US20130017368A1 - Asphaltic membrane with mullite-containing granules - Google Patents
Asphaltic membrane with mullite-containing granules Download PDFInfo
- Publication number
- US20130017368A1 US20130017368A1 US13/538,288 US201213538288A US2013017368A1 US 20130017368 A1 US20130017368 A1 US 20130017368A1 US 201213538288 A US201213538288 A US 201213538288A US 2013017368 A1 US2013017368 A1 US 2013017368A1
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- US
- United States
- Prior art keywords
- mullite
- granules
- article
- substrate
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000008187 granular material Substances 0.000 title claims abstract description 148
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims description 122
- 229910052863 mullite Inorganic materials 0.000 title claims description 122
- 239000012528 membrane Substances 0.000 title claims description 29
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 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 abstract description 38
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 36
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 238000001354 calcination Methods 0.000 claims description 26
- 238000002441 X-ray diffraction Methods 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims 4
- 239000002245 particle Substances 0.000 description 20
- 238000002310 reflectometry Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 description 10
- 239000010426 asphalt Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000002459 porosimetry Methods 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011120 plywood Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001812 pycnometry Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000907788 Cordia gerascanthus Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910004291 O3.2SiO2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021343 molybdenum disilicide Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
- E04D1/12—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface
- E04D1/20—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface of plastics; of asphalt; of fibrous materials
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/08—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of other materials
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/12—Roof covering by making use of flexible material, e.g. supplied in roll form specially modified, e.g. perforated, with granulated surface, with attached pads
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B2001/7691—Heat reflecting layers or coatings
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
- E04D2001/005—Roof covering by making use of tiles, slates, shingles, or other small roofing elements the roofing elements having a granulated surface
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/24—Structural elements or technologies for improving thermal insulation
- Y02A30/254—Roof garden systems; Roof coverings with high solar reflectance
-
- 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
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/24413—Metal or metal compound
Definitions
- Embodiments of the present invention are directed toward roofing articles that carry (i.e. are coated with) mullite-containing granules.
- Asphaltic roofing membranes also known as bituminous membranes, have been employed to cover flat or low-sloped roofs. These membranes are typically installed by unrolling a roll of material on a roof surface and then heat seaming adjacent membranes together to form an impervious water barrier on the roof surface.
- the asphaltic roofing membranes are often coated with granular material.
- the benefits associated with the use of these granules is the ability to reflect and/or block solar radiation, which includes ultraviolet, visible, and infrared radiation, to thereby maintain a cooler roof surface.
- Other benefits include optional color, weatherability, and fire resistance. It is believed that by increasing the reflectivity of the roofing surface, energy savings can be achieved. There is, therefore, a desire to increase the reflectivity of roofing surfaces, particularly those that are covered with asphaltic membrane. Incremental improvements in reflectivity translate into energy savings for the consumer while also providing environmental benefits.
- granules for roofing applications have been comprised of inert mineral particles.
- U.S. Pat. No. 7,241,500 discloses that “suitably sized particles of naturally occurring materials such as talc, slag, granite, silica sand, greenstone, andesite, porphyry, marble, syenite, rhyolite, diabase, greystone, quartz, slate, trap rock, basalt, and marine shells can be used, as well as recycled manufactured materials such as crushed bricks, concrete, porcelain, fire clay, and the like”.
- granules used for roofing applications are of a standard size, and may be classified as full grade or No. 11 grade which, according to U.S. Pat. No. 6,238,794, corresponds to ⁇ 10/+35 U.S. mesh size.
- industry standard granules are typically referred to as 8 ⁇ 40 U.S. mesh whereas the average particle size corresponds to about 19 US mesh (i.e. 0.937 mm sieve opening).
- U.S. Pat. No. 7,241,500 describes the mineral particles, which can be produced by a series of quarrying, crushing, and screening operations, as having a size generally intermediate between sand and gravel, or between about 8 US mesh and 70 US mesh.
- U.S. Pat. No. 3,169,075 discloses conventional mineral roofing granules surfaced with a coating comprised of calcined kaolin, a pigment such as titanium dioxide, and an alkali silicate to form a vitreous coating.
- U.S. Pat. No. 6,933,007 discloses as background that kaolin clay is used extensively in silicate paint formulations for coloring roofing granules, serving as a filler, extender, moisture release agent, and reactant to aid film insolubilization during high temperature firing.
- kaolin clay is used extensively in silicate paint formulations for coloring roofing granules, serving as a filler, extender, moisture release agent, and reactant to aid film insolubilization during high temperature firing.
- kaolin clay alone lacks the brightness and opacity needed to hide the dark underlying base rock of the granule and frequently require appreciable amounts of TiO 2 to achieve desired color specifications.
- U.S. Publication No. 2010/0203336 discloses uncalcined kaolin dispersed with binder and solar reflective particles (such as TiO 2 ) to provide roofing granules which are then cured from about 500 to 800° C. The prior art does not contemplate reflective roofing granules or coatings for granules comprised of additive-free calcined kaolin.
- a roofing article comprising (i) an asphaltic substrate; and (ii) a plurality of granules disposed on a surface of the substrate, said granules including calcined kaolin that has been calcined at a temperature of at least 1000° C. and less than 1300° C.
- One or more embodiments of the present invention provide a roofing article comprising (i) an asphaltic substrate; and (ii) a plurality of granules disposed on a surface of the substrate, said granules characterized by an grain size of at least 0.01 ⁇ m and less than 5 ⁇ m, an alumina content of at least 35 wt % and less than 55 wt %, and a silica content of at least 45 wt % and less than 65 wt %.
- One or more embodiments of the present invention provide an asphaltic membrane comprising (i) an asphaltic substrate; and (ii) a plurality of mullite-containing granules disposed on a planar surface of the substrate, where the mullite-containing granules include mullite-crystallites dispersed within a non-mullite matrix, and where the mullite-containing granules include less than 3.5 wt. % alkali oxides or alkaline earth oxides combined.
- One or more embodiments of the present invention provide a roofing article comprising (i) an asphaltic substrate; and (ii) a plurality of mullite-containing granules disposed on a surface of the substrate, where said mullite-containing granules include a mullite concentration of at least 35 wt % and at most 63 wt % as determined by x-ray diffraction, and where the mullite is in the form of crystallites having an average size of at least 25 nm and at most 65 nm, as determined by the isolated (110) x-ray diffraction peak.
- compositions suitable for roofing granules characterized by a solar reflectance of at least 30%, wherein the composition is further characterized by a mullite phase content of at least 35 wt % and at most 60 wt % as determined by quantitative x-ray diffraction and a mullite crystallite size of at least 25 nm and at most 65 nm as determined by x-ray diffraction line broadening of the isolated (110) diffraction peak
- FIG. 1 is a cumulative percentage representation for Samples 2 &3 of the invention and comparative Samples 1, 5, & 6.
- FIG. 2 is a graph of cumulative hiding power (opacity) and mean index values for Sample 2 of the invention and comparative Sample 8.
- Embodiments of the present invention are based, at least in part, on the discovery of asphaltic membranes having a technologically useful reflectivity to solar radiation that include a plurality of mullite-containing granules characterized by a tailored mullite concentration, a tailored mullite crystallite size, or both a tailored mullite concentration and a tailored mullite crystallite size. These articles are advantageously characterized by exhibiting a high degree of solar reflectivity (e.g. panel reflectivity).
- aluminosilicates for roofing granules
- the aspect ratio of the mullite crystallites within the mullite-containing granules plays an important role in achieving desired panel reflectivity. Without being bound by theory, it is believed that enhanced reflectivity of the granules occurs due to increased light scattering at interfaces, such as at the mullite crystallite boundaries and mullite crystallite/non-mullite matrix boundaries.
- the asphaltic membranes of the one or more embodiments of the present invention include an asphaltic substrate having two major planar surfaces.
- the two planar surfaces may be referred to as first and second planar surfaces, or in other embodiments, as an upper surface and a lower surface.
- the upper surface is positioned toward the environment while the lower surface is positioned toward the roof structure onto which the membrane is installed.
- the upper surface of the membrane carries a plurality of granules. Accordingly, reference may be made to a coated asphaltic membrane. Stated another way, a first planar surface of the membrane is coated with a plurality of granules. These granules are generally affixed to the upper surface of the membrane through adhesive forces offered by the asphaltic substrate. In one or more embodiments, the granules are affixed directly to the asphaltic material; in other words, the structure is devoid of any intermediary layer or coating disposed between the asphaltic substrate and the granules.
- the granules as applied to the substrate are characterized by a surface coverage of at least 85%, in other embodiments at least 90%, in other embodiments at least 95%, or at least 96%, or at least 97%, or at least 98%, or at least 98.5% or at least 99%, or at least 99.5%.
- surface coverage is determined optically by image analysis as is known in the art.
- the roofing articles of the present invention include a bituminous substrate including a first and second planar surface.
- the first planar surface is substantially coated with granules.
- the second planar surface is coated, as is known in the art, with non-stick surface. Examples of non-stick surface coatings include, but are not limited to, release liners and sand.
- the roofing articles of the present invention include a second planar surface that is coated with sand.
- the substrate includes a roofing shingle, which is conventionally used on residential buildings with relatively high-sloped roofs.
- the asphaltic substrate includes modified asphalt membranes, which includes those membranes that are conventionally used on commercial buildings that have flat or low-sloped roofs. Examples of modified asphalt membranes are disclosed in U.S. Pat. Nos. 4,835,199, 4,992,315, 6,486,236, 6,492,439, 6,924,015, 7,070,843, 7,146,771, and 7,442,270, which are incorporated herein by reference.
- the asphaltic sheet includes a reinforcing fabric coated with an asphaltic-based composition.
- the fabric, or reinforcing sheet may be woven or non-woven as is known in the art.
- Non-limiting examples of such fabric, also known as a scrim or fiberglass mesh sheet include scrims that are commercially available.
- fiberglass scrims are available under the trade name STYLETM 930120 (Milliken & Co.; Spartanburg, S.C.) and also available from J. P. Stevens (Greenville, S.C.).
- the reinforcing sheet may be an organic felt.
- asphaltic composition includes asphalt or bitumen, optionally polymer, and optionally other additives such as those conventionally employed in the art.
- the asphaltic substrate may be referred as a polymer-modified membrane.
- the polymer modifier may be polymers or rubbers as known in the art. Non-limiting examples of such polymer modifiers include styrene butadiene rubber (SBR) or atactic polypropylene (APP).
- the mullite-containing granules employed in practicing the present invention include crystallites of mullite (which may also be referred to as mullite crystallites or mullite grains) dispersed within a matrix that includes non-mullite aluminosilicates, non-mullite siliceous materials, or both non-mullite aluminosilicates and non-mullite siliceous materials.
- mullite refers to a subset of crystalline aluminosilicates.
- mullite can be referred to as a solid solution series ranging from 3Al 2 O 3 .2SiO 2 to 2Al 2 O 3 .SiO 2 , (a.k.a 3:2 mullite to 2:1 mullite; which generally includes from 60 to 67 mole percent alumina).
- mullite can be identified by powder x-ray diffraction, and standard x-ray diffraction patterns for mullite are well known (for example, published by U.S. Department of Commerce, National Bureau of Standards, U.S. Government Printing Office, 1964).
- the mullite-containing granules employed in the practice of this invention include a certain amount of mullite, which amount may be referred to as mullite concentration.
- the granules employed in practice of this invention include at least 35 wt %, in other embodiments at least 37 wt %, in other embodiments at least 40 wt %, in other embodiments at least 42 wt %, in other embodiments at least 45 wt %, in other embodiments at least 47 wt % by weight mullite, and in other embodiments at least 50 wt % mullite, as determined by x-ray diffraction.
- the granules employed in practice of this invention include at most 63 wt %, in other embodiments at most 60 wt %, in other embodiments at most 58 wt %, in other embodiments at most 57 wt %, and in other embodiments in other embodiments at most 55 wt % mullite, as determined by x-ray diffraction.
- the granules include from about 35 to about 63 wt %, in other embodiments from about 40 to about 57 wt %, and in other embodiments from about 45 to 55 wt % mullite, as determined by x-ray diffraction.
- reference to x-ray diffraction refers to powder x-ray diffraction.
- the mullite crystallites may a acicular and/or needle-like shape.
- the average mullite crystallite size, as determined by the isolated (110) x-ray diffraction peak is at least 25 nm, in other embodiments at least 30 nm, in other embodiments at least 33 nm, and in other embodiments at least 35 nm. In these or other embodiments, the average mullite crystallite size, as determined by the isolated (110) x-ray diffraction peak, is at most 65 nm, in other embodiments at most 57 nm, in other embodiments at most 60 nm, and in other embodiments at most 55 nm.
- the average mullite crystallite size as determined by the isolated (110) x-ray diffraction, is from about 25 nm to about 65 nm, in other embodiments from about 30 nm to about 60 nm, and in other embodiments from about 35 nm to about 55 nm.
- the average mullite crystallite size as determined by the isolated (001) x-ray diffraction peak, is at least 50 nm, in other embodiments at least 55 nm, in other embodiments at least 60 nm, and in other embodiments at least 65 nm.
- the average mullite crystallite size is at most 1000 nm, in other embodiment at most 700 nm, in other embodiments at most 400 nm, in other embodiments at most 200 nm, in other embodiments at most 150 nm, in other embodiments at most 100 nm, in other embodiments at most 90 nm, and in other embodiments at most 85 nm.
- the average mullite crystallite size as determined by the isolated (001) x-ray diffraction peak, is from about 50 nm to about 100 nm, in other embodiments from about 55 nm to about 90 nm, and in other embodiments from about 60 nm to about 85 nm.
- the upper limit for determination of crystallite size is 100 nm for some instrumentation, but scanning electron micrographs can be utilized to corroborate crystallite dimensions greater than 100 nm.
- the aspect ratio of the mullite crystallites which refers to the ratio of the average mullite crystallite size by the isolated (001) x-ray diffraction peak to the average mullite crystallite size by the isolated (110) x-ray diffraction peak may be at least 1.5, in other embodiments at least 1.6, in other embodiments at least 1.7 in other embodiments at least 1.8, in other embodiments at least 1.9, and in other embodiments at least 2.0.
- the average mullite crystallite size is measured by conventional powder x-ray diffraction line broadening techniques, as are known in the art. See, for example, U.S. Pat. No. 3,989,783 and J. I. Langford and A. J. C. Wilson, “Scherrer after Sixty Years: A Survey and Some New Results in the Determination of Crystallite Size,” J. Appl. Cryst. 11 (1978) pp 102-113.
- the average mullite crystallite size can be calculated based on the theory of line broadening of diffraction line by fine grain size, as described by the Scherrer equation (Equation 1), whereby peak width (B) is inversely proportional to crystallite size (L):
- B is the diffraction broadening at full width at half maximum (a.k.a FWHM); K is the Scherrer constant (assumed to be 0.94 for these calculations); L is the thickness of the crystallite perpendicular to the selected crystal plane, and ⁇ is the angle of incident X-ray radiation.
- the breadth (B) refers the broadening due to the particle size effect alone and is the width of the diffraction peak at one-half of the maximum intensity (full width at half maximum, or FWHM).
- diffraction patterns can be generated using X-ray Diffractometer (Siemens D500 Goniometer, Cu—K ⁇ radiation, Phillips) and an analyzing range from 5° to 70° 2 ⁇ with 0.04° step size and 4 second dwell (count time).
- Phase identification and profile fitting can be conducted using commercial software routines (e.g. Jade+, Version 10.1, Materials Data, Inc., Livermore, Calif., 1995).
- mullite grains may grow with a needle-like or acicular habit.
- the mullite diffraction peaks at 16.4° 2 ⁇ (110) (representing a smaller dimension) and 30.9° 2 ⁇ (001) (representing a longer dimension) were used to calculate the grain size in two different directions.
- the mullite crystallites are dispersed within a non-mullite phase including non-mullite aluminosilicates and/or non-mullite siliceous materials. These non-mullite materials may be referred to as a matrix in which the mullite crystallites are dispersed.
- aluminosilicate is used in a conventional manner.
- these materials include alumina (Al 2 O 3 ) and silica (SiO 2 ), and include compositions that are substantially alumina or substantially silica, although with respect to the latter, the term siliceous material may also be employed.
- alumina Al 2 O 3
- silica SiO 2
- siliceous material may also be employed. See, for example, S. Aramaki & R. Roy in “Revised Phase Diagram for the System Al 2 O 3 —SiO 2 ” Journal of the American Ceramic Society, 45, Issue 5, pages 229-242, published May, 1962 and by R. Davis & J. Pask in “Diffusion and Reaction Studies in the System Al 2 O 3 —SiO 2 ” Journal of the American Ceramic Society, 55 Issue 10, pages 525-531, published October, 1972, which are incorporated herein by reference.
- the matrix includes amorphous material, which as those skilled in the art appreciate, refers to non-crystalline materials such as glassy silica. In one or more embodiments, these amorphous materials lack long-range order typical of crystalline materials. In one or more embodiments, the matrix includes polymorphs of silica, amorphous silica, or combinations thereof.
- At least 50 wt %, in other embodiments at least 60 wt %, in other embodiments at least 70 wt %, in other embodiments at least 80 wt %, in other embodiments at least 90 wt %, and in other embodiments at least 95 wt % of the matrix is amorphous.
- the mullite-containing granules include a major amount of alumina and silica.
- Alumina may be referred to as aluminum oxide or Al 2 O 3
- silica may be referred to as silicon dioxide or SiO 2 .
- the granules include at least 90 wt %, in other embodiments at least 93 wt %, in other embodiments at least 95 wt %, in other embodiments at least 96 wt %, in other embodiments at least 97 wt %, in other embodiments at least 98 wt %, and in other embodiments at least 99 wt % silica and alumina combined.
- the mullite-containing granules include at least 35 wt %, in other embodiments at least 40 wt %, and in other embodiments at least 42 wt % alumina. In these or other embodiments, the granules include at most 55 wt %, in other embodiments at most 50 wt %, and in other embodiments at most 45 wt % alumina.
- the mullite-containing granules include at least 40 wt %, in other embodiments at least 45 wt %, in other embodiments at least 49 wt %, and in other embodiments at least 54 wt % silica. In these or other embodiments, the granules include at most 65 wt %, in other embodiments at most 60 wt %, and in other embodiments at most 55 wt % silica.
- the mullite-containing granules include less than 5 wt % total combined weight of elements or compounds (such as oxides) other than alumina and silica. These elements or compounds include potential impurity metal oxide components such as, but not limited to, oxides such as Fe 2 O 3 , TiO 2 , K 2 O, MgO, CaO, P 2 O 5 , or trace levels in oxide form of compounds containing Ba, Sr, Zr. In one or more embodiments, the granules include less than 4 wt %, in other embodiments less than 3 wt %, and in other embodiments less than 2 wt % total combined weight of elements or compounds (such as oxides) other than alumina and silica.
- the mullite-containing granules includes less than 3.5 wt %, in other embodiments less than 3.0 wt %, in other embodiments less than 2.5 wt %, in other embodiments less than 2 wt %, in other embodiments less than 1.5 wt %, and in other embodiments less than 1.0 wt % alkali oxides (RO) or alkaline earth oxides (R 20 ) combined.
- the granules are essentially devoid of alkali oxides or alkaline earth oxides.
- alkali oxides include, but are not limited to, BaO (Barium Oxide, Baria), CaO (Calcia, Calcium Oxide), MgO (Magnesium Oxide, Magnesia), PbO (Lead Oxide), SrO (Strontium Oxide, Strontia), and ZnO (Zinc Oxide).
- alkaline earth oxides include, but are not limited to, K 2 O (Potassium Oxide), Li 2 O (Lithium Oxide, Lithia), and Na 2 O (Sodium Oxide, Soda).
- alkali oxides and alkaline earth oxides are fluxing oxides, which may act to lower the melting point of refractory oxides such as silica and alumina.
- the chemical composition of aluminosilicate granules may be determined by ICP-ES (inductively coupled plasma emission spectroscopy) or other suitable techniques for determining oxide content. Unless otherwise noted, percentages are in weight percent for normalized oxide equivalent.
- mullite-containing granules having a particular size are employed.
- the size of the granules which may also be referred to as agglomerate size or as particle size, refers to largest axis (e.g., diameter of a spherical particle) of the granule, which may also be referred to as equivalent spherical diameter.
- the mullite-containing granules are characterized by a size of from about ⁇ 31 ⁇ 2 to about +70 mesh, or in other embodiments from about ⁇ 4 to about +35 mesh.
- the particles on average, are of sufficient size so that 90% or more of the material will pass through a 31 ⁇ 2-mesh sieve (particles smaller than 5.66 mm) and be retained by a 70-mesh sieve (particles larger than 0.210 mm).
- the size of the granules corresponds to full grade or No. 11 grade.
- the granules are characterized by a number average particle size of less than 10 mm, in other embodiments less than 3 mm, in other embodiments less than 1 mm, and in other embodiments less than 500 microns. In these or other embodiments, the granules are characterized by an average particle size of at least 10 ⁇ m, in other embodiments at least 100 ⁇ m, and in other embodiments at least 200 ⁇ m.
- particle size distribution may be determined by several techniques. These techniques include, but are not limited to, sieve analysis, sedimentation analysis, and light scattering techniques.
- PSD particle size distribution
- ESD equivalent spherical diameter
- Median particle size is the value, d 50 , at which there are 50% by weight of the particles present in the composition having an ESD less than that value. Unless noted otherwise, the percentages and amounts expressed herein are by weight.
- the mullite-containing granules are characterized by having a blocky, or plate-like, structure.
- the plate-like structure refers to a geometry where one axis (e.g., z axis) is substantially smaller than the other axes (e.g., x and y axes) of the granule.
- the x and/or y axes are at least 1.5, or at least 2, or at least 3.
- the aspect ratio may be determined by optical microscopy techniques in conjunction with image analysis as is known in the art.
- the mullite-containing granules employed in practicing the present invention may be relatively porous or, in other embodiments, relatively non-porous. Porosity as measured by mercury porosimetry techniques known in the art is employed to characterize the open porosity inherent in the granules. Suprisingly, as will be discussed further in the next section, porosity did not contribute greatly to the superior reflectivity of the articles of the invention.
- the porosity of the granules as measured using Hg-porosimetry is greater than or equal to zero (0 ml/g), in other embodiments greater than 0.01 ml/g, in other embodiments greater than 0.02 ml/g, in other embodiments greater than 0.03 ml/g, in other embodiments greater than 0.04 ml/g. In one or more embodiments, the porosity of the granules is less than 0.25 ml/g, in other embodiments less than 0.20 ml/g, in other embodiments greater than 0.19 ml/g, in other embodiments greater than 0.18 ml/g, and in other embodiments greater than 0.16 ml/g.
- the mullite-containing granules are characterized by being white in color.
- the granules have an L* value of at least 75, in other embodiments at least 80, and in other embodiments at least 85.
- the color of granules may be measured to determine L-value by using standard instrumentation such as Hunter L,a,b (Hunter Associates Laboratory, Inc., Reston, Va.) or CIELAB L*, a*, b* (CIELAB, 1976). Values for “L*” indicate the ratio of light to dark.
- Values for “a” refer to the redness-greenness coordinate in certain transformed color spaces, generally used as the difference in “a” between a specimen and a standard reference color. If “a” is positive, there is more redness than greenness; if “a” is negative, there is more greenness than redness. It is normally used with b as part of the chromaticity or chromaticity color difference. Values for “b” refer to the yellowness-blueness coordinate in certain color spaces, generally used as the difference in “b” between a specimen and a standard reference color, normally used with “a” or a as part of the chromaticity difference.
- the mullite-containing granules are characterized by including grains having an average grain size of at least about 0.01 ⁇ m, or at least about 0.05 ⁇ m, or at least about 0.1 ⁇ m, or at least about 0.5 ⁇ m, or at least about 1 ⁇ m.
- the average grain size is less than about 100 ⁇ m, or less than about 50 ⁇ m, or less than about 20 ⁇ m, or less than about 10 ⁇ m, or less than about 5 ⁇ m.
- the mullite-containing granules are characterized by a visible light (about 400 to about 700 nm) reflectivity of at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85%, and in other embodiments at least 90%.
- the granule are characterized by a UV electromagnetic radiation (about 10 nm to about 400 nm) reflectivity of at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85%, and in other embodiments at least 90%.
- the granules are characterized by an infrared electromagnetic radiation (about 700 nm to about 10 ⁇ 3 m) reflectivity of at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85%, and in other embodiments at least 90%.
- the granules are characterized by a terrestrial solar radiation (about 250 nm to about 2500 nm) reflectivity of at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85%, and in other embodiments at least 90%.
- terrestrial solar radiation refers to the solar radiation contacting sea level.
- bituminous substrates applied with granules of the invention are characterized by panel solar reflectance of at least 65%, in other embodiments at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85%, and in other embodiments at least 90%.
- the mullite-containing granules are characterized by a reflectivity according to ASTM C1549 of at least 60%, in other embodiments at least 65%, in other embodiments at least 70%, in other embodiments at least 72%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85%, and in other embodiments at least 90%.
- the mullite-containing granules are characterized as being chemically inert, which refers to the fact that the granules are stable to chemical conditions conventionally experienced on a roof surface.
- the granules are insoluble in water, which refers to a solubility of 0.01 gram per liter or less at standard conditions of temperature and pressure and a pH of 7.
- the granules are insoluble in water under acidic conditions, which refers to a solubility of 0.01 gram per liter or less at standard conditions of temperature and pressure and a pH of 5 or less, or in other embodiments at a pH of 4 or less, or in other embodiments at a pH of 3 or less, or in other embodiments at a pH of 2 or less.
- the granules are insoluble in water under basic conditions, which refers to a solubility of 0.01 gram per liter or less at standard conditions of temperature and pressure and a pH of 8 or more, or in other embodiments at a pH of 9 or more, or in other embodiments at a pH of 10 or more, or in other embodiments at a pH of 11 or more.
- the mullite-containing granules are obtained by calcination of kaolin clay.
- the product of calcination may be referred to as calcined kaolin.
- kaolin exists naturally in the hydrous form.
- kaolinite minerals form crystal structures that are linked together by hydroxyl containing moieties.
- Hydrous kaolin may be converted to calcined kaolin containing a desired amount of mullite by thermal processes. It is believed that these processes result in a dehydroxylation of the kaolin and an aggregation of the particles that converts the crystal structure to an amorphous form.
- practice of one or more embodiments of the present invention is not limited by selection of particular kaolin to provide or produce the calcined kaolin having the desired mullite characteristics.
- crude kaolin, coarse hydrous kaolin, or fine hydrous kaolin may be employed.
- kaolin may mined from various geographic locations including North America, Europe, and Asia.
- the kaolin may optionally be subjected to preliminary processing and/or beneficiation to facilitate transportation, storage, and handling.
- crude kaolin can be subjected to one or more of the following operations: crushing, grinding, delamination (wet milling, slurry milling, wet grinding, and the like), filtration, fractionation, pulverization, flotation, selective flocculation, magnetic separation, floc/filtration, bleaching, and the like before or after the heat treatment.
- calcination is effected by heat treating hydrous kaolin at temperatures ranging from about 500° C. to about 1250° C. (or 1300° C.) or higher.
- the calcined kaolin is thermally prepared at a calcination temperature of at least about 1000° C. and less than about 1300° C., or at least about 1050° C. and less than about 1250° C., or at least about 1100° C. and less than about 1200° C.
- the calcined kaolin is thermally prepared at a calcination temperature of at least 1000° C. and at most 1300° C.
- the kaolin is heated to a temperature of about 1175 to 1200° C. for a time of about 1 minute to about 2 hours.
- Calcined, or calcination as used herein may encompass any degree of calcination, including partial (meta) calcination, full calcination, flash calcination, or combinations thereof.
- Calcining or heat treating may be performed in any suitable manner to provide a major amount of mullite. Heating procedures typically include soak calcining, flash calcining, and/or a combination of flash calcining/soak calcining.
- soak calcining a hydrous kaolin is heat treated at a desired temperature for a period of time (for example, from at least 1 minute to about 5 or more hours), sufficient to dehydroxylate the kaolin and form a major amount of mullite.
- flash calcining a hydrous kaolin is heated rapidly for a period of at most 10 seconds, typically less than about 1 second.
- metakaolin is instantaneously produced during flash calcination and then processed to a finished product requirement using soak calcination. Excess calcination to temperatures above for example 1400° C. may not desirable due to mullite crystallite growth outside of desired range.
- Practice of one more embodiments of the present invention is not limited by the furnace, kiln, or other heating apparatus used to effect heating of the hydrous kaolin.
- Known devices suitable for carrying out soak calcining include high temperature ovens, and rotary and vertical kilns.
- Known devices for effecting flash calcining include toroidal fluid flow heating devices.
- the membranes of one or more embodiments of this invention can achieve a solar reflectance, as defined and determined by the EnergyStar rating or California Title 24 (Cool Roof Rating Council test CRRC-1 in conjunction with ASTM C1549), which reflectance may be referred to as panel reflectance, of at least 60%, in other embodiments at least 65%, in other embodiments at least 67%, in other embodiments at least 69%, in other embodiments at least 70%, in other embodiments at least 72%, and in other embodiments at least 75% reflectivity.
- a solar reflectance as defined and determined by the EnergyStar rating or California Title 24 (Cool Roof Rating Council test CRRC-1 in conjunction with ASTM C1549), which reflectance may be referred to as panel reflectance, of at least 60%, in other embodiments at least 65%, in other embodiments at least 67%, in other embodiments at least 69%, in other embodiments at least 70%, in other embodiments at least 72%, and in other embodiments at least 75% reflectivity.
- the mullite-containing granules are applied to a hot asphaltic substrate by gravity (i.e. they are dropped). In particular embodiments, multiple drops are employed, and in other embodiments, the size of the granules that are applied in a subsequent drop step are smaller than the granules applied in a first drop step.
- the granules employed in the present invention may be further modified by applying coatings or treatment to the granules.
- the granules may be treated for stain resistance.
- Exemplary treatments include those set forth in copending application Nos. 61/301,918 and 61/312,464, which are incorporated herein by reference.
- the roofing articles of the present invention are prepared wherein the temperature at which the plurality of granules is provided to the substrate is at least 150° C. and at most 220° C., or at least 160° C. and at most 195° C., or at least 170° C. and at most 185° C.
- the coated asphaltic membranes of the present invention may be fabricated into in the form of a sheet that is rolled for storage and transport. Upon installation, these sheets are unrolled and adjacent sheets can be heat welded together or sealed with hot asphalt or cold adhesive to form a water-impervious barrier on the top of the roof.
- a planar surface of the membrane is coated with granules.
- the coated surface is typically the surface that is exposed to the environment when installed on a roof, and therefore it may be referred to as the top surface.
- the opposite planar surface which may be referred to as the bottom surface, is typically not coated with the inventive granules and therefore may be devoid or substantially devoid of granules.
- Samples 1 through 5 were believed to be calcined kaolin clays that were calcined at a temperature of about 1175 to 1200° C. for 15 min to 2 hours. Specifically, Samples 1-3 were believed to derive from industrial scale batch calcinations performed in rotary kilns. Samples 4-5 were clays that were calcined within a Thermolyne 46200 High Temperature Furnace (heating element molybdenum disilicide) or a Carbolite RHF 1500 Furnace (heating element silicon carbide). Samples 6 and 7 were commercially available (C-E Minerals, King of Prussia, Pa.) refractory materials, which were believed to be sintered mullites.
- Thermolyne 46200 High Temperature Furnace heating element molybdenum disilicide
- Carbolite RHF 1500 Furnace heating element silicon carbide
- Sample 6 was believed to correspond to M45, which is a sintered mullite with chemical composition corresponding to an alumina content of approximately 45% Al 2 O 3 .
- Sample 7 was believed to correspond to M60, which is a sintered mullite with chemical composition corresponding to an alumina content of approximately 60% Al 2 O 3 .
- Sample 8 was a commercially available tabular alumina (AluChem, Cincinnati, Ohio).
- Samples 9 and 10 were commercially available electrical insulator porcelains (Victor Insulators, Inc., Victor, N.Y.), although as shown in Table 1, Sample 9 was richer is silica while Sample 10 was richer in alumina.
- Samples 2 through 5 are representative of the present invention, while Samples 1 and 6 through 10 are comparative examples.
- Granules were dry dispersed as a single layer of discreet particles directly on photographic paper (Polycontrast II RC, Kodak) or on a clear acetate sheet.
- the paper was exposed, using an enlarger, and the paper processing using standard photographic darkroom techniques.
- the exposure time was determined by qualitatively evaluating the contrast range using an opaque object (a coin).
- the full contrast range was a black background and a white circle where the coin was placed.
- the enlarger was equipped with a 50 mm lens, an f-stop of 22, and a nominal exposure time of eleven (11) seconds.
- the processed image consisted of white-gray regions where the granules were located against a black background.
- results were produced in the form of an Excel spreadsheet with the number of pixels in each gray-scale as 256 data pairs. Between 800 and 2000 grains were measured for each index value. In this analysis, a low number indicated black and a high number indicated white. The greater the value, the higher the hiding power. In this analysis, the background was uniformly centered at an index value of 50 ( ⁇ 3) indicating that the backgrounds of all of the analyzed images were similar. A perfectly black background would have a value of 0; perfectly white, a value of 255 (summing to 256 shades of gray).
- a plurality of highly reflective granules characterized by a tailored mullite concentration and tailored mullite crystallite size is applied to the bituminous substrate by conventional drop method at a temperature of about 177° C.
- the substrate then passes over a cooling water bath and is calendered to an optional second drop location at a temperature of about 121° C.
- the substrate is then further calendered with optional heating prior to a third optional drop at about 32° C.
- Table 3 details aspect ratio of Samples 1-10.
- the aspect ratio of the crystallites was obtained through analysis of isolated mullite phase peaks corresponding to the (110) x-ray peak, perpendicular to the shortest crystallite dimension, and the (001) x-ray peak, perpendicular to the longest crystallite dimension.
- Samples 6 and 7 the mullite phase crystallites are too large to assign values using this technique.
- Sample 8 was not measured using this technique, because the tabular alumina mineralogically consists entirely of alpha-Al 2 O 3 , therefore Sample 8 contains no mullite phase.
- Samples 1-7 and 9-10 were ground to a powder with a particle size of approximately 10 ⁇ m.
- Diffraction patterns were generated using a X-ray Diffractometer (Siemens D500 Goniometer, Cu—K ⁇ radiation, Phillips). The analyzing range was from 5° to 70° 2 ⁇ with 0.04° step size and 4 second dwell (count time). Phase identification and profile fitting were conducted using commercial software routines (Jade+, Version 10.1, Materials Data, Inc., Livermore, Calif., 1995). Grain size was estimated based on the theory of line broadening as discussed previously. Mullite diffraction peaks at 16.4° 2 ⁇ (110) (representing the smallest dimension) and 30.9° 2 ⁇ (001) (representing the longest dimension) were used to calculate the grain size in two different directions.
- the aspect ratio of the granules was obtained by mounting granules in epoxy and then polishing through to reveal cross sections of numerous granules. Using an optical microscope and image analysis, the average aspect ratio of the granules was calculated. Mounted granules were prepared using transparent epoxy (Epo-kwick® resin and hardener, No. 20-8130-128 and 20-8138-032, Buehler). Granules were placed on glass mold (3′′ in diameter and 1 ⁇ 2′′ in depth) and moderately vibrated to achieve a single layer of granules. Then liquid resin and hardener mixture was applied to the mold and cured.
- transparent epoxy Epo-kwick® resin and hardener, No. 20-8130-128 and 20-8138-032, Buehler
- the flat surface (as cast) of the cured epoxy (including embedded granules) was optically scanned to collect the “x-y” dimension of the granules.
- the disc was sliced perpendicular to the case surface using a diamond saw into strips and the cross sections were scanned to collect “z” dimensions.
- the scanned images were analyzed using commercial imaging software (Image-Pro Plus, v. 4.0, Media Cybernetics, Bethesda, Md.).
- the longest and shortest dimensions of each granule were measure in all scanned images. From this data, the overall average and standard deviations were calculated and used to create the aspect ratio by dividing the “x-y” average dimension by the “z” dimension.
- a granule aspect ratio of about one indicates equiaxed grains.
- the average trial panel reflectivity is measured by ASTM C-1549 and is reported on Table 2 based upon two reflectance readings; for Sample 3 the trial panel reflectivity is 72%, and for Sample 4 the trial panel reflectivity is 69%. Subsequent (second and/or third) dropping of granules, which may be characterized by a finer, narrow particle size distribution, have also been shown to further improve panel reflectivity.
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US13/538,288 US20130017368A1 (en) | 2009-12-31 | 2012-06-29 | Asphaltic membrane with mullite-containing granules |
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US29154609P | 2009-12-31 | 2009-12-31 | |
PCT/US2011/020044 WO2011082398A1 (fr) | 2009-12-31 | 2011-01-03 | Membrane en asphalte comprenant des granules qui contiennent de la mullite |
US13/538,288 US20130017368A1 (en) | 2009-12-31 | 2012-06-29 | Asphaltic membrane with mullite-containing granules |
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US13/538,288 Abandoned US20130017368A1 (en) | 2009-12-31 | 2012-06-29 | Asphaltic membrane with mullite-containing granules |
US13/538,244 Abandoned US20130004713A1 (en) | 2009-12-31 | 2012-06-29 | Asphaltic membrane with mullite-containing granules |
US15/385,102 Active US10227780B2 (en) | 2009-12-31 | 2016-12-20 | Asphaltic membrane with mullite-containing granules |
US15/385,167 Abandoned US20170138051A1 (en) | 2009-12-31 | 2016-12-20 | Asphaltic membrane with mullite-containing granules |
US16/252,032 Active US10626615B2 (en) | 2009-12-31 | 2019-01-18 | Asphaltic membrane with mullite-containing granules |
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US13/538,244 Abandoned US20130004713A1 (en) | 2009-12-31 | 2012-06-29 | Asphaltic membrane with mullite-containing granules |
US15/385,102 Active US10227780B2 (en) | 2009-12-31 | 2016-12-20 | Asphaltic membrane with mullite-containing granules |
US15/385,167 Abandoned US20170138051A1 (en) | 2009-12-31 | 2016-12-20 | Asphaltic membrane with mullite-containing granules |
US16/252,032 Active US10626615B2 (en) | 2009-12-31 | 2019-01-18 | Asphaltic membrane with mullite-containing granules |
Country Status (5)
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US (5) | US20130017368A1 (fr) |
EP (1) | EP2519701B1 (fr) |
CA (1) | CA2786288C (fr) |
ES (1) | ES2617748T3 (fr) |
WO (2) | WO2011082374A1 (fr) |
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2010
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2011
- 2011-01-03 WO PCT/US2011/020044 patent/WO2011082398A1/fr active Application Filing
- 2011-01-03 ES ES11728547.8T patent/ES2617748T3/es active Active
- 2011-01-03 EP EP11728547.8A patent/EP2519701B1/fr active Active
- 2011-01-03 CA CA2786288A patent/CA2786288C/fr active Active
-
2012
- 2012-06-29 US US13/538,288 patent/US20130017368A1/en not_active Abandoned
- 2012-06-29 US US13/538,244 patent/US20130004713A1/en not_active Abandoned
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2016
- 2016-12-20 US US15/385,102 patent/US10227780B2/en active Active
- 2016-12-20 US US15/385,167 patent/US20170138051A1/en not_active Abandoned
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2019
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Also Published As
Publication number | Publication date |
---|---|
US10227780B2 (en) | 2019-03-12 |
US20170107721A1 (en) | 2017-04-20 |
WO2011082374A1 (fr) | 2011-07-07 |
US20130004713A1 (en) | 2013-01-03 |
CA2786288C (fr) | 2018-06-05 |
CA2786288A1 (fr) | 2011-07-07 |
US10626615B2 (en) | 2020-04-21 |
US20190169848A1 (en) | 2019-06-06 |
ES2617748T3 (es) | 2017-06-19 |
WO2011082398A1 (fr) | 2011-07-07 |
US20170138051A1 (en) | 2017-05-18 |
EP2519701A4 (fr) | 2015-04-29 |
EP2519701A1 (fr) | 2012-11-07 |
EP2519701B1 (fr) | 2016-11-30 |
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