THE Industry: French Sulphate of Copper

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212 CHEAUSTRY AND INDUSTRY Fcb.

24, 1028

THE FRENCH SULPHATE OF COPPER tioii wliicli mildcw and black rot will alonc cficct in IL

INDUSTRY viiicynrd, if not 1;cpt uiidcr control, is nppalling, aiid


has t o bc sccn to bc rcnliscd. In inorc scnscs tliaii one
By H. E. DREW tlicsc tliscnscs form tlic b&/ciioire of the growcr. Their
Sulphatc of coppcr, popularly k n o w ns blriestonc,” ravng:, nrc prcvciitcd in ordinary circamstaaccs by
If

is, of coiirsc, a wcll-hiown chcniicnl product. Every sprnyiiig tlic vincs wit11 n 2 to 3% solution of tlic sulplintc
farincr, for csnmplc, is advised to apply solutions of (with tlic nddition of about tlic same qu:~ntityof liinc
i t to his crops, pnrticnlitrly potntoes. hnotlicr usc is or cnrbonatc of soda) froin tlic Inomcnt that tlic growtlls
nssocintcd with thc clcctricnl industry. Howcvcr, a attnin four or fivc incltcs i n length, usunlly about tlic
few tons of tlic sulphatc will covcr lnrgc nrcns of cnd of April or bcginning of Xny, nnd this trcntmcnt
potntocs, and d l snfBcc for quitc n considcrablc is repented at vnrious stzges of grox\.th up to about :L
iiiiiiibcr OF clcctrical nccuiniilators aiid cclls. iiiontli or six ivccks before tlic fruit is likely t o bcconic
Tlicn \ d i n t is tlic ultimntc purposc for which itre r i p . A n acre of grnpc vincs thus treated will ~iorninlly
cmployctl the thousands or tons wliicli arc miiiually rcquirc nbout 1 cwt. of sulplintc:
niaiiiilnctnrcd in Grcnt Britniii, Bclgiuin, Italy ? Stn- This spriiyiiig is uniloubtcdly clfcctivc as it prcvcntirc
tistics show tlint tlic rlcst,in:itions of the British cxports incnsurc, but docs not b y any iiiciiiis providc n cure.
arc iiiaiiily those comitrics \~Iicre tlie grnpc vine is Slioiiltl unusunlly \vet wcnthcr be cspcricnccd, wit11
cultiviitcd, wlicther for tho piirposc of producing raisins, frcqucnt intcrvnls 01 hot siinshinc, tltc fungi nrc siirc to
frcsli fruit or wine. Tlic principal consunicrs in lkiropc appear, mid iindcr such conditions mny gct cntirely
iirc l?riiiicc, Spain, l’ortugnl, Italy, Greccc, Runinnin. out of control. Tlic rcsult. is t l i i i t tlic growcr has his
Algcria is also nn irnportaiit custonicr. I h r i n g recent output of winc grcntly rcdiiccd, cvcii t o vniiisliing point..
ycars tlic Uiiitcd Stntcs ol Biiicricn, linvc also pnrc1i:iscd whilst t h quality of wliitt hc docs scciirc will bc impnirctl
i n Ihropc, doubtlcss in vicw of tlicir Iiiglier cost ol pro-
cliictiou-for a t OIIC tinic tlic Aincricniis iiscd to export. NEICI) F O I ~ SCCCXTIFIC Iti.:st.:~\acrr
The V ~ U of C tllc nlmLltlct11rc of coppcr su1ph:rtc lroni Tlicsc fungi :\fiord ii, rcrp lnrgc and proniisiug ficltl
tlic 13ritish point of view ns an industry Ivns n t oiic tinic lor sciciitific rcse:i,rch, aiicl thc discovcrcr of n less costly
neglectcd, ivlicn, straiigc t o sny, tlic priccs obtiiincd iiictliocl of destroying or conibn.tiiig thoin than by tlic
w r c very inucli inorc rcniuncrntivc tlinn t h y :ice now. iisc of coppcr sulpliiitc is ccrtnin of immciisc \\-cslth.
Tlicn tlic iutlustry wns in thc litinrls of :I very sniall I h would bc reasoilable to supposc, for iiistnncc, tlint tlic
iiunibcr of ~riniiufnct~rrcrs, iriicreiis within tlic last fcw ciioriiious qu:i,iititics of sulpliate of coppcr which arc
ycnrs i t lins bccn iiivatlctl by tlic Itdinns, who hnvc ciiiploycd ycnr nftcr y e w on tlic saiiie yincs \vould Ii:ivo
fire or s i s conipnnics cngiigcd thcrcin, aud by tlic 11 dctcrriiig cficct, niid niiglit cvcn lend to tlic stamping
13elginiis ; two B~Igiiiiiiirins nlonc arc capiiblc ol pro- out of tlic diseascs--but this is not so. If a wine growcr
tlucing 1000 tons of coppcr sulpliatc per \rcclc as a should iicglcct to s p w y his vines, or should not do so
tlircct product, ns tlistinct from :I by-product. ‘I’licsc a t tlic opportune moment, tlic vincs arc ccrt.aiii to bc
tiyo coutitrics hiivc clrnngcrl tlie sitinntion cntirely froin nttnckcd, and tio grower woiiIc1 tl1iiik of taking ttic risk.
tlic stnndpoiiit of h i t i s l i iiidust,ry ; not: only ciiii ‘[t.aly Conscquently, in July nnil August thc vincs frcquciitly
producc licr own rcquircnicnts, h i t slic is also iiblc to Iinvc i i n unitttr:ictivc appcarancc uiidcr tlicir covcr of
export, wliilc 13clgiu11iis perlinps still inorc forniidsl)lc, wliitcw;isli, or inorc corrcctly bluc wash, an appcnriiucc!
ns, Iinving no doincstic consitniption, slic relics on licr wliicli is not iiiiprovcd by tlic two or tlirce dustiiigs of
cxports cntircly, with thc coiiscqiiciicc tlliih: nitlctl by dry suIpIiiir which the vincs lirivc by tlicii ~IISOrcceivcd.
clieitp Inbour nut1 it fnvourablc currcncy, slic lins bccii Jt ~ ~ o u also
l d bc rensonnblc to assunic tlrrtt tlic earth
able to ctitcr niniiy mnrkets wlticli \wrc prcvioiisly itself would i n tiiiic bcconic iniprcgnntcd with tlic
sup-plictl froiii Englniid. Oiic direct result is tliat a11 sulplintc, sinoc tlic COplJCr contniiicrl in tlw sulplintc,
Englisli firm, wliicli fornicrly occupicd it Ici~diiigposition npplicd to t.lic lenvcs of tlie vincs, rcturns to cnrth with
in this industry, and nlonc mnnufncturctl up to 1000 cverytliing CISC. But nliiilyscs of soils h n ~ crc\wiIecl
tons of coppcr sulphatc pcr ~ v c c k ,lins closctl d o ~ nits citlicr 110 trncc of tlic stilplinte, or iusuliiciciit in corn-
\~nlunblcpinnt. pnrison with tlic qiiiiiit,itics so continunlly npplicd.
It is prohnbly no csiiggcration to say tlint tlic con- Tlicrc iirc niany OtIicr itspccts of tlicsc tliscnscs wIiicIi nrc
sumption of sulphntc of copper lor tlic prodwtion of but vngucly u11dcrstootl.
winc fornis 76% of tlic total iiianuf:ictiirc, nnd in Frniicc
alonc this consumption iiiny ctisily rcncli 100,000 tons TIII.:ImusTiiY
during n iiorinnl ycnr, worth npproxi1nntcI-y f3,000,000. In vie\\. of tlic vitnl ieiportniice of su1pli:itc of coppcr
Ccrtaiii i t is t h a t without this sulpliatc, winc would bc to w h n t is onc of tlic iiiost vuluablc of tlic l’fcnch intltls-
\ ~ riliicli
y liiglicr in pricc t l i i n i i t is a t prcscnt, if, inttccd, tries, i t is not; surprising that nttcnipts sliodd h v c bcca
tlic winc would not bc uiiprocurnblc. Tlic grnpc vinc mndc to I I W ~ U ~ ~ Ct,lic ~ I Isupplics
~ ~ tit liolnc. There
is sitbjcct to dcndly attncks by niilny k i d s of fuiigi nrc n t prcscnt sevcriil fiictorics in li‘raiicu wlicrc sulphetc
wllich, if not kept in clicclc by copper sulphatc, would of coppcr is proilucccl, but in very fcw iiistitnces is
soon cnusc n viiicynrd, coiitnining, pcrhnps, 100,000 reliniicu plnccd solely on its mnniiliicturc for tlic mnintcti-
viiics, t o bc totally niiproductivc ol grnpcs ; thc lenvcs nncc of n business. A s a rule sulpli~ites ol otltcr
of tho vines n;oultl withct rtnd fall, wiiilc nny signs of inct;ds nru ulso ntndc, or tirtificinl iiiiiniircs nncl o t h r
fruit miglit easily bc rediiccd to a po\vdcr by iiicrcly cliciiiicul products. Although tliu aggregate productioii
rubbing tho buuclies bctwccti tlic hautls. Thc dcvasts- ot Fruncli manufncturcrs ot coppcr sulpbnto is important,
Ycb. 21, 1D28. CHEMISTRY AND INDUSTRY 213

with one or two exccptions they nrc not perfectly GO r.p.m. Furthcr, the liquor is cooled rapidly, in less
cquippcd with tlic spccialisatioii which is iieccssnry for tlinn an hour, by mcans of cold wntcr pnsscd though coils
this industry, nor for tlic purchnsc of tlic raw nintcrial of 13 in. lend piping, of 400 to 500 ft. in length in all,
-copper. Neither in Frnncc nor in hcr colonics arc tlierc placed in tlic tank. Owing to tlic liquor being constantly
copper mines in a vigorous state of dcvelopmcnt, witli tlic in motion the crystnllisntion givcs very small crystals
result that thc copper itself lias to bc imported. London cn.psblc of passing n sicvc liaving from 19 t o 30 meshes to
bcing tlic ccntrc of thc Europenii copper mnrltct, piirclinscs thc linenr inch. M711cn cool t h liquid is filtered,
are invariably based on tlic rntes pmcticcd tlicrc, nnd on tlic gmnulcs arc ilricd in a rotnry hydro-cxtrnctor
stcrliiig prices. Thc snmc reiiinrk applies, indced, to and with liot air, nnd sifted. The main points of
snlcs of “ scrap” coppcr in Frnncc, and a t times so kcen importniicc hcrc arc thc proper strength of tlie original
is thc dcmnnd for this innterinl (old boiler plates iiiid liquor (G2” Twaddcll), rapid cooling, and correct spcetl
tubes, filings, turnings, wire) that tlic prices pnid arc of thc agitator.
oftcn in csccss of thc Iandcd cost of iiiiportcd ingots, These grniiulcs, known in Francc as I‘ ncigc,” nrc used
notwithstnnding that tlic Governinciit prohibitcd tlie for the inanufnctnrc of “ bouillie,” which is a mixturc
csport of crude copper in nny form. containing 50 to GOO/, of coppcr sulpliate, 20 or 301/,of
Tlic purclinsc of copper itself tlicrcforc prcseiits sonic sodiiim cnrbonntc, and the rcmnindcr in china clay or
diIficiilty to tlic ordinary Prcnch mnnufncturcr of similar substnncc to cnnhle thc mistmc to ndherc to thc
sulphntc, for ‘ I standiird ” prices niid tlic differcncc in vincs wlicn iipplicd in n 2 to 3:/0 solution. Wenrly cvcry
currency, with tlicir lioimly fiuctuntions, ilcinnnd very maniifncturcr adds R sn?nll amount of nrtificinl colouring
carcfnl iittention. It is t h e filings iind turnings t1i:it ninttcr, solely to improvc tlic appcnrniicc of thc finished
appcal most strongly t o tlic Frencli innniifocturcr, for nrticlc. The usc of this “ bouillic ‘’ is iucrensing i n
givcn his r n w inaterial in these forms i t is rcndy to bc populnrity, for, being rcndy for iiiixing with tlic \utter;
plnccd direct into tlic dissolving clininbcr, wlicreiis wlicn i b obviates tlic laborious work of wcighing, hnndling and
lnrgc pieccs of iiictal, or ingots, h a w to bc traitctl, it is dissolving tlic siilphate and liinc scpsr:itely in tlie
first iiecessnry to siiiclt. This is usunlly cfiectcd in such viiicynrd, tlioiigh ninny iiscrs claim that tlic siilpliiitc
a nianiicr. as to produce liollow splieres or ’ I sliot,” so iund liiiic, niailc frcslily on tlic spot, is fnr superior to the
that tlic metal ~ i i t ~thusy I>rese1it as 1nl.g~:L siirfiicc :LS ‘ I boiiillic,” wliicli contnins soda in pliice of tlic lime.

possiblc t o tlic dissolving ncid. Tliis is irccoiiiplislicd Tn order to avoid tlic iiac of tlic ’‘ ncigc ” mnnnfncturcrs
by running tlic nioltcn nietnl slowly into 1% deep t i i n k of Iiiivc iit,tcinptcd to iisc for tlicir ’’ 1)ouillic ’’ thc ordinary
hot water, :uid in sonic C ~ S C Stlic niet:il is riin direct from crystnls wlion ground into n powder, but tliis mctliod has
:in oil-fired furnncc. ‘l‘liis pnrticulnr proccss is onc tlic tcndcncy to caii~ctalieAnislied nrticlc to bccoine solid
t l i n t calls for knowlcdgc nnd esperieiicc, if only on account whcn kept for nny lcngtli of time owing to thc cffcct of
of tlic liiglily csplosive gas wliicli inay bc gencrtited in ntmosplicric iiioist,iirc,wlicrcns by tlie iisc of thc ‘ I ncigc,”
tlic tank and niny bc igiiitcd by tlic hot mctal. or coiiiplctc crystnls, this tciidciicy is grcntly rcdiiccd if
‘l’lic coppcr is tlien plncctl into tlic clissolvcr, iisuiilly not cntirclp absent.
constructed of Iiiiisonry, niid capable of liolding 20, 30, J 7 , ~ 1 ~OF
u ~‘rim ‘rR8i\Di.:
o r 40 tons of mctnl. It tlicrc rcccives spr;iys of hCJt
sulpliuric acid from nbovc and jets of steiiin from bclow. Thc following stntistics show that tlic vnIue of t,Iiis
Tlie stciini is one of tlie important fiictors, for it ciisurcs sulplintc tmilc and of tlic necessrury copper therefor has
tlic osidittioii of tlic coppcr. Tlic resulting liquid is not bccn gcncrnlly rccognisccl in lhglniid :-
filtcrcd rind run into Icnd-lincd tnnla, wlicrc nftcr six I!li5 10?.1 l!I9
mrtrlc toiis iiietric toils inctrie toiir
or scvcn days’ rcposc, dcpciiding on tho tcmperiitiirc OF Totiil Iiiiliorts tit copper
.. . . .. .. ..
biilpliiitc i i i t o
Frniice l8,7!l:! 21,875 2O,HJ2
tlic nir, i t cools tiiid crystdliscs on tlic Icnil. T o iwrcnsc Totel eqiorta oi ruplicr siilpliiitc froiii
thc n r c i ~of crystnllisution strips of thc Iciid arc suspcndctl l’riiiice .. ..
Tutnt iiiipurts oc eoppc;ilito
.. ..
I:rnuco..
l;,:ll:I
IW,OGU
8.145
IW,I:I~
11.70U
12ti,i~
I;L. Ijrltnin ..
iu tlic tank. M’licn thc crystnllisntion is coniplctc tlic
rcmniuing liquid is brought to its ncccssary strciigtli
01 wtii~!li froiii
,) )) Ullitctl StiitCJ
iU,326 ... ,
O:I,.LGrJ
::,LOO Il,OiY U,.131l
HI,IVI

with ncw iicid, hentcd, niid fed again t o the dissolver. Tlicrc is st,ill ample scopc in Braiicc for t h c csploitiition
‘l‘lie iiitinufticturc of the sidplintc is tlicii prncticnlly of British cnpitnl in this indust,ry provi‘idcd tlint tlic
complctc, cscept tlint thc crystnls tire wnsliccl, tlriccl, bnsincss is thoroughly wcll cquippcd coiniiiercinlly, as
sifted into largo niid sninll sizcs with a #-in. Ricvc, nnd wcll as tcclinically. licceiit and cvcr-incrcnsing custoins
~ ~ n c k cind sncks. Thc sifting is rciilly II wnstc of time duties on ninnnfncturcd nrticlcs, :ind tlic rclntivcly lowcr
. niid liibour, but ns tlic smaller crystnls on account of their cost of labour i n Frnncc, iiinkc it advisnblc that any uew
size do not show tho chnrnctcristic bluc to tlic s:inic depth dcvclopmcnts sliould I)c conductcd i n tlic country. Good
a8 tlic lurgcr oiics, t h y nrc rcgnrdctl witli riuspicion by lnbonrcrs arc paid n t prcscnt from 3.50 to 4.00 fnincs
tlic wiric grower, iiotwitlistiiiitliiig t l i nt tlic wliolc output i i n hour, nnil nrtisnns from 4-00 to 5-00 francs. 111
is of tlic siiiiic composition. Brnncc tlic total cost of lnbour in tlic iiinnufncturc of
Comincrcid sulphutc of coppcr, lio\vcvcr, is on’crcd snlplllltc of coppcr sl1011ld not cxcccil n t tl1c lllolncnt
also in the foriii of sninll grnnulcs, nnil licrc tlic process GO to SO frnncs p r ton ou an output of, say, 150 tons per
bcitrv markcd diflcrcnccs to tlio mnniifnctiirc of tlie week ; fucl n i i d sulpliuric ncid nrc wcll covcrcd by
ordinury crystals. Tlic liquor froin tlic clissolvcr, whcn 2?O frnncs pcr ton, nntl ns 5 cwt. of coppcr n t f i n avcrngc
run into tho cooling tad;, is in this case stirrctl to kccp it cost of 160 pcr ton will suflicc to ninlc onc ton of sulphntc,
in motion iiistcad of bcing nllowctl to repose. Tlic tlic totnl cost of ~iianufnctitr~, cscliisivc of nll ovcrlicrrtl
stirring is cl’fcctcd by a woodcn ngitntor rotntctl n t 50 to clinrgcs, ninoiints to approximntcly f17 10s. pcr tou of
814 CKEMISTRY AND INDUSTRY Fob. 91, 1928

sulpkate, and yields a gross profit of 35 to 40% 011 Pc(OH), and Bc(OH), to Be, but may not rcmovc
present selling prices. the passivity, although it is considered that an cxccss
It mill bc sccii from the foregoing that thc manu- of hyclrogcn, produced a t the plate by clcctrolytic
facture of sulphatc of copper is a question of spcclal- effects during charge, can rcmovc passivity. Even if
isation rather than one that calls for a high dcgrcc of this assumption is corrccli, it is possible that under
clicmical kno-xlcdgc, for thc principal rcquircmcnt from some conditions of charge thc amount of hydrogen
tlic point of view of chemistry is thc ability to make care- produccd would be iusufficicnt to remove all traces
fill and minute analyses as a clicck on manufacture aiid of passivity, and 011 subscqucnt discliargcs f urthcr
an assurance against waste and loss. As an esample, the passivity would occur, the effect being cumulative.
iinpurities contained in commercial copper include Passivity limits thc discharge obtainable from the
usually gold, silver, tin, zinc, nickel, and carcful cell, and conscqucntly reduces its clectrical cnpncity,
manufacturer recovers the bulk of thcsc impurities in a serious fault. The condition has becn avoidcd as
niuddy deposits found a t the bottom of dissolvers, filters far as possible by using iron powder of estrcme fineness,
and tanks. These impurities, when separated aiid refined, so as to h a w n vcry lnrgc surface, and by the incorporat’ion
add appreciably to his profits. Howcvcr, a t Iirescnt of mcrciiry, or other catalyst, but in spite of this passivity
thcrc arc vcry few firms indeed in Brancc who arc may occur under some conditions of usagc, and will
capable of carrying out the iieccssnry treatment, and show itself in thc following four ways :-
many of thosc who undertnke the work mcrcly csport 1. Smallcr capacity.
the material to countries mhcrc nwtallurgical practice is 2. Lower voltage, and n tcudency to droop in the middlc
iiiorc highly dcvclopcd. of the voltage curve during dischnrgc. This occurs if
passivity has set in 011 prcvious discharges. As soon
AN EXAMPLE OF ANODE PASSIVITY as thc remaining active iron lins bccn screened, the
The Iron Electrode of the Alkaline Accumulator diffcrciice in potcntial found by Niillcr appears.
By C. R. HARDY 3. Thc capcity is especially poor a t the higher rates
of discliarge. 3Iiiller found that higher cnrrcnts quickly
In view of the recent account* of 11.’ J. Wilier's producc passivity, and mhcrc sonic of the iron is alrcady
work on passivity, a brief account of thc application passive, the remaining iron would be quickly affected
of Niiller’s tlicory t o an clcctrochcniical problem of by Iiighcr current densities.
anode passivity niay be oi intcrcst. 4. Tlic active niatcrial of iron platcs of low capacity
Thc altinlinc nccuriiulator, such as thc typc m d c by contains nn csccss 01 hydrated compounds of Fc,O,,
Eilisoii, lins for its “negative” plate a mass of fincly- ivlicrcas a platc 01 good capacity contains little but FcO
divided iron cncloscd in a steel Iramework, and it has compounds, wliich agrees with illiillcr’s statement that
long been rccogniscd that passivity may occur during tlic metal dissolvcs as ions of highcr valency when
the discharge of the ccll, when the iron plate is acting passivity occurs.
as an anode. (Nlieii tlic cell is being clinrgcd, currcnt
is, of coi~se,npplicd in thc rcvcrse direction, and the MATCH COMBINE IN CANADA
iron beconics the cathode.)
The action bctwccn the electrolyte, an aqueous Sonic twenty years ago tho E. 13. Eddy Co., Ltd., of
solution of potassium hydrosidc, and tlic iron plate Hull, Quebec, practically coiitrollcd thc inatoh production
during discharge m:iy be expressed briefly and some-. of Canada. However, since tho mar competition has
\ d i n t incompletely thus :- bccn kccner, duo t o the entry of the World Match
+
PC 2OH- = 2 8+
P~(013)~ Corporation, Ltd. (Scandinavian Trrrst), of Quebcc, and
thc Canndian Match Co., Ltd. (Bryant k May Diamond
As thc hydrosidc is insoluble, tho screening cffcct Xatch Corp., U.S.A.), Pcmbrolic, One. The Dominion
is probably much grcater than that of thc ferrous Uatch Co., Ltd., of Deseronto, Ont., which opcratcd
sulphate in 3Iiillcr’s csperimcnt, but owing to the prior to tlic advent of the Scandinavian-U.S. match
fact that the ncgntivc platc contains t~ w r y large intcrcsts, mas purchosccl a number of years ago by the
n~unberof smnll particlcs, thc aiiiouiit of Be(OII), Eddy concern. Aiinounccinent has now bccn ninclc
forined duriug a normal discharge is perhaps insuflicieiit that a new company has bccn incorporated mliicli will
to scrccn tlic total smfacc of the iron sufficiently to include all tlic foregoing conipanics, aud that Mr. C. W.
cniise more tlinii a slight degree of passivity. Should Paton, of London, England, Chairman and Managing
the dischnrgc be uuduly proloiigcd a more noticcablc Dircctor of Bryant ‘!May, will be l’resitlcnt, with A. G.
degree of passivity rcsults, as is d o i n i by a steep full Woodruff, l\lauagcr of thc Canadian Natoh Co., Ltd.,
in the voltngc curve at this point, followcd by a further l’cmlrokc, Oat., General BIanagcr of thc ncw mcrgcr.
steady fall a t a lower potential, corrcsponding t o the The 3Cddy Go. has 21 match niacliines, 1 G being iu the
opposite cffcct of an incrcnscd potential which Niillcr I-Iull and fivc in tlic Dcscroiito cstnblishnicnts. Tho
found \vhen applying a currcnt to his cspcrimental lattcr factory has not bcen opcrating for several years.
cell. According t o Niiller’s worlc, passivity is present The rcadjustment of operations will iiot bc made until
n t this stagc, accompnnicd by a tendency t o the early i n tlic New Ycar, but it is anticipated that soinc of
prodnction of lWg ions, which would product iu the the factorieswill cerise inanulucturc. This combinntion of
alltaliiic crll compounds of tlie t j y e Pc(OlI),. the inatcli industries in Canada has not bcen a surprise,
The nest clinrgc the ccll rcccivcs should rcduce the as Scandinavian iullucnccs have been long appatcnt in
U. 11. 1<VUllP, l l Y ISIJUSTILY, DCC. 30, lW7, pp. I?lO-l?L!2.
~ I l ~ > l I ~ T AS0 this industry.

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