WO2012160525A1 - Dispersions de nanoparticules dans des matrices polymères - Google Patents

Dispersions de nanoparticules dans des matrices polymères Download PDF

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Publication number
WO2012160525A1
WO2012160525A1 PCT/IB2012/052588 IB2012052588W WO2012160525A1 WO 2012160525 A1 WO2012160525 A1 WO 2012160525A1 IB 2012052588 W IB2012052588 W IB 2012052588W WO 2012160525 A1 WO2012160525 A1 WO 2012160525A1
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WO
WIPO (PCT)
Prior art keywords
comprised
synthetic resin
solution
nanoparticles
titanium dioxide
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/IB2012/052588
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English (en)
Inventor
Roberto Simonutti
Annalisa COLOMBO
Carlotta BECCARIA
Valentina MOMBRINI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FONDAZIONE CASSA DI RISPARMIO DELLE PROVINCE LOMBARDE
Universita degli Studi di Milano Bicocca
Original Assignee
FONDAZIONE CASSA DI RISPARMIO DELLE PROVINCE LOMBARDE
Universita degli Studi di Milano Bicocca
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Application filed by FONDAZIONE CASSA DI RISPARMIO DELLE PROVINCE LOMBARDE, Universita degli Studi di Milano Bicocca filed Critical FONDAZIONE CASSA DI RISPARMIO DELLE PROVINCE LOMBARDE
Publication of WO2012160525A1 publication Critical patent/WO2012160525A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium

Definitions

  • the present invention regards nanoparticle dispersions in polymer matrices, which can be used in consolidation and protection materials, in particular for the preservation and restoration of cultural heritage material .
  • the synthetic resins tend to degrade and turn yellowish over time, they are often added with light stabilizing compounds, such as UV absorbers (benzotriazole) and the hindered amines (HALS) which, besides having a limited duration, tend to migrate to the surface.
  • light stabilizing compounds such as UV absorbers (benzotriazole) and the hindered amines (HALS) which, besides having a limited duration, tend to migrate to the surface.
  • An object of the present invention is thus that of providing a transparent consolidation-protection material for the treatment of a coloured surface, in particular of a cultural heritage material, which does not alter the aesthetic aspect of the artwork and which in particular preserves the formal qualities thereof.
  • a further object of the invention is to provide a transparent consolidation-protection material for the treatment of a coloured surface, in particular of cultural heritage materials, which confers a consolidation of the paint layers and/or a protection prolonged over time from the external agents and from the UV radiation.
  • Still another object of the invention is a method for selecting and preparing the transparent consolidation-protection material which suits the characteristics of the surface to be treated.
  • the invention regards a synthetic resin solution containing a nanoparticle dispersion of a high refractive index inorganic oxide, preferably titanium dioxide.
  • a "polymer composite” is obtained each time an inorganic particle material is introduced into a polymer matrix. This allows obtaining a material which shares the properties associated with the inorganic component and those of the polymer component (flexibility and processability) .
  • the refractive index increases with the increase of the number of particles.
  • the high refractive index inorganic oxide n a n o p a r t i c 1 e s are present in form of aggregates having a Secondary Particle Diameter (SPD) comprised between 10 and 50 nm, preferably between 20 and 30 nm (measured by means of dynamic light scattering DLS in water) .
  • SPD Secondary Particle Diameter
  • the Primary Particle Diameter (PPD) of the particles is comprised between 2 nm and 20 nm, preferably between 5 and 10 nm (measured with a transmission electron microscope TEM) with a surface area comprised between 45 m 2 /g and 350 m 2 /g, preferably between 200 m 2 /g and 300 m 2 /g (Nitrogen absorption BET method) .
  • the high surface area of the primary particle is the cause of the high aggregation tendency.
  • the inventors of the present patent application have developed a method for preparing the aforementioned particle dispersion which provides for the drying and sonication treatment of the dispersion so as to obtain an SPD within the aforementioned range.
  • high refractive index inorganic oxide nanoparticles preferably titanium dioxide, having sufficiently small dimensions revealed to be essential to allow for operating within a wide range of concentrations without causing an opalescence of the dispersion and maintaining the refractive index of the dispersion on high values.
  • the solutions of synthetic resin containing the aforementioned nanoparticle dispersion preserve a substantially transparent aspect over the entire range of concentrations of nanoparticles used.
  • titanium dioxide is in form of anatase.
  • the percentage of nanoparticles dispersed in the synthetic resin solution is comprised between 2% and 50% in weight with respect to the total weight of the dry film, preferably between 5% and 30% in weight.
  • the synthetic resin solution is an aqueous solution.
  • non-aquoues solvents such as for example ketones, esters or alcohols
  • the surface of the oxide must be modified to stabilize the nanoparticles .
  • the surface of the nanoparticles prepared as described herein may be modified with aliphatic amines and phosphonic acids with the aim of making them hydrophobic.
  • capping agents see Cao-Thang Dinh et al . , ACS Nano, 2009.
  • the synthetic resin solution has a concentration comprised between 2% and 20% in weight.
  • the synthetic resin is selected from among the most stable ageing bonding and consolidating agents normally used in the polychrome paintings industry.
  • the following synthetic resins are used: acrylic resins, vinyl resins, cellulosic derivatives or polyamines.
  • the synthetic resin is poly-2-ethyl-2-oxazoline (commercialised under the trade name AQUAZOL ® produced by PCI) .
  • Aqueous solutions of poly-2-ethyl-2-oxazoline at a concentration comprised between 2% and 20% are preferably used, preferably between 2.5% and 10% in weight, depending on the type of substrate .
  • the high refractive index inorganic oxide nanoparticles such as titanium dioxide, perform, in the composition described above, a complete UV filtering action starting from about 350 nm, thus in the near UV range.
  • a synthetic resin solution as defined above in which said inorganic oxide nanoparticles, in particular titanium dioxide, have a filter function in the near UV range from about 350 nm, constitutes a further object of the invention.
  • such solution does not contain light stabilizing additives, such as UV absorbers (benzotriazole) or hindered amines (HALS) .
  • the solution of the invention is applied as a consolidation and/or protection agent on coloured or painted surfaces, in particular on cultural heritage materials, more in particular on paintings characterised by an opaque and/or thin surface, by means of methods known to a man skilled in the art, such as application using a brush or by spraying, so as to form, after evaporation of the solvent, a film.
  • Such protection layer preferably has thicknesses comprised between 10 and 50 micrometres.
  • the film thus obtained is transparent and it preferably has a refractive index comprised between 1.52 and 1.80, which varies proportionally to the amount of nanoparticles present in the film.
  • a nanocomposite consolidation-protection layer for a thin and/or opaque painting surface which can be obtained after applying a synthetic resin solution containing high refractive index inorganic oxide nanoparticles, preferably titanium dioxide, as defined above, having a roughness comprised between 2 and 30 nm constitutes a further object of the invention.
  • a nanocomposite consolidation-protection layer for opaque painted surfaces which can be obtained after application of a synthetic resin solution containing high refractive index inorganic oxide nanoparticles, preferably titanium dioxide, as defined above, having a contact angle ⁇ with water comprised between 20° and 100°, constitutes a further object of the invention.
  • the nanocomposite consolidation- protection layer for an opaque and/or thin painted surface which can be obtained after application of a synthetic resin solution containing high refractive index inorganic oxide nanoparticles, preferably titanium dioxide, as defined above, has a contact angle ⁇ with water increasing from 20° to 100° with the increase of the percentage of the titanium dioxide nanoparticles from 15% to 45% in weight in the dry film.
  • the consolidation-protection layer for a coloured surface or painting preferably selected from among opaque and/or thin polychrome paintings, which can be obtained after application of a synthetic resin solution containing high refractive index inorganic oxide nanoparticles, preferably titanium dioxide, as defined above, has a contact angle ⁇ with the water increasing from 20° to 100° with the increase of the roughness from
  • a further object of the invention is a method for preparing a synthetic resin solution containing high refractive index inorganic oxide n a n o p a r t i c 1 e s , preferably titanium dioxide, as defined above, comprising the following steps:
  • step d) adding said nanoparticle dispersion obtained in step c) to said synthetic resin solution obtained in step a) .
  • the method of the invention may further comprise a step e) for applying said solution obtained in step d) to a substrate, specifically a painted or coloured surface, in which said application may be carried out using a brush or by spraying.
  • a further object of the present invention is represented by a method for modulating the roughness of a consolidation-protection layer to be applied to a substrate having a given roughness, specifically a painted or coloured surface, comprising the following steps :
  • step d) adding said nanoparticle dispersion obtained in step c) to said synthetic resin solution obtained in step a) at amounts such as to obtain, after application of said solution to said substrate, a roughness which can be visually compared to the given roughness of the substrate .
  • the nature and amount of synthetic resin and solvents, the amount of titanium dioxide nanoparticles and the chemical-physical characteristics of said nanoparticles and the resulting protection layer are as defined previously, thus they shall not be described further hereinafter.
  • the reaction occurs in a non-aqueous environment (precisely in benzyl alcohol) , according to the recipe of Stucky (Niederberger M. et al . , Chem. Mater., 2002) .
  • the benzyl alcohol is distilled using Claisen and the introduction of titanium tetrachloride (in a 1:20 ratio with respect to the benzyl alcohol) , synthesis reagent, is carried out slowly under nitrogen flow.
  • titanium dioxide in order for the titanium dioxide to be formed, it is necessary that the reaction acquires moisture from the external environment; this is made possible by simply placing a Petri dish on the neck of a reaction flask.
  • the reaction conditions are 85°C for 24 hours, but possible variants are allowed with the aim of obtaining titanium dioxide of different dimensions, as described in the Stucky' s article mentioned above.
  • Almost 4 grams of titanium dioxide can be obtained from 80 ml of benzyl alcohol and 4 ml of TiCl 4 .
  • titanium dioxide is separated from the reaction environment through centrifugation and washed three times (using ethanol the first time and THF the other two times) .
  • the separation of titanium dioxide from the washing waters is carried out through centrifuge each time.
  • a determinant factor for the success of the nanoparticles is the drying time.
  • the titanium dioxide should neither be moistened nor dried again for too much time when grinding.
  • An ideal drying time under hood is two days. An extra day causes the irremediable aggregation thereof. After these two days, the sample is ground using a mortar to obtain a powder. At this point the titanium dioxide is ready, but it should be dispersed immediately so as to overcome the problem related to a further aggregation.
  • Titanium dioxide is placed in water and subjected to sonication for 15 minutes with 21 ON seconds alternated with 7 OFF seconds with 40% of the power of the 750W probe.
  • the process starts from a maximum percentage of 4% in weight of titanium dioxide in water (example: 4g of powder in 100 ml of water) .
  • a transparent dispersion is obtained which tends towards bluish colour, in which the dimension of the secondary particles under DLS is around 30-40 nm of diameter as the mean value and with a 20 nm maximum polydispersity .
  • the polymer (Aquazol ® 200 in this case) is dissolved in water in a percentage that may range between 20% in weight in water up to about 2.5%, depending on the purpose of use and the needs of the object subject of the intervention.
  • the titanium dioxide dispersion is added, considering the relative ratios between titanium dioxide and water, polymer and water, but above all the relative ratio between the polymer and titanium dioxide.
  • the nanocomposite is characterised solely by the presence of the polymer and titanium dioxide.
  • the general method of preparation of the resin synthetic solutions used for the experimentation provides for the preparation of an Aquazol ® solution in water at a suitable concentration.
  • the titanium dioxide nanoparticles are dispersed in water, they are subjected to sonication to reduce the SPD thereof in the range of 10-50 nm and they are thus added to the aqueous solution of Aquazol ® prepared previously.
  • the films are obtained by evaporating the solvent on Mylar ® sheets .
  • Film “Al” 16% in weight of nanoparticles with a 1.57 expected refractive index of the film
  • Film “A2" 28% in weight of nanoparticles with a 1.60 expected refractive index of the film
  • Film A3 44% in weight of nanoparticles with a 1.65 expected refractive index of the film.
  • the UV-Visible spectroscopy of the films confirms that the particles serve as a ultraviolet filter completed by about 350 nm.
  • model paintings were prepared carried out on new canvases and monochrome backgrounds of different colours.
  • the pigments selected and used were mixed in 1:1 ratio as regards the acrylic and gouache bonding agents, for the samples carried out using the tempera colours, the mixture used was spread at a 2:1 ratio.
  • the bonding agents used for providing the colours are produced by Sennelier, as regards acrylic N133646 and as regards gouache N130508.
  • the powders used for the preparation of the colours are :
  • the temperas in a tube are produced by Windsor&Newton and they are:
  • PB72 5% Paraloid B72 ® in Dowanol ® .
  • the materials were spread using a brush on the acryl surfaces and sprayed on the gouache and tempera backgrounds, for reasons related to the instability of the colour with the water, except for Paraloid B72 ® .
  • the materials that interfered with and modified the optical properties of the samples were mainly Paraloid B72 ® and Lascaux 2063 ® .
  • the material was very different in terms of yield depending on the presence of the nanoparticles and the concentration thereof.
  • the L2063 box has generally made the sample surfaces more opaque and “flattened", while the finished box with PB72 made the surface very bright and saturated.
  • the AO box shows how pure Aquazol ® reveals surface tension problems and thus a very non-homogeneous spreading in which the bright and opaque areas are alternated with the perception of the polymer residues. Boxes Al, A2 , A3, depending on the concentration of nanoparticles present, revealed different effects depending on the colour background. As regards the ochre sample on cotton the best response was that of sample A2, characterised by an intermediate concentration of particles .
  • the least indicated material was Lascaux 2063 ® in that it made the surface too bright, same case applying to Aquazol ® without particles (AO) .
  • box PB72 a saturation and darkening effect of the colour are observed.
  • Aquazol ® with the nanoparticles (boxes Al and A3) instead, provides good results even though the concentration thereof should be dosed depending on the type of pigment and support subject of the intervention.
  • the ochre gouache background on fine linen the most satisfactory results are obtained with spreading Al .
  • the material subject of the present patent application may be used as a coating for printed material (labels, etc.) or non-coloured, non-painted surfaces: for example, walls of different nature and materials.
  • Another possible application is in the field of inks and varnishes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne des dispersions de nanoparticules dans des matrices polymères, qui peuvent être utilisées dans des matériaux de consolidation et de protection, en particulier pour la préservation et la restauration d'un patrimoine culturel. En particulier, la présente invention concerne une solution de résine synthétique contenant une dispersion de nanoparticules d'oxydes inorganiques à indice de réfraction élevé, en particulier du dioxyde de titane, et son application sur un substrat, en particulier un élément d'un patrimoine culturel polychromique, pour former un film transparent de consolidation et/ou de protection. La couche ainsi formée a une propriété de filtrage des ultraviolets dans la plage visible proche et permet de moduler l'indice de réfraction, la rugosité et la tension superficielle de la couche de protection.
PCT/IB2012/052588 2011-05-24 2012-05-23 Dispersions de nanoparticules dans des matrices polymères Ceased WO2012160525A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000921A ITMI20110921A1 (it) 2011-05-24 2011-05-24 Dispersioni nanoparticellari in matrici polimeriche
ITMI2011A000921 2011-05-24

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WO2012160525A1 true WO2012160525A1 (fr) 2012-11-29

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WO (1) WO2012160525A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111745352A (zh) * 2020-07-03 2020-10-09 北京大学 破碎文物支撑系统

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5917652A (en) * 1996-02-05 1999-06-29 Minnesota Mining And Manufacturing Company Durable retroreflective elements
GB2448521A (en) * 2007-04-18 2008-10-22 Piotr Koneczny Paint conservation-restoration composition and method
EP2048116A1 (fr) * 2007-10-09 2009-04-15 ChemIP B.V. Dispersion de nanoparticules dans des solvants organiques
US20100041775A1 (en) * 2008-08-15 2010-02-18 Fujifilm Corporation Inorganic nanoparticle dispersion liquid and method for producing the same, and composite composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5917652A (en) * 1996-02-05 1999-06-29 Minnesota Mining And Manufacturing Company Durable retroreflective elements
GB2448521A (en) * 2007-04-18 2008-10-22 Piotr Koneczny Paint conservation-restoration composition and method
EP2048116A1 (fr) * 2007-10-09 2009-04-15 ChemIP B.V. Dispersion de nanoparticules dans des solvants organiques
US20100041775A1 (en) * 2008-08-15 2010-02-18 Fujifilm Corporation Inorganic nanoparticle dispersion liquid and method for producing the same, and composite composition

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
A. BLEE ET AL.: "NANOPARTICLES AND THE CONSERVATION OF CULTURAL HERITAGE", MATERIALS FORUM VOLUME 32 - 2008 EDITED BY J.M. CAIRNEY, S.P. RINGER AND R. WUHRER, January 2008 (2008-01-01), pages 121 - 128, XP055007843 *
ALLEN N S ET AL: "Behaviour of nanoparticle (ultrafine) titanium dioxide pigments and stabilisers on the photooxidative stability of water based acrylic and isocyanate based acrylic coatings", POLYMER DEGRADATION AND STABILITY, BARKING, GB, vol. 78, no. 3, January 2002 (2002-01-01), pages 467 - 478, XP004388734, ISSN: 0141-3910, DOI: 10.1016/S0141-3910(02)00189-1 *
CAO-THANG DINH ET AL., ACS NANO, 2009
NIEDERBERGER M. ET AL., CHEM. MATER., 2002
RICHARD C. WOLBERS ET AL: "Poly(2-Ethyl-2-Oxazoline): A New Conservation Consolidant", PAINTED WOOD: HISTORY AND CONSERVATION (GETTY CONSERVATION INSTITUTE), PART SIX, SCIENTIFIC RESEARCH, 27 August 1998 (1998-08-27), US, pages 464 - 539, XP055007746, ISBN: 978-0-89-236501-2, Retrieved from the Internet <URL:http://www.getty.edu/conservation/publications_resources/pdf_publications/paintedwood6.pdf> [retrieved on 20110922] *
RODORICO GIORGI ET AL: "Nanoparticles for Cultural Heritage Conservation: Calcium and Barium Hydroxide Nanoparticles for Wall Painting Consolidation", CHEMISTRY - A EUROPEAN JOURNAL, vol. 16, no. 31, 23 July 2010 (2010-07-23), pages 9374 - 9382, XP055007836, ISSN: 0947-6539, DOI: 10.1002/chem.201001443 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111745352A (zh) * 2020-07-03 2020-10-09 北京大学 破碎文物支撑系统

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