WO2011068597A1 - Use of calcium oxide as a water scavenger in solar module applications - Google Patents
Use of calcium oxide as a water scavenger in solar module applications Download PDFInfo
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- WO2011068597A1 WO2011068597A1 PCT/US2010/052726 US2010052726W WO2011068597A1 WO 2011068597 A1 WO2011068597 A1 WO 2011068597A1 US 2010052726 W US2010052726 W US 2010052726W WO 2011068597 A1 WO2011068597 A1 WO 2011068597A1
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 65
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002516 radical scavenger Substances 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 136
- 239000000565 sealant Substances 0.000 claims abstract description 88
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 39
- -1 polyethylene Polymers 0.000 claims description 23
- 230000005540 biological transmission Effects 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 229920006132 styrene block copolymer Polymers 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 229920002367 Polyisobutene Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229920013640 amorphous poly alpha olefin Polymers 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 4
- 150000001565 benzotriazoles Chemical class 0.000 claims description 4
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 235000010216 calcium carbonate Nutrition 0.000 claims description 4
- 235000012241 calcium silicate Nutrition 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 235000012243 magnesium silicates Nutrition 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 238000013008 moisture curing Methods 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229920001083 polybutene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 235000010215 titanium dioxide Nutrition 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims 1
- 239000011164 primary particle Substances 0.000 claims 1
- 239000003707 silyl modified polymer Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000000518 rheometry Methods 0.000 abstract description 2
- 239000002274 desiccant Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12044—OLED
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to use of calcium oxide as a water scavenger in edge sealant formulations for solar modules.
- Photovoltaic solar panels or modules generally include a photovoltaic device that is laminated and/or sandwiched between a plurality of layers.
- the majority of photovoltaic devices are rigid wafer-based crystalline silicon cells or thin film modules having cadmium telluride (Cd-Te), amorphous silicon, or copper-indium-diselenide (CulnSe 2 ) deposited on a substrate.
- the thin film solar modules may be either rigid or flexible. Flexible thin film cells and modules are created by depositing the photoactive layer and any other necessary substance on a flexible substrate. Photovoltaic devices are connected electrically to one another and to other solar panels or modules to form an integrated system.
- edge sealants have the property of having a low rate of moisture vapor transmission, or MVT.
- An additional method for reducing the rate of moisture transmission is through use of a desiccant material.
- a desiccant material is molecular sieves.
- Molecular sieves are comprised of materials containing tiny pores of a precise and uniform size that are used as an adsorbent. Molecules of water are small enough to pass through the pores and are adsorbed within the molecular sieve material.
- a typical molecular sieve can adsorb water up to 22% of its own weight.
- molecular sieves include, but are not limited to, aluminosilicate minerals, clays, porous glasses, microporous charcoals, zeolites, active carbons, or synthetic compounds that have open structures through which small molecules, such as water can diffuse.
- water scavengers Another class of materials that can remove moisture from surroundings include water scavengers. Unlike standard desiccants, water scavengers react with water in a manner that is not reversible under the conditions that the product experiences in its normal lifetime. However, water scavengers are caustic compounds that are corrosive. Accordingly, water scavengers have not been used in solar module applications due to the caustic nature of the compound. Therefore, there is a need in the art for a sealant in solar modules that incorporates a water scavenger that does not release water and that does not corrode the sealant over the lifetime of the solar module and that provides improved water absorption over desiccant materials.
- the present invention provides a photovoltaic solar module with an edge seal.
- the edge sealant incorporates calcium oxide as a water scavenger in place of a desiccant, such as a molecular sieve.
- the calcium oxide within the edge sealant has improved water absorption characteristics over conventional desiccants.
- the calcium oxide does not corrode or reduce the effectiveness of the edge sealant over time.
- a sealant composition includes an olefinic polymer, a silane modified polyolefin, at least one filler, a carbon black, a calcium oxide included in an amount greater than about 2.5% by weight of the total composition, and at least one aging resistor.
- the sealant composition further includes a molecular sieve in an amount greater than about 2.5% by weight of the total composition.
- the sealant composition exhibits a water break through time of greater than 5 hr and a steady state moisture vapor transmission rate of less than 40 g.m2/day for a 0.030 inch thick sample of the sealant composition tested at 85 C and 100% relative humidity.
- the sealant composition exhibits a water break through time of greater than 10 hr and a steady state moisture vapor transmission rate of less than 30 g.m2/day for a 0.030 inch thick sample of the sealant composition tested at 85 C and 100% relative humidity.
- a combination of the calcium oxide and the molecular sieve is included in an amount greater than about 10% by weight and the sealant composition exhibits a water break through time of greater than 5 hr and a steady state moisture vapor transmission rate of less than 40 g.m2/day for a 0.030 inch thick sample of the sealant composition tested at 85 C and 100% relative humidity.
- a combination of the calcium oxide and the molecular sieve is included in an amount greater than about 10% by weight and the sealant composition exhibits a water break through time of greater than 10 hr and steady state moisture vapor transmission rate of less than 30 g.m2/day for a 0.030 inch thick sample of the sealant composition tested at 85 C and 100% relative humidity.
- the sealant composition further includes at least one of a clay, a calcium sulfate, and a silica gel.
- the sealant composition exhibits exhibit a water break through time of greater than 5 hr and a steady state moisture vapor transmission rate of less than 40 g.m2/day for a 0.030 inch thick sample of the sealant composition tested at 85 C and 100% relative humidity.
- the sealant composition further includes at least one of a clay, a calcium sulfate, and a silica gel.
- a combination of the calcium oxide, the molecular sieve, and the sealant composition exhibits a water break through time of greater than 10 hr and steady state moisture vapor transmission rate of less than 30 g.m2/day for a 0.030 inch thick sample of the sealant composition tested at 85 C and 100% relative humidity.
- a combination of the calcium oxide and the molecular sieve is included in an amount from about 10% to about 40% by weight of the total composition.
- a combination of the calcium oxide and the molecular sieve is included in an amount from about 20% to about 40% by weight of the total composition.
- combination of the calcium oxide and the molecular sieve is included in an amount from about 25% to about 35% by weight of the total composition.
- the olefinic polymer is included in an amount from about 30% to about 60% by weight of the total composition
- the silane modified polyolefin is included in an amount from about 10% to about 25% by weight of the total composition
- the carbon black is included in an amount from about 2% to about 20% by weight of the total composition
- the filler is included in an amount from about 20% to about 60% by weight of the total composition
- the calcium oxide is included in an amount from about 2.5% to about 25% by weight of the total composition
- the aging resistor is included in an amount from 0% to about 2% by weight of the total composition.
- the olefinic polymer is included in an amount from about 20% to about 40% by weight of the total composition
- the silane modified polyolefin is included in an amount from about 10% to about 20% by weight of the total composition
- a combination of the carbon black and the filler is included in an amount from about 30% to about 40% by weight of the total composition
- the calcium oxide is included in an amount from about 10% to about 30% by weight of the total composition
- the aging resistor is included in an amount from 0% to about 2% by weight of the total composition.
- the sealant composition further includes a molecular sieve included in an amount from about 2.5% to about 25% by weight of the total composition.
- the sealant composition exhibits less than about 15 gm/((m A 2) * day) moisture vapor transmission rate at steady state for a 0.030 inch thick sample of the sealant composition tested at 85 C and 100% relative humidity.
- the sealant includes balanced properties that keep swelling of the sealant to a predetermined amount upon reaction of the calcium oxide with water.
- the calcium oxide does not substantially react with or corrode other components of the sealant.
- the olefinic polymer includes at least one of a polyethylene, a polypropylene, a polybutene, a polyisobutene, a butyl rubber (polyisobutene-isoprene), styrene block copolymers, and modified forms of styrene block copolymers, wherein the olefinic polymers have a Number average molecular weight of 100 - 700, 000 Da.
- the silane modified polyolefins include at least one of an amorphous poly alpha olefin, a silane grafted PE, a moisture curing catalyst, an alkoxy silane, and an amino silane.
- the fillers include at least one of a ground chalk, a precipitated chalk, a silicate, a silicon oxide, CaCO3, Ca(OH)2, and titanium dioxide.
- the silicate is selected from the group comprising talc, kaolin, mica, silicon oxide, silicas, and calcium or magnesium silicates.
- the aging resistors include at least one of hindered phenols, hindered amines, thioethers, mercapto compounds, phosphorous esters, benzotriazoles, benzophenones, and antizonants.
- FIG. 1 is a top view of an embodiment of a solar module having a border seal composition according to the principles of the present invention
- FIG. 2 is a cross-sectional view of a portion of an embodiment of a solar module having a border seal composition according to the present invention
- FIG. 3 is a graph of moisture vapor transmission rate with time of a sealant composition that includes calcium oxide at 20% by weight
- FIG. 4 is a graph of moisture vapor transmission rate with time of a sealant composition that includes type 3A molecular sieves at 20% by weight.
- an exemplary solar module employing a sealant composition according to the principles of the present invention is generally indicated by reference number 10.
- the solar module 10 may take various forms without departing from the scope of the present invention and generally includes at least one photovoltaic cell 12 located within a chamber 13 defined by a first substrate 14 and a second substrate 16.
- the solar module 10, however, may be a thermoelectric solar module, hybrid solar module, or other light collecting assembly without departing from the scope of the present invention. While a plurality of photovoltaic cells 12 are illustrated, it should be appreciated that any number of photovoltaic cells 12 may be employed.
- the photovoltaic cell 12 is operable to generate an electrical current from sunlight striking the photovoltaic cell 12. Accordingly, the photovoltaic cell 12 may take various forms without departing from the scope of the present invention.
- the photovoltaic cell 12 may be a thin film cell with a layer of cadmium telluride (Cd-Te), amorphous silicon, or copper- indium-diselenide (CulnSe 2 ).
- the photovoltaic cell 12 may be a crystalline silicon wafer embedded in a laminating film or gallium arsenide deposited on germanium or another substrate.
- photovoltaic devices 12 that may be employed include organic semiconductor cells having conjugate polymers as well as dye-sensitized metal oxides including wet metal oxides and solid metal oxides.
- the photovoltaic device 12 may be either rigid or flexible.
- the photovoltaic cells 12 are linked either in series or in parallel or combinations thereof.
- the current produced by the photovoltaic cells 12 are communicated via bus bars or other conductive materials or layers to wires or lead lines 15 that exit the solar module 10.
- the lead lines 15 communicate with a junction box 17 in order to distribute the electrical current generated by the solar module 10 to a power circuit.
- the first substrate 14, or front panel is formed from a material operable to allow wavelengths of sunlight to pass therethrough.
- the first substrate 14 is glass or a plastic film such as polyvinylflouride.
- the second substrate 16, or back panel is selected to provide additional strength to the solar module 10.
- the second substrate 16 is a plastic such as fluorinated ethylene-propylene copolymer (FEP), poly(ethylene-co- tetrafluoroethylene) (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), poly(tetrafluoroethylene) (PTFE) and combinations of these with other polymeric materials.
- FEP fluorinated ethylene-propylene copolymer
- ETFE poly(ethylene-co- tetrafluoroethylene)
- PVDF polyvinylidene fluoride
- PVDF polyvinyl fluoride
- PTFE poly(tetrafluoroethylene)
- the photovoltaic cells 12 are encapsulated by a laminate layer 19 that is preferably a cross-linkable ethyl vinyl acetate (EVA).
- EVA cross-linkable ethyl vinyl acetate
- the laminate layer 19 is used to partially encapsulate the photovoltaic device 12 to protect the photovoltaic device 12 from contamination and from the environment.
- a border or edge seal 18 is located near an edge of the solar module 10 between the first substrate 14 and the second substrate 16.
- the border seal 18 may have various widths.
- a second border seal (not shown) may also be included.
- the second border seal may be comprised of, for example, for example, a silicone, a MS polymer, a Silanated Polyurethane, a butyl, or a polysulfide.
- the border seal 18 is operable to seal the laminate layer 19 and photovoltaic devices 12.
- the border seal 18 must have sufficient weatherability to withstand exposure to outside environments including prolonged ultra-violet radiation exposure, have low moisture vapor transmission (MVT), and have low conductivity.
- the border seal 20 is comprised of a sealant composition having the unique characteristics of high weatherability with low conductivity and MVT, as well as the ability to permanently absorb and react with water during normal operating conditions of the solar module 10.
- the sealant composition of the border seal 18 includes an unsaturated reactive polyolefin, an olefinic polymer, a silane modified polyolefin, inert fillers, calcium oxide, and aging resistors. These components are balanced to produce a sealant having desirable sealing characteristics, high weatherability, desired rheology, low conductivity, and good water absorption.
- Calcium oxide reacts with water to form calcium hydroxide, according to the equation:
- the calcium oxide adsorbs a much greater amount of water vapor at a very low relative humidity than other materials. Calcium oxide is most effective where a low critical relative humidity is necessary, and where there is a high concentration of water vapor present. Calcium oxide removes water from the environment very slowly, often taking days to reach its maximum capacity. In addition, calcium oxide has a low water capacity at room temperature and humidity. As the calcium oxide adsorbs moisture, it swells. Accordingly, the sealant composition must have balanced properties to account for any swelling during use. The properties are balanced by, for example, adjusting the amount of calcium oxide in the composition.
- the density of calcium oxide is 3.25-3.38 g/mL, and the density of calcium hydroxide is 2.24 g/mL, according to the CRC Handbook of Chemistry and Physics, 60 th edition. Therefore, theoretically, there is a limit as to how much calcium oxide may be incorporated into an edge sealant formulation. However, no difficulties have been observed over the incorporation range tested.
- FIGS. 3 and 4 show the break through times associated with use of calcium oxide over molecular sieves. Break through time is the amount of time it takes to reach 5% of the steady state MVTR value after the initial 90 hour predrying phase is complete. As seen by FIG. 3, the breakthrough time for the composition containing calcium oxide is about 9 hours and the break through time for the composition containing the molecular sieve shown in FIG. 4 is about 20 hours.
- Calcium oxide is corrosive and can theoretically react with other components within an edge seal and within a solar module. However, within edge seals in solar modules with the present composition, no corrosive effects manifest. [0046] In addition, calcium oxide can be combined with molecular sieves to further increase the moisture trapping ability of the edge sealant.
- the olefinic polymers may include, for example, polyethylene, polypropylene, polybutene, polyisobutene, butyl rubber (polyisobutene-isoprene), styrene block copolymers, and modified forms of styrene block copolymers.
- the olefinic polymers have number average molecular weights of 100 - 700,000 Da, and preferably have number average molecular weights of 100 - 300,000 Da.
- the silanes may include, for example, DFDA-5451 NT (silane grafted PE available from Dow Chemical of Midland, Ml), DFDA-5481 NT (moisture curing catalyst from Dow Chemical of Midland, Ml), amorphous poly alpha olefins (such as but not restricted to VESTOPLAST 206 and VESTOPLAST 2412 available from Evonik Degussa GmbH of Marl, Germany), alkoxy silanes, and amino silanes.
- DFDA-5451 NT silane grafted PE available from Dow Chemical of Midland, Ml
- DFDA-5481 NT moisture curing catalyst from Dow Chemical of Midland, Ml
- amorphous poly alpha olefins such as but not restricted to VESTOPLAST 206 and VESTOPLAST 2412 available from Evonik Degussa GmbH of Marl, Germany
- alkoxy silanes such as but not restricted to VESTOPLAST 206 and VESTOPLAST 2412 available
- the inert fillers may include, for example, ground and precipitated chalks, silicates, silicon oxides, C black, CaCO3, Ca(OH)2, and titanium dioxide.
- the silicates may include, for example, talc, kaolin, mica, silicon oxide, silicas, and calcium or magnesium silicates.
- the aging resistors may include, for example, hindered phenols, hindered amines, thioethers, mercapto compounds, phosphorous esters, benzotriazoles, benzophenones, and antizonants.
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- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- Sealing Material Composition (AREA)
- Photovoltaic Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/501,923 US20120192946A1 (en) | 2007-09-20 | 2010-10-14 | Use of calcium oxide as a water scavenger in solar applications |
EP10834903A EP2489070A1 (en) | 2009-10-14 | 2010-10-14 | Use of calcium oxide as a water scavenger in solar module applications |
CN2010800568414A CN102742006A (en) | 2009-10-14 | 2010-10-14 | Use of calcium oxide as a water scavenger in solar module applications |
JP2012534369A JP2013509453A (en) | 2009-10-14 | 2010-10-14 | Use of calcium oxide as a moisture scavenger in solar module applications |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25152709P | 2009-10-14 | 2009-10-14 | |
US61/251,527 | 2009-10-14 | ||
US67925010A | 2010-03-19 | 2010-03-19 | |
US12/679,250 | 2010-03-19 |
Publications (1)
Publication Number | Publication Date |
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WO2011068597A1 true WO2011068597A1 (en) | 2011-06-09 |
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ID=44115225
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PCT/US2010/052726 WO2011068597A1 (en) | 2007-09-20 | 2010-10-14 | Use of calcium oxide as a water scavenger in solar module applications |
Country Status (5)
Country | Link |
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EP (1) | EP2489070A1 (en) |
JP (1) | JP2013509453A (en) |
KR (1) | KR20120095902A (en) |
CN (1) | CN102742006A (en) |
WO (1) | WO2011068597A1 (en) |
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CN102779904A (en) * | 2012-08-17 | 2012-11-14 | 常州天合光能有限公司 | Method for preventing adverse polarization and black line phenomena of crystalline-silicon solar module |
KR101251853B1 (en) | 2011-11-21 | 2013-04-10 | 엘지이노텍 주식회사 | Solar cell module and method of fabricating the same |
JP2013119583A (en) * | 2011-12-07 | 2013-06-17 | Mitsubishi Chemicals Corp | Silane-grafted polyolefin, and silane-crosslinked polyolefin resin |
JP2013213122A (en) * | 2012-03-31 | 2013-10-17 | Aica Kogyo Co Ltd | Hot melt sealing composition |
JP2014019837A (en) * | 2012-07-23 | 2014-02-03 | Aica Kogyo Co Ltd | Hot-melt sealing composition |
KR101382774B1 (en) * | 2011-11-16 | 2014-04-09 | 엘지이노텍 주식회사 | Solar cell module |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5855972A (en) * | 1993-11-12 | 1999-01-05 | Kaeding; Konrad H | Sealant strip useful in the fabrication of insulated glass and compositions and methods relating thereto |
US20030162882A1 (en) * | 2000-03-28 | 2003-08-28 | Stefan Grimm | Reactive hot-melt-type adhesive granulate for insulating glass |
WO2008041768A1 (en) * | 2006-10-05 | 2008-04-10 | Kaneka Corporation | Curable composition |
US20090234073A1 (en) * | 2005-05-11 | 2009-09-17 | Mitsui Chemicals, Inc. | Alpha-Olefin/non-conjugated cyclic polyene copolymers, production processes thereof, and crosslinkable compositions including the copolymer |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3016A (en) * | 1843-03-21 | Burning bricks | ||
DE19821355B4 (en) * | 1998-05-13 | 2005-02-24 | Chemetall Gmbh | Use of a sealant for the production of multi-pane insulating glass |
RU2448127C2 (en) * | 2006-07-03 | 2012-04-20 | Дау Корнинг Корпорейшн | Chemically curable all-in-one warm edge spacer and seal |
DE102007045104A1 (en) * | 2007-09-20 | 2009-04-02 | Kömmerling Chemische Fabrik GmbH | Sealant for the production of double or multi-pane insulating glass or solar modules |
-
2010
- 2010-10-14 WO PCT/US2010/052726 patent/WO2011068597A1/en active Application Filing
- 2010-10-14 CN CN2010800568414A patent/CN102742006A/en active Pending
- 2010-10-14 EP EP10834903A patent/EP2489070A1/en not_active Withdrawn
- 2010-10-14 JP JP2012534369A patent/JP2013509453A/en active Pending
- 2010-10-14 KR KR1020127012107A patent/KR20120095902A/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5855972A (en) * | 1993-11-12 | 1999-01-05 | Kaeding; Konrad H | Sealant strip useful in the fabrication of insulated glass and compositions and methods relating thereto |
US20030162882A1 (en) * | 2000-03-28 | 2003-08-28 | Stefan Grimm | Reactive hot-melt-type adhesive granulate for insulating glass |
US20090234073A1 (en) * | 2005-05-11 | 2009-09-17 | Mitsui Chemicals, Inc. | Alpha-Olefin/non-conjugated cyclic polyene copolymers, production processes thereof, and crosslinkable compositions including the copolymer |
WO2008041768A1 (en) * | 2006-10-05 | 2008-04-10 | Kaneka Corporation | Curable composition |
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KR101251853B1 (en) | 2011-11-21 | 2013-04-10 | 엘지이노텍 주식회사 | Solar cell module and method of fabricating the same |
JP2013119583A (en) * | 2011-12-07 | 2013-06-17 | Mitsubishi Chemicals Corp | Silane-grafted polyolefin, and silane-crosslinked polyolefin resin |
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JP2014019837A (en) * | 2012-07-23 | 2014-02-03 | Aica Kogyo Co Ltd | Hot-melt sealing composition |
CN102779904A (en) * | 2012-08-17 | 2012-11-14 | 常州天合光能有限公司 | Method for preventing adverse polarization and black line phenomena of crystalline-silicon solar module |
WO2014147106A3 (en) * | 2013-03-19 | 2014-12-31 | Dinunzio Giuseppe | Thermoplastic polymer formulation containing recycled polyolefins and method of preparing |
CN105555852A (en) * | 2013-03-19 | 2016-05-04 | Igap股份公司 | Thermoplastic polymer formulation containing recycled polyolefins and method of preparing |
FR3019180A1 (en) * | 2014-03-26 | 2015-10-02 | Saint Gobain | THERMOPLASTIC ELASTOMER COMPOSITION FOR ENCAPSULATION |
WO2015145021A1 (en) * | 2014-03-26 | 2015-10-01 | Saint-Gobain Glass France | Thermoplastic elastomer composition for encapsulation |
EA032567B1 (en) * | 2014-03-26 | 2019-06-28 | Сэн-Гобэн Гласс Франс | Thermoplastic elastomer composition for overmolding |
US10669415B2 (en) | 2014-03-26 | 2020-06-02 | Saint-Gobain Glass France | Thermoplastic elastomer composition for encapsulation |
WO2016070087A1 (en) * | 2014-10-30 | 2016-05-06 | Dow Global Technologies Llc | Pv module with film layer comprising micronized silica gel |
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Also Published As
Publication number | Publication date |
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EP2489070A1 (en) | 2012-08-22 |
JP2013509453A (en) | 2013-03-14 |
KR20120095902A (en) | 2012-08-29 |
CN102742006A (en) | 2012-10-17 |
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