US20020139457A1 - Method of suppressing the oxidation characteristics of nickel - Google Patents

Method of suppressing the oxidation characteristics of nickel Download PDF

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Publication number
US20020139457A1
US20020139457A1 US09/824,321 US82432101A US2002139457A1 US 20020139457 A1 US20020139457 A1 US 20020139457A1 US 82432101 A US82432101 A US 82432101A US 2002139457 A1 US2002139457 A1 US 2002139457A1
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Prior art keywords
powder
alloy
weight
melting point
temperature
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Abandoned
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US09/824,321
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Vito Coppola
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Vishay Vitramon Inc
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Vishay Vitramon Inc
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Publication date
Application filed by Vishay Vitramon Inc filed Critical Vishay Vitramon Inc
Priority to US09/824,321 priority Critical patent/US20020139457A1/en
Priority to PCT/US2001/010897 priority patent/WO2002077306A1/en
Priority to EP01924652A priority patent/EP1370701A1/en
Priority to JP2002575343A priority patent/JP4197951B2/en
Assigned to VISHAY INTERTECHNOLOGY, INC. reassignment VISHAY INTERTECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COPPOLA, VITO A
Priority to US10/047,709 priority patent/US6723280B2/en
Assigned to VISHAY VITRAMON INCORPORATED reassignment VISHAY VITRAMON INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VISHAY INTERTECHNOLOGY, INC.
Publication of US20020139457A1 publication Critical patent/US20020139457A1/en
Priority to US11/219,792 priority patent/US7208218B2/en
Abandoned legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/005Electrodes
    • H01G4/008Selection of materials
    • H01G4/0085Fried electrodes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0433Nickel- or cobalt-based alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02Contact members
    • H01R13/03Contact members characterised by the material, e.g. plating, or coating materials
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092Dispersed materials, e.g. conductive pastes or inks
    • 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
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49117Conductor or circuit manufacturing

Definitions

  • Ni nickel
  • This element will oxidize, before the ceramic components in the system have matured, to form a multilayer capacitor consisting of alternating layers of Ni as the conductive plates to form a capacitor.
  • This resultant Ni oxidation can stress the capacitor during the heating cycle, which creates physical defects, such as cracks in the ceramic body.
  • One way to overcome this, which has become very well known in the industry is to use a ceramic capacitor system, which can be fired under an inert or reducing atmosphere, thus not allowing the Ni to oxidize through the thermal processing.
  • this requires the use of reduction resistant ceramics dielectric materials that are typically formulated with expensive high purity oxides and carbonates.
  • the firing process requires expensive kilns with very critical controls for gas flow.
  • a further object of the invention is to produce an alloy of Ni powder and Pt resinate wherein the two ingredients are heated to a temperature of between 500° C. and the respective melting points thereof to create an Ni/Pt alloy.
  • Electro-conductive components serving as electrodes and the like comprise an Ni/Pt alloy created by subjecting the above components to the above temperature range.
  • FIG. 1 is a graph showing the oxidation of Ni Powder (95%) mixed with (5%) by weight of Pt and subjected to various concentrations of heat.
  • the resulting Ni/Pt alloy was then removed from the substrate and tested with the DTA/TGA along with the control Ni/Pt alloy, to measure it's oxidation resistance. No difference in the oxidation characteristic of the control Ni/Pt alloy and this quick heat treated alloy was seen.
  • Pt resinate (a liquid) was used as a convenience.
  • Pt powder in the same proportions can be mixed with Ni powder and then heat treated as described herein to achieve the same resulting alloy.
  • Several samples of this Ni/Pt powder were prepared in the manner described above and heat treated at various different temperature and time to determine if this system might require more heat energy to allow the Pt to alloy with the Ni.
  • the heat treatment profiles were as follows: 500° C. for 4 hours, 1000° C. for 6 hours and 1300° C. for 6 hours.
  • each of the samples was heat treated in a high temperature nitrogen and form gas capable furnace, in an atmosphere of forming gas (1% hydrogen, balance nitrogen).
  • the samples were tested with the DTA/TGA for oxidation characteristics. (See FIG. 1).
  • the 500° C. heat treat sample clearly showed the Ni powder oxidation start point had shifted to 500° C.
  • the oxidation point of the 1000° C. heat treat samples shifted further to between 700° C. and 800° C.
  • the 1300° C. heat treat samples performed even better, shifting the oxidation start point to over 1000° C.
  • a repeat sample was prepared and heat treated at 1300° C. and it performed similar to the previous run.
  • FIG. 1 shows 5 curves on a graph which show the oxidation rate of the 95/5% mixture of Ni and Pt subjected to different temperatures. The increase in weight is caused by the additional weight of NiO produced by the oxidation of the Ni.
  • Ni/Pt Ni/Pt
  • SMT Surface Mount Technology

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Ceramic Capacitors (AREA)

Abstract

A method of providing a resistance to oxidation of Nickel at high temperatures by combining Ni powder with five percent Pt resinate, and heating the same to a temperature of 500° C. to 1300° C. Electro-conductive components serving as electrodes and the like comprise a Ni/Pt powder subjected to temperatures of between 500° C. and the respective melting points of Ni and Pt.

Description

    CROSS REFERENCE TO A RELATED APPLICATION
  • This application is based upon Provisional Application Serial No. ______ filed Mar. 21, 2001.[0001]
  • BACKGROUND OF THE INVENTION
  • One of the major problems for using nickel (Ni) in an air firing ceramic system in the capacitor industry is that this element will oxidize, before the ceramic components in the system have matured, to form a multilayer capacitor consisting of alternating layers of Ni as the conductive plates to form a capacitor. This resultant Ni oxidation can stress the capacitor during the heating cycle, which creates physical defects, such as cracks in the ceramic body. One way to overcome this, which has become very well known in the industry is to use a ceramic capacitor system, which can be fired under an inert or reducing atmosphere, thus not allowing the Ni to oxidize through the thermal processing. Unfortunately, this requires the use of reduction resistant ceramics dielectric materials that are typically formulated with expensive high purity oxides and carbonates. Furthermore the firing process requires expensive kilns with very critical controls for gas flow. [0002]
  • It has been known in various literatures that platinum (Pt) has the capability to suppress oxidation on various metals. It has also been known that Pt suppresses the oxidation characteristics on palladium (Pd). Heretofore, Pt has not been used to suppress the oxidation characteristics of Ni. [0003]
  • It is therefore a principal object of this invention to provide a method for suppressing the high temperature oxidation resistance of Ni through the use of Pt. [0004]
  • A further object of the invention is to produce an alloy of Ni powder and Pt resinate wherein the two ingredients are heated to a temperature of between 500° C. and the respective melting points thereof to create an Ni/Pt alloy. [0005]
  • These and other objects will be apparent to those skilled in the art. [0006]
  • SUMMARY OF THE INVENTION
  • A method of providing a resistance to oxidation of Ni at high temperatures by combining Ni powder with five percent Pt resinate, and heating the same to a temperature of 500° C. to the respective melting points of Ni and Pt to create a Ni/Pt alloy. Electro-conductive components serving as electrodes and the like comprise an Ni/Pt alloy created by subjecting the above components to the above temperature range.[0007]
  • DESCRIPTION OF THE DRAWING
  • FIG. 1 is a graph showing the oxidation of Ni Powder (95%) mixed with (5%) by weight of Pt and subjected to various concentrations of heat.[0008]
  • DESCRIPTION OF THE PREFERRED EMBODIMENT
  • An experiment was conducted with coating a Ni powder using a Pt resinate. Ten grams of Ni powder and Pt resinate (liquid) which when reduced to pure metal would be 5% of the total metal sample weight, were milled in a glass jar with a [0009] 4 ZrO2 media in alcohol. The sample was dried and screened through a 100 mesh sieve. One gram of Ni/Pt powder was mixed with one gram of electrode medium to form a paste, which was painted onto an Al2O3 substrate.
  • The Al[0010] 2O3 substrate, with the Ni/Pt sample painted thereon, was heat treated through a nitrogen atmosphere thick film firing furnace, using a 900° C. peak temperature profile, under the nitrogen atmosphere so that the sample would not oxidize during the cycle. The resulting Ni/Pt alloy was then removed from the substrate and tested with the DTA/TGA along with the control Ni/Pt alloy, to measure it's oxidation resistance. No difference in the oxidation characteristic of the control Ni/Pt alloy and this quick heat treated alloy was seen.
  • It should be understood that the use of Pt resinate (a liquid) was used as a convenience. Pt powder in the same proportions can be mixed with Ni powder and then heat treated as described herein to achieve the same resulting alloy. Several samples of this Ni/Pt powder were prepared in the manner described above and heat treated at various different temperature and time to determine if this system might require more heat energy to allow the Pt to alloy with the Ni. The heat treatment profiles were as follows: 500° C. for 4 hours, 1000° C. for 6 hours and 1300° C. for 6 hours. [0011]
  • Each of the samples was heat treated in a high temperature nitrogen and form gas capable furnace, in an atmosphere of forming gas (1% hydrogen, balance nitrogen). The samples were tested with the DTA/TGA for oxidation characteristics. (See FIG. 1). [0012]
  • The 500° C. heat treat sample clearly showed the Ni powder oxidation start point had shifted to 500° C. The oxidation point of the 1000° C. heat treat samples shifted further to between 700° C. and 800° C. The 1300° C. heat treat samples performed even better, shifting the oxidation start point to over 1000° C. A repeat sample was prepared and heat treated at 1300° C. and it performed similar to the previous run. [0013]
  • It was determined that the resistance to oxidation of the Ni was favorable from 500° C. up to the melting points of Ni and Pt (which are approximately 1453 and 1772° C., respectively). [0014]
  • FIG. 1 shows 5 curves on a graph which show the oxidation rate of the 95/5% mixture of Ni and Pt subjected to different temperatures. The increase in weight is caused by the additional weight of NiO produced by the oxidation of the Ni. [0015]
  • This result has shown that Pt resinate mixed with Ni at 5% by weight of Pt resinate (or the same proportions of Ni and Pt powder), when heat treated properly is capable of suppressing the oxidation characteristics of Ni, so that it can function as air-fireable electrode, with significant cost savings. (The resulting alloy from a mixture of Ni and Pt resinate is comprised of Ni and Pt for the “resinate” is vaporized in the heating process.) [0016]
  • Aside from the capability for multilayer ceramic capacitor conductive plates or electrodes described above, other uses of the Ni/Pt combination are possible: As an air-fireable end termination for an electronic component which requires metallization to make the component circuit broad mountable as a SMT (Surface Mount Technology) product; or as a thick film screen printable air-fireable conductor material. The production of the Ni/Pt alloy is the most significant aspect of this invention. [0017]
  • It is therefore seen that this invention will achieve its stated objectives. [0018]

Claims (17)

What is claimed is:
1. An alloy comprised of Ni and Pt subjected to a heat treatment of between 500° C. to the melting point of Pt.
2. The alloy of claim 1 wherein the alloy is produced by the heat treatment of Ni powder and Pt powder.
3. The alloy of claim 1 wherein the Ni and Pt are present in the proportions of 95% to 5% by weight, respectively.
4. The alloy of claim 2 wherein the Ni and Pt are present in the proportions of 95% to 5% by weight, respectively.
5. An alloy comprised of Ni powder and a Pt resinate subjected to a heat treatment of between 500° C. to the respective melting points of the ingredients.
6. A method of suppressing the oxidation characteristics of nickel, comprising,
combining Ni with Pt in a ratio of approximately 95% Ni powder and 5% Pt by weight, and heat treating the Ni/Pt mixture to a temperature of between 500° C. and the melting point of Pt.
7. The method of claim 6 wherein the heat treating takes place in a nitrogen atmosphere.
8. The method of claim 6 wherein the heat treating atmosphere also comprises about 1% hydrogen.
9. A method of creating an air-fireable and termination element for electronic components which requires metallization, comprising,
making an air-fireable end termination element from a combination of Ni powder with Pt in a ratio of approximately 95% Ni powder and 5% Pt by weight, and heat treating the Ni/Pt mixture to a temperature of between 500° C. and the melting point of Pt.
10. An air-fireable end termination element comprised of Ni and a Pt alloyed product heat treated to a temperature between 500° C. and the melting point of Pt.
11. The device of claim 9 wherein the proportion by weight of Ni to Pt are approximately 95%-5%, respectively.
12. An air-fireable conductor plate for capacitors comprised of Ni powder and Pt heat treated to a temperature between 500° C. and the melting point of Pt.
13. The device of claim 12 wherein the proportion by weight of Ni to Pt is approximately 95%-5%, respectively.
14. A thick film screen printable fireable conductor material comprised of Ni powder and Pt heat treated to a temperature between 500° C. and the melting point of Pt.
15. The device of claim 14 wherein the proportion by weight of Ni to Pt are approximately 95%-5%, respectively.
16. The method of making an alloy of Ni and Pt, comprising, combining Ni powder with Pt,
subjecting the same to a temperature of 500° C. to the melting point of Pt, to create an alloy of Ni and Pt.
17. The method of claim 16 wherein the Ni powder is mixed with the Pt in a ratio of 95-5%, respectively, by weight.
US09/824,321 2001-03-21 2001-04-02 Method of suppressing the oxidation characteristics of nickel Abandoned US20020139457A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US09/824,321 US20020139457A1 (en) 2001-04-02 2001-04-02 Method of suppressing the oxidation characteristics of nickel
PCT/US2001/010897 WO2002077306A1 (en) 2001-03-21 2001-04-04 Method of suppressing the oxidation characteristics of nickel
EP01924652A EP1370701A1 (en) 2001-03-21 2001-04-04 Method of suppressing the oxidation characteristics of nickel
JP2002575343A JP4197951B2 (en) 2001-03-21 2001-04-04 Method for suppressing the oxidation properties of nickel
US10/047,709 US6723280B2 (en) 2001-04-02 2002-01-15 Method of suppressing the oxidation characteristics of nickel
US11/219,792 US7208218B2 (en) 2001-03-21 2005-09-06 Method of suppressing the oxidation characteristics of nickel

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Application Number Priority Date Filing Date Title
US09/824,321 US20020139457A1 (en) 2001-04-02 2001-04-02 Method of suppressing the oxidation characteristics of nickel

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US10/047,709 Division US6723280B2 (en) 2001-04-02 2002-01-15 Method of suppressing the oxidation characteristics of nickel
US11/219,792 Division US7208218B2 (en) 2001-03-21 2005-09-06 Method of suppressing the oxidation characteristics of nickel

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1594146A1 (en) * 2003-02-05 2005-11-09 TDK Corporation Electronic parts and method for manufacture thereof

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JP4197951B2 (en) * 2001-03-21 2008-12-17 ヴィシェイ インターテクノロジー,インコーポレーティッド Method for suppressing the oxidation properties of nickel
EP2468906B1 (en) * 2004-03-01 2014-07-23 JX Nippon Mining & Metals Corporation Method of manufacturing a Ni-Pt alloy
JP4513981B2 (en) * 2005-03-31 2010-07-28 Tdk株式会社 Multilayer ceramic electronic component and manufacturing method thereof
CN110230019A (en) * 2019-06-14 2019-09-13 广东省新材料研究所 A kind of metal material and its surface in situ dissolve out method of modifying
CN112410608A (en) * 2020-11-17 2021-02-26 昆山全亚冠环保科技有限公司 Nickel-platinum alloy sputtering target material and preparation method thereof

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JPS6333563A (en) 1986-07-25 1988-02-13 Tanaka Kikinzoku Kogyo Kk Production of pt-ni alloy for sputtering
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP1594146A1 (en) * 2003-02-05 2005-11-09 TDK Corporation Electronic parts and method for manufacture thereof
EP1594146A4 (en) * 2003-02-05 2010-01-06 Tdk Corp Electronic parts and method for manufacture thereof

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US6723280B2 (en) 2004-04-20

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