CA1187931A - Lead storage battery with expander supply - Google Patents
Lead storage battery with expander supplyInfo
- Publication number
- CA1187931A CA1187931A CA000426472A CA426472A CA1187931A CA 1187931 A CA1187931 A CA 1187931A CA 000426472 A CA000426472 A CA 000426472A CA 426472 A CA426472 A CA 426472A CA 1187931 A CA1187931 A CA 1187931A
- Authority
- CA
- Canada
- Prior art keywords
- expander
- storage battery
- lead storage
- supply
- electrolyte
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
LEAD STORAGE BATTERY WITH EXPANDER SUPPLY
ABSTRACT OF THE DISCLOSURE
The electrodes are supplied with expander material by providing a storage container with corrodible walls located in the acid electrolyte, which liberates its contents only after the original expander content of the negative active mass has already been significantly depleted. The wall material is either a plastic having limited acid resistance, or one of the metals Pb, Sb, Sn, or an alloy thereof. When using Sb, there exists a combined supply of expander and antimony. The latter counteracts the tendency toward crumbling of the positive mass which exists in Sb-free plates.
ABSTRACT OF THE DISCLOSURE
The electrodes are supplied with expander material by providing a storage container with corrodible walls located in the acid electrolyte, which liberates its contents only after the original expander content of the negative active mass has already been significantly depleted. The wall material is either a plastic having limited acid resistance, or one of the metals Pb, Sb, Sn, or an alloy thereof. When using Sb, there exists a combined supply of expander and antimony. The latter counteracts the tendency toward crumbling of the positive mass which exists in Sb-free plates.
Description
3~L
SY~ [F':[CArr`ION
The inventiorl relates to a lead storage batLery hav:irlg a sllpply o:f expander material located wi.thill the electrolyte, :Erom ~h:ich the expander is resuppli.ed durillg at le~ast a portion oE the :I-i.Ee o:E the storage battery.
Fxpallder add:itives to the negat:ive acti.ve mass are :i.nt:ende(l to counteract the formation oE compact lead crysta:Ls by inLerferillg wi.th :lead sepa:rat-ion during charg:ing, and thereby to mainta:in the highly porous s-tructure o:E the elec~trode p].ate~s. Suita~le expander materials are ba:riurll sulphate, high molec.ular organic substances, particu:larly l:i.gnin derivatives, or coloring materials such alizarirl .red :Erom the ser-.ies of hydroxyanthraquinolles.
~ ccclLIse the expander materials have si.gni.ficant solubili~y :Ln su~l.phur:ic acicl, there takes place a progressive leaching out of thc negative e].ectrodes, with the expander also reaching the positive e:Lectrodes in the course oI cyclical operation, where it is destroyed through oxldation. The consequellce o~ this loss of expander is a decrease in capacity andl :Eor starter batter:i.es, particularly a reduction in their performance in cv:Ld starts. The use of h:i.g}ler initia:L expandeI quantit:i.es in the rllass c:ompos; tions has been of on].y lim:itetl remedia:L
e~:fect for this short:com:ing because -this increased in:itial concentration was accompanied by a spreading ef:Lect in the ear:Ly stages of the storage battery liEe which substantiaLly exceeded the degree necessary in order to ach:ieve a predetermined currerlt: de'Live:ry capability.
SY~ [F':[CArr`ION
The inventiorl relates to a lead storage batLery hav:irlg a sllpply o:f expander material located wi.thill the electrolyte, :Erom ~h:ich the expander is resuppli.ed durillg at le~ast a portion oE the :I-i.Ee o:E the storage battery.
Fxpallder add:itives to the negat:ive acti.ve mass are :i.nt:ende(l to counteract the formation oE compact lead crysta:Ls by inLerferillg wi.th :lead sepa:rat-ion during charg:ing, and thereby to mainta:in the highly porous s-tructure o:E the elec~trode p].ate~s. Suita~le expander materials are ba:riurll sulphate, high molec.ular organic substances, particu:larly l:i.gnin derivatives, or coloring materials such alizarirl .red :Erom the ser-.ies of hydroxyanthraquinolles.
~ ccclLIse the expander materials have si.gni.ficant solubili~y :Ln su~l.phur:ic acicl, there takes place a progressive leaching out of thc negative e].ectrodes, with the expander also reaching the positive e:Lectrodes in the course oI cyclical operation, where it is destroyed through oxldation. The consequellce o~ this loss of expander is a decrease in capacity andl :Eor starter batter:i.es, particularly a reduction in their performance in cv:Ld starts. The use of h:i.g}ler initia:L expandeI quantit:i.es in the rllass c:ompos; tions has been of on].y lim:itetl remedia:L
e~:fect for this short:com:ing because -this increased in:itial concentration was accompanied by a spreading ef:Lect in the ear:Ly stages of the storage battery liEe which substantiaLly exceeded the degree necessary in order to ach:ieve a predetermined currerlt: de'Live:ry capability.
-2--In accordance w:itll German Patent :l~uh:L:i.cclt:ion ~O.E~enle--gllrlgssc~lrift) ~,~55,3:1.3 it. Ilas there:Eore a1.rea(ly heen propose(l io store expander rnater:ial in 1 vessel. whic}l is in commuTl:icatio w:i.th the aci d electrolyte through a small Opell:ing, SO that thcre ta~es place delivery o:E expander contirluousl.y, as a furlctiorl of the cross-section of the opening, the satl1ration concerl~-ratio!l, and the difEusi.on coef:Eic-ients, over an exterl(led period o:E time. 'l'he drawback o.E this ar:rangmenl: is that the delivery o:[ spreader mater:i.al from the storage starts as soon as the cel.:L is .E:illed.with the acid. Due to this unrestricted start of the addition of stored material to th~ normal delivery of expander :Erom the negative p].ates theIe a:rises~;n over-supp:ly, -in a manner sirnilar to that previous~l.y desc:ri.bed above.
'l'he reasorl i.s that, in a new storage battery ce:L:I., the quant:ity of spreader materlal in the negative mass is :ini.tia:l:ly made su:Eficient for several. hundred cyc:Les.
~ ccordi.ngly, it is an object of the p:resent inventi.on to provi de a storage arrangement for the ex~parlder m.ltcri.al :in such a manner that .i.ts.consumption is llrevented at least i.n the early stage of the storage battery l.:i.fe, and that it is suppl:ied only Lrom a subsequent point in t:i.me, progressively, an(l in accordance w:i.th the true need.
Th-i.s and other objects lhich wil]. ap~pecll^ are achieved in ac(:ordance with thc! invention by separat.i.ng tlle expander supply l.rom the elect3-olyte by a barr:ier materiLI~l., which disso:lves s-Lowly in the electrolyte and li.berates the expander af-ter a predc~l:ermi.nlbll~ ti.lile period~
7~3~
llpon the start o cycl:ical operation9 the barrier materiaL
:is perlllallently sllbjected to a corrosi.ve alternating attack :in Lhe surrourlcl:ing, su.lphuric ac:id contain~ g n~edium. Th:is mecl:i.um ~:irsL causes an oxidative decompos:itiorl of the barrier nlater:ial, wh:ich initially p:~ovides an inperrneab:Le wal.l between the spreader and the electro~yte. However, :i.t :is only aEter a preclete:rminecl time that the inEluence o:E thc decompos:ing :for.e- ,o welkens the barrier parti-ti.on that ;.t ruptures i.n places, and the expander material which is there no ].onger protectecl :is taicen up by -the su:Lphuric acid, oxid:izes, and begins to dissol.ve. The conti.nuing destruction oE the wal:l causes the resupply of expander material to both electrode polar:it:i.es to continu~ steadily, so that good current loaù
capacity an(l mass uti.liYation are assured at least :Eor an aclclitio~ l po:rtion of the storage battery l:i:Ee.
A suitab].e wall material for the expander supply embodying the :invent:ion is Syntlletic pl.astic. Included7 fo:r this purpose, are all synthetic resin products whicll have lim-ited resistance to a sul.phuric acid medium, both pure po.Lymers~ as well as co- or homo-polymers. These products may exh:ibit the most varied degrees of corrosion resist:lnce, not only because of the:ir chemical structure, but also because oE aclcl:it:i.ves o:E
softeners and stabiliY.ers, so that a user has a wide choice with respect to a suitable wall materia:l..
As the principal parameter influencillg the corrosi.on speed o:E a synthetic p].astic, there may be cons-iclered its degree Or polymeri7ation. Tllils, a low po].ymcr:ic syTIthctic .resin product clecomposes more~ rapidly than a high polymeric ~'7~
pro(lucL wiLh corresl)c)l-ldirlgly higll molecu:Lar we:ight. Unclc!r the preva:i~ing circumstances, t}le decomyosit:i.on duration o.f a p:Lastic, l~h:i.Ch o:E course also clepends uporl wall. thicl<ness, CaTI vary from a few months to many years. ~xarnp:l.es of plast:ics which are suital)le :For the invent:ion are: polyv:inylchloride, polys~ Eonates, epoxy resins, po:l.yethyleneterephtllalate, polybut~l.enetereplltllalate, polyethy]elle, polypropylelle, poly-i.et::r~LIuoret}ly:l.erle, polytrifluo;-ochl.oroeL}Iy]er~e. Howevc~r, th:is lisl::ing is not to be considered as e~clusi.ve.
Anotller sui.table wall material for the expander supply embodying the invention may be a metal, beca~se its at-tack hy corrosi.on proceeds relatively uniform:Ly and in a speci:Eic manller. However, there are preferably selected such metals as do not detrimenta:Lly influence the electrochemiccll per:Eormance o:E -thè ceJ.l, e:ither at all, or to a neg:l.ig;b:Le extent. Particularly des:irable :E:rom th:is standpoint within a lead storage battery are lecLd, antimony, or tin, including b;.nary and ternary alloys o:f these metals. An antimony membrane would hclve the add;tiollal aclvantage that -l:he expander snpply secondari:l.y Eunctions as an antimr-ny supply, sincr-~ the progressive dissolut;.on of tl-le barrier wall causes antimony in the form of ant-imony conta:i.nillg
'l'he reasorl i.s that, in a new storage battery ce:L:I., the quant:ity of spreader materlal in the negative mass is :ini.tia:l:ly made su:Eficient for several. hundred cyc:Les.
~ ccordi.ngly, it is an object of the p:resent inventi.on to provi de a storage arrangement for the ex~parlder m.ltcri.al :in such a manner that .i.ts.consumption is llrevented at least i.n the early stage of the storage battery l.:i.fe, and that it is suppl:ied only Lrom a subsequent point in t:i.me, progressively, an(l in accordance w:i.th the true need.
Th-i.s and other objects lhich wil]. ap~pecll^ are achieved in ac(:ordance with thc! invention by separat.i.ng tlle expander supply l.rom the elect3-olyte by a barr:ier materiLI~l., which disso:lves s-Lowly in the electrolyte and li.berates the expander af-ter a predc~l:ermi.nlbll~ ti.lile period~
7~3~
llpon the start o cycl:ical operation9 the barrier materiaL
:is perlllallently sllbjected to a corrosi.ve alternating attack :in Lhe surrourlcl:ing, su.lphuric ac:id contain~ g n~edium. Th:is mecl:i.um ~:irsL causes an oxidative decompos:itiorl of the barrier nlater:ial, wh:ich initially p:~ovides an inperrneab:Le wal.l between the spreader and the electro~yte. However, :i.t :is only aEter a preclete:rminecl time that the inEluence o:E thc decompos:ing :for.e- ,o welkens the barrier parti-ti.on that ;.t ruptures i.n places, and the expander material which is there no ].onger protectecl :is taicen up by -the su:Lphuric acid, oxid:izes, and begins to dissol.ve. The conti.nuing destruction oE the wal:l causes the resupply of expander material to both electrode polar:it:i.es to continu~ steadily, so that good current loaù
capacity an(l mass uti.liYation are assured at least :Eor an aclclitio~ l po:rtion of the storage battery l:i:Ee.
A suitab].e wall material for the expander supply embodying the :invent:ion is Syntlletic pl.astic. Included7 fo:r this purpose, are all synthetic resin products whicll have lim-ited resistance to a sul.phuric acid medium, both pure po.Lymers~ as well as co- or homo-polymers. These products may exh:ibit the most varied degrees of corrosion resist:lnce, not only because of the:ir chemical structure, but also because oE aclcl:it:i.ves o:E
softeners and stabiliY.ers, so that a user has a wide choice with respect to a suitable wall materia:l..
As the principal parameter influencillg the corrosi.on speed o:E a synthetic p].astic, there may be cons-iclered its degree Or polymeri7ation. Tllils, a low po].ymcr:ic syTIthctic .resin product clecomposes more~ rapidly than a high polymeric ~'7~
pro(lucL wiLh corresl)c)l-ldirlgly higll molecu:Lar we:ight. Unclc!r the preva:i~ing circumstances, t}le decomyosit:i.on duration o.f a p:Lastic, l~h:i.Ch o:E course also clepends uporl wall. thicl<ness, CaTI vary from a few months to many years. ~xarnp:l.es of plast:ics which are suital)le :For the invent:ion are: polyv:inylchloride, polys~ Eonates, epoxy resins, po:l.yethyleneterephtllalate, polybut~l.enetereplltllalate, polyethy]elle, polypropylelle, poly-i.et::r~LIuoret}ly:l.erle, polytrifluo;-ochl.oroeL}Iy]er~e. Howevc~r, th:is lisl::ing is not to be considered as e~clusi.ve.
Anotller sui.table wall material for the expander supply embodying the invention may be a metal, beca~se its at-tack hy corrosi.on proceeds relatively uniform:Ly and in a speci:Eic manller. However, there are preferably selected such metals as do not detrimenta:Lly influence the electrochemiccll per:Eormance o:E -thè ceJ.l, e:ither at all, or to a neg:l.ig;b:Le extent. Particularly des:irable :E:rom th:is standpoint within a lead storage battery are lecLd, antimony, or tin, including b;.nary and ternary alloys o:f these metals. An antimony membrane would hclve the add;tiollal aclvantage that -l:he expander snpply secondari:l.y Eunctions as an antimr-ny supply, sincr-~ the progressive dissolut;.on of tl-le barrier wall causes antimony in the form of ant-imony conta:i.nillg
3-- and 5- valenced ani.ons (SbOSO~, [H5n 5Sbll5nl ) migrates to the electrodes and advantageous]y inf]uences at least the behav.ior o:E the posit:ive electrode. Th:is i.s because, .i.f the electrode grids are of an antimony-f.ree al.loy, e.g.
lead ca].cillm, which is desi:rable because of high hydrogen overpotelltia], t~lell exper~ience hcls sho~n that tllese positive e:l.ecLrocles have a tendency toward increased cr~lrnb:l..ing, a 3~
d:isadv.l[~iag~ whic.h grid plates ~ith anti.rnc)ny---cc,nla-;rlirlg al].oy gri c7~s clo not exh:i.b-it clue to suf'c'iciellt antimorly presellce in the active positive mass.
Because, on the other hand, a posit:ive elect:rode grid of a lead antimony alloy corrodes mLIch mor~ qlliclcly than an arltirllony--free grid, positive e:lectrocles ~;th allt~ lony-Eree gr i dC; Call be L~sed with unrestricted advantage, when the pos;tive active mass :i~s supp:liead with antimony for prevent:ioll of crurnb].illg not from the grid itself, but from the corroding snp~ly barrier wall. This arrangement embodying t.he invetltion is particularly desirable Lor storage batteries wh:ich are s~lbjected to a strong cyclical Load, with occas:ional deep cliscllarge, and which contain antirnony-free grid p~Lates.
lead ca].cillm, which is desi:rable because of high hydrogen overpotelltia], t~lell exper~ience hcls sho~n that tllese positive e:l.ecLrocles have a tendency toward increased cr~lrnb:l..ing, a 3~
d:isadv.l[~iag~ whic.h grid plates ~ith anti.rnc)ny---cc,nla-;rlirlg al].oy gri c7~s clo not exh:i.b-it clue to suf'c'iciellt antimorly presellce in the active positive mass.
Because, on the other hand, a posit:ive elect:rode grid of a lead antimony alloy corrodes mLIch mor~ qlliclcly than an arltirllony--free grid, positive e:lectrocles ~;th allt~ lony-Eree gr i dC; Call be L~sed with unrestricted advantage, when the pos;tive active mass :i~s supp:liead with antimony for prevent:ioll of crurnb].illg not from the grid itself, but from the corroding snp~ly barrier wall. This arrangement embodying t.he invetltion is particularly desirable Lor storage batteries wh:ich are s~lbjected to a strong cyclical Load, with occas:ional deep cliscllarge, and which contain antirnony-free grid p~Lates.
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A lead storage battery having a supply of expander material for location within electrolyte of the battery, from which supply the expander material is suppliable to the electrolyte at least during a portion of the life of the storage battery, the supply of expander material being at least initially separable from the electrolyte by a barrier material which is slow-ly dissolvable in the electrolyte to thereby liberate the expander after a predetermined time.
2. The lead storage battery of claim 1 wherein the barrier material is a synthetic plastic.
3. The lead storage battery of claim 1 wherein the barrier material is a metal.
4. The lead storage battery of claim 3 wherein the metal is lead, antimony, tin, or an alloy of at least two of these metals.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3215489.5 | 1982-04-26 | ||
DE19823215489 DE3215489A1 (en) | 1982-04-26 | 1982-04-26 | LEAD ACCUMULATOR WITH EXPANDER DEPOT |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1187931A true CA1187931A (en) | 1985-05-28 |
Family
ID=6161958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000426472A Expired CA1187931A (en) | 1982-04-26 | 1983-04-22 | Lead storage battery with expander supply |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0092604B1 (en) |
JP (1) | JPS58198869A (en) |
CA (1) | CA1187931A (en) |
DE (2) | DE3215489A1 (en) |
FI (1) | FI831214L (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3237828A1 (en) * | 1982-10-12 | 1984-04-12 | Accumulatorenfabriken Wilhelm Hagen AG, 4770 Soest | Lead-acid accumulator cell |
DE3303142A1 (en) * | 1983-01-31 | 1984-08-02 | Accumulatorenfabriken Wilhelm Hagen AG, 4770 Soest | Lead storage battery cell |
DE3702137C2 (en) * | 1987-01-24 | 1994-09-08 | Vb Autobatterie Gmbh | Electrical accumulator with a device for introducing active substances into the electrolyte |
GB2209241B (en) * | 1987-08-31 | 1992-04-15 | Shin Kobe Electric Machinery | Lead accumulators |
US4751155A (en) * | 1987-09-01 | 1988-06-14 | Globe-Union Inc. | Method and apparatus for the preparation and installation of battery explosion attenuation material |
GB2399215B (en) * | 2000-03-20 | 2004-10-27 | Johan C Fitter | Method and apparatus for achieving prolonged battery life |
AU4584201A (en) | 2000-03-20 | 2001-10-03 | Johan C Fitter | Method and apparatus for achieving prolonged battery life |
FR2846150B1 (en) * | 2002-10-16 | 2005-01-28 | Renault Sa | DEVICE FOR DIAGNOSING THE CORROSION CONDITION OF A BATTERY, IN PARTICULAR A MOTOR VEHICLE |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR356950A (en) * | 1905-08-16 | 1905-12-13 | Max Boloff | Method for increasing the capacity of electric accumulators |
BE684284A (en) * | 1965-07-20 | 1967-01-03 | ||
US3773563A (en) * | 1972-02-22 | 1973-11-20 | Carbone Corp | Life indicator for primary carbon zinc batteries |
DE2736750C2 (en) * | 1977-08-16 | 1979-05-31 | Varta Batterie Ag, 3000 Hannover | Negative electrode for lead-acid batteries and process for their manufacture |
DE2855313A1 (en) * | 1978-12-21 | 1980-07-10 | Varta Batterie | LEAD ACCUMULATOR |
-
1982
- 1982-04-26 DE DE19823215489 patent/DE3215489A1/en not_active Withdrawn
- 1982-11-30 EP EP82111064A patent/EP0092604B1/en not_active Expired
- 1982-11-30 DE DE8282111064T patent/DE3274036D1/en not_active Expired
-
1983
- 1983-04-12 FI FI831214A patent/FI831214L/en not_active Application Discontinuation
- 1983-04-22 CA CA000426472A patent/CA1187931A/en not_active Expired
- 1983-04-25 JP JP58071570A patent/JPS58198869A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0092604B1 (en) | 1986-10-29 |
EP0092604A1 (en) | 1983-11-02 |
JPS58198869A (en) | 1983-11-18 |
DE3274036D1 (en) | 1986-12-04 |
DE3215489A1 (en) | 1983-11-03 |
FI831214A0 (en) | 1983-04-12 |
FI831214L (en) | 1983-10-27 |
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