WO2007132153A1 - Polymeric materials - Google Patents

Polymeric materials Download PDF

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Publication number
WO2007132153A1
WO2007132153A1 PCT/GB2007/001580 GB2007001580W WO2007132153A1 WO 2007132153 A1 WO2007132153 A1 WO 2007132153A1 GB 2007001580 W GB2007001580 W GB 2007001580W WO 2007132153 A1 WO2007132153 A1 WO 2007132153A1
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WO
WIPO (PCT)
Prior art keywords
composition
assembly according
polyaryletherketone
fluoropolymer
wear means
Prior art date
Application number
PCT/GB2007/001580
Other languages
French (fr)
Inventor
John Robinson
Original Assignee
Victrex Manufacturing Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Victrex Manufacturing Limited filed Critical Victrex Manufacturing Limited
Priority to EP07732614A priority Critical patent/EP2019853A1/en
Priority to US12/299,022 priority patent/US20090092827A1/en
Publication of WO2007132153A1 publication Critical patent/WO2007132153A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/20—Homopolymers or copolymers of hexafluoropropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

  • This invention relates to polymeric materials and particularly, although not exclusively, relates to polymeric materials which define a surface of a part, for example polymeric materials which may define a coating on a substrate.
  • coatings may be provided to improve wear properties of parts which are contacted in use by, for example, an abrasive fluid or a solid body.
  • Fluoropolymers are widely used in coating materials .
  • a primer is generally required to enable a fluorocarbon layer to adhere to a substrate.
  • parts coated with fluoropolymers have relatively poor wear properties and as a result the coatings may wear through to reveal the underlying substrate after a relatively short time. Whilst the problem has been addressed by providing multiple coating ' layers, the provision of such layers increases the cost of coating parts.
  • Polyetheretherketone has been proposed for use in coating materials. Polyetheretherketone generally performs better than fluoropolymers but still wears significantly over time usually where high loads are used.
  • an assembly comprising a part arranged to be contacted by wear means in use such that said wear means has a tendency to apply an abrasive force to an outer surface of said part, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer .
  • Said polyaryletherketone polymer preferably comprises, more preferably consists essentially of, a repeat unit of formula
  • said polyaryletherketone polymer is selected from polyetheretherketone, polyetherketone, polyetherketoneketone and polyetherketoneether ketoneketone .
  • said polyaryletherketone polymer is selected from polyetherketone and polyetheretherketone.
  • said polyaryletherketone polymer is polyetheretherketone .
  • Said polyaryletherketone polymer material may have a melt viscosity (MV) in the range 0.05 to 0.7 kNs ⁇ f 2 , preferably in the range 0 . 06 to 0 . 7 kNsirf -2 , more preferably in the range 0 . 14 to 0 . 5 kNsitf 2 , especially in the range 0 . 3 to 0 . 5 kNsrrf 2 .
  • MV melt viscosity
  • MV is suitably measured using capillary rheometry operating at 400°C at a shear rate of 1000s " using tungsten carbide die, 0.5 x 3.175mm.
  • Said fluoropolymer preferably comprises a fluorocarbon resin which may be selected from perfluoroalkoxy tetrafluoroethylene (PFA), polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene ' copolymer resin (FEP) .
  • PFA perfluoroalkoxy tetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene ' copolymer resin
  • a perfluoroalkoxy polymer (herein referred to as PFA) may be represented by the following general formula:
  • Rf is a fluoroalkyl group (so -O-Rf is a perfluoroalkoxy group) .
  • PFA has a melting point of from 302 to 310°C, exhibits melt fluidity at temperatures above the melting point thereof, has high heat resistance and chemical resistance, has a continuous services temperature of 260°C, and is little affected by the usual acids, alkalis, oxidation-reduction agents, halogens, and organic solvents .
  • PFA is sold under the trade name of Teflon PFA by E.I. Du Pont de Nemours & Co., Inc., U.S.A. and Mitsui Fluorochemicals Co., Ltd., Japan.
  • FEP tetrafluoroethylene/hexafluoropropylene copolymer
  • FEP has a melting point of from 250 to 290°C, exhibits melt fluidity at temperatures more than the melting point thereof, has high heat resistance and chemical resistance, and has a continuous service temperature of 200 0 C.
  • FEP is commercially available from E.I. Du Pont de Nemours & Co., Inc., U.S.A. (trade mark: Teflon FEP) and Daikin Kogyo Co., Ltd. (trade name: Neofuron) .
  • Teflon FEP Teflon FEP
  • Neofuron Teflon FEP
  • those copolymers having a hexafluoropropylene content of from 18 to 25% by weight are preferably used.
  • Said fluoropolymer is preferably selected from PFA and PTFE. More preferably, it is PFA.
  • the ratio of the wt% of polyaryletherketone to the wt% of fluoropolymer in said composition at said outer surface is suitably at least 1, is preferably at least 1.5, is more preferably at least 2 and, especially, is at least 2.5.
  • Said ratio is suitably less than 50, preferably less than 25, more preferably less than 15, especially less than 10. In preferred embodiments, the ratio is in the range of 2 to 9, preferably 2 to 7.
  • composition at said outer surface suitably includes at least 40 wt%, preferably at least 50 wt%, more preferably at least 60 wt% of said polaryletherketone .
  • Said composition may include 95wt% or less of said polyaryletherketone .
  • composition of said outer surface suitably includes at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, especially at least 20 wt%, of said fluoropolymer .
  • composition of said outer surface suitably includes 70 to 95 wt% of said polyaryletherketone . (especially polyetheretherketone) and 15 to 30 wt% of said fluoropolymer (especially PFA) .
  • Said part may include at least 1 mg, suitably at least 10 mg, preferably at least 500 mg, more preferably at least 1 g of said composition.
  • a substantial volume of said part may be made up of said composition. For example, greater than
  • said part may be made up of said composition. Substantially the entirety of said part may be made up of said composition.
  • said part may be moulded, for example injection moulded, from said composition.
  • said part may comprise a layer of said composition which layer defines said outer surface of said part.
  • Said layer preferably comprises a substantially homogenous mixture of said polyaryletherketone and said fluoropolymer .
  • Said layer suitably covers an area of at least lcm 2 , preferably at least 5cm 2 , more preferably at least 10cm 2 .
  • It may cover an area of less than Im 2 , preferably less than 0.5m 2 .
  • Said layer may have a coat weight of at least l.Omg/cm 2 , preferably at least 1.2mg/cm 2 .
  • the coat weight may be less than 20mg/cm 2 ' In one embodiment (e.g. where a process using powders is utilised to prepare the layer) the coat weight may be at least 5mg/cm 2 .
  • Said layer may include at least l.Omg, preferably at least 1.2mg of said polyaryletherketone per cm 2 of said layer. Said layer may include less than 20mg of said polyaryletherketone per cm 2 of said layer.
  • Said layer may have a minimum thickness (measured across its whole extent) of 5 ⁇ m, preferably of at least 8 ⁇ m.
  • Said layer may have a maximum thickness (measured across its whole extent) of less than lOOO ⁇ m, preferably less than 500 ⁇ m, more preferably less than 250 ⁇ m, especially less than 150 ⁇ m.
  • Said layer may have an average thickness measured over its whole extent in the range 10 to lOOO ⁇ m, preferably 10 to 150 ⁇ m.
  • Said minimum/maximum thicknesses may be measured using a Sheen Eco Test Plus BFN Coating Thickness Gauge Type 121- 17-00 from Sheen Instruments Ltd.
  • Said layer may have a total weight of at least lmg, preferably at least 5mg, more preferably at least lOrtig, especially at least Ig.
  • Said layer may include at least lmg, preferably at least lOmg, especially at least Ig of said polyaryletherketone.
  • Said part may include at least lOmg, preferably at least 500mg, especially at least Ig of said polyaryletherketone.
  • Said layer preferably includes at least lOmg, preferably at least 500mg, especially at least Ig of said polyaryletherketone .
  • Said part may be for an item of cookware, bakeware, domestic appliance, industrial apparatus or automotive application. It may be a compressor part, piston, liner, piston ring, sealing gasket, valve, impeller, conveyor belt material, seal (or the like) . Said part may comprise any type of bearing surface.
  • said layer may be provided on a substrate, suitably so that it contacts said substrate.
  • Said substrate could itself include a layer of a coating material, for example having a composition as described herein.
  • Said substrate may be flexible or rigid.
  • Said substrate may comprise a fabric which may be woven or non-woven.
  • a said fabric may comprise a glass or carbon-fibre containing fabric.
  • Said substrate may comprise a pressure-sensitive tape.
  • said substrate comprises a metal which may be selected from steel (including stainless steel) , aluminium, copper and iron, including cast versions of any of the aforesaid.
  • the part may have a weight of at least Ig, preferably at least 5g, more preferably at least 1Og.
  • the weight may be less than 10kg, preferably less than lkg.
  • a layer as described may define internal or external surfaces of a said part.
  • a receptacle for example for cookware, it may coat internal and external surfaces thereof.
  • said layer defines a surface of said part which is subject to significant abrasive force, in use.
  • Said layer may be in direct contact with a metal surface of said part.
  • said layer may adhere to said metal surface without the use of a primer.
  • Said part may include a multiplicity of layers each of which may include a polyaryletherketone polymer and a fluoropolymer as described. Each of said layers may independently have any feature of the layer described herein.
  • the coated part may include other coating layers which do not include said polyaryletherketone and fluoropolymer .
  • Said wear means may comprise an abrasive fluid which contacts said outer surface of said part or a solid body which contacts said outer surface. Where said wear means comprises an abrasive fluid, said fluid may comprise abrasive particles, for example a fluidic slurry.
  • said outer surface of said part may be an internal surface of a pump which is contacted in use by a fluidic slurry comprising sand/grit particles.
  • said outer surface may comprise industrial cookware for example a dough machine or other industrial mixer wherein said cookware item is for containing an abrasive fluid such as fluids containing icing sugar, marzipan or other abrasive materials.
  • said outer surface of said part may be a load carrying surface of a conveyor belt, wherein said belt comprises a fabric which is, provided with a layer as- described .
  • said wear means comprises a solid body
  • said solid body may comprise a part made out of a metal or plastics material or other composite material.
  • Said solid body is preferably arranged in said assembly to follow a substantially predetermined travel path wherein it contacts said part and applies an abrasive force thereto in use.
  • Said solid body may be arranged to move relative to said part, suitably between predetermined first and second positions.
  • Said solid body may be arranged to slide between first and second positions/ for example it may contact and slide over said part.
  • said part may be pivotally mounted.
  • a method of manufacturing a part of an assembly which is arranged to be subjected to a wear means in use such that said wear means has a tendency to apply an abrasive force to an outer surface of said part comprising providing said part with an outer surface which comprises a composition which comprises a polaryletherketone polymer and a fluoropolymer .
  • Said method may comprise selecting a precursor composition which comprises a mixture of said polyaryletherketone polymer and said fluoropolymer and forming said part from said precursor composition.
  • the manufacture of said part may include a step of moulding (eg by injection moulding or extrusion) said precursor composition.
  • said method may comprise contacting a substrate with said precursor composition.
  • said precursor composition may comprise a dispersion of polyaryletherketone and fluoropolymer or said polyaryletherketone and fluoropolymer may be provided in a dry powderous form.
  • a layer applied may be lapped to define said outer surface of said part.
  • a layer applied is not lapped and/or otherwise contacted with a solid body to define said outer surface.
  • a part for an assembly said part being arranged to be contacted in use by a wear means such that said wear means has a tendency to apply an abrasive force to an outer surface of said part to abrade it, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer .
  • a composition which comprises a polyaryletherketone polymer and a fluoropolymer in the manufacture of a part which is contacted by a wear means in use which wear means has a tendency to apply an abrasive force to an outer surface of said part to abrade it.
  • a method of operating an assembly which comprises a part having an outer surface which comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer, said method comprising contacting a wear means with said outer surface of said part wherein said wear means applies an abrasive force to said outer surface.
  • the outer surface of said part may be subjected to a temperature of at least -60°C, or even 100°C, or even
  • an operative assembly comprising a part which is contacted with a wear means which applies an abrasive force to an outer surface of said part, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer .
  • Figure 1 is a graphical representation of the wear rates of various coatings.
  • Figure 2 is a graphical representation of the coefficient of friction of various coatings under different loads.
  • Aerosol® OT75%E - a surfactant from Cytec Industries UK Ltd comprising a mixture of sodium dioctyl sulphosuccinate (73-75% wt), ethanol (6-7% wt) and water.
  • PFA 5011 - refers to a PFA sold under the trade mark TEFLON by DUPONT comprising, nominally, lO ⁇ m powder.
  • RYTON - a PPS sold by Chevron Phillips Chemical Company
  • ETFE a powder coating grade of ethylene tetrafluoroethylene
  • PVDF - a powder coating grade of polyvinylidene fluoride
  • OXPEKK - a polyetherketoneketone obtained from Oxford Polymers
  • ECTFE - a powder coating grade of ethylene chloro- trifluoroethylene .
  • Example 2 (Comparative) - Preparation of polyetheretherketone dispersion .
  • Example 1 The procedure described in Example 1 was generally followed except that the step of adding PFA was omitted so that an aqueous dispersion of polyetheretherketone was prepared.
  • Example 1 The procedure described in Example 1 was generally followed except that PTFE in the form of ZONYL MP1400 was added instead of the PFA 5011.
  • the substrates were 60mm x 37mm x 3mm 316 stainless steel grit blasted with an aluminium oxide grade with a mean particle size of 425 - 600 microns.
  • the grit blasted surface had a profile with a Ra and Rz value of 1.83 microns and 1.73 microns respectively.
  • Example 5a Dispersion Coating
  • the coating gun used was a Devilbiss, type SRIW, with a tip size of 0.7 - 1.0mm. Air pressure to the gun was 30 to 40 psi depending on what type of coating was required i.e. wet, dry, thin or thick coating.
  • Procedure for coating A dispersion to be coated was hand mixed with a stirrer rod before pouring into the spray gun reservoir. The substrate to be coated was placed in an air extracted spraying cabinet and two or three wet coats applied. The substrate was then left to dry in air for 5 minutes then placed in an air circulated oven set to 12O 0 C to flash off the remaining water. The substrate was then placed for 10 minutes in an oven set to 390°C-420°C to melt and flow the coating. After removal from the oven the substrates were cooled to room temperature.
  • the powder for coating was dried in an oven at 15O 0 C for 3 hours before use.
  • the substrate to be spray coated was placed in an oven at 400 0 C for 10 minutes, removed from the oven and quickly sprayed with the powder.
  • the powder melted on contact with the substrate.
  • the coated substrate was placed in the oven at 400 0 C for 10 minutes to melt and flow the coating.
  • the substrate was removed from the oven and allowed to cool.
  • Example 5a The method of Example 5a was used to prepare coatings as described in Table 1 below: Table 1
  • Example 6 The coatings described in Example 6 were evaluated by Coefficient of Friction testing using ASTM G133 - 05. The test assessed the Coefficient of Friction measured at 3 loads (50, 100 and 250N) on a Plint TE77 test rig using a 10mm slider @ 20Hz with a stroke of 10mm.
  • the test method uses a linear reciprocating ball on a flat plane geometry.
  • the direction of the relative motion between sliding surfaces reverses in a periodic fashion such that the sliding occurs back and forth in a straight line.
  • the specimens were un- lubricated.
  • Example 6a The wear scars from the assessment were examined. It was observed that the coating of Example 6a resists wear well; only a wear scar was visible and there was no penetration through to the underlying substrate. This is in contrast to the results for Examples 6b and 6c which showed significant penetration of the coating through to the substrate, although the Example 6b coating resisted wear better than that of Example 6c. Table 2 summarises the results of the assessments undertaken.
  • Example 8 Wear rates of a range of different coatings
  • Coatings were prepared as described above having varying levels of polyetheretherketone and PFA and such coatings were compared to respective coatings comprising pure PTFE, PFA and polyetheretherketone. Results are summarised in Figure 2 which shows the coefficients of friction of various coatings under 5ON, IOON and 250N loads. It will be noted that the coefficient of friction for polyetheretherketone/PFA coatings is, in all cases, less than that for pure PFA and pure polyetheretherketone coatings. Also, the coefficient of friction for the majority of polyetheretherketone/PFA coatings is less than that for PTFE which is generally regarded as one of the lowest coefficient of friction fluoropolymers available.
  • polyetheretherketone and/or fluoropolymer dispersions were prepared having compositions described in Table 3.
  • *1 contains a small amount of black pigment.
  • compositions described in Table 3 were coated, generally using the method of Example 5a, onto 100mm x 100mm x 3mm stainless steel plaques which had previously been degreased and grit blasted with aluminium oxide.
  • Plaques coated with the formulations described in Example 10 and other engineering thermoplastics and fluoropolymers were tested for scratch resistance using a Sheen Scratch Tester. A test plaque is clamped to a slide which slowly withdraws the panel while a lmm tungsten carbide tip scratches the surface. The test was conducted using a single specified load of 6 kg. The scratch test was carried out under similar conditions to ISO1518; however as the speed of the needle could not be measured on the equipment the test should be regarded as comparative only.
  • the results were determined by measurement of the average scratch width in mm by light microscopy and the peak valley in ⁇ m across the scratch using a Form Tallysurf Intra Measuring Instrument. Scratch width was determined by measuring the scratch width under 3OX magnification using an Olympus SZHlO microscope. The scratch width is measured in the centre of the scratch and 10mm either side of centre, and an average width calculated from the three readings .
  • Scratch depth was determined using a Form Tallysurf Intra Measuring Instrument. A stylus is pulled over the scratch and a reading of the surface roughness can be measured. The Pv (peak valley) is also shown, this being a measure in ⁇ m of the lowest valley present in the measured coating. Before the Pv can be measured the Tallysurf equipment removes any shape or slope present in the test panel to give a mean average line; therefore the Pv is a measure of the lowest peak to a mean average line.
  • Examples Hg, Hh, Hi, Hj, Hl and Hm were applied by electrostatic powder coating methodology generally as described in Example 5b.
  • each of Examples Hb to Hf show excellent scratch resistance compared to other materials tested in Examples Hg to Hn. Also, Examples Hb to Hf have comparable performance to the material of Example Ha even though the materials of Examples Hb to Hf included fluoropolymers which are generally regarded as significantly softer in comparison to the material in Example 11a.
  • coatings comprising a polyaryletherketone such as polyetheretherketone and a fluoropolymer such as PFA, show surprisingly low wear as determined, for example, by wear rates (see Example 8) and by scratch resistance (see Example 11) and low coefficient of friction compared to coatings comprising polyaryletherketone or fluoropolymer alone.
  • Such coatings may be used to coat parts which are subjected to abrasive forces which may abrade and/or scratch their surfaces, in use, for example by virtue of contact with abrasive fluids such as abrasive slurries or by virtue of contact with other solids for example other metals or plastics materials.
  • polyaryletherketones have excellent resistance to chemicals and heat, the coatings described may be used in relatively harsh environments whilst still maintaining excellent wear properties.

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Abstract

An assembly comprises a part for example a part of an item of cookware, bakeware, domestic appliance or the like which is subjected to a wear means in use such that the wear means may abrade the outer surface of the part. The part is provided with an outer surface which comprises a polyaryletherketone polymer, especially polyetheretherketone, and a fluoropolymer. Such a combination is found to exhibit superior wear properties over other known materials.

Description

POLYMERIC MATERIALS
This invention relates to polymeric materials and particularly, although not exclusively, relates to polymeric materials which define a surface of a part, for example polymeric materials which may define a coating on a substrate.
It is well known to provide parts with coatings to address various problems . For example coatings may be provided to improve wear properties of parts which are contacted in use by, for example, an abrasive fluid or a solid body.
Fluoropolymers are widely used in coating materials . However, disadvantageously, a primer is generally required to enable a fluorocarbon layer to adhere to a substrate.
Furthermore, parts coated with fluoropolymers have relatively poor wear properties and as a result the coatings may wear through to reveal the underlying substrate after a relatively short time. Whilst the problem has been addressed by providing multiple coating ' layers, the provision of such layers increases the cost of coating parts.
Polyetheretherketone has been proposed for use in coating materials. Polyetheretherketone generally performs better than fluoropolymers but still wears significantly over time usually where high loads are used.
It is an object of the present invention to address the above described problems. According to a first aspect of the invention, there is provided an assembly comprising a part arranged to be contacted by wear means in use such that said wear means has a tendency to apply an abrasive force to an outer surface of said part, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer .
Said polyaryletherketone polymer preferably comprises, more preferably consists essentially of, a repeat unit of formula
Figure imgf000003_0001
where t and v independently represent 0 or 1. Preferred polymeric materials have a said repeat unit wherein either t=l or v=0; t=0 and v=0; or t=0 and v=l. More preferred have t=l and v=0; or t=0 and v=0. The most preferred has t=l and v=0.
In preferred embodiments, said polyaryletherketone polymer is selected from polyetheretherketone, polyetherketone, polyetherketoneketone and polyetherketoneether ketoneketone . In a more preferred embodiment, said polyaryletherketone polymer is selected from polyetherketone and polyetheretherketone. In an especially preferred embodiment, said polyaryletherketone polymer is polyetheretherketone .
Said polyaryletherketone polymer material may have a melt viscosity (MV) in the range 0.05 to 0.7 kNsπf2, preferably in the range 0 . 06 to 0 . 7 kNsirf -2 , more preferably in the range 0 . 14 to 0 . 5 kNsitf2, especially in the range 0 . 3 to 0 . 5 kNsrrf2 .
MV is suitably measured using capillary rheometry operating at 400°C at a shear rate of 1000s" using tungsten carbide die, 0.5 x 3.175mm.
Said fluoropolymer preferably comprises a fluorocarbon resin which may be selected from perfluoroalkoxy tetrafluoroethylene (PFA), polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene ' copolymer resin (FEP) .
A perfluoroalkoxy polymer (herein referred to as PFA) may be represented by the following general formula:
Figure imgf000004_0002
Figure imgf000004_0001
wherein Rf is a fluoroalkyl group (so -O-Rf is a perfluoroalkoxy group) . PFA has a melting point of from 302 to 310°C, exhibits melt fluidity at temperatures above the melting point thereof, has high heat resistance and chemical resistance, has a continuous services temperature of 260°C, and is little affected by the usual acids, alkalis, oxidation-reduction agents, halogens, and organic solvents . PFA is sold under the trade name of Teflon PFA by E.I. Du Pont de Nemours & Co., Inc., U.S.A. and Mitsui Fluorochemicals Co., Ltd., Japan.
A tetrafluoroethylene/hexafluoropropylene copolymer (herein referred to as FEP) may be represented by the following general formula:
Figure imgf000005_0001
FEP has a melting point of from 250 to 290°C, exhibits melt fluidity at temperatures more than the melting point thereof, has high heat resistance and chemical resistance, and has a continuous service temperature of 2000C.
FEP is commercially available from E.I. Du Pont de Nemours & Co., Inc., U.S.A. (trade mark: Teflon FEP) and Daikin Kogyo Co., Ltd. (trade name: Neofuron) . Among commercially available FEPs, those copolymers having a hexafluoropropylene content of from 18 to 25% by weight are preferably used.
Said fluoropolymer is preferably selected from PFA and PTFE. More preferably, it is PFA. The ratio of the wt% of polyaryletherketone to the wt% of fluoropolymer in said composition at said outer surface is suitably at least 1, is preferably at least 1.5, is more preferably at least 2 and, especially, is at least 2.5. Said ratio is suitably less than 50, preferably less than 25, more preferably less than 15, especially less than 10. In preferred embodiments, the ratio is in the range of 2 to 9, preferably 2 to 7.
The composition at said outer surface suitably includes at least 40 wt%, preferably at least 50 wt%, more preferably at least 60 wt% of said polaryletherketone . Said composition may include 95wt% or less of said polyaryletherketone .
The composition of said outer surface suitably includes at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, especially at least 20 wt%, of said fluoropolymer .
The composition of said outer surface suitably includes 70 to 95 wt% of said polyaryletherketone . (especially polyetheretherketone) and 15 to 30 wt% of said fluoropolymer (especially PFA) .
Said part may include at least 1 mg, suitably at least 10 mg, preferably at least 500 mg, more preferably at least 1 g of said composition.
In one embodiment, a substantial volume of said part may be made up of said composition. For example, greater than
50%, suitably greater than 60%, preferably greater than
70%, more preferably greater than 80% of said part may be made up of said composition. Substantially the entirety of said part may be made up of said composition. In this case, said part may be moulded, for example injection moulded, from said composition. In other embodiments, said part may comprise a layer of said composition which layer defines said outer surface of said part.
Said layer preferably comprises a substantially homogenous mixture of said polyaryletherketone and said fluoropolymer .
Said layer suitably covers an area of at least lcm2, preferably at least 5cm2, more preferably at least 10cm2.
It may cover an area of less than Im2, preferably less than 0.5m2.
Said layer may have a coat weight of at least l.Omg/cm2, preferably at least 1.2mg/cm2. ■ The coat weight may be less than 20mg/cm2' In one embodiment (e.g. where a process using powders is utilised to prepare the layer) the coat weight may be at least 5mg/cm2.
Said layer may include at least l.Omg, preferably at least 1.2mg of said polyaryletherketone per cm2 of said layer. Said layer may include less than 20mg of said polyaryletherketone per cm2 of said layer.
Said layer may have a minimum thickness (measured across its whole extent) of 5μm, preferably of at least 8μm.
Said layer may have a maximum thickness (measured across its whole extent) of less than lOOOμm, preferably less than 500μm, more preferably less than 250μm, especially less than 150μm. Said layer may have an average thickness measured over its whole extent in the range 10 to lOOOμm, preferably 10 to 150μm.
Said minimum/maximum thicknesses may be measured using a Sheen Eco Test Plus BFN Coating Thickness Gauge Type 121- 17-00 from Sheen Instruments Ltd.
Said layer may have a total weight of at least lmg, preferably at least 5mg, more preferably at least lOrtig, especially at least Ig.
Said layer may include at least lmg, preferably at least lOmg, especially at least Ig of said polyaryletherketone.
Said part may include at least lOmg, preferably at least 500mg, especially at least Ig of said polyaryletherketone.
Said layer preferably includes at least lOmg, preferably at least 500mg, especially at least Ig of said polyaryletherketone .
Said part may be for an item of cookware, bakeware, domestic appliance, industrial apparatus or automotive application. It may be a compressor part, piston, liner, piston ring, sealing gasket, valve, impeller, conveyor belt material, seal (or the like) . Said part may comprise any type of bearing surface.
When said part comprises a layer of said composition said layer may be provided on a substrate, suitably so that it contacts said substrate. Said substrate could itself include a layer of a coating material, for example having a composition as described herein. Said substrate may be flexible or rigid. Said substrate may comprise a fabric which may be woven or non-woven. For example, a said fabric may comprise a glass or carbon-fibre containing fabric. Said substrate may comprise a pressure-sensitive tape. Preferably, said substrate comprises a metal which may be selected from steel (including stainless steel) , aluminium, copper and iron, including cast versions of any of the aforesaid.
The part may have a weight of at least Ig, preferably at least 5g, more preferably at least 1Og. The weight may be less than 10kg, preferably less than lkg.
A layer as described may define internal or external surfaces of a said part. For example in the. case of a receptacle, for example for cookware, it may coat internal and external surfaces thereof. Preferably, said layer defines a surface of said part which is subject to significant abrasive force, in use.
Said layer may be in direct contact with a metal surface of said part. Thus, advantageously, said layer may adhere to said metal surface without the use of a primer.
Said part may include a multiplicity of layers each of which may include a polyaryletherketone polymer and a fluoropolymer as described. Each of said layers may independently have any feature of the layer described herein. The coated part may include other coating layers which do not include said polyaryletherketone and fluoropolymer . Said wear means may comprise an abrasive fluid which contacts said outer surface of said part or a solid body which contacts said outer surface. Where said wear means comprises an abrasive fluid, said fluid may comprise abrasive particles, for example a fluidic slurry. For example, in one embodiment, said outer surface of said part may be an internal surface of a pump which is contacted in use by a fluidic slurry comprising sand/grit particles. In another embodiment, said outer surface may comprise industrial cookware for example a dough machine or other industrial mixer wherein said cookware item is for containing an abrasive fluid such as fluids containing icing sugar, marzipan or other abrasive materials. In a further embodiment, said outer surface of said part may be a load carrying surface of a conveyor belt, wherein said belt comprises a fabric which is, provided with a layer as- described .
When said wear means comprises a solid body, said solid body may comprise a part made out of a metal or plastics material or other composite material. Said solid body is preferably arranged in said assembly to follow a substantially predetermined travel path wherein it contacts said part and applies an abrasive force thereto in use. Said solid body may be arranged to move relative to said part, suitably between predetermined first and second positions. Said solid body may be arranged to slide between first and second positions/ for example it may contact and slide over said part. Alternatively, said part may be pivotally mounted.
According to a second aspect of the invention, there is provided a method of manufacturing a part of an assembly which is arranged to be subjected to a wear means in use such that said wear means has a tendency to apply an abrasive force to an outer surface of said part, said method comprising providing said part with an outer surface which comprises a composition which comprises a polaryletherketone polymer and a fluoropolymer .
Said method may comprise selecting a precursor composition which comprises a mixture of said polyaryletherketone polymer and said fluoropolymer and forming said part from said precursor composition. In one embodiment, wherein a substantial volume of said part is made of said composition as described above, the manufacture of said part may include a step of moulding (eg by injection moulding or extrusion) said precursor composition. In another embodiment wherein said part comprises a layer of said composition, said method may comprise contacting a substrate with said precursor composition. In this case, said precursor composition may comprise a dispersion of polyaryletherketone and fluoropolymer or said polyaryletherketone and fluoropolymer may be provided in a dry powderous form.
When said part comprises a layer of said composition, a layer applied may be lapped to define said outer surface of said part. Preferably, however, a layer applied is not lapped and/or otherwise contacted with a solid body to define said outer surface.
According to a third aspect of the invention, there is provided a part for an assembly, said part being arranged to be contacted in use by a wear means such that said wear means has a tendency to apply an abrasive force to an outer surface of said part to abrade it, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer .
According to a fourth aspect, there is provided the use of a composition which comprises a polyaryletherketone polymer and a fluoropolymer in the manufacture of a part which is contacted by a wear means in use which wear means has a tendency to apply an abrasive force to an outer surface of said part to abrade it.
According to a fifth aspect, there is provided a method of operating an assembly which comprises a part having an outer surface which comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer, said method comprising contacting a wear means with said outer surface of said part wherein said wear means applies an abrasive force to said outer surface.
The outer surface of said part may be subjected to a temperature of at least -60°C, or even 100°C, or even
15O0C, or even 2000C, or even 2600C, during contact thereof by said wear means.
According to a sixth aspect, there is provided an operative assembly comprising a part which is contacted with a wear means which applies an abrasive force to an outer surface of said part, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer . Any feature of any aspect of any invention or embodiment described herein may be combined with any feature of any other aspect of any invention or embodiment described herein mutatis mutandis.
Specific embodiments of the invention will now be described, by way of example, with reference to the accompanying figures, in which:
Figure 1 is a graphical representation of the wear rates of various coatings; and
Figure 2 is a graphical representation of the coefficient of friction of various coatings under different loads.
The following materials are referred to hereinafter.
Polyetheretherketone powder having a melt viscosity of 0.15 kNsπf2 and a D50 of lOμm obtained from Victrex PIc, UK, (referred to herein as "PAEK No.l")
Aerosol® OT75%E - a surfactant from Cytec Industries UK Ltd comprising a mixture of sodium dioctyl sulphosuccinate (73-75% wt), ethanol (6-7% wt) and water.
PFA 5011 - refers to a PFA sold under the trade mark TEFLON by DUPONT comprising, nominally, lOμm powder.
ZONYL MP1400 - a PTFE in powder form obtained from DUPONT.
RYTON - a PPS sold by Chevron Phillips Chemical Company; ETFE - a powder coating grade of ethylene tetrafluoroethylene;
PVDF - a powder coating grade of polyvinylidene fluoride;
OXPEKK - a polyetherketoneketone obtained from Oxford Polymers;
ECTFE - a powder coating grade of ethylene chloro- trifluoroethylene .
Example 1 - Preparation of polyetheretherketone/PFA dispersion
A plastic 5000 ml beaker was charged with demineralised water (1.45kg) and to it was added slowly, with stirring, the surfactant, Aerosol OT75 E (10Og) . When the mixture was homogeneous PAEK No.l (0.9kg) was added slowly. Stirring was continued until the polymer had been fully incorporated. Thereafter PFA 5011 (0.1Kg) was added slowly and incorporated by stirring.
The beaker was placed under a high shear Silverson laboratory mixer with an emulsion head stirrer attachment. The speed of the mixer was slowly increased to 3000 rpm and maintained at that speed for 5 minutes. There was minimal foaming of the sample. Example 2 - (Comparative) - Preparation of polyetheretherketone dispersion .
The procedure described in Example 1 was generally followed except that the step of adding PFA was omitted so that an aqueous dispersion of polyetheretherketone was prepared.
Example 3 - Preparation of polyetheretherketone/PTFE dispersion
The procedure described in Example 1 was generally followed except that PTFE in the form of ZONYL MP1400 was added instead of the PFA 5011.
Example 4 - Preparation of substrates for coating
The substrates were 60mm x 37mm x 3mm 316 stainless steel grit blasted with an aluminium oxide grade with a mean particle size of 425 - 600 microns. The grit blasted surface had a profile with a Ra and Rz value of 1.83 microns and 1.73 microns respectively.
Examples 5a and 5b - General method for coating of substrates
Substrates prepared as described in Example 4 were coated as described in Example 5a if an aqueous dispersion was used or as described in Example 5b if a powder was used. Example 5a - Dispersion Coating
The coating gun used was a Devilbiss, type SRIW, with a tip size of 0.7 - 1.0mm. Air pressure to the gun was 30 to 40 psi depending on what type of coating was required i.e. wet, dry, thin or thick coating. Procedure for coating: A dispersion to be coated was hand mixed with a stirrer rod before pouring into the spray gun reservoir. The substrate to be coated was placed in an air extracted spraying cabinet and two or three wet coats applied. The substrate was then left to dry in air for 5 minutes then placed in an air circulated oven set to 12O0C to flash off the remaining water. The substrate was then placed for 10 minutes in an oven set to 390°C-420°C to melt and flow the coating. After removal from the oven the substrates were cooled to room temperature.
Examples 5b - Powder Coating
The powder for coating was dried in an oven at 15O0C for 3 hours before use. The substrate to be spray coated was placed in an oven at 4000C for 10 minutes, removed from the oven and quickly sprayed with the powder. The powder melted on contact with the substrate. The coated substrate was placed in the oven at 4000C for 10 minutes to melt and flow the coating. The substrate was removed from the oven and allowed to cool.
Example 6
The method of Example 5a was used to prepare coatings as described in Table 1 below: Table 1
Figure imgf000017_0001
Example 7 - Assessment of Coefficient of friction of coatings
The coatings described in Example 6 were evaluated by Coefficient of Friction testing using ASTM G133 - 05. The test assessed the Coefficient of Friction measured at 3 loads (50, 100 and 250N) on a Plint TE77 test rig using a 10mm slider @ 20Hz with a stroke of 10mm.
The test method uses a linear reciprocating ball on a flat plane geometry. The direction of the relative motion between sliding surfaces reverses in a periodic fashion such that the sliding occurs back and forth in a straight line. In the assessments, the specimens were un- lubricated.
The wear scars from the assessment were examined. It was observed that the coating of Example 6a resists wear well; only a wear scar was visible and there was no penetration through to the underlying substrate. This is in contrast to the results for Examples 6b and 6c which showed significant penetration of the coating through to the substrate, although the Example 6b coating resisted wear better than that of Example 6c. Table 2 summarises the results of the assessments undertaken.
Table 2
Figure imgf000018_0001
Example 8 - Wear rates of a range of different coatings
A range of different coatings were prepared by processes analogous to those described above and the time to wear through 25μm of the coatings under a 250N load was measured. Results are recorded in Figure 1 from which it will be noted that a coating comprising 90 wt% polyetheretherketone and 10 wt% PFA did not wear through under the conditions of the test. The aforesaid coating was superior over a coating comprising 100% polyetheretherketone and far superior over various other fluoropolymers tested. For example respective 25μm coatings comprising PVDF and ECTFE wore through in under 2 seconds, whereas the polyetheretherketone/PFA coating had not worn through after greater than 14 minutes.
Example 9 - Comparison of coatings with varying levels of
PFA
Coatings were prepared as described above having varying levels of polyetheretherketone and PFA and such coatings were compared to respective coatings comprising pure PTFE, PFA and polyetheretherketone. Results are summarised in Figure 2 which shows the coefficients of friction of various coatings under 5ON, IOON and 250N loads. It will be noted that the coefficient of friction for polyetheretherketone/PFA coatings is, in all cases, less than that for pure PFA and pure polyetheretherketone coatings. Also, the coefficient of friction for the majority of polyetheretherketone/PFA coatings is less than that for PTFE which is generally regarded as one of the lowest coefficient of friction fluoropolymers available.
Example 10 - Preparation of Materials for scratch resistance testing
Using the method generally described in Example 1 polyetheretherketone and/or fluoropolymer dispersions were prepared having compositions described in Table 3.
Table 3
Figure imgf000019_0001
Figure imgf000020_0001
*1 contains a small amount of black pigment.
The compositions described in Table 3 were coated, generally using the method of Example 5a, onto 100mm x 100mm x 3mm stainless steel plaques which had previously been degreased and grit blasted with aluminium oxide.
Example 11- Scratch resistance testing
Plaques coated with the formulations described in Example 10 and other engineering thermoplastics and fluoropolymers were tested for scratch resistance using a Sheen Scratch Tester. A test plaque is clamped to a slide which slowly withdraws the panel while a lmm tungsten carbide tip scratches the surface. The test was conducted using a single specified load of 6 kg. The scratch test was carried out under similar conditions to ISO1518; however as the speed of the needle could not be measured on the equipment the test should be regarded as comparative only.
The results were determined by measurement of the average scratch width in mm by light microscopy and the peak valley in μm across the scratch using a Form Tallysurf Intra Measuring Instrument. Scratch width was determined by measuring the scratch width under 3OX magnification using an Olympus SZHlO microscope. The scratch width is measured in the centre of the scratch and 10mm either side of centre, and an average width calculated from the three readings .
Scratch depth was determined using a Form Tallysurf Intra Measuring Instrument. A stylus is pulled over the scratch and a reading of the surface roughness can be measured. The Pv (peak valley) is also shown, this being a measure in μm of the lowest valley present in the measured coating. Before the Pv can be measured the Tallysurf equipment removes any shape or slope present in the test panel to give a mean average line; therefore the Pv is a measure of the lowest peak to a mean average line.
Results are provided in Table 4.
Table 4
Figure imgf000021_0001
Figure imgf000022_0001
Examples Hg, Hh, Hi, Hj, Hl and Hm were applied by electrostatic powder coating methodology generally as described in Example 5b.
The coatings of Examples Hk and Hn were found, under the test conditions, to have scratched through to the underlying substrate.
From a consideration of the results in Table 4, it will be noted that each of Examples Hb to Hf show excellent scratch resistance compared to other materials tested in Examples Hg to Hn. Also, Examples Hb to Hf have comparable performance to the material of Example Ha even though the materials of Examples Hb to Hf included fluoropolymers which are generally regarded as significantly softer in comparison to the material in Example 11a.
It should now be appreciated that coatings comprising a polyaryletherketone such as polyetheretherketone and a fluoropolymer such as PFA, show surprisingly low wear as determined, for example, by wear rates (see Example 8) and by scratch resistance (see Example 11) and low coefficient of friction compared to coatings comprising polyaryletherketone or fluoropolymer alone. Such coatings may be used to coat parts which are subjected to abrasive forces which may abrade and/or scratch their surfaces, in use, for example by virtue of contact with abrasive fluids such as abrasive slurries or by virtue of contact with other solids for example other metals or plastics materials. Furthermore, since polyaryletherketones have excellent resistance to chemicals and heat, the coatings described may be used in relatively harsh environments whilst still maintaining excellent wear properties.
The invention is not restricted to the details of the foregoing embodiment (s ). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

Claims
1. An assembly comprising a part arranged to be contacted by wear means in use such that said wear means has a tendency to apply an abrasive force to an outer surface of said part, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropαlymer .
2. An assembly according to claim 1, wherein said polyaryletherketone polymer comprises a repeat unit of formula
Figure imgf000024_0001
where t and v independently represent 0 or 1.
3. An assembly according to claim 1 or claim 2, wherein said polyaryletherketone polymer is polyetheretherketone.
4. An assembly according to any preceding claim, wherein said fluoropolymer comprises a fluorocarbon resin selected from perfluoroalkoxy tetrafluoroethylene (PFA) , polytetrafluoroethylene (PTFE) and tetrafluoroethylene- hexafluoropropylene copolymer resin (FEP) .
5. An assembly according to any preceding claim, wherein the ratio of the wt% of polyaryletherketone to the wt% of fluoropolymer in said composition at said outer surface is at least 1 and is less than 50.
6. An assembly according to claim 5, wherein said ratio is in the range 2 to 9.
7. An assembly according to any preceding claim, wherein the composition at said outer surface includes at least
40wt% and 95wt% or less of said polyaryletherketone.
8. An assembly according to any preceding claim, wherein the composition at said outer surface includes at least 60wt% of said polyaryletherketone.
9. An assembly according to any preceding claim, wherein the composition at said outer surface includes at least 5wt% fluoropolymer .
10. An assembly according to any preceding claim, wherein the composition of said outer surface includes at least 10wt% of said fluoropolymer.
11. An assembly according to any preceding claim, wherein the composition of said outer surface includes 70 to 95wt% of said polyaryletherketone and 5 to 30wt% of said fluoropolymer .
12. An assembly according to any preceding claim, wherein said part comprises a layer of said composition which layer defines said outer surface of said part.
13. An assembly according to claim 12, wherein said layer has a coat weight of at least 1.0mg/cm2 and less than 20mg/cm2, at least 1. Omg of said polyaryletherketone per cm2 and less than 20mg of said polyaryletherketone per cm2.
14. An assembly according to any preceding claim, wherein said part is for an item of cookware, bakeware, domestic appliance, industrial apparatus or automotive application.
15. An assembly according to any preceding claim, wherein said part comprises a bearing surface.
16. An assembly according to any of claims 12 to 15, wherein said layer is in direct contact with a metal surface of said part.
17. An assembly according to any preceding claim, wherein said wear means comprises an abrasive fluid which contacts said outer surface of said part or a solid part which contacts said outer surface.
18. A method of manufacturing a part of an assembly which is arranged to be subjected to a wear means in use such that said wear means has a tendency to apply an abrasive force to an outer surface of said part, said method comprising providing said part with an outer surface which comprises a composition which comprises a polaryletherketone polymer and a fluoropolymer .
19. A part for an assembly, said part being arranged to be contacted in use by a wear means such that said wear means has a tendency to apply an abrasive force to an outer surface of said part to abrade it, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer .
20. The use of a composition which comprises a polyaryletherketone polymer and a fluoropolymer in the manufacture of a part which is contacted by a wear means in use which wear means has a tendency to apply an abrasive force to an outer surface of said part to abrade it.
21. A method of operating an assembly which comprises a part having an outer surface which comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer, said method comprising contacting a wear means with said outer surface of said part wherein said wear means applies an abrasive force to said outer surface .
22. An operative assembly comprising a part which is contacted with a wear means which applies an abrasive force to an outer surface of said part, wherein said outer surface of said part comprises a composition which comprises a polyaryletherketone polymer and a fluoropolymer .
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101440235B (en) * 2008-12-24 2010-10-13 中国地质科学院矿产综合利用研究所 Preparation process of inorganic wear-resistant aggregate suitable for composite wear-resistant coating material
EP2258319B2 (en) † 2009-06-04 2018-12-26 Howmedica Osteonics Corp. Orthopedic paek-on-polymer bearings
US12076246B2 (en) 2009-06-04 2024-09-03 Howmedica Osteonics Corp. Orthopedic PAEK-on-polymer bearings
WO2011098390A3 (en) * 2010-02-09 2011-11-10 Paul Hettich Gmbh & Co. Kg Metal component, method for producing a metal component, and fitting, furniture, and/or large household appliance
EP2612711A1 (en) 2010-02-09 2013-07-10 Paul Hettich GmbH & Co. KG Metallic component, method for producing a metallic component and fitting, piece of furniture and/or large domestic appliance
CN103958608A (en) * 2011-12-13 2014-07-30 大金工业株式会社 Resin composition and molded article
AU2016200329B2 (en) * 2012-02-07 2017-07-20 Swimc Llc Compositions for containers and other articles and methods of using same
EP3339386A1 (en) 2016-12-22 2018-06-27 Arkema France Use of a polymeric material based on polyetherketoneketones for reducing wear
WO2018115490A1 (en) 2016-12-22 2018-06-28 Arkema France Use of a polymeric material based on polyetherketoneketones for reducing wear
US11008492B2 (en) 2016-12-22 2021-05-18 Arkema France Use of a polymeric material based on polyetherketoneketones for reducing wear

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GB2437830A (en) 2007-11-07
US20090092827A1 (en) 2009-04-09
GB0615996D0 (en) 2006-09-20
TW200745283A (en) 2007-12-16
GB0708378D0 (en) 2007-06-06
AR060842A1 (en) 2008-07-16
EP2019853A1 (en) 2009-02-04
GB0608560D0 (en) 2006-06-07

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