Natural cement and monumental restoration

Natural cement, called "Roman” cement, was invented at the end of the 19th century and played an important role in the development of civil engineering works until the 1860s. More surprisingly, it was also used to restore historic buildings, such as gothic cathedrals. This paper deals with the mineralogy and the durability of natural cement in the particular case of the Bourges Cathedral in France. This study illustrates the interest of this material particularly adapted in stone repair or substitution. Contrary to traditional mortars, the present samples are made of neat cement paste, revealed by the absence of mineral additions as quartz or carbonate sand. Several combined techniques (SEM-EDS, TGA, XRD) were carried out to determine the composition of the hydraulic binder rich in calcium aluminate hydrates. The raw marl at the origin of the cement production contains oxidized pyrites which consist in a potential source of sulphate pollution of the surrounding limestone. The exposition of the cement in urban environment leads to some weathering features as atmospheric sulfation. Finally a petrophysical approach, based on water porosity, capillary sorption and compressive strength, has been performed to demonstrate the durability and the compatibility of natural cement applied as an historical building restoration morta

Recommendation of RILEM TC 271-ASC: New accelerated test procedure for the assessment of resistance of natural stone and fired-clay brick units against salt crystallization

This recommendation is devoted to testing the resistance of natural stone and fired-clay brick units against salt crystallization. The procedure was developed by the RILEM TC 271-ASC to evaluate the durability of porous building materials against salt crystallization through a laboratory method that allows for accelerated testing without compromising the reliability of the results. The new procedure is designed to replicate salt damage caused by crystallization near the surface of materials as a result of capillary transport and evaporation. A new approach is proposed that considers the presence of two stages in the salt crystallization test. In the first, the accumulation stage, salts gradually accumulate on or near the surface of the material due to evaporation. In the second, the propagation stage, damage initiates and develops due to changes in moisture content and relative humidity that trigger salt dissolution and crystallization cycles. To achieve this, two types of salt were tested, namely sodium chloride and sodium sulphate, with each salt tested separately. A methodology for assessing the salt-induced damage is proposed, which includes visual and photographical observations and measurement of material loss. The procedure has been preliminarily validated in round robin tests

Effectiveness and Compatibility of a Novel Sustainable Method for Stone Consolidation Based on Di-Ammonium Phosphate and Calcium-Based Nanomaterials

External surfaces of stones used in historic buildings often carry high artistic value and need to be preserved from the damages of time, especially from the detrimental effects of the weathering. This study aimed to test the effectiveness and compatibility of some new environmentally-friendly materials for stone consolidation, as the use thereof has been so far poorly investigated. The treatments were based on combinations of an aqueous solution of di-ammonium phosphate (DAP) and two calcium-based nanomaterials, namely a commercial nanosuspension of Ca(OH)2 and a novel nanosuspension of calcite. The treatments were applied to samples of two porous stones: a limestone and a sandstone. The effectiveness of the treatments was assessed using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, ultrasound pulse velocity test, colour measurements, and capillary water absorption test. The results suggest that the combined use of DAP and Ca-based nanosuspensions can be advantageous over other commonly used consolidants in terms of retreatability and physical-chemical compatibility with the stone. Some limitations are also highlighted, such as the uneven distribution and low penetration of the consolidants

Recommendation of RILEM TC 271-ASC: New accelerated test procedure for the assessment of resistance of natural stone and fired-clay brick units against salt crystallization

This recommendation is devoted to testing the resistance of natural stone and fired-clay brick units against salt crystallization. The procedure was developed by the RILEM TC 271-ASC to evaluate the durability of porous building materials against salt crystallization through a laboratory method that allows for accelerated testing without compromising the reliability of the results. The new procedure is designed to replicate salt damage caused by crystallization near the surface of materials as a result of capillary transport and evaporation. A new approach is proposed that considers the presence of two stages in the salt crystallization test. In the first, the accumulation stage, salts gradually accumulate on or near the surface of the material due to evaporation. In the second, the propagation stage, damage initiates and develops due to changes in moisture content and relative humidity that trigger salt dissolution and crystallization cycles. To achieve this, two types of salt were tested, namely sodium chloride and sodium sulphate, with each salt tested separately. A methodology for assessing the salt-induced damage is proposed, which includes visual and photographical observations and measurement of material loss. The procedure has been preliminarily validated in round robin tests

Natural cement and stone restoration of Bourges Cathedral (France)

Natural cement, also called "Roman cement", was invented at the end of the 18th Century and played an important role in the development of civil engineering works until the 1860s. More surprisingly, it was also used to restore historic buildings, such as gothic cathedrals. This paper deals with the mineralogy and the durability of natural cement, in the particular case of the Bourges Cathedral in France. This study illustrates the interest of this material particularly adapted in stone repair or substitution. Contrary to traditional mortars, the present samples are made of neat cement paste, revealed by the absence of mineral additions as quartz or carbonate sand. Several combined techniques (SEM-EDS, TGA, XRD) were carried out to determine the composition of the hydraulic binder rich in calcium aluminate hydrates. The raw marl at the origin of the cement production contains oxidized pyrites which consist in a potential source of sulphate pollution of the surrounding limestone. The exposition of the cement in urban environment leads to some weathering features as atmospheric sulphation. Finally a petrophysical approach, based on water porosity, capillary sorption and compressive strength, has been performed to demonstrate the durability and the compatibility of roman cement applied as a restoration mortar of historical building

Morphologie et cristallogenèse de microcristaux supergènes de calcite en aiguilles

The morphological study by scanning electron microscopy (S.E.M.) and crystallographical characterization by transmission electron microscopy (T.E.M.) of needle-shaped calcite microcrystals allowed to put in evidence a jagged needle habit that could correspond to a rapid and differentiated crystal growth, followed by dissolution phenomena.L'étude morphologique au microscope électronique à balayage (M.E.B.), et la caractérisation cristallographique au microscope électronique en transmission (M.E.T.) de microcristaux de calcite en aiguilles ont permis de mettre en évidence un faciès dentelé d'aiguilles qui pourrait correspondre à une croissance cristalline rapide et différenciée, suivie de phénomènes de dissolution.Verges-Belmin Véronique, Madon Michel, Bruand Ary, Bocquier Gérard. Morphologie et cristallogenèse de microcristaux supergènes de calcite en aiguilles. In: Bulletin de Minéralogie, volume 105, 4, 1982. pp. 351-356

Phosphate treatments for stone conservation: 3-year field study in the Royal Palace of Versailles (France)

Phosphate treatments for conservation of stone have provided so far encouraging results in laboratory studies, as they exhibit good effectiveness, compatibility and durability to accelerated weathering tests. However, limited data are available about their long-term performance in real environment. Here, a systematic evaluation of phosphate consolidants after prolonged exposure in the field is reported for the first time. Naturally weathered marble specimens and a XVII century marble sculpture located in the Park of the Royal Palace in Versailles were treated by various formulations of the phosphate consolidant. Their conservation state was assessed before treatment by non-destructive methods (ultrasounds, color measurement, water absorption) and, in the case of the specimens, also by slightly destructive tests (SEM, FT-IR, MIP, IC). The conservation state of the specimens and the sculpture was further assessed right after treatment and then periodically monitored during exposure in the Versailles Park. Characterization after field exposure demonstrated that some formulations of the phosphate treatment are able to slow down marble deterioration, although it was not completely inhibited. Limited alterations in water absorption and aesthetic appearance confirmed the general compatibility of the phosphate treatment