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Salt Crystal Intergrowth in Efflorescence on Historic Buildings

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Salt Crystal Intergrowth in Efflorescence on Historic Buildings ART AND CHEMICAL SCIENCES 996 CHIMIA 2001. 55, No, 11 Chimia 55 (2001) 996-1001 © Schweizerische Chemische Gesellschaft ISSN 0009-4293 Salt Crystal Intergrowth in Efflorescence on Historic Buildings Christine Blauer Bohma*, Andreas KOnga, and Konrad Zehnderb Abstract: Salt crystallisation is known to be one of the most powerful weathering factors threatening monuments, with the salts often occurring as efflorescence, normally formed from different species as individual salts growing in aggregates. In rare cases, different salt phases are observed that are closely intergrown on a crystalline scale. This paper reports on this rare type of salt efflorescence. Four types of salt crystal intergrowth in efflorescence have been distinguished up to now; the growth conditions for each are deduced. Keywords: Crystallisation, Efflorescence' Historic buildings' Intergrowth . Salt 1. Introduction vations, and it discusses their implica- place, and on the time scale according to tions on the growth conditions in the spe- the changing daytime and climatic influ- Salt crystallisation is known to be one of cific context of weathering phenomena ences. These systems are thermodynami- the most powerful weathering factors, on building materials. cally open as far as they include the and therefore it is important that it is tak- The salt species which grow in an ef- whole atmosphere in their environment. en into consideration in the conservation florescence depend - as a matter of Cases of observed salt crystal inter- of historic buildings. Salts are commonly course - on the composition of the salt growth are specifically interesting since noticed as efflorescence on buildings as a solution. In addition, it depends on the they may provide valid facts on the dy- general weathering effect. Salt efflores- properties of the substrate and on the en- namics of crystallisation under particular cence forms by crystallisation from salt vironmental conditions during growth. conditions. They represent peculiar states solutions. Though normally one predom- As a result of our observations on many near the equilibrium that have been es- inant salt species is found in an efflores- historic buildings we found that tablished in the object, and they can be cence, there is frequently efflorescence • one or several species may form from compared with theoretical findings from of different species as individual salts a solution containing several ionic thermodynamic predictions as provided growing in close proximity in aggregates. species, and that by Price [1]. On the other hand, salt crystals in an ef- • the species variety may change even florescence can be monocrystals as well on the same place with time. 2. Methodical Approach as polycrystals. Whiskers in an efflores- Hence we deal not only with chemi- cence as an example (explanations for cally complex systems, but also with dy- 2.1. The Phenomenological Approach these and further specific terms see the namically changing conditions during in Conservation is used in our research. end of the text) are frequently composed growth. For example on a wall surface, It is based on observation of the whole of parallel arrangements of crystal fibres the physical and chemical conditions context (site, environment, situations, tied or bundled together. Such polycrys- vary on a microscopic scale from place to salt system, efflorescence, etc.). Efflores- talline individual whiskers are normally composed of one salt species only. How- ever, in rare cases we observe this type of Table 1. The salts so far observed intergrowing in efflorescence with their solubility in water (after intergrowth formed from different salt [5]) and the equilibrium relative humidity of the single salts (after [6]; extended thermodynamic minerals. This paper presents such obser- data of salts can be found in Price [1]). Salt mineral Short Chemical formula Solubility in Equilibrium 'Correspondence: Dr. C. Blauer B6hma name water at 20 C relative Tel.: +41 1 27201 66 [g/100ml] humidity at 20 C Fax: +41 1 2721965 E-Mail: [email protected] aExpert-Center fUr Denkmalpflege Halite Ha NaCI 35.9 75.5% Hardturmstrasse 181 Nltratlne = soda niter Nt NaNOa 92.1 75.4% CH-8005 ZUrich Niter Ni KN03 31.5 94.6% blnstitut fUr Denkmalpflege Mirabilite Mi Na2S04·1OH2O 19.4 93.6% Forschungsstelle Technologie und Konservierung Epsomite Ep MgS04·7H2O 71 90.1% Hardturmstrasse 181 Gypsum Gy CaS04·2H20 0.2 CH-8005 Zurich ART AND CHEMICAL SCIENCES 997 CHIMIA 2001,55, No, 11 cence occurring and disappearing on in- Table 2. Phenomenological description of particular cases referenced in this paper with the site dividual buildings or sites is correlated (i.e. historic building where the efflorescence was found, site number in brackets), date of with monitored local environmental con- sampling, minerals setting up the intergrowth and the type of intergrowth, and further observa- ditions, which allows specific ongoing Site Date Type of Morphology damage mechanisms to be revealed. lntergrowth From this it is normally possible to derive custom-made concepts such as climate Crypt of Grossmilnster, 08.01.85 Nt + Ha (a) The bristly efflorescence mainly control to reduce or prevent further dam- Zurich, Switzerland (1) consists of nitratlne whereas halite age. only occurs in traces as bent fibres which are partly parallel intergrown 2.2. Qualitative Analyses of salts were with nltratine. performed according to the method given Crypt of Grossmunster, 10.03.86 Nt + Ha (a) Up to 0.6 mm long bundles of parallel Zurich, Switzerland (2) by Arnold [2]. It consists of analysing grown fibres of niter and halite. Ni + Ha (a) Bent bundles up to 0.3 mm long salt crystals by means of polarising light composed of parallellntergrown microscopy in combination with micro- fibres of the two sail minerai species. chemical tests for specific ions in aque- Nt+ Ni + Ha Bent bundles up to 0.4 mm long ous solutions of the salts. With regard to (a) whlch are buill up of parallel fibres the analysis of crystalline materials, po- of the mentioned three salt minerals larising light microscopy [3] is a very (Ag 1). powerful tool because it not only allows Cathedral of Chur, 11.01.00 Nt + Ha (1a) Comb-like aggregates of ? parallel the identification of individual species Switzerland (3) crystals oltha two salt species. Inter- but also enables their shape, size and in- growth is not clearly Identifiable In the sample which mainly consists terconnections with other species such as of pain particles and powder from crystals intergrown each other to be ob- the mortar pushed off by salt crys- served. Micro-chemical testing [4] is per- talllzation. formed as a supplementary method to Cathedral of Chur, 03.05.94 Ni + Ha (a) The sample contaIns paint particles further distinguish salts with similar opti- Switzerland (4) and powde and Is rich in aggre- cal properties. With the combination of gates of halite grown parallel. Niter these methods the salts commonly occur- is present only In small amounts ring on monuments can be distinguished and partly parallel intergrown with unambiguously with the exception of a halite Church of St. Martin, 26.02.86 Ni + Mi (1a) ThIs intergrowth Is not evident few salt minerals. For the purpose of this Cazls, Switzerland (5) because the sample contains some paper, it is important to note that the droplets due to dehydration of mlra- method cannot differentiate epsomite billte. Intergrowth may be the resull (MgS04' 7H20) from hexahydrite of recrystallization. (MgS04·6H20). However, in the numer- Church of the MOstair 06.04.82 Ni + Ep (a) Polycrystailine whisker up to 1mm ous cases where we analysed magnesium Convent, Switzerland (6) long consisting of parallel fntergrown sulphate efflorescence by means of X-ray fibres of niter and epsomlte. Also diffraction, we could only detect ep- Ni Ep (e), see site 10. somite but never hexahydrite. For abbre- Crypt of the Church 26.11.97 Ni + Ha (b) Polycrystailine whIsker of 0.1 up to viations and formulas of salt efflores- St. leonhard, Basel, 0.8 mm length With at maximum five Switzerland (7) lIemating layers of parallel Inter- cence occurring in this paper please refer grown crystals of nitretine and hallte to Table 1. (Fig. 2) Norpert's Room in the 04.02.99 Ni + Ha (b) Uke site 7 but with only one layer of 2.3. Quantitative Analysis of salts is Mustair Convent. each salt mineral. performed by extracting the salts with Switzerland (8) water and analysing the ionic content of the solution with standard methods for Crypt of S1. Maria 15.05.91 Nt + Ha (c) Hali e grains of cubic habit forming water analysis such as Ie, AAS and, in im Kapitol, a crust with interstices iIIed by the case of Maria im Kapitol, with pho- Germany (9) nitfaline (Fig 3). tometry (Lange) and use of a sodium ion ChurCh of the Mustalr 06.04.82 Ni + Ep (c) Crust of compact grains of nitratlne selective electrode [7]. Convent, Switzerland and epsomite which are irregularly (10) intergrown 2.4. Climate Control, i.e. the assess- ment of the climatic conditions has been Church of lavin, 05.03.84 Ni + Ep lc) As in the case of site 10. achieved at the different sites described Switzerland (11) hereafter in the course of investigations for several years. In the case of Maria im Crypt of Grossmi.inster, 09.03.82 Ha + Nt Fibres of hellte up to 0.2 mm thick Kapitol (site 9) this was done by means Zurich, Switzerland (12) inclusions (d) with Inclusions of nitratine See Fig. of a hair hygrograph and by spot meas- 4a and 4b. Crypt of Grossmunster, 10.03.86 Ha + Nt Bent bundles of halite up to 0 15 urements with an aspiration psychrometer Zurich, Switzerland (13) inclusions mm long WIth InclUSions of ?llItra [8]. In all other cases electronic datalog- (?d) line.
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