Classifications

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  • B32B3/04—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by at least one layer folded at the edge, e.g. over another layer ; characterised by at least one layer enveloping or enclosing a material
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  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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  • B32B15/00—Layered products comprising a layer of metal
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B7/04—Interconnection of layers
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• • 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
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
  • H02S20/00—Supporting structures for PV modules
  • H02S20/20—Supporting structures directly fixed to an immovable object
  • H02S20/22—Supporting structures directly fixed to an immovable object specially adapted for buildings
  • H02S20/23—Supporting structures directly fixed to an immovable object specially adapted for buildings specially adapted for roof structures
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
  • H02S30/00—Structural details of PV modules other than those related to light conversion
  • H02S30/20—Collapsible or foldable PV modules
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• • 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
  • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
  • Y02B10/00—Integration of renewable energy sources in buildings
  • Y02B10/10—Photovoltaic [PV]
• • 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 light weight, cost effective, photovoltaic modules with excellent fire resistance, durability and wind resistance and a method and system for attaching photovoltaic modules to a roof structure.
• US 6,729,081 describes a light weight photovoltaic module which is self- adhesive and can in principle be glued onto the waterproofing membranes in a cost effective way and without the use of fasteners which perforate the waterproofing membrane and the insulation panels. Gluing operations are however quite delicate on the roof.
• the (self-) adhesive may be further not compatible with the existing waterproofing membrane.
• the plasticizer will migrate into the glue (self- adhesive), resulting in loss of adhesion and brittleness of the PVC sheet.
• waterproofing membrane Another way to obtain a roof with flexible photovoltaic modules attached onto it is to use, as waterproofing membrane, a waterproofing membrane with factory laminated flexible light weight photovoltaic modules on top of it.
• waterproofing membranes are produced by companies like SIT (Solar Integrated) in the USA or by Alwitra in Germany. They consist of several elongated modukes supplied e.g. United Solar Ovonic (Uni-Solar modules) glued in parallel to the polymeric waterproofing membrane. The several Uni-Solar modules are connected in serial under the waterproofing membrane. The connections / soldering are protected (encapsulated) by cast polyamide or cast epoxy or cast polyurethane resin or by similar system.
• SIT Silicon Integrated
• Uni-Solar modules United Solar Ovonic
• the connections / soldering are protected (encapsulated) by cast polyamide or cast epoxy or cast polyurethane resin or by similar system.
• photovoltaic waterproofing membranes and systems are described e.g. in DE 29824045
• a typical composition is a) 50 ⁇ m top layer from fluoro polymers, b) ⁇ 800 ⁇ m layer from ethylene vinyl acetate (EVA) containg a glass fleece or glass fibres or glass beads, c) photovoltaic cells on 120 ⁇ m metal foil, d) 150 ⁇ m EVA layer, e) 100 ⁇ m EVA layer from an EVA with low vinyl acetate (VA) content, f) 50 ⁇ m dielectric film like polyethylene terephthalate (PET), g) 100 ⁇ m EVA layer with low VA content.
• the layers from EVA with low VA content are glued with an polyurethane (PUR) based adhesive to the PET layer.
• PUR polyurethane
• Fire resistance is provided by a combination of the metal foil, the glass fleece or fibres or beads and restriction of EVA layer thickness above the cells to a maximum of 800 ⁇ m.
• the PET extends to the edges of the module which increases the risk for delamination as demonstrated by 4 weeks of immersion of the Uni-Solar module into water at 80 0 C.
• Plastic PV cell(s) may consist of:
• a base plastic film like typically 20 to 250 ⁇ m Kapton ® (polyimide) or PEN (polyethylene naphthalate) or PET (polyethylene terephthalate) film.
• the active layers may be: a-Si cells, tandem cells (a-Si, a-Si or a-Si, microcrystalline silicon, ...), triple junction a-Si/a-SiGe/a-SiGe, Organic Photovoltaic (OPV), CIGS, etc.Oxygen and water vapor Barrier layers may be added under a) and above c) if required.
• Useful barriers are SiOx or AI2O3 layers with hybrid polymers (Ormocers ®) or layers obtained by Atomic Layer Deposition, etc.
• the layers a), b) and c) are interconnected e.g. by lift-up, laser scribing, etching and silk printing of Ag paste processes, ... . They form strips of interconnected cells of typically 5 to 25 mm width. Cost effective encapsulation of such plastic PV Cells remain an issue.
• Waterproofing membranes with low flammability are very well known, like PVC based waterproofing membranes. Such membranes often contain migrating plasticizer and are rigid at low temperature. They are questionnable for integration with plastic PV cells because of the risk of plasticizer migration into the adhesives of the PV module and the stiffness at low temperature. Waterprooving membranes based on thermoplastic polyolefins (TPO) are more adequate but generally have lower fire performances, requiring a high loading of fire retardants. An increase of the concentration of fire retardant in such waterproofing sheet is often not acceptable.
• TPO thermoplastic polyolefins
• the object of the present invention is to provide photovoltaic modules which enable providing of fire safe, durable and cost effective photovoltaic systems.
• the modules and systems according to the invention should have one or more of the following properties:
• the PV module may achieve improved mechanical, impact, scratch and UV stability
• plastic sheet or adhesive layer under the cell is based on a polyolefin, e.g. TPO, and/or a copolymer of ethylene or propylene with vinyl acetate or (meth)acrylate or neutralized acrylic acids (ionomers), the plastic sheet or adhesive layer contains at least 50 g/m 2 , preferably at least 100 g/m 2 halogenated preferably brominated flame retardant and the layers above the plastic sheet or adhesive layer ensure the release of the flame poisoning substances coming from the plastic sheet or adhesive layer, when fire is set to the module.
• a polyolefin e.g. TPO
• the plastic sheet or adhesive layer contains at least 50 g/m 2 , preferably at least 100 g/m 2 halogenated preferably brominated flame retardant and the layers above the plastic sheet or adhesive layer ensure the release of the flame poisoning
• Such flexible photovoltaic modules can be integrated with waterproofing membranes to waterproof the roof (single-layer system) or be used as panels and installed on top of the membrane (double-layer system). In the latter case the panels may be welded or attached with hooks and loops system. In a preferred variant they are attached with profiles on the existing waterproofing membrane.
• the waterproofing membrane is a preferably reinforced flexible TPO waterproofing sheet containing flame retardants.
• the upper layer of the TPO membrane or sheet is free from halogenated flame retardants.
• a transparent front sheet preferably of fluoropolymer film (typically 20 to 200 ⁇ m of ETFE, FEP, PVDF/acrylic ... , containing, if required, stabilizer and possibly long lasting UV absorbers).
• the film is surface treated to improve its adhesion on layer b)
• a transparent adhesive layer e.g. based on EVA, ionomers, silicone, silicone-urea block polymers, tie-layer, tie-layer/transparent TPO/tie-layer, etc.; total thickness 200 to 2000 ⁇ m) or layers.
• the plastic PV cells which may be coated beforehand with barrier layers and/or be surface treated to improve adhesion to layer b) and d).
• An adhesive layer like b)
• a tie-layer or a coextruded layer preferably opaque and if required flame retarded to provide better reaction to fire to the PV TPO waterproofing membrane.
• the TPo of the tie-layer/TPO will improve adhesion with the TPO membrane.
• Suitable lamination machines are vacuum laminators, membrane presses and isobahc double-belt presses, which are well known in the art of lamination.
• Useful EVA films formulation are e.g. described in WO 99/27588.
• a typical lamination temperature for EVA films is 155°C (15 minutes).
• Tie layers are preferably on base of polyolefin copolymers with acrylic acid or grafted with maleic anhydride.
• Useful resins to produce the tie-layers are:
• Primacor 1321 and Primacor 1410 are examples of EAA resins and are supplied by Dow Chemical.
• Orevac C314-2 is an example of PP grafted with maleic anhydride supplied by Arkema.
• Compoline CO/LA and Compoline CO/LL - CO/UL are examples of PO grafted with maleic anhydride and are supplied by Auserpolimeri.
• the resins may be mixed and/or films colaminated to adapt the Rheology and melting temperature of the tie-layers, potentially a multi-layer product.
• copolymers like butyl acrylate may be added during the polymerization step of such resins. This will anyway reduce the melting temperature. Clarifiers are useful mainly for MAH-PP. They are further stabilized to improve durability.
• Other adhesives may be epoxy glues, PUR glues, etc, and will be chosen by the man skilled in the art to obtain good adhesion between the cell substrate film and the TPO waterproofing membrane, which may require a surface treatment to improve adhesion.
• a preferred surface treatment technique to improve adhesion with tie-layers of this invention is reactive sputtering of AI2O3.
• Sputtering is general used to coat the plastic films with the back electrode (aluminium) and to bring the front electrode (a transparent conductive oxide e.g. ITO).
• a transparent conductive oxide e.g. ITO
• Radio Frequence 02 chemical etching of plastic film is usually performed before coating to improve adhesion of the sputtered layer as well known by the man skilled in the art.
• the TPO waterproofing membrane is generally a multi-layer laminated sheet and is reinforced with polyester scrim or fabrics (typically 2 * 2, 1100 dTex) and/or glass fleece (typically 50 g/m 2 ) and may have a polyester backing to attach the sheet to the insulation panels (with glue or hook and loop systems). More rigid reinforcement (heavy glass scrims, like 3 * 3, 1360 dTex, etc.) may be preferred to reduce the deformation of the PV cells during heavy storms.
• the upper layer of the TPO membrane may have a lower melting temperature or higher fluidity than the under layer.
• the total thickness of the sheet is typically between 0,8 mm and 4 mm, preferably between 1 ,2 and 3 mm.
• the transparent TPO layer is preferably a mixture of 30 to 60 % by weight random copolymer of polypropylene and ethylene with 40 to 70 % by weight very low density polyethylene (VLDPE), like Exact 8201 , to reduce the rigidity of the random copolymer and improve impact resistance.
• VLDPE very low density polyethylene
• the transparent TPO layer may be a mixture of: 60 to 80 % ULDPE (like Attane SL 4102 - from Dow) 20 to 40 % Versify 2400 (Dow).
• Migrating and non migrating Hals and UV absorbers like Tinuvin 123, Tinuvin 770, Chimasorb, 2020 Benzophenone and other additives known per se are typically added to these mixtures, and/or clarifiers (to improve transparency).
• Useful TPO compositions to produce the opaque TPO layer, including the TPO in contact with the tie-layer, are based on:
• FPP Flexible PP
• TPV Thermoplastic Vulcanisates with little amount of extension oil like Santoprene, etc.
• LLDPE low density polyethylene
• VLDPE like Exact 0201 or 8201 supplied by Dexplastomers
• OBC Infuse from Dow
• the TPO of the tie-layer/TPO preferably has a higher MFI and/or a lower melting temperature than (at least the lower layer of) the TPO membrane to optimize adhesion.
• These layers further contain pigments, UV light and thermal stabilizers and flame retardants.
• the TPO layers and the TPO core-layers preferably contain acid scavengers (like Hydrotalcite, potentially at the nano-scale for transparency). Anti-acids may be added to the tie-layers if they don't neutralize the reactive functionalities.
• acid scavengers like Hydrotalcite, potentially at the nano-scale for transparency.
• Anti-acids may be added to the tie-layers if they don't neutralize the reactive functionalities.
• these sheets or films and the sheets or films above these sheets or films are selected on the base that they have no or little tendency to char or to form a barrier layer for the release of the flame retardants decomposition products into the flame. Therefore, no glass fleeces should be included or at least are required into the transparent adhesive layer and the layers under the cells should contain layers based on TPO resins and/or polyethylene with adequate comonomers (Vinyl acetate, acrylates, neutralized acrylic acids, ...), containing preferably brominated flame retardants, materials which are known for their low charring tendency. It has been discovered that even a 1 mm thick (> 0,8 mm) EVA transparent adhesive may be used for the front sheet, if enough flame retardant is added to the back layer.
• the adhesive (EVA, "tie-layer/TPO",...) of the back layer (i.e. layer d) may be formulated with halogenated compounds and catalyst (Sb2O3) and will contain at least 50 g/m 2 , preferably at least 100 g/m 2 , of the halogenated, preferably Brominated flame retardant, in order to be able to release enough (Halogene/Bromine) radicals into the flame (to "poison" the flame propagation) when the module catches fire.
• the halogenated flame retardants are preferably brominated flame retardants, preferably in combination with catalysts like Sb2O3 or Sb2O5.
• Other flame retardants may be added like Zink Borates, etc.
• the TPO waterproofing membrane may contain halogen flame retardant in its full thickness.
• the TPO membrane is generally not fully covered by the PV cells and their encapsulation layers, like ETFE (in order to allow for e.g. weldability of the membrane and or replacement of a damaged PV module)
• the addition of halogenated flame retardants in the upper layer of the TPO membrane will lead, due to the TPO photooxidation, to release of halogenated compounds into the environment.
• Halogenated flame retardants are further expensive, especially when UV stability is required. Even with the more stable halogen flame retardants, a decrease of the UV stabilty is expected.
• the invention provides a tie-layer/TPO composition (layer d) to improve the fire performances of PV TPO waterproofing membrane with plastic cells, where the TPO waterproofing membrane contains classical mineral flame retardants like Mg(OH)2 or AI(OH)3 charring flame retardants.
• Such "tie-layer/TPO" layer d) is formulated with halogenated compounds and catalyst (Sb2O3) and will contain at least 50 g/m 2 , preferably at least 100 g/m 2 , of the halogenated, preferably brominated flame retardant.
• tie-layer/TPO composition will allow io increase the thickness of EVA layer b), when superior mechanical properties are required and installation of a PV TPO waterproofing membrane on more critical roof structure (roof structure with lower fire performance).
• a rigid sheet as substrate either a metal sheet or a preferably reinforced plastic sheet.
• the modules are installed e.g. with the help of soft profiles with rigid, preferably with metallic, insert.
• profiles are attached to the roof by one of welding, glueing and mechanically fixing with nails, screws or hook and loop.
• the soft profiles are preferably welded on the waterproofing membrane.
• the rigid substrate of the module is preferably mechanically attached to the profiles with the insert.
• the profiles can also be cup shaped or take the form of strips.
• soft profiles with a rigid (e.g. metallic) insert are welded/glued to a previously installed waterproofing membrane.
• the profiles are preferably equipped with flaps to ease welding, to improve sealing to the waterproofing membrane and to spread wind up-lift forces.
• the rigid, metal or preferably glass reinforced plastic sheet of the photovoltaic modules is attached (e.g. with stainless steel screws or with clips or with glues like MS (modified silicone) polymers) on the upper (rigid) part of the profile or to the insert (then preferably with screws drilling through the plastic profile). It will be recognized that these methods consisting of attaching the rigid metal or glass reinforced plastic sheets with the photovoltaic modules to profiles or cups attached to the waterproofing membrane do not require to perforate the waterproofing membrane.
• Metal sheets suitable as rigid substrate of cells for this invention may be typically:
• the metal sheet may be partly corrugated to improve its flexural rigidity or equipped with ribs or secondary profiles under the sheet, preferably provided with a slight slope (increasing height of the rib/profile).
• Coatings to improve the adhesion of the metal sheets with polymeric films may be PVC-Vac, PUR, Epoxy, Acrylic, etc. based coatings.
• Rigid glass reinforced plastic sheets suitable as rigid substrate are preferably glass reinforced flame retarded PP, preferably corona treated and/or with a primer (e.g. chlorinated polyolefin), or flame retarded epoxy or unsaturated polyester glass fiber composites.
• a primer e.g. chlorinated polyolefin
• flame retarded epoxy or unsaturated polyester glass fiber composites e.g. epoxy or unsaturated polyester glass fiber composites.
• modules with rigid sheet it is further possible to achieve sufficient flame retardancy by using a thick metal sheet as substrate.
• Usual metal substrates of cells/modules are about 120 ⁇ m steel. Using metal sheets of around 1 mm surprisingly provides sufficient flame retardancy even with modules comprising plastic layers of 1 mm that do not contain any added glass nor flame retardants.
• a typical test structure for the assessment of external fire performances is: waterproofing membranelOO mm thick on Rockwool Taurox insulation panels which in turn are attached to a steeldeck "106/250/3" (0,75 mm thick and 106 mm high).
• Figure 1 shows a cross section of the PV waterproofing membrane of the invention
• FIG. 1 shows a multilayer TPO waterproofing membrane (10), typically 1 ,5 mm thick with a reinforcement (10b), typically a polyester scrim or a glass scrim or a polyester/glass fleece combi-mat and with a top layer (10a), typically 0,25 mm thick, which may be without flame retardants.
• the TPO membrane (10) is wider that the PV module: a zone (5) is foreseen for welding purpose (installation, repair, ).
• the TPO membrane contains further heat and UV stabilizers which may migrate into layer d) to avoid any risk of depletion of stabilizers in the layers b) and d) of the module 1 at its edges 1e.
• one laminates On top of the TPO waterproofing membrane, one laminates, e.g. in a classical vacuum laminator or in a membrane press (e.g. WEMHONER VARIOPRESS® - press size 1 ,7 * 6 m 2 ) or in e.g. a double-belt press (semi-continuous process) the following stack of layers: a) A transparent front sheet (1 a) b) A transparent adhesive layer (1 b) c) The plastic PV cells (1c) d) An adhesive layer (1d) [0050] The layer a), b) and d) are wider than c), allowing for edge sealing (1 e) of the plastic PV cell (PET, PEN, ...
• the color of the adhesive layer 1d is preferably white or light grey limiting the temperature at the edges (1e) of the plastic PV cells and the risk of excessive temperature and start of fusion of the e.g. tie-layer/TPO adhesive layer.
• the color of the TPO waterproofing membrane may be white or light grey.
• PV TPO waterproofing membrane or flexible photovoltaic module (110) is assessed for the fire performances. According to ENV 1187 part 1 and 3 or according to the laboratory test described hereafter.
• the test equipment comprises a ZIP firelighter being a pressed block of rough pinewood sawdust and paraffin wax (30*30*17mm), a test box with supporting deck made from metal, and for a draught free test enclosure an exhaust hood to evacuate the smoke production, avoiding draught over the specimen.
• the test specimen is the waterproofing membrane 10 with or without module 1 installed on 5 cm thick rockwool as isolation material, with the following dimension: 150mm in width x 300mm in length.
• the test procedure is as follows:
• Sample A is a polyester reinforced 1 ,5 mm multi-layer TPO waterproofing membrane (10) with halogenated flame retardants according to this invention.
• the composition of the multi-layer membrane is:
• Hifax CA 10 A with usual stabilizers and pigments and with 25 % Saytex BT 93 halogenated flame retardant and 10 % Sb2O3.
• - 600 ⁇ m intermediate layer of Hifax CA 10 A with usual stabilizers and pigments and with 17 % Saytex 8010 halogenated flame retardant and 6 % Sb2O3
• the measured burnt surface after fire testing is 3200 mm 2 .
• Sample B is the same TPO waterproofing membrane (10) with laminated on top of it the following stack of layers simulating a module 1 according to the art: a) 50 ⁇ m ETFE with surface treatment to adhere to b) b) 460 ⁇ m Etimex Vistasolar 486.10 c) a simulated Plastic PV cell (a PET film with an aluminium top coat obtained by PVD; back side treated by atmospheric plasma, as well known by the man skilled in the art) d) 460 ⁇ m Etimex Vistasolar 486.10
• the burnt surface after fire testing is 1700 mm 2 .
• the simulated module 1 comprsing the stack of layers a) to d) does not reduce the fire performance. It is even improved, although the total thickness of non flame retarded film b), c) and d) is 970 ⁇ m.
• Sample C is a conventional polyester reinforced TPO waterproofing membrane (10) on base of Hifax CA 10 A with usual additives and pigments, containing a high loading (45%) of Mg(OH)2 fire retardants.
• This waterproofing membrane needs a polyester reinforcement to compensate for the severe reduction in mechanical properties.
• the burnt surface after fire testing is 2500 mm 2 .
• the burnt part of the sample shows a mineral crust (char). Thus sample C shows better fire performance than sample A).
• Sample D is the same TPO waterproofing membrane as C but with laminated on top of it the same stack of layers as B.
• the burnt surface after fire testing is 5000 mm 2 , ie as expected on base of the teaching of EP 0 769 818 A2, the stack of layers a) to d) with a total thickness of non flame retarded film b), c) and d) of 970 ⁇ m reduces significantly the fire performance of the PV waterproofing membrane (1 +10).
• Sample E is the same TPO waterproofing membrane as C but with laminated on top of it the following stack of layers simulating a module 1 according to the invention: a) 50 ⁇ m ETFE with surface treatment to adhere to b) b) 460 ⁇ m Etimex Vistasolar 486.10 c) a simulated Plastic PV cell (a PET film with an aluminium top coat obtained by PVD; back side treated by N2/NH3 atmospheric plasma, as well known by the man skilled in the art, for adhesion to Orevac C314-2) d) a Tie-Laye ⁇ TPO:
• Tie-layer 100 ⁇ m Orevac C314-2 (MAH grafted PP), II.
• TPO 500 ⁇ m of Hifax CA 60 with usual stabilizers and pigments and containing 25% of Saytex 8010 and 8 % of Sb2O3. The amount of halogenated flame retardant is around 125 g/m 2 .
• the burnt surface after fire testing is 1600 mm 2 .
• the obtainned PV waterproofing membrane (1+10) of this invention shows excellent fire performances.
• Hifax CA 10 A with usual stabilizers and pigments and without fire retardants.
• the burnt surface after fire testing is surprisingly limited to 3300 mm 2 showing that the upper layer of the membrane can be made without flame retardant.
• the obtained PV TPO waterproofing membrane (or module) 1+10 is tested in the laboratory fire test.
• the burnt surface after fire testing is surprisingly limited to 1800 mm 2 .
• Embodiment 1 production of a TPO photovoltaic waterproofing membrane (or flexible module) in one step, with excellent reaction to fire, thick (> 0,8 mm) protective encapsulation layers, and good adhesion between layers.
• a photovoltaic cell is produced according WO 98/13882 and glued onto a plastic film (PEN or PET), cell substrate.
• This PEN or PET film with the active photovoltaic layers is encapsulated in a vacuum laminator according to a well known procedure (release films may be used between the TPO membrane - layer e) - and the heating plate system) and comprises the following layers: a) An ETFE film 50 ⁇ m from DuPont (supplied for PV applications; with classical atmospheric plasma treatment to adhere to EVA) b) Two EVA Vistasolar 486.10 films of +/- 460 ⁇ m c) Several 50 ⁇ m aligned in parallel PEN films supporting the active layers (stripes of interconnected TCO/pin/back electrode) and interconnected. The back side of the PEN film is e.g. treated by reactive sputtering (deposition of a nano-layer of AI2O3) to improve adhesion with the Primacor (EAA) film. d) A coextruded multi-layer of:
• the EAA Primacor layer shows excellent adhesion to PEN films with AI2O3 nano-layer.
• the HALS are not added to the Primacor 1410 or 1321 layer at the extrusion step (compounding stage) but are added to the layers ii) and iii) and migrate from these layers to layer i) during the lamination process and during aging.
• Tinuvin 123 may be preferred above Tinuvin 770.
• Other NOR-HALS less reactive with acids groups
• Acid scavengers (Hydrotalcite) are only added to layers ii) and iii).
• the TPO sheet may contain a reserve of e.g. HALS stabilizers of UV absorbers, which will migrate into layers a), b) and d).
• the top layer of the TPO sheet may contain softening resins like Exact 0201 (lower melting temperature), Hifax CA 60 (lower viscosity) and/or Versify 2400.00 (lower melting temperature and viscosity), to optimize adhesion with layer d), part iii).
• the layers a), b), d) are longer and wider (2 cm on each sides) than the layer c) to seal the edges of the cells efficiently (lower risk of delamination).
• a velour (a Loop fleece) or a hook may be laminated or glued at the back side of the photovoltaic TPO waterproofing membrane (application as flexible module).
• the flexible modules (the photovoltaic TPO membrane) may be installed in big panels with sealed perimeter and connected to venting profiles to limit water accumulation under the modules.
• the flexibles modules may be installed as mono-layer (as photovoltaic integrated waterproofing membrane; preferably on a roof substrate including an enfficient water vapor barrier) or welded on an existing TPO membrane (double-layer system).
• Embodiment 2 PV TPO waterproofing membrane (flexible module) with Broof (t3) 5° and Broof (t1) 45° performance
• the flexible photovoltaic module of Embodiment 1 is adapted to have as layer b) one EVA Vistasolar 486.10 film of +/- 460 ⁇ m, instead of 2 films.
• Layer d) is preferably the same as for embodiment 1) or may be instead an EVA film Vistasolar 486.10 film of +/- 200 ⁇ m with 30 % Saytex 8010 and 8 % Sb2O3. Such film is not preferred as it is difficult to produce.
• the structure of embodiment 1 , with adapted module of embodiment 1 passes the Broof (t1) 45° and Broof (t3) 5° requirements with success.
• the present flexible PV modules/membranes are believed to also meet the Broof (t1) 45° and Broof (t3) 5° requirements on more difficult structure (mono-layer installation on Polystyrene, on foamglass in bitumen bath, etc).
• the membrane may include a glass fleece (innerlayer of as backing).
• compositions and thicknesses of the several layers of the photovoltaic waterproofing membrane (110) may be varied to achieve most of the required fire classes on common subtrates (insulation boards, etc.).
• Embodiment 3 production of a TPO photovoltaic waterproofing membrane (or flexible module) in one step in a semi-continuous process
• a double-belt press with Teflon ® release treatment of the belts
• one laminates press temperature around 185°C
• the following layers a) a 100 ⁇ m ETFE film plasma treated (atmospheric plasma treated - N2/NH3 atmosphere) to adhere with b) a coextruded film (brushed surface) of: i) 25 ⁇ m of Orevac C314-2 with usual stabilisers (not reacting during the extrusion step with the MAH functionalities and allowing transparency) ii) 300 ⁇ m of a transparent TPO composition like e.g.
• the plastic cells are fed with interruptions to the double-belt laminator, i.e. in the form of long rectangles (typically 6 m long; if required several elements in parallel). For this purpose, they are laid by robots with sucking device in parallel, serial connected, on the (metallic) preparation zone of the double-belt press (equipped with synchronized electrostatic attraction device), on the complex d), and. Typically 10 cm without cell are foreseen in the length between the parallel formats of plastic PV cells to allow cutting and edge sealing.
• the layers a) and b) are preferably already laminated during an adequate production process, e.g. by extrusion coating of layer b) on layer a).
• the films a/b) and d) are fed continuously into the double-belt press. They are wider than the plastic cells to seal the edges.
• the final laminate is cut into formats. Electrical connections (perforation - contacts - soldering) are done off-line.
• the several layers may be treated before lamination by Corona or by Atmospheric or Low pressure Plasma and Atmospheric plasma deposition (aerosol assisted, ...), and/or polymerization, or by atomic layer deposition, or sputtering, ... to improve adhesion between layers and improve barrier properties, as will be recognized by the person normally skilled in the art (Plato Plasma Technology and surface, Vito, AcXys, Dow Corning Plasma Solution, AS Coating Star atmospheric plasma, Beneq Oy ).
• a fleece (velour) or hook may be further glued or laminated to the back side of the encapsulated module, i.e. on the backside of the Alkortop 35086 TPO sheet.
• Embodiment 4 Effect of water
• a piece of a Uni-Solar module PVL-series, model PVL 128 has been aged during 3 months in water at 60 0 C and 4 weeks in water 8O 0 C and tested for delamination.
• the Uni-Solar module shows delamination at the level of the inferior PET film (PUR adhesive hydrolysed).
• the module of embodiment 1 with sealed edges (2 cm), doesn't suffer from delamination, as the adhesion between layer b) and d) is excellent (not senitive to hydrolysis).
• Embodiment 5 big size module
• a glass reinforced polypropylene sheet (preferably corrugated; containing usual additives), with a 50 ⁇ m top-layer based on Orevac C314-2 with usual additives and pigments.
• the surface of the preparation table is adapted to cope with the corrugations in the PP sheet.
• the PP sheet improves the flexural properties of the PV module.
• an adhesive layer (to be chosen by the man skilled in the art; a primacor 1410 based film may be useful)
• the plastic "cell” film e.g. 50 ⁇ m Kapton or PEN or PET film
• Layer 2 may be e.g. a PDMS-UREA based film or a stack of layers or a coextruded film of following layers: i) 50 ⁇ m Orevac C314-2 with usual additives (i.e. no reaction with the MAH functionalities) ii) 500 ⁇ m of a Transparent TPO foil (mixture Random polypropylene-ethylene copolymer in mixture with VLDPE like VLDPE Exact 8201 : 60/40 ratio) with migrating and non migrating Hals and UV absorbers, like Tinuvin 770 and 123, Chimassorb 2020 and Benzophenone, with clarifiers to improve transparency and possibly anti-acids (nano-scale hydrotalcite). iii) 50 ⁇ m Orevac C314-2 with usual additives (i.e. no reaction with the
• Layer 4 has the following advantages: cost effective use of raw material, includes a reserve of stabilizer (edge of the modules), is easily flame retarded, and facilitates a reuse of the aluminium substrate (2).
• the low melt temperature of Primacor 1410 allows for ease of pealing from the aluminium substrate (2) at e.g. 125 0 C.
• OREVAC C314-2 may be used as component of the tie-layer.
• Embodiment 6 attachment with profiles Embodiment 6.1 :
• modules 1 For the production of modules 1 according to this invention two photovoltaic cells (2 * 0,4 m * 5,4 m) are produced and transferred onto two plastic films (PEN), as described in WO 98/13882.
• the PEN film is called the (plastic) cell substrate.
• the two PEN films (0,4 m *5,4 m), with their photovoltaic active layers are encapsulated in a vacuum laminator according to a procedure well known in the art.
• the encapsulating layers are 5 cm wider and longer at each edge than the two PEN films and cells. Electrical connections are done as known per se.
• the encapsulated module 1 comprises the following stack of layers: a) An ETFE film 50 ⁇ m from DuPont (with surface treatment to adhere to EVA) b) Two EVA Vistasolar 486.10 films of +/- 460 ⁇ m c) A 50 ⁇ m PEN film supporting the active layers (e.g.
• TCO/pin/back electrode/adhesion layer/adhesive to PEN with appropriate surface treatment on both sides like deposition of a nano-scale AI2O3 layer (reative sputtering)
• An EVA Vistasolar 486.10 film (thickness +/- 460 ⁇ m) each layer containing anti-oxidants (0,3 % Irganox B225 form Ciba), HALS (0,3 % Tinuvin 770 and 0,3 % Chimassorb 944), pigments (5 % TiO 2 Kronos 2220), 24 % Saytex 8010 and 8 % of Sb 2 O 3 .
• a 1 ,2 mm TPO laminated steel sheet as supplied by Renolit Belgium N.V.
• tie-layer/TPO/tie-layer is replaced by tie-layer/TPO/tie-layer and e) is a 1 mm thick aluminium plate (showing excellent corrosion resistance).
• Example of appropriate tie-layer/TPO/tie-layer is a coextruded film of "50 ⁇ EAA Primacor 1410/360 ⁇ m VLDPE Exact 0203/50 ⁇ m EAA Primacor 1410", containing antioxidants (0,3 % Irganox B225 form Ciba), HALS (0,3 % Tinuvin 770 and 0,3 % Chimassorb 944), UV absorbers (0,3 % Chimassorb 81 from Ciba), ), 24 % Saytex 8010 and 8 % of Sb2O3 and and anti-acids. The reactive additives are only added in the VLDPE TPO layer.
• a photovoltaic cell (0,8 m * 5,4 m) is produced according WO 98/13882 and transferred onto a plastic film (PEN), cell substrate.
• PEN plastic film
• This PEN film with the active photovoltaic layers is encapsulated in a vacuum laminator according to a procedure well known in the art.
• the encapsulated module 2 is produced by vacuum lamination as known per se and comprises the following stack of layers: a) An ETFE film 50 ⁇ m from DuPont (with surface treatment to adhere to EVA) b) Two EVA Vistasolar 486.10 films of +/- 460 ⁇ m c) A 50 ⁇ m PEN film (normally supporting the active layers (TCO/pin/back electrode/adhesion layer/adhesive to PEN)), surface treated for adhesion to b) and d). d) an EVA Vistasolar 486.10 film of +/- 460 ⁇ m.
• Embodiment 6.3
• Modules 1 to 3 each without their photoactive layers are tested according to ENV 1187/1.
• the modules 1 and 3 are mounted on profiles with a venting space between the rigid sheet and the waterproofing membrane. These modules pass the ENV 1187/1 requirement at 15° and 45°.
• the quality of the waterproofing membrane and substrate is not critical as the thick metal sheet acts as fire barrier.
• the module 2 is installed on mineral wool insulation boards as usual in the art. These module fails in the test ENV 1187/1 (15°).
• modules M1 to M3 are produced (see table), without the photoelectric layers, and are placed in a frame (30 * 30 cm 2 ) at an angle of 45° against the horizon and submitted during 2 minutes to a gaz burner flame (760 0 C +/- 40 0 C).
• the upper side of the modules i.e. the side normally exposed to the sun
• the time until the modules are estinguished (self-estinguishing time) and the damaged surface area are observed.
• the module constructions have been assessed versus a well-known construction equivalent to the Kalzip ® AluPlusSolar product (M4) approved for pitched roofs with slopes up to 60°.
• M4 Kalzip ® AluPlusSolar product
• Peel and Stick module consisting of 50 ⁇ m ETFE / 500 ⁇ m transparent EVA with glass innerlayers / 120 ⁇ m stainlesss steal foil with active layers / back sheet (EVA/PET/EVA) / EPR adhesive.
• the module M1 behaves at the same level as the reference module M4 (used today with success for metal roofs with slope up to 60°). This is surprising as the thickness of the EVA/PEN/EVA organic films above the metal sheet is more than 800 ⁇ m. This result is achieved thanks to the heat sink effect and thermal conductivity of the thick metal foil.
• the module M3 behaves even better than the reference module M4, although the thickness of EVA above the cell is more than 800 ⁇ m. This result is achieved thanks to the high concentration - g/m 2 - of halogenated flame retardants in the tie-layer/TPO/tie-layer.
• Such modules 1 , 3 and 4 mounted on profiles, fulfill the requirements of the ENV 1187/1 , even at 45° slope.
• the modules M2 are self-estinguishing and will fulfill the requirements of the ENV 1187/1 (15° slope).

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