US20170190845A9 - Microlayer coextrusion for compounding, pelletizing, and masterbatches - Google Patents
Microlayer coextrusion for compounding, pelletizing, and masterbatches Download PDFInfo
- Publication number
- US20170190845A9 US20170190845A9 US14/869,189 US201514869189A US2017190845A9 US 20170190845 A9 US20170190845 A9 US 20170190845A9 US 201514869189 A US201514869189 A US 201514869189A US 2017190845 A9 US2017190845 A9 US 2017190845A9
- Authority
- US
- United States
- Prior art keywords
- layers
- pellet according
- pellet
- axis
- stream
- 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.)
- Granted
Links
- 238000013329 compounding Methods 0.000 title abstract description 7
- 238000005453 pelletization Methods 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000008188 pellet Substances 0.000 claims description 61
- 239000000835 fiber Substances 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 36
- 239000000945 filler Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 239000012768 molten material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- -1 Polyethylene terephthalate Polymers 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002052 molecular layer Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- WJXQFVMTIGJBFX-UHFFFAOYSA-N 4-methoxytyramine Chemical compound COC1=CC=C(CCN)C=C1O WJXQFVMTIGJBFX-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002544 Olefin fiber Polymers 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920001872 Spider silk Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- 241000282485 Vulpes vulpes Species 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 210000000077 angora Anatomy 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 239000002729 catgut Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000000050 mohair Anatomy 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004767 olefin fiber Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- 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
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B29C47/0009—
-
- B29C47/065—
-
- B29C47/128—
-
- B29C47/38—
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/12—Articles with an irregular circumference when viewed in cross-section, e.g. window profiles
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/304—Extrusion nozzles or dies specially adapted for bringing together components, e.g. melts within the die
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/345—Extrusion nozzles comprising two or more adjacently arranged ports, for simultaneously extruding multiple strands, e.g. for pelletising
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29K2101/00—Use of unspecified macromolecular compounds as moulding material
- B29K2101/10—Thermosetting resins
-
- 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
- B29L2031/00—Other particular articles
- B29L2031/772—Articles characterised by their shape and not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
Definitions
- the present disclosure generally relates to pelletizing and compounding extrusion die systems.
- the present disclosure relates to the cyclical extrusion of materials to generate small sized grain features, generally in the range of micro and nanosized grain features.
- Compounding is the process of mixing multiple components including polymers, colorants, additives and fillers. This is often done in an extruder, such as a twin screw extruder.
- Pelletizing is the process of chopping extruded material into small pellets for use in a later process.
- a masterbatch is a compounded batch of pellets which contains a high concentration of an additive or filler in a polymer. Pellets from a masterbatch would be re-compounded along with unfilled pellets to create a desired concentration of additive or filler.
- Pellets are typically fed into an extruder where they are melted and pressurized for subsequent processes. These manufacturing processes include extrusion, injection molding, and blow molding. Pellets can also be used in recycling processes. In recycling processes, the degree of crystallinity of the polymer may be important such as in recycling PET(Polyethylene terephthalate) plastic.
- Nanostructured materials are generally regarded as materials having very small grain feature size, typically in the range of approximately 1-100 nanometers (10 ⁇ 9 meters). Metals, ceramics, polymeric and composite materials may be processed in a variety of ways to form nanosized features. These materials have the potential for wide ranging applications, including for example, industrial, biomedical, 3D printing and electronic applications. As a result, a great deal of study is ongoing to gain a better understanding of the characteristics of these materials.
- the aspects of the disclosed embodiments is directed to the compounding and pelletizing of extruded or coextruded multilayer materials. These materials contain tens to thousands of layers of micro- to nano-polymer layers. These new shapes contain contiguous layers of milli- to nano-polymer layers in three dimensions and these contiguous layers may be twisted or turned to further expand the potential microlayer geometries. These layers can take the form of flat layers, annular or tubular rings as well as multi component structures.
- Suitable geometries for pellets include any shape such as cylindrical, spherical, capsular, conical, conical frustum, cubular, hemispherical, pyramidal, rectangular prismatic, tubular.
- Other examples of flat layer geometries are presented in FIGS. 1 a - b and are depicted with a limited number of layers for illustrative purposes.
- Examples of Tubular Polygonal and Annular geometries are presented in FIGS. 1 c - f .
- Examples of multicomponent geometries are presented in FIGS. 1 g - h.
- Microlayer coextrusion can be used to create products possessing tens to thousands of layers, such as fifty to one hundred layers or one to ten thousand layers or one hundred thousand layers.
- the layers may contain the same or different polymer and contain different fillers, particles or chemicals.
- a pellet wherein at least one layer is 0.1-100 nanometer on one axis.
- Pellets are three dimensional products and as such can be assigned three axes.
- the primary axis is defined such that the layers run longitudinally along it.
- a pellet according to the present invention may comprise at least ten layers which are each 0.1-100 nanometer on this primary axis.
- a pellet may comprise at least one hundred layers each of which are 0.1-100 nanometers on one axis.
- a pellet may comprise at least one thousand layers which are 0.1-100 nanometer on one axis.
- a pellet may comprise at least one layer which is 0.01-1 micrometer on one axis. In another embodiment of the invention, a pellet may comprise at least one layer which is 0.01-1 millimeter on one axis.
- a pellet has a melting point of between 0° C. to about 500° C. Another embodiment relates to those pellets melting near or below room temperature (0° C. to about 30° C.). Another embodiment relates to those pellets melting at relatively low temperatures such as 30° C. to about 150° C. Another embodiment relates to those pellets melting at temperatures from about 150° C. to about 250° C. Another embodiment relates to those pellets melting at relatively high temperatures such as metals, such as from about 300° C. to about 500° C.
- compositions of the layers could contain composition A and composition B and the layers could alternate A-B-A-B-A-B. or even A-B-B-A-B-B-A-B-B.
- Three component compositions containing compositions A, B and C may likewise form alternating layers such as A-B-C-A-B-C-A-B-C.
- Such microlayer extrusions can form their own products or can be applied onto a core.
- Another embodiment relates to products containing a composite inner core extruded with composite milli, micro, or nano layers on the exterior.
- Another embodiment relates to products containing multiple layers of varying components.
- Microlayer coextrusion can be used to blend different materials into a homogenous mixture.
- homogeneous means that the components are spread out randomly within the mixture. If a line were to be drawn through the axis of the stream mixture, all components would be statistically randomly positioned along the line. This is so because at the layer thickness of the invention molecular size or particle size kinetics influence distribution.
- Another way of understanding homogeneity is to appreciate that if layer sizes are brought sufficiently into the nanometer range, the layer sizes are so small that the resultant material is more of a blend of the layer materials rather than a layered structure. This process could be used on its own to create a blend from separate materials or could be used as a secondary process to further ensure a homogenous blend.
- the blended materials could be extruded and pelletized for later use or they can be directly fed into a subsequent process for immediate use.
- Another embodiment relates to an extruder accessory device which could perform the microlayering or multicomponent process to form a stream of molten material comprising of multilayers of milli, micro or nanometer thickness from the output of one or more extruders prior to subsequent processing of the melt stream.
- This device could take the place of a flange which would ordinarily connect an extruder to downstream equipment.
- An example can be seen in FIG. 6 .
- An extruder could have such a device integrated as a component following pressurization by the extruder's one or more screws.
- the device could also be integrated as a flange which would connect to one or more extruders on one end and further processing devices on the other.
- An example schematic of an extruder with integrated layering can be seen in FIG. 7 .
- These aforementioned processing devices could include but are not limited to extrusion dies, molds, and blow molding dies.
- Microlayer coextrusion also allows for enhanced alignment of filler particles or fibers along the direction of the extrusion.
- Filler particles are mostly restrained within each layer and as they approach a magnitude of size similar to the fiber or particle size, shear stresses and confinement by layer boundaries act to align particles in the direction of the extrusion.
- the smallest dimension will be perpendicular to the layer boundary and the longest dimension will be in the direction of the extrusion.
- Platelet or flake-like fillers will align in a two dimensional manner while confined by the layers surrounding them.
- Another embodiment relates to products containing filler particles or fibers. More preferred products contain filler particles or fibers aligned along the extrusion axis.
- the creation of many layers as well as the shear stresses resulting from the repeated spreading and thinning of individual layers of materials can also help to enhance the dispersion of fillers.
- the enhanced dispersion may help to prevent aggregates or agglomerates of the filler and the shear stresses may aid in the deterioration of agglomerates.
- Coloring active ingredients include quinacridones, phthalocyanines azo-type dyes, nickel titanate, titanium dioxide, cobalt, and manganese chrome antimony titanate, said active ingredient in a concentration of at least 60% by weight.
- At least one layer contains a colorant.
- the pellet comprises two compositions wherein one composition comprises hydrophobic agents and the second composition comprises hydrophilic agents.
- the pellet comprises two compositions wherein one composition comprises acidic agents and the second composition comprises basic agents.
- the pellet comprises two compositions wherein one composition comprises a lower density composition and the second composition comprises a higher density composition.
- the pellet comprises two compositions wherein one composition comprises a highly viscous composition and the second composition comprises a non-viscous composition.
- Viscosity is measured in centipoise (cP) and liquids such as glycerin and oils are known as high viscosity materials.
- Liquids such as water, alcohols, and low molecular weight hydrocarbons are known as low viscosity materials.
- the pellet comprises two compositions wherein one composition comprises a material processed at one temperature range and the second composition processes at a higher temperature range.
- Another embodiment involves a method of creating fillers within a pellet by coextruding a first lower temperature material along with either a higher melt temperature material or a thermoset material such that in subsequent processing, the second material resists melting and retains its shape.
- the pellet comprises two compositions wherein one composition comprises a high concentration of one or more agents and the second composition comprises a low concentration of one or more agents or no agent at all.
- Fillers also refers to flakes such as copper or tin flakes.
- Fibers include single fibers or a myriad of other arrangements. Some exemplary arrangements include yarns, a tow of fibers or yarns, a weave, a non-woven, chopped fiber, a chopped fiber mat (with random or ordered formats), or combinations of these formats.
- the chopped fiber mat or nonwoven may be stretched, stressed, or oriented to provide some alignment of the fibers within the nonwoven or chopped fiber mat, rather than having a random arrangement of fibers.
- Fibers also generally possess an average aspect ratio of 10-3000 and more commonly are fibers having an average aspect ratio of 20-1000. Aspect ratios of 20-350 and 50-200 are specifically envisioned.
- Various types of organic and inorganic fibers are suitable either in monofilament or stranded form (including bundles of fibers bonded together to make a single element which serves as a single fiber in the sense of orientation and reinforcement).
- Filler particles or fibers include graphene, wood fibers (including groundwood, thermomechanical pulp (TMP) and bleached or unbleached kraft or sulfite pulps), vegetable fibers (including cellulose, lignin, cotton, hemp, jute, flax, ramie, sisal and bagasse), animal fibers (including proteinaceous strands such as silkworm silk, spider silk, sinew, catgut, wool, sea silk and hair such as cashmere wool, mohair and angora, fur such as sheepskin, rabbit, mink, fox, or beaver), other synthetic polymeric fibers (including rayon, modal, Lyocell polyamide nylon, PET or PBT polyester, phenol-formaldehyde (PF), polyvinyl alcohol fiber (PVA) vinylon, polyvinyl chloride fiber (PVC) vinyon, polyolefins (PP and PE) olefin fiber, acrylic polyesters, pure polyester, aromatic polyamids (aramids) such as Twar
- Dyneema or Spectra polyurethane fiber, and elastomers including spandex
- metallic fibers such as those drawn from ductile metals such as copper, gold or silver and extruded or deposited from more brittle ones, such as nickel, aluminum or iron, stainless steel fibers, silicon carbide fibers, clay particles, carbon fibers or glass fibers.
- Particularly important fibers include the so-called micro and nano fibers including nanocellulous fibers and synthetic nanotubules including carbon nanotubes, inorganic nanotubes and DNA nanotubes.
- Fibers also includes microfibers known as sub-denier fibers (such as polyester drawn to 0.5 dn). Denier and Detex fibers include fibers categorized by weight and length measurements. Fiber designs also includes fibers split into multiple finer fibers. Most synthetic fibers are round in cross-section, but special designs can be hollow, oval, star-shaped or trilobal. The latter design provides more optically reflective properties. Synthetic fibers may also be crimped to provide a woven, non woven or knitted structure. Fiber surfaces can also be dull or bright. Dull surfaces reflect more light while bright tends to transmit light and make the fiber more transparent.
- sub-denier fibers such as polyester drawn to 0.5 dn.
- Denier and Detex fibers include fibers categorized by weight and length measurements. Fiber designs also includes fibers split into multiple finer fibers. Most synthetic fibers are round in cross-section, but special designs can be hollow, oval, star-shaped or trilobal. The latter design provides more optically reflective properties. Synthetic fibers may also be crimped to provide
- Fibers Very short and/or irregular fibers have been called fibrils. Natural cellulose, such as cotton or bleached kraft, show smaller fibrils jutting out and away from the main fiber structure.
- Fibers alignment can also be tailored by the application of external forces such as magnetic fields.
- pellet composition of the present disclosure comprises additives such as ultraviolet light absorbers, light stabilizers, antioxidants, flame-retardants, antibacterial agents, surface tension reducers, deodorizing agents, anti-static agents, anti-blocking agents, plasticizer agents, blowing agents, fillers, and other known additives, or mixtures thereof.
- additives such as ultraviolet light absorbers, light stabilizers, antioxidants, flame-retardants, antibacterial agents, surface tension reducers, deodorizing agents, anti-static agents, anti-blocking agents, plasticizer agents, blowing agents, fillers, and other known additives, or mixtures thereof.
- Another embodiment relates to a method of blending multiple streams and directly feeding the stream into a subsequent process for immediate use.
- FIGS. 1 a -1 b depict examples of flat layer geometries with a limited number of layers for illustrative purposes.
- FIGS. 1 c -1 f depict examples of tubular, polygonal and annular geometries.
- FIGS. 1 g -1 j depict examples of multicomponent geometries.
- FIG. 2 illustrates the tendency of fibers to align along the axis of extruded layers.
- FIG. 3 illustrates larger extrusion layers, no-layers or coated materials containing fibers that have fiber orientations that are more random or less ordered.
- FIG. 4 illustrates a pellet with varying component sections which promotes better control of when and how fillers are dispersed.
- FIG. 5 illustrates a tortuous path a permeate would encounter due to lamellae crystals or high aspect ratio fillers.
- FIG. 6 depicts an extruder with an attached layering device.
- FIG. 7 depicts an example schematic of an extruder with integrated layering.
- the present disclosure is generally directed towards cyclical extrusion of materials to generate small sized grain features, generally in the range of micro and nanosized grain features.
- small sized grain features generally in the range of micro and nanosized grain features.
- Folding methods are also included geometries. All of these geometries may be composed of milli, micro and nano layer streams or extrusions that can also include fillers and fibers. Independent of fibers, the layers may comprise different polymers or soluble components that do not mix. When these streams contain fillers or fibers and are extruded in the small, milli, micro, or nano layers the fibers tend to align along extruded layers such as depicted in FIG. 2 . The relative sizes of fillers to sizes of layers will affect the degree of orientation.
- no-layers or coated materials containing fibers have fiber orientations that are more random or less ordered, such as depicted in FIG. 3 .
- Orientation of fibers and flakes can change, enhance or create many properties of an extruded composite. This is important in the creation of composite materials. Extrusion in general has an orienting effect on fibers, however the inclusion of microlayers will amplify the degree of orientation. If the fiber has stronger mechanical properties than the matrix polymer, the product will be stronger in the direction of the fibers. Platelet or flake-like fillers will provide two-dimensional reinforcement. The benefits of the fiber orientation may be lost if the product is pelletized and then reprocessed. However, if the microlayer compounding process feeds directly into the subsequent process, the process may retain the enhanced alignment.
- Microlayered composites can enhance conductivity by aligning conductive fillers and promoting conductive networks. This could be beneficial in applications such as EMI shielding.
- Microlayers can also help promote and alter the nature of crystallinity of materials.
- a layer of material When a layer of material is confined by another and the layer size approaches the size of a polymer molecule, certain polymer molecules will orient and crystallize when the layers cool or are annealed at a certain temperature.
- the nature of the crystallinity will shift from spherulite crystallinity to creating lamellae which will orient in plane with its layer as the layer size shrinks.
- Crystallinity in polymers can affect many material characteristics including mechanical properties, breathability and barrier properties. The nature and alignment of crystallinity will have different effects.
- Crystallized pellets may be more suitable for handling and processing. This may be particularly useful in recycling processes.
- Lamellae crystallinity as well as two dimensional confinement of platelet like fillers such as clay particles can help to improve or tailor barrier properties.
- An image of a tortuous path a permeate would encounter due to llamelae crystals or high aspect ratio fillers is shown in FIG. 5 .
- the creation of many layers as well as the shear stresses resulting from the repeated spreading and thinning of individual layers of materials can also help to enhance the dispersion of fillers.
- the enhanced dispersion may help to prevent agglomerates of the filler and the shear stresses may aid in the deterioration of agglomerates.
- Three important example fillers in which the reduction of agglomerates would be particularly beneficial include clay particles, nanocellulose fibers and graphene.
- microlayers to enhance fillers and reduce agglomeration could have a positive impact on the effectiveness of masterbatches produced.
- Masterbatches can sometimes be created in multiple steps in which the concentration of filler or additive is changed in each step.
- the use of masterbatches can often increase the dispersion of a filler compared to a single step where the filler and polymer are mixed immediately to the desired concentration.
- microlayer coextrusion it may be possible to achieve the desired dispersion without a masterbatch. This is important because polymers degrade after repeated processing.
- the effects of layering may also help to reduce or minimize the presence of large gels.
- Gels are usually considered defects and contain material which is not fully melted.
- Microlayering may help to disperse gels and prevent large agglomerates which may otherwise become a defect in an end product.
- Microlayering can also help control the way a pellet will melt and disperse. If sections of a pellet are layered with higher molecular weight polymer or higher viscosity polymer, this section of the polymer could melt slower and result in a better dispersion of fillers in this section. Pellets with section of varying components such as FIG. 4 could be used to gain better control of when and how fillers are dispersed. Using multicomponent techniques, one could envision a pellets-within-a-pellet system where sections of slower melting materials are released from a matrix of quicker melting materials. FIG. 1 h could represent a pellet which does this.
- a pellet could be envisioned in which certain layers or components of it are comprised of one or more higher melt temperature plastics or materials such as a metal.
- This higher melt temperature material could have a temperature processing range which is just in or out of the processing range for other materials going into the pellet. This may allow for the creation of features in the pellet which would resist melting when the pellet is processed in its end application at a lower temperature, in essence becoming a filler itself. This could allow for these high temperature features to be released as the pellet melts at lower temperatures and flow within any molten polymer stream.
- the high temperature plastics could be filled and or mixed with other plastics which could create a porous feature or other effects depending on the other material.
- the high temperature features could be created by a multicomponent approach or could be present in certain layers of a pellet made of concentric rings.
- features could be designed to interact with one another with features that may resemble hooks or the features may be formed into specific shapes such that they will orient in a certain manner during processing.
- Concentric rings of these high temperature plastics could result in a filler that is telescopic in nature with the features potentially only partially sliding past each other. If a pellet is tapered or shaped as it is cut/ formed this may provide a barrier for the extent that one layer or feature could slide relative to another.
- the microlayering process may allow or enhance reactions from materials in different layers. As layers get thinner and more numerous, there is an increase in surface area between different materials. This increase in surface area may allow a reaction between different materials to occur, or occur more completely. In addition the ability to order the layers may enable reactions to occur in a specific order. Additionally, molecules or particles could be forced into orientations due to the shear stresses from the layering process which may promote reactions which may otherwise not occur.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
- The present disclosure generally relates to pelletizing and compounding extrusion die systems. In particular, the present disclosure relates to the cyclical extrusion of materials to generate small sized grain features, generally in the range of micro and nanosized grain features.
- Compounding is the process of mixing multiple components including polymers, colorants, additives and fillers. This is often done in an extruder, such as a twin screw extruder. Pelletizing is the process of chopping extruded material into small pellets for use in a later process. A masterbatch is a compounded batch of pellets which contains a high concentration of an additive or filler in a polymer. Pellets from a masterbatch would be re-compounded along with unfilled pellets to create a desired concentration of additive or filler.
- Many manufacturing processes involving plastics incorporate the use of pellets. Pellets are typically fed into an extruder where they are melted and pressurized for subsequent processes. These manufacturing processes include extrusion, injection molding, and blow molding. Pellets can also be used in recycling processes. In recycling processes, the degree of crystallinity of the polymer may be important such as in recycling PET(Polyethylene terephthalate) plastic.
- Nanostructured materials are generally regarded as materials having very small grain feature size, typically in the range of approximately 1-100 nanometers (10−9 meters). Metals, ceramics, polymeric and composite materials may be processed in a variety of ways to form nanosized features. These materials have the potential for wide ranging applications, including for example, industrial, biomedical, 3D printing and electronic applications. As a result, a great deal of study is ongoing to gain a better understanding of the characteristics of these materials.
- Conventional extrusion formed products are limited to approximately twelve layers. Micro-layer extrusion processes can extend these limitations. Micro-layer extrusion processes that provide methods for obtaining small grain features is described in U.S. Pat. No. 7,690,908, (hereinafter the “908 Patent”) and U.S. Patent Publication 2012/0189789 (hereinafter the “789 Publication”) both of which are commonly owned by the assignee of the instant application, the disclosures of which are incorporated herein by reference in their entirety. Further examples of extrusion technology are described in U.S. Pat. Nos. 6,669,458, 6,533,565 and 6,945,764, also commonly owned by the assignee of the instant application and the disclosures of which are incorporated herein by reference in their entirety.
- The aspects of the disclosed embodiments is directed to the compounding and pelletizing of extruded or coextruded multilayer materials. These materials contain tens to thousands of layers of micro- to nano-polymer layers. These new shapes contain contiguous layers of milli- to nano-polymer layers in three dimensions and these contiguous layers may be twisted or turned to further expand the potential microlayer geometries. These layers can take the form of flat layers, annular or tubular rings as well as multi component structures.
- One embodiment relates to a pellet composition comprising:
- a. a solid object of 0.1 mm-1 cm on one axis by 0.1 mm-2 cm on a second axis;
- b. ten to 106 layers per millimeter along at least one axis; and
- c. wherein each layer is 0.1 nanometer to 9 millimeter in width.
- Suitable geometries for pellets include any shape such as cylindrical, spherical, capsular, conical, conical frustum, cubular, hemispherical, pyramidal, rectangular prismatic, tubular. Other examples of flat layer geometries are presented in
FIGS. 1a-b and are depicted with a limited number of layers for illustrative purposes. Examples of Tubular Polygonal and Annular geometries are presented inFIGS. 1c-f . Examples of multicomponent geometries are presented inFIGS. 1g -h. - Microlayer coextrusion can be used to create products possessing tens to thousands of layers, such as fifty to one hundred layers or one to ten thousand layers or one hundred thousand layers. The layers may contain the same or different polymer and contain different fillers, particles or chemicals.
- Another embodiment relates to a pellet wherein at least one layer is 0.1-100 nanometer on one axis. Pellets are three dimensional products and as such can be assigned three axes. For purposes of the present discussion, the primary axis is defined such that the layers run longitudinally along it. Thus, a pellet according to the present invention may comprise at least ten layers which are each 0.1-100 nanometer on this primary axis. In another embodiment of the invention, a pellet may comprise at least one hundred layers each of which are 0.1-100 nanometers on one axis. In another embodiment, a pellet may comprise at least one thousand layers which are 0.1-100 nanometer on one axis.
- In another embodiment, a pellet may comprise at least one layer which is 0.01-1 micrometer on one axis. In another embodiment of the invention, a pellet may comprise at least one layer which is 0.01-1 millimeter on one axis.
- In another embodiment, a pellet has a melting point of between 0° C. to about 500° C. Another embodiment relates to those pellets melting near or below room temperature (0° C. to about 30° C.). Another embodiment relates to those pellets melting at relatively low temperatures such as 30° C. to about 150° C. Another embodiment relates to those pellets melting at temperatures from about 150° C. to about 250° C. Another embodiment relates to those pellets melting at relatively high temperatures such as metals, such as from about 300° C. to about 500° C.
- An example with two compositions of the layers could contain composition A and composition B and the layers could alternate A-B-A-B-A-B. or even A-B-B-A-B-B-A-B-B. Three component compositions containing compositions A, B and C may likewise form alternating layers such as A-B-C-A-B-C-A-B-C. Such microlayer extrusions can form their own products or can be applied onto a core.
- Another embodiment relates to products containing a composite inner core extruded with composite milli, micro, or nano layers on the exterior.
- Another embodiment relates to products containing multiple layers of varying components.
- Microlayer coextrusion can be used to blend different materials into a homogenous mixture. As used herein, homogeneous means that the components are spread out randomly within the mixture. If a line were to be drawn through the axis of the stream mixture, all components would be statistically randomly positioned along the line. This is so because at the layer thickness of the invention molecular size or particle size kinetics influence distribution. Another way of understanding homogeneity is to appreciate that if layer sizes are brought sufficiently into the nanometer range, the layer sizes are so small that the resultant material is more of a blend of the layer materials rather than a layered structure. This process could be used on its own to create a blend from separate materials or could be used as a secondary process to further ensure a homogenous blend. The blended materials could be extruded and pelletized for later use or they can be directly fed into a subsequent process for immediate use.
- Another embodiment relates to an extruder accessory device which could perform the microlayering or multicomponent process to form a stream of molten material comprising of multilayers of milli, micro or nanometer thickness from the output of one or more extruders prior to subsequent processing of the melt stream. This device could take the place of a flange which would ordinarily connect an extruder to downstream equipment. An example can be seen in
FIG. 6 . An extruder could have such a device integrated as a component following pressurization by the extruder's one or more screws. The device could also be integrated as a flange which would connect to one or more extruders on one end and further processing devices on the other. An example schematic of an extruder with integrated layering can be seen inFIG. 7 . These aforementioned processing devices could include but are not limited to extrusion dies, molds, and blow molding dies. - Microlayer coextrusion also allows for enhanced alignment of filler particles or fibers along the direction of the extrusion. Filler particles are mostly restrained within each layer and as they approach a magnitude of size similar to the fiber or particle size, shear stresses and confinement by layer boundaries act to align particles in the direction of the extrusion. In a particle with three characteristic dimensions, the smallest dimension will be perpendicular to the layer boundary and the longest dimension will be in the direction of the extrusion. Platelet or flake-like fillers will align in a two dimensional manner while confined by the layers surrounding them.
- Another embodiment relates to products containing filler particles or fibers. More preferred products contain filler particles or fibers aligned along the extrusion axis.
- The creation of many layers as well as the shear stresses resulting from the repeated spreading and thinning of individual layers of materials can also help to enhance the dispersion of fillers. The enhanced dispersion may help to prevent aggregates or agglomerates of the filler and the shear stresses may aid in the deterioration of agglomerates.
- There are many material properties that can be tailored or modified by filled and unfilled microlayer coextrusion. These include coloring, mechanical properties, optical properties, barrier properties, conductivity, crystallinity, as well as time scales of melting and dissolving.
- Coloring active ingredients include quinacridones, phthalocyanines azo-type dyes, nickel titanate, titanium dioxide, cobalt, and manganese chrome antimony titanate, said active ingredient in a concentration of at least 60% by weight.
- In another embodiment of the invention, at least one layer contains a colorant.
- In another embodiment of the invention, the pellet comprises two compositions wherein one composition comprises hydrophobic agents and the second composition comprises hydrophilic agents.
- In another embodiment of the invention, the pellet comprises two compositions wherein one composition comprises acidic agents and the second composition comprises basic agents.
- In another embodiment of the invention, the pellet comprises two compositions wherein one composition comprises a lower density composition and the second composition comprises a higher density composition.
- In another embodiment of the invention, the pellet comprises two compositions wherein one composition comprises a highly viscous composition and the second composition comprises a non-viscous composition. Viscosity is measured in centipoise (cP) and liquids such as glycerin and oils are known as high viscosity materials. Liquids such as water, alcohols, and low molecular weight hydrocarbons are known as low viscosity materials.
- In another embodiment of the invention, the pellet comprises two compositions wherein one composition comprises a material processed at one temperature range and the second composition processes at a higher temperature range.
- Another embodiment involves a method of creating fillers within a pellet by coextruding a first lower temperature material along with either a higher melt temperature material or a thermoset material such that in subsequent processing, the second material resists melting and retains its shape.
- In another embodiment, the pellet comprises two compositions wherein one composition comprises a high concentration of one or more agents and the second composition comprises a low concentration of one or more agents or no agent at all.
- Fillers also refers to flakes such as copper or tin flakes.
- Fibers include single fibers or a myriad of other arrangements. Some exemplary arrangements include yarns, a tow of fibers or yarns, a weave, a non-woven, chopped fiber, a chopped fiber mat (with random or ordered formats), or combinations of these formats. The chopped fiber mat or nonwoven may be stretched, stressed, or oriented to provide some alignment of the fibers within the nonwoven or chopped fiber mat, rather than having a random arrangement of fibers.
- Fibers also generally possess an average aspect ratio of 10-3000 and more commonly are fibers having an average aspect ratio of 20-1000. Aspect ratios of 20-350 and 50-200 are specifically envisioned. Various types of organic and inorganic fibers are suitable either in monofilament or stranded form (including bundles of fibers bonded together to make a single element which serves as a single fiber in the sense of orientation and reinforcement).
- Filler particles or fibers include graphene, wood fibers (including groundwood, thermomechanical pulp (TMP) and bleached or unbleached kraft or sulfite pulps), vegetable fibers (including cellulose, lignin, cotton, hemp, jute, flax, ramie, sisal and bagasse), animal fibers (including proteinaceous strands such as silkworm silk, spider silk, sinew, catgut, wool, sea silk and hair such as cashmere wool, mohair and angora, fur such as sheepskin, rabbit, mink, fox, or beaver), other synthetic polymeric fibers (including rayon, modal, Lyocell polyamide nylon, PET or PBT polyester, phenol-formaldehyde (PF), polyvinyl alcohol fiber (PVA) vinylon, polyvinyl chloride fiber (PVC) vinyon, polyolefins (PP and PE) olefin fiber, acrylic polyesters, pure polyester, aromatic polyamids (aramids) such as Twaron, Kevlar and Nomex, polyethylene (PE), HMPE (e.g. Dyneema or Spectra), polyurethane fiber, and elastomers including spandex), metallic fibers such as those drawn from ductile metals such as copper, gold or silver and extruded or deposited from more brittle ones, such as nickel, aluminum or iron, stainless steel fibers, silicon carbide fibers, clay particles, carbon fibers or glass fibers.
- Particularly important fibers include the so-called micro and nano fibers including nanocellulous fibers and synthetic nanotubules including carbon nanotubes, inorganic nanotubes and DNA nanotubes.
- Fibers also includes microfibers known as sub-denier fibers (such as polyester drawn to 0.5 dn). Denier and Detex fibers include fibers categorized by weight and length measurements. Fiber designs also includes fibers split into multiple finer fibers. Most synthetic fibers are round in cross-section, but special designs can be hollow, oval, star-shaped or trilobal. The latter design provides more optically reflective properties. Synthetic fibers may also be crimped to provide a woven, non woven or knitted structure. Fiber surfaces can also be dull or bright. Dull surfaces reflect more light while bright tends to transmit light and make the fiber more transparent.
- Very short and/or irregular fibers have been called fibrils. Natural cellulose, such as cotton or bleached kraft, show smaller fibrils jutting out and away from the main fiber structure.
- Fibers alignment can also be tailored by the application of external forces such as magnetic fields.
- Another embodiment of the pellet composition of the present disclosure comprises additives such as ultraviolet light absorbers, light stabilizers, antioxidants, flame-retardants, antibacterial agents, surface tension reducers, deodorizing agents, anti-static agents, anti-blocking agents, plasticizer agents, blowing agents, fillers, and other known additives, or mixtures thereof.
- Another embodiment relates to a method of blending multiple streams and directly feeding the stream into a subsequent process for immediate use.
- These and other aspects and advantages of the exemplary embodiments will become apparent from the following detailed description considered in conjunction with the accompanying drawings. It is to be understood, however, that the drawings are designed solely for purposes of illustration and not as a definition of the limits of the invention, for which reference should be made to the appended claims. Additional aspects and advantages of the invention will be set forth in the description that follows, and in part will be obvious from the description, or may be learned by practice of the invention. Moreover, the aspects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
- The accompanying drawings and Figures illustrate presently preferred embodiments of the present disclosure, and together with the general description given above and the detailed description given below, serve to explain the principles of the present disclosure. As shown throughout the drawings, like reference numerals designate like or corresponding parts.
-
FIGS. 1a-1b depict examples of flat layer geometries with a limited number of layers for illustrative purposes. -
FIGS. 1c-1f depict examples of tubular, polygonal and annular geometries. -
FIGS. 1g-1j depict examples of multicomponent geometries. -
FIG. 2 illustrates the tendency of fibers to align along the axis of extruded layers. -
FIG. 3 illustrates larger extrusion layers, no-layers or coated materials containing fibers that have fiber orientations that are more random or less ordered. -
FIG. 4 illustrates a pellet with varying component sections which promotes better control of when and how fillers are dispersed. -
FIG. 5 illustrates a tortuous path a permeate would encounter due to lamellae crystals or high aspect ratio fillers. -
FIG. 6 depicts an extruder with an attached layering device. -
FIG. 7 depicts an example schematic of an extruder with integrated layering. - The present disclosure is generally directed towards cyclical extrusion of materials to generate small sized grain features, generally in the range of micro and nanosized grain features. As will be understood, the various diagrams, flow charts and scenarios described herein are only examples, and there are many other scenarios to which the present disclosure will apply.
- Rotating small, micro and nano-layer extrusion processes are described in U.S. Pat. No. 7,690,908 and 6,669,458. Small, micro and nano layer Non-rotating extrusion processes are described in U.S. Patent Publication 2012/0189789. U.S. patent application Ser. No. 14/084,601 filed Nov. 19, 2013, entitled “Method Of Creating Multilayered Products Through The Folding Of Continuous Layers” refers to other extrusion processes. Each of the aforesaid patent, publication and application are herein incorporated by reference in their entirety. Altering the die plate orientation around the central extrusion axis allows for the preparation of new geometric extrusion products described in further detail herein. Polygonal and annular geometries are described above. Folding methods are also included geometries. All of these geometries may be composed of milli, micro and nano layer streams or extrusions that can also include fillers and fibers. Independent of fibers, the layers may comprise different polymers or soluble components that do not mix. When these streams contain fillers or fibers and are extruded in the small, milli, micro, or nano layers the fibers tend to align along extruded layers such as depicted in
FIG. 2 . The relative sizes of fillers to sizes of layers will affect the degree of orientation. - Larger extrusion layers, no-layers or coated materials containing fibers have fiber orientations that are more random or less ordered, such as depicted in
FIG. 3 . - Orientation of fibers and flakes can change, enhance or create many properties of an extruded composite. This is important in the creation of composite materials. Extrusion in general has an orienting effect on fibers, however the inclusion of microlayers will amplify the degree of orientation. If the fiber has stronger mechanical properties than the matrix polymer, the product will be stronger in the direction of the fibers. Platelet or flake-like fillers will provide two-dimensional reinforcement. The benefits of the fiber orientation may be lost if the product is pelletized and then reprocessed. However, if the microlayer compounding process feeds directly into the subsequent process, the process may retain the enhanced alignment.
- Microlayered composites can enhance conductivity by aligning conductive fillers and promoting conductive networks. This could be beneficial in applications such as EMI shielding.
- Microlayers can also help promote and alter the nature of crystallinity of materials. When a layer of material is confined by another and the layer size approaches the size of a polymer molecule, certain polymer molecules will orient and crystallize when the layers cool or are annealed at a certain temperature. The nature of the crystallinity will shift from spherulite crystallinity to creating lamellae which will orient in plane with its layer as the layer size shrinks. Crystallinity in polymers can affect many material characteristics including mechanical properties, breathability and barrier properties. The nature and alignment of crystallinity will have different effects. The benefits of layers on crystallinity may be lost if the product is pelletized and then reprocessed, however, the desired or enhanced crystallinity may form as the product cools or is annealed if the microlayer compounding process feeds directly into the subsequent process. Crystallized pellets may be more suitable for handling and processing. This may be particularly useful in recycling processes.
- Lamellae crystallinity as well as two dimensional confinement of platelet like fillers such as clay particles can help to improve or tailor barrier properties. An image of a tortuous path a permeate would encounter due to llamelae crystals or high aspect ratio fillers is shown in
FIG. 5 . - The creation of many layers as well as the shear stresses resulting from the repeated spreading and thinning of individual layers of materials can also help to enhance the dispersion of fillers. The enhanced dispersion may help to prevent agglomerates of the filler and the shear stresses may aid in the deterioration of agglomerates. Three important example fillers in which the reduction of agglomerates would be particularly beneficial include clay particles, nanocellulose fibers and graphene.
- The use of microlayers to enhance fillers and reduce agglomeration could have a positive impact on the effectiveness of masterbatches produced. Masterbatches can sometimes be created in multiple steps in which the concentration of filler or additive is changed in each step. The use of masterbatches can often increase the dispersion of a filler compared to a single step where the filler and polymer are mixed immediately to the desired concentration. However, with microlayer coextrusion it may be possible to achieve the desired dispersion without a masterbatch. This is important because polymers degrade after repeated processing.
- The effects of layering may also help to reduce or minimize the presence of large gels. Gels are usually considered defects and contain material which is not fully melted. Microlayering may help to disperse gels and prevent large agglomerates which may otherwise become a defect in an end product.
- Microlayering can also help control the way a pellet will melt and disperse. If sections of a pellet are layered with higher molecular weight polymer or higher viscosity polymer, this section of the polymer could melt slower and result in a better dispersion of fillers in this section. Pellets with section of varying components such as
FIG. 4 could be used to gain better control of when and how fillers are dispersed. Using multicomponent techniques, one could envision a pellets-within-a-pellet system where sections of slower melting materials are released from a matrix of quicker melting materials.FIG. 1h could represent a pellet which does this. - Similarly, a pellet could be envisioned in which certain layers or components of it are comprised of one or more higher melt temperature plastics or materials such as a metal. This higher melt temperature material could have a temperature processing range which is just in or out of the processing range for other materials going into the pellet. This may allow for the creation of features in the pellet which would resist melting when the pellet is processed in its end application at a lower temperature, in essence becoming a filler itself. This could allow for these high temperature features to be released as the pellet melts at lower temperatures and flow within any molten polymer stream. The high temperature plastics could be filled and or mixed with other plastics which could create a porous feature or other effects depending on the other material. The high temperature features could be created by a multicomponent approach or could be present in certain layers of a pellet made of concentric rings. With the multicomponent approach, features could be designed to interact with one another with features that may resemble hooks or the features may be formed into specific shapes such that they will orient in a certain manner during processing. Concentric rings of these high temperature plastics could result in a filler that is telescopic in nature with the features potentially only partially sliding past each other. If a pellet is tapered or shaped as it is cut/ formed this may provide a barrier for the extent that one layer or feature could slide relative to another. These features if filled or made of special materials such as a metal could allow the end product to have enhanced properties such as strength, conductivity, EMI shielding, ductility, burst strength, and optics. Thermoset plastics could also be used instead of higher melt temperature plastics as they will not melt in subsequent processing.
- The microlayering process may allow or enhance reactions from materials in different layers. As layers get thinner and more numerous, there is an increase in surface area between different materials. This increase in surface area may allow a reaction between different materials to occur, or occur more completely. In addition the ability to order the layers may enable reactions to occur in a specific order. Additionally, molecules or particles could be forced into orientations due to the shear stresses from the layering process which may promote reactions which may otherwise not occur.
- Thus, while there have been shown, described and pointed out, fundamental novel features of the invention as applied to the exemplary embodiments thereof, it will be understood that various omissions and substitutions and changes in the form and details of devices and methods illustrated, and in their operation, may be made by those skilled in the art without departing from the spirit or scope of the invention. Moreover, it is expressly intended that all combinations of those elements and/or method steps, which perform substantially the same function in substantially the same way to achieve the same results, are within the scope of the invention. Moreover, it should be recognized that structures and/or elements and/or method steps shown and/or described in connection with any disclosed form or embodiment of the invention may be incorporated in any other disclosed or described or suggested form or embodiment as a general matter of design choice. It is the intention, therefore, to be limited only as indicated by the scope of the claims appended hereto.
Claims (20)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/869,189 US9908975B2 (en) | 2014-09-29 | 2015-09-29 | Microlayer coextrusion for compounding, pelletizing, and masterbatches |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201462057154P | 2014-09-29 | 2014-09-29 | |
US14/869,189 US9908975B2 (en) | 2014-09-29 | 2015-09-29 | Microlayer coextrusion for compounding, pelletizing, and masterbatches |
Publications (3)
Publication Number | Publication Date |
---|---|
US20170088676A1 US20170088676A1 (en) | 2017-03-30 |
US20170190845A9 true US20170190845A9 (en) | 2017-07-06 |
US9908975B2 US9908975B2 (en) | 2018-03-06 |
Family
ID=58406745
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/869,189 Active 2036-04-29 US9908975B2 (en) | 2014-09-29 | 2015-09-29 | Microlayer coextrusion for compounding, pelletizing, and masterbatches |
Country Status (1)
Country | Link |
---|---|
US (1) | US9908975B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102149820B1 (en) * | 2020-05-28 | 2020-08-31 | 이안스 주식회사 | Method of manufacture of capsular livestock additives |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6447279B1 (en) * | 1998-04-10 | 2002-09-10 | Guill Tool & Engineering Co., Inc. | Extrusion die with rotating components |
US6945764B2 (en) * | 2000-04-10 | 2005-09-20 | Guillemette A Roger | Method and apparatus for distributing material in a profile extrusion die |
US6533565B1 (en) * | 2000-04-10 | 2003-03-18 | A Roger Guillemette | Method and apparatus for distributing material in a profile extrusion die |
US7690908B2 (en) * | 2006-05-31 | 2010-04-06 | Guill Tool & Engineering Co., Inc. | Method and apparatus for forming high strength products |
US7808042B2 (en) * | 2008-03-20 | 2010-10-05 | Micron Technology, Inc. | Systems and devices including multi-gate transistors and methods of using, making, and operating the same |
US9643368B2 (en) * | 2012-08-21 | 2017-05-09 | Guill Tool & Engineering Co., Inc. | Microlayer coextrusion of optical end products |
US9656437B2 (en) * | 2013-02-20 | 2017-05-23 | Guill Tool & Engineering Co., Inc. | Extrudable oriented polymer composites |
US10232541B2 (en) * | 2013-11-19 | 2019-03-19 | Guill Tool & Engineering Co., Inc. | Method of tubular microlayer and multi-component co-extrusion via deflector perturbation |
-
2015
- 2015-09-29 US US14/869,189 patent/US9908975B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
US20170088676A1 (en) | 2017-03-30 |
US9908975B2 (en) | 2018-03-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10583601B2 (en) | Extrudable Oriented Polymer Composites | |
US5225488A (en) | Mixing process for generating in-situ reinforced thermoplastics | |
CN103980595B (en) | A kind of modified ultra-high molecular weight polyethylene for 3D printing and preparation method thereof | |
JP2003534955A5 (en) | ||
EP3356591A1 (en) | Method for producing a fiber matrix semi-finished product | |
WO2015111536A1 (en) | Molding material for injection molding, extrusion molding, or pultrusion molding, carbon-fiber-reinforced thermoplastic resin pellets, molded article, method for producing injection molded article, and injection molded article | |
US9908975B2 (en) | Microlayer coextrusion for compounding, pelletizing, and masterbatches | |
DE102013114669A1 (en) | Endless carbon fiber / thermoplastic resin fiber composite yarn and method of making the same | |
JP6731760B2 (en) | Core-sheath composite fiber | |
DE3887416T2 (en) | Polyolefin matrix composite materials and process for their manufacture. | |
EP2826808B1 (en) | Polyester fibres and filaments prepared by use of pmma pigment masterbatch, production method thereof and use | |
US20170107335A1 (en) | Thermoplastic resin composition and molded products formed thereof | |
JP2010077297A (en) | Method for producing void-containing polypropylene film | |
US20210053266A1 (en) | Multicomponent approach to standard and microlayer coextrusion | |
CN104356610B (en) | A kind of high temperature resistant oriented transparent nanometer flaxen fiber polyester film and preparation method thereof | |
DE69606199T2 (en) | METHOD AND DEVICE FOR PRODUCING A FILM WITH GRANULAR MATERIAL THEREOF | |
Kunchimon et al. | From hybrid fibers to microfibers: The characteristics of polyamide 6/polypropylene blend via one‐step twin‐screw melt extrusion | |
DE3912738C2 (en) | Process for the production of afterglowing synthetic spinning materials and their use | |
TWI629385B (en) | Composite fiber and method for forming the same | |
US9056406B2 (en) | Method of creating multilayered products through the folding of continuous layers | |
DE102019004890A1 (en) | Textile fiber, textile and method of making a textile fiber | |
JP2025008097A (en) | Thermoplastic resin composition, thermoplastic resin composite, and method for producing same | |
EP1598166A1 (en) | Process for extrusion coating with nano-particles containing polyamide | |
EP4363642A1 (en) | Electrically conductive yarn | |
DE102007015318A1 (en) | Process for the preparation of reinforced thermoplastic composites and associated apparatus for carrying out, and composites produced in this way |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GUILL TOO & ENGINEERING, CO.,INC., RHODE ISLAND Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GUILLEMETTE, RICHARD;PETERS, ROBERT;REEL/FRAME:036988/0025 Effective date: 20151027 |
|
AS | Assignment |
Owner name: GUILL TOOL & ENGINEERING, CO., INC., RHODE ISLAND Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE FROM GUILL TOO & ENGINEERING, CO.,INC. TO GUILL TOOL & ENGINEERING, CO.,INC. PREVIOUSLY RECORDED ON REEL 036988 FRAME 0025. ASSIGNOR(S) HEREBY CONFIRMS THE REQUEST FOR CORRECTION OF THE ASSIGNEE FROM GUILL TOO & ENGINEERING, CO.,INC. TO GUILL TOOL & ENGINEERING, CO.,INC.;ASSIGNORS:GUILLEMETTE, RICHARD;PETERS, ROBERT;REEL/FRAME:037113/0907 Effective date: 20151027 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2551); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY Year of fee payment: 4 |