US20170159184A1 - Metallization of low temperature fibers and porous substrates - Google Patents
Metallization of low temperature fibers and porous substrates Download PDFInfo
- Publication number
- US20170159184A1 US20170159184A1 US15/372,108 US201615372108A US2017159184A1 US 20170159184 A1 US20170159184 A1 US 20170159184A1 US 201615372108 A US201615372108 A US 201615372108A US 2017159184 A1 US2017159184 A1 US 2017159184A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- substrate
- temperature
- solution
- coated substrate
- 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.)
- Abandoned
Links
Images
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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
-
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
- C23C18/1865—Heat
-
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
- C23C18/1868—Radiation, e.g. UV, laser
-
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/2033—Heat
-
- 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
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
-
- 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
- C23C18/2006—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
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
-
- 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
- C23C18/31—Coating with metals
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- 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
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
- C23C18/1698—Control of temperature
-
- 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
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Definitions
- the present inventive subject matter relates to methods and systems for generating conductive circuits for flexible substrates and/or temperature-sensitive substrates.
- Metalized plastic, ceramic and composite materials have widespread applications. Metallization of polymer films has previously been achieved under some circumstances using appropriate palladium precursors, followed by thermal treatment, to generate catalytic palladium which initiates electroless metal deposition.
- substrates and polymers that are thermally sensitive such as paper, polyethylene, clear olefinic polymers (COP), acrylonitrile butadiene styrene(ABS), nylon and cotton based materials, plant leaves, protein and keratin based substrates (human hair) can suffer permanent degradation or deformation, and/or cannot be properly metalized at a high temperature, e.g., 100-200° C. or more.
- some materials e.g., ABS material, etc.
- the present inventive subject matter provides metalized temperature-sensitive materials, metalized flexible materials, and systems and methods for metalizing a temperature-sensitive material, which includes papers, polymers, clothes and fibers.
- One aspect of the inventive subject matter includes a method of metalizing a temperature-sensitive material.
- the method begins with a step of applying a catalyst solution on the temperature-sensitive material to form an at least partially catalyst-coated substrate.
- the method continues with a step of incubating the catalyst-coated substrate at a temperature less than 100° C. Once the incubation is substantially completed, then a layer of a metal is deposited on the incubated catalyst-coated substrate using an electroless metal deposition technique.
- Another aspect of the inventive subject matter includes a method of metalizing a fabric.
- the method begins with a step of applying a catalyst solution on the fabric to form a catalyst-coated fabric. Then the method continues with a step of incubating the catalyst-coated substrate at a temperature less than 100° C. Once the incubation is substantially completed, then the catalyst-coated substrate is heated at a temperature at least 250° C. Then, an electroless metal layer is placed on the heated catalyst-coated fabric.
- Another aspect of the inventive subject matter includes a method of metallizing a substrate.
- the method begins with a step of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer. Then, the catalyst precursor layer is substantially dried. Once the catalyst precursor is dried, the substrate is treated with an aqueous or mixed aqueous solution of a reducing agent to converts the catalyst precursor to its active form. Then, an electroless metal layer is placed on the substrate.
- Still another aspect of the inventive subject matter includes a method of metallizing a substrate.
- the method begins with a step of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer. Then, the catalyst precursor layer is substantially dried. Once the catalyst precursor is dried, the substrate is treated with electromagnetic radiation to generate an active catalyst from the catalyst precursor. Then, an electroless metal layer is placed on the substrate.
- FIG. 1 illustrates a perspective view of one embodiment of metalized temperature sensitive material.
- FIG. 2 illustrates a flowchart of a method of metalizing a temperature-sensitive material.
- FIG. 3 illustrates a flowchart of one embodiment of a method of metalizing a fabric.
- FIG. 4 illustrates a flowchart of another embodiment of a method of metalizing a temperature-sensitive material.
- FIG. 5 illustrates a flowchart of still another embodiment of a method of metalizing a temperature-sensitive material.
- the present inventive subject matter relates to methods, systems and devices for metalizing cloth or other temperature-sensitive materials, and, in some embodiments, for constructing circuits for “Smart Clothing”. Further, the present inventive subject matter relates to methods, systems and devices for providing or improving electrostatic safety for large composite structures such as aircraft and wind turbine blades.
- inventive subject matter is considered to include all possible combinations of the disclosed elements.
- inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
- Coupled to is intended to include both direct coupling (in which two elements that are coupled to each other contact each other) and indirect coupling (in which at least one additional element is located between the two elements). Therefore, the terms “coupled to” and “coupled with” are used synonymously.
- the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the inventive subject matter are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the inventive subject matter are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the inventive subject matter may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
- the present inventive subject matter uses a variation of a precursor catalytic ink to print a precursor metalized pattern on a substrate at a range of temperatures suitable for a wide range of substrates and fibers. At least one of advantages of the present inventive subject matter is that it allows for efficient metallization for Smart Clothing, electrically safe composite structures, and lower cost medical applications.
- FIG. 1 shows one exemplary embodiment of a metallized substrate 100 .
- the metalized substrate 100 includes three layers: the substrate layer 105 , the catalyst layer 110 and the electroless metal layer 115 .
- the substrate layer 105 in this embodiment, is a temperature-sensitive material that may include various types of fibers, papers, clothes, fabrics, or thin polymers, as further discussed below.
- the substrate layer 105 comprises a flexible material, and the flexibility of metallized substrate 100 maintains at least 50%, preferably at least 70%, more preferably at least 90% of the flexibility (e.g., rigidity, stiffness, etc.) of the substrate layer 105 . It is also preferred that the metallized substrate 100 substantially maintains the shape of the substrate layer 105 (i.e., without substantial deformation (e.g., wrinkling, shrinking, tearing, loosening, shearing, pilling, etc.) from the original shape of the substrate layer such as)
- FIG. 2 illustrates the flowchart of one embodiment of such method.
- the method 200 begins with a step 205 of applying a catalyst solution on the temperature-sensitive material to form a catalyst-coated substrate.
- a substrate can comprise paper materials, fibers, polyethylene, clear olefininc polymers, acrylonitrile butadiene styrene, cotton based material, clothes, fabrics, textiles, (e.g., nylons, Lycra®, wool, linen, microfiber, silk, etc.), plant leaves, protein, keratin-based materials.
- temperature-sensitive as applied to a material means that the material suffers a temporary or permanent decomposition or deformation as a result of being subjected to a temperature between 100° C. and 200° C. (e.g., directly heated, indirectly exposed, etc.).
- a palladium precursor solution is used as a catalyst solution.
- the palladium precursor solution is prepared in a form of palladium propionate (e.g., palladium (II) propionate-cyclopentylamine complex, etc.). Additional details on preparing a palladium propionate solution are described in the U.S. Pat. No. 8,628,818, which is incorporated herein by reference in its entirety.
- the catalyst layer is thin enough not to substantially change the flexibility or the thickness of the substrate material.
- the catalyst layer has an average thickness of less than 20 atoms, preferably less than 10 atoms, more preferably less than 5 atoms, and most preferably less than 3 atoms.
- the thickness of the catalyst layer is achieved by modulating the concentration of catalyst metals in the solution.
- a palladium propionate solution contains palladium in a concentration less than 10,000 ppm, more preferably 7,000 ppm, most preferably, less than 5,000 ppm.
- the temperature-sensitive material is treated with a solution (e.g., potassium permanganate, sulfuric acid, formic acid, etc.) at a temperature less than 100° C. before applying the catalyst solution.
- a solution e.g., potassium permanganate, sulfuric acid, formic acid, etc.
- the temperature-sensitive material is further treated with acidic solution (e.g., oxalic acid, etc.).
- acidic solution e.g., oxalic acid, etc.
- the temperature-sensitive material is washed with water (e.g., deionized water, distilled water, etc.) and/or methanol before placing the catalyst layer.
- the method continues with a step 210 of incubating the catalyst-coated substrate at a relatively low temperature.
- a relatively low temperature For example, it is contemplated that the catalyst-coated substrate is incubated at a temperature less than 100° C., preferably less than 80° C., more preferably less than 60° C.
- the catalyst-coated substrate can be treated (e.g., washed, etc.) with reducing agent solutions.
- the reducing agent is in an aqueous or mixed aqueous solvent (e.g., alcoholic and water solvent, etc.) or solvents (e.g., aqueous and nonaqueous solvent mixtures, etc.).
- the reducing agent include hydrazineN 2 H 4 in its various forms (e.g., in a form of an aqueous solution, salts, ascorbic acid, aldehydes, alcohols, etc.)
- the method continues with a step 215 of placing an electroless metal layer (e.g., copper, nickel, etc.) on the catalyst-coated substrate.
- an electroless metal layer e.g., copper, nickel, etc.
- this method 200 enables the user to generate the metalized substrate without a substantial deformation or degeneration of the original substrate materials (e.g., the substrate that is prone to be deformed or degenerated at a temperature at or around 100° C., or at a temperature between 100° C. and 200° C., etc.). Because the conventional method of metalizing requires a treatment step at high temperatures (e.g., higher than 200° C., etc.), such conventional method cannot be used to metalize various non heat-resistant or less heat-resistant materials. Thus, this method is contemplated to widen the use and scope of metalizing techniques to more various substrate materials.
- the original substrate materials e.g., the substrate that is prone to be deformed or degenerated at a temperature at or around 100° C., or at a temperature between 100° C. and 200° C., etc.
- Another aspect of the present inventive subject matter includes a method 300 of metalizing a fabric. Similar to the method 200 of metalizing temperature-sensitive materials, The method 300 begins with a step 305 of applying a catalyst solution (e.g., palladium (II) propionate-cyclopentylamine complex, etc.) on the fabric to form a catalyst-coated fabric.
- a catalyst solution e.g., palladium (II) propionate-cyclopentylamine complex, etc.
- a substrate can comprise a carbon fiber cloth, a Kevlar cloth, a cloth containing a natural fiber, or a cloth containing a synthetic fiber.
- the method continues with a step 310 of incubating the catalyst-coated substrate at a relatively lower temperature.
- the catalyst-coated substrate is incubated at a temperature less than 100° C., preferably less than 80° C., more preferably less than 60° C.
- the method continues with an additional step 315 that the catalyst-coated substrate is heated at a temperature at a relatively high temperature (e.g., at least 250° C., at least 300° C., at least 350° C., etc.).
- the method continues with a step 320 of placing an electroless metal layer (e.g., copper, nickel, etc.) on the catalyst-coated substrate.
- an electroless metal layer e.g., copper, nickel, etc.
- this method enables the user to generate a metalized substrate that substantially maintains original characters of the substrate materials so that the metalized substrates can be used for the same purpose as the original substrate materials are used.
- the metalized substrate substantially maintains the original flexibility, texture, and/or shape of the substrate material.
- the coated nylon fabric maintains at least 60%, preferably at least 70%, more preferably at least 90% of the nylon substrate's flexibility.
- the metalized substrate substantially maintains the original shape of the substrate material (i.e., without substantial deformation (e.g., wrinkling, shrinking, tearing, loosening, shearing, pilling, etc.) from the original shape of the substrate layer, etc.). It is also preferred that the metalized substrate substantially maintains the original texture of the original substrate material (e.g., without substantially additional roughness added to the original substrate material, etc.). Further, it is also preferred that the weight of the metalized substrate is no more than 130%, preferably no more than 120%, more preferably no more than 110% of original substrate material.
- the metalized substrate can be also used for clothing without substantially providing discomforts (e.g., excessive weight added on the original fabric substrate, uncomfortable texture, etc.) to the wearer.
- Still another aspect of the present inventive subject matter includes a method 400 of metalizing a substrate.
- the method begins with a step 405 of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer.
- the method continues with a step 410 of drying the catalyst precursor layer (e.g., air-dried, oven-dried, etc.).
- the catalyst coated substrate is substantially dried (e.g., contains less than 50%, preferably less than 30%, more preferably less than 15%, most preferably less than 10% of the water content before the step of drying)
- the method continues with a step 415 of treating the substrate with an aqueous or mixed aqueous solution of a reducing agent to convert the catalyst precursor to its active form.
- the method continues with a step 415 of placing an electroless layer of metal (e.g., copper, nickel, etc.) on the substrate.
- an electroless layer of metal e.g., copper, nickel, etc.
- Still another aspect of the present inventive subject matter includes a method 500 of metalizing a substrate.
- the method begins with a step 505 of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer.
- the method continues with a step 510 of drying the catalyst precursor layer (e.g., air-dried, oven-dried, etc.).
- the catalyst coated substrate is substantially dried (e.g., contains less than 50%, preferably less than 30%, more preferably less than 15%, most preferably less than 10% of the water content before the step of drying)
- the method continues with a step 515 of treating the substrate with coherent or non-coherent electromagnetic radiation to generate an active catalyst from the catalyst precursor.
- the method continues with a step 520 of placing an electroless layer of metal (e.g., copper, nickel, etc.) on the substrate.
- an electroless layer of metal e.g., copper, nickel, etc.
- the step of treating the substrate can be performed with convective heat transfer. In other embodiments, the step of treating the substrate can be performed with conductive heat transfer.
- the palladium solution used herein is not an aqueous solution that are used in metathetical reactions.
- metathetical reactions ionic palladium is converted to catalytic palladium in situ using electroless metal chemistries having reducing agents.
- a reducing agent is used subsequent to the substrate surface treatment followed by electroless metal deposition.
- the ionic palladium precursors are water-based soluble palladium salts.
- metathetical reactions lead to a formation of colloidal, nano, aggregate nano or bulk precipitation of electroless metals.
- a precipitation of barium sulfate from a soluble barium salt followed by treatment with a solution containing SO4 2 ⁇ ions leads to a bulk precipitation of barium sulfate.
- a substrate soaked with an aqueous or a mixed aqueous solution of a metal salt and then treated with a suitable reducing agent or agents reduces the soluble metal salt to metal. Because metals are generally insoluble in water, the reduced metal will be precipitated.
- it is redox reaction that converts a soluble metal salt to a precipitated metal and is similar to a precipitation reaction similar to the example of barium sulfate precipitation from a soluble barium salt.
- the deposition of the catalyst using a soluble metal compound can be depicted as following:
- aqueous solutions instead of aqueous solutions, the inventors use a palladium compound that is water insoluble or has limited water solubility.
- a non-aqueous precursor is deposited on a porous or non-porous substrate followed by treatment with a reducing agent.
- non-aqueous palladium compound the inventors could avoid metathetical reaction of precipitation of palladium in the aqueous medium.
- the inventors could avoid bulk precipitation of palladium metals, the inventors could achieve the formation of near “atomic” or sub-nano palladium particles.
- the above chemical reaction typically represents the generation of the active catalytic palladium according to the present inventive subject matter.
- DMSO dimethyl sulfoxide
- An ABS substrate was dipped in a solution of 5% potassium permanganate (w/v) prepared in 20% sulfuric acid at 60-70 degree Celsius for 3 minutes. The substrate was then dipped in 5% oxalic acid solution in 10% sulfuric acid (w/v) for 1 minute at room temperature followed by washing with water. The substrate was washed with IPA and dried. It was then coated with a coating solution prepared by mixing 1 gm of solution A with 7.26 gm of solution B. The mixed solution was quickly coated on the ABS substrate using Meyer rod #8. The substrate was placed in a convection oven at 85° C. for 40 minutes. The substrate was then dipped in electroless copper solution using commercially available electroless copper from MacDermid (Electroless Copper 22). A copper film was obtained on the substrate. The substrate was washed with de-ionized (DI) water and then with methanol and kept in oven at 60° C. for couple of hours.
- DI de-ionized
- a challenging issue is the metallization of cellulosic porous media (e.g., photocopying paper, filter papers, etc.). These substrates have cellulose as the main component which is composited with suitable binders to fabricate products for different applications.
- a filter paper (e.g., Whatman Filter #1, etc.) is used in teaching and research for routine filtration.
- the filter paper becomes very fragile in aqueous media which is normally the media for routine chemical, physicochemical and even biological applications.
- the filter paper cannot be used in acidic and alkaline media as the cellulose fibers and/or the compositing binders are dissolved or attacked by alkalis or acids thus rendering the filter paper unworthy of use under such conditions.
- the resulting metalized filter paper can be used for neutral, alkaline, acidic aqueous and non-aqueous media.
- a Whatman Filter #5 was coated with a 3000 ppm palladium ink using palladium propionate in amyl acetate.
- the substrate was dried in oven at 50° C. It was then dipped in a 10% solution of formic acid in water at 25-35° C. for 1 minute.
- the filter paper was gently washed with water and methanol and then dipped in electroless copper solution for 15 minutes.
- An electrically conducting copper coated filter paper was obtained that has porosity.
- the above method can also be used to metalize fabrics of different varieties. Thus, for example, a clean room swipe was metalized as described in Example 3.
- a clean room wipe was soak-coated with a 3000 ppm palladium solution as palladium propionate in amyl acetate. It was dried around 25-40° C. for 45 minutes and dipped in a 10% solution of formic acid in water for 1 minute. It was washed with water and then dipped in electroless copper solution (Electroless Copper 22) for 30 minutes. An electrically conducting swipe was obtained.
- Kevlar cloth was soak coated with a 3000 ppm palladium solution as palladium propionate in amyl acetate as described above. It was dried 40-50° C. for 15 minutes and then heated at 300° C. for 9 min followed by treatment by electroless copper solution. A nice copper deposition was obtained on the entire fabric cloth. An electrically conducting swipe was obtained.
- a carbon fiber cloth was soak-coated with a 3000 ppm palladium solution as palladium propionate in amyl acetate as described above. It was dried 40-50° C. for 15 minutes and then heated at 300° C. for 9 min followed by treatment by electroless copper solution. A nice copper deposition was obtained on the entire fabric cloth. An electrically conducting swipe was obtained.
Abstract
Description
- This application claims the benefit of priority to U.S. Provisional Patent Application No. 62/264,237, filed Dec. 7, 2015. Where a definition or use of a term in a reference that is incorporated by reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein is deemed to be controlling.
- The present inventive subject matter relates to methods and systems for generating conductive circuits for flexible substrates and/or temperature-sensitive substrates.
- The following description includes information that may be useful in understanding the present inventive subject matter. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed inventive subject matter, or that any publication specifically or implicitly referenced is prior art.
- Metalized plastic, ceramic and composite materials have widespread applications. Metallization of polymer films has previously been achieved under some circumstances using appropriate palladium precursors, followed by thermal treatment, to generate catalytic palladium which initiates electroless metal deposition. However, substrates and polymers that are thermally sensitive, such as paper, polyethylene, clear olefinic polymers (COP), acrylonitrile butadiene styrene(ABS), nylon and cotton based materials, plant leaves, protein and keratin based substrates (human hair) can suffer permanent degradation or deformation, and/or cannot be properly metalized at a high temperature, e.g., 100-200° C. or more. For example, some materials (e.g., ABS material, etc.) can be sufficiently softened at a temperature higher than 100° C. to become difficult to be properly metalized.
- Thus, while conventional metallization methods can be used to metalize rigid substrates and/or high-temperature resistant subtrates, such methods cannot be practically or efficiently applied to a many non-rigid substrates and fibers.
- Many have made efforts to efficiently metalize fabrics or temperature sensitive materials. For example, Wang et al., in a publication titled “Optimization of process conditions for electroless copper plating on polyester fabric”, published Apr. 16-18, 2011 in 2011 International Conference on Consumer Electronics, Communications and Networks, disclose a method of creating a copper-coated polyester fabric by electroless plating using sodium hypophosphite as a reducing reagent. For another example, U.S. Pat. No. 3,589,962 to Bonjour discloses that metallic layer can be produced over a fabric using a thermoplastic adhesive.
- Others have made effort to metalize fabrics using catalysts. For example, U.S. Pat. No. 2,474,502 to Suchy discloses a method of metallization of non-conductive porous material including fabrics. In Suchy, colloidal silver was deposited on textiles via an electro-deposition process using a catalyzer such as stannous chloride. It is also known in the art that various techniques (e.g., vacuum deposition, ion plating, electroplating, electroless plating) can be used to metalize fabrics. Yet, currently available methods are not very effective in creating a thin metal layer (e.g., atomic layer, etc.) on the fabric.
- Related arts also include the following, each of which is incorporated herein as references in its entirety.
- 1. Ceramic Substrates and Packages for Electronic Applications (Advances in Ceramics. W. S. Young (Editor). 1989. ISBN-10: 0916094359.
- 2. Metalized plastics—fundamentals and applications. Edited by K. L. Mittal, Marcel Dekker, New York, 1998. ISBN 0-8247-9925-9.
- 3. Sunity Sharma, et. al., U.S. Pat. No. 7,981,508.
- 4. Sunity Sharma, et. al., US Pat. Application No. 2012/0100286 A1.
- 5. Sunity Sharma, et. al., US Pat. Application No. 2014/0083748 A1.
- 6. U.S. Pat. No. 8,110,254: FLEXIBLE CIRCUIT CHEMISTRY: Catalytic ink chemistry for flexible circuit applications (5515-3).
- 7. U.S. Pat. No. 7,981,508: ADHESIVELESS FLEXIBLE CIRCUIT: All flexible circuits which are copper directly on substrate with only single molecules of active palladium on the surface and with no tie coat or adhesive layer (5516-3).
- 8. U.S. Pat. No. 8,124,226: ADDITIVE ADHESIVELESS FLEXIBLE CIRCUIT: All flexible circuits which are copper directly deposited on a precursor pattern on a substrate with no tie coat or adhesive layer (5516-5).
- 9. U.S. Pat. No. 7,989,029: REDUCED POROSITY COPPER DEPOSITION: Flex circuits and coatings with reduced copper porosity (5564-2).
- 10. U.S. Pat. No. 8,628,818: CONDUCTIVE PATTERN FORMATION: All flexible circuits which are made using a semi-additive process for which the conductive layer is copper directly deposited on a substrate with only single molecules of active palladium on the surface and with no tied coat or adhesive layer (5553-2).
- Thus, there is still a need for materials and processes that can be used to generate metal films on the surfaces of temperature-sensitive materials due to application of excessive heat and/or radiation.
- The present inventive subject matter provides metalized temperature-sensitive materials, metalized flexible materials, and systems and methods for metalizing a temperature-sensitive material, which includes papers, polymers, clothes and fibers.
- One aspect of the inventive subject matter includes a method of metalizing a temperature-sensitive material. The method begins with a step of applying a catalyst solution on the temperature-sensitive material to form an at least partially catalyst-coated substrate. Then the method continues with a step of incubating the catalyst-coated substrate at a temperature less than 100° C. Once the incubation is substantially completed, then a layer of a metal is deposited on the incubated catalyst-coated substrate using an electroless metal deposition technique.
- Another aspect of the inventive subject matter includes a method of metalizing a fabric. The method begins with a step of applying a catalyst solution on the fabric to form a catalyst-coated fabric. Then the method continues with a step of incubating the catalyst-coated substrate at a temperature less than 100° C. Once the incubation is substantially completed, then the catalyst-coated substrate is heated at a temperature at least 250° C. Then, an electroless metal layer is placed on the heated catalyst-coated fabric.
- Another aspect of the inventive subject matter includes a method of metallizing a substrate. The method begins with a step of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer. Then, the catalyst precursor layer is substantially dried. Once the catalyst precursor is dried, the substrate is treated with an aqueous or mixed aqueous solution of a reducing agent to converts the catalyst precursor to its active form. Then, an electroless metal layer is placed on the substrate.
- Still another aspect of the inventive subject matter includes a method of metallizing a substrate. The method begins with a step of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer. Then, the catalyst precursor layer is substantially dried. Once the catalyst precursor is dried, the substrate is treated with electromagnetic radiation to generate an active catalyst from the catalyst precursor. Then, an electroless metal layer is placed on the substrate.
- Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments, along with the accompanying drawing figures in which like numerals represent like components.
-
FIG. 1 illustrates a perspective view of one embodiment of metalized temperature sensitive material. -
FIG. 2 illustrates a flowchart of a method of metalizing a temperature-sensitive material. -
FIG. 3 illustrates a flowchart of one embodiment of a method of metalizing a fabric. -
FIG. 4 illustrates a flowchart of another embodiment of a method of metalizing a temperature-sensitive material. -
FIG. 5 illustrates a flowchart of still another embodiment of a method of metalizing a temperature-sensitive material. - The present inventive subject matter relates to methods, systems and devices for metalizing cloth or other temperature-sensitive materials, and, in some embodiments, for constructing circuits for “Smart Clothing”. Further, the present inventive subject matter relates to methods, systems and devices for providing or improving electrostatic safety for large composite structures such as aircraft and wind turbine blades.
- The following discussion provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
- As used herein, and unless the context dictates otherwise, the term “coupled to” is intended to include both direct coupling (in which two elements that are coupled to each other contact each other) and indirect coupling (in which at least one additional element is located between the two elements). Therefore, the terms “coupled to” and “coupled with” are used synonymously.
- In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the inventive subject matter are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the inventive subject matter are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the inventive subject matter may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
- As used in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.
- Unless the context dictates the contrary, all ranges set forth herein should be interpreted as being inclusive of their endpoints and open-ended ranges should be interpreted to include only commercially practical values. The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value within a range is incorporated into the specification as if it were individually recited herein. Similarly, all lists of values should be considered as inclusive of intermediate values unless the context indicates the contrary.
- All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the inventive subject matter and does not pose a limitation on the scope of the inventive subject matter otherwise claimed. No language in the application should be construed as indicating any non-claimed element essential to the practice of the inventive subject matter.
- Groupings of alternative elements or embodiments of the inventive subject matter disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.
- The present inventive subject matter uses a variation of a precursor catalytic ink to print a precursor metalized pattern on a substrate at a range of temperatures suitable for a wide range of substrates and fibers. At least one of advantages of the present inventive subject matter is that it allows for efficient metallization for Smart Clothing, electrically safe composite structures, and lower cost medical applications.
- One aspect of the present inventive subject matter includes a metalized temperature-sensitive material.
FIG. 1 shows one exemplary embodiment of a metallizedsubstrate 100. Generally, the metalizedsubstrate 100 includes three layers: thesubstrate layer 105, thecatalyst layer 110 and theelectroless metal layer 115. Thesubstrate layer 105, in this embodiment, is a temperature-sensitive material that may include various types of fibers, papers, clothes, fabrics, or thin polymers, as further discussed below. - Preferably, the
substrate layer 105 comprises a flexible material, and the flexibility of metallizedsubstrate 100 maintains at least 50%, preferably at least 70%, more preferably at least 90% of the flexibility (e.g., rigidity, stiffness, etc.) of thesubstrate layer 105. It is also preferred that the metallizedsubstrate 100 substantially maintains the shape of the substrate layer 105 (i.e., without substantial deformation (e.g., wrinkling, shrinking, tearing, loosening, shearing, pilling, etc.) from the original shape of the substrate layer such as) - Another aspect of the present inventive subject matter includes a method of metalizing a temperature-sensitive material.
FIG. 2 illustrates the flowchart of one embodiment of such method. Themethod 200 begins with astep 205 of applying a catalyst solution on the temperature-sensitive material to form a catalyst-coated substrate. It is contemplated that any suitable type of temperature-sensitive material can be used as a substrate. For example, a substrate can comprise paper materials, fibers, polyethylene, clear olefininc polymers, acrylonitrile butadiene styrene, cotton based material, clothes, fabrics, textiles, (e.g., nylons, Lycra®, wool, linen, microfiber, silk, etc.), plant leaves, protein, keratin-based materials. - As used herein, the term “temperature-sensitive” as applied to a material means that the material suffers a temporary or permanent decomposition or deformation as a result of being subjected to a temperature between 100° C. and 200° C. (e.g., directly heated, indirectly exposed, etc.).
- It is contemplated that many precious metals can be used as catalyst for electroless plating, including for example, palladium, gold, silver, tin, ruthenium and platinum. In a preferred embodiment, a palladium precursor solution is used as a catalyst solution. In this embodiment, it is contemplated that the palladium precursor solution is prepared in a form of palladium propionate (e.g., palladium (II) propionate-cyclopentylamine complex, etc.). Additional details on preparing a palladium propionate solution are described in the U.S. Pat. No. 8,628,818, which is incorporated herein by reference in its entirety.
- In a preferred embodiment, the catalyst layer is thin enough not to substantially change the flexibility or the thickness of the substrate material. Thus, it is preferred that the catalyst layer has an average thickness of less than 20 atoms, preferably less than 10 atoms, more preferably less than 5 atoms, and most preferably less than 3 atoms. In some embodiments, the thickness of the catalyst layer is achieved by modulating the concentration of catalyst metals in the solution. For example, it is preferred that a palladium propionate solution contains palladium in a concentration less than 10,000 ppm, more preferably 7,000 ppm, most preferably, less than 5,000 ppm.
- In some embodiments, the temperature-sensitive material is treated with a solution (e.g., potassium permanganate, sulfuric acid, formic acid, etc.) at a temperature less than 100° C. before applying the catalyst solution. In a preferred embodiment, the temperature-sensitive material is further treated with acidic solution (e.g., oxalic acid, etc.). To remove the acid residue, it is contemplated that the temperature-sensitive material is washed with water (e.g., deionized water, distilled water, etc.) and/or methanol before placing the catalyst layer.
- Once the catalyst layer is placed on the substrate, the method continues with a
step 210 of incubating the catalyst-coated substrate at a relatively low temperature. For example, it is contemplated that the catalyst-coated substrate is incubated at a temperature less than 100° C., preferably less than 80° C., more preferably less than 60° C. - Optionally, the catalyst-coated substrate can be treated (e.g., washed, etc.) with reducing agent solutions. In a preferred embodiment, the reducing agent is in an aqueous or mixed aqueous solvent (e.g., alcoholic and water solvent, etc.) or solvents (e.g., aqueous and nonaqueous solvent mixtures, etc.). For example, the reducing agent include hydrazineN2H4 in its various forms (e.g., in a form of an aqueous solution, salts, ascorbic acid, aldehydes, alcohols, etc.)
- After the incubation of the catalyst-coated substrate, the method continues with a
step 215 of placing an electroless metal layer (e.g., copper, nickel, etc.) on the catalyst-coated substrate. The details of the electroless metal deposition technique are described in the inventors' co-pending application, U.S. Pub. No. US 2016/0113121, which is incorporated in its entirety herein. - It is contemplated that this
method 200 enables the user to generate the metalized substrate without a substantial deformation or degeneration of the original substrate materials (e.g., the substrate that is prone to be deformed or degenerated at a temperature at or around 100° C., or at a temperature between 100° C. and 200° C., etc.). Because the conventional method of metalizing requires a treatment step at high temperatures (e.g., higher than 200° C., etc.), such conventional method cannot be used to metalize various non heat-resistant or less heat-resistant materials. Thus, this method is contemplated to widen the use and scope of metalizing techniques to more various substrate materials. - Another aspect of the present inventive subject matter includes a
method 300 of metalizing a fabric. Similar to themethod 200 of metalizing temperature-sensitive materials, Themethod 300 begins with astep 305 of applying a catalyst solution (e.g., palladium (II) propionate-cyclopentylamine complex, etc.) on the fabric to form a catalyst-coated fabric. Any suitable type of fabric can be used. For example, a substrate can comprise a carbon fiber cloth, a Kevlar cloth, a cloth containing a natural fiber, or a cloth containing a synthetic fiber. - Once the catalyst solution is applied on the fabric, the method continues with a
step 310 of incubating the catalyst-coated substrate at a relatively lower temperature. For example, it is contemplated that the catalyst-coated substrate is incubated at a temperature less than 100° C., preferably less than 80° C., more preferably less than 60° C. In a preferred embodiment, once the catalyst-coated substrate is incubated at a low temperature, then the method continues with anadditional step 315 that the catalyst-coated substrate is heated at a temperature at a relatively high temperature (e.g., at least 250° C., at least 300° C., at least 350° C., etc.). - After the incubation of the catalyst-coated substrate, the method continues with a
step 320 of placing an electroless metal layer (e.g., copper, nickel, etc.) on the catalyst-coated substrate. - It is contemplated that this method enables the user to generate a metalized substrate that substantially maintains original characters of the substrate materials so that the metalized substrates can be used for the same purpose as the original substrate materials are used. For example, it is highly preferred that the metalized substrate substantially maintains the original flexibility, texture, and/or shape of the substrate material. In this example, when the electroless metal is coated on the nylon fabric, the coated nylon fabric maintains at least 60%, preferably at least 70%, more preferably at least 90% of the nylon substrate's flexibility. For another example, the metalized substrate substantially maintains the original shape of the substrate material (i.e., without substantial deformation (e.g., wrinkling, shrinking, tearing, loosening, shearing, pilling, etc.) from the original shape of the substrate layer, etc.). It is also preferred that the metalized substrate substantially maintains the original texture of the original substrate material (e.g., without substantially additional roughness added to the original substrate material, etc.). Further, it is also preferred that the weight of the metalized substrate is no more than 130%, preferably no more than 120%, more preferably no more than 110% of original substrate material. Thus, for example, if the original substrate is suitable for manufacturing clothing (e.g., T-shirts, a jacket, pants, hats, etc.), the metalized substrate can be also used for clothing without substantially providing discomforts (e.g., excessive weight added on the original fabric substrate, uncomfortable texture, etc.) to the wearer.
- Still another aspect of the present inventive subject matter includes a
method 400 of metalizing a substrate. The method begins with astep 405 of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer. Then the method continues with astep 410 of drying the catalyst precursor layer (e.g., air-dried, oven-dried, etc.). Once the catalyst coated substrate is substantially dried (e.g., contains less than 50%, preferably less than 30%, more preferably less than 15%, most preferably less than 10% of the water content before the step of drying), the method continues with astep 415 of treating the substrate with an aqueous or mixed aqueous solution of a reducing agent to convert the catalyst precursor to its active form. Once the catalyst precursor is converted to active catalyst, the method continues with astep 415 of placing an electroless layer of metal (e.g., copper, nickel, etc.) on the substrate. - Still another aspect of the present inventive subject matter includes a
method 500 of metalizing a substrate. The method begins with astep 505 of applying to the substrate a catalyst precursor that has limited solubility in aqueous or mixed aqueous media to form a catalyst precursor layer. Then the method continues with astep 510 of drying the catalyst precursor layer (e.g., air-dried, oven-dried, etc.). Once the catalyst coated substrate is substantially dried (e.g., contains less than 50%, preferably less than 30%, more preferably less than 15%, most preferably less than 10% of the water content before the step of drying), the method continues with astep 515 of treating the substrate with coherent or non-coherent electromagnetic radiation to generate an active catalyst from the catalyst precursor. Once the catalyst precursor is converted to active catalyst, the method continues with astep 520 of placing an electroless layer of metal (e.g., copper, nickel, etc.) on the substrate. In some embodiments, the step of treating the substrate can be performed with convective heat transfer. In other embodiments, the step of treating the substrate can be performed with conductive heat transfer. - It should be noted that the palladium solution used herein is not an aqueous solution that are used in metathetical reactions. In metathetical reactions, ionic palladium is converted to catalytic palladium in situ using electroless metal chemistries having reducing agents. Alternatively, a reducing agent is used subsequent to the substrate surface treatment followed by electroless metal deposition. The ionic palladium precursors are water-based soluble palladium salts. Generally, metathetical reactions lead to a formation of colloidal, nano, aggregate nano or bulk precipitation of electroless metals. For example, a precipitation of barium sulfate from a soluble barium salt followed by treatment with a solution containing SO42− ions leads to a bulk precipitation of barium sulfate. A substrate soaked with an aqueous or a mixed aqueous solution of a metal salt and then treated with a suitable reducing agent or agents reduces the soluble metal salt to metal. Because metals are generally insoluble in water, the reduced metal will be precipitated. Thus it is redox reaction that converts a soluble metal salt to a precipitated metal and is similar to a precipitation reaction similar to the example of barium sulfate precipitation from a soluble barium salt. The deposition of the catalyst using a soluble metal compound can be depicted as following:
- This represents a typical example of generating ionic palladium catalyst.
- Instead of aqueous solutions, the inventors use a palladium compound that is water insoluble or has limited water solubility. A non-aqueous precursor is deposited on a porous or non-porous substrate followed by treatment with a reducing agent. By using non-aqueous palladium compound, the inventors could avoid metathetical reaction of precipitation of palladium in the aqueous medium. As the inventors could avoid bulk precipitation of palladium metals, the inventors could achieve the formation of near “atomic” or sub-nano palladium particles.
- The above chemical reaction typically represents the generation of the active catalytic palladium according to the present inventive subject matter.
- Inventors have successfully developed materials and processes for the metallization of such materials. The following examples illustrate the basic and key features of this inventive subject matter. The process described below is generic enough to be used for those porous materials which can stand high temperatures.
- A solution of palladium propionate was prepared in dimethyl sulfoxide (DMSO) solvent as follows: Solution (A): Pd(II)propionate=9.5 gm of palladium was added to 45 gm dimethyl sulfoxide (DMSO) and warmed to dissolve; Solution (B): The following ingredients were mixed together: 54.45 gm DMSO, 0.66 gm Et3N, 0.25 gm HCOOH, 22 gm isopropyl alcohol (IPA) and 22 gm HCONH2.
- An ABS substrate was dipped in a solution of 5% potassium permanganate (w/v) prepared in 20% sulfuric acid at 60-70 degree Celsius for 3 minutes. The substrate was then dipped in 5% oxalic acid solution in 10% sulfuric acid (w/v) for 1 minute at room temperature followed by washing with water. The substrate was washed with IPA and dried. It was then coated with a coating solution prepared by mixing 1 gm of solution A with 7.26 gm of solution B. The mixed solution was quickly coated on the ABS substrate using Meyer rod #8. The substrate was placed in a convection oven at 85° C. for 40 minutes. The substrate was then dipped in electroless copper solution using commercially available electroless copper from MacDermid (Electroless Copper 22). A copper film was obtained on the substrate. The substrate was washed with de-ionized (DI) water and then with methanol and kept in oven at 60° C. for couple of hours.
- A challenging issue is the metallization of cellulosic porous media (e.g., photocopying paper, filter papers, etc.). These substrates have cellulose as the main component which is composited with suitable binders to fabricate products for different applications. A filter paper, (e.g., Whatman Filter #1, etc.) is used in teaching and research for routine filtration. One of the issues is that the filter paper becomes very fragile in aqueous media which is normally the media for routine chemical, physicochemical and even biological applications. The filter paper cannot be used in acidic and alkaline media as the cellulose fibers and/or the compositing binders are dissolved or attacked by alkalis or acids thus rendering the filter paper unworthy of use under such conditions. However, if the filter paper is metalized in such a way that the fibers of the filtering substrate are completely covered by the metal with the retention of porosity, the resulting metalized filter paper can be used for neutral, alkaline, acidic aqueous and non-aqueous media.
- A Whatman Filter #5 was coated with a 3000 ppm palladium ink using palladium propionate in amyl acetate. The substrate was dried in oven at 50° C. It was then dipped in a 10% solution of formic acid in water at 25-35° C. for 1 minute. The filter paper was gently washed with water and methanol and then dipped in electroless copper solution for 15 minutes. An electrically conducting copper coated filter paper was obtained that has porosity. The above method can also be used to metalize fabrics of different varieties. Thus, for example, a clean room swipe was metalized as described in Example 3.
- A clean room wipe was soak-coated with a 3000 ppm palladium solution as palladium propionate in amyl acetate. It was dried around 25-40° C. for 45 minutes and dipped in a 10% solution of formic acid in water for 1 minute. It was washed with water and then dipped in electroless copper solution (Electroless Copper 22) for 30 minutes. An electrically conducting swipe was obtained.
- A Kevlar cloth was soak coated with a 3000 ppm palladium solution as palladium propionate in amyl acetate as described above. It was dried 40-50° C. for 15 minutes and then heated at 300° C. for 9 min followed by treatment by electroless copper solution. A nice copper deposition was obtained on the entire fabric cloth. An electrically conducting swipe was obtained.
- A carbon fiber cloth was soak-coated with a 3000 ppm palladium solution as palladium propionate in amyl acetate as described above. It was dried 40-50° C. for 15 minutes and then heated at 300° C. for 9 min followed by treatment by electroless copper solution. A nice copper deposition was obtained on the entire fabric cloth. An electrically conducting swipe was obtained.
- It should be apparent to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the appended claims. Moreover, in interpreting both the specification and the claims, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms “comprises” and “comprising” should be interpreted as referring to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced. Where the specification claims refers to at least one of something selected from the group consisting of A, B, C . . . and N, the text should be interpreted as requiring only one element from the group, not A plus N, or B plus N, etc.
Claims (20)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/372,108 US20170159184A1 (en) | 2015-12-07 | 2016-12-07 | Metallization of low temperature fibers and porous substrates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562264237P | 2015-12-07 | 2015-12-07 | |
US15/372,108 US20170159184A1 (en) | 2015-12-07 | 2016-12-07 | Metallization of low temperature fibers and porous substrates |
Publications (1)
Publication Number | Publication Date |
---|---|
US20170159184A1 true US20170159184A1 (en) | 2017-06-08 |
Family
ID=58798940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/372,108 Abandoned US20170159184A1 (en) | 2015-12-07 | 2016-12-07 | Metallization of low temperature fibers and porous substrates |
Country Status (1)
Country | Link |
---|---|
US (1) | US20170159184A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190394888A1 (en) * | 2018-06-21 | 2019-12-26 | Averatek Corporation | Patterning of electroless metals |
CN111005026A (en) * | 2019-12-24 | 2020-04-14 | 广东省新材料研究所 | Carbon fiber-based composite material and preparation method thereof |
Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
US3684534A (en) * | 1970-07-06 | 1972-08-15 | Hooker Chemical Corp | Method for stabilizing palladium containing solutions |
US3787698A (en) * | 1972-10-11 | 1974-01-22 | Us Army | Recording of fast neutron images |
US4764401A (en) * | 1981-12-05 | 1988-08-16 | Bayer Aktiengesellschaft | Process for activating substrate surfaces for electroless metallization |
US4775449A (en) * | 1986-12-29 | 1988-10-04 | General Electric Company | Treatment of a polyimide surface to improve the adhesion of metal deposited thereon |
US4830880A (en) * | 1986-04-22 | 1989-05-16 | Nissan Chemical Industries Ltd. | Formation of catalytic metal nuclei for electroless plating |
US4937608A (en) * | 1988-08-19 | 1990-06-26 | Fuji Photo Film Co., Ltd. | Photographic processing apparatus |
US4969842A (en) * | 1989-11-30 | 1990-11-13 | Amp Incorporated | Molded electrical connector having integral spring contact beams |
US5108786A (en) * | 1989-05-01 | 1992-04-28 | Enthone-Omi, Inc. | Method of making printed circuit boards |
US5114812A (en) * | 1989-07-07 | 1992-05-19 | Hoechst Aktiengesellschaft | Electrodes for primary and secondary electric cells |
US5302750A (en) * | 1993-05-25 | 1994-04-12 | Exxon Chemical Patents Inc. | Method for producing n-octadienol from butadiene |
US5373629A (en) * | 1989-08-31 | 1994-12-20 | Blasberg-Oberflachentechnik Gmbh | Through-hole plate printed circuit board with resist and process for manufacturing same |
US5411795A (en) * | 1992-10-14 | 1995-05-02 | Monsanto Company | Electroless deposition of metal employing thermally stable carrier polymers |
US20010019928A1 (en) * | 1999-12-07 | 2001-09-06 | Susumu Takagi | Metal coated fiber materials |
US20050009334A1 (en) * | 2003-07-07 | 2005-01-13 | Semiconductor Technology Academic Research Center | Method of producing multilayer interconnection structure |
US20080029294A1 (en) * | 2004-06-01 | 2008-02-07 | Fujifilm Corporation | Multi-Layer Circuit Board And Production Method Thereof |
US20100155255A1 (en) * | 2007-05-22 | 2010-06-24 | Okuno Chemical Industries Co., Ltd. | Pretreatment process for electroless plating of resin molded body, method for plating resin molded body, and pretreatment agent |
US20110174524A1 (en) * | 2006-09-12 | 2011-07-21 | Sri International | Flexible circuits |
US7989029B1 (en) * | 2007-06-21 | 2011-08-02 | Sri International | Reduced porosity copper deposition |
WO2015006418A1 (en) * | 2013-07-09 | 2015-01-15 | United Technologies Corporation | Plating adhesion promotion |
-
2016
- 2016-12-07 US US15/372,108 patent/US20170159184A1/en not_active Abandoned
Patent Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
US3684534A (en) * | 1970-07-06 | 1972-08-15 | Hooker Chemical Corp | Method for stabilizing palladium containing solutions |
US3787698A (en) * | 1972-10-11 | 1974-01-22 | Us Army | Recording of fast neutron images |
US4764401A (en) * | 1981-12-05 | 1988-08-16 | Bayer Aktiengesellschaft | Process for activating substrate surfaces for electroless metallization |
US4830880A (en) * | 1986-04-22 | 1989-05-16 | Nissan Chemical Industries Ltd. | Formation of catalytic metal nuclei for electroless plating |
US4775449A (en) * | 1986-12-29 | 1988-10-04 | General Electric Company | Treatment of a polyimide surface to improve the adhesion of metal deposited thereon |
US4937608A (en) * | 1988-08-19 | 1990-06-26 | Fuji Photo Film Co., Ltd. | Photographic processing apparatus |
US5108786A (en) * | 1989-05-01 | 1992-04-28 | Enthone-Omi, Inc. | Method of making printed circuit boards |
US5114812A (en) * | 1989-07-07 | 1992-05-19 | Hoechst Aktiengesellschaft | Electrodes for primary and secondary electric cells |
US5373629A (en) * | 1989-08-31 | 1994-12-20 | Blasberg-Oberflachentechnik Gmbh | Through-hole plate printed circuit board with resist and process for manufacturing same |
US4969842A (en) * | 1989-11-30 | 1990-11-13 | Amp Incorporated | Molded electrical connector having integral spring contact beams |
US5411795A (en) * | 1992-10-14 | 1995-05-02 | Monsanto Company | Electroless deposition of metal employing thermally stable carrier polymers |
US5302750A (en) * | 1993-05-25 | 1994-04-12 | Exxon Chemical Patents Inc. | Method for producing n-octadienol from butadiene |
US20010019928A1 (en) * | 1999-12-07 | 2001-09-06 | Susumu Takagi | Metal coated fiber materials |
US20050009334A1 (en) * | 2003-07-07 | 2005-01-13 | Semiconductor Technology Academic Research Center | Method of producing multilayer interconnection structure |
US20080029294A1 (en) * | 2004-06-01 | 2008-02-07 | Fujifilm Corporation | Multi-Layer Circuit Board And Production Method Thereof |
US20110174524A1 (en) * | 2006-09-12 | 2011-07-21 | Sri International | Flexible circuits |
US20100155255A1 (en) * | 2007-05-22 | 2010-06-24 | Okuno Chemical Industries Co., Ltd. | Pretreatment process for electroless plating of resin molded body, method for plating resin molded body, and pretreatment agent |
US7989029B1 (en) * | 2007-06-21 | 2011-08-02 | Sri International | Reduced porosity copper deposition |
WO2015006418A1 (en) * | 2013-07-09 | 2015-01-15 | United Technologies Corporation | Plating adhesion promotion |
Non-Patent Citations (1)
Title |
---|
62-223812 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190394888A1 (en) * | 2018-06-21 | 2019-12-26 | Averatek Corporation | Patterning of electroless metals |
CN112789368A (en) * | 2018-06-21 | 2021-05-11 | 艾瑞科公司 | Patterned electroless metal |
CN111005026A (en) * | 2019-12-24 | 2020-04-14 | 广东省新材料研究所 | Carbon fiber-based composite material and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11324123B2 (en) | Printed circuit nanofiber web manufacturing method | |
KR101888734B1 (en) | Fused metal nanostructured networks, fusing solutions with reducing agents and methods for forming metal networks | |
Wu et al. | Solution deposition of conformal gold coatings on knitted fabric for e‐textiles and electroluminescent clothing | |
AU635393B2 (en) | Catalytic, water-soluble polymeric films for metal coatings | |
TWI627885B (en) | Method for producing three-dimensional conductive pattern structure and material for three-dimensional molding used there | |
CN103219243A (en) | Manufacturing method of patterning metal lines | |
US20170159184A1 (en) | Metallization of low temperature fibers and porous substrates | |
CN100516348C (en) | Carbon fiber surface silica dioxide coating preparation method | |
JPS6354791B2 (en) | ||
CN111432560A (en) | Manufacturing method of ultra-low resistance flexible conductive circuit | |
CN102733179B (en) | Method for chemically plating and electroplating copper on artificial fibers and textile | |
CA1232498A (en) | Method of activating non-conducting or semi-conducting substrate with a silver compound for electroless metallisation | |
EP0280918A2 (en) | Process for metal plating of substrates | |
JP2004502055A (en) | Fabric having gold layer formed thereon and method for producing same | |
CN110983763A (en) | Chemical copper plating process suitable for clothing cotton fabric | |
JP5160057B2 (en) | Fiber material with silver plating | |
KR102119476B1 (en) | Method of manufacturing printed circuit nano-fiber web, printed circuit nano-fiber web thereby and electronic device comprising the same | |
JPH10500734A (en) | Catalytic crosslinked polymer film for metal electroless deposition | |
CN109183392B (en) | Graphene modified conductive cellulose fiber and preparation method and application thereof | |
JP3682526B2 (en) | Method for producing internal metallized polymer composite | |
JP6085833B2 (en) | Electroless plating method on paper | |
JP2628659B2 (en) | Manufacturing method of metal fiber body | |
KR100344958B1 (en) | Method for making conductive fabric | |
JP2003286588A (en) | Process for preparing composite conductive material | |
JP5117656B2 (en) | Electroless plating pretreatment method and conductive material using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: AVERATEK CORPORATION, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SHARMA, SUNITY K.;VINSON, MICHAEL RILEY;KADIWALA, DIVYAKANT P.;REEL/FRAME:044034/0050 Effective date: 20161220 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |