costa, v. y thickett, d. metals coupons environmental sensors. 2010

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



English HeritageMeasuring Environments

Compare environments

Find problems

Research into environments

Research into mitigation methods

Compliance testing



English Heritage

Tetrault, Studies in Conservation 1998



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



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



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



English HeritageDosimeters

Dosimeter

Object

Composition

Metallurgy

UseHistory

Conservation

Environment

RH

condensation[SO2]

[NOx]

[O3]

[H2S][COS]

[HCl]

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

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



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



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



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



English HeritageX-ray Diffraction

Image omitted for copyright



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



English Heritage



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



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)



English Heritage

EFFECT OF DUST



English HeritageCorrosion Control

RH

Chemical gases

Dust

Coatings

Chemical Inhibitors

Solid phase, BTA

Vapour phase



English Heritage



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



English HeritageWalmer, apsley, brodsworth

2 maritime

2 rural 2 urban

Ag, Cu, Pb and steel



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



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



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)



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



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



English HeritageResults Other Metals

Lead no difference

Mild Steel – method needs developing however –

Obvious visual differences



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



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



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



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



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)

http://www.iso.org/iso/iso_catalogue/catalogue_tc/catalogue_detail.htm?csnumber=42634

http://www.iso.org/iso/iso_catalogue/catalogue_tc/catalogue_detail.htm?csnumber=42634

costa, v. y thickett, d. metals coupons environmental sensors. 2010

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