CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

CONSERVATION OF STONE MONUMENTS AND ARTIFACTS: NEW POSSIBILITIES OFFERED BY THE AMMONIUM OXALATE BASED TREATMENT
Mauro Matteini Mauro Matteini
CNR - Istituto per la Conservazione e la Valorizzazione dei Beni Culturali ICVBC CNR - Istituto per la Conservazione e la Valorizzazione dei Beni Culturali ICVBC Florence, Rome, Milan Florence, Rome, Milan

International Meeting on Science and Technology for Cultural Heritage La Havana, Cuba, February 7th-10th 2007

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

Introduction

About 15 years ago the first experiments were carried out in the Scientific About 15 years ago the first experiments were carried out in the Scientific Laboratory of the Opificio delle Pietre Dure in Florence in order to test the Laboratory of the Opificio delle Pietre Dure in Florence in order to test the possibility of a new approach to the problem of protecting marble and possibility of a new approach to the problem of protecting marble and limestone monuments and artifacts exposed outside from acid attack. limestone monuments and artifacts exposed outside from acid attack. In place of giving hydrophobic properties to their surfaces, as usually done, by In place of giving hydrophobic properties to their surfaces, as usually done, by applying hydro-repellent barrier-coatings, it could be tried a different way: applying hydro-repellent barrier-coatings, it could be tried a different way: making their surfaces acid-resistant through a passivating treatment. making their surfaces acid-resistant through a passivating treatment. The new approach could result particularly advantageous in case of porous The new approach could result particularly advantageous in case of porous calcareous materials located outdoors in polluted urban centers. calcareous materials located outdoors in polluted urban centers. This category of artifacts are highly exposed to acid rains and fogs as well as This category of artifacts are highly exposed to acid rains and fogs as well as affected by salts migration followed by cyclic crystallization in their porous affected by salts migration followed by cyclic crystallization in their porous structure with formation of very devastating sub-florescences, favored by the structure with formation of very devastating sub-florescences, favored by the hydrophobic external protections. hydrophobic external protections.

Introduction Introduction

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

A suitable passivating agent could be calcium oxalate as A suitable passivating agent could be calcium oxalate as demonstrated by the highly durable naturally formed calcium demonstrated by the highly durable naturally formed calcium oxalate patinas on the majority of monuments, particularly oxalate patinas on the majority of monuments, particularly when exposed outside. when exposed outside.

natural patinas are usually colored natural patinas are usually colored due to colored inclusions entrapped due to colored inclusions entrapped in their bulk during their formation in their bulk during their formation while pure calcium oxalate (both while pure calcium oxalate (both Whevellite and Weddellite) is a Whevellite and Weddellite) is a colorless or whitish substance. colorless or whitish substance.

Introduction Introduction

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

Solubility properties of calcium oxalate are shown in the graph below, in Solubility properties of calcium oxalate are shown in the graph below, in comparison with calcium carbonate. comparison with calcium carbonate.
0 -1 -2 -3

Log molar solubility calcium carbonate calcium oxalate

-4 -5

10

12

14

CaC2O4 has a very low water solubility, also in strongly acid CaC2O4 has a very low water solubility, also in strongly acid environment, differently from calcium carbonate. environment, differently from calcium carbonate.

Introduction Introduction

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

A suitable treatment to passivate calcium carbonate based surfaces A suitable treatment to passivate calcium carbonate based surfaces (limestones, marble, plasters, decorated plasters, etc.) with a moderate and (limestones, marble, plasters, decorated plasters, etc.) with a moderate and controlled formation of calcium oxalate was found in the following reaction controlled formation of calcium oxalate was found in the following reaction with ammonium oxalate (AmOx). with ammonium oxalate (AmOx).

CaCO3 + calcium carbonate insoluble

(NH4)2C2O4 ammonium oxalate soluble

CaC2O4 calcium oxalate very insoluble

2NH3 + H2O + CO2 ammonia water carbon dioxide gas volatile gas

A poultice treatment of 5% water solution of AmOx for not less than 5 hours A poultice treatment of 5% water solution of AmOx for not less than 5 hours is usually necessary. is usually necessary.

Introduction Introduction

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

The following photo shows a well known test for demonstrating The following photo shows a well known test for demonstrating passivation. Small Travertine cubes, both not treated (upper line) and passivation. Small Travertine cubes, both not treated (upper line) and treated (lower line) with the AmOx method are immersed in solutions at treated (lower line) with the AmOx method are immersed in solutions at different pH, changing from 5 to 1. different pH, changing from 5 to 1.

The not treated samples stain red from pH 4 with Ponceau Red, a sensitive complexing agent The not treated samples stain red from pH 4 with Ponceau Red, a sensitive complexing agent for free Ca ions, while the treated samples remain unstained. for free Ca ions, while the treated samples remain unstained.

Introduction Introduction

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

The sketch below illustrates a possible interpretation of the The sketch below illustrates a possible interpretation of the passivating process. passivating process.

before treatment

lime-stone
CaCO3 + (NH4)C2O4 CaC2O4

after treatment

400 -500 m depth

passivation of limestone by formation of

artificial calcium oxalate

Introduction Introduction

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

Extensive investigation has been carried out at the Scientific Laboratories of Extensive investigation has been carried out at the Scientific Laboratories of the Opificio in Florence and, in the following years, at the Istituto di Scienze the Opificio in Florence and, in the following years, at the Istituto di Scienze e Tecnologie Molecolari (ISTM/CNR) in Perugia and at the ICVBC in e Tecnologie Molecolari (ISTM/CNR) in Perugia and at the ICVBC in Florence and Milan. Florence and Milan.

More recently, the AmOx treatment has been included in the Joint Research Activity 1 of the More recently, the AmOx treatment has been included in the Joint Research Activity 1 of the EUARTECH Project, dedicated to more deeply investigate mechanisms and behavior of the EUARTECH Project, dedicated to more deeply investigate mechanisms and behavior of the inorganic treatments for the consolidation and protection of stone artifacts and monuments.. inorganic treatments for the consolidation and protection of stone artifacts and monuments.. About 10 years ago the first in situ applications started on monuments and artifacts in Florence About 10 years ago the first in situ applications started on monuments and artifacts in Florence and many other parts of Italy. and many other parts of Italy. Among the many objects now treated with this method we want to mention the big marble statue Among the many objects now treated with this method we want to mention the big marble statue Eterno Padre by Baccio Bandinelli and the graffiti faade of Palazzo Barbolani Montauto, both Eterno Padre by Baccio Bandinelli and the graffiti faade of Palazzo Barbolani Montauto, both in Florence. in Florence.
Eterno Padre by Baccio Bandinelli

the Barbolani Montauto graffiti faade

Introduction Introduction

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In deep laboratory investigation was recently carried out at the ICVBC In deep laboratory investigation was recently carried out at the ICVBC in Florence on more than 20 different types of limestones to monitor in Florence on more than 20 different types of limestones to monitor possible changes of color, water absorption, crystalline structure of the possible changes of color, water absorption, crystalline structure of the surface under Optical microscope, SEM, etc. Some example are the surface under Optical microscope, SEM, etc. Some example are the following following

   

&

  ' 

"

under
treated not treated

optical
treated not treated

microscope
treated not treated

SEM
treated treated

images
treated

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

oxalate as a passivating (protecting) agent

(for marble, limestones and lime-based plasters) (for marble, limestones and lime-based plasters)

The above mentioned in situ cases and many others are examples of AmOx The above mentioned in situ cases and many others are examples of AmOx method used as a passivating inorganic treatment for calcium carbonate based method used as a passivating inorganic treatment for calcium carbonate based objects, which is the primary aim for which it was proposed and tested. objects, which is the primary aim for which it was proposed and tested.

Its protection role is crucial in case of external exposure associated with high Its protection role is crucial in case of external exposure associated with high porosity and possible presence of soluble salts, a situation which is very porosity and possible presence of soluble salts, a situation which is very frequent. frequent. A further recent example is given by the Portale of Santa Maria delle Grazie in A further recent example is given by the Portale of Santa Maria delle Grazie in Milan. Milan.

Portale of Santa Maria delle Grazie - Milan

passivation (protection) and consolidation with AmOx
detail of a capital

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

before

after cleaning and passivation

passivation (protection) with AmOx

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

Portale di Santa Maria delle Grazie -- Milan Portale di Santa Maria delle Grazie Milan

detail of the fronton

before

after cleaning and passivation

Portale di Santa Maria delle Grazie -- Milan Portale di Santa Maria delle Grazie Milan

passivation (protection) with AmOx

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

part of the pilaster on the right

before

after cleaning and passivation

Other role of the AmOx based treatment

In the following years, after the first applications, new properties of this treatment were gradually considered and explored. Most of them are still today under study.

These additional roles may be summarized as : - consolidating action: - desulphating action; - ability to enhance the chromatic contrast in stone artifacts and painted facades.

oxalate as a consolidating agent

(for marble, limestones and lime-based plasters) (for marble, limestones and lime-based plasters)

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

The consolidating action of AmOx The consolidating action of AmOx was first observed on highly was first observed on highly disaggregated marble (the so called disaggregated marble (the so called sugar-like marble). sugar-like marble). Experiments were carried out both Experiments were carried out both in the laboratory and as pilot tests, in the laboratory and as pilot tests, in situ, on small areas. in situ, on small areas. At the moment most of the research At the moment most of the research in this direction is in progress and in this direction is in progress and the EUARTECH Research Project the EUARTECH Research Project will give more precise answers. will give more precise answers. A preliminary measurement is A preliminary measurement is shown in the figure on the right shown in the figure on the right where a marble fragment, a where a marble fragment, a tortiglione from the Florence tortiglione from the Florence Cathedral, has been examined with Cathedral, has been examined with the drilling equipment after the the drilling equipment after the AmOx treatment. AmOx treatment.
treated

not treated

oxalate as a consolidating agent oxalate as a consolidating agent

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

A first example was offered 5 years ago by the old marble statues (of A first example was offered 5 years ago by the old marble statues (of roman origin?) exposed outside in the Loggia dei Lanzi in Florence. roman origin?) exposed outside in the Loggia dei Lanzi in Florence. The parts exposed of the female figures (some fingers, a nose, etc.) were The parts exposed of the female figures (some fingers, a nose, etc.) were broken and corroded. In the broken parts the marble had the typical sugar broken and corroded. In the broken parts the marble had the typical sugar like consistency. The application of AmOx gave efficient consolidating like consistency. The application of AmOx gave efficient consolidating effect. Photos are not shown in this presentation. effect. Photos are not shown in this presentation.

A second example is the following: capitals and other sculptured details on the faade of the church A second example is the following: capitals and other sculptured details on the faade of the church of San Pierino in Pisa. of San Pierino in Pisa.
The restoration work was carried out by Sandra Andreoni, a private restorer of the M.I.D.A. company, under the coordination of the Soprintendenza of Cultural Heritage in Pisa.

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

oxalate as a desulphating agent

AmOx reacts with gypsum in a similar way as it reacts with calcium carbonate AmOx reacts with gypsum in a similar way as it reacts with calcium carbonate (NH4)2C2O4 + CaSO4 CaC2O4 + (NH4)2SO4 (NH4)2C2O4 + CaSO4 CaC2O4 + (NH4)2SO4 Gypsum is partially or totally insolubilized by the treatment similarly but more Gypsum is partially or totally insolubilized by the treatment similarly but more efficiently than the well known and widely used desulphating action of ammonium efficiently than the well known and widely used desulphating action of ammonium carbonate carbonate (NH4)2CO3 + CaSO4 CaCO3 + (NH4)2SO4 (NH4)2CO3 + CaSO4 CaCO3 + (NH4)2SO4 The reaction with AmOx is favored - compared to that with AmCarb - by the higher The reaction with AmOx is favored - compared to that with AmCarb - by the higher lowering of water-solubility from gypsum into oxalate instead of carbonate lowering of water-solubility from gypsum into oxalate instead of carbonate
LOG solubilit moli/litro da g/litro 0 -0,5 -1 -1,5 -2 -2,5 -3 -3,5 -4 -4,5 -5 CaSO4.2H2O CaCO3 CaC2O4.2H2O

oxalate as a desulphating agent oxalate as a desulphating agent

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

AmOx is also an efficient de-calcifying agent because of its ability to insolubilize AmOx is also an efficient de-calcifying agent because of its ability to insolubilize any soluble calcium salt. any soluble calcium salt. This may turn out advantageous in the case of soluble nitrates - mainly calcium This may turn out advantageous in the case of soluble nitrates - mainly calcium nitrate which are converted into ammonium nitrate, a salt with a lower tendency to nitrate which are converted into ammonium nitrate, a salt with a lower tendency to crystallize due to its very high water solubility, as shown in the graph. crystallize due to its very high water solubility, as shown in the graph.
LOG solubilit moli/litro 1,6 1,4 1,2 1 0,8 0,6 0,4 0,2 0 Ca(NO3)2.4H2O NH4NO3

oxalate as a desulphating agent oxalate as a desulphating agent

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

An interesting example is that of the sandstone faade of the Pieve of Santa Maria in An interesting example is that of the sandstone faade of the Pieve of Santa Maria in Arezzo. FT-IR analyses (carried out by Mara Camaiti of the ICVBC) showed a Arezzo. FT-IR analyses (carried out by Mara Camaiti of the ICVBC) showed a notable decrease of the gypsum amount on the stone surface after treatment with a notable decrease of the gypsum amount on the stone surface after treatment with a correspondent increase of calcium oxalate. correspondent increase of calcium oxalate. Similar results were observed also in the case of San Domenico Church in Arezzo. Similar results were observed also in the case of San Domenico Church in Arezzo.

The restoration work was carried out by Sandra Andreoni, a private restore of the M.I.D.A. company, under the surveillance of the Soprintendenza of Cultural Heritage of Arezzo.

the Pieve of Santa Maria in Arezzo

the church of San Domenico in Arezzo

ICVBC/CNR

oxalate to enhance the chromatic contrast

(on limestones, lime based plasters and calcium carbonate mosaic tesserae) (on limestones, lime based plasters and calcium carbonate mosaic tesserae)
The effect of AmOx to improve the chromatic contrast of limestones and plasters was first The effect of AmOx to improve the chromatic contrast of limestones and plasters was first observed in a decorated faade in the courtyard of a XVII cent. palace in North Italy (Besta observed in a decorated faade in the courtyard of a XVII cent. palace in North Italy (Besta Palace -- Teglio near Sondrio North Italy). Palace Teglio near Sondrio North Italy). The almost monochrome paintings, after cleaning, appeared covered by whitish films, partially The almost monochrome paintings, after cleaning, appeared covered by whitish films, partially caused by residues of old polymeric fixatives, and also non-homogeneous natural oxalate caused by residues of old polymeric fixatives, and also non-homogeneous natural oxalate patinas causing scattering of light. patinas causing scattering of light. AmOx was applied with the aim to protect (passivate) the painted faade from the washing AmOx was applied with the aim to protect (passivate) the painted faade from the washing effects of rain. effects of rain.

first intervention (2003)

second intervention (2005)

Besta Palace Teglio (Sondrio) XVII cent.

ICVBC/CNR
oxalate to enhance the chromatic contrast oxalate to enhance the chromatic contrast

on painted plasters on painted plasters

Unexpectedly, the treatment showed to notably enhance the chromatic contrast of the faded Unexpectedly, the treatment showed to notably enhance the chromatic contrast of the faded paintings. paintings. Such optical effect is still under investigation (by Fabio Fratini and Silvia Rescic at the ICVBC). Such optical effect is still under investigation (by Fabio Fratini and Silvia Rescic at the ICVBC). Apparently, a reduction of surface light scattering is caused in rough surfaces. Apparently, a reduction of surface light scattering is caused in rough surfaces. In the following images the effect of AmOx was compared with that of the Barium Hydroxide In the following images the effect of AmOx was compared with that of the Barium Hydroxide method. method.

The restoration work was carried out by a private company (Studio Barbara Ferriani of Milan) under the coordination of the Lombardia Regional Direction of Cultural Heritage.

preliminary tests with preliminary tests with barium hydroxide barium hydroxide and and ammonium oxalate ammonium oxalate

Besta Palace Teglio (Sondrio) XVII cent.

oxalate to enhance the chromatic contrast oxalate to enhance the chromatic contrast

on painted plasters on painted plasters

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

Besta Palace Teglio (Sondrio) XVII cent.

before AmOx applied after cleaning

after

oxalate to enhance the chromatic contrast oxalate to enhance the chromatic contrast

on painted plasters on painted plasters

CNR ISTITUTO PER LA CONSERVAZIONE E LA VALORIZZAZIONE DEI BENI CULTURALI Firenze

Besta Palace Teglio (Sondrio) XVII cent.

before

AmOx applied after cleaning

after

ICVBC/CNR
oxalate to enhance the chromatic contrast oxalate to enhance the chromatic contrast

on limestones faades on limestones faades

4 -- The restoration work was carried out by 4 The restoration work was carried out by
Sandra Andreoni, a private restorer of the Sandra Andreoni, a private restorer of the M.I.D.A. company, under the coordination of the M.I.D.A. company, under the coordination of the Soprintendenza of Cultural Heritage in Pisa.. Soprintendenza of Cultural Heritage in Pisa

1 -- Another very 1 Another very interesting case is that of interesting case is that of the two-colours the two-colours limestone faade of limestone faade of San Pierino in Pisa San Pierino in Pisa (white marble alternated (white marble alternated to gray cherty limestone). to gray cherty limestone). 2 -- The latter is affected by 2 The latter is affected by natural fading (a washing out natural fading (a washing out effect ?) which causes loss of effect ?) which causes loss of saturation in the gray stone. saturation in the gray stone.

3 -- After the AmOx treatment a 3 After the AmOx treatment a notable increase of the optical notable increase of the optical saturation was observed. saturation was observed. Unfortunately, only preliminary tests Unfortunately, only preliminary tests could be carried out because of could be carried out because of insufficient financing for extending insufficient financing for extending the treatment to the whole faade. the treatment to the whole faade.

not treated

details of the faade of the church of San Pierino in Pisa

treated

ICVBC/CNR
oxalate to enhance the chromatic contrast oxalate to enhance the chromatic contrast

on limestones mosaic tesserae on limestones mosaic tesserae

Quite innovative is the application of an inorganic treatment for the conservation of floor Quite innovative is the application of an inorganic treatment for the conservation of floor mosaics in archaeological sites. mosaics in archaeological sites. The famous roman mosaics in the Villa del Casale in Piazza Armerina (Sicily) are in a very The famous roman mosaics in the Villa del Casale in Piazza Armerina (Sicily) are in a very bad state of preservation both under the physical and the aesthetical point of view. bad state of preservation both under the physical and the aesthetical point of view. Salts crystallization, Salts crystallization, powders deposits fixed by powders deposits fixed by wax-based coatings, wax-based coatings, cement consolidation cement consolidation causing calcium carbonate causing calcium carbonate whitish patinas, whitish patinas, mechanical abrasion to mechanical abrasion to flatten the tesserae, flatten the tesserae, moister and water fluxes moister and water fluxes everywhere, are some of everywhere, are some of the causes which affect the the causes which affect the present state of the present state of the wonderful mosaics. wonderful mosaics.

ICVBC/CNR
oxalate to enhance the chromatic contrast oxalate to enhance the chromatic contrast

on limestones mosaic tesserae on limestones mosaic tesserae

Our Institute is part of the team for the conservation program directed by the Centro Regionale Our Institute is part of the team for the conservation program directed by the Centro Regionale del Restauro di Palermo with the task of optimizing the operations for the intervention on del Restauro di Palermo with the task of optimizing the operations for the intervention on mosaics and painted plasters, i.e. cleaning, desalting, consolidation, protection and, as a mosaics and painted plasters, i.e. cleaning, desalting, consolidation, protection and, as a priority target, improving the chromatic contrast of the mosaics. priority target, improving the chromatic contrast of the mosaics. As far as the last point is concerned, we a As far as the last point is concerned, we a priori excluded the use of any wax or priori excluded the use of any wax or polymeric material because clearly polymeric material because clearly incompatible with a so dynamic physical incompatible with a so dynamic physical system (salts, water, high summer system (salts, water, high summer temperatures, uncontrollable atmospheric temperatures, uncontrollable atmospheric powders, etc.). powders, etc.).

The inorganic approach was first tested in The inorganic approach was first tested in the laboratory on fragments of the the laboratory on fragments of the original mosaics, with the use of barium original mosaics, with the use of barium hydroxide, ethyl silicate, mixed systems hydroxide, ethyl silicate, mixed systems and others, without significant results. and others, without significant results. Finally, as the majority of tesserae are of Finally, as the majority of tesserae are of a carbonatic nature, the AmOx method a carbonatic nature, the AmOx method too was experimented too was experimented

ICVBC/CNR
oxalate to enhance the chromatic contrast oxalate to enhance the chromatic contrast

cleaned with Am Carb +EDTA in Carbogelv

on limestones mosaic tesserae on limestones mosaic tesserae

Results were very promising. After cleaning with AmCarb followed by EDTA in Arbocel and Results were very promising. After cleaning with AmCarb followed by EDTA in Arbocel and then treating with AmOx, the colored tesserae, and particularly the blackish ones, recovered then treating with AmOx, the colored tesserae, and particularly the blackish ones, recovered enough color saturation, without modification of their inorganic properties, such as water enough color saturation, without modification of their inorganic properties, such as water wettability, permeability etc. wettability, permeability etc.
Tests carried out by the restorer Sabino Giovannoni, under the scientific coordination of Mara Camaiti and Fabio Fratini of the ICVBC

treated w treated with ith BaHydr (5 BaHydr (5% 6 % 6 h)) h

ocel then EDTA in arb el Carb then EDTA in arboc Cleaned with AmCarb Cleaned with Am

Cleaned with Cleaned with Am Carb then AmCarb then EDT A in gel EDTA in gel

before cle before clean in g aning

h) (5% 17 h) treated with AmOx (5% 17 treated with AmOx