Effectiveness of oxalic acid treatments for the protection of marble surfaces

Burgos-Cara, Alejandro; Ruíz-Agudo, Encarnación; Rodríguez-Navarro, Carlos

doi:10.1016/j.matdes.2016.11.037

Cited by 44 publications

(28 citation statements)

References 36 publications

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“…Chemical action of the oxalate anion has already been studied and used to provide a surface protection for marble [41,42]; electron microscope observations showed a structural correspondence between the calcium oxalate and the calcite crystals of the marble [43]. The chemical reaction is thought to be based on the transformation of calcium carbonate from the marble into calcium oxalate [44].…”

Section: Cement Paste Manufacturingmentioning

confidence: 99%

Cementitious materials in biogas systems: Biodeterioration mechanisms and kinetics in CEM I and CAC based materials

Voegel

Giroudon

Bertron

et al. 2019

Cement and Concrete Research

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In anaerobic digestion plants, biological activities transform biowaste into a renewable energy: the biogas. This process produces aggressive and complex media in direct contact with the structure. Few studies have focused on the deterioration of concrete in such environments. In order to support the sustainable development of biogas production growing sector, this study intends to provide thorough information on the biowaste chemical composition and on materials biodeterioration mechanisms occurring in biogas plants. Cementitious materials with various surface compositions (pastes of CEM I, CAC and CEM I treated with oxalic acid) were immersed in the liquid phase of laboratory bioreactors reproducing anaerobic digestion conditions. Altered depths measurements in time highlighted the better resistance of the CAC material. The microbial biofilm coverage on the material's surface was delayed by the surface pretreatment with oxalic acid and was less dense for the CAC paste. Chemical and mineralogical analyses mainly showed leaching and carbonation phenomena.

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Section: Cement Paste Manufacturingmentioning

confidence: 99%

Cementitious materials in biogas systems: Biodeterioration mechanisms and kinetics in CEM I and CAC based materials

Voegel

Giroudon

Bertron

et al. 2019

Cement and Concrete Research

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“…Even if the so-formed layer of whewellite generally exhibits a good ability to completely cover marble surfaces, still the solubility of whewellite is only slightly lower than that of calcite ( Table 1), so that only limited protecting efficacy is achieved [16]. To improve the performance of the oxalate treatment, several innovative approaches are being explored [17,18].…”

Section: Introductionmentioning

confidence: 99%

Calcium phosphate coatings for marble conservation: Influence of ethanol and isopropanol addition to the precipitation medium on the coating microstructure and performance

et al. 2018

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The effect of adding ethanol and isopropanol to aqueous solutions of diammonium hydrogen phosphate, used to create a passivating layer of calcium phosphates over marble, was investigated. Thanks to its weakening effect on the hydration sphere of ions in solution, ethanol allowed complete coverage of marble surface by a crackfree and pore-free layer of octacalcium phosphate. Even better results were obtained using isopropanol, because it has lower adsorption affinity to calcite than ethanol. Treatments involving alcohols provided good acid protection and also restored cohesion among calcite grains in weathered marble.

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“…Both compounds feature an improved solubility in water and alcoholic-water mixtures with respect to AmOx [10]. Furthermore, a treatment with oxalic acid has been investigated for the formation of protective CaOx rims on marble surface [11]. The created CaOx rims on the surface of marble showed a higher acid resistance [11], but an acidic treatment of carbonate-based stones remains questionable from a conservator point of view.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, a treatment with oxalic acid has been investigated for the formation of protective CaOx rims on marble surface [11]. The created CaOx rims on the surface of marble showed a higher acid resistance [11], but an acidic treatment of carbonate-based stones remains questionable from a conservator point of view. From 2011, an alternative approach to calcium oxalate has been explored in the form of hydroxyapatite (HAP) and calcium phosphates (CaP) [12].…”

Section: Introductionmentioning

confidence: 99%

Protection of Stone Monuments Using a Brushing Treatment with Ammonium Oxalate

Mudronja¹,

Vanmeert

Fazinić

et al. 2021

Coatings

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Stone monuments and buildings are susceptible to weathering. Carbonate-based stones are especially vulnerable in acidic environments, whereas magmatic acidic stones are more susceptible to chemical weathering in basic environments. To slow down surface corrosion of limestone and marble artworks/buildings, protective coatings which inhibit calcite dissolution have been proposed. In this work, samples from two stone types with different porosity were treated with ammonium oxalate (AmOx) to create a protective layer of calcium oxalate (CaOx) using the previously developed brushing method. Two different synchrotron microscopy experiments were performed to determine its protective capability. X-ray powder diffraction (SR-μ-XRPD) in transmission geometry allowed visualization of the distributions of calcium carbonate and oxalates along the sample depths. In a second step, X-ray fluorescence (SR-μ-XRF) was used to check the efficiency/integrity of the protective surface coating layer. This was done by measuring the sulfur distribution on the stone surface after exposing the protected stones to sulfuric acid. XRPD showed the formation of a protective oxalate layer with a thickness of 5–15 µm on the less porous stone, while a 20–30 µm thick layer formed on the more porous stone. The XRF study showed that the optimal treatment time depends on the stone porosity. Increasing the treatment time from 1 to 3 h resulted in a decreased efficiency of the protective layer for the low porosity stone. We assume that this is due to the formation of vertical channels (cracks) in the protective layer.

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Effectiveness of oxalic acid treatments for the protection of marble surfaces

Cited by 44 publications

References 36 publications

Cementitious materials in biogas systems: Biodeterioration mechanisms and kinetics in CEM I and CAC based materials

Cementitious materials in biogas systems: Biodeterioration mechanisms and kinetics in CEM I and CAC based materials

Calcium phosphate coatings for marble conservation: Influence of ethanol and isopropanol addition to the precipitation medium on the coating microstructure and performance

Protection of Stone Monuments Using a Brushing Treatment with Ammonium Oxalate

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