Classifications

• • 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
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
• • 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
  • C23C18/1633—Process of electroless plating
  • C23C18/1635—Composition of the substrate
  • C23C18/1644—Composition of the substrate porous substrates
• • 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
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
  • C23C18/2073—Multistep pretreatment
  • C23C18/208—Multistep pretreatment with use of metal first
• • 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
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

• Porous solids are becoming increasingly important as adsorbents and catalysts. They differ from other solid bodies in that they have a cavity structure. This cavity structure is formed by a system of pores. The shape and opening width of the pores range from macroscopic depressions and cracks with a diameter of a few microns to cavities with opening widths that are in the order of magnitude of molecular diameters. The majority of synthetically produced adsorbents have pores that span different size ranges, and their distribution is rarely homogeneous.
• Porous solids can be found in numerous chemical classes. These include inorganic compounds such as silicon derivatives, metal oxides, activated carbons etc. but also porous metals and alloys as well as partially cross-linked polymers, especially ion exchangers.
• Porous solids have orders of magnitude higher specific surfaces than metals. As a result, the effects of surface reactions on such solids are greater. It is therefore of interest to use a method that can be used to change the chemical properties of the surface or the matrix by depositing a thin, diffuse metal layer.
• One of the most important advantages of combining the metal with the cavity geometry of the carrier material is, for example, easier dissipation of heat of reaction, due to the high thermal conductivity of the metal; Control of layer densities and intermediate grain volumes as well as the avoidance of the associated pressure losses by applying external magnetic fields when used in a fluidized or floating bed.
• the production of metallized porous solids is known per se.
• the general procedure is to load the porous substrates with ions of the transition metals, preferably Ru, Pd, Pt, Ag and Ni, and then with a reducing agent, preferably hydrogen (cf. DE 16 43 044, DE 25 53 762 , US 35 38 019, US 30 13 987 and DDR 40 953) or hydrazine, dithionite, borohydride etc. (see. DE 28 49 026, DE 20 03 522, DE 18 00 380, FR 22 70 238, US 40 76 622 Chem. Abstr. 67, 36671 s (1967)) treated or thermally decomposed metal compounds applied to the substrates (cf. US 30 13 987 and 39 54 883).
• a reducing agent preferably hydrogen (cf. DE 16 43 044, DE 25 53 762 , US 35 38 019, US 30 13 987 and DDR 40 953) or hydrazine, dithionite, borohydride
• transition metals can be applied to the substrates mentioned correctly, that is to say without any significant impairment of the pore structure, if these are mixed with the metal ions of the elements of the 1st or 8th subgroup of the periodic system before or after loading with transition metal ions or their compounds activated and the activation ions, if they are still present, sensitized with, for example, a snC1 2 solution.
• Activation is possible both with ionogenic and / or colloidal and with organic adducts of the elements of subgroups 1 and 8 of the periodic table, the elements Au, Ag, Pd, Pt and Cu being used with particular preference.
• Their amount per liter of solvent should be 0.1-15 g, the amounts of 0.3-1.5 g / 1 being used with particular preference.
• Palladium as sol or in particular in the form of an organometallic compound is preferred as the activation metal.
• the groups of the organic part of the organometallic compounds required for the metal bond are known per se (cf. DE 30 25 307). These are, for example, CC or CN double and triple bonds and groups which form a chelate complex can train, e.g. OH, SH, CO or COOH groups.
• the use of the organometallic compounds which, in addition to the groups necessary for metal bonding, have at least one further functional group has the advantage that the activation nuclei are better fixed on the substrate surface.
• Functional groups such as carboxylic acid groups, carboxylic acid halide groups, carboxylic acid hydride groups, carboxylic ester groups, carbonamide and carbonimide groups, aldehyde and ketone groups, ethers are particularly suitable for fixing the activator to the substrate surface groups, sulfonic acid halide groups, sulfonic acid ester groups, halogen-containing heterocyclic radicals, such as chlorotriazinyl, pyrazinyl, pyrimidinyl or quinoxalinyl groups, activated double bonds, such as in the case of vinylsulfonic acid or acrylic acid derivatives, amino groups, hydroxyl groups, isocyanate and mercapto groups, and acetylene groups, also olefleno groups, and olefin groups higher-chain alkyl or alkenyl radicals from C -f in particular oleic, linoleic, stearic or palmiting groups.
• the organometallic activators are used as a solution, dispersion, emulsion or suspension in an organic solvent or as a mixture with an organic solvent. Solvent mixtures can also be used. In contrast, it is not advisable to incorporate polymers, prepolymers or other paint-forming systems into these solvents.
• Particularly suitable solvents are polar, protic and aprotic solvents such as water, methylene chloride, chloroform, trichlorethylene, perchlorethylene, acetone, ethylene glycol and tetrahydrofuran, which can be blended with other solvents such as petrol, ligroin, toluene etc.
• polar, protic and aprotic solvents such as water, methylene chloride, chloroform, trichlorethylene, perchlorethylene, acetone, ethylene glycol and tetrahydrofuran, which can be blended with other solvents such as petrol, ligroin, toluene etc.
• the matrices of the substrates to be metallized are wetted with these solutions, the exposure time preferably being 1 second to 20 minutes. Methods such as immersing the particles in the solutions or spraying them with the activation solutions are particularly suitable for this purpose.
• the solvent is removed.
• Low-boiling solvents are preferably evaporated, e.g. in vacuum, removed.
• other methods such as extraction with a solvent in which the organic compounds are insoluble, are appropriate.
• the activation can also be carried out before loading with metal ions.
• the surfaces pretreated in this way may need to be sensitized.
• the solids activated in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surface of any residual sensitizing agent.
• the metallization is preferably carried out in aqueous solution.
• Other solvents such as alcohols, ethers, hydrocarbons can also be used.
• Suspensions or slurries of the reducing agents can also be used.
• Preferred reducing agents are alkali boranes, dimethyl, diethyl aminoboranes, alkali hypophosphite or formalin or their mixtures. Their amounts should preferably be 10-200 g / 1, in special cases they can be above or below.
• the reduction can be carried out at temperatures from -15 to the respective boiling point of the solvent, with room temperature being particularly preferred.
• the reduction baths In special cases, complexing agents such as citrate ions (sodium citrate, ammonium citrate, citric acid) and ammonium cations (NH 4 OH, NH 4 Cl) or ammonia can be added.
• porous solids with a surface area of 1 - 2000 m 2 / g are suitable for carrying out the new process.
• those based on SiO 2 , activated carbon, metal oxides and organic polymers such as polystyrene, divinylbenzene, polyurethane, polyisoprene, polybutadiene, polyvinyl chloride, polyvinyl pyridine, phenolic resins and epoxy resins should be mentioned.
• the metal content of the solids loaded according to the process should be 5-95% by weight.
• 10 g of macroporous solids according to Example 1 are loaded with Co 2+ ions under the action of slightly acidic aqueous 8% CoSO solution (pH 5), dried according to Example 1, activated and then metallized in a reduction bath according to Example 1. You get a fully metallized sample, the porous structure of which is not affected by the metal coating.
• 10 g of the above-mentioned metallized solids were mixed in an autoclave with 160 ml of ethanol and 24.62 g of nitrobenzene, stirred at 100 bar H 2 pressure and 100 ° C. for 2.5 h until the pressure was constant. After the reaction medium had been filled and the porous solids had been filtered, the reaction solution was examined by gas chromatography. The analyzes show that the nitrobenzene used has been reduced to aniline.
• Example 4 10 g of macroporous solids according to Example 4 are loaded with N i 2t ions according to Example 1, activated according to Example 2, dried and then metallized in a reduction bath of 15 g dimethylaminoborane and 82 g distilled water at 60 ° C. over a period of 45 minutes. A macroporous sample is metallized both on the surface and in the matrix.
• Example 10 g of the solids listed in Example 1 are loaded with Ni 2+ and Co 2+ ions at room temperature under the action of weakly acidic, aqueous salt solution of 3% NiSO 4 and 9% CoCl 2 , and then metallized according to Example 4.
• a porous sample is metallized on the surface or in the matrix.
• Example 10 g of the macroporous solids listed in Example 1 are loaded with Co 2+ ions according to Example 3, activated according to Example 1 and then in a reduction bath which consists of 15 g sodium hypophosphite, 17 g (NH 4 ) 2 SO 4 and 200 ml distilled water, at RT over 35 minutes with a macroporous metal coating.
• Example 2 10 g of the porous solids listed in Example 2 are loaded according to Example 1 with Ni 2 + ions, in an activation bath consisting of 0.7 g of 1,5-cyclooctadiene palladium chloride and 1 1 of trichloroethane, activated over the course of 2 minutes , washed with methanol and then metallized in a reducing agent consisting of 23 g dimethylaminoborane, 21 g malonic acid, 15 g (NH 4 ) 2 SO 4 at 40 ° C. in the course of 45 minutes. You get a porous, metallized sample.
• Example 10 50 g of the porous solids listed in Example 10 are loaded under the action of neutral, aqueous 15% CuSO 4 solution, dried at 50 ° C. under vacuum, activated according to Example 9 and then metallized in a reduction bath according to Example 2. A porous, metallized sample with a metal coating of 8% by weight is obtained.

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• 1982
  • 1982-12-31 DE DE19823248778 patent/DE3248778A1/de not_active Withdrawn
• 1983
  • 1983-12-17 EP EP19830112721 patent/EP0115006A1/fr not_active Withdrawn
  • 1983-12-23 US US06/565,081 patent/US4563371A/en not_active Expired - Fee Related
  • 1983-12-28 JP JP58245609A patent/JPS59133372A/ja active Pending

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