EP1643016A1 - Utilisation de particules à surface modifiée pour la galvanotechnique - Google Patents

Utilisation de particules à surface modifiée pour la galvanotechnique Download PDF

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Publication number
EP1643016A1
EP1643016A1 EP04023599A EP04023599A EP1643016A1 EP 1643016 A1 EP1643016 A1 EP 1643016A1 EP 04023599 A EP04023599 A EP 04023599A EP 04023599 A EP04023599 A EP 04023599A EP 1643016 A1 EP1643016 A1 EP 1643016A1
Authority
EP
European Patent Office
Prior art keywords
particles
metals
modified
surfactants
electroplating
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Withdrawn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
EP04023599A
Other languages
German (de)
English (en)
Inventor
Jan Dr. Steinbach
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to EP04023599A priority Critical patent/EP1643016A1/fr
Priority to PCT/EP2005/054608 priority patent/WO2006037721A1/fr
Priority to US11/664,566 priority patent/US20080193789A1/en
Publication of EP1643016A1 publication Critical patent/EP1643016A1/fr
Withdrawn legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic

Definitions

  • the invention relates to the use of surface-modified particles in electroplating, a process for their preparation and the particles themselves.
  • Particles of metals, semimetals, alloys of metals and / or semimetals and of compounds of metals or semi-metals play an important role in many technical processes, for example in electroplating. For many of these applications, particles with average particle sizes of about 0.1 .mu.m to about 1 .mu.m (so-called submicroscale particles) and partly with particle sizes below 100 nm (so-called nanoscale powder) are required.
  • NiCo-XYZ powder where X, Y and Z stand for conventional minor alloying elements
  • metal alloy powder of the basic elements iron, tantalum, niobium, platinum and palladium it is found that their non-modifying storage can not be guaranteed satisfactorily and their processability is difficult.
  • the specific surface of the powder increases with decreasing particle size, which can lead to undesirable reactions or changes to the surface, especially with regard to their subsequent use.
  • the agglomeration of small particles is observed to larger agglomerates, which may also affect their further processability, because z. B. the redispersion of these agglomerates to the original particle size often not or only partially possible.
  • German patent application DE 195 15 820 A1 describes a method in which amorphous or partially crystalline nanoscale particles for the production of glass or ceramic are modified with at least one surface-blocking substance.
  • the surface-blocking substances may be, inter alia, emulsifiers and nonionic surfactants.
  • the use of the producible by this process ceramic powder in electroplating is not taught in DE 195 15 820 A1.
  • the organic compounds proposed in the prior art for modifying the particle surface have a disturbing effect on final processing, especially in electroplating, and must first be eliminated by combustion, thermal decomposition or by means of chemical reactions.
  • This object is achieved according to the invention by the use of surface-modified particles in electroplating, the surface of which is modified with at least one surface-active or surface-active substance to form a coating layer on the particles.
  • the use according to the invention of the particles modified in the electroplating technique with at least one surface-active or surface-active substance gives the dispersed powders good storage stability.
  • the at least one surface-active substance forms a coating layer around each particle of the powder and thus prevents for a long time the undesired chemical or physical change of the powder, for example by reaction with atmospheric oxygen or agglomeration.
  • the use according to the invention also permits the problem-free further processing of the powder in the galvanotechnical process, because the coating layer can be readily removed from the at least one surface-active or surface-active substance without affecting this process or interfering with it.
  • Preferred in the present invention is the use of particles having an average particle size of not more than about 1 ⁇ m.
  • the average particle size in a particularly preferred embodiment is about 1 ⁇ m to about 0.1 ⁇ m (i.e., the particles are submicroscale particles).
  • the particles are nanoscale particles having an average particle size in a range from about 1 nm to about 100 nm.
  • the particle size here refers to the particles without a coating layer of at least one surface-active or surface-active substance.
  • the surface-modified particles are preferably particles of metals or semimetals, which are preferably used in electroplating for coating workpieces. More preferably, the metals and semimetals are selected from the group comprising Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd and Pt.
  • oxide, nitride, carbide or boride compounds and mixed compounds thereof of metals or semimetals are preferred.
  • the particles of metals or semi-metals are in elemental form or in the form of alloys.
  • the at least one surface-active substance which forms the coating layer of the particles used according to the invention can be any conventional surfactant or wetting agent. There may be more than one surface or surface-active substance, for. B. two, three or four different such substances, are used, but it is preferred to use only one surface or surface active substance.
  • Such surfactants or wetting agents are characterized by the fact that they reduce the interfacial tension or surface tension of a system containing them. They are (at least) bifunctional (amphiphilic) chemical compounds having at least one hydrophobic and at least one hydrophilic moiety. The hydrophobic residue is z.
  • hydrocarbon surfactants a mostly linear hydrocarbon chain of eight to 22 carbon atoms; in siloxane surfactants, the hydrophobic moiety of (dimethyl) siloxane chains is formed in perfluorocarbon chain perfluorocarbon surfactants.
  • the hydrophilic moiety is either an electrically negative or positively charged (hydratable) or a neutral polar head group.
  • the molecules of the at least one surfactant interact with the particle surface of the powder particles to form a cladding layer to effect stabilization of the surface.
  • coating layer in the present context is not necessarily to be understood that the surface of the particles must be completely covered, but circumscribing the function of the surface or surface-active substance, which modifies the particles modified with it among other things from air and moisture protects and so significantly increases their storage stability.
  • the exact structure of the cladding layer is not known. It will depend inter alia on the nature and size of the particles as well as the specific choice of surfactant.
  • the at least one surface or surface-active substance is a surfactant or wetting agent, which in the further galvanoischen processing, for. B. used in the pretreatment baths used there and in particular in the process solutions or suspensions used for the actual metallic coating, anyway.
  • the cladding layer is removed from the at least one surface-active or surface-active substance, eliminated or proves to be non-irritating in the further process steps of electroplating.
  • the medium to long-chain molecules of the at least one wetting agent forming the coating layer can be attracted or repelled electrostatically from the polarized electrode surface by their polarized (or polarizable) regions.
  • the wetting agents customary in electroplating form a metal ion-permeable film on the cathode surface, which facilitates the "stripping" of the water dipole envelopes and their classification in the crystal structure.
  • the wetting agent molecules can also be transported to a certain extent by the particles in the cathode near and compensate for losses by electrochemically induced decomposition of the wetting agent molecules in the immediate vicinity of the cathode.
  • this surface-active or surface-active substance forming the coating layer also finds use as the usual wetting agent in the US Pat Electroplating process solution or suspension - which is preferred - thus additional disturbing influences are not expected by this substance and no special precautions must be taken to ausschlleusen them from the process solution or suspension. The further processing or disposal of the process solution or suspension does not usually have to be changed or adjusted.
  • the surface-active or surface-active substance is particularly preferably selected from the group comprising hydrocarbon surfactants, siloxane surfactants and perfluorocarbon surfactants.
  • the surfactant is sodium dodecyl sulfate.
  • a further embodiment of the invention relates to the use of the surface-modified particles in a process solution or a process suspension for electroplating, wherein before and / or during the electroplating, the surface-modified particles are brought into contact with at least one substance which removes residue-free the coating layer.
  • a solvent is selected as the substance which is able to dissolve the surfactant (wetting agent) forming the coating layer.
  • the removal can also be done for example by thermal treatment.
  • this is at least one wetting agent, which forms the cladding layer, but selected so that it does not interfere with the further electroplating of the surface-modified particles, z. B. because - as stated above - it forms a permeable to the metal ions in the electric field film.
  • the term "electroplating” is to be understood in the broadest sense and includes the treatment of metallic and non-metallic surfaces of workpieces, pre-, semi-finished and finished products, for example to beautify them, against environmental influences. especially corrosion and abrasion, to protect or to improve their properties in the form of composite materials.
  • preferred electroplating processes are layer-applying processes in which functional layers which usually largely determine the properties of the workpiece or product are applied to the base materials with a thickness of only a few ⁇ m in chemical or electrochemical processes using the surface-modified particles.
  • the electroless chemical deposition in which, after introduction of (surface-modified) metal powders into a coating solution or suspension to form metal ions by the use of chemical reducing agents without application of an external electric field by the reduction of the metal ions the deposition of the metal (protective) layer is effected on the workpiece surface to be coated, and electrochemical deposition processes (electroplating, electroplating, electroplating in the strict sense), in which the metal ions or charged metal alloys formed from the metal powders in galvanizing solutions or suspensions Particles migrate in an externally applied electric field to the workpiece connected as a cathode and there reduced to the metal to form the desired protective layer or be incorporated into an existing metal or alloy matrix, especially vorz suffices.
  • a preparatory treatment of the workpieces to be machined is required, inter alia, for degreasing, pickling and activating surfaces etc. in pre-treatment baths in which surfactants or wetting agents are generally used.
  • the actual treatment baths contain, in addition to the actual coating agent and reducing agent or electrolyte, further additives, including surfactants or Wetting agents.
  • a means for residue-free removal of the surface-modifying substance may be added to these process plating baths, as necessary or desired. This agent can also be added to the pretreatment baths if the residue-free removal of the surface-modifying substance from the particles is to take place before the actual plating or deposition step.
  • the present invention further relates to processes for the preparation of surface-modified particles having a coating layer of at least one surface-active or surface-active substance, wherein, for example, the final fractionation of the particle powder immediately after its preparation by conventional methods known in the art (for example dispersion with Ultrasonic or stirring and shaking devices) with a solution of the envelope layer forming substance / s is soaked and thereby a pre-suspension of the subsequent process solution or suspension is formed.
  • solvent or suspending agent for example, in addition to water, short-chain aliphatic alcohols and other volatile organic solvents may be used.
  • Another object of the invention are the surface-modified particles described above for use in electroplating, the surface of which with at least one surface or surface-active Substance is modified to form a cladding layer on the particles, and the particles of metals or semimetals, wherein these particles are present in elemental form, in the form of an alloy or as oxides, nitrides, carbides, borides or as mixed compounds thereof of the metals or semimetals.
  • the surface-modified particles according to the invention are preferably nanoscale particles or submicron-scale particles having an average particle size of from about 0.1 ⁇ m to about 1 ⁇ m.
  • the particles are furthermore preferably particles of metals, particularly preferably of the metals Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd and Pt, very particularly preferably the metals Ni, Cr, Co and Al, in particular in elemental form or in the form of alloys.
  • modified surface alloy particles of the present invention are nickel-cobalt alloys and chromium-aluminum-XYZ alloys, where X, Y and Z are minor alloy elements suitable for high-temperature materials or coatings, in particular Re, Y, Si , Ti, Ta, W, Mn, Mo, Nb, Zr, Hf, in customary amounts or proportions, more preferably.
  • CrAl-XYZ or "chromium-aluminum-XYZ” alloy is here a shortened notation for such chromium-aluminum alloys with suitable secondary alloying elements; it should neither name the exact number of other elements besides Cr and Al - ie there may be one, two, three, four or more different minor alloying elements - nor be understood as an indication of the proportions of the alloying elements among themselves.
  • Examples of preferred CrAl-XYZ alloys are Cr 62 Al 32 YRe 5 , Cr 58.8 Al 34.6 Y 1.4 Re 5.2 , Cr 76 Al 21 Y 1.6 Si 1.4 , Cr 57 Al 40 Y 2 Si and Cr 53.8 Al 11.4 Ti 11.4 Ta 5.9 W 8.7 Mo 5.9 Nb 2.8 .
  • Surfactants used to modify the particle surface are preferably selected from the group comprising Hydrocarbon surfactants, siloxane surfactants and perfluorocarbon surfactants, especially sodium dodecyl sulfate. Furthermore, it is preferred that the surface-modified particles of the invention are present in a solution or suspension, wherein the solvent or solvent mixture used is selected so that it does not interfere with the further galvanotechnische processing. Examples of suitable solvents are, for example, in addition to water, short-chain aliphatic alcohols and other volatile organic solvents.
  • metal and “semimetal” have the usual meanings in inorganic chemistry, as they are known for. In Hollemann-Wiberg, Lehrbuch der Anorganischen Chemie, 91.-100. Edition, 1985, pp. 301-302 and pp. 731-733.
  • semimetals are in particular boron, gallium, silicon, germanium, tin, arsenic, antimony, bismuth, selenium and tellurium
  • metals include nickel, palladium, platinum, cobalt, iron, aluminum, chromium, titanium, manganese, molybdenum , Tungsten, vanadium, niobium, tantalum, hafnium, etc. are.
  • a finely dispersed powder with an average particle size of about 1 .mu.m of the base composition Cr 62 Al 32 YRe 5 is added immediately after its preparation by sputtering (or alternatively atomization, grinding or melt atomization) with a solution of sodium dodecyl sulfate in water.
  • the resulting suspension can be processed further directly (see Example b)); Alternatively, the surface-modified from the suspension Particles are obtained by freeze-drying in powder form.
  • the suspension from example a) is dispersed in a nickel-cobalt plating bath. Electrodeposition on the cathode surface leads to the incorporation of the alloy powder particles into the Ni-Co layer (Ni-Co matrix) growing on the cathode, while at the same time the shell layer molecules desorb from the particle surface and remain in the electrolyte suspension.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
EP04023599A 2004-10-04 2004-10-04 Utilisation de particules à surface modifiée pour la galvanotechnique Withdrawn EP1643016A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP04023599A EP1643016A1 (fr) 2004-10-04 2004-10-04 Utilisation de particules à surface modifiée pour la galvanotechnique
PCT/EP2005/054608 WO2006037721A1 (fr) 2004-10-04 2005-09-16 Utilisation de particules a surface modifiee en galvanoplastie
US11/664,566 US20080193789A1 (en) 2004-10-04 2005-09-16 Use of Surface-Modified Particles in Electroplating Technology

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP04023599A EP1643016A1 (fr) 2004-10-04 2004-10-04 Utilisation de particules à surface modifiée pour la galvanotechnique

Publications (1)

Publication Number Publication Date
EP1643016A1 true EP1643016A1 (fr) 2006-04-05

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EP04023599A Withdrawn EP1643016A1 (fr) 2004-10-04 2004-10-04 Utilisation de particules à surface modifiée pour la galvanotechnique

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US (1) US20080193789A1 (fr)
EP (1) EP1643016A1 (fr)
WO (1) WO2006037721A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113061949A (zh) * 2021-04-20 2021-07-02 深圳市鸿信顺电子材料有限公司 一种片式元件的镀前处理试剂及改性工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0748883A1 (fr) * 1995-06-12 1996-12-18 ABB Management AG Pièce munie d'un revêtement électrolytique et procédé de réalisation de couches par électrodéposition
DE10125290A1 (de) * 2001-05-15 2002-11-28 Siemens Ag Verfahren zum Aufbereiten von Nano-Dispersanten
US20030038034A1 (en) * 2001-08-27 2003-02-27 Griego Thomas P. Electrodeposition apparatus and method using magnetic assistance and rotary cathode for ferrous and magnetic particles
US20040179800A1 (en) * 2003-03-11 2004-09-16 3M Innovative Properties Company Coating dispersions for optical fibers
US20040191641A1 (en) * 2003-03-27 2004-09-30 Ray Kevin Barry Nanopastes as ink-jet compositions for printing plates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0748883A1 (fr) * 1995-06-12 1996-12-18 ABB Management AG Pièce munie d'un revêtement électrolytique et procédé de réalisation de couches par électrodéposition
DE10125290A1 (de) * 2001-05-15 2002-11-28 Siemens Ag Verfahren zum Aufbereiten von Nano-Dispersanten
US20030038034A1 (en) * 2001-08-27 2003-02-27 Griego Thomas P. Electrodeposition apparatus and method using magnetic assistance and rotary cathode for ferrous and magnetic particles
US20040179800A1 (en) * 2003-03-11 2004-09-16 3M Innovative Properties Company Coating dispersions for optical fibers
US20040191641A1 (en) * 2003-03-27 2004-09-30 Ray Kevin Barry Nanopastes as ink-jet compositions for printing plates

Also Published As

Publication number Publication date
WO2006037721A1 (fr) 2006-04-13
US20080193789A1 (en) 2008-08-14

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