US20130302636A1 - Porous metal article and about method for manufacturing same - Google Patents

Porous metal article and about method for manufacturing same Download PDF

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Publication number
US20130302636A1
US20130302636A1 US13/942,233 US201313942233A US2013302636A1 US 20130302636 A1 US20130302636 A1 US 20130302636A1 US 201313942233 A US201313942233 A US 201313942233A US 2013302636 A1 US2013302636 A1 US 2013302636A1
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Prior art keywords
metal layer
porous metal
porous
substrate
micrometers
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US13/942,233
Inventor
Hsin-Pei Chang
Wen-Rong Chen
Huann-Wu Chiang
Cheng-Shi Chen
Lone-Wen Tai
Shun-Mao Lin
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Priority to US13/942,233 priority Critical patent/US20130302636A1/en
Assigned to HON HAI PRECISION INDUSTRY CO., LTD., HONG FU JIN PRECISION INDUSTRY (SHENZHEN) CO., LTD. reassignment HON HAI PRECISION INDUSTRY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHANG, HSIN-PEI, CHEN, Cheng-shi, CHEN, WEN-RONG, CHIANG, HUANN-WU, LIN, Shun-mao, TAI, LONE-WEN
Publication of US20130302636A1 publication Critical patent/US20130302636A1/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00Electrolytic etching or polishing
    • C25F3/02Etching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12479Porous [e.g., foamed, spongy, cracked, etc.]

Definitions

  • the exemplary disclosure generally relates to porous metal articles and methods for manufacturing the porous metal articles.
  • Noble metals such as ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold, are resistant to corrosion and oxidation in moist air. Therefore these materials can be used as accelerators for purifying exhaust gas.
  • the accelerating function of the noble metals is much related to their surfaces.
  • a typical way to improve the accelerating function of the noble metals, is introducing porous holes in their surfaces. However, porous holes in noble metals surfaces may still result.
  • the FIGURE illustrates a cross-sectional view of an exemplary embodiment of an porous metal article.
  • an exemplary method for manufacturing a porous metal article 10 may include the least the following steps.
  • the substrate 11 is pretreated.
  • the substrate 11 is washed with a solution (e.g., NaOH), and then washed with a deionized water, to remove grease, dirt, and/or impurities, followed by drying.
  • a solution e.g., NaOH
  • a green coating is formed on the substrate 11 by hot-tip coating process.
  • the green coating includes a noble metal and M, wherein M comprises at least one selected from the group consisting of zinc, aluminum, magnesium and calcium.
  • the content of M in the green coating is between about 30 wt % and about 70 wt % of the total weight of noble metal, M.
  • the noble metal comprises at least one selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.
  • the substrate 11 passes through a molten bath of noble metal and M at a temperature that is above a melting point of a noble metal M alloy about 50 Celsius degree (° C.), for about 1 minute to about 3 minutes.
  • the green coating has a thickness between about 5 micrometers and about 10 minutes.
  • the green coating on the substrate 11 is electrochemically etched to remove M from an outer surface of the green coating to form a porous silicon layer 15 on the outer surface of the green coating.
  • the portion of the green coating in which M is not removed forms a metal layer 13 on the substrate 11 .
  • the green coating acts as an anode
  • a platinum plate acts as cathode, using hydrochloric acid, formic acid, acetic acid, oxalic acid or sulphuric acid as electrolyte.
  • the content of the hydrochloric acid or sulphuric acid is between about 3 wt % and about 15 wt % of the total weight of the electrolyte.
  • a constant power applied between the anode and the cathode may have a voltage between about 2 volts and about 5 volts, a current density between about 0.5 mA/cm2 and about 4 mA/cm 2 for about 5 minutes to about 20 minutes to form the porous metal layer 15 .
  • the porous metal layer 15 has a thickness between 2 micrometers and 4 micrometers.
  • the porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size between about 50 nanometers (nm) and about 120 nm.
  • the porous metal article 10 manufactured by the present method includes a substrate 11 , a metal layer 13 formed on the substrate 11 , and a porous metal layer 15 formed on the metal layer 13 .
  • the substrate 11 is made of stainless steel or plastic.
  • the metal layer 13 includes a noble metal and M, wherein M comprises at least one selected from the group consisting of aluminum, magnesium and calcium.
  • the content of M in the metal layer 13 is between about 30 wt % and about 70 wt % of the total weight of noble metal, M.
  • the noble metal is at least one selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.
  • the metal layer 13 has a thickness between about 1 micrometer and about 8 micrometers.
  • the porous metal layer 15 has a thickness between about 2 micrometers and about 4 micrometers.
  • the porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size between about 50 nanometers (nm) and about 120 nm.
  • the substrate 11 passes through a molten bath of golden and calcium at a temperature of about 950 V, for about 3 minutes.
  • the green coating has a thickness of about 10 micrometers.
  • golden-to-calcium mass ratio is about 1:2.
  • the green coating is electrochemically etched to form a porous silicon layer 15 .
  • the green coating acts as an anode
  • a platinum plate acts as cathode
  • using sulphuric acid as electrolyte The content of the sulphuric acid is about 15 wt % of the total weight of the electrolyte.
  • a constant power applied between the anode and the cathode may have a voltage about of about 5 volts, a current density of about 4 mA/cm 2 for about 20 minutes to form the porous metal layer 15 .
  • the porous metal layer 15 has a thickness of about 4 micrometers.
  • the porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 50 nm.
  • the substrate 11 passes through a molten bath of palladium and magnesium at a temperature of about 1350° C., for about 2 minutes.
  • the green coating has a thickness of about 5 micrometers.
  • golden-to-magnesium mass ratio is about 63.7:36.3.
  • the green coating is electrochemically etched to form a porous silicon layer 15 .
  • the green coating acts as an anode
  • a platinum plate acts as cathode
  • acetic acid as electrolyte.
  • the content of the acetic acid is about 3 wt % of the total weight of the electrolyte.
  • a constant power applied between the anode and the cathode may have a voltage about 3 volts, a current density of about 0.5 mA/cm 2 for about 5 minutes to form the porous metal layer 15 .
  • the porous metal layer 15 has a thickness of about 2 micrometers.
  • the porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 120 nm.
  • the substrate 11 passes through a molten bath of platinum, ruthenium and aluminum at a temperature of about 1127° C., for about 3 minutes.
  • the green coating has a thickness of about 10 micrometers.
  • platinum-to-ruthenium-to-aluminum mass ratio is about 25:25:50.
  • the green coating is electrochemically etched to form a porous silicon layer 15 .
  • the green coating acts as an anode
  • a platinum plate acts as cathode
  • hydrochloric acid as electrolyte.
  • the content of the hydrochloric acid is about 10 wt % of the total weight of the electrolyte.
  • a constant power applied between the anode and the cathode may have a voltage about 3 volts, a current density of about 3.5 mA/cm 2 for about 15 minutes to form the porous metal layer 15 .
  • the porous metal layer 15 has a thickness of about 6 micrometers.
  • the porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 80 nm.
  • the substrate 11 passes through a molten bath of iridium, osmium and magnesium at a temperature of about 950° C., for about 2 minutes.
  • the green coating has a thickness of about 5 micrometers.
  • iridium-to-osmium-to-magnesium mass ratio is about 30:30:40.
  • the green coating is electrochemically etched to form a porous silicon layer 15 .
  • the green coating acts as an anode
  • a platinum plate acts as cathode
  • using formic acid and sulphuric acid as electrolyte is about 5 wt % of the total weight of the electrolyte.
  • a constant power applied between the anode and the cathode may have a voltage about 5 volts, a current density of about 3 mA/cm 2 for about 6 minutes to form the porous metal layer 15 .
  • the porous metal layer 15 has a thickness of about 3 micrometers.
  • the porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 60 nm.
  • the substrate 11 passes through a molten bath of platinum, silver and aluminum at a temperature of about 1400° C., for about 3 minutes.
  • the green coating has a thickness of about 10 micrometers.
  • platinum-to-silver-to-aluminum mass ratio is about 35:35:30.
  • the green coating is electrochemically etched to form a porous silicon layer 15 .
  • the green coating acts as an anode
  • a platinum plate acts as cathode, using hydrochloric acid and oxalic acid as electrolyte.
  • the content of the hydrochloric acid and oxalic acid is about 3 wt % of the total weight of the electrolyte.
  • a constant power applied between the anode and the cathode may have a voltage about 4 volts, a current density of about 3 mA/cm 2 for about 17 minutes to form the porous metal layer 15 .
  • the porous metal layer 15 has a thickness of about 4 micrometers.
  • the porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 80 nm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
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  • ing And Chemical Polishing (AREA)
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Abstract

A porous metal article includes a substrate, a metal layer formed on the substrate, and a porous metal layer formed on the metal layer. The metal layer is a noble metal layer doped with M, M comprising an element selected from the group consisting of magnesium and calcium, the content of M in the metal layer is between about 30 wt % and about 70 wt %.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a divisional application of U.S. Ser. No. 13/217,915, filed Aug. 25, 2011, the contents of which are hereby incorporated by reference. The patent application Ser. No. 13/217,915 in turn claims the benefit of priority under 35 USC 119 from Chinese Patent Application 201110070389.3, filed on Mar. 23, 2011.
  • This application is one of the three related co-pending U.S. patent applications listed below. All listed applications have the same assignee. The disclosure of each of the listed applications is incorporated by reference into another listed application.
  • U.S. Ser. No. Title Inventors
    13/217,915 POROUS METAL ARTICLE AND HSIN-PEI
    ABOUT METHOD FOR CHANG et al.
    MANUFACTURING SAME
    13/217,906 POROUS SILICON ARTICLE AND HSIN-PEI
    ABOUT METHOD FOR CHANG et al.
    MANUFACTURING SAME
    13/217,909 POROUS METAL ARTICLE AND HSIN-PEI
    ABOUT METHOD FOR CHANG et al.
    MANUFACTURING SAME
  • BACKGROUND
  • 1. Technical Field
  • The exemplary disclosure generally relates to porous metal articles and methods for manufacturing the porous metal articles.
  • 2. Description of Related Art
  • Noble metals, such as ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold, are resistant to corrosion and oxidation in moist air. Therefore these materials can be used as accelerators for purifying exhaust gas. The accelerating function of the noble metals is much related to their surfaces. A typical way to improve the accelerating function of the noble metals, is introducing porous holes in their surfaces. However, porous holes in noble metals surfaces may still result.
  • Therefore, there is room for improvement within the art.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Many aspects of the exemplary embodiments can be better understood with reference to the following drawings. The components in the drawings are not necessarily drawn to scale, the emphasis instead being placed upon clearly illustrating the principles of the exemplary embodiment of a porous metal article and method for manufacturing the porous metal article. Moreover, in the drawings like reference numerals designate corresponding parts throughout the several views. Wherever possible, the same reference numbers are used throughout the drawings to refer to the same or like elements of an exemplary embodiment.
  • The FIGURE illustrates a cross-sectional view of an exemplary embodiment of an porous metal article.
  • DETAILED DESCRIPTION
  • Referring to Figure, an exemplary method for manufacturing a porous metal article 10 may include the least the following steps.
  • Providing a substrate 11 made of plastic or stainless steel.
  • The substrate 11 is pretreated. For example, the substrate 11 is washed with a solution (e.g., NaOH), and then washed with a deionized water, to remove grease, dirt, and/or impurities, followed by drying.
  • A green coating is formed on the substrate 11 by hot-tip coating process. The green coating includes a noble metal and M, wherein M comprises at least one selected from the group consisting of zinc, aluminum, magnesium and calcium. The content of M in the green coating is between about 30 wt % and about 70 wt % of the total weight of noble metal, M. The noble metal comprises at least one selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. During forming the green coating, the substrate 11 passes through a molten bath of noble metal and M at a temperature that is above a melting point of a noble metal M alloy about 50 Celsius degree (° C.), for about 1 minute to about 3 minutes. The green coating has a thickness between about 5 micrometers and about 10 minutes.
  • The green coating on the substrate 11 is electrochemically etched to remove M from an outer surface of the green coating to form a porous silicon layer 15 on the outer surface of the green coating. The portion of the green coating in which M is not removed forms a metal layer 13 on the substrate 11. During electrochemical etching, the green coating acts as an anode, a platinum plate acts as cathode, using hydrochloric acid, formic acid, acetic acid, oxalic acid or sulphuric acid as electrolyte. The content of the hydrochloric acid or sulphuric acid is between about 3 wt % and about 15 wt % of the total weight of the electrolyte. A constant power applied between the anode and the cathode may have a voltage between about 2 volts and about 5 volts, a current density between about 0.5 mA/cm2 and about 4 mA/cm2 for about 5 minutes to about 20 minutes to form the porous metal layer 15. The porous metal layer 15 has a thickness between 2 micrometers and 4 micrometers. The porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size between about 50 nanometers (nm) and about 120 nm.
  • The porous metal article 10 manufactured by the present method includes a substrate 11, a metal layer 13 formed on the substrate 11, and a porous metal layer 15 formed on the metal layer 13. The substrate 11 is made of stainless steel or plastic. The metal layer 13 includes a noble metal and M, wherein M comprises at least one selected from the group consisting of aluminum, magnesium and calcium. The content of M in the metal layer 13 is between about 30 wt % and about 70 wt % of the total weight of noble metal, M. The noble metal is at least one selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold. The metal layer 13 has a thickness between about 1 micrometer and about 8 micrometers. The porous metal layer 15 has a thickness between about 2 micrometers and about 4 micrometers. The porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size between about 50 nanometers (nm) and about 120 nm.
  • EXAMPLES
  • Experimental examples of the present disclosure are following.
  • Example 1
  • 1. Forming the green coating on the substrate 11 made of stainless steel, such as type 304 stainless.
  • The substrate 11 passes through a molten bath of golden and calcium at a temperature of about 950 V, for about 3 minutes. The green coating has a thickness of about 10 micrometers. In this exemplary embodiment, golden-to-calcium mass ratio is about 1:2.
  • 2. The green coating is electrochemically etched to form a porous silicon layer 15.
  • The green coating acts as an anode, a platinum plate acts as cathode, using sulphuric acid as electrolyte. The content of the sulphuric acid is about 15 wt % of the total weight of the electrolyte. A constant power applied between the anode and the cathode may have a voltage about of about 5 volts, a current density of about 4 mA/cm2 for about 20 minutes to form the porous metal layer 15. The porous metal layer 15 has a thickness of about 4 micrometers. The porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 50 nm.
  • Example 2
  • 1. Forming the green coating on the substrate 11 made of ceramic, such as aluminum oxide.
  • The substrate 11 passes through a molten bath of palladium and magnesium at a temperature of about 1350° C., for about 2 minutes. The green coating has a thickness of about 5 micrometers. In this exemplary embodiment, golden-to-magnesium mass ratio is about 63.7:36.3.
  • 2. The green coating is electrochemically etched to form a porous silicon layer 15.
  • The green coating acts as an anode, a platinum plate acts as cathode, using acetic acid as electrolyte. The content of the acetic acid is about 3 wt % of the total weight of the electrolyte. A constant power applied between the anode and the cathode may have a voltage about 3 volts, a current density of about 0.5 mA/cm2 for about 5 minutes to form the porous metal layer 15. The porous metal layer 15 has a thickness of about 2 micrometers. The porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 120 nm.
  • Example 3
  • 1. Forming the green coating on the substrate 11 made of ceramic, such as aluminum oxide.
  • The substrate 11 passes through a molten bath of platinum, ruthenium and aluminum at a temperature of about 1127° C., for about 3 minutes. The green coating has a thickness of about 10 micrometers. In this exemplary embodiment, platinum-to-ruthenium-to-aluminum mass ratio is about 25:25:50.
  • 2. The green coating is electrochemically etched to form a porous silicon layer 15.
  • The green coating acts as an anode, a platinum plate acts as cathode, using hydrochloric acid as electrolyte. The content of the hydrochloric acid is about 10 wt % of the total weight of the electrolyte. A constant power applied between the anode and the cathode may have a voltage about 3 volts, a current density of about 3.5 mA/cm2 for about 15 minutes to form the porous metal layer 15. The porous metal layer 15 has a thickness of about 6 micrometers. The porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 80 nm.
  • Example 4
  • 1. Forming the green coating on the substrate 11 made of stainless steel, such as type 304 stainless.
  • The substrate 11 passes through a molten bath of iridium, osmium and magnesium at a temperature of about 950° C., for about 2 minutes. The green coating has a thickness of about 5 micrometers. In this exemplary embodiment, iridium-to-osmium-to-magnesium mass ratio is about 30:30:40.
  • 2. The green coating is electrochemically etched to form a porous silicon layer 15.
  • The green coating acts as an anode, a platinum plate acts as cathode, using formic acid and sulphuric acid as electrolyte. The content of the formic acid and sulphuric acid is about 5 wt % of the total weight of the electrolyte. A constant power applied between the anode and the cathode may have a voltage about 5 volts, a current density of about 3 mA/cm2 for about 6 minutes to form the porous metal layer 15. The porous metal layer 15 has a thickness of about 3 micrometers. The porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 60 nm.
  • Example 5
  • 1. Forming the green coating on the substrate 11 made of ceramic, such as aluminum oxide.
  • The substrate 11 passes through a molten bath of platinum, silver and aluminum at a temperature of about 1400° C., for about 3 minutes. The green coating has a thickness of about 10 micrometers. In this exemplary embodiment, platinum-to-silver-to-aluminum mass ratio is about 35:35:30.
  • 2. The green coating is electrochemically etched to form a porous silicon layer 15.
  • The green coating acts as an anode, a platinum plate acts as cathode, using hydrochloric acid and oxalic acid as electrolyte. The content of the hydrochloric acid and oxalic acid is about 3 wt % of the total weight of the electrolyte. A constant power applied between the anode and the cathode may have a voltage about 4 volts, a current density of about 3 mA/cm2 for about 17 minutes to form the porous metal layer 15. The porous metal layer 15 has a thickness of about 4 micrometers. The porous metal layer 15 defines a plurality of nano-pores, and each nano-pore has a pore opening size of about 80 nm.
  • It is to be understood, however, that even through numerous characteristics and advantages of the exemplary disclosure have been set forth in the foregoing description, together with details of the system and function of the disclosure, the disclosure is illustrative only, and changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the disclosure to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.

Claims (8)

What is claimed is:
1. A porous metal article, comprising:
a substrate;
a metal layer formed on the substrate ; and
a porous noble metal layer formed on the metal layer;
wherein the metal layer comprises a noble metal and an element M, wherein M comprises an element selected from the group consisting of magnesium and calcium, the content of M in the metal layer is between about 30 wt % and about 70 wt %.
2. The porous metal article as claimed in claim 1, wherein the porous metal layer defines a plurality of nano-pores, and each nano-pore has a pore opening size between about 50 nm and about 120 nm.
3. The porous metal article as claimed in claim 1, wherein the metal layer has a thickness between about 1 micrometer and about 8 micrometers.
4. The porous metal article as claimed in claim 1, wherein the noble metal is one element selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.
5. The porous metal article as claimed in claim 1, wherein the porous metal layer has a thickness between about 2 micrometers and about 4 micrometers.
6. The porous metal article as claimed in claim 1, wherein the substrate is made of stainless steel or ceramic.
7. The porous metal article as claimed in claim 6, wherein the ceramic is silicone carbide.
8. The porous metal article as claimed in claim 7, wherein the stainless steel is type 304 stainless.
US13/942,233 2011-03-23 2013-07-15 Porous metal article and about method for manufacturing same Abandoned US20130302636A1 (en)

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