Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/40—Coatings comprising at least one inhomogeneous layer
  • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant

Definitions

• the present invention relates to a glass article whose chemical resistance is high and improved over known glass articles.
• the invention overcomes these disadvantages by providing an improved chemical resistance glass which is stable under various environmental conditions, possibly in aqueous alkaline media, and which is durable for extended periods of use.
• this improved chemical resistance glass may no longer be subjected to a Na + and / or K + depletion treatment or, conversely, it may be subjected to a complementary treatment of Na + ion depletion. and / or K + which would further increase its chemical resistance.
• the invention relates to a glass article as defined in claim 1.
• Figure 1 shows a section of a glass article according to a particular embodiment of the invention.
• Figure 2 shows a section of a glass article according to another particular embodiment of the invention.
• FIG. 4 represents a photograph obtained by transmission electron microscopy of a glass article according to the invention.
• FIG. 5 represents another photograph obtained by transmission electron microscopy of a glass article according to the invention.
• the glass article according to the invention is formed of an inorganic type of glass that can belong to various categories.
• the inorganic glass may thus be a soda-lime glass, a boron glass, a lead glass, a glass comprising one or more additives homogeneously distributed in its mass, such as, for example, at least one inorganic dye, a oxidizing compound, a viscosity controlling agent and / or a melt facilitating agent.
• the inorganic glass may also have undergone a thermal toughening intended to improve its surface hardness.
• the glass article according to the invention is formed of a soda-lime glass clear or colored in the mass.
• soda-lime glass is used here in its broad sense and concerns any glass which contains the following basic components (expressed in percentages by total weight of glass):
• the glass article has not been covered by any layer prior to the treatment of the present invention, at least on the surface whose chemical resistance is to be improved.
• the glass article according to the invention can be covered by any layer after the treatment of the present invention.
• the layer may be deposited on the surface which has been treated according to the invention or on the surface opposite to that which has been treated according to the invention.
• the glass article according to the invention has improved chemical resistance. By this is meant better chemical resistance than known glasses.
• chemical agents we understand the atmospheric agents such as rainwater optionally comprising pollutants usually encountered in the atmosphere, in the dissolved state or suspension, of same as certain synthetic solutions, in particular aqueous solutions, comprising chemical agents for alkalinization, acidification and / or oxidation-reduction in the possible presence of various organic or inorganic solvents.
• the strength of the article according to the invention is manifested by an absence of corrosion or weight loss under the prolonged influence of the chemical agents for periods of time which may extend over several years or, at least, a significant reduction of this corrosion or loss of weight up to insignificant values for the use of the article.
• the glass article comprises at least one chemical reinforcing agent.
• This chemical reinforcing agent is a chemical composition that can contain components totally foreign to the composition of the glass mass of the article. It may also alternatively comprise, on the contrary, one or more chemical compounds already present in the composition of the glass mass of the article.
• the particles (2) have a portion of their volume in the glass (1) and the other part of their volume in the external environment.
• the particles (3) according to the invention have a part of their volume in the glass (1) and the other part of their volume in the material of said layer (4).
• the particles (5) according to the invention have a part of their volume in the glass (1) and the other part of their volume which is distributed between the material of said layer (4) and the external medium.
• Each particle according to the invention is formed of a single chemical compound of chemical reinforcing agent. It may also, alternatively, be formed of a composition of several different chemical reinforcing agents. In the latter case, the composition is not necessarily homogeneous.
• the inorganic chemical compound constituting the particles is chosen from oxides, nitrides, carbides and combinations of at least two oxides and and / or nitrides and / or carbides.
• the inorganic compound is selected from magnesium oxide, calcium oxide, strontium oxide, barium oxide or among the oxides, nitrides and carbides of scandium, yttrium, lanthanum, titanium, zirconium, vanadium, niobium, tantalum, aluminum, gallium, indium, silicon, germanium, tin, and combinations of at least two of the above compounds.
• the inorganic compound is selected from among magnesium, calcium, aluminum, silicon and tin oxides, and combinations of at least two of these compounds.
• aluminum oxide and silicon oxide have given the best results.
• Aluminum oxide 111 (Al 2 O 3 ) used alone has been found to be a very interesting chemical reinforcing agent.
• the silicon oxide IV (SiO 2 ) alone has also provided a glass effectively reinforced by particles.
• the surface enrichment of aluminum oxide is greater than or equal to 0.02% by weight and, preferably, greater than or equal to 0.05%.
• the surface enrichment of aluminum oxide according to the invention is less than 20% by weight and preferably less than 15%.
• the surface enrichment of silicon oxide is greater than 0.02% by weight and, preferably, is greater than 0.05%.
• the surface enrichment of aluminum oxide is less than 25% by weight and, preferably, is less than
• the particles have a size which is not smaller than 5 nm and, preferably, which is not smaller than 50 nm.
• the particles have a size that is not greater than 1500 nm and preferably not more than 1000 nm. By size we mean the largest dimension of the particles.
• the particles are at least partially crystallized, that is to say they comprise at least a proportion of 5% of their weight constituted by crystals.
• the crystals may belong to several different crystallization systems. Alternatively, they can all be of the same crystallization system. Preferably, at least 50% of the weight of the inclusions is in a crystallized form. Most preferably, all the particles are in the crystallized form.
• the glass article according to the invention may comprise, in addition to particles (2) partially incorporated in the mass of the glass (1), particles (6) totally incorporated in the mass of the glass (1) and that one found under the surface of the glass, close to it. This particular embodiment is shown in FIG.
• the glass article according to the invention may also comprise particles deposited on the surface of article and who adhere to it.
• the glass article may be subjected to a complementary depletion treatment. in Na + ions which makes it possible to eliminate or greatly reduce the sodium and / or potassium content in a thin zone close to the surface of the glass.
• the glass article which has undergone a depletion treatment has a sodium content on the glass surface which is less than the sodium content in the core of the glass article.
• the depletion treatment is carried out by a known method which consists in treating the surface of the glass with the aid of sulfur dioxide, SO 2 , which pumps the Na + ions to the surface of the glass, forming a layer of sodium sulfate on this same surface.
• the glass of the article according to the invention consists of a flat glass sheet.
• the flat glass sheet may be the subject of the treatment according to the invention on one side or, alternatively, on both sides.
• the treatment according to the invention is advantageously carried out on the non-printed face of the sheet if it is printed on one side.
• the glass of the article according to the invention consists of a flat glass sheet of soda-lime type.
• the article according to the invention can be obtained by any method capable of generating and partially including particles in the mass of the glass of said article.
• the invention relates to an article according to the foregoing descriptions which is obtained by a method which comprises (a) the producing particles, (b) depositing particles on the surface of said article, and (c) supplying energy to the particles and / or said surface such that the particles diffuse / incorporate into the glass.
• the particles are generated by atomizing a solution of at least one chemical precursor into an aerosol transported in a flame where combustion occurs. to form solid particles. These particles can then be deposited directly on a surface placed near the end of the flame. This method in particular has given good results.
• the formation and deposition of particles on the surface of the glass article can be performed consecutively in two steps.
• the particles are generated beforehand in solid form or in the form of a suspension in a liquid by steam, by the wet route (sol-gel, precipitation, hydrothermal synthesis, etc.) or by the dry route (mechanical grinding, mechanochemical synthesis, ).
• An example of a method for generating particles in solid form beforehand is the method known as condensation.
• Combustion-Enhanced Chemical Vapor Injection or CCVC. This method involves converting into a flame a precursor vapor phase solution that undergoes a combustion reaction to provide particles that are ultimately collected.
• the previously generated particles can be transferred to the surface of the glass article by various known methods.
• the energy required for diffusion / partial incorporation of the particles into the bulk of the glass may, for example, be provided by heating the glass article to a suitable temperature.
• the energy required for the diffusion / partial incorporation of the particles into the mass of the glass can be provided at the moment of the deposition of the particles or after the deposition.
• Hydrogen and oxygen were introduced into a linear burner to generate a flame at the outlet of said burner.
• the burner used was 20 cm wide and had five nozzles for the introduction of the solution.
• the washed glass sheet was preheated in an oven at a temperature of
• Aluminum oxide particles were thus generated in the flame and collected on the surface of the glass sheet. The glass sheet was then cooled in ambient air.
• the analyzes carried out showed that the aluminum was incorporated in the form of particles of aluminum oxide partially incorporated in the mass of the glass.
• the particles have an almost spherical shape and they have a size that varies from
• the particles 200 to 1000 nm.
• the particles are predominantly crystalline.
• the surface enrichment of aluminum oxide is 0.9% by weight.
• Figure 4 shows a picture obtained by transmission electron microscopy of a section of the treated glass sheet. It shows an aluminum oxide particle partially embedded in the mass of the glass. The glass is located in the upper part of the plate while the external environment is in the lower part. This particle is almost spherical and has a size of about 250 nm.
• the burner was supplied with hydrogen and oxygen to generate a flame at the outlet of said burner and was placed above the glass sheet of the unprinted side at a distance of 120 mm.
• Aluminum oxide particles were thus generated in this flame and collected on the surface of the glass sheet.
• the glass sheet finally passed to the cooling gallery where it was cooled in a controlled manner under the conditions usually used for printed flat glass.
• the glass sheet treated as described above was analyzed by the same techniques as those described in Example 1.
• Figure 5 shows a photograph obtained by transmission electron microscopy of a section of the treated glass sheet. It shows an aluminum oxide particle partially embedded in the mass of the glass. The glass is located in the upper part of the plate while the external environment is in the lower part. This particle is nearly spherical and has a size of about 430 nm.
• the untreated reference glass sheet After 2 days in the climatic chamber, the untreated reference glass sheet showed a corrosion phenomenon.
• the glass sheet treated by the method described above only showed a corrosion phenomenon after 10 days in the climatic chamber.
• the particles that have been used have a size ranging from 5 to 150 nm and they are predominantly crystallized.
• the glass sheet was then cooled in ambient air.
• the analyzes have shown that aluminum oxide particles have been partially incorporated into the glass mass and the results obtained in terms of size and crystallinity are in agreement with the starting characteristics of the particles injected into the air stream. .
• the treated glass sheet also has particles totally incorporated into the mass of the glass.
• the surface enrichment of aluminum oxide is 2.5% by weight.

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• Chemical & Material Sciences (AREA)
• Composite Materials (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Glass Compositions (AREA)
• Surface Treatment Of Glass (AREA)

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Publications (1)

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Citations (4)

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• 2009
  • 2009-10-19 BR BRPI0919924A patent/BRPI0919924A2/pt not_active IP Right Cessation
  • 2009-10-19 US US13/122,638 patent/US20110183831A1/en not_active Abandoned
  • 2009-10-19 WO PCT/EP2009/063651 patent/WO2010046336A1/fr active Application Filing
  • 2009-10-19 CN CN2009801412928A patent/CN102186788A/zh active Pending
  • 2009-10-19 EA EA201100657A patent/EA201100657A1/ru unknown
  • 2009-10-19 JP JP2011531513A patent/JP2012505817A/ja active Pending
  • 2009-10-19 CA CA2739563A patent/CA2739563A1/fr not_active Abandoned
  • 2009-10-19 EP EP09736956A patent/EP2346790A1/fr not_active Withdrawn

Patent Citations (4)

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