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8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Metal Coupons As
Environmental Sensors
Virginia Costaand
David Thickett
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageMeasuring Environments
Compare environments
Find problems
Research into environments
Research into mitigation methods
Compliance testing
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English Heritage
Tetrault, Studies in Conservation 1998
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English Heritage
0
5
10
15
20
25
08/1
0/2003
29/1
0/2003
19/1
1/2003
10/1
2/2003
31/1
2/2003
21/0
1/2004
11/0
2/2004
04/0
3/2004
25/0
3/2004
15/0
4/2004
06/0
5/2004
27/0
5/2004
17/0
6/2004
08/0
7/2004
29/0
7/2004
19/0
8/2004
Temperature in °C
0
1020
3040
50
6070
8090
100
Relative Humidity in %
Relative Humidity
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage Particulates
0
1000
2000
3000
4000
5000
6000
1.00 1.25 1.50 1.75 2.00
time (days)
number of particles
>0.75μm >1.0μm
>2.0μm >3.5μm
>5.0μm >7.5μm
>10.0μm >15.0μm
0
1000
2000
3000
4000
5000
6000
2.20 2.45 2.70 2.95 3.20
time (days)
number of parti
cles
>0.75μm >1.0μm
>2.0μm >3.5μm
>5.0μm >7.5μm
>10.0μm >15.0μm
Overnight only All day
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Seasonal Variationdata from MASTER project
0
200
400
600
800
1000
1200
1400
1600
1800
2000
jan feb mar apr may jun jul aug sep oct nov dec
0
10
20
30
40
50
60
70
80
[ethanoic]
RH
temp
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageDosimeters
Dosimeter
Object
Composition
Metallurgy
UseHistory
Conservation
Environment
RH
condensation[SO2]
[NOx]
[O3]
[H2S][COS]
[HCl]
particulates
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Pb(CHO2)2 143
PbO 108
PbCO3 129
Pb(CH3CO2)2 157 2PbCO3.Pb(OH)2 125
6PbCO3.3Pb(OH)2.PbO 120
Pb(CH3CO2)2.3H2O 183
Pb(CH3CO2)2.Pb(OH)2.H2O 141
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Corrosion Rate Determination
Mass gain
Metal mass loss
(chemical)
Need to quantify corrosion products for
comparison
Need to correct for stripping agent effect on metal
problems re-corrosion on drying
y = -0.42x + 155.15
150
155
160
165
170
0 1 2 3 4 5 6 7 8 9 10
Immersion Number
w
eight (mg)
Metal & Corrosion
Solution
Metal Solution
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageInstrumental Analysis
X-ray diffraction
Fourier transform infra-red spectroscopy
Scanning electron microscopy
Image analysis
X-ray fluorescence
X-ray photoelectron spectroscopy
Secondary ion mass spectrometry Mossbauer spectroscopy
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageAnalytical Regimes for Silver Tarnish
COUPONS
Colorimetry b* or Y probably whole depth
Voltametry AgS, AgCl, AgO whole depth
SEM-EDX S,Cl,O,C ~1µm
XPS S, SO4, O, C species 10nm
Static SIMS species <300Da 0.3nm Dynamic SIMS as above whole depth
OBJECTS
Colorimetry b* or Y probably whole depth XRF S, Cl
Raman AgCl, AgS, AgO 10.8µm
SEM-EDX S,Cl,O,C ~1µm
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Voltametry Comparison with
SEM-EDX Error approximately 6-7% of value cf SEM-EDX
calibrated with CRMs, non systematic
Error consecutive readings on same coupon (expo Tyvek
10um dust cover) approx 10% of value
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageX-ray Diffraction
Image omitted for copyright
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English HeritageFTIR calibration – iron 342 spectra
Geothite 123456 Lepidocrite 123456
Akaganeite 123456 Geothite 12345678910
Magnetite 123456
Maghemite 123456
Hematite 123456 Green rust I 123456
Green rust II 123456
Fe(II)Cl 123456
Fe(III)Cl 123456
Amorph A 123456
Amorph B 123456
Quartz 123456 Lepidocrite 12345678910
Kaolinite 123456 Lepidocrite 12345678910
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
8*
9*
7*
5*6#
4#
1#
2*
3*
RE P E AT E R S T AT I O
N
T E L E P HONE
E XCHANGE
AP P ARAT US ROOM
Barrier
Fan
Metal coupons
& dust slides
Metal coupons
& dust slides &
logger
*
#
ADMI RAL T Y CAS E MAT E
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Location results
Thickett, Metallicus Ligas, 2009
Brimblecombe, Thickett and Yoon, Journal of Cultural Heritage, 2009
0 0,5 1 1,5 2 2,5 3
Telephone Exchange at barrier
Telephone Exchange 3m in
Telephone Exchange inside unit
Repeater Station at barrier
Repeater Station 1m in
Repeater Station 3m in
Apparatus Room
Admiralty 1m
Admiralty 3m
corrosion rate (g/m2/yr)
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
EFFECT OF DUST
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageCorrosion Control
RH
Chemical gases
Dust
Coatings
Chemical Inhibitors
Solid phase, BTA
Vapour phase
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageShowcase Sealing Effectiveness
0
10
20
30
40
50
60
70
80
0 0,5 1 1,5 2 2,5
dust
NO2
calc
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageWalmer, apsley, brodsworth
2 maritime
2 rural 2 urban
Ag, Cu, Pb and steel
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageSite Corrosion Risk
RH NO2 O3 SO2 H2S Dust chloride
% ppb ppb ppb ppb %cov/30d mg/cm2/d
Apsley
Rangers
Brodsworth
Audley End
Walmer
Dover
<65 <5 <0.4 <0.2 <0.05 <0.2
>65 5-15 0.4-1 0.2-0.4 0.05-0.1 0.2-1
>80 >15 >1 >0.4 >0.1 >1
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageFurther characterisation
0
10
20
30
40
50
60
70
80
90
100
Apsley
dining room
Apsley plate
& china
room
Rangers
limoge room
Brodsworth
dining room
Audley End
dining room
Walmer
dining room
silver
copper
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
-2,0 -1,5 -1,0 -0,5-2000
-1500
-1000
-500
0
i (A/cm²)
E (VMSE
)
APSELY (Ag / H)China roomDinning roomChina case
Apsley / Ag (site)
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Apsley / Ag (side)
-1,5 -1,0 -0,5-600
-400
-200
0
i (A/cm²)
E (Vmse)
APSLEY (Ag/CCase)HB
-2,0 -1,5 -1,0 -0,5-1500
-1000
-500
0
i (A/cm²)
E (Vmse)
APSLEY (Ag/DR)HB
-2,0 -1,5 -1,0 -0,5-2000
-1500
-1000
-500
0
i (A/cm²)
E(Vmse)
APSLEY (Ag/CR)
HB
same peaks
≠ areas
A l ifi i
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage APSLEY (Ag)
0
100
200
300
400500
600
700
h b h b h b
PCRroom PCcase Droom
charge (uC/cm²)
APSLEY (Cu)
0
50
100
150
200
250
h b h b h b
PCRroom PCcase Droom
charge (uC/cm²)
Apsley / quantification
Ag ~ Cu
« protective » effect of case
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageResults Other Metals
Lead no difference
Mild Steel – method needs developing however –
Obvious visual differences
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageResults - dust
00,20,40,60,8
11,21,4
Apsley
P&C room
Apsle
y P&C case
Rangers Jewelry
Rangers silver
B
rodsworth
B
rodsworth
B
rodsworth
B
rodsworth
Audley End
Walmer dining
Dover
telephone …
Dover repeater
top
underside
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
0
50
100
150
200
250
300
350
<2 <3 <4 <5 <10 <20 <30 <40
top
C it A C Pb ll
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English Heritage
Coupon purity, Ag, Cu, Pb, all
99.98%
Trace Elements inLead
Purity used(%)
Solubility limit or reported limiteffect on corrosion rate* (%)
Tin <0.005
Antimony <0.005 0.01*
Arsenic <0.00004 0.05*
Bismuth <0.015
Calcium <0.002 0.01
Copper <0.001 0.005
Iron <0.001
Nickel <0.001Silver <0.001 0.02
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageReferences 1
ASTM G92 - 86(2003) Standard Practice forCharacterization of Atmospheric Test Sites
ASTM G1 - 03 Standard Practice for Preparing, Cleaning,
and Evaluating Corrosion Test Specimens
P. Brimblecombe, D. Thickett and Y. H. Yoon, Thecementation of coarse dust to indoor surfaces, Journal of
Cultural Heritage 10 (2009) 410– 414
K. Eremin, and P.Wilthew, Monitoring concentrations of
organic gases within the National Museums of Scotland,SSCR Journal, 9(1), 1998, 15-19
ISO 9223:1992 Corrosion of metals and alloys --
Corrosivity of atmospheres – Classification
8/7/2019 Costa, V. y Thickett, D. Metals Coupons Environmental Sensors. 2010
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English HeritageReferences 2
ISO 8407:2009 Corrosion of metals and alloys -- Removal
of corrosion products from corrosion test specimens
Thickett, D., Investigation into the role of inert dusts in
corrosions and corrosion mitigation in an aggressive
maritime environment, Ligas Metalicas, Univerity of
Porto, (2008), 75-90
D. Thickett, The use of Infra-red and Raman
Spectroscopies for Iron Corrosion Products, Postprints of
Sixth Infra-Red Users Group, Florence, Il PratoElsevier,
Padua, (2005), 86-93
D. Thickett, F. David and N. Luxford, Air Exchange Rate;
A dominant parameter for showcases, The Conservator ,
(2006), 19-34
D. Thickett, Presentation in situ through microclimates,
Postprints of IIC Meeting London (2008)