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Indoor corrosivity in the National Museum Depositary,


Prague, the Czech Republic
Dagmar Knotkova1, Katerina Kreislova1, Blanka Kreibichova2, Ivan Kudlacek3
1
SVUOM s.r.o.
2
National Museum
3
Czech Technical University
SVUOM s.r.o.
U Mestanskeho pivovaru 934
Prague, 170 00, CZECH REPUBLIC
Phone:++420 220809996
Fax: ++420 220809981
e-mail: kreislova@svuom.cz

The corrosivity of the indoor atmospheres of historic buildings and museums has a significant importance for
long-term storage of cultural heritage objects. The corrosivity classification of indoor atmospheres and meth-
ods of its determination and estimation is a subject of the standard ISO 11844. Method of the determination of
the corrosion rates by resistance measurement is suitable for continuous or repeatable evaluation of corrosion
attack. The results obtained in National Museum Depositary in Prague, the Czech Republic together with eval-
uation of corrosion effects on exposed metal coupons representing typical materials used in these environ-
ments show the significance of assessment of this characteristic for indoor environments.

Keywords: indoor corrosivity, resistance sensors, specific pollution, silver, copper and bronze coupons

1. INTRODUCTION indoor atmospheres. The possible pollutants in the in-


door atmospheres are SO2, NO2, O3, H2S, Cl2, NH3, HCl,
The information of indoor atmospheric corrosivity of HNO3, Cl-, NH4+, organic acids (e.g., acetic acid, formic
historic buildings, museums and galleries has significant acid, etc.), aldehydes (e.g., formaldehyde, acetaldehyde)
importance for the assessment of the environment stress and particles [1 - 3]. The environmental characteristics
on stored or exposed cultural heritage objects. SVUOM involve the informative estimation of corrosivity consid-
specialists studied these issues in framework of national ering the specific corrosion effects in respect to various
and international projects. The projects’ results have been metals and metallic coatings. The final corrosion effect is
used for the elaboration of the specific international stan- the result of influence from many factors. The determi-
dardized classification system. In this paper, the survey of nation of indoor atmospheric corrosivity is based on the
the atmospheric corrosivity classification systems is given measurement of corrosion attack of the standard speci-
together with the experimental results for selected deposi- mens of four reference metals (carbon steel, zinc, cop-
tary rooms of National museum building, Prague, the per, silver) after one year of exposure.
Czech Republic. The mass balance models were elaborated for the
penetration of outdoor air pollution into the indoor envi-
2. METAL CORROSION IN THE INDOOR ATMOS- ronment (IMPAC model) [2, 4]. The ratio of outdoor
PHERES WITH LOW CORROSIVITY and indoor pollution concentrations (I/O) varies for each
compound of the air pollutants (SO2, NO2, O3) and it is
The metals and metallic coatings show specific corro- affected by construction parameters of each building, hu-
sion behaviour in the indoor atmospheres. The indoor man factors, pollution sources in indoor environment
corrosivity increases with increasing relative humidity and other characteristics of the system evaluated. The re-
and depends on the type and the concentration of the ferred model assumes that the interactions by individual
pollution. The corrosion of many metals is significantly compounds are not significant and there are no pollution
affected by the synergistic effects of various types of the sources in indoor environments. The model results are in
pollution. The frequency of relative humidity and tem- good agreement with measured values for SO2 but less
perature values at given intervals, and the frequency and for NO 2 and O 3. The measured ratio I/O for NO 2 was
time of condensation are important characteristics for 0,24 [2].
atmospheric corrosivity. Besides the outdoor sources of
air pollution, the specific pollutants form directly in the
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Indoor corrosivity in the National Depositary, Prague, the Czech Republic

2.1 Atmospheric Corrosivity Classification Systems 2.2 Methods of the determination of indoor corrosivity
There exist few general classification systems for the according to ISO 11844
evaluation of the atmospheric corrosivity using various The indoor corrosivity can be determined on the basis
classification criteria. The standards ISO 9223, IEC 654- of the corrosion rate calculated from mass changes of the
4 and ISA S71.04-1985 are based on the classification cri- standard specimens after exposure in given period prefer-
teria of the corrosion effect of the standard metals as cri- ably after one year. For evaluation of corrosion attack, the
terion for classified environmental conditions: following methods are used:
— the standard ISO 9223 Corrosion of metals and alloys — the determination of corrosion rate by direct mass
- Corrosivity of atmospheres - Classification defines the change measurement (mass loss, mass increase),
corrosivity categories (C1 - C5) based on the corro- — the determination of corrosion rate by electrolytic ca-
sion of standard specimens of carbon steel, zinc, cop- thodic reduction of corrosion product layers on copper,
per and aluminium expressed as mass losses after respective on silver,
one year exposure, — the determination of corrosion rate by resistance mea-
surement (according to the specific metal sensors' re-
— the standard IEC 654-4 Operating conditions for in-
sistance change measurement).
dustrial-process measurements and control equipment.
Part 4: Corrosive and erosive influences classifies the
reactivity of environment by determination of thick-
ness of the copper corrosion layer after 30 days expo-
sure,
— the standard ISA S71.04-1985 Environmental condi-
tions for process measurement and control systems:
Airborne contaminants defines the severity levels (G1,
G2, G3 a GX) based on copper coupon corrosion
film thickness which build up with one month of ex-
posure.
Standard ISO 9223 classifies the atmospheric environ-
ment in general (outdoor and indoor) into five cate-
gories of corrosivity. Indoor atmospheres with low corro-
Figure 1 – Corrosivity classification for copper according
sivity belong to atmospheres with corrosivity category C1
to standards ISO, IEC a ISA as presented in ISO 11844-1
(very low) or C2 (low) according to ISO 9223. This clas-
sification is too wide for an environment where the his- For the indoor corrosivity determination of the Na-
toric artefacts are displayed and exposed. For these pur- tional Museum Depositary, the resistance change
poses, it is necessary to divide the categories of corrosivi- method was applied. The method of the corrosion rate
ty C1 and C2 into five categories of indoor atmospheric determination by resistance measurement is suitable for
corrosivity (IC1 - IC 5) according to standard ISO continuous or repeated monitoring of the corrosion at-
11844:2006 Corrosion of metals and alloys - Classification tack. The technique is easy-to-use, and it is possible to
of low corrosivity of indoor atmospheres, which consists of use the commercial resistance sensors. The resistance
three parts: sensors are used for the corrosion rate determination on
— Part 1: Determination and estimation of indoor corro- the basis of resistance changes of corroded thin metallic
sivity films. The resistance sensor is formed by vapour deposit-
— Part 2: Determination of corrosion attack in indoor at- ed metallic layer in the meander shape with electrode
mospheres outlets on the each end and in the middle. This lay-out
— Part 3: Measurement of environmental parameters af- represents two identical resistance parts form which the
fecting indoor corrosivity. one represents measuring corroded surface and the sec-
In order to compare ISO, IEC and ISA classification sys- ond is a reference part used to compensate the tempera-
tems, corrosion figures for copper are used in ISO ture effect. The reference part is covered by a protective
11844-1, copper being the only metal common to all film, which protects the surface against the corrosion at-
standards. The comparison of the classification stan- tack of measured atmospheres. The changes in electric
dards is presented on Figure 1. The comparison is based resistance of reference and corroded parts of sensors
on the copper corrosion rate and assumption that the correspond to the corrosion rate. There are used silver,
dominant copper corrosion products are CuO, copper and steel sensors with layer thickness from 50 nm
Cu4SO4(OH)6 and Cu2S. All corrosion rate values given to 2500 nm. The most suitable for the given purposes are
in these standards are transformed to one year corrosion sensors with 250 nm thickness [5]. The resistance
mass increase. changes of the exposed and the reference parts of sensor
should be measured in regular intervals for minimum pe-
riod of three months.
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D. Knotkova et al.

The corrosion rate is given by equation: structed between 1885 to 1888, and was occupied in 1891 as
the Museum of the Kingdom of Bohemia (Figure 2). The
collections’ Department of Prehistory and Protohistory is
dated since 1893. During 1893-1911, it collected ca 50,000
artefacts, and today it contains over 500,000 artefacts. The
collection contains various metal artefacts (copper,
where bronze, iron, silver, gold), pottery, glass, stone and bone
rcorr is the corrosion rate in mg/m2.a, materials.
Rexp is the resistance for the non-protected part of
the specimen after exposure,
(Rprot)expis the resistance for the protected part of the speci-
men after exposure,
R0 is the resistance for the non-protected part of
the specimen before exposure,
(Rprot)0 is the resistance for the protected part of the
specimen before exposure,
dmetal is the density of the metal, i.e.. Ag = 10,50 g/cm;
Cu = 8,93 g/cm3
C is a constant, specific for the specimen and giv-
en by the manufacturer in 10-10 m,
t is the exposure time, in years.
Figure 2 - National Museum
The other non standardized measurement systems can
be applied for measurement of the corrosion effect (the The National Museum is located in one of the most
quartz microbalance method, the oscillation sensors). polluted areas of Prague City caused by very heavy traf-
fic. Pollution of the outdoor atmosphere is measured
3. CORROSIVITY OF SELECTED MICROCLIMA- on monitoring test site on building of National Museum
TES IN NATIONAL MUSEUM BUILDING since 1994 by the automatic equipment. The yearly av-
erage values of these measurements are presented in
The National Museum building had been under con- Table 1.

Table 1 - Yearly average pollution data on National Museum - outdoor atmosphere [6]
3.1 Environmental characteristics of selected microcli- tion, was a working place of museum researcher in De-
mates in National Museum building positary No 103 until 2002, which was a source of humidi-
Measurements of the indoor corrosivity in National ty and significant anthropogenic pollution in the mea-
Museum were carried out during the last decade. In Na- surement period 1999-2001.
tional Museum building, the basic climatic parameters and The air pollution was measured during the period 1999
indoor pollution were measured and evaluated repeatedly - 2001 at four microclimates by passive samplers according
at different periods and locations (depositaries in the cellar to ISO 9225. The monthly maximum SO2 concentration in
(No 2b, No 2c), on the ground floor (No 103, No 104) and indoor atmospheres was 1,8 Ìg.m-3 compared to concen-
on the II. floor (No 222, No 276d)). tration 7 Ìg.m-3 in outdoor atmosphere in this locality. The
In Table 2, gives the ranges of measured values of ratio I/O for SO2 was 0,26. The monthly maximum NOx
temperature and relative humidity in these microcli- concentration in indoor atmosphere was 45,7 Ìg.m-3 com-
mates. According to ISO 11844-1, it is possible to divide pared to concentration ca 90 Ìg.m-3 in outdoor atmosphere
these National Museum microclimates into different lev- in this locality. This high NOx indoor concentration was
els of relative humidity: rooms No. 2b and No 2c in cellar measured in the entering hall of building, where the higher
at level III and rooms No 103, 104, 222 and 276d at level penetration of the outdoor air into building occurs. The ra-
II. During the period 2005-06, the relative humidity in tio I/O for NOx was 0,50.
Depositary No 103 was at level I (Figure 3). At this loca- In the other rooms, the maximum monthly NOx con-
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Indoor corrosivity in the National Depositary, Prague, the Czech Republic

centration ranged from 27 to 29 Ìg.m-3. The ratio I/O for Level SO2 NO2 O3 NH3
NOx was 0,31 here. During the period 2005-2006, the in- I c<1 c<1 c<1 c<5
door nitrogen oxide pollution was measured only due to II 1£c<5 1£c<5 1£c<5 5£c<10
the extreme load of this locality with this type of pollution
(average yearly outdoor concentration was 46,2 Ìg.m-3 dur- III 5£c<10 5£c<10 5£c<10 10£c<20
ing this period). The average monthly NOx concentration IV c≥10 c≥10 c≥10 c≥20
in Depositary No 103 was 10,7 Ìg.m-3 and maximum
monthly NOx concentration was 15,1 Ìg.m-3; the ratio I/O Table 3 – The level of gaseous pollution in mg/m3
was 0,21. These values were compared to classified infor- (ISO 11844-1)
mative pollution levels according to ISO 11844-1 (Table 3)
- the NOx pollution is at level III. NOx is pollution which af- Other pollution typical for indoor atmospheres (SO2,
fects the corrosion of copper alloys. The synergistic corro- O3, H2S, Cl2, Cl-, NH3, HCl, HNO3, organic acids, aldehy-
sion effect can be expected, NO2 acts as oxidizer of SO2. des and particles) were not measured, since for many of
them passive samplers were not available. Only some of
mentioned pollutants were expected to exist in Depositary,
since there is no source of pollution, with exception of or-
ganic acids and aldehydes (wooden furniture).
The effect of pollution on indoor corrosivity is specific
for individual metals and interdependent (combination of
pollution, effect of humidity and temperature).

3.1 The corrosion attack on exposed coupons and resis-


tance sensors
During the period 2000-2001, the copper and silver
coupons with dimensions 80 x 30 x 0,5 mm were exposed in
all assessed rooms at the National Museum. The coupons
were evaluated visually after one year of exposure. The
smallest corrosion changes of copper were found in rooms
No 2c and 222, the corrosion attack of silver was more dis-
tinctive. The very distinctive corrosion attack was found in
rooms No 103 and 104 for both exposed metals and for
copper in room No 2b, too. The distinctive corrosion at-
tack of silver was found in rooms No 222 and 276d. The ap-
pearance of coupons after one year exposure is given in
Figure 4. According to this evaluation, the corrosivity of in-
door atmospheres can be estimated as high (IC 4) up to
Table 2 - The range of measured values of temperature very high (IC 5) practically at all rooms of the National
and relative humidity Museum.
During the period 2005-2006, the copper, bronze
and silver coupons were exposed in Depositary No 103.
The coupons’ surfaces were evaluated on monthly inter-
vals for 12 months. The visual evaluation of copper and
silver coupons surfaces shows the corrosivity of micro-
climate decreased in comparison to the previous period
as a result of the removal of the anthropogenic effect
(caused by the museum researcher). The significant
corrosion effect formed on ca 5% of exposed bronze
area. The corrosion layers formed on the surface of
these coupons after one year exposure but the mass
change was negligible.
After 12 months of exposure, the surface layers were
analyzed by scanning electron microscope XL 30 ESEM-
TMP PHILLIPS equipped with the EDAX multi-channel
Figure 3 - Climatic parameters in Depositary 103 spectrometer for element microanalysis (Figure 5 and
in period 10/2005 - 09/2006 Table 4). The analysis was carried out on the whole imaged
area, and in spots with specific character. The selected ex-
posed metals have different sensitivity to the influence of
the environment:
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D. Knotkova et al.

— the dark spots formed on bronze surface contain a sig- bly a mixture of ZnO, Zn(OH) 2, ZnCO 3 and
nificant amount of sulphur and they are probably a Zn5(CO3)2(OH)6. These compounds were detected
mixture of CuO/CuO2, sulphide and sulphate copper during a previous exposure.
corrosion products, — the corrosion layer of copper demonstrated the specific
— the white and/or grey spots formed on the surface non- sensitivity of copper to NO2 effect,
uniformities (in pits, holes, cracks), where the mois- — the significant amount of nitrogen and sulphur was
ture condensates, are a mixture of corrosion products identified on the silver surface, but the sulphur content
of lead, probably 2PbCO3*Pb(OH)2, and zinc, proba- was lower than on bronze surface.

Figure 4 - Copper and silver coupons exposed 12 months in various microclimates of National Museum

Table 4 - Results of SEM/EDAX analysis of coupon surfaces after 12 months exposure (± 3 % error)

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Indoor corrosivity in the National Depositary, Prague, the Czech Republic

Figure 5 - The examples of surface of coupons and analysed areas (optical and scanning electron microscopy)

In Depositary No 103, the Rorhback resistance sensors sure, the steel sensor failed. The copper Rohrback sensor
of steel, copper and silver were placed for determination of measurement showed the corrosivity of Depositary is
indoor corrosivity. The sensors' parameters (electric resis- medium (IC3) for this metal - maximum monthly corrosion
tance changed as a function of thickness of metal layer) rate for copper sensor was 160 Aˇ . After one year exposure,
had been measured in monthly intervals (Figure 6). The the corrosion mass loss was ca 144 mg/m2.a. The silver
steel Rohrback sensor showed the high corrosion rate with Rohrback sensor measurement showed the corrosivity of
maximum monthly value 390 ∞ ˇ . After 8 months of expo- Depositary is very low (IC 1) for this metal - maximum
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D. Knotkova et al.

monthly corrosion rate for silver sensor was 2,5 Aˇ . After coupons or special sensors. The results from the period
one year exposure, the corrosion mass loss was ca 7,7 1999-2001 gave data for the assessment of the corrosivity in
mg/m2.a. selected microclimates in National Museum. The results
The corrosivity of Depositary No 103 is different for from the period 2005-06 presented the measurement of re-
individual exposed metals. In the indoor atmospheres the sistance changes of specific sensors to allow the corrosivity
accumulation rates of anions and cations from pollution determination for selected locality.
differentiate on surface of the single metals [5]. The cop- The need to classify the environments with respect to
per is a very sensitive metal to existing climatic and pollu- their corrosivity is important for the application the pre-
tion influence in this indoor microclimate, and the corro- ventive conservation approach in museums, too. One way
sivity for copper is on IC 3 category according to ISO to characterise an indoor environment is to determine the
11844-1. The bronze corrosion behaviour is similar to cop- corrosivity by measuring the corrosion attack on coupons
per with the exception of sensitivity to ozone effect. The of metals exposed to the atmosphere. The aim of present
corrosion rate of bronze is lower than the corrosion rate study was to evaluate the agreement between different
of copper about 30%. measuring techniques for the evaluation of the corrosion
effects of silver and copper in indoor conditions. The mea-
surements based on resistance sensors have been evaluat-
ed as very important. The possible corrosion effect of par-
ticulates in indoor atmospheres was not covered by this
study.
The recorded temperature and relative humidity data
can be treated in direct relation to the environmental cor-
rosivity on informative level only. These data without any
further information about the type and level of pollution
are not sufficient for the estimation the effect of the envi-
ronment for metal materials. The estimation of indoor cor-
rosivity by application of the passive pollution samplers
and monitoring of the other environmental conditions is
difficult and expensive. The most accurate information is
Figure 6 - The course of measurement by Rohrback sensors given by direct determination of the corrosivity of low cor-
rosive indoor environments by special sensors or standard
4. CONCLUSION coupons exposure.

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