkpulvers entspricht;
    - erster Zyklus aus Waschen mit entmineralisiertem Wasser, Zentrifugation zur Trennung der Talkteilchen, Verdampfen des Wassers in einem Trockenschrank und Deagglomeration;
    - zweiter Zyklus aus Waschen/Zentrifugation/Verdampfung/Deagglomeration unter denselben Bedingungen;
    - Sieben.
EP03815090A 2002-12-09 2003-12-08 Verbundwerkstoff aus einer metallmatrix und talk Expired - Lifetime EP1570116B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0215507 2002-12-09
FR0215507A FR2848219B1 (fr) 2002-12-09 2002-12-09 Materiau composite utilisable comme revetement lubrifiant
PCT/FR2003/003625 WO2004063428A2 (fr) 2002-12-09 2003-12-08 Materiau composite constitue par une matrice metallique et du talc.

Publications (2)

Publication Number Publication Date
EP1570116A2 EP1570116A2 (de) 2005-09-07
EP1570116B1 true EP1570116B1 (de) 2008-04-30

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EP03815090A Expired - Lifetime EP1570116B1 (de) 2002-12-09 2003-12-08 Verbundwerkstoff aus einer metallmatrix und talk

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US (1) US7659008B2 (de)
EP (1) EP1570116B1 (de)
AT (1) ATE393844T1 (de)
AU (1) AU2003296779A1 (de)
BR (1) BR0316854A (de)
CA (1) CA2507456C (de)
DE (1) DE60320673D1 (de)
FR (1) FR2848219B1 (de)
WO (1) WO2004063428A2 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6676718B2 (en) 2001-01-12 2004-01-13 Rodel Holdings, Inc. Polishing of semiconductor substrates
CN100445430C (zh) * 2004-12-03 2008-12-24 中国科学院金属研究所 一种耐氯离子腐蚀的Ni-Cr纳米复合镀层的应用
FR2925529B1 (fr) * 2007-12-19 2010-01-22 Luzenac Europ Sas Materiau composite constitue par une matrice metallique dans laquelle sont reparties des nanoparticules phyllosilicatees lamellaires synthetiques
CN104109895B (zh) * 2014-07-09 2016-09-14 哈尔滨工程大学 一种在钢表面形成高耐蚀性镍与铬复合镀层的方法
CN104726908A (zh) * 2015-03-25 2015-06-24 西南石油大学 一种镍钨云母复合镀液、镀膜及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL267500A (de) * 1960-07-26
US3591350A (en) * 1968-06-17 1971-07-06 M & T Chemicals Inc Novel plating process
FR2674515B1 (fr) * 1991-03-29 1993-09-03 Talc Luzenac Substances talqueuses presentant des proprietes specifiques de surface et procedes de fabrication.
US6565646B1 (en) * 2001-11-02 2003-05-20 Luzenac America, Inc. Talc composition and use in paper products

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Publication number Publication date
AU2003296779A1 (en) 2004-08-10
CA2507456A1 (fr) 2004-07-29
WO2004063428A2 (fr) 2004-07-29
DE60320673D1 (de) 2008-06-12
ATE393844T1 (de) 2008-05-15
FR2848219A1 (fr) 2004-06-11
CA2507456C (fr) 2011-11-22
US7659008B2 (en) 2010-02-09
FR2848219B1 (fr) 2006-12-01
US20060162655A1 (en) 2006-07-27
WO2004063428A3 (fr) 2004-10-14
BR0316854A (pt) 2005-10-18
EP1570116A2 (de) 2005-09-07

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