Professional Documents
Culture Documents
Instituto de Geociencias IGEO (CSIC, UCM), C/Jos Antonio Novais 12, 28040 Madrid, Spain
Facultad Ciencias Geolgicas, Universidad Complutense de Madrid (UCM), C/Jos Antonio Novais 12, 28040 Madrid, Spain
h i g h l i g h t s
Long-term effectiveness, suitability and durability of conservation treatments.
Need for preliminary studies to ensure successful restoration.
Use of petrological techniques to determine treatment mechanisms.
Unsuitable use of cements and synthetic resins on decayed dolostone.
Salt-induced loss of restored ornaments.
a r t i c l e
i n f o
Article history:
Received 6 February 2015
Received in revised form 13 May 2015
Accepted 14 July 2015
Available online 25 July 2015
Keywords:
Dolostone
Conservation treatments
Cements
Synthetic resins
Architectural heritage
Decay
Petrological techniques
a b s t r a c t
Preliminary studies are an imperative when determining the impact of conservation treatments on
historical materials. The Romanesque apse on a church at Talamanca de Jarama, Madrid, Spain, whose
dolostone was severely decayed by rainwater and salts, was treated in the past with substances that ravaged the restored area. Petrological techniques showed that salts leached out of the cement under the
roof onto the stone cornice whose surface had been coated with synthetic resins. During evaporation,
the salts precipitated in the stone and underneath the resin, inducing blistering, ssuring, aking, scaling
and detachment of part of the restored decorative elements.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Time and weathering (water, wind, solar radiation, temperature
variations, air pollution. . .) are the chief agents of decay in most
stone materials comprising the built heritage. The impact of such
decay varies depending on the composition and texture of the
materials involved [13].
The need to conserve the cultural heritage has driven the
appearance on the market of many restoration products, designed
and manufactured primarily to retard stone decay and increase its
durability [47]. These products may be: inorganic (such as lime
wash Ca(OH)2 (aq) used in the nineteenth century and presently
recovered in the form of nanolime Ca(OH)2 alcoholic colloidal
Corresponding author at: Instituto de Geociencias IGEO (CSIC, UCM), C/Jos
Antonio Novais 12, 28040 Madrid, Spain.
E-mail address: mjvaras@geo.ucm.es (M.J. Varas-Muriel).
http://dx.doi.org/10.1016/j.conbuildmat.2015.07.087
0950-0618/ 2015 Elsevier Ltd. All rights reserved.
612
613
Fig. 2. Richly carved cornice and modillions on the upper part of the church, restored in 1990: cement mortar lling in inter-ashlar joints and laid directly on the cornice
underneath the Spanish tile roof.
Fig. 3. Decaying cornice and modillions in 2004, showing substantial amounts of cement on the cornice and the near total loss of ornaments on modillions and cornice.
614
3. Results
3.1. Cornice: state of conservation
The yellow dolostone on the cornice was found to be severely
decayed and many of its decorative elements to have been totally
or partially lost after the 1990 restoration (Fig. 3). Some of the conservation treatments contributed to the decay of the dolomite substrate (Fig. 5). The main forms of decay detected were: (a) surface
gloss and change in hue from yellow to grey in the carved stone
due to the presence of a viscous lm (Figs. 4b and 5); (b) blistering,
ssuring, aking and scaling both in the surface treatment and the
carved stone, resulting on occasion in detachment (Fig. 5); (c) saline sub-eforescence and crypto-eforescence beneath the treatments, affecting the carved stone; and (d) surface wear (Figs. 2, 3
and 5).
3.2. Characterisation and condition of the stone substrate
The dolostone on the cornice is a carbonate rock, uniform in
appearance whose 20% porosity consisted of pores of <500 lm
in diameter (visual estimate; Fig. 4a). The sub-parallel cracks up
to 1.5 cm deep on the surface exposed to the elements induced
scaling and detachment with the concomitant loss of the gures
carved in the stone (Figs. 5 and 6).
Fig. 4. Samples of dolostone on around the cornice: (a) cross-section of yellow dolostone core: (b) decayed fragment from cornice surface, showing the obvious contrast
between the glossy grey treatments and the yellowish dolostone. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version
of this article.).
615
Fig. 5. Grey treatment scaling and aking on cornice and modillions, baring the yellow stone substrate and inducing the loss of the original restored ornament. (For
interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.).
Fig. 6. Cross-section of scale removed from cornice, showing three zones: upper grey layer with white particles and varying depth (restoration mortar), middle layer where
the stone substrate exhibits cracks parallel to the surface and a few white spots, and lower layer where the yellow substrate is compact. (For interpretation of the references
to colour in this gure legend, the reader is referred to the web version of this article.).
The PM study revealed that this massive dolostone is characterised by rhomboid micritic dolomite crystals measuring <10 lm
on average and 2025% intercrystalline porosity (Fig. 7a and b).
Some of these subrounded (mean diameter = 225 lm) or irregularly shaped (mean diameter = 975 lm) pores were lled with
P30-lm sparry calcite crystals. Disperse monocrystalline quartz
grains (5%) with a mean size of <150 lm (very ne sand) were
observed inside the dolomicritic mass (Fig. 7a). The numerous dark
iron gel spots also observed were partially responsible for the
yellow-golden tone of this variety of stone (Fig. 7a), classiable
as a dolomudstone [31]. The mineralogy detected under the PM
(dolomite and some quartz) was conrmed by the XRD ndings.
The intense cracking on the sample surfaces increased in the
outward direction (Fig. 7b). These cracks, parallel and
sub-parallel to one another and to the outer surface of the sample,
were 75 lm thick on average and over 250 lm thick in the
outer-most areas.
Further to the petrophysical ndings (Table 1) this is a dense
(>2800-kg m 3) but highly open porosity (2426%) stone, properties that were observed to vary from the outer-most decayed
(05 cm) to the inner (510 cm) intact inner area of the cores.
The porosity in the outer stone was up to 8% higher than in the
inner stone, which translated into 10% greater water sorptivity.
Such higher surface porosity was conrmed by the nearly
1000-m s 1 lower ultrasonic P-wave velocity (Vp) in that area than
in the inner stone.
616
Fig. 7. PM images of yellow dolostone on the upper part of the apse: (a) no decay but substantial original porosity (left: parallel nicols; right: crossed nicols); and (b) cracks
and nodules indicative of decay (parallel nicols). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.).
Table 1
Petrophysical properties of decayed (outer 5 cm) and undecayed (at depths of 5
10 cm) dolostone.
Dolostone
Outer area
Inner area
2821
2077
26.36
12.69
1843
2824
2237
24.31
11.38
2873
the graphite coating on the samples, the dark binder area (point A
in Fig. 9) exhibited a much higher C (organic component) concentration than the lighter aggregate area (point B in Fig. 9), which in
contrast had more Ca (calcite) than the binder. Other chemical elements present in the two areas, although more prominently in the
binder, included Si, Mg, Al, Na and Cl (neither Cl nor Na were found
in the aggregate). A detailed study of the binder revealed the presence of small (35-lm) Ca (calcite) particles inside a C-high dark,
dense gel with some Si.
The FTIR spectrum for this mortar (Fig. 10) contained a vibration band in the 1740-cm 1 region associated with carbonyl
(C@O) and an especially intense vibration band at around
1440 cm 1 attributed to carbonate groups (ACO@
3 ). The bands
detected at around 714, 730, 876, 1440, 1800 and 2530 cm 1 were
attributed to calcite (CO3Ca). The intense vibration band in the
3430 to 3540 cm 1 region as well as the absorption band at around
617
Fig. 8. Scaling on cornice: (a) PM image with parallel nicols; (b) lXRD diffractogram showing the mineralogy of the two components of the restoration mortar; (c) SEM-SE
image of a thin section: A restoration mortar, B gypsum layer, C cracked stone substrate with gypsum nodules.
Fig. 9. SEM-SE image of a fragment of restoration mortar and EDS point chemical composition: A binder; B aggregate.
migrate outward to the stone surface where they formed the layer
of variable thickness under the restoration mortar (Fig. 14a). No
gypsum ll was found in the cracks in the stone substrate.
4. Discussion
The main type of decay found in the Piedra de Reduea [2] dolostone forming the carved cornice on the Romanesque apse was
intense inner cracking parallel to the surface, at depths of up to
1.5 cm (Figs. 6 and 8). On the surface, this cracking translated into
aking and scaling liable to detachment. The main agents of decay
identied were rainwater and soluble salts due to continuous leaking and surface runoff, by the poor pre-1990 condition of the roof
and the total absence of gargoyles and gutters to evacuate rainwater. Cracking, characteristic of this variety of stone when exposed
to water and salts [32], was the type of decay exhibited by the
dolostone in the cornice prior to the 1990 restoration [25].
This stones high open porosity (25%, Table 1) makes it a readily workable and easy to carve but at the same time scantly durable
material [2,32]. For that reason, it was used on the upper areas of
the apse, including the cornice, while a similar but less porous
618
Fig. 11. Fragment of restoration mortar surface, showing: A surface acrylic, B binder and C aggregate (both in the underlying restoration mortar), under: (a) PM (parallel
nicols) and (b) SEM-SE. EDS point chemical composition of synthetic resins (A acrylic and B epoxy + acrylic) forming part of the two treatments (with Ca as the sole
chemical element in the C aggregate).
detection of NaCl (point A in Fig. 9), which may have arisen during
hardening [4]. Both types of resins were called for in the 1982
design. The quartz (lXRD Fig. 8b), Si and Al (EDS point A in
Fig. 9) and SiAOASi groups (FTIR Fig. 10) found in this restoration
mortar, in turn, suggested the possible presence of a third, silica
compound-based consolidant [12,17,18] or a possible chemical
change in one of the synthetic resins used. No written information
was available to corroborate the presence of such a third conservation product.
The viscous, glossy lm covering both the aforementioned
restoration mortar and at times the dolostone itself contained both
Ca and C (Figs. 11 and 13). The identication of C@O, CAO and CAH
groups was an indication that it may have been an acrylic resin
[5,28] mixed with lime powder (Fig. 12).
In another vein, the treatment applied prior to the restitution
mortar in 1990 was designed to consolidate the decayed dolostone
by sealing its cracks (Figs. 8 and 13). The EDS identication of silicon (Si) and aluminium (Al) with very little carbon (C) may have
been the result of the presence of a silica compound-based product
619
Fig. 13. SEM-SE image and EDS point chemical composition of a scaling fragment,
showing: A surface treatment, B restoration mortar, C gypsum layer and D
cracked stone substrate.
620
Fig. 14. PM (parallel nicols) images of: (a) gypsum nodules inside the cracked dolostone; and (b) capillary connections.
Acknowledgements
This study was funded under project of MICCIN
(CGL2011-27902) and forms part of the GEOMATERIALES-2CM
(S2013/MIT-2914) research programme. The authors are members
of the Complutense University of Madrids Research Group:
Alteracin y Conservacin de los Materiales Ptreos del Patrimonio
(ref. 921349) and of the CEI-Moncloa (UCM-UPM) through
RedLabPat. Thanks are owed to the Archbishopric of Alcal de
Henares, Madrid, and all the persons associated with the church
in Talamanca for their assistance throughout this study.
Manuscript edited by Margaret Clark, professional translator and
English language science editor.
References
[1] L. Binda, A. Saisi, C. Tedeschi, Compatibility of materials used for repair of
masonry buildings: research and applications, in: S.K. Kourkoulis (Ed.),
Fracture and Failure of Natural Building Stone, Netherlands, Springer, 2006,
pp. 167182.
[2] R. Fort, M.J. Varas, M. lvarez de Buergo, D.M. Freire, Determination of
anisotropy to enhance the durability of natural stone, J. Geophys. Eng. 8 (2011)
S132S144.
[3] J.J. Guardia-Olmedo, M.J. Varas-Muriel, F.J. Surez-Medina, Castle-Palace of La
Calahorra, Granada: inuence of climatic and architectural factors in the
differential deterioration of stone masonries, Mater. Constr. 63 (312) (2013)
597612.
[4] W.S. Ginell, R. Coffman, Epoxy resin-consolidated Stone: appearance change on
aging (architectural restoration), Stud. Conserv. 43 (4) (1998) 242248.
[5] A.K. Banthia, A.P. Gupta, Role of acrylic resin in the conservation of
deteriorated khondalite stones, Polym. Preprint (ACS) 41 (1) (2000) 277278.
[6] V. Cnudde, J.P. Cnudde, C. Dupuis, P.J.S. Jacobs, X-ray micro-CT used for the
localization of water repellents and consolidants inside natural building
stones, Mater. Charact. 53 (2004) 259271.
621
622
[36] H.G. Machel, E.A. Burton, Burial diagenetic sabkha like gypsum and
anhydrite nodules, Sed. Geol. 61 (1991) 394405.
[37] A. Zamannejad, D. Jahani, M. Lotfpour, B. Movahed, Mixed evaporite/carbonate
characteristics of the Triassic Kangan Formation, offshore area, Persian Gulf,
Rev. Mex. Cienc. Geol. 30 (3) (2013) 540551.