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Copper,Brass, andBronzeSurfaces

ZAHNER’SARCHITECTURALMETALSSERIES

Zahner’sArchitecturalMetalsSeriesoffersin-depthcoverageofmetalsusedinarchitectureandart today.Metalsinarchitectureareselectedfortheirdurability,strength,andresistancetoweather. Themetalscoveredinthisseriesareusedextensivelyinthebuiltenvironmentsthatmakeupour worldandalsoattractandfascinatetheartist.Theseheavilyillustratedguidesoffercomprehensive coverageofhoweachmetalisusedincreatingsurfacesforbuildingexteriors,interiors,andart sculpture.Theseriesprovidesarchitects,metalfabricatorsanddevelopers,designprofessionals, andstudentsofarchitectureanddesignwithalogicalframeworkfortheselectionanduseofmetal buildinganddesignmaterials.ForthcomingbooksinZahner’sArchitecturalMetalsSerieswillcover steelandzincsurfaces.

TitlesinZahner’sArchitecturalMetalsSeriesinclude:

StainlessSteelSurfaces:AGuidetoAlloys,Finishes,Fabrication,andMaintenanceinArchitecture andArt

AluminumSurfaces:AGuidetoAlloys,Finishes,Fabrication,andMaintenanceinArchitecture andArt

Copper,Brass,andBronzeSurfaces:AGuidetoAlloys,Finishes,Fabrication,andMaintenancein ArchitectureandArt

Copper,Brass, andBronzeSurfaces

AGuidetoAlloys,Finishes, Fabrication,andMaintenance

inArchitectureandArt

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LibraryofCongressCataloging-in-PublicationData:

Names:Zahner,L.William,author.

Title:Copper,brass,andbronzesurfaces:aguidetoalloys,finishes, fabrication,andmaintenanceinarchitectureandart/L.WilliamZahner.

Description:Hoboken,NewJersey:Wiley,2020.|Series:Zahner’s architecturalmetalsseries|Includesbibliographicalreferencesand index.

Identifiers:LCCN2019045098(print)|LCCN2019045099(ebook)| ISBN9781119541660(paperback)|ISBN9781119541677(adobepdf)| ISBN9781119541684(epub)

Subjects:LCSH:Copper.|Brass.|Bronze.|Architecturalmetal—work.| Artmetal—work.

Classification:LCCTS620.Z342020(print)|LCCTS620(ebook)|DDC 739—dc23

LCrecordavailableathttps://lccn.loc.gov/2019045098

LCebookrecordavailableathttps://lccn.loc.gov/2019045099

PrintedintheUnitedStatesofAmerica 10987654321

ThisbookisinhonorofSalvatoreOrlando. Hewasagoodfriendandadvocateoftheredmetal.

ATin–BronzeAlloy76

Nickel–SilverAlloys77

AManganese–BronzeAlloy78

CHAPTER3SurfaceFinishes79

Introduction79

MillSurfaces80

MechanicalFinishesandTemporaryProtection81

ColorfromOxidationandChemicalReactions91

Textures123

Tin-CoatedCopper135

MeltedCopperAlloySurfacing136

CopperandGlass137

ProtectingtheSurface138

CHAPTER4ExpectationsoftheVisualSurface139

Introduction139

Intent:AnUnchangedSurfaceAppearance143

Intent:ASurfaceAppearanceThatChangesNaturally154

Flatness155

TexturingtheSurface160

InitialOxidationonCopperAlloys161

InSituPatination163

Prepatination164

TheEffectofSealants166

TheCastSurface167 ArrivingattheBestPossibleOutcome167

CHAPTER5DesigningwiththeAvailableForms173

ABriefHistory173 WroughtForms176

TheCastForm204

CHAPTER6FabricationProcessesandTechniques211

Introduction211

Forming213 V-cutting215

CuttingCopperAlloys220

Machining227

Soldering,Brazing,andWelding231

Casting241

CHAPTER8MaintainingtheCopperAlloySurface295

APPENDIXAComparativeAttributesofMetalsUsedinArtandArchitecture337

APPENDIXBHardwareFinishCodesandDescriptions341 APPENDIXCNumberingSystemsUsedforCopperAlloys345

Preface

Thepassageoftimeisreflectedinthecolorofcopper.

Ofallthemetalsusedinartandarchitecture,copperisthemostengaging.

Throughouthistory,mankindhashadaspecialrelationshipwithcopper.Copperhasaweight andfeelingofsubstance.Itcanbeshapedandformedintousefulobjects,andmoreimportantly, ithasanappearanceasnaturalasthecolorsofanoakforestinthefall:acolorthatshowsvalueand thepassageoftime.

Powerandforceareneededtoshapetheothermetalsusedinartandarchitecture.Copper,on theotherhand,shapesandmovesundertheblowsofhandheldchasingtools.Itcanbeeasilyfolded, curved,stretched,andembossed.Onegetsclosetothemetalwhenworkingwithcopper.

Throughouthumantimecopperandcopperalloyshaveplayeddifferentandexpandingroles. Bronzesculpturesofancientdeitiesandheroeshaveoutlivedtheircivilizations,evenwhilerestingundertheseaforthousandsofyears.Copperhasbeenminedbyeverymajorcivilizationand convertedandcastintobothusefultoolsanddecorativestatues.

Themaritimeworldembracedcopperalloys,particularlybrass.Alloyswithnamessuchas AdmiraltyBronzeandNavalBrassrecallatimewhenthismetalservedasbiocladdingontheundersideofashipandornamentationonthetop.Considerthatthemilitaryterm“brass”relatesto someoneofhighrank:theonewiththebrassmetalsorthebrass-adornedhat.

Copperalloys,boththosewithnew,untarnishedsurfacesandthosewithcolorfulpatinas,offer theartistandthedesigneranamazingpaletteofcolortochoosefromanddesignwith.Oxidecolors willbepredictabletoapoint,butbeyondthatitisnaturethatwilltakeoverthedesign.Thesecolors willalsoactaspotentinhibitorsofcorrosion.Butnotethatbothnatural,untarnishedsurfacesand beautifulpatinasonartandarchitectureformswillrequiresomethingadditional—eitherinthe formofacoatingorintheformofenergyappliedfromanelbow—tokeepthemlookinggood.

Ihaveworkedwithcopperandmanyofitsalloysfordecades.Ihavehammeredit,cutit,welded it,andshapeditintobeautifulpiecesofart.Ihaveexperimentedwithcreatingcoloronthesurface ofthemetalwithchemicalinteraction,heat,andselectiveelectroplating.Ihaveworkedwithfriends tocastitandIhaveformeditssheetstocreateincrediblesurfaces.

Copperisspecialforitsamazingabilitytobeshapedandstretchedandforitsabilitytoreact withotherelementsandcompoundstoachieveauniqueandbeautifulsurface.

Coppercanbecastintoglass,andtheglassacceptsit.Itcanbeseverelyshaped,andityieldsto takethenewshape.Itcanwithstandtheattackofpowerfulacidsandbases,allthewhileforminga naturalmineralsurfacethatslowsfurtherreactionwhilegivingabeautifulpatina.

xii Preface

Thisisthethirdinaseriesofbooksonmetalsusedinartandarchitecture.Ihaveattemptedto covermanyofthecopperalloysthathavefoundtheirwayintouseinartandarchitecture.Newand innovativeusesofthemetal,alongwithadvancesinfabricationtechniquesandarenewedinterest inpatination,arefuelingarenaissanceintheuseofcopperalloys.

Itisthesurfaceofcopperalloys—thepartthatinteractswiththeenvironmentandthepart thatabsorbsandreflectslightinuniqueandspecialways—thatwefindinterestingasamaterial ofdesign.Butindustryisalsolookingforwaysofcapitalizingontheantimicrobialbenefitsofthe copperalloysurface.Testshaveprovenbacteriaandvirusesdonotthriveandwilldiminishwhen inproximitytocopperions.

Thecorrosionresistantbehaviorofthecopperalloysurfaceisunmatched.Fewcorrosivematerialscangetthroughtheprotectivebehavioroftheoxidesurface.Allofthisisanimportantand essentialqualityofthemetal,butitistheuniquecolorthatdrawsustoit.Thereisnoothermetal thatcomesclosetotheintensebeautyofcopperalloys.

Theearlyalchemistsassociatedeachofsevenmetalswithaplanet.Copper,oneoftheoldestmetalsknowntoman,wasassociatedwiththeplanetVenus,oneofancientman’s“wandering stars.”Copperwasthoughttorepresentthecharacteristicsoffemininebeauty,caringandnurturing, loveandlust.

ThesymbolforcopperisthefemalesymbolthatisalsothesymbolfortheplanetVenus.

Thebookisintendedtogivetheartistanddesignermoreknowledgeaboutcopper,itsalloys andthisamazingsurface.Thosewhoareinterestedinthemetalwillacquireinformationonhowto workwiththedifferentcopperalloys,howtheywillinteractwiththeenvironmentwithtimeand exposure.Copperandcopperalloyshaveavasthistory,butthestoryisfarfromover.

CHAPTER 1 Introduction—Element29

CopperandCopperAlloys

INTRODUCTION

Ofthemetals,onlycopperandgoldpossesscolorsotherthangrayorsilverintheirnaturalforms. Whencopperiscombinedwithdifferentelements,elegantcolorsandtonescanbeproducedboth naturallyandartificially.Thisisthereasonwhyourancientancestorsfirstworkedwiththismetal: theycouldidentifyitamongrocksandstonesmoreeasilyanditwasmoreabundantthangold. Thebrightlycoloredoresofcopper,malachite,andazuritesurelyattractedtheattentionofearly humans.Thesewerenotyournormalrocks.

Copperiselement29intheperiodictable(Figure1.1).Itfallsbetweenelement28(nickel)and element30(zinc).Copperisinthesamegroupassilverandgold:metalsthatitmixeswithandthat possesssimilarpropertiesofelectricalandthermalconductivity.Likecopper,goldandsilverwere alsohighlyvaluedbyearlyman.Beingmoreabundant,coppertookontheheaviestworkload.The agenamedforitmarksanadvanceincivilization.

Copperpossessesaface-centeredcubicstructureinitspurestate,butthisstructurechangesas alloyingelementsareadded(Figure1.2).Thisface-centeredstructureissharedwithmanyother metals,suchasaluminumandiron.

Theatomicmakeupofcopperisresponsibleformanyoftheuniqueattributesthismetaloffers (Figure1.3).Theatomicnumberof29meansthatcopperhas29protonsinthenucleuswith29electronsmakingupitsoutershells.Itistheloneelectroninitsfourthorbitalthatgivescopperoneof

Copper’spositionintheperiodictableofelements.

FIGURE1.1

FIGURE1.2 Face-centeredcubicstructureofacoppercrystal.

Outer shell has only one electron

29 Electrons Copper Atom

29 Protons 34 Neutrons

FIGURE1.3 Copperatom.

itsmostimportanttraits.Thiselectronisfreetomoveabout,allowingelectricalcurrenttomove easilyfromatomtoatom.

Thislowerresistancecomingfromasingleelectronintheouterorbitgivescopperitsexceptionalabilitytotransportelectricity.Themetalswhoseatomshavethefewestelectronsintheirouter (orvalence)shelloffertheleastresistancetothemovementofelectricityfromoneatomtothenext. Gold,silver,andcopperaremetalsthathaveonlyoneelectronintheirvalenceshells,whichgives themtheirabilitytoconductelectricalcurrentmoreefficientlythanatomswithmorethanone electron.Thisloneelectronmovesfreelyaroundandthroughthelatticestructureofthemetal, transferringtheelectricalcurrentwithlittleresistance.Aluminumhasthreeelectronsinitsvalence orbit,whilezinc,nickel,iron,andtitaniumhavetwo(Table1.1).

Operatingunderaprinciplesimilartoelectricalconductivity,theconductivityofheathasthe sameorderacrossmetals.Alloyingwillchangetheheatconductivityofaparticularmetal,asit doestheelectricalconductivity.Forinstance,mostbronzealloysofcopperwillnotconductaswell asmanyaluminumalloys.Thealloyingelementsinbronzediminishitsabilitytomoveanelectricalcharge.

Astheyareessentiallyshared,thesevalenceelectronsarefreetoflowinandaroundtheatoms, creatinga“sea”ofchargedparticles.Thisseaofelectronsallowsthechargetomoverapidlyand withlittleresistanceasenergyistransferredfromelectrontoelectronthatcollectivelymakeupthe seaaroundthecopperatoms(Figure1.4).

MostofthecopperfoundontheEarth’ssurfaceisfromhydrothermalactivitythatbroughtthe metaltoornearthesurface.Othersurfacecopperisdriftcopper,depositedbyglacieractivityand randomlysetinrubble.Coppermakesupapproximately0.0068%oftheuppermineralcrustofthe Earthandiswidelydistributedwithconcentrationsinselectregions.

Copperhasapoorstrength-to-weightratioascomparedtoothermetalsusedinindustry.However,copperalloys,suchasbrassalloys,haveastrength-to-weightratioequivalenttostainlesssteels.

MetalSiemensm 1

Silver6.30 × 107

× 107

× 107

× 107

× 107

× 107

× 107

× 106

TABLE1.1 Electricalconductivityofvariousmetals insiemensm 1 at20 ∘ C.

FIGURE1.4 Seaofsharedelectronsaroundthemetalatomsofcopper.

Othercharacteristicsofcopperincludeexcellentductility,adeepformingability,highfracture toughness,highelasticity(resiliencyundershockloading),andsoftedges.

Copperisalsonontoxic—althoughcoppersaltsareconsideredecotoxicincertaininstances— andhassuperiorcorrosionresistanceinmanynaturalenvironments.

Copper:Element29

Atomicnumber29

CrystalstructureFace-centeredcube

MainmineralsourceChalcopyriteandchalcocite

ColorSalmonred

OxideBrowntoblack Density8960kg/m 3

Specificgravity8.8

Meltingpoint1083 ∘ C

Thermalconductivity401W/m 1 ∘ C

Coefficientoflinearexpansion16 × 10 6 /∘ C

Electricalconductivity100%IACS

Modulusofelasticity110GPa

FinishesMillspecularandnonspecular Polishedsatinandmirror Glassbead

Coppercanbepaintedbutthisisrarelydone.

Porcelainenamelisanartprocessusedextensivelyoncopper. Platingwithothermetalssuchassilver,nickel,andgoldiseasilyaccomplishedoncopper (continued)

(continued)

ArtificialpatinaGreens,browns,yellows,reds,blacks,andcombinationsare achievableoncopperandcopperalloys;thedevelopmentofchemical patinasonthesurfaceofcopperalloysisunmatchedinanyothermetal BrightappearanceCopperabsorbsandreflectstheredendofthevisiblespectrum;alloys alterthisreflectionbyemittingyellowwavelengthsalongwiththered endofthevisiblespectrum

Reflectance ofultravioletVerygood ofinfraredPoor;copperabsorbsinfraredwavelengths

RelativecostMedium

StrengtheningColdworkingisthemainmethodusedtostrengthencopperand copperalloys

RecyclabilityVeryeasilyrecycled;recycledcopperandcopperalloysretaina highvalue

WeldingandjoiningCopperandcopperalloyscanbewelded,brazed,andsoldered CastingCopperandcopperalloysarefrequentlycastinallcasting methodologies

PlatingCopperandcopperalloyscanbeelectroplated EtchingandmillingCopperandcopperalloyscanbeetchedandchemicallymilled

IACS = InternationalAnnealedCopperStandard;GPa = gigapascal.

COLOR

Anotherattributeofcopperanditsalloysiscolor.Thereareonlytwometalsthatpossessatone otherthangrayorsilver:goldandcopper.

Whenlightfallsonthemetalsurfaceitisintenselyabsorbedbytheatomsatthesurface.The electromagneticwavethatwecalllightonlypenetratesaverysmallfractionaldistance—lessthan awavelength—intothemetal’ssurface.Butthisabsorptionisintenseduetoatomiccharacteristics specifictometalsandtheelectronsthatmakeuptheseathatflowaroundtheatoms.

Thisintenseabsorptionoftheelectromagneticwaveonthesurfacecausesapulseofalternating current,whichthenexcitesthisseaofchargedparticlesandreemitslight.Thisisluster:theintense reflectionfromapolishedmetalsurface.Thesmootherthesurfaceis,thegreaterthereflection.If thesurfaceiscoarse,adiffusereflectionoccurs.Forexample,inthecaseoftarnish—athickened, diffuseoxidethatcandeveloponthesurfaceofcopper—acontrastingdarkersurfaceisapparent, dullingthecopper’sluster.Tarnishisamineralformationthatcapturestheelectronsandmakesthe metalslightlylessconductive.

Thecolorofcopperandgoldisdeterminedbythemakeupoftheiratoms.Whenalightwave strikesacopperorgoldsurface,theportionofthewavelengthfrom600to700nmisstrongly

absorbed,asFigure1.3shows.Inmetals,thisabsorptionleadstoreemissionasreflectedlight. Atthesametime,bothofthesemetalsabsorbthewavelengthsattheblueandvioletendofthe spectrumpoorly.Thisgivescopperareddishcolorandgoldayellowishcolor.Itisthissignificant drop-offinabsorption—strongononeendofthespectrumandweakontheotherend—thatgives thesemetalstheircharacteristiccolor.

Forexample,ironabsorbsthewavelengthsassociatedwithblueandvioletmuchmorethan copper,butitdoesnotabsorbthewavelengthsassociatedwithred,orange,andyellow.Ithasa fairlyflatabsorptionlineacrossallthewavelengths.1 Stainlesssteelissimilartoiron’sreflectivity, buttheaddedchromiumincreasesthereflectionofportionsofthelightwaveover60%.Stainless steelissaidtoreflect,onaverage,60%ofthelightwave(Figure1.5).

FIGURE1.5 Reflectivityofaluminum,silver,stainlesssteel,copper,andgold.

Source:Dataplottedfrom NASATechnicalNoteD-5353,“SolarAbsorptancesandSpectralReflectancesof 12MetalsforTemperaturesRangingfrom300to500K.”

1 KurtNassau, ThePhysicsandChemistryofColor (NewYork:Wiley,1983),161.

COLORSOFALLOYS

Thecolorofcopperalloysisdeterminedbyseveralfactors.Theadditionofvariousalloyingconstituentsinfluencesthecoloruptothepointatwhichthecrystalstructureofthemetalchanges. Whenthisoccurs,thedensityandformofthecrystalchangesandlightabsorptioncanpotentially changeaswell.

Forexample,aszincisaddedtomoltencopperitdissolvesandintegratesintoasinglecrystal structure,orphase,alongwiththecopperatoms.Thealloybecomesprogressivelymoreyellowin color.Atthepointatwhich35%zincisalloyedwithcopper,themetalreachesasaturationpointand thecolorwillbeyellow.ThisisthealloyC27000,alsoknownasyellowbrass.Aszincisaddedbeyond this35%level,aphasechangeoccursinthecrystalmakeup,theyellowcolorlosesintensity,andthe colorgoesbacktoabronzetone.Thecoppercrystallatticecannolongertakethezincatomsinand twophasesdevelop:analphaphase,withaface-centeredcubicstructure,andabetaphase,witha body-centeredstructure.Forexample,alloyC28000,commonlyknownasMuntzmetal,contains 40%zincandislessyellow.BothalphaandbetagrainsareapparentinalloyC28000(seeFigure1.6 forcomparisonsofthenaturalcolorsofcopperalloys).

Mechanicalcharacteristicsalsochangeasalloyingconstituentsareadded.Aszincisadded, brassalloysgetstronger.However,theircorrosionresistance,particularlytotheconditionknown asdezincification,willdecrease.Oncethedualphaseappearsinthealloy,whichoccursataround 40%zinc,coldworkingabilitydeclines.TheC28000alloyishardertocoldworkthanalloyswith lesszinc.

Copperanditsalloyshavetheabilitytocreateamazingcolorswhentheycombinewithnonmetalelementssuchassulfur,chlorine,carbon,andoxygen(Figure1.7).Almosteveryoneisfamiliar withthebeautifulpatinasthatareapparentoncopperroofsbuiltacenturyago.Theseattractive, natural-lookinggreensurfacesdevelopedovertimeandwithexposuretotheatmosphere.Theywere notprecoloredbutallowedtoabsorbthecarbon,sulfur,andchlorinefromtheair.Inarealsense, coppercapturestheindustrialpollutantsofsulfurandcarbondioxidefromtheairandformsthese beautifulsurfacescomposedofcoppersulfate,copperchlorides,andcoppercarbonates.

Forinstance,thegreenpatinaadorningtheroofsofmanycenturies-oldbuildingsincities aroundtheworldisaformofthemineralbrochantite.ThismineralhastheformulaCu4 SO4 (OH)6

FIGURE1.6 Imageofdifferentalloysandcolors.

anddisplaysthecharacteristiccolorofpalegreen.Thecopperbeganasabrightsalmon-redcolor, butasitwasexposedtotheair,naturalhumidity,andrainthecoppercombinedwiththesulfur andformedthemineralonthesurface(Figure1.8).

Thepatinaisthecoppersurfacecorroding,butthedifferenceisthatonceformed,thistightly adheredcompoundprotectstheunderlyingmetal.Therateofcorrosionslowswaydownasthis inert,mineralformofcopperachievesalevelofequilibriumwiththesurroundingenvironment.

TheStatueofLiberty(Figure1.9)initiallyhadthecolorofapennywhendelivered.Itwasnot polishedcopperbuthadtherichcoppercolorofaslightlyagedpenny.Dedicatedin1886,itwas subjecttoyearsofexposuretothepollutedenvironmentofindustrialNewYorkinthelaterpart ofthe1800sandearly1900s.Exposedtoboththechloride-richseasideandpollutionfromheavy industryontheEastCoast,thegreenpatinaweseetodayformed.Astheinertminerallayerof brochantite,antlerite,andatacamitethatmadeupthepatinaformed,itprotectedthecopperplates fromdegradation.2

2 ThomasGraedelandJohnFraney, FormationandCharacteristicsoftheStatueofLibertyPatina (Houston:National AssociationofCorrosionEngineers,1990),101–108.

FIGURE1.7 Colorchangesinbrassalloys.

FIGURE1.8 Anaturallyformedpatina.

FIGURE1.9 TheStatueofLiberty.

PerseuswiththeHeadofMedusa,byBenvenutoCellini.

Intheworldofart,thisnaturaloxidationisasignthatthemetaliscorroding.Bronzestatuesandcopperalloyartifactsmustbeprotected,orthesurfaceswillcorrodetosomedegreeand canbevisuallyaffectedasthesurfacemetalcombinestoformthevariouscorrosionsalts.Sculpture,ifnotmaintained,willoxidizeanddevelopapatina.Inseverecases,particularlyinchloride environments,thecopperalloycanundergoadestructivecorrosionconditionknownas“bronze disease.”However,oneonlyhastolookattheancientsculpturesthathavebeenresidingunder theseaforcenturiestoobservethattheymayhavecorrosionproducts,buttheyarestillintactand recognizable.

Whensomemaintenanceisperformed,bronzesculpturescanlastcenturiesandappearasif theywerecastinrecenttimes.Figure1.10showsthefamoussculpture PerseuswiththeHeadof Medusa,createdbyBenvenutoCelliniaround1550andlocatedintheLoggiadeiLanziinFlorence, Italy.Oneofthemostintricateandbeautifulcastsculpturesinexistence,itstandsat5.2m(approximately18ft.)asmeasuredfromthestonebasetothetopofMedusa’shead.Thisremarkable,nearly 500-year-oldsculptureiswellmaintained.

FIGURE1.10

COPPERMINERALS

Copperandthebrassandbronzealloysofcopperaremetalsthathavebeenwithmankindsince antiquity.Gold,silver,platinum,andcopperaretheonlymetalsfoundintheirnativestate.Copper, beinglessrareandoccasionallyfoundonthesurface,wasmoreavailabletoearlyman.Whenthe natureofthematerialwasdiscoveredanddisseminatedbyourearlyancestors,theStoneAgewas overandtheCopperAgewasuponmankind.Usefultoolsthatcouldbereusedandreshapedoriginatedwiththemetalcopper.

Coppermakesuponlyabout0.007%oftheEarth’suppermineralstrata.Likeironandnickelit isadensermetal,soonewouldexpectcoppertobefounddeeperintheEarth,aslighterelements suchassiliconandaluminumwouldbeexpectedtofloatoverheavierelements(Table1.2).

Primarycopperoresarecalled“porphyrydeposits.”Theseoresarethevirgin,nonrecycled sourcesofcopper.Theyflowduringmagmareleasesbuttheyoftencombinewithsulfurtoform heavycopperandironsulfides,suchasthemineralschalcopyrite(CuFeS2 ),amineralcomposedof copper,iron,andsulfur,andbornite(Cu2 FeS4 ).MostcopperismilesbelowthesurfaceoftheEarth. AstheEarthwasformedtheseheaviermetalssank,leavingasurfacewithverylittlecopper.These heavycompoundstendedtosinkdeeperinthefluidflowsandwerethenexpelledinmagmaduring aneruption.3 ThisoccurredintheRockyMountainregionintheUnitedStatesandintheformation oftheAndesinSouthAmerica.

Bothoftheseregionsareareaswherelargedepositsofcoppermineralsarestillbeingmined. Similarregionswherevolcanicactivityovertheeonsmovedmineralsontothesurfaceoftheplanet existaroundtheworld;placessuchasPapuaprovince,wheretheSudirmanMountainsarelocated, andthesouthernCongoarerichinporphyrymineraldeposits.

TABLE1.2 Approximatepercentagesofelementsin theEarth’suppermineralstrata.

3 Geology 66,no.255(2008); Science 319,no.5871(March28,2008);RiceUniversity,“CopperChains:Earth’s Deep-SeatedHoldonCopperRevealed,” ScienceDaily (April5,2012).

TABLE1.3 Mineralformsofcopper.

CommonmineralnameFormulaColor

CupriteCu2 ORedoxide

TenoriteCuOBlack

MalachiteCuCO3 (OH)2

Intensegreenwithbanding

PseudomalachiteCu5 (PO4 )2 (OH) 4 Emeraldgreen

AzuriteCu3 (CO3 )2 (OH)2

BorniteCu5 FeS4

Intenseblue

Darkredwithslightiridescence

ChalcociteCuSBlackorblackgray

BrochantiteCu4 SO4 (OH)6 Green

AntleriteCu3 SO4 (OH)6 Green

NantokiteCuClPalegreen

AtacamiteCu2 (OH)3 ClCrystallinegreen

Themineralformofametalismorestableandslowtochange.Whenexposedtotheatmosphere copperanditsalloyscandevelopanoxidelayerthatapproachesoneofthemorecommonmineral formsofcopper.Cuprite,forinstance,formsonexposedcopperalloysurfaceswhensubjectedto heatandhumidity.Nantokitewithatacamitecanformoncopperalloysexposedtochlorideswhen nearthesea(Table1.3).

Bronzesculpturesthathavebeenexposedtotheenvironmentforalongperiodoftimecan formseveralofthesemineralcompounds,whichcanappearasspotsorstreaksonthesurfaceofthe originalpatinaprovidedbythefoundry(Figure1.11).

HISTORY

Thedistinctivecolorcopperpossessesdifferentiatesitfromothernaturalminerals.Theoccasional purenativeformofthemetalwouldhaveattractedearlymantothisheavy,denserock—arockthat wouldnotfracturebutthatwouldyieldtoblowsandtakeadifferentshape.Itsweightandmalleable naturemadecopperausefuldiscovery,andbecauseoftheseattributesearlymanprobablycollected itwhenhecameacrossit.

Easilyrecognizablebyitscolorandtactilenature,thesubstancewouldhavearousedtheinquisitivenatureofearlyhumans.Thesurfaceofnativecopperallowedearlymantoshapeitbyhammeringitwithstoneorwood.Initialhammeringwasprobablyperformedusingroundstonesorshaped logs,afterwhichthesubstancewashammeredintowoodenforms.Theplasticityofthemetalwould havebeenlikenoothermaterialknown.Formsofcopper,coldhammeredintojewelry,weapons,

Variousmineralsofcopper.

andtools,havebeenfoundinAnatoliadatingbackto9000 BCE.Skillsusedinmakingclaypottery, developedpriortotheCopperAge,wouldhavebeenadaptedtothismetal,althoughmoreforce wouldhavebeenneededandhardermaterialsnecessarytoshapethecopperintoausefulform.

Oncesomeonefoundthatyoucouldsoftenthemetalfurtherbyheatingit,theselumpsofcopper couldbeflattenedtoplatelikeforms,evenblades.Ashammeringisrepeatedonthecopperformit thinsoutasitisbeingshapedandtheworkedmetalhardens,losingsomeofitselasticity.Anedge canbesharpenedoncoarserocks,makingabladeformthatcanactasatooloraweapon.Acopper edgeisshort-lived,buttheutilityitwouldhaveofferedandtheeaseofworkingthemetalwould havemadecopperanimportantearlymaterial.

Everyearlycivilizationusedcopperinartanddecoration.FromtheSumeriansandChaldeans inMesopotamia,acrossEgypt,topresent-dayTurkeyandontoIndia,copperwasapartofearly civilizationsdatingbacknearlyto8000 BC.Weknowthisbythecharacterofthemetalitselfand itscorrosionresistance.Artifactsmadefromcopperexhibitonlyminordecay,evenafterallthese centuries(Figure1.12).

IntheUpperPeninsulaofMichiganontheshoresofLakeSuperior,intheareaknownas Keweenaw,ancientcoppermineshavebeenfoundalongwithcoppertools.4 Thoughttodateback asfaras4000 BC,theseancientminesshowthatpeopledugshallowminesinsearchofcopper.Large copperbouldersandmile-longveinswereintermixedwithgeneralrockandrubbleinthisregion.

4 CharlesWhittlesey, AncientMiningontheShoresofLakeSuperior (Washington,DC:SmithsonianInstitution,1863).

FIGURE1.11

FIGURE1.12 Approximatetimeperiodsofmajorcopperactivityinancienttimes.

High-puritycopperlumpswereintermixedwiththerubbleonornearthesurface.Surfacecopper, sometimesreferredtoas“driftcopper,”wasdepositedbytherecedingglaciers.Theseearlyinhabitantshadnoavailablemeansofcuttingthelargechunksofmetaldown,sotheygatheredthesmaller, moremanageableportionsandleftthelargesectionswithsomeoftheirbrokentools.EarlyNative Americansarebelievedtohaveventuredyearlytothissitetogathercoppertomakeornamentationandotheritems.Oldstonehammersandaxeshavebeenfoundwheretheseearlyinhabitants attemptedtocarveoffsectionstheycouldtransportbacktotheirvillages.Somesectionsweresimplytoomassivetotransport.Youcanseeoneofthelargerbouldersofnearlypurecopper,calledthe OntonagonBoulder,intheSmithsonian’sNationalMuseumofNaturalHistory.Thislargeboulder weighsinat1682kg(3708lb.).TheKeweenawIndiansclaimeditasasacredobjectandtheysought itsreturn.5 Thisboulderwasoneofthe“proofs”givenin1843forstartingthemineralrushtothe UpperPeninsularegionofMichigan(Figure1.13).

ThisregionoftheUnitedStateswasinvaluableinbringingAmericaintotheIndustrialRevolution.ItwasthefirstsiteofamadrushformineralwealthandprecededtheCaliforniaGoldRushby

5 OfficeofRepatriation(2000).ExecutiveSummaryAssessmentofaRequestfortheRepatriationoftheOntonagon BoulderbytheKeweenawBayIndianCommunity.

Source:WikimediaCommons;publicdomain. anumberofyears.Fromtheearly1800sandfornearlythenext150years,copperwasheavilymined inthisregion.Morethan6billionkgaresaidtohavebeenminedduringthistime.Artifactshave beenrecoveredfromtheseandotherancientcivilizationsstillintact,demonstratingthediverseuses thismetalwasputtobyearlymankind.

Theductilenatureofcopperwasoneofthefirstcharacteristicsofthemetalthatearlymanwas abletousetohisadvantage.Copperwashammeredthinandusedincrudewater-pipingsystems inearlyEgypt,theRomansusedthinplatesofcoppertocladtheroofofstructuressuchasthe Pantheon,andhelmetsandshieldswerecreatedbyartisansfamiliarwithworkingwiththispliable metal(Figure1.14).

FIGURE1.13 ImageoftheOntonagoncopperboulder.
FIGURE1.14 Romanhelmetsmadefromcopper.

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