SPAMT-Test

Use of Ecorr vs time plots for the qualitative

analysis of copper-based elements from
scientific and technical objects

Christian Degrigny
Leiden, 11-15 January 2010
 Context

• Need in conservation of simple

analytical tools that are non-
invasive and portable for the on-site
Clock, Louis XVI, Vauchez
diagnosis of heritage metal artefacts

• Spot tests: invasive and use of

corrosive chemicals
Dynamometer
17th century, Lycée Hoche
Versailles, INRP

Leiden, 11-15 January 2010

 Preliminary research

Device used:
- Objet: connected to the V
output of a multimeter;
- Reference electrode (with a
COM V I
known potential): placed next to
the metal surface. Connected to
Reference
electrode the COM output of the multimeter;
- A drop of solution is placed
between the object and the
electrode;
- Measurement made (Ecorr) on
the multimeter
- Monitoring vs time (5 à 10
multimeter minutes): characteristic of the
artefact
metal studied.

Leiden, 11-15 January 2010

 1st tests: brass alloys in sodium
sesquicarbonate

0
0 100 200 300 400 -reproducible results on
-50 polished brass coupons;
-100
-no alteration of the
-150
metal studied (no visible
Ecorr (V/Ag-AgCl)

-200 marks);
I3, S2 (I)
I2, S1 (II)
-250
I4, S2 (II) -requires a small surface
-300
Zn Ò Brass st
of the metal and a small
I5, S2 (III)

-350
I1, S5 (IV)
I1, S6 (IV)
volume of solution: local
I1, S4 (V) spot test;
-400 I4, S3 (V)

-450 -can be used for the

temps (secondes) qualitative analysis of
metals;

Leiden, 11-15 January 2010

 2nd tests: other families of copper
alloys + 2 solutions
Objective: electrochemical behaviour of 16 reference
copper-based alloys in sodium sesquicarbonate (SS) and
mineralised water
185
110

180

100

175

Mineral water
90
170
Ecorr (V/She)

Ecorr(V/She)
165
80

160

Copper--arsenic 70

95,4%Cu / 4.6%As Sodium sesquicarbonate 155

60
0 100 200 300 400 500 600 700 800 900 1000 150
Time (seconds) 0 100 200 300 400 500 600 700 800 900 1000
Time (seconds)

Conclusion
-Family of alloys (tin bronzes, brass…) are easy to identify;
-The analysis is more difficult if the metal contains more than
2 elements.

Leiden, 11-15 January 2010

 Advantages and drawbacks of the
technique

Advantages
-Easy to use for conservators
-Cheap
-Portable, makes on-site measurements possible
-Relatively non invasive

Drawbacks
-High dependance towards the user
-Need to define a protocol of measurement and a
thorough monitoring process
-Results might be very close for 2 different materials
-Need to work on polished metal artefacts

Leiden, 11-15 January 2010

 The SPAMT-Test project

Objectives:
z Increase the number of reference metals
tested
z Addition of a 3rd testing solution
z Definition of a precise protocol of
measurement
z Construction of a database for copper-
based alloys;
z Application to scientific, technical and
horology objects

Leiden, 11-15 January 2010

 1st step: setup of the methodology of the
project
Reference Collection of reference materials (66)
materials
collected from:

EU IMMACO
project
-EU Eureka
E2210! Bronzart
project

-ICMPE-CECM
-INSTN
SDE analysis
-V&A laboratory
-CCI
- ISC
-Swissmetal
-private collectors
-Foundation HAM
-MIH

Solutions tested
KNO3 (1%(w/v), pH=6), mineral Swiss water Henniez (pH=7,6),
Leiden, 11-15 January 2010 sodium sesquicarbonate (pH=9,6)
 Materials tested
Family Alloys
Arsenic-copper CuAs3.3S

Bronze (Cu/Sn) CuSn7.7, CuSn9.1Ni, CuSn10, CuSn14, CuSn15Pb, CuSn9.4Si3.6,

CuSn9Si3.8Bi2.3, CuSn11Ni3.3, CuSn11Zn1.3Ni1.9, CuSn14Zn2.1
Silver bronze CuSn5.6Ag12, CuSn5.7Ag5.9, CuSn6.5Ag
(Cu/Sn/Ag)

Some Leaded bronze CuSn12Pb11NiMn

(Cu/Sn/Pb)
families are Brass CuZn5.3, CuZn5.8, CuZn7.8, CuZn12, CuZn11, CuZn14.84, CuZn24.9,
more (Cu/Zn) CuZn30, CuZn32, CuZn34, CuZn35, CuZn36, CuZn46.1

covered Tin brass CuZn5.8Sn6PbNi, CuZn14Sn2.7PbFe, CuZn35Sn1, CuZn36Sn1.7

(Cu/Zn/Sn)
than Leaded brass CuZn35Pb1.6Si, CuZn35Pb2.1Sn1.2Ni, CuZn35Pb3.1, CuZn36Pb1NiFe,
others… (Cu/Zn/Pb) CuZn37Pb1.7, CuZn38Pb0.7, CuZn38Pb3, CuZn39Pb1.6NiFe,
CuZn39Pb2NiFe, CuZn39Pb2.6Fe, CuZn39Pb2.1, CuZn40Pb, CuZn40Pb1.3,
CuZn40Pb1.8, CuZn42Pb2,3Al, CuZn43Pb
Nickel silver CuZn24Ni12PbFe, CuZn26Ni12Fe, CuZn34Ni14Mn4Pb1.2,
(Cu/Zn/Ni) CuZn34Ni14Mn5.3Pb, CuZn37Ni8.4Mn2.9Pb1.8

Quaternary bronze CuSn3.9Zn4.3Pb3.8, CuSn5.3Zn5.5Pb1.5NiFe, CuSn5.6Zn2.4Pb2.5,

(Cu/Sn/Zn/Pb) CuSn5.8Zn2.4Pb1.6Ni1.1Si, CuSn5.8Zn3.3Pb3.4Si1.3Ni1.1,
CuSn9,1Zn7,5Pb5,6NiFeMn, CuSn11Zn1.7Pb2.7SiNi
Beryllium-copper CuBe2

Nickel-copper CuNi25Mn

Aluminium-copper CuAl8.5Ni2, CuAl11Ni1,5Fe1,2, CuAl13Ni5,8Fe3,8Mn

Leiden, 11-15 January 2010
 Experimental conditions for plotting
Ecorr vs time curves

-Prior testing of the reference electrode (RE);

-Preparation of the test solution (stirred before
use), rinsing and filling the JPT with it (except in
the case of Henniez water);
-Insertion of the RE into the JPT and
overtightening with Teflon sealing tape. This step
must be effected 30 minutes before beginning
measurements, so as to ensure the stability of the
system;
-Polishing of the metallic surfaces of the studied
materials (handled with latex or vinyl gloves)
before each plot is made with fine silicon carbide
paper (Struers 4000);
-Placing of the RE/JPT system at a distance of
2mm from the surface of the polished metal;
-Application of the drop of solution (40µL)
between the membrane of the JPT and the metal
surface with a syringe (rinsed out with the test
solution (stirred before use));
-Ecorr measurement for 5 and/or 15 minutes.
Leiden, 11-15 January 2010
 2nd step: construction of the database

In total: more than 600 Ecorr vs time plots

(2x5min + 1x15min) for 66 alloys in 3 solutions

-Binary alloys were done first (to appreciate

the effect of the major element)
-Same operator to cover the same family of
copper alloys
-If reproducible plots were obtained (maximum
Electric contacts
difference of 5mV accepted), we moved on to
to limit the impact
on the reference
the next material in the table of materials
materials studied.
-In case of lack of reproducibility (alloys
containing lead), increase of the number of
plots and change of the operator
Leiden, 11-15 January 2010
 A few examples
40 80 -20

20 60 -40

0 40 -60
E corr (mV/Ag-AgCl)

E corr (mV/Ag-AgCl)

E corr (mV/Ag-AgCl)
-20 20 -80

-40 0 -100

-60
CuSn3.9 -20
CuSn3.9 -120

-80 -40 -140

CuSn3.9
-100 -60 -160

-120 -80 -180

0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Time (minutes) Time (minutes) Time (minutes)

Mineral water KNO3 Sodium sesquicarbonate

Reproducible results
0 0 0
-50 -50 -50

-100 -100 -100

E corr (mV/Ag-AgCl)

E corr (mV/Ag-AgCl)

E corr (mV/Ag-AgCl)
-150 -150 -150
-200
-200 -200
CuZn40Pb1.8 -250
CuZn40Pb1.8
-250 -250

-300
CuZn40Pb1.8 -300
-300
-350
-350 -350
-400
-400 -400 -450
-450 -450 -500
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Time (minutes) Time (minutes) Time (minutes)

Mineral water KNO3 Sodium sesquicarbonate

Non reproducible results

in mineral water
Leiden, 11-15 January 2010
 General trends
Family General trend of Comments
Ecorr vs time plots
Cu/As Depending on the - EKNO3>EEH>ESS
solution - In SS: passivation (Ecorr increases vs time),
- In KNO3 and HW: Ecorr first decreases and then increases
Bronze (Cu/Sn) Progressive passivation - EKNO3>EEH>ESS
for all solutions - In HW and SS: 1 or 2 slopes (beyond 7-10 w% Sn, 1st step is quick, 2nd step is slow)
Silver bronze (Cu/Sn/Ag) Progressive passivation - EKNO3>EEH>ESS
for all solutions Almost no effect of Ag
Brass (Cu/Zn) Quick passivation (Ecorr - EKNO3>EEH>ESS
gets stable between 5 - In KNO3: decrease of Ecorr after a preliminary increase (10 min.) when cZn < 13w%
and 10 min.) - In HW and SS: 1 or 2 slopes (beyond 35 w% Zn, 1st step is slow and 2nd step is quick)
Tin brass (Cu/Zn/Sn) Quick passivation for all - Quicker if cZn > 35w%
solutions - In KNO3 and HSS: Ecorr is similar after 5 min.
Leaded brass (Cu/Zn/Pb) Passivation for all - In HW and SS: Ecorr is more or less constant after 12min.
solutions - Poor reproducibility.
Nickel silver (Cu/Zn/Ni) Passivation - Slower passivation when cZn is between 24 and 37w%
- 1 or 2 slopes
Quaternary alloy Passivation - In most cases, EHW>ESS>EKNO3
(Cu/Sn/Zn/Pb) - In KNO3: 1st values of Ecorr are very negative and slow passivation depending on the ratio
CPb/CZn
- Poor reproducibility

Cu/Be Progressive passivation - EKNO3>EEH>ESS

for all solutions
Cu/Ni Depending on the - EKNO3>EEH>ESS
solution - In HW: corrosion since Ecorr decreases steadily
- In KNO3 and SS: passivation in 1 or 2 slopes
Cu/Ni/Al Depending on the - EKNO3>EEH>ESS
solution - In HW: the passivation is favoured
Leiden, 11-15 January 2010 - In SS: more uncertain behaviour and passivation in KNO3
 Tin bronzes: effect of Sn on the plots

-40

-60 Cu
-80 CuSn3.9
(m V /A g -A g C l)

CuSn7.7
-100 CuSn10
CuSn14
-120

-140
Conc. Sn Ò
c o rr

-160
E

-180

-200

-220
0 2 4 6 8 10 12 14 16 18 20
Time (minutes)

In sodium sesquicarbonate
Leiden, 11-15 January 2010
 3rd step: validation
2 collections: Swiss Army Historical Material
Foundation (HAM Foundation) and the
International Museum of Horology (IMH)

Selection in each collection of 5

representative artefacts.

Foundation HAM

IMH
Leiden, 11-15 January 2010
 Methodology followed on 2 examples

Condition survey

Stamped and cold worked:

brass (35-40 Zn% (w/v) +
Pb?
Watch frame, IMH

Cold worked: brass (30-40

Zn% (w/v))
Cartridge case, HAM

Leiden, 11-15 January 2010

 Use of the « SPAMT-Test » tool
0

On the watch frame -50

Ecorr (mV/Ag-AgCl)
-100
CuZn39Pb1,6NiFe

-150
E78-MIH
-200
Comments:
-250

-300
0 2 4 6 8 10 12 14 16 -Reproducible values;
Temps (minutes)
HW
0

-50
CuZn39Pb1,6NiFe
-Measurements very
-100 similar to

Ecorr (mV/Ag-AgCl)
-150

-200
CuZn39Pb1.6NiFe of
-250

-300
E78 - MIH the database;
-350

-400 -Higher potentials in

-450
0 2 4 6 8 10 12 14 16 SS at the start:
Temps (minutes)
KNO3 certainly because of
0
-50
-100
the remaining oxide
-150
layer on the surface
Ecorr (mV/Ag-AgCl)

-200 CuZn39Pb1,6
-250
-300
of the metal.
-350
E78-MIH
-400
-450
-500
-550
Leiden, 11-15 January 2010 0 2 4 6 8 10 12 14 16
Temps (minutes) SS
 0
-20
On the cartridge case -40
CuZn24,9

Ecorr (mV/Ag-AgCl)
-60
-80
-100
-120
-140
E83-SAM Comments:
-160
-180
-200
0 2 4 6 8 10 12 14 16
-Reproducible values;
Temps (minutes)
HW
0 -Measurements very
-50
CuZn24,9
similar to CuZn24.9
of the database;

Ecorr (mV/Ag-AgCl)
-100

-150
E83-SAM
-200 -Higher potentials in
-250 SS at the start:
-300
0 2 4 6 8 10 12 14 16
certainly because of
Temps (minutes)
KNO3 the remaining oxide
0

-50
layer on the surface
-100
CuZn24,9
of the metal.
Ecorr (mV/Ag-AgCl)

-150

-200

-250
E83-SAM
-300

-350

-400
Leiden, 11-15 January 2010 0 2 4 6 8 10 12 14 16
Temps (minutes) SS
 EDS analysis of the artefacts

Composition proposed Composition obtained

by the “SPAMT-Test” by EDS
Comparison tool
between proposals MIH E77 CuSn14Zn2.1 CuSn18Zn1.4FeMn
and analysis:
MIH E78 CuZn39Pb1.6NiFe CuZn39Pb1.7
-Rather accurate for
MIH E79 CuZn30-34 CuZn30SiNiFe
binary alloys
MIH E80 CuSn5.3Zn5.5Pb1.5NiFe CuSn4.3Zn24Pb2.9Fe
-Major elements are
revealed for alloys MIH E86 CuSn6Zn5.8PbNi CuSn9Zn6Pb1.5FeSi
containing more HAM E37 CuZn30 CuZn30
than one major
elements HAM E81 CuZn5.3-7.8 CuZn8
HAM E82 CuZn30 CuZn30
HAM E83 CuZn24.9 CuZn28
HAM E85 CuZn26Ni12Fe CuZn27Ni8

To add to the database

Leiden, 11-15 January 2010

 Conclusion
The “SPAMT-Test” tool is adapted to the requirements of
conservation-restoration professionals:
-easy to use;
-relatively non invasive;
-easy to transport;
-inexpensive.

Results:
-Determination of the nature of the elements present in
the tested alloy;
-In certain cases (binary alloys): accurate compositions;
-The precision of the tool depends on the database
coverage.

Limitations:
Need of a good surface preparation: adapted for technical,
scientific, and horology objects which are rarely covered
Leiden, 11-15 January 2010
with a thick corrosion layer.
 Input of end-users

Throughout the project:

measurements made by conservators
specialized in technical, scientific, and
horology objects (i.e. by potential end-
users of the “SPAMT-Test” tool).

-Able to make initial suggestions

concerning the composition of the
objects (based on their technological
knowledge of the objects and the
materials they are made of);

- Application of the ethics in

conservation: minimal impact.

Leiden, 11-15 January 2010

 Further developments

Development of a software:
-would offer composition propositions almost
instantly, based on electrochemical
measurements;
-would make possible the addition of new data.

Improvement so as to simplify on-site use:

Possibility to isolate the RE/JPT/drop system
so as to prevent a contamination which might
influence the results.

Leiden, 11-15 January 2010

 Acknowledgements

-the Haute Ecole Spécialisée de Suisse Occidentale (HES-SO -

The University of Applied Sciences of Western Switzerland) for
financially supporting the SPAMT-Test project,
-the research team at the Haute Ecole de Conservation-
Restauration (HECR) Arc for their administrative support.

Colleagues who provided reference copper-based

materials for the construction of our database: A. Adriaens
(Gent University, BE); K. Kreislova (SVUOM, Prague, CZ); L.
Beck (Centre for Restoration and Conservation of French
Museums, Paris, F); J. Muller (ICMPE-CECM, UPR 2801 /
CNRS, Vitry-sur-Seine, F); G. Martin (Victoria & Albert Museum,
London, UK); L. Selwyn (CCI, Ottawa, Ca); P. Mottner (ISC,
Bronnbach, D); M. Penna (Swissmetal, CH); T. Schenkel (HECR
Arc, La Chaux-de-Fonds, CH) and H. Habbeger (HAM, Thun,
CH).

Leiden, 11-15 January 2010