CA1151238A - Wrought lead-calcium-strontium-tin ( barium) alloy for battery components - Google Patents
Wrought lead-calcium-strontium-tin ( barium) alloy for battery componentsInfo
- Publication number
- CA1151238A CA1151238A CA000373887A CA373887A CA1151238A CA 1151238 A CA1151238 A CA 1151238A CA 000373887 A CA000373887 A CA 000373887A CA 373887 A CA373887 A CA 373887A CA 1151238 A CA1151238 A CA 1151238A
- Authority
- CA
- Canada
- Prior art keywords
- lead
- weight percent
- alloy
- tin
- strontium
- 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
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 17
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 16
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000003860 storage Methods 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 13
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910003522 Sr-Sn Inorganic materials 0.000 abstract description 4
- 229910052718 tin Inorganic materials 0.000 description 10
- 229910001128 Sn alloy Inorganic materials 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 7
- 238000005482 strain hardening Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000011262 electrochemically active material Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- AGNPPWAGEICIGZ-UHFFFAOYSA-N strontium tin Chemical compound [Sr].[Sn] AGNPPWAGEICIGZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- 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
- H01M4/685—Lead alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
C-3243' D-5,344 WROUGHT LEAD-CALCIUM-STRONTIUM-TIN
(?-BARIUM) ALLOY FOR BATTERY COMPONENTS
Abstract of the Disclosure A work hardenable Pb-Ca-Sr-Sn alloy having anti-recrystallization stability at temperatures below about 66°C. The alloy comprises by weight:
0.03 % to 0.04% calcium; 0.15% to 0.4% strontium;
0.15% to 0.9% tin; 0% to 0.1% barium; and the balance principally lead. The alloy is useful in the manufacture of cold-worked Pb-acid storage battery components and particularly grids made by the expanded, wrought lead strip process.
(?-BARIUM) ALLOY FOR BATTERY COMPONENTS
Abstract of the Disclosure A work hardenable Pb-Ca-Sr-Sn alloy having anti-recrystallization stability at temperatures below about 66°C. The alloy comprises by weight:
0.03 % to 0.04% calcium; 0.15% to 0.4% strontium;
0.15% to 0.9% tin; 0% to 0.1% barium; and the balance principally lead. The alloy is useful in the manufacture of cold-worked Pb-acid storage battery components and particularly grids made by the expanded, wrought lead strip process.
Description
~151238 +WROUGHT LEAD-CALCIUM-STRONTIUM-TIN
(-BARIUM) ALLOY FOR BATTERY COMPONENTS
Background 'o'f'*h'e' Invention This invention relates to lead-acid storage batteries of the maintenance-free type which employ antimony-free lead alloys therein to reduce water consumption and battery self discharge. More specifi-cally, this invention relates to wrought lead-calcium-strontium-tin alloys (with or without barium) for use: in the grids used to support the electro-chemically active material of such batteries; and inother lead components used in the battery.
In recent years the battery industry has moved toward the "maintenance free" SLI automobile battery which has reduced gasing tendencies and an ability to retain most of its original electrolyte throughout its normal useful life. A key element in the manufacture of such batteries-is the elimina-tion of antimony from the battery components and particularly from the grid used to support the batteries electro-chemically active materials. Some manufacturers have abandoned the traditional approach of casting these grids and begun forming the grids by expanding wrought lead alloy strip such as, for example, by the process disclosed in United States patent, Daniels et al 3,853,626 issued December 10, 1974. Such expansion processes have heretofore used such wrought lead-calcium-tin alloys as are disclosed in United States patent, Prengaman 3,953,244 issued April 27, 1976 and United States patent, Matter 4,228,580 issued October 21, 1980. Other manufacturers have continued to cast the grids using lead-calcium-tin alloys. Other castable alloys ~lS~3~
including various combinations of lead, calcium, strontium, tin and barium have been proposed. One such alloy is disclosed in United States patent, Nees et al 4,137,378 issued January 30, 1979.
While such other alloys offer a number of casting advantages (e.g., fluidity and rapid age hardenability) they are not satisfactory for the manufacture of grids by the expanded wrought strip method or for other cold-worked battery components.
In this regard, these other alloys recrystallize after cold working such that their tensile strength can fall to as low as about 20,685 kPa after only a few months standing at room temperature. Retained tensile strengths in excess of about 34,500 kPa are most desirable for such grids. In this regard, loss of tensile strength in battery grids promotes early failure of the batteries due to the breaking of grid wires incident to the vibration and shock automotive batteries normally experience in service. Moreover, weakened, recrystallized grids have less resistance to plate growth and are often susceptible to catastrophic intergrannular corrosive attack. The problem of wrought alloy selection is particularly acute in the warmer climates where the battery is consistently exposed to elevated, under-the-hood temperatures which promote recrystallization and loss of strength of alloys which would otherwise be stable at room temperature.
Other battery components (e.g., plate straps, connectors, terminals, etc.) are often cold-worked in the process of assembling the battery and accordingly must have acceptable metallurgical properties not only for the cold-working operation itself, but also in order to complete the mission that part must perform in the battery. Cold-worked terminals, for example, need to be ductile for readily mechanically (i.e., upsetting) attaching them to the case, and once attached need to retain ~,' ~ . ~
115~238 their strength lest they loosen from the case causing electrolyte leakage and perchance separation of the terminal from the container. Cast lead-antimony alloys (i.e. 2~-6~ Sb) commonly used for these pQrts have relatively coarse dendritic cast structures which age harden rapidly, yielding high strengths but poor ductility, making these alloys difficult to use where extensive cold deformation is required. More-over at room temperature, cold-worked antimony alloys tend to soften with time due to a breakup of the antimony strengthening phase causing tensile strengths to fall rapidly ~i.e. from about 48,300 kPa to about 31,000 kPa). Because of this loss of strength, the parts must be over-designed for cold working to com-pensate for the loss of strength and inherently poorductility of these alloys. Ideally a lead battery alloy for cold working would be ductile in the as-cast condition and be capable of being worked over a broad range of reduction percentages and have a retained tensile strength of at least about 34,500 kPa after aging at both room temperature or at temperatures up to about 66C for at least six (6) months.
~ ccordingly, it is an object of the present invention to provide a ductile, lead-calcium-strontium-tin alloy particularly suitable for the manufacture of cold-worked lead-acid storage battery components which components have both room temperature and high temperature (i.e. up to about 66C.) anti-recrystallization stability, as well as excellent corrosion resistance. It is a further object of the present invention to provide a wrought, expanded, lead-acid storage battery grid consisting essentially of lead, calcium, strontium and tin (with or without barium) which grid has both room temperature and high temperature (i.e. up to about 66C.) tensile strengths in excess of about 34,500 kPa, and excellent 1151~38 corrosion resistance.
These and other objects and advantages of the present invention will become more readily apparent from the detailed description thereof which follows:
~ Figure 1 illustrates an expanded, wrought, Pb-Ca-Sr-Sn alloy battery grid according to ~the present invention; and ~ Figures 2 and 3 respectively illustrate, in side section, a Pb-Ca-Sr-Sn battery terminal before-and after cold working to secure the terminal to a~'battery cover.
The Invention .
~ ~ The present invention comprehends ductile (as-cast) lead-calcium-strontium-tin alloys (with or without barium) which, when work hardened (e.g. by a rolling'mill), do not recrystallize, but rather exhibit room temperature and high temperature (i.e. up to about~66C.) tensile strengths in excess of about 34,500 kPa after six months following rolling. More specifically this invention comprehends wrought alloys having the aforesaid anti-recrystallization stability as well as other properties suitable for lead-acid storage battery components and consist essentially of (by weight):
calcium about 0.03% - 0.04%
strontium about 0.15% - 0.4%
tin about 0.15% - 0.9%
barium about 0 - .1%
lead remainder (i.e.
including normal impurities).
Well known casting aids, such as small amounts (i.e. up to about .06~) of aluminum, may be used effectively without disturbing the alloy's ductility or strength stability.
The wrought alloys of this invention have demonstrated high levels of retained (i.e. after six months) tensile strength, excellent corrosion resis-tance, and excellent weldability to other lead parts inside the battery. Long term (i.e. aged more than 137 days between rolling and testing) stress rupture values in excess of 2,000 hours (i.e. at 20,685 kPa), and room temperature tensile strengths around 68,950 kPa are possible with tin levels in the range of about 0.65~ to about 0.9% by weight. However, when the strontium levels are below 0.3% at these higher tin levels, the high temperature tensile strength (i.e. after six months) is low (i.e. about 24,132 kPa), and grids made therefrom are more susceptible to corrosion in the battery than the lower tin content alloys at the same strontium level. To combat this corrosion susceptibility and high temperature tensile strength loss, about 0.025% to about 0.07% barium is added to the high tin alloys whose strontium level is below 0.3%. Adding barium in excess of about 0.07%
to such alloys is seen to reduce the long term high temperature tensile strength to unacceptable levels.
Barium, however, may be used at higher levels (e.g.
0.1%) with the lower tin alloys, but no particular benefit is apparent from such use. In the presence of the 0.025% - 0.07% barium, the six month high temperature tensile strength levels were maintained above about 34,500 kPa range for the hiqh tin-low strontium content alloys. As a practical matter, the lower tin alloys are preferred for cost reasons alone, as the cost of tin dictates that its use be minimized wherever possible.
While the precise metallurgical mechanism is not understood, the relatively low calcium con-centration appears to be responsible for impartingthe anti-recrystallization properties and stable ~15~238 tensile strengths to strontium-tin alloyed lead.
Moreover such low calcium levels do not result in excessive oxidation of the alloy. As a result, these low calcium content alloys have the further advantage of being more readily weldable than alloys having higher calcium contents. Hence grids made from alloys in accordance with the present invention can be readily welded to other grids as by the well known cast-on-strap process, and other battery small parts (e.g., plate straps) can be readily resistance welded to other parts (e.g., plate straps) by such processes as, for example, are described in United States patent, Matter 3,947,290 issued March 30, 1976.
The preferred compositions of the Pb-Ca-Sr-Sn (-Ba) alloys of the present invention will depend on which property is considered more important and hence sought to be optimized. The most effective alloys for developing stable room temperature tensile strengths in excess of 51,700 Kilopascals (kPa) are seen to be those containing: about 0.03% - 0.04%
calcium; about 0.15~ - 0.25% strontium; about 0.3% -0.8% tin; from 0 to about 0.1% barium; and the balance principally lead -- with the barium varying from about 0.25% - about 0.07~ when the tin content exceeds about 0.65%. Alloys having stable tensile strengths in excess of about 41,370 at temperatures up to 66C as well as excellent corrosion resistance and weldability are seen to be best developed with alloys containing: about 0.03% - 0.04% calcium;
about 0.15% - 0.35% strontium; about 0.15% - 0.35%
tin; and the balance principally lead.
The aforesaid preferred concentrations were determined on the basis of alloys prepared according to a cold working schedule in which a 1.91 cm thick billet was passed in one direction through a series of seven rolls wherein each roll reduced the thickness of the billet by 35% per roll. Tensile strengths ~' :
were measured after the worked alloys had aged six (6) months at room temperature and at 66C respectively.
Corrosion was evaluated subjectively following completion of a standardized accelerated corrosion S test. The results of these tests are set forth in the Table.
TABLE
- - ~ Tensile Str. ~kPa) Elongation Sample Alloy Corrosion66C RT 66C RT
1 0 ~ `24 Sn .04 Sr - Slight25,68430,924 193 17~
(-BARIUM) ALLOY FOR BATTERY COMPONENTS
Background 'o'f'*h'e' Invention This invention relates to lead-acid storage batteries of the maintenance-free type which employ antimony-free lead alloys therein to reduce water consumption and battery self discharge. More specifi-cally, this invention relates to wrought lead-calcium-strontium-tin alloys (with or without barium) for use: in the grids used to support the electro-chemically active material of such batteries; and inother lead components used in the battery.
In recent years the battery industry has moved toward the "maintenance free" SLI automobile battery which has reduced gasing tendencies and an ability to retain most of its original electrolyte throughout its normal useful life. A key element in the manufacture of such batteries-is the elimina-tion of antimony from the battery components and particularly from the grid used to support the batteries electro-chemically active materials. Some manufacturers have abandoned the traditional approach of casting these grids and begun forming the grids by expanding wrought lead alloy strip such as, for example, by the process disclosed in United States patent, Daniels et al 3,853,626 issued December 10, 1974. Such expansion processes have heretofore used such wrought lead-calcium-tin alloys as are disclosed in United States patent, Prengaman 3,953,244 issued April 27, 1976 and United States patent, Matter 4,228,580 issued October 21, 1980. Other manufacturers have continued to cast the grids using lead-calcium-tin alloys. Other castable alloys ~lS~3~
including various combinations of lead, calcium, strontium, tin and barium have been proposed. One such alloy is disclosed in United States patent, Nees et al 4,137,378 issued January 30, 1979.
While such other alloys offer a number of casting advantages (e.g., fluidity and rapid age hardenability) they are not satisfactory for the manufacture of grids by the expanded wrought strip method or for other cold-worked battery components.
In this regard, these other alloys recrystallize after cold working such that their tensile strength can fall to as low as about 20,685 kPa after only a few months standing at room temperature. Retained tensile strengths in excess of about 34,500 kPa are most desirable for such grids. In this regard, loss of tensile strength in battery grids promotes early failure of the batteries due to the breaking of grid wires incident to the vibration and shock automotive batteries normally experience in service. Moreover, weakened, recrystallized grids have less resistance to plate growth and are often susceptible to catastrophic intergrannular corrosive attack. The problem of wrought alloy selection is particularly acute in the warmer climates where the battery is consistently exposed to elevated, under-the-hood temperatures which promote recrystallization and loss of strength of alloys which would otherwise be stable at room temperature.
Other battery components (e.g., plate straps, connectors, terminals, etc.) are often cold-worked in the process of assembling the battery and accordingly must have acceptable metallurgical properties not only for the cold-working operation itself, but also in order to complete the mission that part must perform in the battery. Cold-worked terminals, for example, need to be ductile for readily mechanically (i.e., upsetting) attaching them to the case, and once attached need to retain ~,' ~ . ~
115~238 their strength lest they loosen from the case causing electrolyte leakage and perchance separation of the terminal from the container. Cast lead-antimony alloys (i.e. 2~-6~ Sb) commonly used for these pQrts have relatively coarse dendritic cast structures which age harden rapidly, yielding high strengths but poor ductility, making these alloys difficult to use where extensive cold deformation is required. More-over at room temperature, cold-worked antimony alloys tend to soften with time due to a breakup of the antimony strengthening phase causing tensile strengths to fall rapidly ~i.e. from about 48,300 kPa to about 31,000 kPa). Because of this loss of strength, the parts must be over-designed for cold working to com-pensate for the loss of strength and inherently poorductility of these alloys. Ideally a lead battery alloy for cold working would be ductile in the as-cast condition and be capable of being worked over a broad range of reduction percentages and have a retained tensile strength of at least about 34,500 kPa after aging at both room temperature or at temperatures up to about 66C for at least six (6) months.
~ ccordingly, it is an object of the present invention to provide a ductile, lead-calcium-strontium-tin alloy particularly suitable for the manufacture of cold-worked lead-acid storage battery components which components have both room temperature and high temperature (i.e. up to about 66C.) anti-recrystallization stability, as well as excellent corrosion resistance. It is a further object of the present invention to provide a wrought, expanded, lead-acid storage battery grid consisting essentially of lead, calcium, strontium and tin (with or without barium) which grid has both room temperature and high temperature (i.e. up to about 66C.) tensile strengths in excess of about 34,500 kPa, and excellent 1151~38 corrosion resistance.
These and other objects and advantages of the present invention will become more readily apparent from the detailed description thereof which follows:
~ Figure 1 illustrates an expanded, wrought, Pb-Ca-Sr-Sn alloy battery grid according to ~the present invention; and ~ Figures 2 and 3 respectively illustrate, in side section, a Pb-Ca-Sr-Sn battery terminal before-and after cold working to secure the terminal to a~'battery cover.
The Invention .
~ ~ The present invention comprehends ductile (as-cast) lead-calcium-strontium-tin alloys (with or without barium) which, when work hardened (e.g. by a rolling'mill), do not recrystallize, but rather exhibit room temperature and high temperature (i.e. up to about~66C.) tensile strengths in excess of about 34,500 kPa after six months following rolling. More specifically this invention comprehends wrought alloys having the aforesaid anti-recrystallization stability as well as other properties suitable for lead-acid storage battery components and consist essentially of (by weight):
calcium about 0.03% - 0.04%
strontium about 0.15% - 0.4%
tin about 0.15% - 0.9%
barium about 0 - .1%
lead remainder (i.e.
including normal impurities).
Well known casting aids, such as small amounts (i.e. up to about .06~) of aluminum, may be used effectively without disturbing the alloy's ductility or strength stability.
The wrought alloys of this invention have demonstrated high levels of retained (i.e. after six months) tensile strength, excellent corrosion resis-tance, and excellent weldability to other lead parts inside the battery. Long term (i.e. aged more than 137 days between rolling and testing) stress rupture values in excess of 2,000 hours (i.e. at 20,685 kPa), and room temperature tensile strengths around 68,950 kPa are possible with tin levels in the range of about 0.65~ to about 0.9% by weight. However, when the strontium levels are below 0.3% at these higher tin levels, the high temperature tensile strength (i.e. after six months) is low (i.e. about 24,132 kPa), and grids made therefrom are more susceptible to corrosion in the battery than the lower tin content alloys at the same strontium level. To combat this corrosion susceptibility and high temperature tensile strength loss, about 0.025% to about 0.07% barium is added to the high tin alloys whose strontium level is below 0.3%. Adding barium in excess of about 0.07%
to such alloys is seen to reduce the long term high temperature tensile strength to unacceptable levels.
Barium, however, may be used at higher levels (e.g.
0.1%) with the lower tin alloys, but no particular benefit is apparent from such use. In the presence of the 0.025% - 0.07% barium, the six month high temperature tensile strength levels were maintained above about 34,500 kPa range for the hiqh tin-low strontium content alloys. As a practical matter, the lower tin alloys are preferred for cost reasons alone, as the cost of tin dictates that its use be minimized wherever possible.
While the precise metallurgical mechanism is not understood, the relatively low calcium con-centration appears to be responsible for impartingthe anti-recrystallization properties and stable ~15~238 tensile strengths to strontium-tin alloyed lead.
Moreover such low calcium levels do not result in excessive oxidation of the alloy. As a result, these low calcium content alloys have the further advantage of being more readily weldable than alloys having higher calcium contents. Hence grids made from alloys in accordance with the present invention can be readily welded to other grids as by the well known cast-on-strap process, and other battery small parts (e.g., plate straps) can be readily resistance welded to other parts (e.g., plate straps) by such processes as, for example, are described in United States patent, Matter 3,947,290 issued March 30, 1976.
The preferred compositions of the Pb-Ca-Sr-Sn (-Ba) alloys of the present invention will depend on which property is considered more important and hence sought to be optimized. The most effective alloys for developing stable room temperature tensile strengths in excess of 51,700 Kilopascals (kPa) are seen to be those containing: about 0.03% - 0.04%
calcium; about 0.15~ - 0.25% strontium; about 0.3% -0.8% tin; from 0 to about 0.1% barium; and the balance principally lead -- with the barium varying from about 0.25% - about 0.07~ when the tin content exceeds about 0.65%. Alloys having stable tensile strengths in excess of about 41,370 at temperatures up to 66C as well as excellent corrosion resistance and weldability are seen to be best developed with alloys containing: about 0.03% - 0.04% calcium;
about 0.15% - 0.35% strontium; about 0.15% - 0.35%
tin; and the balance principally lead.
The aforesaid preferred concentrations were determined on the basis of alloys prepared according to a cold working schedule in which a 1.91 cm thick billet was passed in one direction through a series of seven rolls wherein each roll reduced the thickness of the billet by 35% per roll. Tensile strengths ~' :
were measured after the worked alloys had aged six (6) months at room temperature and at 66C respectively.
Corrosion was evaluated subjectively following completion of a standardized accelerated corrosion S test. The results of these tests are set forth in the Table.
TABLE
- - ~ Tensile Str. ~kPa) Elongation Sample Alloy Corrosion66C RT 66C RT
1 0 ~ `24 Sn .04 Sr - Slight25,68430,924 193 17~
2 04 Ca - .07 Sr - Very Slight 24,201 43,576 25S 10~1%
3 .03 Ca - .20 Sr - fievere24,47771,019 20~ 7.5S
.8 Sn 15 Sb Too soft Too soft Too ~oft Too soft 25 Sn Very Slight41,370 51,871 17.50 l9.S~
8 Sn None 43,47347,355 22~ 22~5~
7 .03 Ca - .3 Sr - Very Slight 42,515 46,134 21.50 22.6%
.25 Sn 8 .03 Ca - .2 Sr - None27,78759,221 30.50 16 .8 Sn - .1 Ba 9 .03 Ca - .2 Sr - None26,39449,348 32.50 ls.so .8 Sn - .2 Ba .03 Ca - .2 Sr - None37,31652,574 22.5~ 16.5 .a Sn - .OS Ba 11 .Oi Ca - .07 sr - Very Slight 24,925 47,948 36.5~ 160 .25 Sn - 0.1 Ba 12 .03 Ca - .2 Sr - Very Sllght 40,225 54,705 160 18 .25 Sn - 0.1 Ba 13 .08 Ca - .02 Sr - -24,13247,57520.3~ 14S
.17 Sn 35 14 .19 Sr - 1.1 Sn -22,06435,164 36i 16t .11 Sr - .67 Sn -22,06428,959 400 - -16 03 Ca - .25 Sr -42,40460,67634.50 23~30 17 03 Ca - .25 Sr - 43,43957,S73 350 26.5S
~lSi;~3~
The nature of the cold working or rolling schedule is not seen to be particularly critical in achieving the results observed. In this regard, several different rolling schedules were tested to determine what, if any, effect they might have on the results observed. The alloys of the present invention demonstrated no significant sensitivity to property variations from one rolling schedule to the next except for slight reductions in stress rupture values as cold~working severity increased. The varying work schedules tested included constant percentage reduction rolling schedules to wit: reducing a 3.05 cm thick billet to a 0.11 cm thick strip by passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 45%;
reducing a 1.4 cm thick billet to a 0.~1 cm thick strip by~passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 35%; reducing a 0.6 cm thick billet to a 0.11 cm thick strip by passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 25%; and reducing a 0.28 cm thick billet to a 0.11 cm thick strip by passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 15%. The rolling schedule tests also included constant thickness reductionsto wit: reducing a 3.05 cm thick billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the billet by 0.35 cm per roll; reducing a Z.0 cm billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the billet by 0.21 cm per roll; reducing a 1.4 cm thick billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the 1~5~238 billet by 0.14 cm per roll; and reducing a 0.6 cm thick billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the billet by 0.56 cm per roll.
The drawings illustrate two battery components which are cold-worked in the process of manufacturing a battery and which require stable strengths throughout the useful life of the battery~
Figure 1 depicts a typical Pb-acid storage kattery grid 2 expanded from a strip o~ wrought antimony-free lead alloy. The grid 2 includes an upper current collecting border 4, a lower plate-supporting border 6 and a plurality of interconnected grid wires 8 extending therebetween for receiving and retaining the plate's active material.
Figures 2 and 3 depict a portion of a battery cover 10 sectioned through a terminal insert 12 before (i.e. Figure 2) and after (i.e. Figure 3) the insert 12 is attached to the cover 10 by cold upsetting the underside thereof. The insert 12 includes an annular tapered tower 14, a flange 16 and a depending skirt 18. During assembly of the insert 12 to the cover 10 the skirt 18 is inserted into an aperture 22 in the cover 10 (see Figure 2) and thereafter spin-riveted over (see Figure 3) so as to pull the flange 16 down tight against the surface of the cover 10. The riveting cold works the skirt 18 causing it to flare outwardly as at 24 and tightly engage the underside of the cover 10 around the mouth of the aperture 22. Annular bosses 26 circumscribe the aperture 22 on the top and bottom surfaces of the cover 10 and bite into the flange 16 and flare 24 as illustrated to enhance sealing. The cold-worked flare 24 must retain its strength throughoutthe life of the battery to prevent loosening of 115~;~38 the insert 12 which can result in electrolyte leakage around the insert 12 or separation of the terminal from the battery. As strength retention is not critically dependent on the amount of cold work involved, the riveting operation is not particularly critical in the sense of having to carefully control the~nature of the cold work effected on the skirt 18 in forming the flare 24. In fact, the ductility of parts made in accordance with the present invention actuàlly improves the riveting operation itself.
When~the~cover 10 is assembled to the container, an opening 20 in the insert 12 receives an upstanding post from the battery's innards (not shown) and is welded thereto to form the battery terminal.
- While this invention has been disclosed in terms of specific embodiments thereof it is not intended to be limited thereto, but rather only to the extent set forth hereafter in the claims which follow. ~
.
.8 Sn 15 Sb Too soft Too soft Too ~oft Too soft 25 Sn Very Slight41,370 51,871 17.50 l9.S~
8 Sn None 43,47347,355 22~ 22~5~
7 .03 Ca - .3 Sr - Very Slight 42,515 46,134 21.50 22.6%
.25 Sn 8 .03 Ca - .2 Sr - None27,78759,221 30.50 16 .8 Sn - .1 Ba 9 .03 Ca - .2 Sr - None26,39449,348 32.50 ls.so .8 Sn - .2 Ba .03 Ca - .2 Sr - None37,31652,574 22.5~ 16.5 .a Sn - .OS Ba 11 .Oi Ca - .07 sr - Very Slight 24,925 47,948 36.5~ 160 .25 Sn - 0.1 Ba 12 .03 Ca - .2 Sr - Very Sllght 40,225 54,705 160 18 .25 Sn - 0.1 Ba 13 .08 Ca - .02 Sr - -24,13247,57520.3~ 14S
.17 Sn 35 14 .19 Sr - 1.1 Sn -22,06435,164 36i 16t .11 Sr - .67 Sn -22,06428,959 400 - -16 03 Ca - .25 Sr -42,40460,67634.50 23~30 17 03 Ca - .25 Sr - 43,43957,S73 350 26.5S
~lSi;~3~
The nature of the cold working or rolling schedule is not seen to be particularly critical in achieving the results observed. In this regard, several different rolling schedules were tested to determine what, if any, effect they might have on the results observed. The alloys of the present invention demonstrated no significant sensitivity to property variations from one rolling schedule to the next except for slight reductions in stress rupture values as cold~working severity increased. The varying work schedules tested included constant percentage reduction rolling schedules to wit: reducing a 3.05 cm thick billet to a 0.11 cm thick strip by passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 45%;
reducing a 1.4 cm thick billet to a 0.~1 cm thick strip by~passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 35%; reducing a 0.6 cm thick billet to a 0.11 cm thick strip by passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 25%; and reducing a 0.28 cm thick billet to a 0.11 cm thick strip by passing it through six rolls wherein each roll in succession reduced the thickness of the billet by 15%. The rolling schedule tests also included constant thickness reductionsto wit: reducing a 3.05 cm thick billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the billet by 0.35 cm per roll; reducing a Z.0 cm billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the billet by 0.21 cm per roll; reducing a 1.4 cm thick billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the 1~5~238 billet by 0.14 cm per roll; and reducing a 0.6 cm thick billet to a 0.11 cm thick strip by passing it through nine rolls wherein each roll in succession reduced the thickness of the billet by 0.56 cm per roll.
The drawings illustrate two battery components which are cold-worked in the process of manufacturing a battery and which require stable strengths throughout the useful life of the battery~
Figure 1 depicts a typical Pb-acid storage kattery grid 2 expanded from a strip o~ wrought antimony-free lead alloy. The grid 2 includes an upper current collecting border 4, a lower plate-supporting border 6 and a plurality of interconnected grid wires 8 extending therebetween for receiving and retaining the plate's active material.
Figures 2 and 3 depict a portion of a battery cover 10 sectioned through a terminal insert 12 before (i.e. Figure 2) and after (i.e. Figure 3) the insert 12 is attached to the cover 10 by cold upsetting the underside thereof. The insert 12 includes an annular tapered tower 14, a flange 16 and a depending skirt 18. During assembly of the insert 12 to the cover 10 the skirt 18 is inserted into an aperture 22 in the cover 10 (see Figure 2) and thereafter spin-riveted over (see Figure 3) so as to pull the flange 16 down tight against the surface of the cover 10. The riveting cold works the skirt 18 causing it to flare outwardly as at 24 and tightly engage the underside of the cover 10 around the mouth of the aperture 22. Annular bosses 26 circumscribe the aperture 22 on the top and bottom surfaces of the cover 10 and bite into the flange 16 and flare 24 as illustrated to enhance sealing. The cold-worked flare 24 must retain its strength throughoutthe life of the battery to prevent loosening of 115~;~38 the insert 12 which can result in electrolyte leakage around the insert 12 or separation of the terminal from the battery. As strength retention is not critically dependent on the amount of cold work involved, the riveting operation is not particularly critical in the sense of having to carefully control the~nature of the cold work effected on the skirt 18 in forming the flare 24. In fact, the ductility of parts made in accordance with the present invention actuàlly improves the riveting operation itself.
When~the~cover 10 is assembled to the container, an opening 20 in the insert 12 receives an upstanding post from the battery's innards (not shown) and is welded thereto to form the battery terminal.
- While this invention has been disclosed in terms of specific embodiments thereof it is not intended to be limited thereto, but rather only to the extent set forth hereafter in the claims which follow. ~
.
Claims (5)
1. A lead-acid storage battery component comprising a corrosion-resistant, lead based alloy having anti-recrystallization stability at temperatures up to at least 66°C for periods of at least six months, said alloy consisting essentially of about 0.03 to about 0.04 weight percent calcium, about 0.15 to about 0.4 weight percent strontium, about 0.15 to about 0.9 weight percent tin and lead, said alloy also containing barium in a concentration ranging from about 0.025 to about 0.07 weight percent when said alloy contains less than 0.3 percent by weight strontium and more than about 0.65 weight percent tin.
2. A lead-acid storage battery component comprising a cold-worked,corrosion-resistant, lead alloy having anti-recrystallization stability at temperatures below about 66°C for periods of at least six months, said alloy consisting essentially of about 0.03 to about 0.04 weight percent calcium, about 0.15 to about 0.35 weight percent strontium, about 0.15 to about 0.35 weight percent tin and the balance principally lead.
3. A lead-acid storage battery component comprising a cold-worked, corrosion-resistant, lead alloy having anti-recrystallization stability at temperatures below about 66°C for periods of at least six months, said alloy consisting essentially of about 0.03 to about 0.04 weight percent calcium, about 0.15 to less than 0.3 weight percent strontium, about 0.65 to about 0.9 weight percent tin, about 0.025 to about 0.07 weight percent barium and the balance principally lead.
4. A lead-acid storage battery component comprising a cold-worked, corrosion-resistant, lead alloy having anti-recrystallization stability at tempera-tures below about 66°C for periods of at least six months, said alloy consisting essentially of about 0.03 to about 0.04 weight percent calcium, at least 0.3 to about 0.4 weight percent strontium about 0.65 to about 0.9 weight percent tin, and the balance principally lead.
5. A lead-acid storage battery component comprising a cold-worked, corrosion-resistant, lead alloy having anti-recrystallization stability at temperatures below about 66°C for periods of at least six months, said alloy consisting essentially of about 0.03 to about 0.04 weight percent calcium, at least 0.3 to about 0.4 weight percent strontium, about 0.15 to about 0.35 weight percent tin, and the balance princi-pally lead.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15333380A | 1980-05-27 | 1980-05-27 | |
| US153,333 | 1980-05-27 | ||
| US06/240,070 US4358518A (en) | 1980-05-27 | 1981-03-03 | Wrought lead-calcium-strontium-tin (±barium) alloy for battery components |
| US240,070 | 1981-03-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1151238A true CA1151238A (en) | 1983-08-02 |
Family
ID=26850437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000373887A Expired CA1151238A (en) | 1980-05-27 | 1981-03-26 | Wrought lead-calcium-strontium-tin ( barium) alloy for battery components |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4358518A (en) |
| EP (1) | EP0040951A1 (en) |
| CA (1) | CA1151238A (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1214528B (en) * | 1986-09-23 | 1990-01-18 | Aquila Piombo Per Caccia E Tir | PROCEDURE FOR THE CREATION OF AN ELECTRIC BATTERY POLE OR TERMINAL, EQUIPMENT TO IMPLEMENT THIS PROCEDURE, AS WELL AS ELECTRIC BATTERY POLE OR TERMINAL SO OBTAINED. |
| US5077892A (en) * | 1990-03-21 | 1992-01-07 | Nugent Robert R | Method for the manufacture of structurally homogeneous flash-free lead battery terminals |
| US6180286B1 (en) * | 1991-03-26 | 2001-01-30 | Gnb Technologies, Inc. | Lead-acid cells and batteries |
| US5691087A (en) * | 1991-03-26 | 1997-11-25 | Gnb Technologies, Inc. | Sealed lead-acid cells and batteries |
| US5874186A (en) * | 1991-03-26 | 1999-02-23 | Gnb Technologies, Inc. | Lead-acid cells and batteries |
| US5373720A (en) * | 1992-09-03 | 1994-12-20 | Water Gremlin Company | Method of making battery terminal with necked flange |
| US5296317A (en) * | 1992-09-03 | 1994-03-22 | Water Gremlin Co. | High torque battery terminal and method of making same |
| FR2745009B1 (en) * | 1996-02-16 | 1998-05-07 | Metaleurop Sa | LEAD-CALCIUM ALLOYS, ESPECIALLY FOR BATTERY GRIDS |
| FR2766622B1 (en) * | 1997-07-25 | 1999-10-22 | Metaleurop Sa | PROCESS FOR THE CONTINUOUS MANUFACTURE OF POSITIVE BATTERY GRIDS, AND POSITIVE GRID OBTAINED ACCORDING TO SUCH A METHOD |
| US20050112470A1 (en) * | 1998-06-26 | 2005-05-26 | Johnson Controls Technology Company | Alloy for battery grids |
| AU777119B2 (en) * | 1999-07-30 | 2004-09-30 | Wirtz Manufacturing Co., Inc. | Battery grids |
| US20020182500A1 (en) * | 2001-06-04 | 2002-12-05 | Enertec Mexico, S. De R.L. De C.V. | Silver-barium lead alloy for lead-acid battery grids |
| US6701998B2 (en) | 2002-03-29 | 2004-03-09 | Water Gremlin Company | Multiple casting apparatus and method |
| KR100566624B1 (en) * | 2002-04-18 | 2006-03-31 | 후루카와 덴치 가부시키가이샤 | Leadbased alloy for lead storage battery, plate for lead storage battery and lead storage battery |
| WO2003092101A1 (en) * | 2002-04-26 | 2003-11-06 | The Furukawa Battery Co., Ltd. | Process for producing lead or lead alloy plate grid for lead storage battery and lead storage battery |
| US20040110067A1 (en) * | 2002-12-06 | 2004-06-10 | Johnson Controls Technology Company | Alloy for battery grids |
| US20050158629A1 (en) * | 2003-05-26 | 2005-07-21 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery, grid for lead-acid battery and lead-acid battery |
| US7338539B2 (en) | 2004-01-02 | 2008-03-04 | Water Gremlin Company | Die cast battery terminal and a method of making |
| US8701743B2 (en) | 2004-01-02 | 2014-04-22 | Water Gremlin Company | Battery parts and associated systems and methods |
| JP4148175B2 (en) * | 2004-03-31 | 2008-09-10 | 新神戸電機株式会社 | Lead alloy and lead storage battery using the same |
| US7704452B2 (en) * | 2006-02-23 | 2010-04-27 | Rsr Technologies, Inc. | Alloy and anode for use in the electrowinning of metals |
| PL2425478T3 (en) | 2009-04-30 | 2019-04-30 | Water Gremlin Co | Battery parts having retaining and sealing features and associated methods of manufacture and use |
| US9748551B2 (en) | 2011-06-29 | 2017-08-29 | Water Gremlin Company | Battery parts having retaining and sealing features and associated methods of manufacture and use |
| US9954214B2 (en) | 2013-03-15 | 2018-04-24 | Water Gremlin Company | Systems and methods for manufacturing battery parts |
| CN105925840B (en) * | 2016-06-14 | 2017-12-22 | 界首市南都华宇电源有限公司 | A kind of preparing process of lead-acid accumulator rare earth alloy |
| US11283141B2 (en) | 2018-12-07 | 2022-03-22 | Water Gremlin Company | Battery parts having solventless acid barriers and associated systems and methods |
| JP7214692B2 (en) | 2020-09-17 | 2023-01-30 | プライムプラネットエナジー＆ソリューションズ株式会社 | Terminal, secondary battery with the same, and manufacturing method thereof |
| JP7214693B2 (en) * | 2020-09-17 | 2023-01-30 | プライムプラネットエナジー＆ソリューションズ株式会社 | Terminal, secondary battery with the same, and manufacturing method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB433653A (en) * | 1934-02-01 | 1935-08-19 | S & T Metal Company | Improvement in lead alloy bearing metal |
| US2013487A (en) * | 1934-06-07 | 1935-09-03 | Robert H Canfield | Lead alloy |
| US2170650A (en) * | 1936-09-02 | 1939-08-22 | Bell Telephone Labor Inc | Alloy |
| FR851686A (en) * | 1938-08-10 | 1940-01-12 | Nat Lead Co | Improvements in hardened lead alloys, particularly suitable for the production of bearings |
| US3706605A (en) * | 1970-10-05 | 1972-12-19 | St Joe Minerals Corp | Superplastic lead alloys |
| US4170470A (en) * | 1976-02-18 | 1979-10-09 | Globe-Union Inc. | High strength lead alloy |
| US4137378A (en) * | 1977-05-31 | 1979-01-30 | General Battery Corporation | Calcium-strontium-lead grid alloy for use in lead-acid batteries |
-
1981
- 1981-03-03 US US06/240,070 patent/US4358518A/en not_active Expired - Fee Related
- 1981-03-26 CA CA000373887A patent/CA1151238A/en not_active Expired
- 1981-05-20 EP EP81302236A patent/EP0040951A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0040951A1 (en) | 1981-12-02 |
| US4358518A (en) | 1982-11-09 |
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