CA1186169A - Low antimony alloy - Google Patents
Low antimony alloyInfo
- Publication number
- CA1186169A CA1186169A CA000402809A CA402809A CA1186169A CA 1186169 A CA1186169 A CA 1186169A CA 000402809 A CA000402809 A CA 000402809A CA 402809 A CA402809 A CA 402809A CA 1186169 A CA1186169 A CA 1186169A
- Authority
- CA
- Canada
- Prior art keywords
- antimony
- weight percent
- alloy
- alloys
- lead
- 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
- 239000002141 low-antimony alloy Substances 0.000 title abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 43
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 38
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 11
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 3
- QQHJESKHUUVSIC-UHFFFAOYSA-N antimony lead Chemical compound [Sb].[Pb] QQHJESKHUUVSIC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 11
- 239000002140 antimony alloy Substances 0.000 description 10
- 230000005496 eutectics Effects 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910014474 Ca-Sn Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000001999 grid alloy Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910001264 Th alloy Inorganic materials 0.000 description 1
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000009826 distribution Methods 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
- 239000012530 fluid Substances 0.000 description 1
- 239000002142 lead-calcium alloy Substances 0.000 description 1
- -1 leàd-calcium-tin Chemical compound 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 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
- C22C11/08—Alloys based on lead with antimony or bismuth as the next major constituent
- C22C11/10—Alloys based on lead with antimony or bismuth as the next major constituent with tin
-
- 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)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Glass Compositions (AREA)
- Sampling And Sample Adjustment (AREA)
- Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
LOW ANTIMONY ALLOY
Abstract of the Disclosure Low antimony lead alloys suitable for use as grid material in maintenance free high capacity lead acid batteries are disclosed. The alloys comprise 0.6 to 1.1 weight percent antimony, 0.06 to 0.25 weight percent arsenic, 0.1 to 0.4 weight percent tin, 0.06 to 0.11 weight percent copper and the balance lead. A preferred alloy contains 0.8 weight percent antimony, 0.15 weight percent arsenic, 0.02 weight percent tin and 0.08 weight percent copper.
Abstract of the Disclosure Low antimony lead alloys suitable for use as grid material in maintenance free high capacity lead acid batteries are disclosed. The alloys comprise 0.6 to 1.1 weight percent antimony, 0.06 to 0.25 weight percent arsenic, 0.1 to 0.4 weight percent tin, 0.06 to 0.11 weight percent copper and the balance lead. A preferred alloy contains 0.8 weight percent antimony, 0.15 weight percent arsenic, 0.02 weight percent tin and 0.08 weight percent copper.
Description
1~86~6~3?
a) Field of the Invention This invention relates to lead alloys having a low antimony content and containing arsenic, tin and copper~
The alloys have utility in high capacity, maintenance-free battery grids.
b~ State of the Art Lead-antimony alloys have been used as grid materials for lead acid batteries. Antimony is used to increase the strength and/~r other physical properties of lead, thereby faciliating various aspects of battery manufacture. In the case of lead-acid battery grids, this is particularly important in order for the grids to withstand normal handling during battery manufacturing and service.
The battery industry has begun produciny batteries which requlre little or no maintenance, such as addition of water to maintain the electrolyte level during the service ]ife of a battery. In such batteries it is the practice to either seal the battery or use vent plugs for the filling ports which are not easily removed by the ultimate battery user. Since the purpose of such batteries is to eliminate the need for filling, a lead alloy system must be selected in which the supply of electrolyte will not be significantly diminished over the intended life of the battery. The presence of antimony typically causes excessive gas generation in lead-acid batteries, especially during periods of charging or overcharging, which ultimately depletes the quantity of electrolyte. Such gassing is unacceptable in reduced or no maintenance batteries particularly if they are o~ the completely sealed type.
Alloys containing no antimony, such as leàd-calcium-tin, lead-strontium-tin-aluminum, and lead-calcium-,..~, --1-- ~
~6~6g tin-aluminum alloys have been introduced as maintenance-free battery grid alloys and to meet the requirements of cold cranking performance of the batteries. Lead-antimony alloys having abov~ 2.5% antlmony are not adequate for high capacity, maintenance-free battery grid alloys; rather the antimony content must be further reduced to reduce water loss or gassing in batteries during charging and increase the conductivity of the grid alloy, thus increasing the cold cranking performance of the battery. However, elimination of antimony from the battery can result in formation of non-conducting layers at the grid-active material interface, thereby reducing battery performance.
~ ccording to the lead-antimony phase diagram, the freeæing range becomes a maximum at about 3.5% antimony and antimony alloys containing less than 3.5% antimony should have reduced freezing range and no eutectic liquid. In fact, the amount of eutectic liquid is greatly reduced.
However, because of segregation effects during solidification, some eutectic may be present in alloys of l~ antimony or less indica ing that the freezing range, instead of becoming narrower, becomes wider as the antimony content is decreased.
~he combination of increased freezing range and reduced eutectic liquid make alloys in the 1-2% antimony content range very difficult to cast without cracking. To permit the use of alloys in this range, resort has been made to addition of nucleants, such as selenium, sulphur, copper, phosphorous, or aluminum, to prevent cracking. In these alloys, problems of temperature control, loss of nucleants and adverse reactions may occur and lead to loss of the alloying elements in use and produce cracking.
It has now been discovered that by restricting the antimony content of alloys to less than 1.1%, both the ~reezing range and amount of eutectic material are reduced.
However, where such alloys are cast as battery grids, at the grid intersec-tions or points where there are large differences in cross section which can cause soliclification at different r-ates some cracking can still occur due to concentration of eutectic liquid. It has further been discovered that such crac~ing can be eliminated by the addition of copper to the alloy. The low antimony alloys of the invention are suitable ror use as battery grids in maintenance-free, high capacity batteries.
c~ Summary of the Invention This invention provides a low antimony alloy which comprises 0.6 to 1.1 weight percent antimony, preferably 0.8 weight percent antimony, 0.06 to 0.25 weight percent arsenic, preferably 0.15 weight percent arsenic, 0.1 to 0.4 weight percent tin, preferably 0.20 weight percent tin, 0.06 to 0.11 weight percent copper, preferably 0.08 weight percent copper and the balance lead. The alloys are suitable for use in the grids of maintenance-free high capacity lead acid batteries.
d) Detailed Description of the Invention The present invention provides low antimony lead alloys for acid battery grids. The alloy comprises 0.6 to 1.1 weight percent antimony, preferably 0.8 weight percent antimony, 0.06 to 0.25 weight percent arsenic, preferably 0.15 weight percent arsenic, 0.1 to 0.4 weight percent tin, preferahly 0.20 weight percent tin, 0.06 to 0.11 weight percent copper, preferably 0.08 weight percent copper and the balance of lead.
-~8~
Because the alloy contains some antimony, the formation of non conducting layers at the grid-active material interface is avoided. However, because the antimony level is reduced, relatively little ~assing is observed, thus rendering the alloy suitable for use in maintenance-free batteries. Further the reduced antintony content increases the conductivity of the alloy thus increasing cold cranking performance of batteries employing the alloy as grid material.
The alloys of the invention are very fluid and can be cast into fine grain, crack and corrosion resistant battery grids which are as thin as any commercially available.
Casting can be effected by conventional grid casting techniques or by continuous grid casting processes.
A comparison was made of ~.055 inch thick grids cast from alloys of the following compositions:
Alloy A Alloy B
(Weight Percent)tWeight Percent) Antimony0.75 0.75 Tin 0.20 0.20 Arsenic0.16 0.16 Copper 0.03 0.083 Lead Balance Balance Visual inspection of the grids using 80x magnification inaicated that Alloy ~ had a large grain size with so~e cracking at grid wire intersections. In contrast ~lloy B, which is within the scope of the present invention, had a markedly reduced grain size and was very resistant to cracking and resultant penetrating corrosion.
Reduction of the antimony content of an alloy for use in battery grids results in an increase in conductivity.
This is evidenced by the data in Table I which shows the 6316~
electrical resistivity of various lead alloys.
Table Electrical Resistivity of Various lead Alloys Electrical Resistivity _1~ at 2noc OHM-cm Pure lead .00002065 Pure lead & As & Sn & Cu . 0000212 0.8% Sb Alloy .00002185 1.0~; Sb-Lead .0000220
a) Field of the Invention This invention relates to lead alloys having a low antimony content and containing arsenic, tin and copper~
The alloys have utility in high capacity, maintenance-free battery grids.
b~ State of the Art Lead-antimony alloys have been used as grid materials for lead acid batteries. Antimony is used to increase the strength and/~r other physical properties of lead, thereby faciliating various aspects of battery manufacture. In the case of lead-acid battery grids, this is particularly important in order for the grids to withstand normal handling during battery manufacturing and service.
The battery industry has begun produciny batteries which requlre little or no maintenance, such as addition of water to maintain the electrolyte level during the service ]ife of a battery. In such batteries it is the practice to either seal the battery or use vent plugs for the filling ports which are not easily removed by the ultimate battery user. Since the purpose of such batteries is to eliminate the need for filling, a lead alloy system must be selected in which the supply of electrolyte will not be significantly diminished over the intended life of the battery. The presence of antimony typically causes excessive gas generation in lead-acid batteries, especially during periods of charging or overcharging, which ultimately depletes the quantity of electrolyte. Such gassing is unacceptable in reduced or no maintenance batteries particularly if they are o~ the completely sealed type.
Alloys containing no antimony, such as leàd-calcium-tin, lead-strontium-tin-aluminum, and lead-calcium-,..~, --1-- ~
~6~6g tin-aluminum alloys have been introduced as maintenance-free battery grid alloys and to meet the requirements of cold cranking performance of the batteries. Lead-antimony alloys having abov~ 2.5% antlmony are not adequate for high capacity, maintenance-free battery grid alloys; rather the antimony content must be further reduced to reduce water loss or gassing in batteries during charging and increase the conductivity of the grid alloy, thus increasing the cold cranking performance of the battery. However, elimination of antimony from the battery can result in formation of non-conducting layers at the grid-active material interface, thereby reducing battery performance.
~ ccording to the lead-antimony phase diagram, the freeæing range becomes a maximum at about 3.5% antimony and antimony alloys containing less than 3.5% antimony should have reduced freezing range and no eutectic liquid. In fact, the amount of eutectic liquid is greatly reduced.
However, because of segregation effects during solidification, some eutectic may be present in alloys of l~ antimony or less indica ing that the freezing range, instead of becoming narrower, becomes wider as the antimony content is decreased.
~he combination of increased freezing range and reduced eutectic liquid make alloys in the 1-2% antimony content range very difficult to cast without cracking. To permit the use of alloys in this range, resort has been made to addition of nucleants, such as selenium, sulphur, copper, phosphorous, or aluminum, to prevent cracking. In these alloys, problems of temperature control, loss of nucleants and adverse reactions may occur and lead to loss of the alloying elements in use and produce cracking.
It has now been discovered that by restricting the antimony content of alloys to less than 1.1%, both the ~reezing range and amount of eutectic material are reduced.
However, where such alloys are cast as battery grids, at the grid intersec-tions or points where there are large differences in cross section which can cause soliclification at different r-ates some cracking can still occur due to concentration of eutectic liquid. It has further been discovered that such crac~ing can be eliminated by the addition of copper to the alloy. The low antimony alloys of the invention are suitable ror use as battery grids in maintenance-free, high capacity batteries.
c~ Summary of the Invention This invention provides a low antimony alloy which comprises 0.6 to 1.1 weight percent antimony, preferably 0.8 weight percent antimony, 0.06 to 0.25 weight percent arsenic, preferably 0.15 weight percent arsenic, 0.1 to 0.4 weight percent tin, preferably 0.20 weight percent tin, 0.06 to 0.11 weight percent copper, preferably 0.08 weight percent copper and the balance lead. The alloys are suitable for use in the grids of maintenance-free high capacity lead acid batteries.
d) Detailed Description of the Invention The present invention provides low antimony lead alloys for acid battery grids. The alloy comprises 0.6 to 1.1 weight percent antimony, preferably 0.8 weight percent antimony, 0.06 to 0.25 weight percent arsenic, preferably 0.15 weight percent arsenic, 0.1 to 0.4 weight percent tin, preferahly 0.20 weight percent tin, 0.06 to 0.11 weight percent copper, preferably 0.08 weight percent copper and the balance of lead.
-~8~
Because the alloy contains some antimony, the formation of non conducting layers at the grid-active material interface is avoided. However, because the antimony level is reduced, relatively little ~assing is observed, thus rendering the alloy suitable for use in maintenance-free batteries. Further the reduced antintony content increases the conductivity of the alloy thus increasing cold cranking performance of batteries employing the alloy as grid material.
The alloys of the invention are very fluid and can be cast into fine grain, crack and corrosion resistant battery grids which are as thin as any commercially available.
Casting can be effected by conventional grid casting techniques or by continuous grid casting processes.
A comparison was made of ~.055 inch thick grids cast from alloys of the following compositions:
Alloy A Alloy B
(Weight Percent)tWeight Percent) Antimony0.75 0.75 Tin 0.20 0.20 Arsenic0.16 0.16 Copper 0.03 0.083 Lead Balance Balance Visual inspection of the grids using 80x magnification inaicated that Alloy ~ had a large grain size with so~e cracking at grid wire intersections. In contrast ~lloy B, which is within the scope of the present invention, had a markedly reduced grain size and was very resistant to cracking and resultant penetrating corrosion.
Reduction of the antimony content of an alloy for use in battery grids results in an increase in conductivity.
This is evidenced by the data in Table I which shows the 6316~
electrical resistivity of various lead alloys.
Table Electrical Resistivity of Various lead Alloys Electrical Resistivity _1~ at 2noc OHM-cm Pure lead .00002065 Pure lead & As & Sn & Cu . 0000212 0.8% Sb Alloy .00002185 1.0~; Sb-Lead .0000220
2.0~s Sb Lead . O000227
3.0% Sb-Lead .0000234
4.0% Sb-Lead .000024 0
5.09~ Sb-Lead .0000246 Pb-0.1 Ca-0.3 Sn .0000219 The data indicate that the 0.8% antimony alloy is 11% more conductive than conventional 5% antimony and 6%
more conductive than 2.75% low antimony alloys and equal in conductivi ty to the Pb-Ca-Sn alloy.
Since corrosion of the antimony from the positive grid and transfer to the negative is the major cause of gassing in batteries, the reduced amount of antimony and the dispersed nature of the antimony particles due to the copper additive will reduce antimony corrosion from the positive grid and concomitant transfer to the negative grid where alloys of the present invention are employed.
A major problem with low antimony alloys has been sufficient strenyth and rate of strengthening for processing after casting. The presence of arsenic and copper in the alloy of the invention gives the alloy initial hardness and adequate handling strength due to precipitation of the copper and arsenic throughout the alloy.
Table II below shows the rate of aging and ultimate hardness levels of the 0.8% antimony alloy compared to conventional low antimony alloy and an alloy of 0. 09% Ca-0.3% tin. The alloys were cast into 1/4" thick plates andcooled by blowing air over the surface. The hardness was ~ ~L8~
measured by the R~ckwell ~R" scale (1/2" D Ball with an applied load of 60 Kg). The duration of the test was 30 seconds.
Table II
Rate of ~ardening of Various Alloys After Casting Rockwell "R" Hardness of Alloys ~ging Time New fter Castin~2. 75~o Sb Pb-0.09 Ca-0.3 Sn 0.8~ Sb Alloy l Minute 40 ~ 10 5 Minutes 69 22 60 15 Minutes 80 40 7Q
l Hour 82 6~ 76 24 Hours 86 76 79 4 Days 88 78 79 7 Days 30 79 79 14 Days 92 80 79 30 Days 92 83 80 The first -test was conducted one minute after casting. The samples were still hot at this time and this represents the hardening condition of a much thinner battery grid soon aEter ejection Erom the mold as it would be handled for trimming. The new 0.8% antimony alloy is slightly stronger than the 0.09% Calcium-0.3% tin alloy due to the slight amount of eutectic and copper second phase particles in the structure. The 0.8% Sb alloy, however, is weaker than the conventional low antimony alloy ~2.75~ Sb) which contains more strengthening antimony eutectic network.
The 0.8~ antimony alloy strengthens rapidly as it cools, reaches 95~ of its strength in one hour and is virtually fully aged in one day. The 2.75~ antimony and the lead-calcium alloys continue to slowly harden. ~fter seven days, the lea~-calcium and the 0.8% antimony alloy are at the same hardness with b~th alloys softer than the 2.75% antimony alloy. The mechanical properties of the fully aged (30 days) alloys are shown in Table III.
Table III
Mechanical Properties of Various Alloys ~ged 30 Days 2.75% Sb O.O9Ca-0.3 Sn 0.8% Sb UTS (psi) 7000 6500 5500 YS (psi) 5800 4B00 3750 Elongation 10% 30% 30~
Based on the hardness tests of Table II, the alloy hardens sufficiently after seven days to be processed through casting, trimming, and pasting comparably to the Pb - 0.09 Ca -0.3 Sn alloy. After 3~ days, the alloy is slightly weaker than the Pb-Ca-Sn alloy and significantly weaker than the conventional low (2.75%) antimony alloy. The reduced strength is due to the reduced antimony content.
Overall -the low antimony alloy of the inven-tion would be significantly more conductive than conventional low antimony alloys containing greater amounts of antimony.
Thus cold cranking performance comparable to Pb-Ca-Sn alloy batteries could be achieved. Further gassing rate can b~
greatly reduced compared to conventional low antimony alloys because of the reduced antimony eutectic content and increased distribution of the antimony. The alloy has suEficient hot str~ngth and aged mechanical properties to be handled in casting and pasting. The reduced antimony content, and the addition of copper produce a reduced freezing range and uniform fine grained crack-resistant grain structure.
Finally, the a~loy is very Eluid and can be easily cast into -the thinnest commercially available grids.
The alloy of the invention may contain nucleating agents such as are present in conventional low antimony alloys. For example, sulfur, selenium, tellurium, phosphorous and/or aluminum may be incorporated into the alloy of the
more conductive than 2.75% low antimony alloys and equal in conductivi ty to the Pb-Ca-Sn alloy.
Since corrosion of the antimony from the positive grid and transfer to the negative is the major cause of gassing in batteries, the reduced amount of antimony and the dispersed nature of the antimony particles due to the copper additive will reduce antimony corrosion from the positive grid and concomitant transfer to the negative grid where alloys of the present invention are employed.
A major problem with low antimony alloys has been sufficient strenyth and rate of strengthening for processing after casting. The presence of arsenic and copper in the alloy of the invention gives the alloy initial hardness and adequate handling strength due to precipitation of the copper and arsenic throughout the alloy.
Table II below shows the rate of aging and ultimate hardness levels of the 0.8% antimony alloy compared to conventional low antimony alloy and an alloy of 0. 09% Ca-0.3% tin. The alloys were cast into 1/4" thick plates andcooled by blowing air over the surface. The hardness was ~ ~L8~
measured by the R~ckwell ~R" scale (1/2" D Ball with an applied load of 60 Kg). The duration of the test was 30 seconds.
Table II
Rate of ~ardening of Various Alloys After Casting Rockwell "R" Hardness of Alloys ~ging Time New fter Castin~2. 75~o Sb Pb-0.09 Ca-0.3 Sn 0.8~ Sb Alloy l Minute 40 ~ 10 5 Minutes 69 22 60 15 Minutes 80 40 7Q
l Hour 82 6~ 76 24 Hours 86 76 79 4 Days 88 78 79 7 Days 30 79 79 14 Days 92 80 79 30 Days 92 83 80 The first -test was conducted one minute after casting. The samples were still hot at this time and this represents the hardening condition of a much thinner battery grid soon aEter ejection Erom the mold as it would be handled for trimming. The new 0.8% antimony alloy is slightly stronger than the 0.09% Calcium-0.3% tin alloy due to the slight amount of eutectic and copper second phase particles in the structure. The 0.8% Sb alloy, however, is weaker than the conventional low antimony alloy ~2.75~ Sb) which contains more strengthening antimony eutectic network.
The 0.8~ antimony alloy strengthens rapidly as it cools, reaches 95~ of its strength in one hour and is virtually fully aged in one day. The 2.75~ antimony and the lead-calcium alloys continue to slowly harden. ~fter seven days, the lea~-calcium and the 0.8% antimony alloy are at the same hardness with b~th alloys softer than the 2.75% antimony alloy. The mechanical properties of the fully aged (30 days) alloys are shown in Table III.
Table III
Mechanical Properties of Various Alloys ~ged 30 Days 2.75% Sb O.O9Ca-0.3 Sn 0.8% Sb UTS (psi) 7000 6500 5500 YS (psi) 5800 4B00 3750 Elongation 10% 30% 30~
Based on the hardness tests of Table II, the alloy hardens sufficiently after seven days to be processed through casting, trimming, and pasting comparably to the Pb - 0.09 Ca -0.3 Sn alloy. After 3~ days, the alloy is slightly weaker than the Pb-Ca-Sn alloy and significantly weaker than the conventional low (2.75%) antimony alloy. The reduced strength is due to the reduced antimony content.
Overall -the low antimony alloy of the inven-tion would be significantly more conductive than conventional low antimony alloys containing greater amounts of antimony.
Thus cold cranking performance comparable to Pb-Ca-Sn alloy batteries could be achieved. Further gassing rate can b~
greatly reduced compared to conventional low antimony alloys because of the reduced antimony eutectic content and increased distribution of the antimony. The alloy has suEficient hot str~ngth and aged mechanical properties to be handled in casting and pasting. The reduced antimony content, and the addition of copper produce a reduced freezing range and uniform fine grained crack-resistant grain structure.
Finally, the a~loy is very Eluid and can be easily cast into -the thinnest commercially available grids.
The alloy of the invention may contain nucleating agents such as are present in conventional low antimony alloys. For example, sulfur, selenium, tellurium, phosphorous and/or aluminum may be incorporated into the alloy of the
6~
invention in amounts which do not destroy its mechanical or operational characteristics. However, such additives are not necessary for achieving the above~described beneficial characteristics oE the alloy of the invention.
invention in amounts which do not destroy its mechanical or operational characteristics. However, such additives are not necessary for achieving the above~described beneficial characteristics oE the alloy of the invention.
Claims (2)
1. A lead alloy for use in lead-acid batteries comprising 0.6 to 1.1 weight percent antimony, 0.06 to 0.25 weight percent arsenic, 0.1 to 0.4 weight percent tin, 0.06 to 0.11 weight percent copper and the balance lead.
2. The alloy of Claim 1 containing 0.8 weight percent antimony, 0.15 weight percent arsenic, 0.20 weight percent tin and 0.08 weight percent copper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/270,134 US4376093A (en) | 1981-06-03 | 1981-06-03 | Low antimony alloy |
| US270,134 | 1981-06-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1186169A true CA1186169A (en) | 1985-04-30 |
Family
ID=23030046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000402809A Expired CA1186169A (en) | 1981-06-03 | 1982-05-12 | Low antimony alloy |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4376093A (en) |
| EP (1) | EP0071001B1 (en) |
| JP (1) | JPS6020455B2 (en) |
| AT (1) | ATE19794T1 (en) |
| AU (1) | AU530569B2 (en) |
| BR (1) | BR8203214A (en) |
| CA (1) | CA1186169A (en) |
| DE (1) | DE3271120D1 (en) |
| MX (1) | MX164793B (en) |
| PH (1) | PH19538A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6229063A (en) * | 1985-07-29 | 1987-02-07 | Shin Kobe Electric Mach Co Ltd | Positive electrode plate for lead storage battery |
| US5120429A (en) * | 1987-07-10 | 1992-06-09 | Lummus Crest Inc. | Co-processing of carbonaceous solids and petroleum oil |
| JP2748126B2 (en) * | 1988-08-15 | 1998-05-06 | 日本製箔株式会社 | Lead alloy rolled foil |
| NL9101376A (en) * | 1990-08-16 | 1992-03-16 | Digital Equipment Corp | AN IMPROVED ERROR DETECTION CODING SYSTEM. |
| US5352549A (en) * | 1992-08-19 | 1994-10-04 | Gnb Battery Technologies Inc. | Lead oxide composition for use in lead-acid batteries |
| US5508125A (en) * | 1994-03-21 | 1996-04-16 | Globe-Union Inc. | Battery straps made of a lead-based alloy containing antimony, arsenic, tin and selenium |
| US6114067A (en) * | 1998-04-08 | 2000-09-05 | East Penn Manufacturing Company, Inc. | Corrosion resistant lead alloy for lead-acid batteries |
| US20050112470A1 (en) * | 1998-06-26 | 2005-05-26 | Johnson Controls Technology Company | Alloy for battery grids |
| US20040110067A1 (en) * | 2002-12-06 | 2004-06-10 | Johnson Controls Technology Company | Alloy for battery grids |
| CN100385720C (en) * | 2006-01-05 | 2008-04-30 | 赵恒祥 | Alloy material of battery positive grid and preparation method thereof |
| US9168647B2 (en) * | 2008-10-21 | 2015-10-27 | Michael A. Logan | Automobile rim hammer |
| CN114284583A (en) * | 2021-12-27 | 2022-04-05 | 河南超威正效电源有限公司 | Method for reducing EFB power-on and power-off pool water loss |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA542499A (en) | 1957-06-18 | National Lead Company | Grid metal alloy | |
| US682330A (en) * | 1901-04-10 | 1901-09-10 | Hans Leyendecker | Alloy. |
| US1021997A (en) * | 1912-02-24 | 1912-04-02 | William Morrison | Storage-battery conductor or support. |
| US1674958A (en) * | 1924-06-21 | 1928-06-26 | Western Electric Co | Alloy |
| GB473911A (en) | 1936-06-04 | 1937-10-22 | Goodlass Wall & Lead Ind Ltd | Improvements in the manufacture of lead alloys |
| US2446996A (en) * | 1942-06-06 | 1948-08-17 | Bell Telephone Labor Inc | Metal objects coated with lead alloys |
| US2694628A (en) * | 1951-07-14 | 1954-11-16 | Nat Lead Co | Grid metal alloy |
| US2841491A (en) * | 1955-12-16 | 1958-07-01 | Gould National Batteries Inc | Battery grid alloy |
| DE1113579B (en) * | 1959-03-11 | 1961-09-07 | Accumulatoren Fabrik Ag | Lead-antimony alloy for the grid of the plates of electrical accumulators |
| US3287165A (en) * | 1964-12-03 | 1966-11-22 | Eltra Corp | High capacity lead acid battery with lead calcium negative grids |
| GB1461260A (en) * | 1973-03-15 | 1977-01-13 | Electric Power Storage Ltd | Electric storage battery grids |
| US3912537A (en) * | 1974-03-07 | 1975-10-14 | Electric Power Storage Ltd | Electric storage battery grids |
| GB1461266A (en) * | 1973-03-15 | 1977-01-13 | Electric Power Storage Ltd | Electric storage battery grids |
| DE2319711A1 (en) * | 1973-04-18 | 1974-10-31 | Metallgesellschaft Ag | Lead-antimony-arsenic alloys - used for constructional elements requiring high creep strength |
| DE2337708C2 (en) * | 1973-07-25 | 1983-03-24 | Accumulatorenfabriken Wilhelm Hagen Ag Soest-Kassel-Berlin, 4770 Soest | Lead-antimony alloy |
| FR2259156B1 (en) * | 1974-01-28 | 1979-09-28 | Metallgesellschaft Ag | |
| US3990893A (en) * | 1974-08-19 | 1976-11-09 | Varta Batterie Aktiengesellschaft | Lead alloy for battery grid |
| US4113476A (en) * | 1976-10-20 | 1978-09-12 | General Battery Corporation | Method of treating low antimony alloy battery grid material with phosphorus |
| US4158563A (en) * | 1977-10-11 | 1979-06-19 | N L Industries, Inc. | Low antimonial lead alloy for making grids for use in maintenance free batteries |
| DE2826590A1 (en) | 1978-06-19 | 1980-01-03 | Metallgesellschaft Ag | Lead alloy for mfg. accumulator grids - contains tin pref. together with arsenic and selenium and has relatively low antimony content to reduce cost |
| US4159908A (en) * | 1978-08-14 | 1979-07-03 | N L Industries, Inc. | Alkali metal containing battery grid lead alloy |
| DE2907227C2 (en) * | 1979-02-23 | 1985-05-09 | Metallgesellschaft Ag, 6000 Frankfurt | Use of a lead alloy |
-
1981
- 1981-06-03 US US06/270,134 patent/US4376093A/en not_active Expired - Fee Related
-
1982
- 1982-05-12 CA CA000402809A patent/CA1186169A/en not_active Expired
- 1982-05-20 AU AU83864/82A patent/AU530569B2/en not_active Ceased
- 1982-05-31 PH PH27377A patent/PH19538A/en unknown
- 1982-06-01 JP JP57093928A patent/JPS6020455B2/en not_active Expired
- 1982-06-01 MX MX7942A patent/MX164793B/en unknown
- 1982-06-02 DE DE8282104818T patent/DE3271120D1/en not_active Expired
- 1982-06-02 AT AT82104818T patent/ATE19794T1/en not_active IP Right Cessation
- 1982-06-02 BR BR8203214A patent/BR8203214A/en not_active IP Right Cessation
- 1982-06-02 EP EP82104818A patent/EP0071001B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| PH19538A (en) | 1986-05-20 |
| JPS6020455B2 (en) | 1985-05-22 |
| US4376093A (en) | 1983-03-08 |
| EP0071001A1 (en) | 1983-02-09 |
| DE3271120D1 (en) | 1986-06-19 |
| MX164793B (en) | 1992-09-24 |
| BR8203214A (en) | 1983-04-12 |
| ATE19794T1 (en) | 1986-05-15 |
| AU530569B2 (en) | 1983-07-21 |
| JPS581039A (en) | 1983-01-06 |
| EP0071001B1 (en) | 1986-05-14 |
| AU8386482A (en) | 1982-12-09 |
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