English Heritage

Metal Coupons As
Environmental Sensors
Virginia Costa
and
David Thickett
English Heritage
Measuring Environments
 Compare environments
 Find problems
 Research into environments
 Research into mitigation methods
 Compliance testing
English Heritage

Tetrault, Studies in Conservation 1998

 English Heritage

Temperature in °C

0
5
10
15
20
25
08/10/2003
29/10/2003
19/11/2003
10/12/2003
31/12/2003
21/01/2004
11/02/2004
04/03/2004
25/03/2004
15/04/2004
06/05/2004
27/05/2004
17/06/2004
08/07/2004
29/07/2004
Relative Humidity

19/08/2004
0
10
20
30
40
50
60
70
80
90
100

Relative Humidity in %
English Heritage Particulates

6000 6000

5000 >0.75μm >1.0μm >0.75μm >1.0μm

5000
number of particles

>2.0μm >3.5μm >2.0μm >3.5μm

number of particles
4000 4000
>5.0μm >7.5μm >5.0μm >7.5μm
3000 >10.0μm >15.0μm 3000 >10.0μm >15.0μm

2000 2000

1000 1000

0 0
1.00 1.25 1.50 1.75 2.00 2.20 2.45 2.70 2.95 3.20
time (days) time (days)

Overnight only All day

English Heritage
Seasonal Variation
data from MASTER project
2000 80
1800 70
1600
60
1400
1200 50 [ethanoic]
1000 40 RH
800 30 temp
600
20
400
200 10
0 0
jan feb mar apr may jun jul aug sep oct nov dec
English Heritage
Dosimeters

Dosimeter
Environment
RH
condensation
[SO2] Object
[NOx] Composition
[O3] Metallurgy
[H2S] Use
[COS] History
[HCl] Conservation
particulates
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
English Heritage
Corrosion Rate Determination
 Mass gain  Need to quantify corrosion products for
comparison

 Metal mass loss  Need to correct for stripping agent effect on metal
(chemical)  problems re-corrosion on drying

170

165
weight (mg)

160

Metal Solution
y = -0.42x + 155.15
155

Metal & Corrosion

Solution

150
0 1 2 3 4 5 6 7 8 9 10
Immersion Number
English Heritage
Instrumental 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
 Analytical Regimes for Silver Tarnish
English Heritage

 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
 Voltametry Comparison with
English Heritage

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
English Heritage
X-ray Diffraction
 Image omitted for copyright
 FTIR calibration – iron 342 spectra
English Heritage

 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
English Heritage
English Heritage

EXCHANGE
TELEPHONE
7*

REPEATER STATION
5*6#

APPARATUS ROOM
Barrier
4#
Fan

ADMIRALTY CASEMATE
Metal coupons
* & dust slides

Metal coupons
1# & dust slides &
# logger
2*

8*
3*

9*
English Heritage

Location results
Admiralty 3m
Admiralty 1m
Apparatus Room
Repeater Station 3m in
Repeater Station 1m in
Repeater Station at barrier
Telephone Exchange inside unit
Telephone Exchange 3m in
Telephone Exchange at barrier

0 0,5 1 1,5 2 2,5 3

corrosion rate (g/m2/yr)

Thickett, Metallicus Ligas, 2009

Brimblecombe, Thickett and Yoon, Journal of Cultural Heritage, 2009
English Heritage

EFFECT OF DUST
English Heritage
Corrosion Control
 RH
 Chemical gases
 Dust
 Coatings
 Chemical Inhibitors
 Solid phase, BTA
 Vapour phase
English Heritage
English Heritage
English Heritage
Showcase Sealing Effectiveness
80
70
60
50
40
30
20 dust
NO2
10
calc
0
0 0,5 1 1,5 2 2,5
English Heritage
Walmer, apsley, brodsworth

 2 maritime
 2 rural
 2 urban
 Ag, Cu, Pb and steel
English Heritage
Site 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
English Heritage
Further characterisation
100
90
80
70
60 silver
50 copper
40
30
20
10
0
Apsley Apsley plate Rangers Brodsworth Audley End Walmer
dining room & china limoge room dining room dining room dining room
room
 Apsley / Ag (site)

0
English Heritage

-500

i (A/cm²)
-1000
APSELY (Ag / H)
China room
Dinning room
-1500 China case

-2000
-2,0 -1,5 -1,0 -0,5
E (VMSE)
 Apsley / Ag (side)
0
English Heritage

-500

i (A/cm²)
-1000
APSLEY (Ag/CR)
H
B
-1500
0

-2000
-2,0 -1,5 -1,0 -0,5

-500 E(Vmse)
i (A/cm²)

APSLEY (Ag/DR)
-1000 H
B

0
-1500
-2,0 -1,5 -1,0 -0,5
E (Vmse)

-200

i (A/cm²)
APSLEY (Ag/CCase)
same peaks -400
H
B

≠ areas
-600
-1,5 -1,0 -0,5
E (Vmse)
 Apsley / quantification

English Heritage APSLEY (Ag)

700
600

charge (uC/cm²)
500
400
300
200
100
0
h b h b h b

PCRroom PCcase Droom

Ag ~ Cu

APSLEY (Cu)
« protective » effect of case
250
charge (uC/cm²)

200

150

100

50

0
h b h b h b

PCRroom PCcase Droom

English Heritage
Results Other Metals
 Lead no difference
 Mild Steel – method needs developing however –
Obvious visual differences
 English Heritage

0,6
0,8
1,2
1,4

0,2
0,4

0
1
Apsley P&C room
Apsley P&C case
Rangers Jewelry…
Rangers silver…
Brodsworth…
Brodsworth…
Brodsworth…
Brodsworth…
Audley End…
Walmer dining…
Dover telephone…
Dover repeater…
Results - dust

top
underside
English Heritage

350
300
250
200
150 top

100
50
0
<2 <3 <4 <5 <10 <20 <30 <40
 Coupon purity, Ag, Cu, Pb, all
English Heritage

99.98%
Trace Elements in Purity used Solubility limit or reported limit
Lead (%) effect 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 <0.001
Silver <0.001 0.02
English Heritage
References 1
 ASTM G92 - 86(2003) Standard Practice for
Characterization 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, The
cementation 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
English Heritage
References 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)