WO2015076981A1 - Method and system for impregnating fibers to form a prepreg - Google Patents
Method and system for impregnating fibers to form a prepreg Download PDFInfo
- Publication number
- WO2015076981A1 WO2015076981A1 PCT/US2014/062325 US2014062325W WO2015076981A1 WO 2015076981 A1 WO2015076981 A1 WO 2015076981A1 US 2014062325 W US2014062325 W US 2014062325W WO 2015076981 A1 WO2015076981 A1 WO 2015076981A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- web material
- pressure
- impregnation
- fibers
- moving
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000835 fiber Substances 0.000 title claims description 81
- 229920005989 resin Polymers 0.000 claims abstract description 84
- 239000011347 resin Substances 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 77
- 238000005470 impregnation Methods 0.000 claims abstract description 73
- 239000002657 fibrous material Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 230000007480 spreading Effects 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004634 thermosetting polymer Substances 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 229920002748 Basalt fiber Polymers 0.000 claims 1
- 229920006231 aramid fiber Polymers 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 description 19
- 230000003068 static effect Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 8
- 230000002787 reinforcement Effects 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 238000009727 automated fiber placement Methods 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 238000009787 hand lay-up Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- -1 tackifiers Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 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
- 238000009940 knitting Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
- B30B11/18—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses using profiled rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/16—Cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/45—Joining of substantially the whole surface of the articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
- B29C66/7212—Fibre-reinforced materials characterised by the composition of the fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
- B29C66/7214—Fibre-reinforced materials characterised by the length of the fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
- B29C66/7214—Fibre-reinforced materials characterised by the length of the fibres
- B29C66/72141—Fibres of continuous length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/82—Pressure application arrangements, e.g. transmission or actuating mechanisms for joining tools or clamps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B3/00—Presses characterised by the use of rotary pressing members, e.g. rollers, rings, discs
- B30B3/04—Presses characterised by the use of rotary pressing members, e.g. rollers, rings, discs co-operating with one another, e.g. with co-operating cones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
- B29C70/506—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
Definitions
- Prepreg composite materials have been widely used in various high-performance structures, such as aircraft and automobile components, and sport equipment (e.g., fishing rods, golf club shafts, badminton rackets, tennis rackets, etc.).
- a prepreg is a fiber reinforcement that is pre-impregnated with a matrix resin, typically a thermoset resin. The fibers reinforce the matrix resin, bearing the majority of the load supported by the prepreg material, while the resin matrix bears a minority portion of the load supported by the prepreg material and also transfers load from broken fibers to intact fibers. In this manner, the prepreg material can support greater loads than either the matrix resin or fibers can support alone. Furthermore, by tailoring the reinforcing fibers in a particular geometry or orientation, a composite material can be efficiently designed to minimize weight and volume while maximizing strength.
- Prepregs may be manufactured by impregnating a web of continuous fibers or a fabric with a matrix resin, creating a pliable and tacky sheet of material.
- the reinforcing fibers are impregnated with the matrix resin in a controlled fashion.
- the precise specification of the fibers, their orientation and the formulation of the resin matrix can be specified to achieve the optimum performance for the intended use of the prepregs.
- the mass of fibers per square meter can also be specified according to requirements.
- the term "impregnate” refers to the introduction of a matrix resin to reinforcement fibers so as to partially or fully encapsulate the fibers with the resin.
- the impregnation process controls the amount of resin inside the fiber bed and at the surface of the fiber bed. Furthermore, the resin impregnation level impacts the methods used to assemble the finished composite part and the part's quality.
- the matrix resin for making prepregs may take the form of resin films or liquids. Typically, impregnation is facilitated by the application heat and/or pressure.
- the resulting prepregs produced from the prepreg fabrication process is in an uncured or curable state (i.e., not hardened) and may be frozen in order to inhibit the polymerization of the resin.
- the cold prepregs are thawed to room temperature, cut to size, and assembled on a molding tool through various methods, such as hand layup, Automated Tape Layup (ATL), and Advanced Fiber Placement (AFP).
- the prepreg material for each assembly method requires different levels of impregnation and different levels of tack.
- Level of "tack” refers to how well prepregs stick to one another and to a tool surface. For example, for hand layup, there is less need for high level of impregnation and greater need for tack while with AFP the fiber bed requires much higher levels of impregnation.
- the prepregs are consolidated and cured under pressure to achieve the required fiber volume fraction with minimal voids.
- FIG. 1 illustrates the general concept of Relative Speed Impregnation technique according to the present disclosure.
- FIG. 2 illustrates a conventional technique of applying static pressure nip to affect impregnation.
- FIG. 3 is a graph showing the relationship between pressure-at-time and relative velocity (V re i) between a moving web material and the pressure nip applied during
- FIG. 4 shows an embodiment of a prepreg fabrication system.
- FIG. 5 shows an embodiment a static pressure applicator for pressing an idler roller against a web material.
- FIG. 6 shows another embodiment of a static pressure applicator for pressing an idler roller against a web material.
- FIG. 7 illustrates the roller chain progression under static pressure applicators according to an embodiment of applying pressure against a moving web material.
- the impregnation technique disclosed herein is related to resin film impregnation in which at least one resin film is pressed against each of the top and bottom surfaces of a continuous fibrous web to produce a continuous prepreg, in which the fibrous material is embedded within a matrix resin.
- the fibrous web is composed of reinforcement fibers and may be in the form of unidirectional fibers or a fabric (woven or nonwoven).
- the term "impregnate” as used herein refers to the introduction of a curable matrix resin to reinforcement fibers so as to partially or fully encapsulate the fibers with the matrix resin.
- An objective of the RSI technique is to produce the fastest prepreg production speed with the least fiber bed distortion and minimum pressure to achieve a desired impregnation level.
- an impregnation zone configuration is designed so that a web of resin- fiber material moving at a first velocity (V w ), often called "line speed," through an
- V n a second velocity
- the moving pressure nip is formed between a moving pressure roller and a moving surface supporting the web material.
- the moving surface is configured so as to mitigate the friction forces to the contacting surface of the web material.
- the moving surface is part of a rotating drum with a relative large cross-sectional diameter.
- V w and V n are the operating velocities relative to a fix point on the ground.
- V w is different from V n , whereby the difference between V w and V n is the relative velocity (V re ,) between the web material and the pressure nip.
- the level of impregnation is affected by the relative velocity
- FIG. 1 illustrates the general concept of the RSI technique.
- the web material W (composed of a layer reinforcement fibers sandwiched between two resin films) is moving at a line speed of 21 m/min while pressure is applied by the moving pressure nip formed between rollers 1 and 2, each roller rotating about its own central axis.
- the pressure nip is moving in the same direction as that of the web material W at a velocity of 18 m/min.
- the relative velocity (V re ,) between the web material W and the moving pressure nip is 3 m/min.
- the line speed (i.e. production rate) of the web material is 7 times that of the relative velocity (V re ,).
- the line speed speeds as discussed in the present disclosure may be measured using conventional speed sensing devices such as
- the advantage of the RSI process is that the physics of impregnation is decoupled from the line speed of the web material, thereby enabling a significantly higher prepreg production rate at identical levels of impregnation as compared to conventional impregnation methods using static pressure nips or belts. These conventional methods generally require immense forces and complicated control systems.
- pressure-at-time is required—the pressure applied to web material (not too high or too low) and time provided by slow speed.
- Pressure-at-time may be calculated as PI V re , - the linear force (P) applied to the web material divided by the relative velocity (V re i), and is measurable in units of Pascal-second (Pa » s), equivalent to kg/m/s.
- the linear force (P) is the downward force per linear width, e.g. pounds per inch (PLI) or Newtons per meter (N/m), exerted by the pressure roller (upper roller 1 , FIG. 1 ), which is measured along the width of the web material.
- V re i The relationship between pressure- at-time and relative velocity V re i is hyperbolic as illustrated in FIG. 3. As V re i is decreased, pressure-at-time dramatically increases. And the impregnation level goes up with pressure- at-time. As such, it is desirable to keep V re , as low as possible.
- the optimum V re is dependent on the resin properties (e.g. viscosity) and permeability of the fiber web (e.g. openings or voids in the fiber layer, spacing/interstices between fibers, etc.).
- the RSI process is carried out by moving a web material (which is composed of a fiber layer sandwiched between two resin films) through an impregnation assembly having one or more moving pressure nips applying pressure-at-time of up to 10 MPa » s, or up to 7 MPa » s in certain embodiments, to achieve the required level of impregnation, e.g. up to 100% impregnation level.
- the pressure-at-time in this context refers to that applied by the entire impregnation assembly.
- the level of impregnation refers to how far the resin has penetrated through the thickness of the fiber layer.
- the line speed of a high viscosity web material with a thick fiber bed may be up to 15 ft/min (3 m/min), while the RSI process is capable of increasing the line speed by more than 10 fold.
- FIG. 4 An embodiment of a prepreg fabrication system with means for implementing the RSI process is shown in FIG. 4.
- the prepreg fabrication process starts with conveying continuous fiber bundles 1 1 from a fiber supply unit 10 to a fiber spreading section 12.
- the fiber supply unit 10 includes a plurality of spools for winding the fiber bundles and creels for supporting the spools.
- Each fiber bundle is composed of a plurality of fiber filaments.
- the fiber spreading section 12 is equipped with suitable means for spreading the fiber bundles before contacting the fibers with the resin films. As such, the spread fibers appear as a sheet of unidirectionally aligned fiber filaments with small spacing between adjacent filaments.
- the spread fiber filaments from the fiber spreading section 12 are then combined with an upper resin film 13a and a lower resin film 13b with the aid of rollers 14 so that the fiber filaments are sandwiched between the two resin films.
- Each resin film is supplied by its own supply roll and the surface that is not in contact with the fiber filaments is covered by a release paper.
- the resulting web material 15 is next conveyed through an impregnation zone 16, which includes an insulated chamber 17 enclosing a pre-heating roll 18, a rotating drum 19, an endless roller chain 20 of linking idler rollers, and a thermally-isolated, chill roll 21 .
- the pre-heating roll 18 is positioned at the beginning of the impregnation zone and upstream of the drum 19. Prior to entering the impregnation zone 16, the resin films are in a solid state and may be kept at a cold temperature during storage in order maintain their solidified state. Immediately after the web material 15 enters the chamber 17, the preheating roll 18 applies heat to the web material in an amount sufficient to decrease the resin viscosity so that the resin is softened but not high enough to cause substantial curing of the resin.
- the chamber 17 is equipped with suitable temperature control mechanisms (not shown), for example, infra-red sensors mounted onto the sidewall of the chamber 17, to provide temperature data for the web material, the drum 19, the roller chain 20 as well as the tension of the web material entering and exiting the chamber 17.
- suitable temperature control mechanisms for example, infra-red sensors mounted onto the sidewall of the chamber 17, to provide temperature data for the web material, the drum 19, the roller chain 20 as well as the tension of the web material entering and exiting the chamber 17.
- the temperature in chamber 17 may be maintained within the range of 50 ° C to 120 ° C, which is sufficient for most commercially available resin systems.
- the resin penetrates into the interstices/spacing between the fiber filaments.
- the resin viscosity is stabilized and maintained at a desired level as the web material travels through the entire impregnation zone with the aid of the temperature control mechanism in the chamber 17. According to one embodiment, the viscosity of the resin during
- the drum 19 provides a moving support surface for the web material during impregnation and cooperates with the roller chain 20 to establish moving pressure nips through which the web material passes.
- the web material wraps around a portion of the drum's outer surface as the drum rotates.
- the large cross-sectional diameter of the drum 19 provides a physical platform for handling the nip pressures with the least amount of curvature possible.
- the roller chain 20 is configured to carry a series of closely spaced, idler rollers having elongated, cylindrical bodies with lengths extending transversely to the travel direction of the web material, each idler roller being freely rotatable about its own axis.
- the idler rollers are linked to each other by suitable linking mechanisms, for example, each idler roller may have a pin (a connecting mechanism) at one axial end connected to a
- the roller chain 20 is caused to revolve by a suitable chain drive.
- the number of idler rollers in the chain 20 may be varied depending on factors such as the required levels of force and web pressure, the desired web width and commensurate deflection needs.
- the roller chain 20 revolves in a direction opposite to the rotational direction of the drum 19 while some of the idler rollers in the roller chain 20 are pressed against a portion of the drum's outer surface and against the web material passing there between, thereby creating a plurality of pressure nips moving at velocity V n .
- the rotational velocity of the drum 19, which is driven by a suitable drive motor, is equivalent to the line speed V w of the web material as it moves through the impregnation zone 16, and the revolving velocity of the chain roller 20 is equivalent to the velocity V n of the moving pressure nips.
- the web material is being compressed by the outer circumferential surface of the rotating drum 19 and the moving idler rollers in the chain 20 to affect impregnation.
- V re i V w - V n .
- the chill roll 21 is located downstream from the drum 19 in a separate, thermally-isolated compartment, and is configured to lower the temperature of the web material sufficiently to increase the resin viscosity and lock in impregnation.
- the cooled, web material exiting the impregnation zone 16 is a prepreg 22 with a set thickness and solidified resin component. After the prepreg 22 exited the impregnation zone 16, the release paper 23 on one side of the prepreg 22 is peeled off, and then the prepreg 22 is taken up by a winding roll 24.
- FIG. 5 shows an embodiment for pressing down onto a chain link connected to the idler roller in the roller chain 20 using a static pressure applicator.
- one of the idler rollers 51 in the roller chain 20 is shown to have a shaft idler 51 a at its axial end connected to a corresponding link 52, which is part of an endless link chain.
- the static pressure applicator includes a piston 53 connected to a pressure roller 54 so as to drive the movement of the pressure roller 54 either up or down.
- the pressure roller 54 is freely rotatable about its own axis and is configured to move in and out of engaging contact with the chain link 52.
- the piston 53 is positioned above the pressure roller 54 and is controlled to provide the necessary pressure downward onto the chain link 52 or to release the pressure.
- FIG. 6 shows an embodiment for pulling down onto the chain link connected to the idler roller using a static pressure applicator.
- the pressure roller 54 for engaging the chain link 52 is connected to piston 55 via extension arm 56 positioned below the idler roller 51 .
- the movement of the pressure roller 54 together with extension arm 56 is driven by the piston 55.
- the pressure roller 54 can be pulled down into engaging contact with or lifted away from the chain link 52 by the piston 55.
- a plurality of pressure applicators of the type shown in FIG. 5 or FIG. 6 may be positioned adjacent to the section of the roller chain 20 that faces the drum 19 so as to engage each idler roller in the roller chain 20 that comes into contact with the web material passing between the roller chain 20 and the drum 19, or only selected contacting idler rollers (e.g. every other idler roller).
- FIGS. 7A-7C show the roller chain progression in an embodiment in which an array of static pressure applicators (of the type shown in FIG. 5) cooperates with the roller chain 20 to apply pressure over the drum 19 such that the pressure experienced by the chain idler rollers smoothly transitions from one idler roller to the next.
- FIGS. 7A-7C represents a snapshot at different time in the roller chain progression.
- load cells can be employed, or hydraulic/pneumatic pressures can be derived from the loading systems of the rollers.
- the creel-containing unit 10 and the spreader section 12 are replaced by mechanisms for supplying a continuous, self-supporting fabric web.
- the self-supporting fabric web may be a woven fabric or a non-woven fabric (e.g. non-crimp fabric) composed of reinforcement fibers.
- FIG. 4 depicts a two-film impregnation method, in which an upper resin film and a lower resin film are pressed against the top and bottom surfaces of the fiber web, respectively, so that the fiber web is sandwiched between the two resin films.
- an additional impregnation zone may be added downstream from the impregnation zone 16 and additional resin films may be applied onto both the upper surface and the lower surface of the impregnated web material exiting from the impregnation zone 16, in the same manner for applying the resin films 13a and 13b, but with the removal of the release papers from both sides of the web material exiting from the impregnation zone 16.
- the RSI process disclosed herein decouples resin infiltration rate (pressure, viscosity and time limitations) from production rate by moving the pressure points (i.e. nips) with the web material such that the web material experiences longer time at pressure even though the web material and nips are moving fast.
- the use of a rotatable drum as shown in FIG. 4 instead of a second belt or a flat plate as known in the prior art mitigates the difficulties associated with upper and lower roll alignment and static plate friction which would rip apart the paper.
- the reinforcement fibers for fabricating the prepregs may take the form continuous fibers, tows, or self-supporting woven or non-woven fabrics.
- Fiber structures may comprise a plurality of tows, each tow composed of multiple filaments, e.g. 3-12 thousands of filaments.
- the non-woven fabrics may include non-crimp fabrics in which the tows may be held in position by cross-tow stitches, weft-insertion knitting stitches, or a small amount of resin binder, such as a thermoplastic resin.
- the fiber material includes, but are not limited to, glass (including Electrical or E- glass), carbon, graphite, aramid, polyamide, high-modulus polyethylene (PE), polyester, poly-p-phenylene-benzoxazole (PBO), boron, quartz, basalt, ceramic, and combinations thereof.
- glass including Electrical or E- glass
- carbon graphite
- aramid high-modulus polyethylene
- PET high-modulus polyethylene
- PET poly-p-phenylene-benzoxazole
- boron quartz
- quartz basalt
- ceramic boron
- the reinforcing fibers have a tensile strength of greater than 3500 MPa.
- the matrix resin for impregnating the reinforcement fibers is based on a curable resin system containing thermoset or thermoplastic resins as the major component in combination with minor amounts of additives such as curing agents, catalysts, co- monomers, rheology control agents, tackifiers, rheology modifiers, inorganic or organic fillers, thermoplastic or elastomeric toughening agents, stabilizers, inhibitors, pigments/dyes, flame retardants, reactive diluents, and other additives well known to those skilled in the art for modifying the properties of the resin matrix before or after curing.
- additives such as curing agents, catalysts, co- monomers, rheology control agents, tackifiers, rheology modifiers, inorganic or organic fillers, thermoplastic or elastomeric toughening agents, stabilizers, inhibitors, pigments/dyes, flame retardants, reactive diluents, and other additives well known to those skilled in the art for modifying the properties of the resin
- thermoset resins may include, but are not limited to, epoxy, unsaturated polyester resin, bismaleimide, polyimide, cyanate ester, phenolic, etc.
- the resin matrix is an epoxy-based resin formulation which contains one or more
- multifunctional epoxy resins i.e. polyepoxides
- main polymeric component i.e. polyepoxides
- Suitable epoxy resins include polyglycidyl derivatives of aromatic diamine, aromatic mono primary amines, aminophenols, polyhydric phenols, polyhydric alcohols,
- suitable epoxy resins include polyglycidyl ethers of bisphenols such as bisphenol A, bisphenol F, bisphenol S and bisphenol K; and polyglycidyl ethers of cresol and phenol based novolacs.
- the addition of curing agent(s) and/or catalyst(s) may increase the cure rate and/or reduce the cure temperatures of the matrix resin.
- the curing agent for thermoset resins is suitably selected from known curing agents, for example, guanidines (including substituted guanidines), ureas (including substituted ureas), melamine resins, guanamine derivatives, amines (including primary and secondary amines, aliphatic and aromatic amines), amides, anhydrides (including polycarboxylic anhydrides), and mixtures thereof.
- the matrix resin may include toughening agents such as thermoplastic and elastomeric polymers, and polymeric particles such as core-shell rubber particles, polyimide particles, and polyamide particles.
- the matrix resin may also include inorganic fillers such as fumed silica quartz powder, alumina, and platy fillers such as mica, talc or clay (e.g., kaolin).
- the matrix resin may be prepared in liquid form and then coated onto a release paper (i.e. carrier) to form a film of suitable areal weight. After drying, the resin film is then wound up onto a supply roll.
- a prepreg with width of 12.5 in may be made by impregnating a layer of unidirectional carbon fibers with epoxy-based resin films (e.g. CYCOM 977-3 from Cytec Industries Inc.; film areal weight of 35 gsm per side) using the impregnation system shown in FIG. 4 based on the following parameters:
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Abstract
Description
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Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
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MX2016006487A MX2016006487A (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibers to form a prepreg. |
AU2014353437A AU2014353437B2 (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibers to form a prepreg |
KR1020167014933A KR102167574B1 (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibers to form a prepreg |
MYPI2016000691A MY183218A (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibers to form a prepreg |
CN201480063837.9A CN106103057B (en) | 2013-11-22 | 2014-10-27 | Fiber is impregnated to form the method and system of prepreg |
JP2016529984A JP6403771B2 (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibers to form a prepreg |
ES14796633T ES2931957T3 (en) | 2013-11-22 | 2014-10-27 | Fiber impregnation method and system to form a prepreg |
RU2016124564A RU2680505C1 (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibres to form prepreg |
CA2927942A CA2927942C (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibers to form a prepreg |
EP14796633.7A EP3071399B1 (en) | 2013-11-22 | 2014-10-27 | Method and system for impregnating fibers to form a prepreg |
BR112016010087-5A BR112016010087B1 (en) | 2013-11-22 | 2014-10-27 | METHOD FOR IMPREGNATION OF A FIBROUS MATERIAL WITH A THERMOCURABLE RESIN |
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WO2018173618A1 (en) | 2017-03-22 | 2018-09-27 | 東レ株式会社 | Method for producing prepreg and method for producing fiber-reinforced composite material |
WO2018173619A1 (en) | 2017-03-22 | 2018-09-27 | 東レ株式会社 | Production method for prepreg, and production method for fiber-reinforced composite material |
WO2018173617A1 (en) | 2017-03-23 | 2018-09-27 | 東レ株式会社 | Production method and coating device for coating-liquid-impregnated sheet-like reinforcing-fiber bundle and sheet-like integrated object |
WO2019235237A1 (en) | 2018-06-05 | 2019-12-12 | 東レ株式会社 | Coating-liquid-impregnated fiber-reinforced fabric, sheet-shaped integrated object, prepreg, prepreg tape, and method for manufacturing fiber-reinforced composite material |
WO2020031766A1 (en) | 2018-08-09 | 2020-02-13 | 東レ株式会社 | Method for manufacturing prepreg, coating device, and apparatus for manufacturing prepreg |
WO2020040154A1 (en) | 2018-08-22 | 2020-02-27 | 東レ株式会社 | Production method for prepreg, prepreg tape, and fiber reinforced composite material, and prepreg production device |
WO2020040150A1 (en) | 2018-08-22 | 2020-02-27 | 東レ株式会社 | Production method for prepreg, prepreg tape, and fiber reinforced composite material, and coating device |
WO2020040153A1 (en) | 2018-08-22 | 2020-02-27 | 東レ株式会社 | Prepreg manufacturing method and manufacturing apparatus |
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CN107839137A (en) * | 2017-11-17 | 2018-03-27 | 张家港保税区纳莱凯斯汽车配件有限公司 | A kind of thermocompression forming mechanism of automobile trunk gusset composite fibre Nomex plate |
CN109968691B (en) * | 2017-12-27 | 2020-12-08 | 中国科学院宁波材料技术与工程研究所 | Fiber thermoplastic casting vibration infiltration pre-dipping machine |
CN117325485B (en) * | 2023-11-30 | 2024-03-08 | 乌镇实验室 | Carbon fiber reinforced polyamide composite material for wind power blade and preparation method thereof |
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ES2931957T3 (en) | 2023-01-05 |
CN106103057A (en) | 2016-11-09 |
EP3071399B1 (en) | 2022-08-31 |
CN106103057B (en) | 2018-02-27 |
AU2014353437B2 (en) | 2018-08-16 |
AU2014353437A1 (en) | 2016-05-05 |
JP2016539824A (en) | 2016-12-22 |
US9782930B2 (en) | 2017-10-10 |
EP3071399A1 (en) | 2016-09-28 |
CA2927942A1 (en) | 2015-05-28 |
MX2016006487A (en) | 2017-01-18 |
BR112016010087A2 (en) | 2017-08-01 |
BR112016010087B1 (en) | 2021-09-08 |
KR102167574B1 (en) | 2020-10-19 |
KR20160090305A (en) | 2016-07-29 |
US10155344B2 (en) | 2018-12-18 |
RU2016124564A (en) | 2017-12-27 |
TW201529307A (en) | 2015-08-01 |
CA2927942C (en) | 2021-06-22 |
TWI628076B (en) | 2018-07-01 |
RU2680505C1 (en) | 2019-02-21 |
MY183218A (en) | 2021-02-18 |
US20170361542A1 (en) | 2017-12-21 |
JP6403771B2 (en) | 2018-10-10 |
US20150145163A1 (en) | 2015-05-28 |
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