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EP1354073A2 - Procede de traitement de pieces a usiner au moyen d'une solution colloidale de palladium - Google Patents

Procede de traitement de pieces a usiner au moyen d'une solution colloidale de palladium

Info

Publication number
EP1354073A2
EP1354073A2 EP01949313A EP01949313A EP1354073A2 EP 1354073 A2 EP1354073 A2 EP 1354073A2 EP 01949313 A EP01949313 A EP 01949313A EP 01949313 A EP01949313 A EP 01949313A EP 1354073 A2 EP1354073 A2 EP 1354073A2
Authority
EP
European Patent Office
Prior art keywords
palladium
solution
work pieces
liquid
colloid solution
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Withdrawn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
EP01949313A
Other languages
German (de)
English (en)
Inventor
Hermann Middeke
Mariola Brandes
Brigitta Dyrbusch
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.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
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 Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP1354073A2 publication Critical patent/EP1354073A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/20—Regeneration of process solutions of rinse-solutions

Definitions

  • the present invention relates to a method for the treatment of work pieces with a palladium colloid solution, preferably to a method for the treatment with a hydrochloric palladium colloid solution being stabilized with tin.
  • the surfaces thereof For the electroplating of work pieces the surfaces thereof must first be treated to render them electrically conductive if the work pieces have electrically nonconducting surfaces.
  • the work pieces are dipped into a solution containing colloidal palladium.
  • the palladium particles thereupon adsorbed on the surfaces serve as activators for initiating electroless metal deposition, which results in the production of an electrically conductive layer on the surface of the work pieces.
  • This conductive layer may afterwards be electroplated with any metal.
  • This process may for example be applied to the production of printed circuit boards and of sanitary appliances, metallized parts for automotive industry and of furniture mountings, especially for chromium plating of plastics parts.
  • Palladium containing activating solutions are also used for direct plating on electrically nonconducting surfaces without using electroless plating methods.
  • the adsorbed layer containing palladium is converted into an electrically conducting layer, which may be used to directly electrodeposit metal on an activated nonconducting surface.
  • a higher concentration of the palladium colloid particles of about 200 mg palladium per liter solution is required.
  • Drag out of palladium from the activating solution amounts to about 50 mg/m 2 if conventional direct plating procedures are applied.
  • adsorption of the palladium particles may be enhanced considerably to about 50 mg/m 2 surface area of the work pieces. All the same still about 50 % of the employed palladium is lost due to drag out. Only 50 % are still available for electroplating of the work piece surfaces.
  • a further process for recovering palladium from spent catalytic colloidal palladium baths is disclosed in US-A-4,435,258, these baths being used for activating nonconductive surfaces for subsequent electroless metallization.
  • the activating solutions are worked up by dissolving colloidal palladium by adding an oxidizing agent to the solution, for example hydrogen peroxide, thereby forming a true solution, subsequently heating the solution to destroy residual hydrogen peroxide and afterwards precipitating palladium at a cathode by electrodepositing palladium.
  • the problem of the present invention therefore consists in avoiding the disadvantages of the known methods and especially in finding a method to treat work pieces with a palladium colloid solution which may be carried out easily. Only small amounts of additional chemicals shall be required for performing the method. Moreover the method shall be carried out with low expense of energy and time.
  • the method according to the invention serves to treat work pieces with a palladium colloid solution by bringing the work pieces into contact with the colloid solution.
  • the invention relates to the treatment of work pieces with a hydrochloric palladium colloid solution being stabilized with tin.
  • the method according the present invention advantageously leads to complete separation of palladium between the concentrate part and the permeate part of the liquid.
  • the known method suffers from the fact that a considerable part of palladium is oxidized to bivalent soluble palladium during the precipitation method. Therefore palladium cannot be separated entirely from the solution by filtration. For this reason palladium is lost partly due to the recovery method.
  • the method according to the present invention advantageously does not require considerable expenditure of additional chemicals, such as for example of metallic tin, as well as of additional energy and time for heating the colloid solution as is the case if the known method would be carried out.
  • the method according to the invention also has the additional advantage to be a single-stage recovery method. This is in contrast to the method as described in US-A-4,435,258. Therefore the method according to the invention is very easy to perform. Furthermore palladium can be removed essentially completely from palladium containing solutions, whereas, if the method as described in US-A-4,435,258 is used, only a very low current yield may be achieved when the palladium concentration is low which is normally the case after prolonged electrolysis time. Therefore complete removal of palladium is very complicated oder not at all possible if this known method is used.
  • the method according to the invention is especially suited for continuous operation.
  • the method described in this prior art document moreover does not manage without additional chemicals.
  • Colloidal palladium activating solutions contain palladium particles which are surrounded by a protective coating (protective colloid).
  • HREM high-resolution electron microscopy
  • AFM atomic force microscopy
  • the palladium particles have a diameter of at least 2.5 nm.
  • the size distribution is extremely narrow: It has proven that no considerable deviations from the mean particle size of 2.5 nm occurs in solutions containing colloidal palladium that are usually used to activate nonconductor surfaces.
  • Normally colloid solutions are acidic and very often contain hydrochloric acid. Further they often contain chloride ions and if necessary bivalent and tetravalent tin or organic polymeric stabilizers and reducing agents. With the exception of polymers, which are used in very small amounts, all other components contained in these solutions are ionic. It is guessed that these ionic components are considerably smaller in size than the palladium particles.
  • membranes made of various materials are known that can be used for carrying out the present invention.
  • molecular filters made of polysulfones, especially polyethersulfones (PES), perfluorinated polymers and ceramics made advantageously be applied.
  • PES polyethersulfones
  • perfluorinated polymers and ceramics made advantageously be applied.
  • the type to be used for carrying out the present invention it has proven that it depends only on a sufficient stability of the membrane material towards the liquid to be treated, for example the activating solution which may contain up to 15 wt.-% hydrochloric acid.
  • the porosity of the molecular filter is not critical at all for the performance of separation of the palladium particles from the liquid if a molecular filter is chosen with an exclusion pore size of from 200 Dalton to 10.000 Dalton, since in this case the palladium particles completely remain in the concentrate liquid.
  • molecular filters are used that preferably have an exclusion pore size of from 200 Dalton to 10.000 Dalton.
  • exclusion pore size of at least 500 Dalton is especially preferred. Most advantageous has proven an exclusion pore size of at least 2.000 Dalton. These further lower limits of the range represent preferred embodiments of the present invention, presenting an even better selectivity of separation between palladium particles and tin compounds under the circumstances mentioned.
  • the molecular filters are preferably made of a material, selected from the group comprising polysulfones, especially polyethersulfones (PES), perfluorinated polymers, for example polytetrafluorethylene (for example TEFLON ®, trade name of DuPont de Nemours), and ceramics. These materials are sufficiently chemically resistant towards the strongly acidic solutions containing hydrochloric acid.
  • PES polyethersulfones
  • perfluorinated polymers for example polytetrafluorethylene (for example TEFLON ®, trade name of DuPont de Nemours)
  • TEFLON ® trade name of DuPont de Nemours
  • the work pieces are brought into contact with the colloid solution for activating the work pieces.
  • the colloid solution adhering to the surfaces of the work pieces is removed from the surfaces with a rinsing liquid.
  • the rinsing liquid is pressurized und thus led through the molecular filter, the liquid being led through the molecular filter being a permeate liquid and the liquid not being led through the molecular filter being a concentrate liquid.
  • a palladium colloid solution is produced by using the concentrate liquid and adding suitable replenishment agents to the concentrate liquid in appropriate amounts.
  • the work pieces preferably made from nonconducting material are rinsed with a rinsing liquid in an appropriate device. Rinsing is preferably performed by spraying in order to minimize the volume of rinsing liquid.
  • hydrochloric acid Prior to separating the colloid particles from the liquid by means of the molecular filter hydrochloric acid can be added to the solution even during spraying the rinsing liquid to the work pieces. If a sufficient amount of hydrochloric acid is added to the liquid, the tin compounds contained in the liquid do not hydrolyze so that cloudiness does not occur and precipitates are not formed due to these compounds.
  • the rinsing liquid is pressed through the selective molecular filter membrane by means of a pressurized pump, the membrane holding back the palladium particles und letting pass the rinsing liquid, especially rinsing water, and all other components contained in the rinsing liquid.
  • the permeate liquid can then be led to waste water treatment.
  • the palladium being held back and present as a homogeneous metal dispersion concentrate can be used to produce an activating solution.
  • tin(II) or tin(IV) salts and hydrochloric acid in higher or lower amounts are to be added to the concentrate liquid.
  • the palladium held back may be dissolved und be used as a solution, for example a palladium chloride solution, in order to produce an activating solution or alternatively to use this solution for any other purpose.
  • fig. 1 shows a schematic drawing of an apparatus, that may be used for carrying out the ultrafiltration or nanofiltration of a palladium colloid solution.
  • the work pieces After treatment in the palladium colloid solution has been cariied out the work pieces (not shown) are transferred to a spraying container 1 in which the work pieces are held vertically and are rinsed by spraying rinsing water to the pieces. Spraying is carrier out by using spray nozzles 2 which are located are the lateral side walls of the rinsing spraying container 1. The water being sprayed to the surfaces of the work pieces wet the surfaces of the work pieces so that the colloid solution is rinsed off the surfaces.
  • rinsing liquid Z from a further rinsing station is used, in which the work pieces being rinsed in this spraying container 1 will be rinsed again with rinsing liquid.
  • the spent rinsing liquid is led to the spray nozzles 2 via a pipeline 4 by means of a pump 3.
  • the liquid will only be sprayed into the spraying container 1 if work pieces are present in this container 1.
  • Regulation of the rinsing liquid is performed by means of a valve 5 which only allows the liquid to pass to the container 1 is work pieces are to be treated.
  • the rinsing liquid running down at the surfaces of the work pieces and containing colloid solution due to the rinsing treatment accumulate at the bottom of the rinsing container 1. This liquid is removed from the rinsing container 1 via a pipeline 6.
  • Concentrated hydrochloric acid contained in the container 7 is admixed via a further pipeline 8 to the rinsing liquid coming out from the container 1 , thereby lowering the pH of the rinsing liquid. Due to this lowering cloudiness does not occur and precipitates do not form in the rinsing liquid though tin compounds are present in the liquid.
  • the rinsing liquid made acidic with hydrochloric acid is afterwards led to the molecular filter unit 10 via a pump 9.
  • a filter membrane is arranged inside the molecular filter 10.
  • the liquid present in the region in front of the filter membrane in the molecular filter is pumped in a circuit (not shown). Therefore the colloid particles are permanently in motion in the region in front of the filter membrane, so that the pores of the membrane may not be clogged (cross- flow).
  • the part of the liquid that has passed through the filter membrane represents the permeate liquid P.
  • the part of the liquid that has not passed through the filter membrane represents the concentrate liquid K. This part K is intermittently or continuously removed from the filtration unit 10.
  • Example 1 The experiment of example 1 was repeated by using a membrane made of polysulfone (PES). This membrane had an exclusion pore size of 1000 Dalton. The flux through this membrane was less than that experienced from example 1 though the same pressure was applied (10 bar ⁇ 10 6 Pa). However a decrease of flux during the experiment, which lasted 1 hour, could not be detected.
  • PES polysulfone
  • Example 1 was repeated with three further membranes which were made from PVDF.
  • the exclusion pore size of these three membranes were 250 Dalton, 400 Dalton and 6.000 Dalton, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemically Coating (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé destiné à traiter des pièces à usiner au moyen d'une solution colloïdale de palladium par mise en contact de ces pièces à usiner avec la solution colloïdale, le palladium étant recouvert après l'utilisation de cette solution colloïdale. Pour ce faire, on sépare des particules colloïdales de palladium du liquide colloïdal à l'aide d'un filtre moléculaire. Grâce à ce procédé, on peut facilement séparer la totalité du palladium des solutions de traitement utilisées de manière continue, en peu de temps et sans faire intervenir une quantité importante de produits chimiques et d'énergie. La solution de traitement utilisée peut notamment être traitée après la séparation de la partie de la solution contenant le palladium de façon que ce palladium puisse être entièrement récupéré et réutilisé en vue d'un traitement ultérieur.
EP01949313A 2000-05-15 2001-05-04 Procede de traitement de pieces a usiner au moyen d'une solution colloidale de palladium Withdrawn EP1354073A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10024239A DE10024239C1 (de) 2000-05-15 2000-05-15 Verfahren zum galvanotechnischen Behandeln von Werkstücken mit einer Palladiumkolloidlösung
DE10024239 2000-05-15
PCT/EP2001/005064 WO2001088211A2 (fr) 2000-05-15 2001-05-04 Procede de traitement de pieces a usiner au moyen d'une solution colloidale de palladium

Publications (1)

Publication Number Publication Date
EP1354073A2 true EP1354073A2 (fr) 2003-10-22

Family

ID=7642432

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01949313A Withdrawn EP1354073A2 (fr) 2000-05-15 2001-05-04 Procede de traitement de pieces a usiner au moyen d'une solution colloidale de palladium

Country Status (6)

Country Link
US (1) US20030155250A1 (fr)
EP (1) EP1354073A2 (fr)
JP (1) JP2004500976A (fr)
CA (1) CA2404620A1 (fr)
DE (1) DE10024239C1 (fr)
WO (1) WO2001088211A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10148632C1 (de) * 2001-09-26 2003-06-05 Atotech Deutschland Gmbh Verfahren und Vorrichtung zum galvanotechnischen Behandeln von Werkstücken mit einer Edelmetalle enthaltenden Flüssigkeit
EP1314788B1 (fr) * 2001-11-21 2004-09-29 Shipley Co. L.L.C. Procédé de récupération de métaux catalytiques utilisant un filtre en métal poreux
US6908496B2 (en) * 2002-01-02 2005-06-21 William Marsh Rice University Method for scalable production of nanoshells using salt assisted purification of intermediate colloid-seeded nanoparticles
EP1884278A1 (fr) * 2006-07-24 2008-02-06 ATOTECH Deutschland GmbH Appareil et méthode pour rincer des liquides de pièces à façonner
JP6340302B2 (ja) * 2014-10-24 2018-06-06 田中貴金属工業株式会社 廃液の処理方法、廃液の処理装置および廃液の再利用方法
EP3133175A1 (fr) 2015-08-19 2017-02-22 Enthone, Inc. Système et procédé de récupération de métal noble catalytique à partir de solution de traitement galvanique aqueuse
CN106987877A (zh) * 2017-04-01 2017-07-28 厦门建霖工业有限公司 一种塑料电镀用胶体钯回收及水回用的系统及方法
CN115282789B (zh) * 2022-01-24 2023-09-29 浙江师范大学 一种ABS-Ni复合分离膜及其制备方法与应用
US12209325B2 (en) * 2023-03-01 2025-01-28 Applied Materials, Inc. Nanofiltration for wafer rinsing

Citations (1)

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WO1999023263A1 (fr) * 1997-10-30 1999-05-14 Hw Process Technologies, Inc. Procede pour eliminer des contaminants de liquides a traiter dans des procedes de rendement metal

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DE2240317C3 (de) * 1971-08-21 1975-07-10 Asahi Kasei Kogyo K.K., Osaka (Japan) Verfahren zur Wiedergewinnung erneut einsetzbarer palladiumhaltiger Katalysatoren aus flüssigen Reaktionsgemischen, die bei der Herstellung von Essigsäurearylestern anfallen
CA1053994A (fr) * 1974-07-03 1979-05-08 Amp Incorporated Sensibilisation de polymeres de type polyimide pour deposition non electrolytique de metal
US4008343A (en) * 1975-08-15 1977-02-15 Bell Telephone Laboratories, Incorporated Process for electroless plating using colloid sensitization and acid rinse
US4078918A (en) * 1976-11-26 1978-03-14 Perman Craig A Method for precious metal recovery
DE3040631A1 (de) * 1980-10-29 1982-05-27 Merck Patent Gmbh, 6100 Darmstadt Verfahren zur abtrennung von metallkatalysatoren und verwendung von membrantrennvorrichtungen
US4435258A (en) * 1982-09-28 1984-03-06 Western Electric Co., Inc. Method and apparatus for the recovery of palladium from spent electroless catalytic baths
US4600699A (en) * 1983-02-14 1986-07-15 Enthone, Incorporated Reclamation of a palladium-tin based electroless plating catalyst from the exhausted catalyst solution and accompanying rinse waters
DE4217245A1 (de) * 1992-05-25 1993-12-02 Degussa Verfahren zur Abtrennung katalysatorfreier Arbeitslösung aus dem Hydrierkreislauf des Anthrachionverfahrens zur Herstellung von Wasserstoffperoxid
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DE60106498T2 (de) * 2000-01-20 2006-07-13 Westfalia Separator Ag Verfahren und Vorrichtung für die Reinigung und/oder Behandlung von edelmetallhaltigen Suspensionen mittels Membranfiltration
EP1224972A1 (fr) * 2001-01-18 2002-07-24 Shipley Co. L.L.C. Procédé de récupération des métaux catalytiques à partir d'une solution colloidale

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WO1999023263A1 (fr) * 1997-10-30 1999-05-14 Hw Process Technologies, Inc. Procede pour eliminer des contaminants de liquides a traiter dans des procedes de rendement metal

Non-Patent Citations (1)

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Title
See also references of WO0188211A3 *

Also Published As

Publication number Publication date
DE10024239C1 (de) 2001-09-20
WO2001088211A3 (fr) 2003-08-28
US20030155250A1 (en) 2003-08-21
CA2404620A1 (fr) 2001-11-22
JP2004500976A (ja) 2004-01-15
WO2001088211A2 (fr) 2001-11-22

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