org
PreHispanicAuPtAlloysExperimental
SimulationUsingSolidStateDiffusion
M.E.Noguez*1,G.Salas2,J.Ramrez3
DepartamentodeIngenieraMetalrgica,UniversidadNacionalAutnomadeMxico
FacultaddeQumica,EdificioD,CiudadUniversitaria,C.P.04510,Mxico,D.F.Mxico
*1
nogueza@unam.mx;2salasb@unam.mx;3jgrv@unam.mx
Abstract
platedAu.
AuPtalloysmadeinSouthAmericafrom300BC400ADby
the Prehispanic inhabitants from TumacoLa Tolita region
(south Colombianorth Ecuador) exemplify an engineering
way of solving troubles when making alloys using high
melting point raw materials as Pt (1768C). In this paper
metallurgicalworkhasbeendonesimulatingexperimentally
the fabrication of several AuPt Prehispanic alloys using
only solid state processing at 950C: 88%Au 12% Pt, Pt
Plated Au alloy and Pt Pt sheets. The employed
manufacturingprocessispresentedasatechnicalpossibility
compared with the one normally accepted and
experimentally experienced by the authors of this work,
consisting of agglomeration of Pt particles by melted Au,
which has been reported elsewhere. The viability of using
pure solid state processes in Prehispanic times is evident
according to what it is known now about solid state
diffusionprocessesandbecauseoftheexperiencespresented.
Keywords
PrehispanicAlloys;GoldplatinumAlloys;SolidStateDiffusion;
DiffusionAlloying
Introduction
Modern Archaeometallurgical methods consider the
fabricationofalloyandobjectreplicasasanimportant
steptowardsthestudyofthealloysandtheinvolved
manufacturing process. Reproducing the alloys using
severalmetallurgicalalternatives,basedonthestudies
made to the archaeological alloys, leads to the most
probable metallurgical model of fabrication [Escobar
andBustamante,2011].
Archaeologists have reported the AuPt alloys
findings in South America: north Ecuadorsouth
ColombiainTumacoLaTolitaregionandaredatedin
300BC400AD,Figure1.FromD.ScottandW.Bray
[1994] AuPt objects archaeological classification, the
diversityoftheAuPtalloysisasfollows:1)nativePt;
2) sintered AuPt 1 from 0% to 70% Au and 3) Pt
1
FIGURE1MAPFROMTHETUMACOLATOLITAREGIONIN
SOUTHAMERICA
Heimitatedsomealloysusingautogenouswelderbut
did not reported either obtained macro or
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FIGURE2.THEAUPTPHASEDIAGRAMSHOWINGTHE
IMMISCIBILITYAREA
Oneofthemainobjectivesinthisworkistofabricate
AuPtalloysbytheallsolidstateprocess:hotandcold
forgingplussometimeinthefurnace.Thesequencein
getting the full homogenized alloy will be compared
to the one of another alloy fabricated with the initial
liquid gold coating and reported in [Noguez et al.,
2006].Thetimetogetauniformmacroscopiccolouris
recorded. The intention is to get the homogeneity at
themicroscopeandwithmicroanalysis.
Gold is the most malleable and ductile material. Ramsey [1973] sets that
pure gold can recrystallize at room temperature and Tawara, Matsukawa
and Kiritani [2003] states that there could be a dislocation-free plastic
deformation in gold. These findings could explain the special
characteristics of this element.
Regardingtheplatinumplatedprocess,theobjectiveis
tofabricateaplatingalloyandtovisualizetheprocess
fromthediffusionpointofview.
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Experimentation
Inordertogettheobjectives,threetypesofalloyswill
befabricated:
1.
2.
PtPt(andAuAu)bydiffusionbonding.
3.
PtplatedAualloybydiffusionbonding.
Weightofthesamples:1g.
Analyzing modes: Optical microscope, Scanning
Electron Microscope (JEOL JSM5900 LV) with X ray
microanalysis.
Procedure
Two alloys type 1 were made, the procedure can be
describedasfollows:a)initially,particleswereheated
at950Cfor3hinafurnace;b)hotforging(900950C)
with a small torch, folding the sample as needed,
measuringthenumberofblows;c)lettingstandfor10
hinafurnaceat950C;d)analyzingthesamplewith
themicroscopeandmicroanalysis.Afterthefirstcycle
thesequenceis:10hdiffusionat950Chotforging
10 h diffusion at 950C analysis, until getting the
homogeneitybymicroanalysis.
FIGURE3.PTANDAUINITIALPARTICLES(SCALEINMM)
Foralloystype2,theprocedurewashotforgingwith
thetorchat900950Cuntilgettingasmallsheet.
Foralloystype3usingatype1alloysheet,Ptparticles
wereplacedbehindit,heatat950C,hotforge,heatin
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FIGURE4.MACROSCOPICAPPEARANCEOFALLOY1AFTER
28H
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FIGURE5.MICROSTRUCTUREOFTHEALLOY1,AFTER28H,
SHOWINGWHITEPTPARTICLES(RIGHT)
Cycle
DiffusionTime(h)
Blows
Foldings
132
28
310
10
48
202
20
68
386
28
88
472
33
Type 2 Alloys
Joining Au particles to Au particles by hot forging is
an easy task. It takesaround 25 minutes and around
20 blows to obtain a sheet using the small particles.
JoiningPtparticlestakeslonger:2025minuteswith80
blows. The following figures display the initial and
finalimages.
FIGURE6.AFTER88HTOTALHOMOGENEITYISOBSERVED.
TWININGSAREVISIBLE
FIGURE7.FINALAPPEARANCESHOWINGTOTAL
HOMOGENEITY
FIGURE9.INITIALAUPARTICLES(SCALEINCM)
FIGURE10.INITIALPTPARTICLES(SCALEINMM)
FIGURE8.ALLOY1AUANDPTCONTENTOVERANALYTICAL
POINTSFOREACHCYCLE.DIFFUSIONTEMPERATUREWAS
950C,WHILEBLOWINGFOLDINGTEMPERATUREWAS730
100C.FEATURESOFEACHCYCLEARESHOWNINTABLEI
FIGURE11.FINALAUANDPTPARTICLES(SCALEINCM)
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Type 3 Alloys
A platinum plated sample was obtained using the
small82%Au18%Ptalloysheetfabricatedastype1
alloyandPtparticles.
ScottandBray[1994]setthatPtparticlesshouldcover
thealloybeforetheforging.Itwasconsideredbetterto
getthePtparticlesbehindthealloy,thenhotforgeand
reheatat950Cinafurnace.Theparticleswerebehind
for an easy and better hammering, otherwise the
particles could jump out. This alloy was made to
witness the feasibility of the solid diffusion when
plating the AuPt. Figures 12, 13, and 14 illustrate
differentstepsduringtheexperimentation.
FIGURE12.INITIALBASEALLOYANDPTPARTICLES(SCALE
INCM)
FIGURE13.LOWMAGNIFICATIONSTRUCTURE
However,afterforging,thisequilibriumisrepresented
in figure 15 at an average distance of 140 m (point
a)and,after4hrsdiffusion,around110m(pointb).
From another point of view, the point c, at 120 m
(72% Au and 28% Pt) after forging changes to point
d (12% Au and 88% Pt) after diffusion. Points b
anddarealsoindicatedinfigure14.
Discussion
FIGURE14.SEMMICROSTRUCTURESHOWINGTHELINE
WHEREANALYSESWEREPERFORMEDAFTER4HDIFFUSION
FromFig13and14,itisclearlyseenthatthePtcoatis
very irregular which could obey to the irregular
position of Pt particles and/or to the width
irregularities of the initial AuPt alloy. Typical solid
statediffusionvoidsareseenintheGold.
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them,acomparisonoftheprocessesismadeinTable2.
The theoretical time calculated with one of the
engineeringmodels(sinusoidal)isexhibittovisualize
the enhancing diffusion during the experimental
processes.
TABLE2.COMPARISONOFEXPERIMENTALRESULTSWITHA
THEORETICALMODEL
Alloy
Process
DiffusionTime(h)
Blows
Foldings
Time
(%)
Theoretical
Model
548
100
Au88%
Pt12%
2inliquidAu+190
240
(L)A
20
35.7
Au82%
Pt18%
88
476
(M)A
33
16.0
Au82%
Pt18%
40
630
(H)B
20
7.3
Conclusions
It is technically possible to fabricate AuPt alloys
without using the Gold melting temperature.
Consequently, Prehispanic inhabitants could use this
process when making their alloys and objects,
reaching a pertinent engineering solution. From this,
another model in archaeometallurgy for AuPt alloys
inPrehispanictimesisproposed.
AHotandColdForging;BHotForging;(H)530N,(M)480N,
(L)450N
Acknowledges
TheauthorsgivespecialthankstoGuadalupeVillegas
for working on the topic and to Ivan Puente and
Guillermina Gonzlez for their work with SEM,
including Microanalysis. Also to the B.S. student Luz
Elena Rosales for their disposition to support with
laboratoryworkwhenneeded.
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Mxico,D.F.,Mxico,2009.
MaraEugeniaNoguez.BorninMexico
City, Mexico on June 4th 1947; B.S. in
Metallurgical Chemical Engineering at
Facultad de Qumica, Universidad
Nacional Autnoma de Mxico
(UNAM,
19641968).
M.S.
in
Metallurgical Engineering at School of
Engineering, University of Pittsburgh,
1973. Major field of interest: physical
metallurgyandengineeringeducation.
She started to work professionally in the Automotive
Industry as a Quality Laboratory Technician and in the
FoundryIndustryasaManufacturingEngineer.AtUNAM,
shestartedasaLecturerin1968.Aftergraduatestudies,she
becameanAssociateProfessorin1974andProfessorin1984.
Actual position: Professor at the Facultad de Qumica,
UNAM. She has directed 37 B.S. theses. She has published
around 80 papers in different areas: solidification, structure
of materials, archaeometallurgy and engineering education.
She has presented research and educational works in 85
metallurgicalcongresses.
Ms. Noguez obtained the Latin American Program of
AmericanUniversities(LASPAU)scholarshiptodograduate
studiesinUSA(19711973).AtUNAMFacultaddeQumica,
she was elected member of the Technical Council as a
student (19651968), then as a teacher for 3 periods (1976
1983,19831989,19952001);coordinatoroftheBSstudieson
Metallurgical Chemical Engineering (19791981), and
coordinator of graduate studies in Metallurgy (19831985);
she won the Ernesto Rios del Castillo award lecturer
position (19951997). She has been member of the AFS, The
MetallurgicalSocietyofAIME,AITSandTMS.
JournalofMetallurgicalEngineering(ME)Volume2Issue1,January2013www.mejournal.org
learning.
He worked professionally partial time in the industry of
manufacturefornear6years.AttheNationalUniversityof
Mexico, he started as a lecturer in 1974. He became an
Associate Professor in 1979 and Professor in 1987. Actual
position: Professor at the Facultad de Qumica, UNAM. He
hasdirected30B.S.theses,publishedmorethan80papersin
different areas: solidification, structure and properties of
materials, archaeometallurgy and engineering education,
and presented research and educational works in 85
metallurgicalcongresses.
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