CA2062144A1 - Composites from plastics and iron oxide fibers - Google Patents
Composites from plastics and iron oxide fibersInfo
- Publication number
- CA2062144A1 CA2062144A1 CA 2062144 CA2062144A CA2062144A1 CA 2062144 A1 CA2062144 A1 CA 2062144A1 CA 2062144 CA2062144 CA 2062144 CA 2062144 A CA2062144 A CA 2062144A CA 2062144 A1 CA2062144 A1 CA 2062144A1
- Authority
- CA
- Canada
- Prior art keywords
- iron oxide
- fibers
- plastics
- rate
- nylon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 229920003023 plastic Polymers 0.000 title claims abstract description 13
- 239000004033 plastic Substances 0.000 title claims abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 8
- 239000012783 reinforcing fiber Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 18
- 229920002292 Nylon 6 Polymers 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 235000013980 iron oxide Nutrition 0.000 description 9
- -1 polypropylene Polymers 0.000 description 9
- 235000019445 benzyl alcohol Nutrition 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052598 goethite Inorganic materials 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101150080898 GPA4 gene Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001274660 Modulus Species 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 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 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
O.Z. 0050/42257 Abstract of the Disclosure: The composites are based on plastics and iron oxide fibers having a diameter of less than 1000 nm.
Description
~.~z~ 0/-~2257 Composites from plastic~ and iron oxide ibers The present invention relates to composite materials compo~ed o~ t:hermoplastics or thermoset materials and reinforcing fibers.
To reinforce plastics materials, they are mixed with fibrous additives. The most widely used reinforcing fibers are glass ~ibers, but use is also made of crystalline inorganic fibers, for example based on titanates, aluminum oxide or ~ilicon carbide, which appreciably improve the sti~fne~c and strength. ~owever, in general there i~ a need to Lmprove these two properties still further.
Iron oxide fiber and processe~ ~or making them are known per se. ~owever, becauqe of their high density they have hitherto not been used as reinforcing fibers for plastics, and because of their small ~ize they were hitherto thought to be fairly difficult to incorporate into plastics.
The addition to plastics of iron oxide powder in spherical form a~ a pigment is known. I~ such powders are used as fillers for improving the mechanical properties, comparatively large amounts need to be used in order to achieve an adequate increase in strength and stiffness.
It is an object of the present i~vention to pro~ide composite materials of extremely high stiffness and strengthO
We have found that this object is achieved when the rein~orcing fibers used are iron oxide fibers having a diameter o~ less than 1000 nm~
Suitable thermopla~tics are for e~ample poly-ethylene, polypropylene, block copolymers of polyethylene a~d polypropylene, polybutene-1, poly(4-methylpentene-1), polyvinyl chloride, polystyrene, ~tyrene-acrylonitrile copolymers, Rtyrene-acrylonitrile-butadiene copolymers, acrylonitrile-~tyrene-acrylate copolymers, polyoxy-methylene, thermoplastic tetrafluoroethylene copolymers, polyamide~;, polycarbonates, polyesters r polyphenylen~
... ~ .
, . . . ~
, 20~21~!1 - 2 - O.Z. 0050/42257 ethers, polyether ketones, polysulfone, polyether sulfone, polyphenylene sul~ide, polyether imides, liquid crystalline polyesters, thermoplastic polyurethanes, and mixtures thereof.
5SuitablP thermoset plastics are ~or example curing products of phenol-~ormaldehyde resins, melamine-formaldehyde resins, urea-formaldehyde resins, un~aturated polyester resins, epoxy resins, vinyl ester resins, vinyl ester urethane resins and phthalate resins.
10Preferred iron oxides are ~-Fe2O3, ~-Fe2O3 and Fe3O4. The iron oxides are present in the form of fibers having a diameter of less than 1000 nm, pre~erably from 1 to 150 ~m, in particular from 5 to 100 nm. It ha~ been found that, as the fiber diameter decrease , the breAking 15strength and toughness, in particular the notched impact toughness, of the composite materials increases. The length to diameter ratio of the fibers is preferably ~rom 3 : 1 to 100 : 1, in particular from 4 . 1 to 80 : 1.
The ~ibrous iron oxide pigments used according to 20the present invention can be prepared by a wide variety of known methods. For instance, DE-B 12 04 644 describes the basic method for preparing goethite, whereas DE-B 11 76 111 and G~-A 2 111 471 describe the acid method of goethite synthe~is. Instead of goethite it is 25also possible to use lepidokrokite as starting material for preparing the oxides used according to the pre~ent inventionO This material can be prepared ~or example a~
described in US-A 4 176 172. The conversion of the iron oxide hydrate~ into the fibrous iron oxides of the 30present invention can be carried out for example as described in DE-A 23 52 440. Finally, suitable r~inforcing materials for the purposes of the present invention also inGlude directly synthesized, acicular ~-iron oxide pigment~ having a parkicularly high length 35to diameter ratio a~ described in EP-A 237 944.
The fibers are prefera~ly present in the composite :in amounts of from 1 to 60, in particular from .... , . . , . . . , . -; : : ~ , . . .
; :
.:. ~ ' . : - : :.~ ~ .:
~2~
- 3 - O.Z. 0050/42257 5 to 40, % by volume. As well as fibers, the compo~ite materials may additional:Ly contain further customary additives, for example antioxidants, flame retardants, nucleating agents and color pigments.
When incorporating the iron oxide fibers into the plastics matrix, care must be taken to ensure that the fibers are very substantia.Lly deagglomer~ted, sincP only this ensures homogeneou dispersion in the matrix and eliminates ~racture-inducing agglomerates.
Methods for deagglomerating fine particles are known, eg. vigorous di~persing. For instance, a dispersion of iron oxide fibers can be prepared in a aqueous or organic phase in which the fiber content can be within the range from 4 to 65, in particular from 10 to 50, ~ by weight. Customary dispersants can be used, for example polyacrylic acid~ maleic acid/styrene copolymers or copolymers o~ sodium maleate and diisobutene in the case of an aqueous dispersion and hydroxystearic ~cid derivatives or C13-C~5 oxo alcohols in the case of a dispersion in benzyl alcohol, in either case in amounts of from 0.1 to 5% by weight. The deagglomerating can be effected by continuous grinding in stirred ball mills or other high-shearing apparatus based on the rotor~stator principle.
The dispersion medium can then be removed, for example by spray drying, and the ~ibers obtained in-corporated into the plastica melt or liquid, for which customary mixing apparatus, for example extruders or kneaderY, can be used. In the case of a thermosPtting plastic this is then followed by the curing process.
To incorporate fiber~ into thermosettinq pla~tics the dispersion of the fibers can be incorporated directly into the plastics melt, for example by metering as a liquid, and ~ubsequently the dispersion medium de-volatiliæed.
The composite materials of the present invention are notable ~or excellent stif~ness, toughness and , .
.
, .: :~
`
~2~ ~
To reinforce plastics materials, they are mixed with fibrous additives. The most widely used reinforcing fibers are glass ~ibers, but use is also made of crystalline inorganic fibers, for example based on titanates, aluminum oxide or ~ilicon carbide, which appreciably improve the sti~fne~c and strength. ~owever, in general there i~ a need to Lmprove these two properties still further.
Iron oxide fiber and processe~ ~or making them are known per se. ~owever, becauqe of their high density they have hitherto not been used as reinforcing fibers for plastics, and because of their small ~ize they were hitherto thought to be fairly difficult to incorporate into plastics.
The addition to plastics of iron oxide powder in spherical form a~ a pigment is known. I~ such powders are used as fillers for improving the mechanical properties, comparatively large amounts need to be used in order to achieve an adequate increase in strength and stiffness.
It is an object of the present i~vention to pro~ide composite materials of extremely high stiffness and strengthO
We have found that this object is achieved when the rein~orcing fibers used are iron oxide fibers having a diameter o~ less than 1000 nm~
Suitable thermopla~tics are for e~ample poly-ethylene, polypropylene, block copolymers of polyethylene a~d polypropylene, polybutene-1, poly(4-methylpentene-1), polyvinyl chloride, polystyrene, ~tyrene-acrylonitrile copolymers, Rtyrene-acrylonitrile-butadiene copolymers, acrylonitrile-~tyrene-acrylate copolymers, polyoxy-methylene, thermoplastic tetrafluoroethylene copolymers, polyamide~;, polycarbonates, polyesters r polyphenylen~
... ~ .
, . . . ~
, 20~21~!1 - 2 - O.Z. 0050/42257 ethers, polyether ketones, polysulfone, polyether sulfone, polyphenylene sul~ide, polyether imides, liquid crystalline polyesters, thermoplastic polyurethanes, and mixtures thereof.
5SuitablP thermoset plastics are ~or example curing products of phenol-~ormaldehyde resins, melamine-formaldehyde resins, urea-formaldehyde resins, un~aturated polyester resins, epoxy resins, vinyl ester resins, vinyl ester urethane resins and phthalate resins.
10Preferred iron oxides are ~-Fe2O3, ~-Fe2O3 and Fe3O4. The iron oxides are present in the form of fibers having a diameter of less than 1000 nm, pre~erably from 1 to 150 ~m, in particular from 5 to 100 nm. It ha~ been found that, as the fiber diameter decrease , the breAking 15strength and toughness, in particular the notched impact toughness, of the composite materials increases. The length to diameter ratio of the fibers is preferably ~rom 3 : 1 to 100 : 1, in particular from 4 . 1 to 80 : 1.
The ~ibrous iron oxide pigments used according to 20the present invention can be prepared by a wide variety of known methods. For instance, DE-B 12 04 644 describes the basic method for preparing goethite, whereas DE-B 11 76 111 and G~-A 2 111 471 describe the acid method of goethite synthe~is. Instead of goethite it is 25also possible to use lepidokrokite as starting material for preparing the oxides used according to the pre~ent inventionO This material can be prepared ~or example a~
described in US-A 4 176 172. The conversion of the iron oxide hydrate~ into the fibrous iron oxides of the 30present invention can be carried out for example as described in DE-A 23 52 440. Finally, suitable r~inforcing materials for the purposes of the present invention also inGlude directly synthesized, acicular ~-iron oxide pigment~ having a parkicularly high length 35to diameter ratio a~ described in EP-A 237 944.
The fibers are prefera~ly present in the composite :in amounts of from 1 to 60, in particular from .... , . . , . . . , . -; : : ~ , . . .
; :
.:. ~ ' . : - : :.~ ~ .:
~2~
- 3 - O.Z. 0050/42257 5 to 40, % by volume. As well as fibers, the compo~ite materials may additional:Ly contain further customary additives, for example antioxidants, flame retardants, nucleating agents and color pigments.
When incorporating the iron oxide fibers into the plastics matrix, care must be taken to ensure that the fibers are very substantia.Lly deagglomer~ted, sincP only this ensures homogeneou dispersion in the matrix and eliminates ~racture-inducing agglomerates.
Methods for deagglomerating fine particles are known, eg. vigorous di~persing. For instance, a dispersion of iron oxide fibers can be prepared in a aqueous or organic phase in which the fiber content can be within the range from 4 to 65, in particular from 10 to 50, ~ by weight. Customary dispersants can be used, for example polyacrylic acid~ maleic acid/styrene copolymers or copolymers o~ sodium maleate and diisobutene in the case of an aqueous dispersion and hydroxystearic ~cid derivatives or C13-C~5 oxo alcohols in the case of a dispersion in benzyl alcohol, in either case in amounts of from 0.1 to 5% by weight. The deagglomerating can be effected by continuous grinding in stirred ball mills or other high-shearing apparatus based on the rotor~stator principle.
The dispersion medium can then be removed, for example by spray drying, and the ~ibers obtained in-corporated into the plastica melt or liquid, for which customary mixing apparatus, for example extruders or kneaderY, can be used. In the case of a thermosPtting plastic this is then followed by the curing process.
To incorporate fiber~ into thermosettinq pla~tics the dispersion of the fibers can be incorporated directly into the plastics melt, for example by metering as a liquid, and ~ubsequently the dispersion medium de-volatiliæed.
The composite materials of the present invention are notable ~or excellent stif~ness, toughness and , .
.
, .: :~
`
~2~ ~
- 4 - ~.z. 0050/42~57 strength, these properties being achieved even with comparatively low filler contents.
They can be used for example as injection molding compositions, extrusion molding compositions for profiles and films, or for blow molcling.
Combination of polyamide and alpha-Fe203 Dried, deagglomerated ~-Fe2O3 powder (~iber length: 700 nm, fiber diameter: 40 nm~ is added at a rate of 5 kgJh from an ancillary extruder to a nylon 6 melt (X value according to DIN 53 727:80; mass flow S kg/h). The granules obtai~ed following homogenization and extrusion have a solids content of 7.7% by volume of ~-Fe203 -Combination of polypropylene and Fe304 Dried, deagglomerated Fe3Ob powder (fiber length:
800 ~m, fiber diameter: 35 nm) is added at a rate of 5 kg/h from an ancillary extruder to a polypropylene melt (MFI 230/2.16; mass flow 5 kg~h). The granules obtained following homogenization and extrusion have a solids content of 6.1% by volume of Fe3O4.
~XAMPLE 3 Combination of polyether sulfo~e and ~-Fe203 Dried, deagglomerated ~-FezO3 powder (fiber length: 800 nm, fiber diameter: 35 nm) is added at a rate of S kg/h from an ancillary extruder to a polyether sulfone melt (mass flow 5 kg/h) at an extruder temperature of 305C. The granules obtained following 3C homogeniz~tion and extrusion have a solids content of A8 % by volume of ~-Fe203-Combination of nylon 6 and ~-FeiO3 A dispersion of 35% by weight of acicular ~-Fe2O3 (length: 900 nm, thickness: 40 nm) in benzyl alcohol is deagglomerated in a stirred ball mill i~ the pre~ence of 0.35~ by weight o~ polyhydroxystearic acid as . .. . . .
:
.~ ' .
':~ ' "~ ' :
,. ,' ; . ', :
- 5 -- O.Z. 0050/42257 dispersant for 1 h. ~his dispersion is added at a rate of 6 l/h to the second stage of a twin-screw extruder where it is mixed at 280C with 21 nylon 6 melt produced in the first stage and added at a :rate o~ 5 kg/h. The nylon used is characterized by a K value of 80 (DIN 53 727).
Downstream of the mixing zone, benzyl alcohol is distilled off in the devolatilization zone at 30 mbar at a rate of 5.5 l/h. The granules obtained contain 11% by volume of ~-Fe2O3.
EXAMæ~E S
Combination of nylon 6 and ~-Fe203 Acicular ~-Fe2O3 present in di~tilled water in a concentration of 35% by weight is deagglomerated in a stirred ball mill in the presence of 0.2% by weighk of sodium polyacrylate as dispersant for 1 h. This dispersion is added at a rate of 6 l/h to the second stage of a twin-screw extruder where it is mixed at 280C
with a nylon 6 melt produced in the first stage and added at a rate of 5 kg/h. The nylon used is characterized by a K value of 80 (DIN 53 727~. Downstream of the mixing zone, water i5 distilled off in the devolatilization zone at 25 mbar at a rate of 5.5 l/h. The granule~ obtained contain ll~ by volume of ~-Fe203.
Combination of nylon 6 and Fe3O4 Acicular Fe304 (length: 800 nm, thickness~
30 nm) present in benzyl alcohol in a concentration of 35% by weight is deagglomerated in a stirred ball mLll in the presence of 0.5~ by weight of polyhydroxystearic acid as dispersant for 1 h. This dispersion is added at a rate of 8 l/h to the second stage of a twin-screw extruder where it i5 mixed at 280C with a nylon 6 melt produced in the first stage and added at ~ rate of S kg/h. The nylo~ used is characterized by a R value of 80 (DIN 53 727). Downstream of the mixing zone, benzyl alcohol is distilled of~ in the devolatilization zone at 30 mbar at a rate of 5.5 l/h. The granules obtained ., . - . - i .
- ; ~
. ' . . ~ ~
.
:
~ ~3 ;~
j .
- - 6 - o.z. 0050/~2257 contain 11% by volume of Fe3O4.
Combination of polyamide and ~-Fe203 Dried, deagglomerated spherical ~-FezO3 (particle size 100 nm) is added at a rate of 2.8 kg/h from an ancillary extruder to a nylon 6 melt (K value according to DIN 53 727-80; mass flow 5 kg/h). The granules obtained following homogenization and extrusion have a olids content of 11% by volume comprising spherical ~-Fe2O3~
Combination of nylon 6 and Fe30~
Spherical Fe3O4 (particle size 80 nm) present in benzyl alcohol in a concentration of 35% by volume is deagglomerated in a stirred ball mill in the presence of 0.2% by weight of polyhydroxystearic acid as dispersant for 1 h. This dispexsion is added at a rate of 8 l/~. to the second stage of a twin-screw extruder where it i9 mixed at 280C with a nylon 6 melt produced in the flrst stage and added at a rate of 5 kg/h. The nylon use~l is characterized by a K value of ~0 (DIN 53 727). Downstr~
of the mixing zQn~`~, benzyl alcohol is distilled off in the devolatilization zone at 30 mbar at a rate of 6 l/h.
The granules obtained contain 14% by volume of Fe3~4.
COMP~RATIVE EXAMP~ 3 Combination of nylon 6 and glass fiber ~ylon 6 is compounded with glass fiber at 280C
in a twin-screw extruder~ The fiber ~ontent of the compound i~ 11% by volume, the maximum fiber diameter is 15,000 nm and the averag~ length is 200,000 nm.
Mechanical data of composites ob~ained The dried granules wexe proces4ed in a gcrew injectio~ molding machine to prepare specimen~ for tensile testing according to DIN 53 4$5 (strength) and DIN 53 457 (stiffness, modulu~ of élasticity). ~he melt temperature was ~60C.
, , `~ - 7 - o.z.~0~5~4~2~ 7 ~ he results obtained are listed in the following table~
Example Filler Fiber Tensile Modulus content stre~gth of elas-% by MPa ticity volume GPa 4 ~-Fez03 11 212 19.5 ~-Fe203 11 223 20 6 Fe304 11 244 20.5 Comparison 1 ~-Fez03 11 142 7.1 Comparison 2 Fe304 14 140 7 Comparison 3 Glass 11 165 13 , . . . .
'. :. :, :
, ~, , :
.
They can be used for example as injection molding compositions, extrusion molding compositions for profiles and films, or for blow molcling.
Combination of polyamide and alpha-Fe203 Dried, deagglomerated ~-Fe2O3 powder (~iber length: 700 nm, fiber diameter: 40 nm~ is added at a rate of 5 kgJh from an ancillary extruder to a nylon 6 melt (X value according to DIN 53 727:80; mass flow S kg/h). The granules obtai~ed following homogenization and extrusion have a solids content of 7.7% by volume of ~-Fe203 -Combination of polypropylene and Fe304 Dried, deagglomerated Fe3Ob powder (fiber length:
800 ~m, fiber diameter: 35 nm) is added at a rate of 5 kg/h from an ancillary extruder to a polypropylene melt (MFI 230/2.16; mass flow 5 kg~h). The granules obtained following homogenization and extrusion have a solids content of 6.1% by volume of Fe3O4.
~XAMPLE 3 Combination of polyether sulfo~e and ~-Fe203 Dried, deagglomerated ~-FezO3 powder (fiber length: 800 nm, fiber diameter: 35 nm) is added at a rate of S kg/h from an ancillary extruder to a polyether sulfone melt (mass flow 5 kg/h) at an extruder temperature of 305C. The granules obtained following 3C homogeniz~tion and extrusion have a solids content of A8 % by volume of ~-Fe203-Combination of nylon 6 and ~-FeiO3 A dispersion of 35% by weight of acicular ~-Fe2O3 (length: 900 nm, thickness: 40 nm) in benzyl alcohol is deagglomerated in a stirred ball mill i~ the pre~ence of 0.35~ by weight o~ polyhydroxystearic acid as . .. . . .
:
.~ ' .
':~ ' "~ ' :
,. ,' ; . ', :
- 5 -- O.Z. 0050/42257 dispersant for 1 h. ~his dispersion is added at a rate of 6 l/h to the second stage of a twin-screw extruder where it is mixed at 280C with 21 nylon 6 melt produced in the first stage and added at a :rate o~ 5 kg/h. The nylon used is characterized by a K value of 80 (DIN 53 727).
Downstream of the mixing zone, benzyl alcohol is distilled off in the devolatilization zone at 30 mbar at a rate of 5.5 l/h. The granules obtained contain 11% by volume of ~-Fe2O3.
EXAMæ~E S
Combination of nylon 6 and ~-Fe203 Acicular ~-Fe2O3 present in di~tilled water in a concentration of 35% by weight is deagglomerated in a stirred ball mill in the presence of 0.2% by weighk of sodium polyacrylate as dispersant for 1 h. This dispersion is added at a rate of 6 l/h to the second stage of a twin-screw extruder where it is mixed at 280C
with a nylon 6 melt produced in the first stage and added at a rate of 5 kg/h. The nylon used is characterized by a K value of 80 (DIN 53 727~. Downstream of the mixing zone, water i5 distilled off in the devolatilization zone at 25 mbar at a rate of 5.5 l/h. The granule~ obtained contain ll~ by volume of ~-Fe203.
Combination of nylon 6 and Fe3O4 Acicular Fe304 (length: 800 nm, thickness~
30 nm) present in benzyl alcohol in a concentration of 35% by weight is deagglomerated in a stirred ball mLll in the presence of 0.5~ by weight of polyhydroxystearic acid as dispersant for 1 h. This dispersion is added at a rate of 8 l/h to the second stage of a twin-screw extruder where it i5 mixed at 280C with a nylon 6 melt produced in the first stage and added at ~ rate of S kg/h. The nylo~ used is characterized by a R value of 80 (DIN 53 727). Downstream of the mixing zone, benzyl alcohol is distilled of~ in the devolatilization zone at 30 mbar at a rate of 5.5 l/h. The granules obtained ., . - . - i .
- ; ~
. ' . . ~ ~
.
:
~ ~3 ;~
j .
- - 6 - o.z. 0050/~2257 contain 11% by volume of Fe3O4.
Combination of polyamide and ~-Fe203 Dried, deagglomerated spherical ~-FezO3 (particle size 100 nm) is added at a rate of 2.8 kg/h from an ancillary extruder to a nylon 6 melt (K value according to DIN 53 727-80; mass flow 5 kg/h). The granules obtained following homogenization and extrusion have a olids content of 11% by volume comprising spherical ~-Fe2O3~
Combination of nylon 6 and Fe30~
Spherical Fe3O4 (particle size 80 nm) present in benzyl alcohol in a concentration of 35% by volume is deagglomerated in a stirred ball mill in the presence of 0.2% by weight of polyhydroxystearic acid as dispersant for 1 h. This dispexsion is added at a rate of 8 l/~. to the second stage of a twin-screw extruder where it i9 mixed at 280C with a nylon 6 melt produced in the flrst stage and added at a rate of 5 kg/h. The nylon use~l is characterized by a K value of ~0 (DIN 53 727). Downstr~
of the mixing zQn~`~, benzyl alcohol is distilled off in the devolatilization zone at 30 mbar at a rate of 6 l/h.
The granules obtained contain 14% by volume of Fe3~4.
COMP~RATIVE EXAMP~ 3 Combination of nylon 6 and glass fiber ~ylon 6 is compounded with glass fiber at 280C
in a twin-screw extruder~ The fiber ~ontent of the compound i~ 11% by volume, the maximum fiber diameter is 15,000 nm and the averag~ length is 200,000 nm.
Mechanical data of composites ob~ained The dried granules wexe proces4ed in a gcrew injectio~ molding machine to prepare specimen~ for tensile testing according to DIN 53 4$5 (strength) and DIN 53 457 (stiffness, modulu~ of élasticity). ~he melt temperature was ~60C.
, , `~ - 7 - o.z.~0~5~4~2~ 7 ~ he results obtained are listed in the following table~
Example Filler Fiber Tensile Modulus content stre~gth of elas-% by MPa ticity volume GPa 4 ~-Fez03 11 212 19.5 ~-Fe203 11 223 20 6 Fe304 11 244 20.5 Comparison 1 ~-Fez03 11 142 7.1 Comparison 2 Fe304 14 140 7 Comparison 3 Glass 11 165 13 , . . . .
'. :. :, :
, ~, , :
.
Claims (6)
1. A composite material composed of a plastics material and reinforcing fibers, wherein the fibers are iron oxide fibers having a diameter of less than 1000 nm.
2. A composite material as claimed in claim 1, wherein the plastics material is a thermoplastic.
3. A composite material as claimed in claim 1, wherein the plastics material is a thermoset plastic.
4. A composite material as claimed in claim 1, wherein the fibers have a length to diameter ratio of from 3 : 1 to 100 : 1.
5. A composite material as claimed in claim 1, containing from 1 to 60% by volume of iron oxide fibers.
6. A composite material as claimed in claim 1, wherein the iron oxide used is Fe2O3 or Fe3O4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4106656.1 | 1991-03-02 | ||
| DE19914106656 DE4106656A1 (en) | 1991-03-02 | 1991-03-02 | COMPOSITES MADE OF PLASTICS AND IRON OXIDE FIBERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2062144A1 true CA2062144A1 (en) | 1992-09-03 |
Family
ID=6426306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2062144 Abandoned CA2062144A1 (en) | 1991-03-02 | 1992-03-02 | Composites from plastics and iron oxide fibers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0502380A3 (en) |
| JP (1) | JPH0565419A (en) |
| CA (1) | CA2062144A1 (en) |
| DE (1) | DE4106656A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4202871A (en) * | 1977-11-14 | 1980-05-13 | Sakai Chemical Industry Co., Ltd. | Production of acicular ferric oxide |
| DE3533574A1 (en) * | 1985-09-20 | 1987-03-26 | Basf Ag | THERMOPLASTIC POLYMER MATERIALS WITH MOLECULAR INORGANIC REINFORCING FIBERS |
| DE3807042A1 (en) * | 1988-03-04 | 1989-09-14 | Basf Ag | METHOD FOR PRODUCING NEEDLE-SHAPED (ALPHA) -FE (ARROW DOWN) 2 (ARROW DOWN) O (ARROW DOWN) 3 (ARROW DOWN) |
-
1991
- 1991-03-02 DE DE19914106656 patent/DE4106656A1/en not_active Withdrawn
-
1992
- 1992-02-14 JP JP4027896A patent/JPH0565419A/en not_active Withdrawn
- 1992-02-21 EP EP19920102941 patent/EP0502380A3/en not_active Withdrawn
- 1992-03-02 CA CA 2062144 patent/CA2062144A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0502380A3 (en) | 1993-01-20 |
| JPH0565419A (en) | 1993-03-19 |
| EP0502380A2 (en) | 1992-09-09 |
| DE4106656A1 (en) | 1992-09-03 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Dead |