EP1643016A1 - Use of surface modified particles in electroplating - Google Patents
Use of surface modified particles in electroplating Download PDFInfo
- 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- Withdrawn
Links
- 239000002245 particle Substances 0.000 title claims abstract description 100
- 238000009713 electroplating Methods 0.000 title claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 29
- 150000002739 metals Chemical class 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 239000011247 coating layer Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- 239000000839 emulsion Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000080 wetting agent Substances 0.000 description 13
- 239000011651 chromium Substances 0.000 description 12
- 239000010955 niobium Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- -1 semimetals Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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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Abstract
Die Erfindung betrifft die Verwendung von oberflächenmodifizierten Partikeln in der Galvanotechnik, ein Verfahren zu deren Herstellung sowie die Partikel selbst.The invention relates to the use of surface-modified particles in electroplating, a process for their preparation and the particles themselves.
Description
Die Erfindung betrifft die Verwendung von oberflächenmodifizierten Partikeln in der Galvanotechnik, ein Verfahren zu deren Herstellung sowie die Partikel selbst.The invention relates to the use of surface-modified particles in electroplating, a process for their preparation and the particles themselves.
Partikel aus Metallen, Halbmetallen, Legierungen von Metallen und/oder Halbmetallen sowie aus Verbindungen von Metallen oder Halbmetallen spielen in vielen technischen Prozessen, beispielsweise in der Galvanotechnik, eine bedeutende Rolle. Für zahlreiche dieser Anwendungen sind Partikel mit durchschnittlichen Teilchengrößen von etwa 0,1 µm bis etwa 1 µm (so genannte submikroskalige Partikel) und zum Teil mit Teilchengrößen unter 100 nm (so genannte nanoskalige Pulver) erforderlich.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.
Verfahren zur Herstellung solcher hochdisperser Pulver sind dem Fachmann gut bekannt. Allerdings zeigen sich bei diesen hochdispersen Pulvern erhebliche Probleme bei der Lagerung und/oder Verarbeitung. So kann bei Partikeln im submikroskaligen oder nanoskaligen Bereich, welche leicht Passivierungsschichten ausbilden, wie z. B. Legierungen mit hohem Chromanteil, die Ausbildung einer äußeren Oxidschicht zwar die Lagerstabilität erhöhen, gerade diese Oxidschicht für die weitere Verarbeitung jedoch hinderlich sein. In vielen Anwendungsfällen, wie etwa den verschiedenen Verfahren der Galvanotechnik, stellt die Entfernung dieser Oxidschicht während der letzten Verarbeitungsschritte ein erhebliches technisches Problem dar, das bislang nicht zufriedenstellend gelöst ist.Methods of making such highly dispersed powders are well known to those skilled in the art. However, these fumed powders show considerable problems during storage and / or processing. Thus, for particles in the sub-microscale or nanoscale range, which easily form passivation layers, such as. B. alloys with high chromium content, the formation of an outer oxide layer, although increase the storage stability, just this oxide layer for further processing, however, be a hindrance. In many applications, such as the various electroplating techniques, the removal of this oxide layer during the final processing steps presents a significant technical problem that has not yet been satisfactorily solved.
Bei Pulvern, die trotz hoher Affinität gegenüber (Luft-)Sauerstoff selbst keine passivierende Oxidschutzschicht bilden, wie z. B. feindisperse CrAl-XYZ-Pulver (wobei X, Y und Z für übliche Nebenlegierungselemente stehen) und Metall-Legierungspulver der Basismetalle Titan, Zirconium, Vanadium, Molybdän und Wolfram, sowie bei Pulvern, welche wenig affin gegenüber Sauerstoff sind und keine oder nur eine geringe Neigung zur Ausbildung einer Passivierungsschicht besitzen, wie z. B. feindisperse NiCo-XYZ-Pulver (wobei X, Y und Z für übliche Nebenlegierungselemente stehen) und Metall-Legierungspulver der Basiselemente Eisen, Tantal, Niob, Platin und Palladium, zeigt sich, dass ihre veränderungsfreie Lagerung häufig nicht zufriedenstellend gewährleistet werden kann und sich ihre Verarbeitbarkeit schwierig gestaltet. So vergrößert sich die spezifische Oberfläche der Pulver mit abnehmender Teilchengröße, was vor allem im Hinblick auf ihre spätere Verwendung zu unerwünschten Reaktionen oder Veränderungen an der Oberfläche führen kann. Auch wird die Agglomeration von kleinen Teilchen zu größeren Agglomeraten beobachtet, was ebenfalls ihre weitere Verarbeitbarkeit beeinträchtigen kann, weil z. B. die Redispergierung dieser Agglomerate auf die ursprüngliche Teilchengröße oft nicht oder nur zum Teil möglich ist.For powders that do not form a passivating oxide protective layer in spite of high affinity to (air) oxygen itself, such. B. finely dispersed CrAl-XYZ powder (where X, Y and Z stand for common secondary alloying elements) and metal alloy powder of the base metals titanium, Zirconium, vanadium, molybdenum and tungsten, as well as in powders which are less affine to oxygen and have no or only a slight tendency to form a passivation layer, such. As finely dispersed NiCo-XYZ powder (where X, Y and Z stand for conventional minor alloying elements) and 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. Thus, 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. Also, 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.
Im Stand der Technik sind Verfahren vorgeschlagen worden, die Oberflächen derartiger Pulver reaktiver Materialien mit geringer Teilchengröße mit Hilfe organischer Verbindungen zu modifizieren, um so beispielsweise die Agglomeration der Pulver-Teilchen zu unterdrücken. So beschreibt die deutsche Patentanmeldung DE 195 15 820 A1 ein Verfahren, in welchem amorphe oder teilkristalline nanoskalige Teilchen für die Herstellung von Glas oder Keramik mit mindestens einer oberflächenblockierenden Substanz modifiziert werden. Bei den oberflächenblockierenden Substanzen kann es sich unter anderem um Emulgatoren und nichtionische Tenside handeln. Die Verwendung der nach diesem Verfahren herstellbaren keramischen Pulver in der Galvanotechnik wird in der DE 195 15 820 A1 nicht gelehrt.Methods have been proposed in the art for modifying the surfaces of such powders of small particle size reactive materials with the aid of organic compounds so as to suppress agglomeration of the powder particles, for example. For example, 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.
Die im Stand der Technik zur Modifizierung der Partikeloberfläche vorgeschlagenen organischen Verbindungen wirken sich - ähnlich wie eine passivierende Oxidschicht - insbesondere in der Galvanotechnik bei der Endverarbeitung störend aus und müssen zuvor durch Verbrennung, thermische Zersetzung oder mittels chemischer Reaktionen beseitigt werden.Similar to a passivating oxide layer, 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.
Der vorliegenden Erfindung liegt daher als eine Aufgabe zugrunde, disperse Partikel für die Verwendung in der Galvanotechnik bereitzustellen, die zum einen hinreichend lagerstabil sind und sich zum anderen in den galvanotechnischen Verfahrensschritten gut verarbeiten lassen.It is therefore an object of the present invention to provide disperse particles for use in electroplating technology, which on the one hand are sufficiently stable in storage and on the other hand can be easily processed in the electroplating process steps.
Diese Aufgabe wird erfindungsgemäß gelöst durch die Verwendung von oberflächenmodifizierten Partikeln in der Galvanotechnik, deren Oberfläche mit wenigstens einer oberflächen- bzw. grenzflächenaktiven Substanz unter Ausbildung einer Hüllschicht auf den Partikeln modifiziert ist.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.
Die erfindungsgemäße Verwendung der mit wenigstens einer oberflächen- bzw. grenzflächenaktiven Substanz modifizierten Partikel in der Galvanotechnik verleiht den dispersen Pulvern eine gute Lagerstabilität. Die wenigstens eine oberflächen- bzw. grenzflächenaktive Substanz bildet eine Hüllschicht um jedes Teilchen des Pulvers und verhindert so über lange Zeit die unerwünschte chemische oder physikalische Veränderung des Pulvers etwa durch Reaktion mit Luftsauerstoff oder Agglomeration. Zugleich erlaubt die erfindungsgemäße Verwendung auch die problemlose weitere Verarbeitung des Pulvers in den galvanotechnischen Verfahren, weil sich die Hüllschicht aus der wenigstens einen oberflächen- bzw. grenzflächenaktiven Substanz ohne Weiteres rückstandsfrei entfernen lässt bzw. diese Verfahren nicht störend beeinflusst.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. At the same time, 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.
Bevorzugt ist in der vorliegenden Erfindung die Verwendung von Partikeln, die eine durchschnittliche Teilchengröße von nicht mehr als etwa 1 µm aufweisen. Dabei beträgt die durchschnittliche Teilchengröße in einer besonders bevorzugten Ausführungsform etwa 1 µm bis etwa 0,1 µm (d. h. die Partikel sind submikroskalige Teilchen). In einer zweiten besonders bevorzugten Ausführungsform der Erfindung sind die Partikel nanoskalige Teilchen mit einer durchschnittlichen Teilchengröße in einem Bereich von etwa 1 nm bis etwa 100 nm. Die Teilchengröße bezieht sich hierbei auf die Partikel ohne Hüllschicht aus wenigstens einer oberflächen- bzw. grenzflächenaktiven Substanz.Preferred in the present invention is the use of particles having an average particle size of not more than about 1 μm. The average particle size in a particularly preferred embodiment is about 1 μm to about 0.1 μm (i.e., the particles are submicroscale particles). In a second particularly preferred embodiment of the invention, 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.
Bevorzugt sind die oberflächenmodifizierten Partikel Teilchen von Metallen oder Halbmetallen, die vorzugsweise in der Galvanotechnik zum Beschichten von Werkstücken Verwendung finden. Besonders bevorzugt sind die Metalle und Halbmetalle ausgewählt aus der Gruppe, umfassend Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd und Pt.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.
Dabei können die Teilchen von Metallen oder Halbmetallen - sieht man von der oberflächenmodifizierenden Hüllschicht ab - in elementarer Form, z. B. als Nickelpulver, in Form von Legierungen, z. B. als Pulver von Chrom-Aluminium-Legierungen der Basiszusammensetzung CrA1-XYZ, wobei X, Y und Z für Nebenlegierungselemente stehen, die für Hochtemperaturwerkstoffe bzw. Beschichtungen geeignet sind, insbesondere für Re, Y, Si, Ti, Ta, W, Mn, Mo, Nb, Zr, Hf, und zwar in üblichen Mengen bzw. Mengenverhältnissen, oder als chemische Verbindungen von Metallen bzw. Halbmetallen vorliegen. Im letzteren Fall sind Oxid-, Nitrid-, Carbid- bzw. Borid-Verbindungen sowie Mischverbindungen daraus von Metallen bzw. Halbmetallen bevorzugt. Besonders bevorzugt liegen die Teilchen von Metallen oder Halbmetallen in elementarer Form oder in Form von Legierungen vor.In this case, the particles of metals or semimetals - apart from the surface-modifying coating layer - in elemental form, z. B. as nickel powder, in the form of alloys, for. As a powder of chromium-aluminum alloys of the basic composition CrA1-XYZ, where X, Y and Z are minor alloy elements which are suitable for high temperature materials or coatings, in particular for Re, Y, Si, Ti, Ta, W, Mn , Mo, Nb, Zr, Hf, in customary amounts or proportions, or as chemical compounds of metals or semi-metals. In the latter case, oxide, nitride, carbide or boride compounds and mixed compounds thereof of metals or semimetals are preferred. Most preferably, the particles of metals or semi-metals are in elemental form or in the form of alloys.
Die wenigstens eine oberflächen- bzw. grenzflächenaktive Substanz, welche die Hüllschicht der erfindungsgemäß verwendeten Partikel bildet, kann jedes herkömmliche Tensid oder Netzmittel sein. Es können mehr als eine oberflächen- bzw. grenzflächenaktive Substanz, z. B. zwei, drei oder vier verschiedene derartige Substanzen, eingesetzt werden, es ist jedoch bevorzugt, nur jeweils eine oberflächen- bzw. grenzflächenaktive Substanz zu verwenden.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.
Derartige Tenside oder Netzmittel zeichnen sich dadurch aus, dass sie die Grenzflächenspannung bzw. Oberflächenspannung eines sie enthaltenden Systems herabsetzen. Sie sind (zumindest) bifunktionelle (amphiphile) chemische Verbindungen mit mindestens einem hydrophoben und mindestens einem hydrophilen Molekülteil. Der hydrophobe Rest ist z. B. in Kohlenwasserstoff-Tensiden eine - zumeist lineare - Kohlenwasserstoff-Kette mit acht bis 22 Kohlenstoffatomen; in Siloxan-Tensiden wird der hydrophobe Rest von (Dimethyl) Siloxan-Ketten, in Perfluorkohlenwasserstoff-Tensiden von perfluorierten Kohlenwasserstoff-Ketten gebildet. Der hydrophile Rest ist entweder eine elektrisch negativ oder positiv geladene (hydratisierbare) oder eine neutrale polare Kopfgruppe.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. In 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.
Ohne an eine bestimmte Theorie gebunden werden zu wollen, wird angenommen, dass die Moleküle der wenigstens einen oberflächen- bzw. grenzflächenaktiven Substanz mit der Teilchenoberfläche der Pulver-Partikel unter Ausbildung einer Hüllschicht in Wechselwirkung treten und so die Stabilisierung der Oberfläche bewirken. Der Ausdruck "Hüllschicht" ist im vorliegenden Zusammenhang nicht zwingend so zu verstehen, dass die Oberfläche der Partikel vollständig bedeckt sein muss, sondern umschreibt die Funktion der oberflächen- bzw. grenzflächenaktiven Substanz, welche die mit ihr modifizierten Partikel unter anderem vor Luft- und Feuchtigkeitseinflüssen schützt und so deren Lagerstabilität wesentlich erhöht. Die genaue Struktur der Hüllschicht ist dabei nicht bekannt. Sie wird unter anderem von der Natur und Größe der Partikel sowie der spezifischen Auswahl der oberflächen- bzw. grenzflächenaktiven Substanz abhängen.Without wishing to be bound by any particular theory, it is believed that 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. The term "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.
Bevorzugt ist die wenigstens eine oberflächen- bzw. grenzflächenaktive Substanz ein Tensid oder Netzmittel, welches bei der weiteren galvanotechnischen Verarbeitung, z. B. in den dort eingesetzten Vorbehandlungsbädern und insbesondere in den für die eigentliche metallische Beschichtung eingesetzten Prozesslösungen oder -suspensionen, ohnehin Verwendung findet. Bei der galvanotechnischen Endverarbeitung unter Verwendung der oberflächenmodifizierten Partikel wird die Hüllschicht aus der wenigstens einen oberflächen- bzw. grenzflächenaktiven Substanz abgelöst, beseitigt oder erweist sich in den weiteren Prozessschritten der Galvanotechnik als nicht störend. So können beispielsweise bei den elektrochemischen galvanotechnischen Verfahren die mittel- bis langkettigen Moleküle des wenigstens einen die Hüllschicht bildenden Netzmittels durch ihre polarisierten (bzw. polarisierbaren) Bereiche elektrostatisch von der polarisierten Elektrodenoberfläche angezogen bzw. abgestoßen werden. Dabei ergeben sich Kraftwirkungen zwischen den Molekülen und den Elektroden. Diese können eine Ablösung der Netzmittelmoleküle von der Partikeloberfläche oder eine räumliche Ausrichtung der Partikel mit schwer ablösbaren Adsorbaten zur Elektrodenoberfläche bewirken. Die in der Galvanotechnik üblichen Netzmittel bilden einen für Metallionen durchlässigen Film auf der Kathodenoberfläche, welcher ihnen das "Abstreifen" der Wasserdipolhüllen und deren Einordnung in den Kristallverband erleichtert. Die Netzmittelmoleküle können hier auch zu einem gewissen Teil durch die Partikel in die Kathodennähe transportiert werden und Verluste durch elektrochemisch induzierte Zersetzung der Netzmittelmoleküle in unmittelbarer Kathodennähe ausgleichen. Findet diese die Hüllschicht bildende oberflächen- bzw. grenzflächenaktive Substanz auch Verwendung als übliches Netzmittel in der galvanotechnischen Prozesslösung oder -suspension - was bevorzugt ist -, sind somit zusätzlich störende Einflüsse durch diese Substanz nicht zu erwarten und es müssen keine besonderen Vorkehrungen getroffen werden, um diese aus der Prozesslösung bzw. -suspension auszuschleusen. Auch die Weiterverarbeitung bzw. Entsorgung der Prozesslösung oder -suspension muss in der Regel nicht verändert oder angepasst werden.Preferably, the at least one surface or surface-active substance is a surfactant or wetting agent, which in the further galvanotechnischen 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. In electroplating finishing using the surface-modified particles, 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. Thus, for example, in the electrochemical electroplating process, 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. This results in force effects between the molecules and the electrodes. These can cause a detachment of the wetting agent molecules from the particle surface or a spatial alignment of the particles with hard-to-remove adsorbates to the electrode surface. 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. If 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.
Besonders bevorzugt ist die oberflächen- bzw. grenzflächenaktive Substanz ausgewählt aus der Gruppe, umfassend Kohlenwasserstoff-Tenside, Siloxan-Tenside und Perfluorkohlenwasserstoff-Tenside. Ganz besonders bevorzugt ist das Tensid Natriumdodecylsulfat.The surface-active or surface-active substance is particularly preferably selected from the group comprising hydrocarbon surfactants, siloxane surfactants and perfluorocarbon surfactants. Most preferably, the surfactant is sodium dodecyl sulfate.
Eine weitere Ausführungsform der Erfindung betrifft die Verwendung der oberflächenmodifizierten Partikel in einer Prozesslösung oder einer Prozesssuspension zum Galvanisieren, wobei vor und/oder während des Galvanisierens die oberflächenmodifizierten Partikel mit wenigstens einer die Hüllschicht rückstandsfrei entfernenden Substanz in Kontakt gebracht werden. Dabei wird als Substanz ein solches Lösungsmittel gewählt, welches das die Hüllschicht bildende Tensid (Netzmittel) zu lösen vermag. Die Entfernung kann aber auch beispielsweise durch thermische Behandlung erfolgen. Bevorzugt ist das wenigstens eine Netzmittel, welches die Hüllschicht bildet, jedoch so ausgewählt, dass es bei der weiteren galvanotechnischen Verarbeitung der oberflächenmodifizierten Partikel nicht stört, z. B. weil - wie oben dargelegt - es einen für die Metallionen im elektrischen Feld durchlässigen Film bildet.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. In this case, such 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. Preferably, 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.
Im Zusammenhang mit der vorliegenden Erfindung ist der Ausdruck "Galvanotechnik" im weitesten Sinne zu verstehen und umfasst die Behandlung von metallischen und nichtmetallischen Oberflächen von Werkstücken, Vor-, Halb- und Fertigprodukten, um diese beispielsweise zu verschönern, vor Umgebungseinflüssen, insbesondere Korrosion und Abrieb, zu schützen oder ihre Eigenschaften in Gestalt von Verbundwerkstoffen zu verbessern.In the context of the present invention, 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.
Hier bevorzugte galvanotechnische Verfahren sind schichtauftragende Verfahren, bei denen in chemischen oder elektrochemischen Prozessen unter erfindungsgemäßer Verwendung der oberflächenmodifizierten Partikel funktionale Schichten, die die Eigenschaften des Werkstücks bzw. Produkts meist weitgehend bestimmen, mit einer Dicke von nur wenigen µm auf die Grundmaterialien aufgebracht werden. Neben der Galvanoplastik sind hier vor allem die stromlos erfolgende chemische Abscheidung, bei der nach Einbringen von (oberflächenmodifizierten) Metallpulvern in eine Beschichtungslösung bzw. -suspension unter Bildung von Metallionen durch Einsatz von chemischen Reduktionsmitteln ohne Anlegen eines äußeren elektrischen Feldes durch die Reduktion der Metallionen auf der zu beschichtenden Werkstückoberfläche die Abscheidung der Metall(-schutz)-schicht bewirkt wird, und elektrochemische Abscheidungsverfahren (Elektroplattierung, Galvanostegie, Galvanisieren im engeren Sinne), bei denen die aus den Metallpulvern in Galvanisierlösungen bzw. -suspensionen gebildeten Metallionen oder geladene Metall-Legierungs-Partikel in einem von außen angelegten elektrischen Feld zu dem als Kathode geschalteten Werkstück wandern und dort zum Metall unter Ausbildung der gewünschten Schutzschicht reduziert bzw. in eine vorhandene Metall- oder Legierungsmatrix inkorporiert werden, besonders bevorzugt. In diesen Verfahren ist eine vorbereitende Behandlung der zu bearbeitenden Werkstücke unter anderem zum Entfetten, Beizen und Aktivieren von Oberflächen usw. in Vorbehandlungsbädern erforderlich, in welchen in der Regel Tenside oder Netzmittel eingesetzt werden. Auch die eigentlichen Behandlungsbäder (Prozesslösungen bzw. -suspensionen) enthalten neben dem eigentlichen Beschichtungsmittel und Reduktionsmittel bzw. Elektrolyten weitere Zusätze, unter anderem aus Tensiden oder Netzmitteln. Im Falle der erfindungsgemäßen Verwendung kann diesen Prozessbädern zum Galvanisieren, soweit erforderlich oder erwünscht, ein Mittel zum rückstandsfreien Entfernen der oberflächenmodifizierenden Substanz hinzugefügt werden. Dieses Mittel kann auch den Vorbehandlungsbädern zugesetzt werden, wenn das rückstandsfreie Entfernen der oberflächenmodifizierenden Substanz von den Partikeln vor dem eigentlichen Galvanisierungs- bzw. Abscheidungsschritt erfolgen soll.Here, 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 μm in chemical or electrochemical processes using the surface-modified particles. In addition to galvanoplastics, 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. In these processes, 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 (process solutions or suspensions) contain, in addition to the actual coating agent and reducing agent or electrolyte, further additives, including surfactants or Wetting agents. In the case of the use according to the invention, 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.
Die vorliegende Erfindung betrifft ferner Verfahren zur Herstellung von oberflächenmodifizierten Partikeln mit einer Hüllschicht aus wenigstens einer oberflächen- bzw. grenzflächenaktiven Substanz, wobei beispielsweise die Endfraktionierung des Partikelpulvers unmittelbar nach seiner Herstellung mittels üblicher, im Stand der Technik bekannter Verfahren (z. B. Dispergierung mit Ultraschall oder Rühr- und Schüttelvorrichtungen) mit einer Lösung der die Hüllschicht bildenden Substanz/en getränkt wird und dadurch eine Vorsuspension der späteren Prozesslösung bzw. -suspension gebildet wird. Dabei kann durch Entfernen des Lösungsmittels, Trocknen usw. auch ein Pulver der nunmehr oberflächenmodifizierten Partikel erhalten werden. Als Lösungsmittel bzw. Suspensionsmittel können hierbei beispielsweise neben Wasser kurzkettige aliphatische Alkohole und andere leichtflüchtige organische Lösungsmittel dienen.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. In this case, by removing the solvent, drying, etc., a powder of the now surface-modified particles can be obtained. As solvent or suspending agent, for example, in addition to water, short-chain aliphatic alcohols and other volatile organic solvents may be used.
Die Verwendung der oberflächenmodifizierten Partikel, die in einer für die weitere galvanotechnische Verarbeitung geeigneten Lösung oder Suspension vorliegen, stellt eine weitere bevorzugte Ausführungsform der vorliegenden Erfindung dar.The use of the surface-modified particles, which are present in a solution or suspension suitable for further electroplating, represents a further preferred embodiment of the present invention.
Ein weiterer Gegenstand der Erfindung sind die oben für die Verwendung in der Galvanotechnik beschriebenen oberflächenmodifizierten Partikel, deren Oberfläche mit wenigstens einer oberflächen- bzw. grenzflächenaktiven Substanz unter Ausbildung einer Hüllschicht auf den Partikeln modifiziert ist, und die Teilchen von Metallen oder Halbmetallen sind, wobei diese Teilchen in elementarer Form, in Form einer Legierung oder als Oxide, Nitride, Carbide, Boride oder als Mischverbindungen daraus der Metalle oder Halbmetalle vorliegen.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.
Bevorzugt sind die erfindungsgemäßen oberflächenmodifizierten Partikel nanoskalige Teilchen oder submikroskalige Teilchen mit einer durchschnittlichen Teilchengröße von etwa 0,1 µm bis etwa 1 µm. Die Partikel sind ferner bevorzugt Teilchen von Metallen, besonders bevorzugt der Metalle Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd und Pt, ganz besonders bevorzugt der Metalle Ni, Cr, Co und Al, insbesondere in elementarer Form oder in Form von Legierungen. Unter den erfindungsgemäßen Legierungs-Partikeln mit modifizierter Oberfläche sind Nickel-Cobalt-Legierungen und Chrom-Aluminium-XYZ-Legierungen, wobei X, Y und Z für Nebenlegierungselemente stehen, die für Hochtemperaturwerkstoffe bzw. Beschichtungen geeignet sind, insbesondere für Re, Y, Si, Ti, Ta, W, Mn, Mo, Nb, Zr, Hf, und zwar in üblichen Mengen bzw. Mengenverhältnissen, besonders bevorzugt. Die Bezeichnung "CrAl-XYZ"- bzw. "Chrom-Aluminium-XYZ"-Legierung ist hier eine verkürzte Schreibweise für derartige Chrom-Aluminium-Legierungen mit geeigneten Nebenlegierungselementen; sie soll weder die genaue Zahl weiterer Elemente neben Cr und Al benennen - d. h. es können eins, zwei, drei, vier oder mehr verschiedene Nebenlegierungselemente vorhanden sein - noch als Angabe über die Mengenverhältnisse der Legierungselemente untereinander verstanden werden. Beispiele bevorzugter CrAl-XYZ-Legierungen sind Cr62Al32YRe5, Cr58,8Al34,6Y1,4Re5,2, Cr76Al21Y1,6Si1,4, Cr57Al40Y2Si und Cr53,8Al11,4Ti11,4Ta5,9W8,7Mo5,9Nb2,8.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 μm to about 1 μm. 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. Among the 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. The term "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 .
Zur Modifizierung der Partikel-Oberfläche verwendete oberflächen- bzw. grenzflächenaktive Substanzen sind bevorzugt ausgewählt aus der Gruppe, umfassend Kohlenwasserstoff-Tenside, Siloxan-Tenside und Perfluorkohlenwasserstoff-Tenside, insbesondere Natriumdodecylsulfat. Ferner ist es bevorzugt, dass die erfindungsgemäßen oberflächenmodifizierten Partikel in einer Lösung oder Suspension vorliegen, wobei das verwendete Lösungsmittel oder Lösungsmittelgemisch so ausgewählt ist, dass es die weitere galvanotechnische Verarbeitung nicht störend beeinflusst. Beispiele geeigneter Lösungsmittel sind beispielsweise neben Wasser kurzkettige aliphatische Alkohole und andere leichtflüchtige organische Lösungsmittel.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.
Im Zusammenhang mit der vorliegenden Erfindung haben die Begriffe "Metall" und "Halbmetall" die in der anorganischen Chemie üblichen Bedeutungen, wie sie z. B. in Hollemann-Wiberg, Lehrbuch der Anorganischen Chemie, 91.-100. Auflage, 1985, S. 301-302 und S. 731-733, erläutert sind. Beispiele für Halbmetalle sind insbesondere Bor, Gallium, Silicium, Germanium, Zinn, Arsen, Antimon, Bismut, Selen und Tellur, während Beispiele für Metalle unter anderem Nickel, Palladium, Platin, Cobalt, Eisen, Aluminium, Chrom, Titan, Mangan, Molybdän, Wolfram, Vanadium, Niob, Tantal, Hafnium usw. sind.In the context of the present invention, the terms "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. Examples of semimetals are in particular boron, gallium, silicon, germanium, tin, arsenic, antimony, bismuth, selenium and tellurium, while examples of metals include nickel, palladium, platinum, cobalt, iron, aluminum, chromium, titanium, manganese, molybdenum , Tungsten, vanadium, niobium, tantalum, hafnium, etc. are.
Die Erfindung wird nachfolgend durch Beispiele weiter veranschaulicht, die sie jedoch nicht beschränken sollen.The invention will be further illustrated by examples which are not intended to be limiting, however.
Ein feindisperses Pulver mit einer durchschnittlichen Teilchengröße von ca. 1 µm der Basiszusammensetzung Cr62Al32YRe5 wird unmittelbar nach seiner Herstellung mittels Zerstäubung (oder alternativ Atomisierung, Zermahlung oder Schmelzverdüsung) mit einer Lösung von Natriumdodecylsulfat in Wasser versetzt. Die entstehende Suspension kann direkt weiterverarbeitet werden (siehe Beispiel b)); alternativ können aus der Suspension die oberflächenmodifizierten Partikel durch Gefriertrocknung in Pulverform gewonnen werden.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.
Die Suspension aus Beispiel a) wird in einem galvanischen Nickel-Cobalt-Abscheidebad dispergiert. Die galvanische Abscheidung an der Kathodenoberfläche führt zur Inkorporierung der Legierungspulverpartikel in die auf der Kathode wachsenden Ni-Co-Schicht (Ni-Co-Matrix), während zugleich die Hüllschichtmoleküle von der Partikeloberfläche desorbieren und in der Elektrolytsuspension verbleiben.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.
Claims (15)
dadurch gekennzeichnet, dass
die Partikel eine durchschnittliche Teilchengröße von nicht mehr als etwa 1 µm aufweisen.Use of surface-modified particles according to claim 1,
characterized in that
the particles have an average particle size of not more than about 1 μm.
dadurch gekennzeichnet, dass
die Partikel Teilchen von Metallen oder Halbmetallen, ausgewählt aus der Gruppe, umfassend Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd und Pt, sind.Use according to at least one of the preceding claims,
characterized in that
the particles are particles of metals or semimetals selected from the group comprising Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd, and Pt.
dadurch gekennzeichnet, dass
die Teilchen von Metallen oder Halbmetallen Pulver der Metalle oder Halbmetalle in elementarer Form oder in Form von Legierungen sind.Use according to claim 3,
characterized in that
the particles of metals or semimetals are powders of the metals or semimetals in elemental form or in the form of alloys.
dadurch gekennzeichnet, dass
die Partikel Oxid-, Nitrid-, Carbid- bzw. Borid-Verbindungen sowie Mischverbindungen daraus von Metallen oder Halbmetallen sind.Use according to at least one of claims 1 to 3,
characterized in that
the particles are oxide, nitride, carbide or boride compounds and mixed compounds thereof of metals or semimetals.
dadurch gekennzeichnet, dass
die wenigstens eine oberflächen- bzw. grenzflächenaktive Substanz der Hüllschicht der Partikel ausgewählt ist aus der Gruppe, umfassend Kohlenwasserstoff-Tenside, Siloxan-Tenside und Perfluorkohlenwasserstoff-Tenside.Use according to at least one of the preceding claims,
characterized in that
the at least one surfactant of the shell layer of the particles is selected from the group comprising hydrocarbon surfactants, siloxane surfactants and perfluorocarbon surfactants.
dadurch gekennzeichnet, dass
das Tensid Natriumdodecylsulfat ist.Use according to claim 6,
characterized in that
the surfactant is sodium dodecyl sulfate.
dadurch gekennzeichnet, dass
die oberflächenmodifizierten Partikel in einer Lösung oder Suspension vorliegen.Use according to at least one of the preceding claims,
characterized in that
the surface-modified particles are present in a solution or suspension.
dadurch gekennzeichnet, dass
die Partikel submikroskalige oder nanoskalige Teilchen sind.Particles according to claim 10,
characterized in that
the particles are submicroscale or nanoscale particles.
dadurch gekennzeichnet, dass
sie Teilchen der Metalle, ausgewählt aus der Gruppe, umfassend Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd und Pt, sind.Particles according to at least one of claims 10 or 11,
characterized in that
they are particles of the metals selected from the group comprising Ni, Cr, Co, Fe, Al, Ti, Zr, Mn, Mo, W, Hf, V, Ta, Nb, Pd and Pt.
dadurch gekennzeichnet, dass
sie Teilchen einer Metall-Legierung, insbesondere einer CrA1-XYZ-Legierung sind.Particles according to at least one of claims 10 to 12,
characterized in that
they are particles of a metal alloy, in particular a CrA1-XYZ alloy.
dadurch gekennzeichnet, dass
die wenigstens eine oberflächen- bzw. grenzflächenaktive Substanz aus der Gruppe, umfassend Kohlenwasserstoff-Tenside, Siloxan-Tenside und Perfluorkohlenwasserstoff-Tenside, ausgewählt ist und insbesondere Natriumdodecylsulfat ist.Particles according to at least one of claims 10 to 13,
characterized in that
which is at least one surface-active or surfactant selected from the group comprising hydrocarbon surfactants, siloxane surfactants and perfluorocarbon surfactants, and in particular sodium dodecyl sulfate.
dadurch gekennzeichnet, dass
die Partikel in einer Lösung oder Suspension vorliegen.Particles according to at least one of claims 10 to 14,
characterized in that
the particles are present in a solution or suspension.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04023599A EP1643016A1 (en) | 2004-10-04 | 2004-10-04 | Use of surface modified particles in electroplating |
| PCT/EP2005/054608 WO2006037721A1 (en) | 2004-10-04 | 2005-09-16 | Use of surface-modified particles in electroplating technology |
| 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 (en) | 2004-10-04 | 2004-10-04 | Use of surface modified particles in electroplating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1643016A1 true EP1643016A1 (en) | 2006-04-05 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04023599A Withdrawn EP1643016A1 (en) | 2004-10-04 | 2004-10-04 | Use of surface modified particles in electroplating |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20080193789A1 (en) |
| EP (1) | EP1643016A1 (en) |
| WO (1) | WO2006037721A1 (en) |
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| CN113061949A (en) * | 2021-04-20 | 2021-07-02 | 深圳市鸿信顺电子材料有限公司 | Plating pretreatment reagent and modification process for chip component |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0748883A1 (en) * | 1995-06-12 | 1996-12-18 | ABB Management AG | Workpiece with an electroplated coating and process for realising electroplated layers |
| DE10125290A1 (en) * | 2001-05-15 | 2002-11-28 | Siemens Ag | Production of nano-dispersants comprises adsorbing tensides on the surface of non-dispersants by bringing the nano-dispersants with the tensides into an aqueous or non-aqueous suspension, grinding and drying |
| 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 |
-
2004
- 2004-10-04 EP EP04023599A patent/EP1643016A1/en not_active Withdrawn
-
2005
- 2005-09-16 US US11/664,566 patent/US20080193789A1/en not_active Abandoned
- 2005-09-16 WO PCT/EP2005/054608 patent/WO2006037721A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0748883A1 (en) * | 1995-06-12 | 1996-12-18 | ABB Management AG | Workpiece with an electroplated coating and process for realising electroplated layers |
| DE10125290A1 (en) * | 2001-05-15 | 2002-11-28 | Siemens Ag | Production of nano-dispersants comprises adsorbing tensides on the surface of non-dispersants by bringing the nano-dispersants with the tensides into an aqueous or non-aqueous suspension, grinding and drying |
| 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 |
|---|---|
| US20080193789A1 (en) | 2008-08-14 |
| WO2006037721A1 (en) | 2006-04-13 |
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