US3929513A - Lead alloy products - Google Patents
Lead alloy products Download PDFInfo
- Publication number
- US3929513A US3929513A US162605A US16260571A US3929513A US 3929513 A US3929513 A US 3929513A US 162605 A US162605 A US 162605A US 16260571 A US16260571 A US 16260571A US 3929513 A US3929513 A US 3929513A
- Authority
- US
- United States
- Prior art keywords
- product
- grains
- lead
- lead alloy
- percent
- 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.)
- Expired - Lifetime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/02—Alloys based on lead with an alkali or an alkaline earth metal as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/12—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of lead or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- ABSTRACT A corrosion resistant lead alloy product having a thin surface layer of large elongated grains overlying a matrix of substantially smaller grains or crystals having random orientation.
- This invention relates generally to corrosion resistant lead alloy products and, more specifically, to corrosion resistant calcium-lead alloy products for use in pressure cast battery grids.
- the pressure cast method of producing battery grids is greatly preferred because pressure cast grids can be made faster and cheaper than gravity cast grids. However, pressure cast grids are susceptible to corrosion. Because of their susceptibility to corrosion, pressure cast battery grids have been used for negative grids while positive grids have been made from more corrosion-resistant gravity castings.
- corrosion resistance is directly related to the area of the grain boundaries and the greater the grain boundary area, the more susceptible to corrosion is the grid.
- the narrow grain boundaries produced by fine grain structures should have superior corrosion resistance to the wider grain boundaries such as found in the large grain structures of gravity castings.
- the fine grain structure resulting from the rapid solidification of pressure casting produces highly-stressed, narrow grain boundaries that corrode much more rapidly than the stress-free wide boundaries found in gravity castings. Consequently, positive battery grids have been gravity cast to improve their corrosion resistance.
- FIG. 1 in the accompanying drawings is a photomicrograph of a calcium-lead alloy produced in accordance with the invention and shows, in cross-section, a monograin layer along the surface of the heat-treated specimen;
- FIG. 2 shows a portion of a battery grid
- FIG. 3 shows an enlarged portion of the grid surface shown in FIG. 2;
- FIG. 4 is a sectional view of the grid segment of FIG. 3.
- Battery grids are well known in the art and although 5 they may take a variety of forms, shapes and sizes, they typically have a screen-like structure which is sufficiently strong to support the battery plates. Normally, some alloying element such as calcium or lithium are added to the lead to produce a lead alloy having sufficient structural strength to support both the grid and the active material applied to the grid.
- One such grid contains an amount of calcium ranging from 0.05 percent to 0.07 percent by weight in the lead.
- These grids vary greatly in design, however, they generally have protrusions which can be connected to other grids or plates by welding or the like, or the grids can also be attached to the battery terminal post.
- pure lead would provide the best electrochemical performance but experience has shown that grids of this nature are of insufficient strength for use in the ordinary lead-acid battery. Therefore, as previously mentioned, the lead must be alloyed with some type of hardening or strengthening agent such as calcium or lithium.
- the preferred method of manufacturing calcium-lead battery grids is by the pressure casting process. In this process, the lead alloy is forced into a mold under pressure thereby quickly producing a battery grid. Battery grids produced by pressure casting contain a fine grain structure in contrast to the large grain structure found in the slower cooled gravity castings. However, these pressure cast battery grids contain a large number of highly stressed grain boundaries where rapid corrosion occurs.
- the heat-treating and quenching of the battery grid greatly reduces the exterior grain boundary area by producing a surface layer of grains that are thinner, larger, and longer than the matrix of grains on the interior of the battery grid.
- this surface layer has a thickness ranging on the order from 0.6 to 1.2 mils.
- This type of surface layer is referred to herein as a monograin surface layer or a monocrystalline surface layer because the thickness of the layer is only one grain, i.e., only one layer of thin, elongated grains is formed along the outer surface.
- Heat-treating a battery grid in accordance with my invention converts the small numerous surface grains into a significantly lesser number of thin larger surface grains thereby greatly reducing the grain boundary area. This phenomenon occurs only along the surface layer as the interior grains do not grow as rapidly in the elongated direction.
- the reduction of the surface grain boundary area reduces significantly the susceptibility to corrosion which occurs at grain boundaries to thereby produce a battery grid having greatly enhanced corrosion resistance with little sacrifice of grid strength.
- FIG. 1 shows an actual photomicrograph of the grain structure of the exterior and the interior of the lead alloy product of my invention.
- FIG. 2 shows a portion of a battery grid 10 employing my monograin surface layers.
- the battery grid shown is of the type having an offset web with rounded corners.
- Reference numeral 11 designates the various horizontal cross members of the grid which arestaggered or; offset to produce a stronger grid.
- a typical, radius, for the rounded corner may be 1/16 of an .inch for a grid having an opening of square inches.
- a portion of grid 10designated by reference numeral 13 has been enlarged and shown in FIG. ,3 and.
- FIG. 4. These figures more clearly show the relationship of the interior grain structure to theexterior grain structure, I
- the designated portion 13 of grid has been greatly enlarged toshow theappearance of the exteriorgrain structure on the surface of; the battery grid.
- The,-exterior grain structure comprises large grains having a characteristicdimension 1 andw. Di-
- mensions 1 and w arearbitrarily' assigned to indicate approximate dimensions in a mutually perpendicular axis. As the grain size is irregular and does not conform to a regular shape, it will be understood thepurpose of these dimensions is only for reference purposes.
- ary area areon the exterior of the grid, they shield the interior grains from corrosion.
- a pressure cast product having a cross-sectional thickness of about 0.175 inch to 0.180 inch requires heat treatment for a minimum of approximately 6 hours within the temperature range of about 450F to 550F. If the cross sectional thickness of the product is thicker the time'of heat treatment will increase. Likewise, if the cross sectional thickness of the product is thinner the time of heat treating will decrease. Also, for a specific product thickness and a temperature near the upper limit of the temperature range, the heat treating time will be less than what the temperatureis near the lower end of the temperature range.
- a second set of flat elongated grains located on the exterior of said product, said flat elongated grains substantially longer and wider than said irregular shaped grains; said flat, elongated grains coacting to thereby produce a surface layer on the exterior of said product having relatively few grain bound-
Abstract
Description
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US162605A US3929513A (en) | 1968-07-25 | 1971-07-14 | Lead alloy products |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74925768A | 1968-07-25 | 1968-07-25 | |
US162605A US3929513A (en) | 1968-07-25 | 1971-07-14 | Lead alloy products |
Publications (1)
Publication Number | Publication Date |
---|---|
US3929513A true US3929513A (en) | 1975-12-30 |
Family
ID=26858905
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US162605A Expired - Lifetime US3929513A (en) | 1968-07-25 | 1971-07-14 | Lead alloy products |
Country Status (1)
Country | Link |
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US (1) | US3929513A (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4948551A (en) * | 1987-08-24 | 1990-08-14 | Framatome | Method of protecting a pressurized water nuclear reactor against failures in its emergency stop means |
US20020157743A1 (en) * | 2001-02-26 | 2002-10-31 | Clark Douglas G. | Continuous extruded lead alloy strip for battery electrodes |
US20030017398A1 (en) * | 2001-07-19 | 2003-01-23 | Lu Zhang | Coated positive grid for lead-acid battery and methods of forming |
US6589298B1 (en) | 2000-05-26 | 2003-07-08 | Integran Technologies, Inc. | Surface treatment of metallic components of electrochemical cells for improved adhesion and corrosion resistance |
US20040151982A1 (en) * | 2003-01-31 | 2004-08-05 | Indian Institute Of Science | Rapid coating process and its application to lead-acid batteries |
US6921611B2 (en) | 1999-07-09 | 2005-07-26 | Johnson Controls Technology Company | Method of making a battery |
US6953641B2 (en) * | 2001-01-05 | 2005-10-11 | Johnson Controls Technology Company | Battery grid |
US7767347B2 (en) | 2005-05-23 | 2010-08-03 | Johnson Controls Technology Company | Battery grid |
US8586248B2 (en) | 2010-04-14 | 2013-11-19 | Johnson Controls Technology Company | Battery, battery plate assembly, and method of assembly |
US9130232B2 (en) | 2010-03-03 | 2015-09-08 | Johnson Controls Technology Company | Battery grids and methods for manufacturing same |
US9577266B2 (en) | 2007-03-02 | 2017-02-21 | Johnson Controls Technology Company | Negative grid for battery |
US9748578B2 (en) | 2010-04-14 | 2017-08-29 | Johnson Controls Technology Company | Battery and battery plate assembly |
US10170768B2 (en) | 2013-10-08 | 2019-01-01 | Johnson Controls Autobatterie Gmbh & Co. Kgaa | Grid assembly for a plate-shaped battery electrode of an electrochemical accumulator battery |
US10418637B2 (en) | 2013-10-23 | 2019-09-17 | Johnson Controls Autobatterie Gmbh & Co. Kgaa | Grid arrangement for plate-shaped battery electrode and accumulator |
US10892491B2 (en) | 2011-11-03 | 2021-01-12 | CPS Technology Holdings LLP | Battery grid with varied corrosion resistance |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1531784A (en) * | 1921-12-13 | 1925-03-31 | Cleveland Trust Co | Sheet metal |
US1780261A (en) * | 1928-06-08 | 1930-11-04 | Michael G Corson | Lead alloy amenable to hardening by heat treatment |
US1880746A (en) * | 1929-10-30 | 1932-10-04 | Bell Telephone Labor Inc | Lead alloy |
US1890013A (en) * | 1928-06-29 | 1932-12-06 | Western Electric Co | Lead alloy |
-
1971
- 1971-07-14 US US162605A patent/US3929513A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1531784A (en) * | 1921-12-13 | 1925-03-31 | Cleveland Trust Co | Sheet metal |
US1780261A (en) * | 1928-06-08 | 1930-11-04 | Michael G Corson | Lead alloy amenable to hardening by heat treatment |
US1890013A (en) * | 1928-06-29 | 1932-12-06 | Western Electric Co | Lead alloy |
US1880746A (en) * | 1929-10-30 | 1932-10-04 | Bell Telephone Labor Inc | Lead alloy |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4948551A (en) * | 1987-08-24 | 1990-08-14 | Framatome | Method of protecting a pressurized water nuclear reactor against failures in its emergency stop means |
US8252464B2 (en) | 1999-07-09 | 2012-08-28 | Johnson Controls Technology Company | Method of making a battery grid |
US8034488B2 (en) | 1999-07-09 | 2011-10-11 | Johnson Controls Technology Company | Battery grid |
US20100304219A1 (en) * | 1999-07-09 | 2010-12-02 | Johnson Controls Technology Company | Battery grid |
US7799463B2 (en) | 1999-07-09 | 2010-09-21 | Johnson Controls Technology Company | Method of producing battery plates |
US8709664B2 (en) | 1999-07-09 | 2014-04-29 | Johnson Controls Technology Company | Battery grid |
US6921611B2 (en) | 1999-07-09 | 2005-07-26 | Johnson Controls Technology Company | Method of making a battery |
US20050164091A1 (en) * | 1999-07-09 | 2005-07-28 | Johnson Controls Technology Company | Method of producing battery plates |
US6589298B1 (en) | 2000-05-26 | 2003-07-08 | Integran Technologies, Inc. | Surface treatment of metallic components of electrochemical cells for improved adhesion and corrosion resistance |
US6953641B2 (en) * | 2001-01-05 | 2005-10-11 | Johnson Controls Technology Company | Battery grid |
US6797403B2 (en) * | 2001-02-26 | 2004-09-28 | Teck Cominco Metals Ltd. | Continuous extruded lead alloy strip for battery electrodes |
US20020157743A1 (en) * | 2001-02-26 | 2002-10-31 | Clark Douglas G. | Continuous extruded lead alloy strip for battery electrodes |
US20030017398A1 (en) * | 2001-07-19 | 2003-01-23 | Lu Zhang | Coated positive grid for lead-acid battery and methods of forming |
US6889410B2 (en) * | 2003-01-31 | 2005-05-10 | Indian Institute Of Science | Rapid coating process and its application to lead-acid batteries |
US20040151982A1 (en) * | 2003-01-31 | 2004-08-05 | Indian Institute Of Science | Rapid coating process and its application to lead-acid batteries |
US8399135B2 (en) | 2005-05-23 | 2013-03-19 | Johnson Controls Technology Company | Battery grid |
US7955737B2 (en) | 2005-05-23 | 2011-06-07 | Johnson Controls Technology Company | Battery grid |
US7767347B2 (en) | 2005-05-23 | 2010-08-03 | Johnson Controls Technology Company | Battery grid |
US8974972B2 (en) | 2005-05-23 | 2015-03-10 | Johnson Controls Technology Company | Battery grid |
US8980419B2 (en) | 2005-05-23 | 2015-03-17 | Johnson Controls Technology Company | Battery grid |
US9577266B2 (en) | 2007-03-02 | 2017-02-21 | Johnson Controls Technology Company | Negative grid for battery |
US9130232B2 (en) | 2010-03-03 | 2015-09-08 | Johnson Controls Technology Company | Battery grids and methods for manufacturing same |
US10985380B2 (en) | 2010-04-14 | 2021-04-20 | Cps Technology Holdings Llc | Battery and battery plate assembly with highly absorbent separator |
US9748578B2 (en) | 2010-04-14 | 2017-08-29 | Johnson Controls Technology Company | Battery and battery plate assembly |
US8586248B2 (en) | 2010-04-14 | 2013-11-19 | Johnson Controls Technology Company | Battery, battery plate assembly, and method of assembly |
US11824204B2 (en) | 2010-04-14 | 2023-11-21 | Cps Technology Holdings Llc | Battery and battery plate assembly with absorbent separator |
US10892491B2 (en) | 2011-11-03 | 2021-01-12 | CPS Technology Holdings LLP | Battery grid with varied corrosion resistance |
US11539051B2 (en) | 2011-11-03 | 2022-12-27 | Cps Technology Holdings Llc | Battery grid with varied corrosion resistance |
US10170768B2 (en) | 2013-10-08 | 2019-01-01 | Johnson Controls Autobatterie Gmbh & Co. Kgaa | Grid assembly for a plate-shaped battery electrode of an electrochemical accumulator battery |
US10840515B2 (en) | 2013-10-08 | 2020-11-17 | Clarios Germany Gmbh & Co. Kgaa | Grid assembly for a plate-shaped battery electrode of an electrochemical accumulator battery |
US11611082B2 (en) | 2013-10-08 | 2023-03-21 | Clarios Germany Gmbh & Co. Kg | Grid assembly for a plate-shaped battery electrode of an electrochemical accumulator battery |
US10418637B2 (en) | 2013-10-23 | 2019-09-17 | Johnson Controls Autobatterie Gmbh & Co. Kgaa | Grid arrangement for plate-shaped battery electrode and accumulator |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GNB BATTERIES INC., 1110 HIGHWAY 110, MENDOTA HEIG Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GOULD INC.,;REEL/FRAME:004213/0299 Effective date: 19840106 |
|
AS | Assignment |
Owner name: CITIBANK, N.A. 641 LEXINGTON AVENUE NEW YORK NY 10 Free format text: SECURITY INTEREST;ASSIGNOR:GNB BATTERIES INC.;REEL/FRAME:004253/0176 Effective date: 19840406 |
|
AS | Assignment |
Owner name: GNB INCORPORATED Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:004508/0472 Effective date: 19840406 |
|
AS | Assignment |
Owner name: GNB INCORPORATED Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:005386/0504 Effective date: 19871021 |