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WO2008009771A1 - Procédé et produit destinés à la protection et à la consolidation de matériaux de construction et d'ornementation - Google Patents

Procédé et produit destinés à la protection et à la consolidation de matériaux de construction et d'ornementation Download PDF

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Publication number
WO2008009771A1
WO2008009771A1 PCT/ES2007/000448 ES2007000448W WO2008009771A1 WO 2008009771 A1 WO2008009771 A1 WO 2008009771A1 ES 2007000448 W ES2007000448 W ES 2007000448W WO 2008009771 A1 WO2008009771 A1 WO 2008009771A1
Authority
WO
WIPO (PCT)
Prior art keywords
consolidation
protection
distilled water
ornamental materials
application
Prior art date
Application number
PCT/ES2007/000448
Other languages
English (en)
Spanish (es)
Inventor
Maria Teresa GONZALEZ MUÑOZ
Carlos Rodriguez Navarro
Concepcion Jimenez Lopez
Manuel Rodriguez Gallego
Original Assignee
Universidad De Granada
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universidad De Granada filed Critical Universidad De Granada
Publication of WO2008009771A1 publication Critical patent/WO2008009771A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide

Definitions

  • the object of the present invention is a product and its method of application to achieve the activation of the microbiota that inhabits construction and ornamental materials so as to induce the formation of a calcium carbonate cement with applications to the protection and consolidation in situ of surfaces of calcareous building and ornamental materials in general, and of natural stone in particular, both of historical buildings, sculptures, of natural stone and mortars / cements used in modern buildings and constructions.
  • organic resins of very different type and composition have been used (eg, epoxy and acrylic), and various organic polymers (Lazzarini and Tabasso (1980) Il restauro della pietra. Cedam Papua. Italy.
  • the regenerated layer is only a few micrometers. In addition, these bacteria are not completely harmless.
  • the culture media used contain NaCl, Na 2 CO 3 -H 2 O, nitrates (calcium nitrate as a source of Ca) and sulfates (ammonium sulfate), compounds that could be potentially dangerous as a source of salts (problems of salt crystallization alteration) (Price, CA. (1996) Op. cit). They also include sugars and / or polysaccharides (glucose), which could enhance the growth of acidogenic microbiota (eg, fungi) in the treated materials.
  • it is necessary to prepare a bacterial culture before the application of the treatment which can be complicated and laborious, requiring appropriate specialists and laboratories (microbiologists).
  • a variant of this method is proposed in the UK2208867 patent and contemplates the surface treatment of a building material with nutritive solutions that promote the growth of algae, lichens and bacteria to obtain a surface that acquires a biological patina in a short time.
  • the objective of the present invention consists of a product and method that activates the microbiota that naturally inhabits the construction materials, so that the formation of a calcium carbonate cement is induced, with applications to the protection and consolidation in situ of these materials.
  • the activation is achieved, among the microorganisms that inhabit the material, of those that meet a series of favorable characteristics for the carbonatogenesis process.
  • the new calcium carbonate cement formed is compatible with the material, respects its porosity and improves its degree of consolidation.
  • the procedure described in this invention can be used both in the restoration of deteriorated stone material and in the protection of new material that replaces damaged parts, and in materials for new construction. Its use is intended for construction materials, mainly minerals. The results are particularly notable in the case of calcareous materials.
  • This invention has a number of advantages over products / methods used and marketed today. Among others, it should be noted:
  • the invention consists of a product capable of activating the carbonatrogenic microbiota that lives in building materials, so that the precipitation of calcium carbonate is induced, compatible with the original material and that increases the degree of consolidation of the treated material.
  • the product is prepared by mixing the different components and adding water. It is left to decant and is applied to the surface of the material to be treated by means of a suitable system (drip irrigation, brush, spray, imbibition in cellulose pulp and / or Japanese letter dressing and surface application, among others).
  • the product object of the invention is a solution comprising a source of amino acids as the sole source of carbon and nitrogen, calcium acetate as a source of calcium and carbon, carbonates and / or phosphate buffer as the only other salts and its pH must be between 7.5 and 8.5.
  • the preferred source of calcium is calcium acetate since this avoids the permanence of any anionic moiety that could generate unwanted salts.
  • calcium bicarbonate could be used. However, its low solubility does not make it ideal.
  • the proposed product contains between 0.1 and 5% protein hydrolyzate, between 0.1 and 5% Ca (CH2COO) 2, between 0.1, 0.5% carbonate, may contain 5 to 15 mM phosphate buffer, distilled water and has a pH between 7.5 and 8.5.
  • hydrolyzate Protein between 1 and 50 g of Ca (CH2COO) 2 , between 1 and 50 g of carbonate, can contain between 0.7 and 3 g of phosphate salt, leaving its pH in a range between 7.5 and 8.5.
  • microorganisms that inhabit the stones and calcareous materials to be treated are frequently fungi, algae, lichen, photosynthetic bacteria, actinomycetes, chemilithotrophic bacteria and chemoganotrophs.
  • fungi fungi
  • algae lichen
  • photosynthetic bacteria actinomycetes
  • chemilithotrophic bacteria chemoganotrophs.
  • chemoganotrophic bacteria although some algae and photobacteria, should be highlighted. The development of phototrophic microorganisms is not desirable because they could produce pigmentation of the stone in question.
  • the Acetate forms the acetic / acetate pair that acts by buffering the solution and preventing pH drops that could stop the calcium carbonate precipitation process and even dissolve the previously formed carbonate or that of the treated material itself. It is important that the proposed product does not contain other salts except carbonates and / or phosphate buffer (such as chlorides, sulfates, nitrates ...) that generate a decrease in pH and act in the opposite direction to the proper functioning of the acetic / acetate buffer.
  • carbonates and / or phosphate buffer such as chlorides, sulfates, nitrates
  • the application of the aforementioned solution will activate the microbiota that naturally inhabits the material, particularly the bacteria that are chemoganotrophs capable of using the amino acids as a source of carbon and nitrogen. These bacteria capable of creating, as a result of their metabolism, favorable conditions for the precipitation of calcium carbonate.
  • This method of activating the natural microbiota of the materials has the fundamental advantage of not introducing any microorganism external to the environment of the material to be treated, thus avoiding the short and long term disadvantages that this could generate.
  • the present invention is a method for the protection and consolidation of building and ornamental materials comprising the following steps:
  • the material is protected from light sources between 24 and 48 h.
  • the source of amino acids can be a casein hydrolyzate, an enzymatic casein hydrolyzate, a protein hydrolyzate (in particular, of vegetable origin), the calcium source is calcium acetate.
  • One form of application of the method comprises the following steps:
  • the starting mixture consist of 1% hydrolyzed casein, 1% Ca (CH2COO) 2 4H2O, and 0.2% K2CO3 1 / 2H2O.
  • Another way of applying the method would be similar, but using a mixture containing between 0.1 and 5% hydrolyzed casein, between 0.1% and 5% Ca (CH2COO) 2 between 0.1% and 0.5% of K2CO3 1 / 2H2O, between 0.01 and 0.2% of phosphate buffer.
  • the product itself for the protection and consolidation of building and ornamental materials soluble in distilled water, which comprises between 0.1 and 5% of casein hydrolyzate, between 0.1 and 5% of Ca (CH2COO) 2, between 0.1 and 0.5% of K2CO3 1 / 2H2O and have a pH between 7.5 and 8.5, preferably 8.
  • Another similar and preferable version of the product object of the invention for the protection and consolidation of construction and ornamental materials, soluble in distilled water comprises between 0.1 and 5% hydrolyzed casein, between 0.1% and 5% Ca (CH2COO) 2 between 0.1% and 0.5% of K2CO3 1 / 2H2O, between 0.01 and 0.2% phosphate buffer in distilled water and has a pH between 7.5 and 8.5, preferably 8.
  • composition comprises 1% hydrolyzed casein, 1% Ca (CH2COO) 2 4H2O, 0.2% K2CO3 1 / 2H2O, 0.14% phosphate buffer in distilled water and has a pH between 7.5 and 8.5, preferably 8.
  • the product for the protection and consolidation of construction and ornamental materials has the following composition, for each liter of distilled water:
  • the product could be manufactured with the following composition, for each liter of distilled water:
  • composition of solution 1 (w / v): 1% hydrolyzed casein, 1%
  • Solution 1 and altered calcarenite from a pinnacle of the damaged Granada cathedral and recently replaced in a restoration procedure was used.
  • the experimental procedure is the same as that of embodiment 1.
  • Stone sheets are altered calcarenite are introduced vertically in a Petri dish containing 20 mL of solution 1. The system is covered to maintain dark conditions. The stone is irrigated once a day for a period of 7 days with 5 mL of solution 1. During the consolidation treatment the temperature ranges between 18 and 30 0 C.
  • composition of solution 2 (w / v): 1% hydrolyzed casein, 1% Ca (CH 2 COO) 2 4H 2 O, 0.2% K 2 CO 3 1 / 2H 2 O, 10 mM phosphate buffer in distilled water, pH 8.
  • composition of solution 2 for each liter of distilled water would be: 1 g g casein hydrolyzate, 10 g Ca (CH 2 COO) 2 4H 2 O, 2 g K 2 CO 3 1 / 2H 2 O, 1.4 g of KH 2 PO 4 , and has a pH 8.
  • the results of these tests show that the solutions used were able to activate part of the microbiota present in the stone.
  • the activation of these bacteria produced an alkalinization of the medium that It resulted in a massive precipitation of calcium carbonate, as seen in Figures 1a and 1b.
  • the new cement formed consists of calcium carbonate, in its calcite and / or vaterite varieties, depending on the solution used. This cement is perfectly compatible with the original stone and respects the porous system of the stone (Table 1).
  • the calcarenite stone treated in this way is in all cases more compacted than the original stone, since it has a greater resistance to mechanical stress, as evidenced by a lower weight loss compared to an ultrasound treatment than the original stone (Table 1 ).
  • the new cement created is rooted in the original stone to a depth that varies between 1 and 5 mm depending on the solution and stone used.
  • Figure 1 Evolution of the pH and concentration of calcium, Ca ⁇ ( a q) > in the solution in which the treated stone is immersed, a) Solution 1 and b) Solution 2. pH increases are caused by the alkalization resulting from the metabolism of the microbiota that inhabits the stone, activated by the application of the solution. Decreases in calcium concentration indicate precipitation of calcium carbonate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Biotechnology (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne un procédé et un produit destinés à la protection et à la consolidation de matériaux de construction et d'ornementation, permettant d'activer le microbiote naturel présent dans les matériaux de construction de façon à induire la formation de carbonate de calcium. La présente invention permet d'activer sélectivement les micro-organismes à capacité carbonatogène qui génèrent un nouveau ciment de carbonate de calcium compatible avec le matériau de départ, ne modifiant pas sa porosité et améliorant son degré de consolidation.
PCT/ES2007/000448 2006-07-19 2007-07-19 Procédé et produit destinés à la protection et à la consolidation de matériaux de construction et d'ornementation WO2008009771A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200602030A ES2289950B1 (es) 2006-07-19 2006-07-19 Metodo y producto para la proteccion y consolidacion de materiales de construccion y ornamentales.
ESP200602030 2006-07-19

Publications (1)

Publication Number Publication Date
WO2008009771A1 true WO2008009771A1 (fr) 2008-01-24

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PCT/ES2007/000448 WO2008009771A1 (fr) 2006-07-19 2007-07-19 Procédé et produit destinés à la protection et à la consolidation de matériaux de construction et d'ornementation

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Country Link
ES (1) ES2289950B1 (fr)
WO (1) WO2008009771A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013120847A1 (fr) 2012-02-13 2013-08-22 Universiteit Gent Biodéposition à haute performance permettant le renforcement de matériaux
US11472738B2 (en) 2010-04-27 2022-10-18 Biomason Inc. Methods for the manufacture of colorfast masonry
US11518687B2 (en) 2017-10-05 2022-12-06 Biomason Inc. Biocementation method and system
US11795108B2 (en) 2016-10-31 2023-10-24 Biomason Inc. Microorganism loaded aggregate and manufacturing methods
US12195392B2 (en) 2015-03-10 2025-01-14 Biomason Inc. Compositions and methods for dust control

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2064673T3 (es) * 1989-03-17 1995-02-01 Univ Paris Curie Procedimiento de tratamiento biologico de una superficie artificial.
FR2734261A1 (fr) * 1995-05-17 1996-11-22 Calcite Nouvelles compositions pour mortier biologique, procede de recouvrement d'une surface ou de comblement d'une cavite a l'aide des compositions
WO2002094737A1 (fr) * 2001-05-12 2002-11-28 Geogenomics, Ltd A Uk And Wales Corporation Procede de traitement de surfaces dures pour creer un aspect d'alteration par l'action d'agents atmospheriques
FR2836502A1 (fr) * 2002-02-25 2003-08-29 Freyssinet Int Stup Procede de renforcement d'une structure par un materiau composite et renfort obtenu par ce procede

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2064673T3 (es) * 1989-03-17 1995-02-01 Univ Paris Curie Procedimiento de tratamiento biologico de una superficie artificial.
FR2734261A1 (fr) * 1995-05-17 1996-11-22 Calcite Nouvelles compositions pour mortier biologique, procede de recouvrement d'une surface ou de comblement d'une cavite a l'aide des compositions
WO2002094737A1 (fr) * 2001-05-12 2002-11-28 Geogenomics, Ltd A Uk And Wales Corporation Procede de traitement de surfaces dures pour creer un aspect d'alteration par l'action d'agents atmospheriques
FR2836502A1 (fr) * 2002-02-25 2003-08-29 Freyssinet Int Stup Procede de renforcement d'une structure par un materiau composite et renfort obtenu par ce procede

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CARLOS RODRIGUEZ NAVARRO ET AL.: "Conservation of Ornamental Stone by Myxococcus Xanthus-Induced Carbonate Biomineralization", APPLIED AND ENVIRONMENTAL MICROBIOLOGY, vol. 69, April 2003 (2003-04-01), pages 2182 - 2193, XP002448928, DOI: doi:10.1128/AEM.69.4.2182-2193.2003 *
GONZALEZ MUNOZ T. ET AL.: "Conservacion of rocas oranmentales by biomineralizacion bacteriana", ROC MAQUINA: PIEDRAS NATURALES, MAQUINARIA AND EQUIPOS, vol. 83, September 2003 (2003-09-01), pages 14 - 17 *
LE METAYER-LEVREL G. ET AL.: "Applications of bacterial carbonatogenesis to the protection and regeneration of limestones in buildings and historic patrimony", SEDIMENTARY GEOLOGY, vol. 126, March 1999 (1999-03-01), pages 25 - 34, XP002448927, DOI: doi:10.1016/S0037-0738(99)00029-9 *
MONTOYA C. ET AL.: "Caracterizacion of cristales of calcita biopreciptada by un aislamiento nativo of Bacillus subtilis", REV. COLOMB. BIOTECNOL., vol. VII, no. 2, December 2005 (2005-12-01), pages 19 - 25 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11472738B2 (en) 2010-04-27 2022-10-18 Biomason Inc. Methods for the manufacture of colorfast masonry
WO2013120847A1 (fr) 2012-02-13 2013-08-22 Universiteit Gent Biodéposition à haute performance permettant le renforcement de matériaux
US12195392B2 (en) 2015-03-10 2025-01-14 Biomason Inc. Compositions and methods for dust control
US11795108B2 (en) 2016-10-31 2023-10-24 Biomason Inc. Microorganism loaded aggregate and manufacturing methods
US11518687B2 (en) 2017-10-05 2022-12-06 Biomason Inc. Biocementation method and system
US12187620B2 (en) 2017-10-05 2025-01-07 Biomason Inc. Biocementation method and system

Also Published As

Publication number Publication date
ES2289950B1 (es) 2009-02-16
ES2289950A1 (es) 2008-02-01

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