EP1457732A2 - Pressurized containers and method of making thereof - Google Patents
Pressurized containers and method of making thereof Download PDFInfo
- Publication number
- EP1457732A2 EP1457732A2 EP04251063A EP04251063A EP1457732A2 EP 1457732 A2 EP1457732 A2 EP 1457732A2 EP 04251063 A EP04251063 A EP 04251063A EP 04251063 A EP04251063 A EP 04251063A EP 1457732 A2 EP1457732 A2 EP 1457732A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- pressurized container
- reinforced
- polyesters
- container
- fibers
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000728 polyester Polymers 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 21
- 239000012744 reinforcing agent Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 claims description 2
- 238000003856 thermoforming Methods 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims 1
- 238000000071 blow moulding Methods 0.000 claims 1
- 238000000748 compression moulding Methods 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 235000013405 beer Nutrition 0.000 abstract description 20
- 235000014214 soft drink Nutrition 0.000 abstract description 2
- 235000014171 carbonated beverage Nutrition 0.000 abstract 1
- -1 polypropylene Polymers 0.000 description 22
- 239000011521 glass Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 229920001225 polyester resin Polymers 0.000 description 13
- 239000004645 polyester resin Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 235000013361 beverage Nutrition 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000011152 fibreglass Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical class OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CDPPYCZVWYZBJH-UHFFFAOYSA-N 2,2,3,3-tetramethylbutanedioic acid Chemical compound OC(=O)C(C)(C)C(C)(C)C(O)=O CDPPYCZVWYZBJH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 101100072702 Drosophila melanogaster defl gene Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- MGIAHHJRDZCTHG-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=CC(C(O)=O)=C1 MGIAHHJRDZCTHG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000004879 dioscorea Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940075473 medical gases Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/02—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
- F17C1/04—Protecting sheathings
- F17C1/06—Protecting sheathings built-up from wound-on bands or filamentary material, e.g. wires
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2201/00—Vessel construction, in particular geometry, arrangement or size
- F17C2201/01—Shape
- F17C2201/0104—Shape cylindrical
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2201/00—Vessel construction, in particular geometry, arrangement or size
- F17C2201/05—Size
- F17C2201/056—Small (<1 m3)
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2201/00—Vessel construction, in particular geometry, arrangement or size
- F17C2201/05—Size
- F17C2201/058—Size portable (<30 l)
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/01—Reinforcing or suspension means
- F17C2203/011—Reinforcing means
- F17C2203/012—Reinforcing means on or in the wall, e.g. ribs
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0602—Wall structures; Special features thereof
- F17C2203/0612—Wall structures
- F17C2203/0614—Single wall
- F17C2203/0617—Single wall with one layer
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0636—Metals
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0636—Metals
- F17C2203/0639—Steels
- F17C2203/0643—Stainless steels
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
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- F17C2203/00—Vessel construction, in particular walls or details thereof
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- F17C2203/00—Vessel construction, in particular walls or details thereof
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- F17C2203/00—Vessel construction, in particular walls or details thereof
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- F17C2203/00—Vessel construction, in particular walls or details thereof
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- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/011—Oxygen
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- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/013—Carbone dioxide
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- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/03—Mixtures
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- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
- F17C2223/0107—Single phase
- F17C2223/0123—Single phase gaseous, e.g. CNG, GNC
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- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
- F17C2223/0146—Two-phase
- F17C2223/0153—Liquefied gas, e.g. LPG, GPL
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- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
- F17C2223/033—Small pressure, e.g. for liquefied gas
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- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
- F17C2223/035—High pressure (>10 bar)
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- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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- F17C2260/00—Purposes of gas storage and gas handling
- F17C2260/03—Dealing with losses
- F17C2260/035—Dealing with losses of fluid
- F17C2260/036—Avoiding leaks
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/02—Applications for medical applications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/05—Applications for industrial use
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/05—Applications for industrial use
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- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/05—Applications for industrial use
- F17C2270/0563—Pneumatic applications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/07—Applications for household use
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/07—Applications for household use
- F17C2270/0754—Fire extinguishers
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
Definitions
- the present invention relates to pressurized containers or vessels made from reinforced thermoplastics and methods for making pressurized containers or vessels from reinforced thermoplastics.
- plastics for pressurized containers primarily for containing beverages, but increasingly for other utilities such as containers to dispense either gaseous or liquid carbon dioxide for use in pneumatic power devices such as garden pressure sprayers, power tools, etc. wherein the high pressure carbon dioxide provides mechanical power.
- plastic containers in applications such as fire extinguishers, cylinders containing medical gases for distribution in laboratories and larger (e.g. 5 to 50 liters capacity), and cylinders such as those used in the distribution of oxygen, nitrogen, carbon dioxide and the like to industrial users.
- U.S. Patent No. 3,712,497 discloses bottles formed of thin walled, flexible synthetic plastics, in separate parts which are later friction welded together forming the bottles, capable of withstanding internal pressures of up to 75 psi.
- U.S. Patent No. 4,591,066 discloses a unitary molded plastic body for containing pressurized liquid beverage made out of polystyrene, PET, or polypropylene.
- these containers are quite permeable to carbon dioxide.
- beer stored in the plastic containers of the prior art will have lost so much of its carbon dioxide content after a few days that the remaining beer will no longer be palatable and flat-tasting.
- EP 0 578 711B1 discloses an improved container for beer and other beverages in the form of a layered construction of at least two plastic materials, with the plastic materials being arranged in adjacent layers fastened together, or being laminated together.
- the improved container herein can withstand pressure of up to approximately 420kPA or about 65 psi.
- the first plastic material is a polyethylene terepthalate
- the second plastic material is nylon.
- the invention relates a pressurized container made of reinforced polyesters having sufficient creep resistance, impact strength, CO 2 and O 2 barrier resistance, wherein upon being filled with a liquid having a dissolved carbon dioxide content of in the range of 0.4 - 0.6 wt % at an internal pressure of at least 1 bar, said pressurized container maintains a dissolved carbon dioxide content of at least about 0.25 wt % after 6 months at a storage temperature of about 30 to 35 °C, and an O 2 -permeation of less than 1.0 ppm.
- the invention also relates to the use of long-glass fiber reinforced polyesters in pressurized containers for excellent creep resistance, impact strength, water and CO 2 /O 2 barrier properties.
- reinforced plastic materials i.e., polyesters reinforced with various materials, e.g., long-glass fibers, provide a combination of excellent barrier and physical properties such as low permeability to gases, high strength, and low creep at elevated temperatures, thus excellent for packaging applications such as pressurized containers for beverages and foodstuff.
- polyester resins utilized in this invention include, in general, linear saturated condensation products of diols and dicarboxylic acids, or reactive derivatives thereof. Polyesters are well known as film and fiber formers, and they are manufactured by methods known in the art including those disclosed in U.S. Pat. Nos. 2,465,319 and 3,047,539.
- the polyesters comprise condensation products of aromatic dicarboxylic acids and aliphatic diols.
- the polyesters are poly(1,4-dimethylol cyclohexane dicarboxylates, e.g., terephthalates).
- terephthalates small amounts of other aromatic dicarboxylic acids, such as isophthalic dicarboxylic acid, naphthalene dicarboxylic acid, or aliphatic dicarboxylic acids, such as adipic acid, can also be present in the resins.
- the diol constituent can likewise be varied, in some embodiments, by adding small amounts of cycloaliphatic diols.
- the polyesters comprise a poly(alkylene terephthalate, isophthalate or mixed isophthalate-terephthalate, e.g., up to 30 mole percent isophthalate), with the alkylene groups containing from 2 to 10 carbon atoms, e.g., poly(ethylene terephthalate) (“PET”) or poly(1,4-butylene terephthalate) (“PBT”).
- PET poly(ethylene terephthalate)
- PBT poly(1,4-butylene terephthalate)
- the polyester resins may comprise entirely of PET, PBT, or a combination thereof.
- the polyesters comprise a mixture of PBT to PET at a weight ratio of about 1:1 to about 20:1.
- the poly(1,4-butylene terephthalate) resin used is one obtained by polymerizing a glycol component at least 70 mol %, preferably at least 80 mol %, of which consists of tetramethylene glycol and an acid or ester component at least 70 mol %, preferably at least 80 mol %, of which consists of terephthalic acid, and polyester-forming derivatives therefore.
- the polyester is a poly(1,4-butylene terephthalate) homopolyester.
- copolyesters are used. These comprise at least about 70 mole percent, based on total monomer content, of butylene and terephthalate units.
- the comonomer may be either a dicarboxylic acid or diol or a combination of the two. Suitable dicarboxylic acid comonomers include the C 8 to C 16 aromatic dicarboxylic acids, including the benzene dicarboxylic acids, i.e. phthalic and isophthalic acids and their alkyl, e.g.
- Suitable diol comonomers include but are not limited to C 2 to C 8 aliphatic and cycloaliphatic diols, e.g. ethylene glycol, hexanediol, butanediol and 1,2-, 1,3- and 1,4-cyclohexanedimethanol.
- the polyester resin having a coefficient of thermal expansion (CTE) higher than that of the intended reinforcing material used, so that the polyester material shrinks around the reinforcing material causing compressive stresses which grip the reinforcing material in place.
- CTE coefficient of thermal expansion
- the polyesters may be blended with a polycarbonate resin.
- Polycarbonate resins useful in preparing the blends of the present invention are generally aromatic polycarbonate resins.
- the polyesters may be modified with additives such as a high molecular weight polyetherimide base material (e.g. an polyetherimide ester elastomer) as a warpage control additive.
- a high molecular weight polyetherimide base material e.g. an polyetherimide ester elastomer
- additives such as (co-)polyolefins or polyethylenes are added for improved impact strength.
- the impact strength additive is selected from ethylene-vinyl acetate (EVA), linear low-density polyethylene (LLDPE), and alpha-olefin-glycidyl methacrylate copolymers and terpolymers.
- a copolymer or interpolymer comprising glycidyl 2-alkenoates and alpha-olefins is added to the polyester for improved impact strength and improved melt viscosity to facilitate the construction of the finished pressurized containers.
- the polyesters may further contain one or more conventional additives such as, for example, antioxidants, carbon black, reinforcing agents, plasticizers, lubricity promoters, color stabilizers, ultraviolet absorbers, X-ray opacifiers, dyes, pigments, fillers including mineral fillers, mold release agents such as polyethylene, and the like.
- additives such as, for example, antioxidants, carbon black, reinforcing agents, plasticizers, lubricity promoters, color stabilizers, ultraviolet absorbers, X-ray opacifiers, dyes, pigments, fillers including mineral fillers, mold release agents such as polyethylene, and the like.
- mineral fillers include alumina, amorphous silica, anhydrous aluminum silicates, feldspar, talc, milled glass, phenolic resins, glass microspheres, metal oxides such as titanium dioxide, zinc sulfide, ground quartz, clays such as hydrated aluminum silicate, and the like are used in the polyester matrix.
- thermal, oxidative and/or ultraviolet stabilizers comprise phenols and their derivatives, amines and their derivatives, compounds containing both hydroxyl and amine groups, hydroxyazines, oximes, polymeric phenolic esters and salts of multivalent metals may be optionally added to the polyester resins.
- the reinforcing agents are fibers in the form of fiberglass, carbon or aramid fibers in roving, woven fabric form, or in combination of fiberglass and carbon or aramid fibers.
- the reinforcing agents are metals drawn into wire or filaments, or polyamide polymers characterized by the presence of the amide group - CONH.
- the reinforcing agents are solely glass fibers available in roving, continuous strand mat, and stitched rovings (0°, 90°, and ⁇ 45° orientations).
- the fibers are precoated with a binder to enhance compatibility with the polyester resin matrix.
- the coating can comprise normal fiberglass coating materials: polyurethane resin, polyacrylate resin, polyester resin, polyepoxide resin, and functional silanes, especially epoxy or amine functional alkoxy silanes.
- the amount of the coating agent employed is generally that amount which is sufficient to bind the filaments into a continuous strand. Generally, this may be about 1.0 weight percent based on the weight of the glass filament.
- the fiber diameters typically range from about 3 to 50 microns.
- the filaments in the form of glass fibers have a diameter of about 5 to 30 microns.
- the fiber has a diameter of about 10 to 20 microns.
- the fibers in the form of chopped fiberglass strands have a length of about 1/8" to about 1".
- long-fibers with lengths of more than 1" are used, for increased strength and moldability of the containers.
- the fiberglass fibers are comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass.
- other glasses are used as well e.g., the low soda glass known as "C.”
- glass filaments known as G-filaments are used.
- the glass filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling. In one embodiment, the filaments are made by mechanical pulling. In one embodiment, the filaments are in the form of being bundled into fibers and the fibers bundled in turn to yams, ropes or rovings, for final use in reinforcing the polyesters for use in the pressurized containers of the invention.
- the reinforcing agents comprise a range of materials other than glass fibers and in the form other than filaments, e.g., microspheres. These include but are not limited to glass, ceramic materials such as graphite, wollastonite, carbons, metals, e.g., aluminum, iron, nickel, stainless steel and the like, titanates, e.g., titanate whiskers, quartz, clay, mica, talc, mixtures of the foregoing and the like.
- the metal and metal glass fiber materials that can be used include those disclosed in the U.S. Pat. No. 4,525,314, the entire disclosure of which is incorporated herein by reference.
- the ceramic materials from which the reinforcing fibers can be made include silicon carbide, silicon nitride, carbon, graphite and aluminum oxide.
- the metal, ceramic, and glass microspheres than can be used as reinforcing agents include those disclosed in U.S. Pat. No. 4671994, the entire disclosure of which is incorporated herein by reference.
- reinforcing agents are used in an amount ranging from about 5 to about 60 weight percent based on the total weight of the thermoplastic blend composition.
- the concentration of the reinforcing agents is expressed as volume %, and ranging from about 1 to about 50 volume % (vol. %).
- the volume percent can be calculated by comparing the total area of the cross section of a finished part with the cross sectional area of the fibers. In another embodiment, this amount is less than about 40 vol. %. In a third embodiment, it is less than 30 vol. %. In a fourth embodiment, it is about 5 to 20 vol. %.
- the reinforcing agents used are long fibers
- a pultrusion process known in the art is used to form the components into shape.
- the long glass fiber material is drawn through a bath containing the polyester resins plus any additives.
- the long glass fiber material is first impregnated with the polyester resin of the invention (plus any optional additives).
- Laminate formed is pulled through a heated die controlled to precise tolerances depending on the final container application specifications.
- the finished product is cut and tooled into various parts of the container, e.g., sidewall, top or bottom part and the like. The parts are subsequently welded forming the finished containers.
- a process as generally described in EP 0 820848B1 is used for a lineal structure particularly useful for a tall pressurized container, which reference is expressedly incorporated herein.
- This process comprises feeding the melted polyester materials of the invention into a die having an inlet for receiving the melted material, and an outlet having a geometry corresponding to the desired part of the container of the invention.
- the outlet is positioned downstream from the inlet wherein the melted polyester resin flows from the inlet to the outlet.
- a plurality of fiber bundles are introduced to the stream at predetermined spaced apart radial positions for providing the fiber reinforcement to the lineal profile.
- the fiber bundles extend in the longitudinal direction at predetermined locations in the profile.
- the finished product is cut and tooled into various parts of the container, e.g., sidewall, top or bottom part and the like.
- the containers can be further reinforced with additional bands of materials as generally taught in EP0852695B1 for "Blast Resistant And Blast Directing Containers.”
- the pressurized container further comprises a plurality of spaced, substantially parallel composite strips attached to and reinforcing the container with each strip being a tape of unidirectional high strength fibers or oriented film encircling the container in a hoop direction at least once.
- chopped glass strands are used as reinforcing agents.
- the chopped glass strands may be first blended with the polyester resin and then fed to an extruder and the extrudate cut into pellets.
- they may be separately fed to the feed hopper of an extruder to preparing reinforced polyester pellets.
- the pellets so prepared when cutting the extrudate may be one-fourth inch long or less.
- the dispersed glass fibers are reduced in length as a result of the shearing action on the chopped glass strands in the extruder barrel.
- the reinforced polyester resins are subsequently shaped into pressurized containers or parts thereof, via common processes known in the art, such as extrusion blow molding, injection blow molding, profile extrusion, pipe extrusion, co-extrusion, extrusion coating, foam molding, foam extrusion, thermoforming, and the like.
- the parts can be subsequently welded to form the finished pressurized containers.
- the reinforced polyester pressurized containers of 2-4 mm thickness are used as beer containers, i.e., beer kegs
- the reinforced polyester pressurized containers of the invention have inherently low CO 2 and oxygen permeation properties, wherein upon being filled with a liquid having a dissolved carbon dioxide content of 0.4 - 0.6 wt % at an internal pressure of at least 1 bar, said pressurized container maintains a dissolved carbon dioxide content of at least 0.25 wt % after 0.5 year at a storage temperature of about 30 to 35 °C and an O 2 -permeation of less than 1.0 ppm.
- the pressurized containers made out of reinforced polyesters, used at an initial internal pressure of 1-5 bar have a creep ⁇ 3 % after 0.5 year at room temperature.
- the reinforced polyesters containers of the present invention do not import unacceptable levels flavoring changes to the products.
- reinforced polyester compositions comprising PBT (poly(butyleneterephthalate) with molecular weight of approximately 80,000 (as expressed as PS molecular weight), 0.15 % Irganox 1010 as a stabilizer, approximately 1 % of a polyethylene as release agent., and from 30 to 50 wt. % of glass fiber.
- compositions are referred to as 30% SGF, 50% LGF, 30% LGF, and 50% LGF, depending on whether short glass or long glass fiber is used.
- the short glass fiber is in the form of E-glass chopped strands commercially available from NEG as T-120.
- the long glass fiber e.g. E-glass based
- a finishing agent such as a silane-based coupling agent, greige goods such as urethane-based resins or epoxy-based resins, a thermal stabilizer such as typically phosphite-based resins, or any other adequate surface-treating agents depending upon aimed uses, if required.
- the LGF compositions are made according to the pultrusion process as generally disclosed in U.S. Patent No. 4,559,262, the entire disclosure of which is incorporated herein by reference.
- PBT polymer melts are prepared in a bath of about 260°C.
- Fiber glass filaments in the form of a glass roving
- the impregnated roving is pulled through a 3 mm diameter die in the wall of the bath and then cooled, for a completely wetted material.
- the amount of PBT in the finished product (for 30 or 50 wt. % concentration of fiber) is controlled by the length of the path over which the fiber band contacts the heated spreader surface.
- the products obtained by the continuous pultrusion are subsequently chopped to form pellets having a length in the range of at least 5 - 10 mm.
- the used LGF products are supplied by LNP under the name of Verton AF 7006 (30 % LGF) and WF 700 10 (50 % LGF).
- the SGF blends are made by dry blending of ingredients with exception of the glass fiber.
- the blends are subsequently compounded on a WP25 mm co-rotating extruder, where the glass is separately fed down-stream the extruder.
- the melt temperature was approx. 250-260°C and at RPM of 300.
- the products obtained are extrudated to form pellets.
- the SGF and LGF products are molded into samples using an Engel 75 tons machine with a temperature setting of 240-260°C (from throat to nozzle) and a mold temperature of 60°C. Prior to molding the pellets were predried at 120°C for 2 hours.
- SGF short-glass fiber
- LGF long-glass fiber
- Example 2 the 50% LGF composition in Example 2 is used in a fiber-reinforced polyester pressurized vessel, i.e., beer kegs, with a pultrusion process is used to form the components of the beer kegs.
- a fiber-reinforced polyester pressurized vessel i.e., beer kegs
- the beer kegs are filled from beer tanks at suitable internal pressure of about 2 bars and at temperature of about 20 to 35 °C, and with the beer having a dissolved carbon dioxide content of about 0.5 wt %.
- the beer in the fiber-reinforced polyester beer kegs of the present invention has a dissolved carbon dioxide content of at least 0.25 wt. %. It is also found that the beer is not flat when dispensed and consumed. It is also found that after the beer is partially consumed and in storage in the keg at about 20 to 35°C for two to three days, the remaining beer still contains a dissolved carbon dioxide volume of about 0.25 wt %. Additionally, the beer also retains a palatable taste and is not flat, all without the need for any external pressure source.
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Abstract
Description
- The present invention relates to pressurized containers or vessels made from reinforced thermoplastics and methods for making pressurized containers or vessels from reinforced thermoplastics.
- There has been a growing interest in using plastics for pressurized containers, primarily for containing beverages, but increasingly for other utilities such as containers to dispense either gaseous or liquid carbon dioxide for use in pneumatic power devices such as garden pressure sprayers, power tools, etc. wherein the high pressure carbon dioxide provides mechanical power. There is also an increased interest in the use of plastic containers in applications such as fire extinguishers, cylinders containing medical gases for distribution in laboratories and larger (e.g. 5 to 50 liters capacity), and cylinders such as those used in the distribution of oxygen, nitrogen, carbon dioxide and the like to industrial users.
- For use in beverage container applications, U.S. Patent No. 3,712,497 discloses bottles formed of thin walled, flexible synthetic plastics, in separate parts which are later friction welded together forming the bottles, capable of withstanding internal pressures of up to 75 psi.
- Also for beverage containers, U.S. Patent No. 4,591,066 discloses a unitary molded plastic body for containing pressurized liquid beverage made out of polystyrene, PET, or polypropylene. However, in packaging draft beer in containers as disclosed herein, it is found that these containers are quite permeable to carbon dioxide. Generally, when used for beer storage and with the migration of carbon dioxide through the plastic membrane / wall being temperature related (higher at room temperature than at 30-32°F), beer stored in the plastic containers of the prior art will have lost so much of its carbon dioxide content after a few days that the remaining beer will no longer be palatable and flat-tasting. EP 0 578 711B1 discloses an improved container for beer and other beverages in the form of a layered construction of at least two plastic materials, with the plastic materials being arranged in adjacent layers fastened together, or being laminated together. The improved container herein can withstand pressure of up to approximately 420kPA or about 65 psi. In one embodiment of the container, the first plastic material is a polyethylene terepthalate, and the second plastic material is nylon.
- Applicants have found that the use of reinforced polyesters in pressurized containers offers a package with gas and moisture barrier properties as well as excellent physical properties in terms of minimal creep or dimensional changes from the effects of pressure in storage or usage, as well as sufficient impact strength for safety in storage and handling.
- The invention relates a pressurized container made of reinforced polyesters having sufficient creep resistance, impact strength, CO2 and O2 barrier resistance, wherein upon being filled with a liquid having a dissolved carbon dioxide content of in the range of 0.4 - 0.6 wt % at an internal pressure of at least 1 bar, said pressurized container maintains a dissolved carbon dioxide content of at least about 0.25 wt % after 6 months at a storage temperature of about 30 to 35 °C, and an O2-permeation of less than 1.0 ppm.
- The invention also relates to the use of long-glass fiber reinforced polyesters in pressurized containers for excellent creep resistance, impact strength, water and CO2 /O2 barrier properties.
- Applicants have found that reinforced plastic materials, i.e., polyesters reinforced with various materials, e.g., long-glass fibers, provide a combination of excellent barrier and physical properties such as low permeability to gases, high strength, and low creep at elevated temperatures, thus excellent for packaging applications such as pressurized containers for beverages and foodstuff.
- Reinforced Thermoplastic Materials for the Containers. The polyester resins utilized in this invention include, in general, linear saturated condensation products of diols and dicarboxylic acids, or reactive derivatives thereof. Polyesters are well known as film and fiber formers, and they are manufactured by methods known in the art including those disclosed in U.S. Pat. Nos. 2,465,319 and 3,047,539.
- In one embodiment, the polyesters comprise condensation products of aromatic dicarboxylic acids and aliphatic diols. In another embodiment, the polyesters are poly(1,4-dimethylol cyclohexane dicarboxylates, e.g., terephthalates). In addition to phthalates, small amounts of other aromatic dicarboxylic acids, such as isophthalic dicarboxylic acid, naphthalene dicarboxylic acid, or aliphatic dicarboxylic acids, such as adipic acid, can also be present in the resins. The diol constituent can likewise be varied, in some embodiments, by adding small amounts of cycloaliphatic diols.
- In one embodiment, the polyesters comprise a poly(alkylene terephthalate, isophthalate or mixed isophthalate-terephthalate, e.g., up to 30 mole percent isophthalate), with the alkylene groups containing from 2 to 10 carbon atoms, e.g., poly(ethylene terephthalate) ("PET") or poly(1,4-butylene terephthalate) ("PBT"). In yet another embodiment the polyester resins may comprise entirely of PET, PBT, or a combination thereof. In one embodiment, the polyesters comprise a mixture of PBT to PET at a weight ratio of about 1:1 to about 20:1.
- In one embodiment, the poly(1,4-butylene terephthalate) resin used is one obtained by polymerizing a glycol component at least 70 mol %, preferably at least 80 mol %, of which consists of tetramethylene glycol and an acid or ester component at least 70 mol %, preferably at least 80 mol %, of which consists of terephthalic acid, and polyester-forming derivatives therefore.
- In another embodiment, the polyester is a poly(1,4-butylene terephthalate) homopolyester. In yet another embodiment, copolyesters are used. These comprise at least about 70 mole percent, based on total monomer content, of butylene and terephthalate units. The comonomer may be either a dicarboxylic acid or diol or a combination of the two. Suitable dicarboxylic acid comonomers include the C8 to C16 aromatic dicarboxylic acids, including the benzene dicarboxylic acids, i.e. phthalic and isophthalic acids and their alkyl, e.g. methyl, derivatives and C4 to C16 aliphatic and cycloaliphatic dicarboxylic acids including, for example, sebacic acid; glutaric acid; azelaeic acid; tetramethyl succinic acid; 1,2-, 1,3- and 1,4-cyclohexane dicarboxylic acids and the like. Suitable diol comonomers include but are not limited to C2 to C8 aliphatic and cycloaliphatic diols, e.g. ethylene glycol, hexanediol, butanediol and 1,2-, 1,3- and 1,4-cyclohexanedimethanol.
- In one embodiment, the polyester resin having a coefficient of thermal expansion (CTE) higher than that of the intended reinforcing material used, so that the polyester material shrinks around the reinforcing material causing compressive stresses which grip the reinforcing material in place.
- In anther embodiment of the present invention, the polyesters may be blended with a polycarbonate resin. Polycarbonate resins useful in preparing the blends of the present invention are generally aromatic polycarbonate resins.
- Optional Additives to the Polyester Resin Matrix. In one embodiment of the invention, the polyesters may be modified with additives such as a high molecular weight polyetherimide base material (e.g. an polyetherimide ester elastomer) as a warpage control additive.
- In another embodiment of the invention wherein the polyester is PBT, additives such as (co-)polyolefins or polyethylenes are added for improved impact strength. In one example, the impact strength additive is selected from ethylene-vinyl acetate (EVA), linear low-density polyethylene (LLDPE), and alpha-olefin-glycidyl methacrylate copolymers and terpolymers.
- In yet another embodiment of the invention wherein the weight ratio of polyester to the reinforcing agent is equal to or below about 2.25, a copolymer or interpolymer comprising glycidyl 2-alkenoates and alpha-olefins is added to the polyester for improved impact strength and improved melt viscosity to facilitate the construction of the finished pressurized containers.
- In another embodiment, the polyesters may further contain one or more conventional additives such as, for example, antioxidants, carbon black, reinforcing agents, plasticizers, lubricity promoters, color stabilizers, ultraviolet absorbers, X-ray opacifiers, dyes, pigments, fillers including mineral fillers, mold release agents such as polyethylene, and the like.
- In one embodiment, mineral fillers include alumina, amorphous silica, anhydrous aluminum silicates, feldspar, talc, milled glass, phenolic resins, glass microspheres, metal oxides such as titanium dioxide, zinc sulfide, ground quartz, clays such as hydrated aluminum silicate, and the like are used in the polyester matrix.
- In yet another embodiment, thermal, oxidative and/or ultraviolet stabilizers comprise phenols and their derivatives, amines and their derivatives, compounds containing both hydroxyl and amine groups, hydroxyazines, oximes, polymeric phenolic esters and salts of multivalent metals may be optionally added to the polyester resins.
- Reinforcing Agents for the Polyester Resin Matrix. In one embodiment, the reinforcing agents are fibers in the form of fiberglass, carbon or aramid fibers in roving, woven fabric form, or in combination of fiberglass and carbon or aramid fibers. In another embodiment, the reinforcing agents are metals drawn into wire or filaments, or polyamide polymers characterized by the presence of the amide group - CONH. In yet another embodiment, the reinforcing agents are solely glass fibers available in roving, continuous strand mat, and stitched rovings (0°, 90°, and ± 45° orientations).
- In one embodiment, the fibers are precoated with a binder to enhance compatibility with the polyester resin matrix. The coating can comprise normal fiberglass coating materials: polyurethane resin, polyacrylate resin, polyester resin, polyepoxide resin, and functional silanes, especially epoxy or amine functional alkoxy silanes. The amount of the coating agent employed is generally that amount which is sufficient to bind the filaments into a continuous strand. Generally, this may be about 1.0 weight percent based on the weight of the glass filament.
- The fiber diameters typically range from about 3 to 50 microns. In another embodiment, the filaments in the form of glass fibers have a diameter of about 5 to 30 microns. In yet another embodiment, the fiber has a diameter of about 10 to 20 microns.
- In embodiment of fibers as reinforcing agents, the fibers in the form of chopped fiberglass strands have a length of about 1/8" to about 1". In another embodiment, long-fibers with lengths of more than 1" are used, for increased strength and moldability of the containers. In yet another embodiment, the fiberglass fibers are comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass. In other embodiments, other glasses are used as well e.g., the low soda glass known as "C." In another embodiment, glass filaments known as G-filaments are used.
- The glass filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling. In one embodiment, the filaments are made by mechanical pulling. In one embodiment, the filaments are in the form of being bundled into fibers and the fibers bundled in turn to yams, ropes or rovings, for final use in reinforcing the polyesters for use in the pressurized containers of the invention.
- In one embodiment of the invention, the reinforcing agents comprise a range of materials other than glass fibers and in the form other than filaments, e.g., microspheres. These include but are not limited to glass, ceramic materials such as graphite, wollastonite, carbons, metals, e.g., aluminum, iron, nickel, stainless steel and the like, titanates, e.g., titanate whiskers, quartz, clay, mica, talc, mixtures of the foregoing and the like. The metal and metal glass fiber materials that can be used include those disclosed in the U.S. Pat. No. 4,525,314, the entire disclosure of which is incorporated herein by reference. The ceramic materials from which the reinforcing fibers can be made include silicon carbide, silicon nitride, carbon, graphite and aluminum oxide. The metal, ceramic, and glass microspheres than can be used as reinforcing agents include those disclosed in U.S. Pat. No. 4671994, the entire disclosure of which is incorporated herein by reference.
- In one embodiment, reinforcing agents are used in an amount ranging from about 5 to about 60 weight percent based on the total weight of the thermoplastic blend composition. In another embodiment, the concentration of the reinforcing agents is expressed as volume %, and ranging from about 1 to about 50 volume % (vol. %). The volume percent can be calculated by comparing the total area of the cross section of a finished part with the cross sectional area of the fibers. In another embodiment, this amount is less than about 40 vol. %. In a third embodiment, it is less than 30 vol. %. In a fourth embodiment, it is about 5 to 20 vol. %.
- Processing of the Reinforced Polyesters / Forming the Pressurized Containers. In one embodiment of the invention, wherein the reinforcing agents used are long fibers, a pultrusion process known in the art is used to form the components into shape. In a pultrusion process, the long glass fiber material is drawn through a bath containing the polyester resins plus any additives. In one embodiment of the pultrusion process, the long glass fiber material is first impregnated with the polyester resin of the invention (plus any optional additives). Laminate formed is pulled through a heated die controlled to precise tolerances depending on the final container application specifications. The finished product is cut and tooled into various parts of the container, e.g., sidewall, top or bottom part and the like. The parts are subsequently welded forming the finished containers.
- In yet another embodiment, a process as generally described in EP 0 820848B1 is used for a lineal structure particularly useful for a tall pressurized container, which reference is expressedly incorporated herein. This process comprises feeding the melted polyester materials of the invention into a die having an inlet for receiving the melted material, and an outlet having a geometry corresponding to the desired part of the container of the invention. The outlet is positioned downstream from the inlet wherein the melted polyester resin flows from the inlet to the outlet. A plurality of fiber bundles are introduced to the stream at predetermined spaced apart radial positions for providing the fiber reinforcement to the lineal profile. The fiber bundles extend in the longitudinal direction at predetermined locations in the profile. The finished product is cut and tooled into various parts of the container, e.g., sidewall, top or bottom part and the like.
- Subsequent to the pultrusion or extrusion process forming the parts, and the assembling of the parts via welding or other processes known to the art to form the finished containers, the containers can be further reinforced with additional bands of materials as generally taught in EP0852695B1 for "Blast Resistant And Blast Directing Containers." In one embodiment, the pressurized container further comprises a plurality of spaced, substantially parallel composite strips attached to and reinforcing the container with each strip being a tape of unidirectional high strength fibers or oriented film encircling the container in a hoop direction at least once.
- In another embodiment of the invention, chopped glass strands are used as reinforcing agents. The chopped glass strands may be first blended with the polyester resin and then fed to an extruder and the extrudate cut into pellets. In another example, they may be separately fed to the feed hopper of an extruder to preparing reinforced polyester pellets. The pellets so prepared when cutting the extrudate may be one-fourth inch long or less. The dispersed glass fibers are reduced in length as a result of the shearing action on the chopped glass strands in the extruder barrel.
- The reinforced polyester resins are subsequently shaped into pressurized containers or parts thereof, via common processes known in the art, such as extrusion blow molding, injection blow molding, profile extrusion, pipe extrusion, co-extrusion, extrusion coating, foam molding, foam extrusion, thermoforming, and the like. The parts can be subsequently welded to form the finished pressurized containers.
- Properties of the Pressurized Containers. In one embodiment of the invention, wherein the reinforced polyester pressurized containers of 2-4 mm thickness are used as beer containers, i.e., beer kegs, it is found that the reinforced polyester pressurized containers of the invention have inherently low CO2 and oxygen permeation properties, wherein upon being filled with a liquid having a dissolved carbon dioxide content of 0.4 - 0.6 wt % at an internal pressure of at least 1 bar, said pressurized container maintains a dissolved carbon dioxide content of at least 0.25 wt % after 0.5 year at a storage temperature of about 30 to 35 °C and an O2-permeation of less than 1.0 ppm.
- With respect to creep properties, in one embodiment of the invention, the pressurized containers, made out of reinforced polyesters, used at an initial internal pressure of 1-5 bar have a creep < 3 % after 0.5 year at room temperature.
- With respect to impact break resistance properties, in embodiments wherein long-glass-fibers are used as reinforcing agents and pultrusion technology is used to fabricate the pressurized containers of the present invention, tests on a number of differently designed and produced 15 liter vessels of 2-4 mm thickness show that pressurized containers (50% filled and 80 % filled) are break-resistant upon being dropped from heights ranging from 0.45 - 1 m.
- In food applications, e.g., as beer kegs or pressurized containers for soft drinks and a variety of foodstuffs, it is found that the reinforced polyesters containers of the present invention do not import unacceptable levels flavoring changes to the products.
- EXAMPLE. The examples below are merely representative of the work that contributes to the teaching of the present application.
- Examples 1 - 4. In this example, reinforced polyester compositions comprising PBT (poly(butyleneterephthalate) with molecular weight of approximately 80,000 (as expressed as PS molecular weight), 0.15 % Irganox 1010 as a stabilizer, approximately 1 % of a polyethylene as release agent., and from 30 to 50 wt. % of glass fiber.
- The compositions are referred to as 30% SGF, 50% LGF, 30% LGF, and 50% LGF, depending on whether short glass or long glass fiber is used. The short glass fiber is in the form of E-glass chopped strands commercially available from NEG as T-120. The long glass fiber (e.g. E-glass based) can be treated with a finishing agent such as a silane-based coupling agent, greige goods such as urethane-based resins or epoxy-based resins, a thermal stabilizer such as typically phosphite-based resins, or any other adequate surface-treating agents depending upon aimed uses, if required.
- The LGF compositions are made according to the pultrusion process as generally disclosed in U.S. Patent No. 4,559,262, the entire disclosure of which is incorporated herein by reference. In the examples, PBT polymer melts are prepared in a bath of about 260°C. Fiber glass filaments (in the form of a glass roving) are pulled through the molten polymer over one spreader bar situated in the bath at a rate of 30 cm/minute, giving a dwell time in the bath of 30 seconds. The impregnated roving is pulled through a 3 mm diameter die in the wall of the bath and then cooled, for a completely wetted material. The amount of PBT in the finished product (for 30 or 50 wt. % concentration of fiber) is controlled by the length of the path over which the fiber band contacts the heated spreader surface.
- The products obtained by the continuous pultrusion are subsequently chopped to form pellets having a length in the range of at least 5 - 10 mm. The used LGF products are supplied by LNP under the name of Verton AF 7006 (30 % LGF) and WF 700 10 (50 % LGF).
- The SGF blends are made by dry blending of ingredients with exception of the glass fiber. The blends are subsequently compounded on a WP25 mm co-rotating extruder, where the glass is separately fed down-stream the extruder. The melt temperature was approx. 250-260°C and at RPM of 300. The products obtained are extrudated to form pellets.
- The SGF and LGF products are molded into samples using an Engel 75 tons machine with a temperature setting of 240-260°C (from throat to nozzle) and a mold temperature of 60°C. Prior to molding the pellets were predried at 120°C for 2 hours.
- The properties of the short-glass fiber (SGF) and long-glass fiber (LGF) samples in Examples 1-4 are measured according to the following procedures:
- Notched Izod (NI) and Unnotched Izod (UNI): This test procedure is based on the ISO180 method, with the notched (INI) and the unnotched (UNI) impact strengths being obtained by testing a notched or unnotched specimen. The results of the test is reported in terms of energy absorbed per unit of specimen width, and expressed in kilojoules per square meter (kJ/m2). Typically, the final test result is calculated as the average of test results of five test bars.
- The Flexed Plate Impact Test: This test procedure is used to determine maximum
force, energy at max, energy at break and deflection at break, based on the ISO6603
method and used at different speeds.
Type Max.Force (N) @ 4 m/s Max.Force (N) @ 0.1 m/s Energy @ Max (J) @ 4 m/s Energy @ Break (J) @ 4 m/s Defl. @ Brk (mm) @ 4 m/s INI (kJ/m2) acc. LNP INI (kJ/m2) acc. GEP UNI (kJ/m2) acc GEP 50% SGF 2526 2780 8.1 13.8 10.4 13.4 14.1 45.9 50% LGF 2834 2741 8 17.9 15.1 40 42.1 59.2 30% LGF 2656 2519 9.5 15.9 11.9 30 32.5 56.2 30% SGF 2292 2365 9.3 12.1 12.8 9.9 48.9 -
- Example 2. In this example, the 50% LGF composition in Example 2 is used in a fiber-reinforced polyester pressurized vessel, i.e., beer kegs, with a pultrusion process is used to form the components of the beer kegs.
- The beer kegs are filled from beer tanks at suitable internal pressure of about 2 bars and at temperature of about 20 to 35 °C, and with the beer having a dissolved carbon dioxide content of about 0.5 wt %.
- After a shelf life of approx. six months and at a temperature of 20 to 35 °C, it is found that the beer in the fiber-reinforced polyester beer kegs of the present invention has a dissolved carbon dioxide content of at least 0.25 wt. %. It is also found that the beer is not flat when dispensed and consumed. It is also found that after the beer is partially consumed and in storage in the keg at about 20 to 35°C for two to three days, the remaining beer still contains a dissolved carbon dioxide volume of about 0.25 wt %. Additionally, the beer also retains a palatable taste and is not flat, all without the need for any external pressure source.
- It should be understood that the foregoing description is only illustrative of the invention. Various alternative modifications can be employed by those skilled in the art without departing from the scope of the invention. Accordingly, the present invention is intended to embrace all such alternative, modifications and variances, which fall within the scope of the appended claims.
Claims (10)
- A pressurized container made of reinforced polyesters wherein upon being filled with a liquid having a dissolved carbon dioxide content of about 0.4 - 0.6 wt % at an internal pressure of at least 1 bar, said pressurized container maintains a dissolved carbon dioxide content of at least 0.25 wt % after 0.5 year at a storage temperature of about 30 to 35 °C.
- The pressurized container of claim 1, wherein the polyesters are reinforced by reinforcing agents selected from glass fibers, carbon fibers, metal fibers, aromatic polyamide fibers, and combinations thereof.
- The pressurized container of claim 1, obtainable by a conventional thermoplastic processing method selected from injection molding, thermoforming, hot-press molding, injection-compression molding, blow molding, pultrusion, extrusion, or combinations thereof.
- The pressurized container of claim 1, further comprising a plurality of reenforcing strips attached to and reinforcing said container with each strip encircling the container in a hoop direction at least once.
- The pressurized container of claim 1, wherein the reinforcing agents are glass fibers having a length of at least 0.5 cm.
- The pressurized container of claim 1, wherein the polyesters are reinforced by glass fibers in an amount of at least 20 wt. % based on the total weight of said reinforced polyesters.
- The pressurized container of claim 1, wherein the polyesters are reinforced by glass fibers in an amount of about 1 to about 50 volume % (vol. %).
- The pressurized container of claim 1, having a wall thickness of at least 0.2 mm.
- The pressurized container of claim 1, having a total liquid volume of at least 15 liters.
- A pressurized container made of reinforced polyesters having a wall thickness of at least 0.2 mm and a carbon dioxide permeability property of less than 0.8 g / 100 sq in. in 24 hours per mil.
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US661444 | 2003-09-12 |
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- 2004-02-26 EP EP04251063A patent/EP1457732A3/en not_active Withdrawn
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Also Published As
Publication number | Publication date |
---|---|
JP2004256176A (en) | 2004-09-16 |
EP1457732A3 (en) | 2008-10-22 |
US20040166266A1 (en) | 2004-08-26 |
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