NZ614041B2 - Hybrid sol-gel coated glass containers - Google Patents
Hybrid sol-gel coated glass containers Download PDFInfo
- Publication number
- NZ614041B2 NZ614041B2 NZ614041A NZ61404112A NZ614041B2 NZ 614041 B2 NZ614041 B2 NZ 614041B2 NZ 614041 A NZ614041 A NZ 614041A NZ 61404112 A NZ61404112 A NZ 61404112A NZ 614041 B2 NZ614041 B2 NZ 614041B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- gel
- hybrid sol
- degrees celsius
- set forth
- method set
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 157
- 238000000576 coating method Methods 0.000 claims abstract description 97
- 239000011248 coating agent Substances 0.000 claims abstract description 95
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000077 silane Inorganic materials 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000000903 blocking Effects 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N Dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 7
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 7
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 7
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- -1 cerium alkoxide Chemical class 0.000 claims description 5
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical class CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- UWNCQPGIQLKINJ-UHFFFAOYSA-N C(C1CO1)OCCC[SiH2]OCC(OC)OC Chemical compound C(C1CO1)OCCC[SiH2]OCC(OC)OC UWNCQPGIQLKINJ-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinylpyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N Barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N Bismuth(III) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical compound [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001929 titanium oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000499 gel Substances 0.000 description 98
- 238000000137 annealing Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 229940075894 denatured ethanol Drugs 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- 239000004698 Polyethylene (PE) Substances 0.000 description 2
- 102000014961 Protein Precursors Human genes 0.000 description 2
- 108010078762 Protein Precursors Proteins 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- SIWNOIGHWNVCHR-UHFFFAOYSA-N diethoxy(dimethyl)silane;triethoxy(methyl)silane Chemical compound CCO[Si](C)(C)OCC.CCO[Si](C)(OCC)OCC SIWNOIGHWNVCHR-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- UWONUAJRKDRMBC-UHFFFAOYSA-N CCO[Si](OCC)(OCC)c1ccccc1.CCO[Si](OCC)(c1ccccc1)c1ccccc1 Chemical compound CCO[Si](OCC)(OCC)c1ccccc1.CCO[Si](OCC)(c1ccccc1)c1ccccc1 UWONUAJRKDRMBC-UHFFFAOYSA-N 0.000 description 1
- RVHXCFKEGYLMJW-UHFFFAOYSA-N CO.CO[Si](OC)(OC)c1ccccc1.CO[Si](OC)(c1ccccc1)c1ccccc1 Chemical compound CO.CO[Si](OC)(OC)c1ccccc1.CO[Si](OC)(c1ccccc1)c1ccccc1 RVHXCFKEGYLMJW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229940098458 Powder Spray Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 230000003678 scratch resistant Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
-
- 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
- C03C17/001—General methods for coating; Devices therefor
- C03C17/003—General methods for coating; Devices therefor for hollow ware, e.g. containers
- C03C17/005—Coating the outside
-
- 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
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
- Y10T428/1317—Multilayer [continuous layer]
Abstract
method of coating an exterior surface of a glass container 110 that includes the steps of providing a hybrid sol-gel 15 having a solids content of greater than 90% by volume and being formed from a composition including at least one silane and at least one solvent, heating the hybrid sol-gel 15 to produce a heated hybrid sol-gel 15 having a target viscosity between 0.025 Pa•s and 0.05 Pa•s, coating an exterior glass surface of a glass container with the heated hybrid sol-gel 15, and heating the coated exterior glass surface of the glass container to cross-link the hybrid sol-gel 15 and result in a transparent coating on the exterior glass surface of the glass container having greater than 90% silicate-based material by weight. produce a heated hybrid sol-gel 15 having a target viscosity between 0.025 Pa•s and 0.05 Pa•s, coating an exterior glass surface of a glass container with the heated hybrid sol-gel 15, and heating the coated exterior glass surface of the glass container to cross-link the hybrid sol-gel 15 and result in a transparent coating on the exterior glass surface of the glass container having greater than 90% silicate-based material by weight.
Description
HYBRID SOL-GEL COATED GLASS CONTAINERS
The present disclosure is directed to glass containers, and coating
processes for glass containers including methods and materials for coating glass
containers (e.g., glass bottles and jars).
Background and Summary of the Disclosure
Various processes have been developed to apply coatings to glass
containers for different purposes, including glass strengthening for damage prevention
and fragment retention. For example, U.S. Patent 3,522,075 discloses a process for
coating a glass container in which the glass container is formed, coated with a layer of
metal oxide such as tin oxide, cooled through a lehr, and then coated with an
organopolysiloxane resin-based material over the metal oxide layer. In another example,
U.S. Patent 3,853,673 discloses a method of strengthening a glass article by, for example,
applying to a surface of the article a clear solution of a soluble, further hydrolyzable
metallosiloxane, and maintaining the glass article at an elevated temperature sufficiently
high to convert the metallosiloxane to a cross-linked polymetallosiloxane gel structure.
In a further example, U.S. Patent 3,912,100 discloses a method of making a glass
container by heating the glass container and applying a polyurethane powder spray to the
glass container.
A general object of the present disclosure, in accordance with one aspect
of the disclosure, is to provide an improved method of increasing strength and/or
fragment retention of a glass container, and/or to provide the public with a useful choice.
The present disclosure embodies a number of aspects that can be
implemented separately from or in combination with each other.
In accordance with an aspect of the present invention, there is provided a
method of coating an exterior surface of a glass container that includes the steps of:
providing a hybrid sol-gel having a solids content of greater than 90% by
volume and being formed from a composition including at least one silane and at least
one solvent;
heating the hybrid sol-gel to produce a heated hybrid sol-gel having a
target viscosity between 0.025 Pa·s and 0.05 Pa·s;
coating an exterior glass surface of a glass container with said heated
hybrid sol-gel; and
heating said coated exterior glass surface of the glass container to cross-
link said hybrid sol-gel and result in a transparent coating on said exterior glass surface of
the glass container having greater than 90% silicate-based material by weight.
A method of coating an exterior surface of a glass container in accordance
with one aspect of the disclosure includes the steps of (a) providing a heated hybrid sol-
gel having a composition including at least one silane and at least one solvent, (b) coating
the exterior glass surface of the glass container with the heated hybrid sol-gel, and (c)
heating the coated exterior glass surface of the glass container to cross-link the hybrid
sol-gel and result in a coating on the exterior glass surface of the glass container having
greater than 90% silicate-based material by weight.
In accordance with a further aspect of the disclosure, there is provided a
glass container that includes an axially closed base at an axial end of the glass container,
a body extending axially from the base and being circumferentially closed, an axially
open mouth at another end of the glass container opposite of the base, and an exterior
glass surface. The glass container also includes a hybrid sol-gel cross-linked on at least a
portion of the exterior glass surface.
In accordance with an additional aspect of the disclosure, there is provided
a glass container that includes an axially closed base at an axial end of the glass
container, a body extending axially from the base and being circumferentially closed, an
axially open mouth at another end of the glass container opposite of the base, and an
exterior glass surface. The glass container also includes a coating of hybrid sol-gel on at
least a portion of the exterior glass surface, wherein the hybrid sol-gel includes at least
one silane and at least one solvent.
In accordance with another aspect of the disclosure, there is provided a
method of manufacturing a glass container including the steps of forming the glass
container, applying a hot end coating to an exterior glass surface of the glass container,
and annealing the glass container. The method also includes heating a hybrid sol-gel to a
temperature of between 70 degrees Celsius and 130 degrees Celsius, wherein a
composition of the hybrid sol-gel includes 50% to 60% by weight of at least one silane
and 40% to 50% by weight of at least one solvent wherein the heated hybrid sol-gel has a
viscosity of between 0.001 Pa-s and 100 Pa-s, coating the exterior glass surface of the
glass container with the heated hybrid sol-gel, at a temperature between 80 degrees
Celsius and 140 degrees Celsius, and heating the coated exterior glass surface of the glass
container at a temperature between 140 degrees Celsius and 160 degrees Celsius for a
time between ten minutes and ten hours to cross-link the hybrid sol-gel and result in a
coating on the exterior glass surface of the glass container having greater than 90%
silicate-based material by weight to increase at least one of strength or fragment retention
of the glass container. The method further includes applying a cold end coating to the
exterior glass surface of the glass container.
Brief Description of the Drawings
The disclosure, together with additional objects, features, advantages and
aspects thereof, will be best understood from the following description, the appended
claims and the accompanying drawings, in which:
is an elevational view of a glass container in accordance with an
exemplary embodiment of the present disclosure;
is a cross-sectional view of the glass container body before coating;
is an enlarged sectional view of the glass container, taken from
circle 3 of
is a sectional view of a glass container according to another
embodiment;
is micrograph taken of portion of a glass container before a
hybrid sol-gel coating is applied and cross-linked in accordance with Example #1
described herein below;
is micrograph taken of portion of a glass container including the
cross-linked hybrid sol-gel coating in accordance with Example #1 described herein
below;
is micrograph taken of portion of a glass container before a
hybrid sol-gel coating is applied and cross-linked in accordance with Example #2
described herein below;
is micrograph taken of portion of a glass container including the
cross-linked hybrid sol-gel coating in accordance with Example #2 described herein
below;
is micrograph taken of portion of a glass container before a
hybrid sol-gel coating is applied and cross-linked in accordance with Example #3
described herein below;
is micrograph taken of portion of a glass container including the
cross-linked hybrid sol-gel coating in accordance with Example #3 described herein
below;
is micrograph taken of portion of a glass container before a
hybrid sol-gel coating is applied and cross-linked in accordance with Example #4
described herein below; and
is micrograph taken of portion of a glass container including the
cross-linked hybrid sol-gel coating in accordance with Example #4 described herein
below.
Detailed Description of Preferred Embodiments
illustrates an exemplary embodiment of a glass container 10 that
may be produced in accord with an exemplary embodiment of a manufacturing process
presently disclosed hereinbelow. The glass container 10 includes a longitudinal axis A, a
base 10a at one axial end of the container 10 that is closed in an axial direction, a body
10b extending in an axial direction from the axially closed base 10a, and a mouth 10c at
another axial end of the container 10 opposite of the base 10a. Accordingly, the glass
container 10 is hollow. In the illustrated embodiment, the container 10 also includes a
neck 10d that may extend axially from the body 10b, may be generally conical in shape,
and may terminate in the mouth 10c. However, the container 10 need not include the
neck 10d and the mouth 10c may terminate the body 10b, such as in a glass jar
embodiment or the like. The body 10b may be of any suitable shape in cross-section
transverse to the axis A as long as the body 10b is circumferentially closed. For example,
as shown in the body 10b may be of cylindrical transverse cross-sectional shape
that is circumferentially closed. In other embodiments, the body 10b may be generally
oval, square, rectangular, or of any other suitable transverse cross-sectional shape. As
used herein, the term “circumferentially” applies not only to circular or cylindrical
transverse cross-sectional shapes but also applies to any transverse cross-sectional shape.
illustrates that the container 10 includes a glass substrate 12, and
may further include a hot end coating 14 applied to an exterior glass surface of the
container 10 on the substrate 12. The container 10 also includes a cross-linked hybrid
sol-gel coating 15 applied to the exterior glass surface of the container 10. The coating
15 may be applied over the hot end coating 14 or directly to the substrate 12. The
container 10 further may include a cold end coating 16 applied to the exterior glass
surface of container 10 over the cross-linked hybrid sol-gel coating 15, and an organic
coating 18 applied to the exterior glass surface of the container 10 over the cold end
coating 16. Although the various coatings 14-18 are shown as adjacent layers overlying
one another sequentially, one or more of the coatings may penetrate into or even through
one or more of the other coatings, and one or more of the coatings may be omitted.
Accordingly, the various coatings 14-18 may be fairly described as being applied
generally to the glass container 10, regardless of how or to what extent any given coating
contacts any of the other coatings and/or the substrate 12. Similarly, when a material is
described as being applied to an exterior glass surface of the glass container 10, the
material may be applied over one or more of the coatings 14-18 and/or to the glass
substrate 12 itself.
In some embodiments, the cross-linked hybrid sol-gel coating 15 may
replace one or more of the other coatings. For example, in one embodiment, the cross-
linked hybrid sol-gel coating 15 may replace the hot end coating 14. In another
embodiment, cross-linked hybrid sol-gel coating 15 may replace the cold end coating 16.
Therefore, the container 10 may be free of conventional hot end and cold end coatings.
In other words, the container 10 may be coated without conventional hot end and cold
end coatings. One example of a container 110 of these embodiments is illustrated in FIG.
The coating 15 is produced by cross-linking a hybrid sol-gel that has the
potential to increase the strength of glass containers by healing surface anomalies that
may be present in the exterior surface of the container 10, and by preventing further
creation of surface anomalies. For example, a heated hybrid sol-gel may flow into a
crack in glass and be retained therein after cross-linking, thereby bridging and blunting a
crack tip to increase a burst strength of the container 10. In another example, the heated
hybrid sol-gel may uniformly cover an exterior surface of a glass container and, after
cross-linking, may provide a uniform glass fragment retention layer for retention of glass
fragments if the container breaks or becomes fractured.
For purposes of the present disclosure, a hybrid sol-gel is a sol-gel that is a
hybrid of inorganic and organic components or precursors and is produced by a sol-gel
process, but retains some of the organic nature of the organic precursor(s). The hybrid
sol-gel is highly viscous at room temperature and has a relatively long “pot life” which
lends itself to use in a glass container manufacturing environment. The viscosity of the
hybrid sol-gel may be such that it barely flows under its own weight at room temperature.
The hybrid nature of the hybrid sol-gel allows the precursor materials to flow and behave
like an organic material when heated, until a cross-linking reaction occurs at a suitable
cross-linking temperature to provide the coating 15. After cross-linking, the presently
disclosed coating 15 is rigid, scratch resistant, and transparent. Therefore, unlike many
conventional surface-sealing coatings, the coating 15 looks and feels like glass.
Moreover, the applied coating 15 may be relatively temperature stable and may survive
severe temperature extremes, for example, from -100 degrees Celsius to 450 degrees
Celsius.
The glass container 10 can be produced in any suitable manner. This
typically would involve a “hot end” including one or more melting furnaces, forming
machines, and beginning portions of annealing lehrs, and a “cold end” that may include
end portions of annealing lehrs and includes inspection equipment and packaging
machines. Accordingly, a hot end coating is a coating applied at the hot end of the glass
container manufacturing process, and a cold end coating is a coating applied at the cold
end of the glass container manufacturing process.
After forming a plurality of the glass container 10 with forming machines,
but prior to annealing, the glass containers may be hot-end coated in any suitable manner
with any suitable hot-end coating materials to produce the hot-end coating 14.
The glass containers then may be annealed in any suitable manner, for
example, in an annealing lehr. At an entry, hot end, or upstream portion of the annealing
lehr, the temperature therein may be between 750 and 550 degrees Celsius. Through the
lehr, the temperature may be brought down gradually to a downstream portion, cool end,
or exit of the lehr, for example, to a temperature therein of between 130 degrees Celsius
and 65 degrees Celsius.
In one embodiment, the hybrid sol-gel is applied to the containers at any
temperature suitable for such application and, for example, in an intermediate portion of
the annealing lehr that is upstream of the downstream portion of the lehr but downstream
of the upstream portion of the lehr. In other words, the hybrid sol-gel may be applied to
the containers after annealing begins but before annealing ends.
The temperature for applying the hybrid sol-gel cannot exceed its
consolidation temperature, e.g. about 200 degrees Celsius, above which the sol-gel
irreversibly hardens. Preferably, however, the hybrid sol-gel may be applied before the
end of the annealing lehr where temperatures are insufficient for proper application of the
hybrid sol-gel to the containers. Accordingly, in one embodiment, the hybrid sol-gel may
be applied in the annealing lehr, upstream of a cold or downstream end thereof. In
another embodiment, the glass containers may be directed off-line from the annealing
lehr, coated with the hybrid sol-gel, and directed back on-line into the annealing lehr.
In a further embodiment, the hybrid sol-gel may be applied to the glass
containers in a separate oven, lehr, or the like, downstream of the annealing lehr. In other
embodiments, the hybrid sol-gel may be applied to the glass containers in any suitable
location in a glass container manufacturing process.
A hybrid sol-gel is prepared for application to the containers to provide the
coating 15. Specific examples of preparations are described herein below. In general,
however, the hybrid sol-gel is composed of at least one silane and at least one solvent.
Accordingly, in a preferred embodiment, the hybrid sol-gel is a liquid-silicate-based
material have a very high solids content, for example, greater than 90% by volume.
The silane may be composed of one or more of the following silanes:
methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane,
diphenyldiethoxysilane, phenyltrimethoxysilane, or diphenyldimethoxysilane. The
silanes may be obtained from Gelest, Inc. of Morrisville, PA, or any other suitable
source(s). In other embodiments, the silane may include one more of the following
silanes: 3-glycidoxypropyltrimethoxisilane, 3-glycidoxypropyldimethoxyethoxysilane,
aminopropylmethyldimethosilane, aminopropyltrimethoxysilane, gamma
mercaptopropyltrimethoxysilane, or vinyltrimethoxysilane. In one embodiment, the
hybrid sol-gel includes a first silane and a multiple of the first silane. For example, the
hybrid sol-gel may include methyltriethoxysilane and dimethyldiethoxysilane, or
phenyltriethoxysilane and diphenyldiethoxysilane, or phenyldimethoxysilane and
diphenyldimethoxysilane.
The solvent may be composed of one or more of the following solvents:
denatured ethanol, anhydrous ethanol, or methanol. The solvents may be high purity
solvents, and may be obtained from Fisher Scientific of Hampton, NH, or any other
suitable source(s). In other embodiments, the solvent may include one or more of the
following solvents: normal propanol, isopropanol, butanol, diethylene glycol, acetones,
methylethylketones, tryethyleneglycols, vinylpyrrolidones, toluene, glycerine, phenol,
benzyl alcohol, or dioxane.
In one embodiment, the silane may be 50% to 60% of the hybrid sol-gel
by weight, and the solvent may be 40% to 50% of the hybrid sol-gel by weight.
Accordingly, the weight ratio of silane to solvent may be between 1.5:1 and 1:1. In
another embodiment, the silane may be between 52% and 58% of the hybrid sol-gel by
weight, and the solvent may be between 42% and 46% of the hybrid sol-gel by weight.
In a more particular embodiment, the silane may be about 56% of the hybrid sol-gel by
weight, and the solvent may be about 44% of the hybrid sol-gel by weight. Accordingly,
the weight ratio of silane to solvent may be about 1.3:1. As used herein, the term “about”
means within two to three percent. In one embodiment, the hybrid sol-gel may consist
essentially of the silane and solvent materials.
In another embodiment, the base composition of the hybrid sol-gel may be
modified with other, additional materials. For example, the hybrid sol-gel may be doped
with a dopant or doping material, for instance, an ultraviolet blocking material.
Accordingly, materials for providing strengthening and ultraviolet blocking properties
may be applied in only one step. Accordingly, an ultraviolet blocking material need not
be applied in a coating step separate from the hybrid sol-gel coating step. As used herein,
the phrase “ultraviolet blocking” includes reducing ultraviolet transparency and not
necessarily resulting in 100% ultraviolet opacity. The ultraviolet blocking material may
include one or more metal oxides, for example, at least one of cerium oxide, titanium
oxide, zinc oxide, bismuth oxide, or barium titanate. In another embodiment, the
ultraviolet blocking material may include one or more metal alkoxides, for example, at
least one of cerium alkoxide or titanium dialkoxide. Accordingly, in this embodiment,
the doped hybrid sol-gel may include, and preferably may consist essentially of, the
silane, solvent, and one or more of the doping materials or dopants. In one embodiment,
the ultraviolet blocking material may be 0% to 10% of the hybrid sol-gel by weight.
In any case, before the hybrid sol-gel is applied to the container, the
hybrid sol-gel is heated to a temperature suitable to achieve a target viscosity of between
0.001 Pa-s and 100 Pa-s as the hybrid sol-gel is applied to the container. In a more
particular embodiment, the target viscosity is between 0.025 Pa-s and 0.05 Pa-s. In a
preferred embodiment, the target viscosity is about 0.0375 Pa-s. In one embodiment, the
temperature of the hybrid sol-gel is between 70 degrees Celsius and 130 degrees Celsius.
In a more particular embodiment, the temperature of the hybrid sol-gel is between 90
degrees Celsius and 110 degrees Celsius. In a preferred embodiment, the temperature of
the hybrid sol-gel is about 100 degrees Celsius.
The exterior glass surface of the container is coated with the heated hybrid
sol-gel in any suitable manner. For example, the heated hybrid-sol gel may be sprayed
onto the exterior glass surface in any suitable manner, the container may be dipped in the
heated hybrid sol-gel in any suitable manner, or the like. The hybrid sol-gel is coated to
the container at a temperature in the oven or lehr of between 80 degrees Celsius and 140
degrees Celsius. In a more particular embodiment, the temperature is between 95 degrees
Celsius and 125 degrees Celsius. In a preferred embodiment, the temperature is about
110 degrees Celsius. Preferably, the temperature is higher than the temperature of the
heated hybrid sol-gel. For example, the temperature differential is preferably between 5
degrees Celsius and 15 degrees Celsius and, more preferably, about 10 degrees Celsius.
The coated exterior glass surface of the container is heated for a time and
at a temperature suitable to cross-link the hybrid sol-gel to result in the coating 15 having
greater than 90% silicate-based material by weight to increase strength of the container.
For example, the coating 15 may have greater than 90% silica-based material. The
silicate-based material may bond to the glass container 10 in any suitable manner. In one
embodiment, the temperature in the oven or lehr is between 130 degrees Celsius and 170
degrees Celsius for a time of between ten minutes and ten hours. In a more particular
embodiment, the temperature is between 140 degrees Celsius and 160 degrees Celsius.
In a preferred embodiment, the temperature is about 150 degrees Celsius. The precursors
are hydrolysed in the reaction, which is followed by a condensation reaction, but no
cross-linker materials need be used. Accordingly, the cross-linking reaction may be free
of cross-linkers.
In one embodiment, where the coated containers pass continuously
through the annealing lehr, the lehr may be constructed and operated to decrease the
temperature of the glass containers to a level suitable for applying the hybrid sol-gel, then
increase the temperature of the glass containers to a level suitable for cross-linking the
hybrid sol-gel, and then decrease the temperature of the glass containers to the
downstream end temperature of the lehr. In other embodiments, the cross-linking may be
conducted in an off-line loop parallel with the annealing lehr before the containers are
brought back into the lehr, may be conducted downstream of the lehr, or the like.
At the end, or downstream of, the annealing lehr, the glass containers may
be cold-end coated in any suitable manner. For example, the glass containers may be
coated with the cold end coating 16, which may be a protective organic coating applied
downstream or at an end of the annealing lehr. The cold end coating 16 may include a
polyethylene material, like a polyethylene wax or the like, or may include any other
suitable cold end coating material.
After the cold end coating is applied, the glass containers may be
inspected for any suitable characteristics and in any suitable manner. For example, the
glass containers may be manually or automatically inspected for cracks, inclusions,
surface irregularities, hot end and/or cold end coating properties, and/or the like.
The organic coating 18 may be applied to the glass containers in any
suitable manner by any suitable equipment. For example, the organic coating 18 may be
electrostatically applied to exterior glass surfaces of the glass containers, for example,
after inspection.
After applying the organic coating, the glass containers may be cured in
any suitable manner. For example, the curable organic coating may be a radiation-
curable organic coating cured by any suitable type of radiation like, for instance,
ultraviolet or electron beam radiation.
After curing, the glass containers may be packaged in any suitable
manner.
The manufacturing process may or may not include all of the disclosed
steps or be sequentially processed or processed in the particular sequence discussed, and
the presently disclosed manufacturing process and coating methods encompass any
sequencing, overlap, or parallel processing of such steps.
The present disclosure provides advancements in the art. For example, the
cross-linked hybrid sol-gel coating can increase glass container strength by better healing
of glass surface anomalies. In another example, the cross-linked hybrid sol-gel coating
can increase glass container strength by retaining glass fragments, without using
polyurethane or conventional additives. As used herein, the terminology fragment-
retention is a characteristic well known to those of ordinary skill in the art of glass
container manufacturing that relates to holding of glass fragments in the event that a glass
container fractures or breaks, for example, from being dropped on hard ground.
Conventionally, it has been understood that sol-gels can be uniformly
applied to flat glass to achieve a thin and somewhat brittle coating to increase glass
strength. But it was also understood that it was not cost-effective or was impossible to
uniformly apply the same sol-gels in solid and continuous films over exterior surfaces of
glass containers to achieve reliable glass strengthening results. Contrary to conventional
wisdom, it is now possible and cost-effective to produce glass containers with a cross-
linked hybrid sol-gel coating applied with relatively uniform coverage to achieve a
relatively thicker and stronger coating.
It has also been conventionally understood that fragment retention
coatings for glass containers are composed of a polyurethane base formed from an
isocyanate monomer or prepolymers of isocyanates, and additives like bisphenol A,
melamine, benzoguanamine, and the like to enable room temperature curing. But
isocyanates and such additives tend to be cost-prohibitive and undesirable. Contrary to
conventional wisdom, it is now possible to produce glass containers with an isocyanate-
free and amine-group-free fragment retention coating that is cost-effective and desirable.
Therefore, the presently disclosed method provides simple but elegant
solutions to problems in the art of glass container manufacturing that have long been
experienced but apparently unappreciated.
Examples
Below, with reference to Table 1, several examples of hybrid sol-gels and
their preparation are provided and explained, as well as a coating technique and
performance results.
Examples Silane #1 Silane #2 Solvent Coating
Examples #1 MethyltriethoxySilane DimethyldiethoxySilane Denatured Ethanol Haze
Examples #2 MethyltriethoxySilane DimethyldiethoxySilane Anhydrous Ethanol Transparent
PhenyltriethoxySilane DiphenyldiethoxySilane Anhydrous Ethanol Transparent
Examples #3
Examples #4 PhenyltrimethoxySilane DiphenyldimethoxySilane Methanol Transparent
Table 1
Example #1
Solution Preparation
A solution A was prepared using 8.1 ml of H O, 0.15gm of HCl (37.1%)
and 13.84 gm of denatured ethanol. Solution A was then stirred for 15 minutes.
A solution B was prepared using 27.04 gm of methyltriethoxysilane
(Silane #1) and 13.79 gm of methanol. Solution B was then stirred for 15 minutes.
Then, solution B was added to solution A very slowly under continuous
magnetic stirring. A beaker containing the combined solution A+B was covered with a
PARAFILM brand foil. The stirring was kept constant for 3 hours.
A solution C was prepared using 7.64 gm of dimethyldiethoxysilane
(Silane #2) and 9.21 gm of denatured ethanol, at about 2 hours and 45 minutes after
beginning stirring of the combined solution A+B. Solution C was stirred for 15 minutes.
Then, solution C was added drop wise to the combined solution A+B and
stirred for 3 more hours. The stirring of the combined solution A+B+C was continued in
a closed system for another 2 hours.
2.78 micro liters of ammonium hydroxide 30% were added after the
aforementioned 2 hours of stirring the combined solution A+B+C. The stirring of the
combined solution A+B+C+ammonium hydroxide was continued in a closed system for
another one hour.
Then, the PARAFILM brand foil was removed and continuous mixing
was conducted for 48 hours. A very viscous gel was obtained.
This gel was dried overnight at 70 degrees Celsius to remove the rest of
the alcohol.
To the so prepared gel, 10 ml of pure acetone were added and stirred for 2
hours.
Thereafter, the solution was filtrated using a Buchner funnel to remove the
byproducts. The solution obtained after filtration was continuously stirred for 5-7 hours
until all acetone was evaporated. A hazy clear gel was obtained.
Then, the gel was thermally treated for 24 hours at 70 degrees Celsius to
remove any trace of acetone and alcohol. Another thermal treatment was performed at
110 degrees Celsius for 24 hours to remove water traces and obtain the hybrid sol-gel.
Coating Formation
Glass substrates of 2" by 2" size were cleaned by soap and water. The
glass substrates were then wiped by isopropanol and dried well.
On a first sample of the glass substrates, a crack was formed on the glass
substrate using a Vickers hardness instrument at 25 gf for 30 sec. The glass substrate was
coated with the hybrid sol-gel using a drawdown bar (#8). The coating was then cured at
150 degrees Celsius for 6 hours to cross link the hybrid sol-gel.
Performance After Curing
On the first sample, the coating was analyzed by optical microscopy to
analyze the healing effect on the crack. Micrographs of the crack were taken before and
after the coatings as illustrated in FIGS. 4A and 4B, respectively, and indicated that the
crack was filled by the coating.
On an opposite, uncoated, side of the second sample, a line was scribed
along the glass substrate by a diamond cutter. The second sample was flipped over, held
along one edge, and struck with a rounded side of the diamond cutter to create a fragment
fractured along the scribed line. The fragment was held to the rest of the second sample
by the cross-linked hybrid sol-gel coating.
Example #2
Example #2 was similar to example #1 in solution preparation and coating
formation. The silane #1 and silane #2 used in example #2 are methyltriethoxysilane and
dimethyldiethoxysilane respectively. The solvent used in this example was anhydrous
ethanol instead of denatured ethanol.
On a first sample, micrographs of the crack were taken before and after the
coatings as illustrated in FIGS. 5A and 5B, respectively, and indicated that the crack was
filled by the coating.
After scribing and striking a second sample, the fragment was held to the
rest of the second sample by the cross-linked hybrid sol-gel coating.
Example #3
Example #3 was similar to example #1 in solution preparation and coating
formation. The silane #1 and silane #2 used in example #3 are phenyltriethoxysilane and
diphenyldiethoxysilane respectively. The solvent used in this example was anhydrous
ethanol instead of denatured ethanol
On a first sample, micrographs of the crack were taken before and after the
coatings, as illustrated in FIGS. 6A and 6B, respectively, and indicated that the crack
was filled by the coating.
After scribing and striking a second sample, the fragment was held to the
rest of the second sample by the cross-linked hybrid sol-gel coating.
Example #4
Example #4 was similar to example #1 in solution preparation and coating
formation. The silane #1 and silane #2 used in example #4 are phenyltriethoxysilane and
diphenyldiethoxysilane respectively. The solvent used in this example was methanol
instead of denatured ethanol.
On a first sample, micrographs of the crack were taken before and after the
coatings, as illustrated in FIGS. 7A and 7B, respectively, and indicated that the crack
was filled by the coating.
After scribing and striking a second sample, the fragment was held to the
rest of the second sample by the cross-linked hybrid sol-gel coating.
There thus has been disclosed methods of coating glass containers and
methods of manufacturing glass containers that at least partially satisfy one or more of
the objects and aims previously set forth. The disclosure has been presented in
conjunction with several exemplary embodiments, and additional modifications and
variations have been discussed. Other modifications and variations readily will suggest
themselves to persons of ordinary skill in the art in view of the foregoing discussion.
Claims (20)
- What we claim is: A method of coating an exterior surface of a glass container that includes the steps of: 5 (a) providing a hybrid sol-gel having a solids content of greater than 90% by volume and being formed from a composition including at least one silane and at least one solvent; (b) heating the hybrid sol-gel to produce a heated hybrid sol-gel having a target viscosity between 0.025 Pa·s and 0.05 Pa·s; 10 (c) coating an exterior glass surface of a glass container with said heated hybrid sol-gel; and (d) heating said coated exterior glass surface of the glass container to cross-link said hybrid sol-gel and result in a transparent coating on said exterior glass surface of the glass container having greater than 90% silicate-based material by weight.
- The method set forth in claim 1 wherein said composition in step (a) includes between 50% and 60% by weight of at least one silane and between 40% and 50% by weight of at least one solvent, said hybrid sol-gel is heated to a temperature 20 between 70 degrees Celsius and 130 degrees Celsius in step (b), step (c) is carried out at a temperature between 90 degrees Celsius and 130 degrees Celsius, and step (d) is carried out at a temperature of between 130 degrees Celsius and 170 degrees Celsius and for a time between ten minutes and ten hours.
- The method set forth in claim 1 wherein said composition in step (a) includes between 52% and 58% by weight of at least one silane and between 42% and 5 46% by weight of at least one solvent, said hybrid sol-gel is heated in step (b) to a temperature between 90 degrees Celsius and 110 degrees Celsius, step (c) is carried out at a temperature between 95 degrees Celsius and 125 degrees Celsius, and step (d) is carried out at a temperature of between 140 degrees Celsius and 160 degrees Celsius. 10 4.
- The method set forth in claim 1 wherein said composition in step (a) includes about 56% by weight of at least one silane and about 44% by weight of at least one solvent, said hybrid sol-gel is heated to a temperature of about 100 degrees Celsius in step (b), step (c) is carried out at a temperature of about 110 degrees Celsius, and step (d) 15 is carried out at a temperature of about 150 degrees Celsius.
- The method set forth in claim 1 wherein said at least one silane in step (a) includes at least one of methyltriethoxysilane, dimethyldiethoxysilane, 20 phenyltriethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3 glycidoxypropyltrimethoxisilane, 3 glycidoxypropyldimethoxyethoxysilane, aminopropylmethyldimethosilane, aminopropyltrimethoxysilane, gamma mercaptopropyltrimethoxysilane, or vinyltrimethoxysilane, and wherein said at least one solvent in step (a) includes at least one of anhydrous ethanol, methanol, normal propanol, isopropanol, butanol, diethylene glycol, acetones, methylethylketones, tryethyleneglycols, vinylpyrrolidones, toluene, glycerine, phenol, benzyl alcohol, or dioxane.
- The method set forth in claim 1 wherein said at least one silane in step (a) includes methyltriethoxysilane and dimethyldiethoxysilane, and wherein said at least one solvent includes at least one of methanol or anhydrous ethanol.
- The method set forth in claim 1 wherein said at least one silane in step (a) includes phenyltriethoxysilane and diphenyldiethoxysilane, and wherein said at least one solvent includes anhydrous ethanol.
- The method set forth in claim 1 wherein said at least one silane in step (a) includes phenyltrimethoxysilane and diphenyldimethoxysilane, and wherein said at least one solvent includes methanol.
- The method set forth in claim 1 wherein said composition provided in step (a) has a silane to solvent weight ratio of between 1.5:1 and 1:1.
- The method set forth in claim 1 wherein said composition in step (a) has a 5 silane to solvent weight ratio of about 1.3:1.
- The method set forth in claim 1 wherein said hybrid sol-gel provided in step (a) is doped with an ultraviolet blocking material, and an ultraviolet blocking 10 material is not applied to the exterior surface of the glass container in a separate step.
- The method set forth in claim 11 wherein said hybrid sol-gel provided in step (a) is doped with an ultraviolet blocking material selected from the group consisting 15 of cerium oxide, titanium oxide, zinc oxide, bismuth oxide, and barium titanate.
- The method set forth in claim 1 wherein said hybrid sol-gel provided in step (a) is doped with at least one metal alkoxide.
- The method set forth in claim 13 wherein said at least one metal alkoxide is at least one of cerium alkoxide or titanium dialkoxide.
- The method set forth in claim 1 wherein said at least one silane in step (a) 5 includes at least one of methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3 glycidoxypropyltrimethoxisilane, 3 glycidoxypropyldimethoxyethoxysilane, aminopropylmethyldimethosilane, aminopropyltrimethoxysilane, gamma mercaptopropyltrimethoxysilane, or 10 vinyltrimethoxysilane.
- The method set forth in claim 1 wherein said at least one solvent includes at least one of anhydrous ethanol, methanol, normal propanol, isopropanol, butanol, 15 diethylene glycol, acetones, methylethylketones, tryethyleneglycols, vinylpyrrolidones, toluene, glycerine, phenol, benzyl alcohol, or dioxane.
- The method set forth in claim 1 wherein said hybrid sol-gel provided in 20 step (a) is highly viscous at room temperature such that it barely flows under its own weight.
- The method set forth in claim 1 wherein said step (c) is performed at a temperature between 5 degrees Celsius and 15 degrees Celsius higher than the temperature at which the hybrid sol-gel is heated in said step (b).
- The method set forth in claim 1 wherein said transparent coating of said step (d) comprises greater than 90% silica-based material by weight. 10
- 20. The method as set forth in claim 1, substantially as herein described with reference to any embodiment disclosed.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/034,407 | 2011-02-24 | ||
US13/034,407 US10450221B2 (en) | 2011-02-24 | 2011-02-24 | Hybrid sol-gel coated glass containers |
PCT/US2012/026562 WO2012166221A1 (en) | 2011-02-24 | 2012-02-24 | Hybrid sol-gel coated glass containers |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ614041A NZ614041A (en) | 2015-06-26 |
NZ614041B2 true NZ614041B2 (en) | 2015-09-29 |
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