US20040247848A1 - Plastic article comprising bundle drawn stainless steel fibers - Google Patents
Plastic article comprising bundle drawn stainless steel fibers Download PDFInfo
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- US20040247848A1 US20040247848A1 US10/771,276 US77127604A US2004247848A1 US 20040247848 A1 US20040247848 A1 US 20040247848A1 US 77127604 A US77127604 A US 77127604A US 2004247848 A1 US2004247848 A1 US 2004247848A1
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- plastic article
- stainless steel
- steel fibers
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/062—Fibrous particles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49801—Shaping fiber or fibered material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4981—Utilizing transitory attached element or associated separate material
- Y10T29/49812—Temporary protective coating, impregnation, or cast layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
- Y10T428/12438—Composite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
Definitions
- the present invention relates to stainless steel fibers and bundles of stainless steel fibers, obtained by the bundled drawing of wires.
- the invention further relates to a process for manufacturing such stainless steel fibers.
- the invention relates further to threads, grain and plastic articles comprising such stainless steel fibers and which have ESD or EMI shielding properties.
- the metal matrix material has a lower chemical resistance and allows the stainless steel fibers to be freed from the matrix material in a leaching process quite easily.
- An important drawback of using a metal as matrix material is the mutual solubility of stainless steel and matrix material that may be observed during heat treatments. This drawback is observed especially with stainless steels that have quick cold work hardening and therefore require frequent heat treatments e.g. AISI 302.
- stainless steel fibers obtained by the bundled drawing of stainless steel wires embedded in a matrix material and/or in an envelope material, have a composition comprising iron and the following components expressed in percent by weight:
- ‘matrix material’ is to be understood as the material applied on the individual stainless steel wires for the bundled drawing process.
- Such matrix material may for example be copper, iron or a copper or iron alloy.
- the envelope material is defined as the material applied on a bundle of stainless steel wires on which a matrix material is applied.
- Such an enveloped bundle of stainless steel wires, being embedded in a matrix material is hereafter referred to as ‘composite wire’.
- an obtained bundle of stainless steel fibers as subject of the invention comprises 50 to 2000 stainless steel fibers. Most preferably 90 to 1000 stainless steel wires are bundled.
- the stainless steel fibers according to the present invention have an equivalent diameter ranging between 0.5 and 100 ⁇ m, and preferably between 1 and 50 ⁇ m. Equivalent diameter is defined as the diameter of an imaginary circle, of which the surface area is identical to the surface area of a cross section of the stainless steel fiber.
- the bundle of stainless steel fibers have substantially equal properties over the length of the fibers and a substantially homogeneous composition, with less contamination due to diffusion of matrix material, over the whole surface of the fibers.
- the diffusion of individual elements from the matrix material, such as copper or iron, into the stainless steel fiber is less than 1 at % at a depth of 100 nm below the surface of the stainless steel fiber, independent from the process used to remove the matrix and enveloping material, e.g. by chemical or electrochemical leaching.
- Such improved properties are obtained since these bundles of stainless steel fibers require less annealing treatments during the drawing of the composite wire to its final diameter. It is possible to reduce the number of annealing treatments because the steel composition allows high deformation between two annealing treatments.
- the depth of diffusion of matrix elements into the stainless steel wires in the composite wire increases; during reduction of the diameter of the composite wire, the depth of diffusion decreases proportionally with the diameter reduction.
- the high deformability of the steel described in the present invention can advantageously be used to reduce the number of annealing treatments and to increase the deformation between annealing treatments or reduction towards the final diameter.
- the homogeneity of the stainless steel fiber according to the present invention is an important advantage over other stainless steel fibers known in the art, since even a small change in the surface composition of the fibers may have influences on the properties of the stainless steel fibers. For example the oxidation and corrosion resistance of stainless steel fibers is dependent upon the compositional homogeneity of the stainless steel fiber surfaces.
- the composition of the stainless steel satisfies the following relationship:
- MI 551 ⁇ 462 ⁇ (C %+N %) ⁇ 9.2 ⁇ Si % ⁇ 20 ⁇ Mn % ⁇ 13.7 ⁇ Cr % ⁇ 29 ⁇ (Ni %+Cu %) ⁇ 18.5 ⁇ Mo %.
- MI ⁇ 55 Most preferable, MI ⁇ 55.
- the alloy of the stainless steel fibers as subject of the invention provide several advantages.
- the carbon content is lower than 0.05 wt %, because otherwise too much martensite makes the drawn material brittle. Typically, the carbon content is higher than 0.005 wt % because it is difficult to obtain a lower content during steel decarburisation.
- the manganese content is lower than 5 wt % to obtain deformable sulfide inclusions.
- the silicon content is lower than 2 wt % and attributes to cold work hardening.
- the nickel content is between 8 and 12 wt % to guarantee an austenitic crystal structure during wire rod rolling and after annealing treatments.
- the chromium content is between 15 wt % and 20 wt % to obtain a good corrosion resistance and to keep the efforts for pickling at an acceptable level.
- the molybdenum content is lower than 3 wt % and improves the corrosion resistance.
- the copper content is preferably limited to 4 wt % to avoid wire rod rolling difficulties.
- the content of nitrogen is limited to 0.05 wt % to avoid brittleness. Typically, the N content is higher tan 0.005 wt %.
- the sulfur content is limited to 0.03 wt % to avoid fractures.
- the content of phosphorus is limited to 0.05 wt % to avoid wire rod rolling defects.
- initial cross-section S 1 is meant the cross-section of the composite wire measured after a heat treatment and before the composite wire is further drawn.
- final cross-section S 2 is meant the cross-section of the composite wire after deformation (drawing) without an intermediate heat treatment.
- This deformation may comprise different drawing steps, one after another without intermediate heat treatment.
- S 2 is measured after the last drawing step and before the next heat treatment step if any.
- the method according to the invention comprises the following steps:
- the final reduction provides a composite wire with a final diameter.
- the components of the alloy satisfy the following relationship:
- MI 551 ⁇ 462 ⁇ (C %+N %) ⁇ 9.2 ⁇ Si % ⁇ 20 ⁇ Mn % ⁇ 13.7 ⁇ Cr % ⁇ 29 ⁇ (Ni %+Cu %) ⁇ 18.5 ⁇ Mo %;
- the stainless steel wires or wire rods provided in step a preferably have a diameter between 100 ⁇ m and 20 mm.
- the stainless steel wires are embedded in the matrix material by applying a layer of a matrix material on each of the stainless steel wires in a first step.
- the matrix material comprises for example copper, iron or a copper or iron alloy.
- the thickness of this layer is for example between 1 ⁇ m and 2 mm.
- the diameter of the coated wires is reduced by a drawing step.
- the wires may be brought together to form a bundle.
- an envelope material comprising for example copper or iron or a copper or iron alloy is applied around the bundle to form a composite wire.
- the method comprises a step of subjecting the composite wire to a heat treatment before reducing the diameter of the composite wire.
- the reducing of the composite wire comprises the drawing of the wire by any technique known in the art.
- the reduction of the diameter may be obtained by a rolling operation.
- the composite wire is reduced in diameter and subjected to a heat treatment.
- the reductions may comprise several subsequent reduction passes, e.g. drawing operations on wire drawing machines.
- such large reduction is used during the final reduction, providing a final diameter to the composite wire.
- Stainless steel fibers so obtained benefit most of the improvement of properties over its surface as subject of the invention.
- the removing of the matrix material comprises preferably the leaching of the composite wire using sulfuric or nitric acid.
- this deformation ⁇ is kept less than 3, or even less than 2.5.
- matrix material is diffused over a depth of the stainless steel wires, which depends largely on the temperature used during the heat treatment.
- the depth over which diffusion is observed after this diameter reduction with large ⁇ is significantly smaller than if ⁇ is to be kept smaller than 3, as was known in the art.
- Stainless steel fibers according to the present invention can be used in many applications. They can for example be used in filter media, electrically conductive textiles, flocking on metal or polymer substrates, heat-resistant textiles, gas burner membranes or tubes, heating elements, conductive plastics or for EMI-shielding and ESD applications.
- EMI-shielding is to be understood as “electromagnetic interference shielding”.
- ESD is to be understood as “electrostatic discharge”.
- fibers as subject of the invention may have improved fracture strength, being more than e.g. 2000 MPa, or even more than 2100 MPa.
- the ductility of the fiber, expressed as strain at fracture, may be more than 1% or even more than 1.1% such as more than 1.2%.
- the stainless steel fibers after being leached, are present as stainless steel fiber slivers. These slivers may be used to provide threads and grains as subject of the invention.
- a sliver of stainless steel fibers as subject of the invention is provided with an impregnating resin, being a polymer material preferably having a relatively low molecular weight.
- an impregnating resin being a polymer material preferably having a relatively low molecular weight.
- polyvinylalcohol PVA
- PE polyethylene
- PP polypropylene
- PS polystyrene
- PVC polyvinylchloride
- PET polyester
- polyacrylate polymethacrylate or copolymers of these polymers
- This impregnation resin may be applied in many different ways to the sliver, such as by an extrusion of the resin around the sliver, or by applying a dipping process of the sliver in a bath comprising the resin.
- the amount of impregnating resin may vary to large extent, such as between 5 and 95% vol of the thread.
- Such thread may be shopped into grains comprising stainless steel fibers and impregnation resin, as subject of the invention.
- Such threads and grains as subject of the invention may be obtained in a similar way as described on column 3 line 5 to column 5 line 45 of U.S. Pat. No. 4,664,971, hereby incorporated by reference.
- the thread is cut into small but preferably uniform lengths ranging preferably from 0.5 mm to 12 mm, most preferably between 3 mm and 6 mm.
- the amount of impregnating resin may vary to large extent, such as between 1 and 99% vol of the grain or thread, but preferably between 5% vol and 95% vol.
- a plastic article as subject of the invention comprises at least one of an ESD or EMI-shielding layer having a polymer matrix and stainless steel fibers as subject of the invention.
- the stainless steel fibers are obtained by the bundled drawing of stainless steel wires, wherein the stainless steel fibers having an equivalent diameter of more than 0.5 ⁇ m, this equivalent diameter being less than 100 ⁇ m, and wherein the stainless steel fibers have a composition comprising iron and the following components expressed in percent by weight:
- the components of the alloy of the stainless steel fibers of the plastic article satisfy the following relationship:
- MI 551 ⁇ 462 ⁇ (C %+N %) ⁇ 9.2 ⁇ Si % ⁇ 20 ⁇ Mn % ⁇ 13.7 ⁇ Cr % ⁇ 29 ⁇ (Ni %+Cu %) ⁇ 18.5 ⁇ Mo %;
- the volume of the stainless steel fibers represent more than or equal to 0.1% vol of the plastic article.
- the volume of the stainless steel fibers represent preferably less than or equal to 5% vol of the ESD or EMI-shielding layer of the plastic article, even less than or equal to 2.5% vol or even less than or equal to 1.5% vol of the ESD or EMI-shielding layer of the plastic article.
- the stainless steel fiber volume represents less than 1% vol of the volume of the ESD or EMI-shielding layer of the plastic article.
- the ESD or EMI-shielding layer of the plastic article may have a thickness T, which is preferably less than or equal to 5 mm, such as less than or equal to 3 mm or even less than or equal to 1 mm. It is understood that this thickness is to be understood as the average thickness of the layer over its surface, not taking into account the surface of the apertures which may be present in the ESD or EMI-shielding layer of the plastic article. Most preferably, the local thickness of the ESD or EMI-shielding layer is substantially equal over its surface.
- the ESD or EMI-shielding layer of the plastic article may be provided using thermo-set or thermoplastic polymer matrix.
- the polymer matrix is chosen out of the group consisting of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyethylene napthalate (PEN), polybuteen terephthalate (PBT) polyvinylchloride (PVC), polyamide (PA), polyester (PES), polyimide (PI), polycarbonate (PC), styrene acrilonitryl (SAN), acrylonitril-butadiene-styrene (ABS), thermoplastic polyurethane (TPU), thermoplastic polyolefins (TPO), thermoplastic copolyetheresters, copolymers of these polymers or any mixture of these polymers.
- a preferred mixture of these polymers is a mixture comprising polycarbonate and acrylonitril-butadiene-styrene
- the ESD or EMI-shielding layer may have an EMI-shielding effect of more than or equal to 5 dB, such as more than or equal to 20 dB, even more than or equal to 30 dB such as more than or equal to 35 dB.
- Such EMI shielding effectiveness may be obtained when the thickness T of the ESD or EMI-shielding layer is less than 3 mm, or even less than or equal to 1 mm, even in case only less than or equal to 1.5% vol of the ESD or EMI-shielding layer of the article is provided by the stainless steel fibers.
- Such shielding effectiveness may be obtained in far field and near field, using an TEM-t and a H-t cell test.
- the shielding effect is obtained in the range of 0.4 GHz to 1 Ghz.
- the stainless steel fibers as subject of the invention may be provided to the ESD or EMI-shielding layer of the plastic article in many different ways, e.g. injection molding, extrusion, over-extrusion, casting foaming or press molding.
- the stainless steel fibers are added in the master batch of the polymer matrix as so-called grains, as described in US4664971, hereby incorporated by reference. These grains are added to and blended with the master batch of the polymer matrix, which blend is transformed into the ESD or EMI-shielding layer of a plastic article.
- the stainless steel fibers present in the ESD or EMI-shielding layer of the plastic article preferably have a length of more than 0.5 mm.
- FIG. 1 shows the deformation ⁇ that can be reached between two annealing steps as a function of the index MI.
- FIG. 2 shows schematically a preferred bundled drawing process as subject of the invention.
- FIG. 3 shows fracture strength and strain at fracture of stainless steel fibers as subject of the invention, compared to presently known stainless steel fibers.
- FIG. 4 shows schematically the ESD or EMI-shielding layer of a plastic article as subject of the invention.
- Table I gives the composition of stainless steel fibers according to the present invention.
- FIG. 1 illustrates the deformation ⁇ as function of the index MI defined by the composition of the alloy.
- the bold line (1) represents the deformability limit
- the lines (2) represent lines of constant tensile strength.
- Stainless steel fibers as subject of the invention may be provided by using following preferred process, as schematically shown in FIG. 2.
- Stainless steel wires ( 201 ) of diameter between 0.5 and 1.5 mm, e.g. 1.4 mm and having a steel composition according to one of the examples above are provided in step 21 .
- These stainless steel wires are coated by e.g. electrolytic coating with a layer of Cu ( 202 ) in step 22 .
- this layer ranges from 3 to 100 ⁇ m, e.g. 5 ⁇ m thickness.
- the coated stainless steel wires are reduced to a diameter ranging from 0.1 to 1 mm, e.g. 0.35 mm.
- Several coated wires, e.g. 1000, possibly reduced in diameter are enveloped in an iron envelope ( 203 ), so providing a composite wire having a diameter in the range of 5 to 15 mm during step 23 .
- This composite wire ( 204 ) is alternatingly reduced with several ⁇ (e.g. ⁇ 1, ⁇ 2) higher than 0.5, e.g. 1.5 and than annealed at a temperature in the range of 800 to 1100° C., E.g. 1030° C. This heat treatment takes 0.05 to 5 minutes, e.g. 2 minutes. These steps are represented as step 24 .
- a final reduction 25 reduces the composite diameter with E being higher than 4.5. This final reduction 25 provides the final diameter to the composite wire.
- the matrix and enveloping material is removed ( 26 ) by pickling with an acid, e.g. nitric acid.
- Stainless steel fibers ( 205 ) with a diameter in the range of e.g. 6 to 15 ⁇ m are obtained, which have an Cu-diffusion of less than 1 at % over a depth of 100 nm over the whole surface of the fibers.
- the stainless steel fibers as subject of the invention have improved fracture strength and strain at fracture, as compared to similar presently known stainless steel fibers.
- the fracture strength (horizontal axis 310 in FIG. 3) of the stainless steel fibers as subject of the invention is more than 2000 MPa having a standard deviation of less than 180 MPa.
- the strain at fracture (in vertical axis 320 in FIG. 3) of the stainless steel fibers as subject of the invention is more than 1.1% meanwhile having a standard deviation of less than 0.15%. It is clear that these values are significantly different from the values for fracture strength, strain at fracture and standard deviation on these parameters, as in presently known fibers 302 a , 302 b , 303 a and 303 b.
- FIG. 4 shows schematically the ESD or EMI-shielding layer 400 of a plastic article as subject of the invention.
- the ESD or EMI-shielding layer 400 of the plastic article comprises a polymer matrix 401 and a plurality of stainless steel fibers 402 as subject of the invention, being identical as the fibers of which the composition of the alloy is given in Table I.
- the stainless steel fibers in the ESD or EMI-shielding layer of the plastic article have an average length L of more than 0.5 mm. L is measured by making the average length of L1 to Ln, n being a statistically representative number of fibers in the ESD or EMI-shielding layer of the plastic article.
- the thickness T of the ESD or EMI-shielding layer of the article is the average thickness of the ESD or EMI-shielding layer of the plastic article, obtained by making the average of t1 to Tm, wherein m is statistically representative number of thickness measurements over the ESD or EMI-shielding layer surface, excluding possible apertures in the surface of the ESD or EMI-shielding layer.
- the amount of stainless steel fibers may be reduced with 33% when using stainless steel fibers as subject of the invention, providing the same shielding effectiveness, especially when more than 0.5 vol % stainless steel fibers are used in the ESD or EMI-shielding layer of the plastic article.
- the ESD or EMI-shielding layer of the plastic article as shown in FIG. 4 was obtained by injection molding of a master batch, comprising pallets of polyamide 12 and grains as subject of the invention, comprising 75% vol stainless steel fibers as subject of the invention, and 25% vol PVA-polymer. These grains were obtained by cutting a thread having the same constitution, into lengths of 5 mm.
Abstract
The invention relates to plastic articles comprising stainless steel fibers obtained by bundled drawing of stainless steel wires embedded in a matrix material. The composition of the stainless steel fibers comprises iron and the following components expressed in percent by weight: C≦0.05%, Mn≦5%, Si≦2%, 8≦Ni≦12%, 15%≦Cr≦20%, Mo≦3%, Cu≦4%, N≦0.05%, S≦0.03% and P≦0.05%.
Description
- The present invention relates to stainless steel fibers and bundles of stainless steel fibers, obtained by the bundled drawing of wires. The invention further relates to a process for manufacturing such stainless steel fibers. The invention relates further to threads, grain and plastic articles comprising such stainless steel fibers and which have ESD or EMI shielding properties.
- In bundled drawing of stainless steel fibers a number of stainless steel wires are bundled and drawn together. The individual wires are separated from one another by covering each stainless steel wire, possibly even on wire rod diameter, with a suitable matrix material. All stainless steel wires, covered with matrix material, are enveloped in an envelope material. Once the bundle of enveloped wires, also called the composite wire, is drawn to the desired diameter, the envelope material and the matrix material are removed, usually by leaching. Very often a metal such as iron or copper is used as matrix and/or envelope material. The use of such metal as matrix material is advantageous since a metal has similar deformability properties as the stainless steel wire that has to be drawn into stainless steel fibers. The metal matrix material is compatible with the stainless steel wires during the drawing and annealing operations. The metal matrix material has a lower chemical resistance and allows the stainless steel fibers to be freed from the matrix material in a leaching process quite easily. An important drawback of using a metal as matrix material is the mutual solubility of stainless steel and matrix material that may be observed during heat treatments. This drawback is observed especially with stainless steels that have quick cold work hardening and therefore require frequent heat treatments e.g. AISI 302.
- Intermediate heat treatments, performed between two drawing steps, result in a diffusion of elements of the matrix material into the stainless steel wires and/or in a diffusion of the elements of the stainless steel wires into the matrix material. This has as consequence that the composition of the steel may be changed to some extent after a heat treatment. This effect is most pronounced at the surface of the stainless steel fibers.
- Differences in the composition of the stainless steel due to diffusion may cause unreliability of the properties of the stainless steel fibers, for example in the electrical and chemical properties or in the behavior of the stainless steel fibers exposed to high temperatures.
- Prior art provides only one solution to the drawback of inhomogeneous surface composition of stainless steel fiber, being the use of electrochemical leaching as process for removing the matrix material as described in EP337517A1. This method is not industrially attractive due to excessive investment costs, causing significant cost price increase of the fibers so obtained.
- Another consequence of the diffusion is that more matrix material is necessary in order to assure a separation of the stainless steel fibers during manufacturing of the stainless steel fibers.
- It is an object of the present invention to provide stainless steel fibers having more reliable properties over the length and circumference of the fibers and with less contamination by diffusion of matrix elements into the fiber over the whole surface of the fibers.
- According to the present invention, stainless steel fibers, obtained by the bundled drawing of stainless steel wires embedded in a matrix material and/or in an envelope material, have a composition comprising iron and the following components expressed in percent by weight:
- C≦0.05%
- Mn≦5%
- Si≦2%
- 8≦Ni≦12%
- 15%≦Cr≦20%
- Mo≦3%
- Cu≦4%
- N≦0.05%
- S≦0.03%
- P≦0.05%
- Since the stainless steel fibers are obtained by bundled drawing process, ‘matrix material’ is to be understood as the material applied on the individual stainless steel wires for the bundled drawing process. Such matrix material may for example be copper, iron or a copper or iron alloy. During bundled drawing, usually a bundle of stainless steel wires are enveloped after being embedded into a matrix material. The envelope material is defined as the material applied on a bundle of stainless steel wires on which a matrix material is applied. Such an enveloped bundle of stainless steel wires, being embedded in a matrix material is hereafter referred to as ‘composite wire’.
- Usually, 50 to 2000 stainless steel wires are bundled into a composite wire. After reduction of the diameter of the composite wire, and removing of the enveloping and matrix material, an obtained bundle of stainless steel fibers as subject of the invention comprises 50 to 2000 stainless steel fibers. Most preferably 90 to 1000 stainless steel wires are bundled.
- The stainless steel fibers according to the present invention have an equivalent diameter ranging between 0.5 and 100 μm, and preferably between 1 and 50 μm. Equivalent diameter is defined as the diameter of an imaginary circle, of which the surface area is identical to the surface area of a cross section of the stainless steel fiber.
- According to the present invention, it was found that the bundle of stainless steel fibers have substantially equal properties over the length of the fibers and a substantially homogeneous composition, with less contamination due to diffusion of matrix material, over the whole surface of the fibers. The diffusion of individual elements from the matrix material, such as copper or iron, into the stainless steel fiber is less than 1 at % at a depth of 100 nm below the surface of the stainless steel fiber, independent from the process used to remove the matrix and enveloping material, e.g. by chemical or electrochemical leaching. Such improved properties are obtained since these bundles of stainless steel fibers require less annealing treatments during the drawing of the composite wire to its final diameter. It is possible to reduce the number of annealing treatments because the steel composition allows high deformation between two annealing treatments.
- During annealing treatments, the depth of diffusion of matrix elements into the stainless steel wires in the composite wire increases; during reduction of the diameter of the composite wire, the depth of diffusion decreases proportionally with the diameter reduction. The high deformability of the steel described in the present invention can advantageously be used to reduce the number of annealing treatments and to increase the deformation between annealing treatments or reduction towards the final diameter. These two advantages have both positively effect on the compositional homogeneity of the stainless steel fibers as compared to what is presently known. First of all, diffusion depth may be reduced by a factor 3 or more. Further, the length over which product properties change may be increased by a
factor 10 or more, compared to presently known stainless steel fibers. - The homogeneity of the stainless steel fiber according to the present invention is an important advantage over other stainless steel fibers known in the art, since even a small change in the surface composition of the fibers may have influences on the properties of the stainless steel fibers. For example the oxidation and corrosion resistance of stainless steel fibers is dependent upon the compositional homogeneity of the stainless steel fiber surfaces.
- It was found that the properties of the stainless steel fibers according to the present invention are more uniform over a taken length of a stainless steel fiber as subject of the invention, compared to a presently known stainless steel fiber, obtained by bundled drawing. Such improved compositional homogeneity provides associated fiber properties, which are more reliable and predictable, and allow a more reliable and economical preventive replacement of such fibers and products comprising these stainless steel fibers.
- Preferably, to reach a preferred level of deformability of the composite wire, the composition of the stainless steel satisfies the following relationship:
- MI≦−40, where
- MI=551−462×(C %+N %)−9.2×Si %−20×Mn %−13.7×Cr %−29×(Ni %+Cu %)−18.5×Mo %.
- Most preferable, MI≦−55.
- Steel with such a composition is known from EP953651 and used for cold heading, because of its high deformability, or for rubber reinforcement, because of the favorable combination of tensile strength and cost of manufacturing. According to the MI of the alloy, a maximum for the deformation ε may be used during diameter reduction of the composite wire.
- The alloy of the stainless steel fibers as subject of the invention provide several advantages.
- The carbon content is lower than 0.05 wt %, because otherwise too much martensite makes the drawn material brittle. Typically, the carbon content is higher than 0.005 wt % because it is difficult to obtain a lower content during steel decarburisation.
- The manganese content is lower than 5 wt % to obtain deformable sulfide inclusions.
- The silicon content is lower than 2 wt % and attributes to cold work hardening.
- The nickel content is between 8 and 12 wt % to guarantee an austenitic crystal structure during wire rod rolling and after annealing treatments.
- The chromium content is between 15 wt % and 20 wt % to obtain a good corrosion resistance and to keep the efforts for pickling at an acceptable level.
- The molybdenum content is lower than 3 wt % and improves the corrosion resistance.
- The copper content is preferably limited to 4 wt % to avoid wire rod rolling difficulties.
- The content of nitrogen is limited to 0.05 wt % to avoid brittleness. Typically, the N content is higher tan 0.005 wt %.
- The sulfur content is limited to 0.03 wt % to avoid fractures.
- The content of phosphorus is limited to 0.05 wt % to avoid wire rod rolling defects.
- Using an alloy as described above, and preferably but not necessarily satisfying above relationship, allows to obtain a deformation ε of the composite wire during drawing of the composite wire, which is higher than 4.5, for example higher than 4.8 or even 5.2 without necessitating an intermediate heat treatment.
-
- With initial cross-section S1 is meant the cross-section of the composite wire measured after a heat treatment and before the composite wire is further drawn. With final cross-section S2 is meant the cross-section of the composite wire after deformation (drawing) without an intermediate heat treatment.
- This deformation may comprise different drawing steps, one after another without intermediate heat treatment. S2 is measured after the last drawing step and before the next heat treatment step if any.
- According to a second aspect of the present invention a process for the manufacturing of stainless steel fibers by bundled drawing is provided.
- The method according to the invention comprises the following steps:
- a. providing stainless steel wires having a composition comprising iron and the following components expressed in percent of weight:
- C≦0.05%
- Mn≦5%
- Si≦2%
- 8≦Ni≦12%
- 15%≦Cr≦20%
- Mo≦3%
- Cu≦4%
- N≦0.05%
- S≦0.03%
- P≦0.05%
- b. embedding the stainless steel wires in a matrix material;
- c. enveloping the embedded stainless steel wires with enveloping material to form a composite wire;
- d. alternatingly subjecting the composite wire to a diameter reduction, subjecting the reduced composite wire to a heat treatment and applying a final reduction; at least once a reduction with a deformation ε of at least 4.5, being used;
- e. providing stainless steel fibers by removing the matrix material and enveloping material from the composite wire.
- The final reduction provides a composite wire with a final diameter.
- Preferably, the components of the alloy satisfy the following relationship:
- MI≦−40, where
- MI=551−462×(C %+N %)−9.2×Si %−20×Mn %−13.7×Cr %−29×(Ni %+Cu %)−18.5×Mo %;
- Most preferably, MI≦−55.
- The stainless steel wires or wire rods provided in step a preferably have a diameter between 100 μm and 20 mm.
- In a preferred method the stainless steel wires are embedded in the matrix material by applying a layer of a matrix material on each of the stainless steel wires in a first step. The matrix material comprises for example copper, iron or a copper or iron alloy. The thickness of this layer is for example between 1 μm and 2 mm.
- Possibly, the diameter of the coated wires is reduced by a drawing step.
- After the application of a layer of a matrix material on the individual wires and possibly after the drawing of the coated wires, the wires may be brought together to form a bundle. Subsequently, an envelope material comprising for example copper or iron or a copper or iron alloy is applied around the bundle to form a composite wire.
- Possibly, the method comprises a step of subjecting the composite wire to a heat treatment before reducing the diameter of the composite wire.
- The reducing of the composite wire comprises the drawing of the wire by any technique known in the art. Alternatively, the reduction of the diameter may be obtained by a rolling operation. Alternatingly, the composite wire is reduced in diameter and subjected to a heat treatment. The reductions may comprise several subsequent reduction passes, e.g. drawing operations on wire drawing machines.
- According to the present invention, at least once a deformation ε of 4.5 or more is used to reduce the diameter of the composite wire.
- Preferably, such large reduction is used during the final reduction, providing a final diameter to the composite wire. Stainless steel fibers so obtained benefit most of the improvement of properties over its surface as subject of the invention.
- Possibly, although not preferred, a heat treatment is applied after the final reduction.
- Possibly, but not necessarily, a deformation c of more than 4.5 is used for all drawing steps.
- The removing of the matrix material comprises preferably the leaching of the composite wire using sulfuric or nitric acid.
- For presently known stainless steel bundled drawn fibers, this deformation ε is kept less than 3, or even less than 2.5. To draw a composite wire from diameter immediately after the bundling step, to the final diameter of the composite wire, before removing the enveloping and matrix material, a lot of heat treatments are required when this ε is kept less than 3, especially because of the logarithmic nature of ε. During each heat treatment, matrix material is diffused over a depth of the stainless steel wires, which depends largely on the temperature used during the heat treatment.
- When a large diameter reduction may follow a heat treatment, as subject of the invention, the depth over which diffusion is observed after this diameter reduction with large ε, is significantly smaller than if ε is to be kept smaller than 3, as was known in the art. The variation of this depth, caused by temperature variation during the heat treatment before the reduction with large ε, becomes less in absolute value, as compared to presently known bundle drawing processes. Further, this variation is spread over a larger length of the stainless steel wires in the composite wire, since the composite wire elongates more due to this large E as compared to presently known bundle drawing processes.
- Stainless steel fibers according to the present invention can be used in many applications. They can for example be used in filter media, electrically conductive textiles, flocking on metal or polymer substrates, heat-resistant textiles, gas burner membranes or tubes, heating elements, conductive plastics or for EMI-shielding and ESD applications. “EMI-shielding” is to be understood as “electromagnetic interference shielding”. “ESD” is to be understood as “electrostatic discharge”.
- At present, when stainless steel fibers are used in EMI shielding and ESD applications, there is a need for mechanically improved stainless steel fibers, having increased fracture strength, meanwhile having a better ductility.
- It was found that fibers as subject of the invention may have improved fracture strength, being more than e.g. 2000 MPa, or even more than 2100 MPa. The ductility of the fiber, expressed as strain at fracture, may be more than 1% or even more than 1.1% such as more than 1.2%.
- Most surprisingly it was found that even providing such improved mechanical properties, the standard deviation on these parameters of fracture strength and strain at fracture are significantly less, compared to the parameters of presently known stainless steel fibers. Standard deviations of less than 180 MPa, or even less than 140 MPa such as less than 130 MPa for the fracture strength may be obtained. Standard deviations of less than 0.15%, or even less than 0.12% or even less than 0.1%, for the strain at fracture may be obtained.
- The stainless steel fibers, after being leached, are present as stainless steel fiber slivers. These slivers may be used to provide threads and grains as subject of the invention.
- To obtain a thread as subject of the invention, a sliver of stainless steel fibers as subject of the invention is provided with an impregnating resin, being a polymer material preferably having a relatively low molecular weight. As an example, polyvinylalcohol (PVA), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinylchloride (PVC), polyester (PES), polyacrylate, polymethacrylate or copolymers of these polymers may be used. This impregnation resin may be applied in many different ways to the sliver, such as by an extrusion of the resin around the sliver, or by applying a dipping process of the sliver in a bath comprising the resin. The amount of impregnating resin may vary to large extent, such as between 5 and 95% vol of the thread.
- Such thread may be shopped into grains comprising stainless steel fibers and impregnation resin, as subject of the invention. Such threads and grains as subject of the invention may be obtained in a similar way as described on column3 line 5 to column 5 line 45 of U.S. Pat. No. 4,664,971, hereby incorporated by reference.
- However, the thread is cut into small but preferably uniform lengths ranging preferably from 0.5 mm to 12 mm, most preferably between 3 mm and 6 mm. The amount of impregnating resin may vary to large extent, such as between 1 and 99% vol of the grain or thread, but preferably between 5% vol and 95% vol.
- It is an other subject of the present invention to provide a plastic article which is useful as a conductive plastic article, as an article having EMI-shielding properties and/or improved electrostatic discharge properties. A plastic article as subject of the invention comprises at least one of an ESD or EMI-shielding layer having a polymer matrix and stainless steel fibers as subject of the invention.
- Preferably the stainless steel fibers are obtained by the bundled drawing of stainless steel wires, wherein the stainless steel fibers having an equivalent diameter of more than 0.5 μm, this equivalent diameter being less than 100 μm, and wherein the stainless steel fibers have a composition comprising iron and the following components expressed in percent by weight:
- C≦0.05%,
- Mn≦5%,
- Si≦2%,
- 8≦Ni≦12%,
- 15%≦Cr≦20%,
- Mo≦3%
- Cu≦4%
- N≦0.05%,
- S≦0.03%,
- P≦0.05%.
- Preferably, the components of the alloy of the stainless steel fibers of the plastic article satisfy the following relationship:
- MI≦−40, where
- MI=551−462×(C %+N %)−9.2×Si %−20×Mn %−13.7×Cr %−29×(Ni %+Cu %)−18.5×Mo %;
- Most preferably, MI≦−55.
- Preferably, the volume of the stainless steel fibers represent more than or equal to 0.1% vol of the plastic article. The volume of the stainless steel fibers represent preferably less than or equal to 5% vol of the ESD or EMI-shielding layer of the plastic article, even less than or equal to 2.5% vol or even less than or equal to 1.5% vol of the ESD or EMI-shielding layer of the plastic article. Possibly, the stainless steel fiber volume represents less than 1% vol of the volume of the ESD or EMI-shielding layer of the plastic article.
- The ESD or EMI-shielding layer of the plastic article may have a thickness T, which is preferably less than or equal to 5 mm, such as less than or equal to 3 mm or even less than or equal to 1 mm. It is understood that this thickness is to be understood as the average thickness of the layer over its surface, not taking into account the surface of the apertures which may be present in the ESD or EMI-shielding layer of the plastic article. Most preferably, the local thickness of the ESD or EMI-shielding layer is substantially equal over its surface.
- The ESD or EMI-shielding layer of the plastic article may be provided using thermo-set or thermoplastic polymer matrix. Preferably, the polymer matrix is chosen out of the group consisting of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyethylene napthalate (PEN), polybuteen terephthalate (PBT) polyvinylchloride (PVC), polyamide (PA), polyester (PES), polyimide (PI), polycarbonate (PC), styrene acrilonitryl (SAN), acrylonitril-butadiene-styrene (ABS), thermoplastic polyurethane (TPU), thermoplastic polyolefins (TPO), thermoplastic copolyetheresters, copolymers of these polymers or any mixture of these polymers. A preferred mixture of these polymers is a mixture comprising polycarbonate and acrylonitril-butadiene-styrene.
- It was found that the ESD or EMI-shielding layer, even when having only a thickness T in the range of less than 3 mm, may have an EMI-shielding effect of more than or equal to 5 dB, such as more than or equal to 20 dB, even more than or equal to 30 dB such as more than or equal to 35 dB. Such EMI shielding effectiveness may be obtained when the thickness T of the ESD or EMI-shielding layer is less than 3 mm, or even less than or equal to 1 mm, even in case only less than or equal to 1.5% vol of the ESD or EMI-shielding layer of the article is provided by the stainless steel fibers.
- Such shielding effectiveness may be obtained in far field and near field, using an TEM-t and a H-t cell test. In general, the shielding effect is obtained in the range of 0.4 GHz to 1 Ghz.
- The stainless steel fibers as subject of the invention may be provided to the ESD or EMI-shielding layer of the plastic article in many different ways, e.g. injection molding, extrusion, over-extrusion, casting foaming or press molding.
- Preferably, in case of injection molding or extrusion, the stainless steel fibers are added in the master batch of the polymer matrix as so-called grains, as described in US4664971, hereby incorporated by reference. These grains are added to and blended with the master batch of the polymer matrix, which blend is transformed into the ESD or EMI-shielding layer of a plastic article.
- The stainless steel fibers present in the ESD or EMI-shielding layer of the plastic article preferably have a length of more than 0.5 mm.
- The invention will now be described into more detail with reference to the accompanying drawings wherein
- FIG. 1 shows the deformation ε that can be reached between two annealing steps as a function of the index MI.
- FIG. 2 shows schematically a preferred bundled drawing process as subject of the invention.
- FIG. 3 shows fracture strength and strain at fracture of stainless steel fibers as subject of the invention, compared to presently known stainless steel fibers.
- FIG. 4 shows schematically the ESD or EMI-shielding layer of a plastic article as subject of the invention.
- In FIG. 5, the shielding effectiveness (ordinate) in function of the volume percentage (abscissa) of the stainless steel fibers is shown.
- Table I gives the composition of stainless steel fibers according to the present invention.
TABLE I Steel Steel Steel composition A composition B composition C Content C 0.007 0.011 0.012 (in wt %) Mn 1.28 1.75 0.88 Si 0.74 0.36 0.68 Ni 9.81 11.174 9.49 Cr 18.19 18.76 17.5 Mo 0.43 0.24 0.2 Cu 0.35 0.26 3.15 N 0.020 0.032 0.015 S 0.001 0.009 0.001 P 0.025 0.019 0.023 MI −46 −100 −95 - FIG. 1 illustrates the deformation ε as function of the index MI defined by the composition of the alloy.
- The bold line (1) represents the deformability limit, whereas the lines (2) represent lines of constant tensile strength. During reduction of the diameter of the composite wire, and thereby of the stainless steel wires in this composite wire, a deformation ε is to be chosen lower than the deformation limit (1), corresponding with the MI of the alloy chosen.
- Stainless steel fibers as subject of the invention may be provided by using following preferred process, as schematically shown in FIG. 2. Stainless steel wires (201) of diameter between 0.5 and 1.5 mm, e.g. 1.4 mm and having a steel composition according to one of the examples above are provided in
step 21. These stainless steel wires are coated by e.g. electrolytic coating with a layer of Cu (202) instep 22. Preferably, this layer ranges from 3 to 100 μm, e.g. 5 μm thickness. Possibly the coated stainless steel wires are reduced to a diameter ranging from 0.1 to 1 mm, e.g. 0.35 mm. Several coated wires, e.g. 1000, possibly reduced in diameter, are enveloped in an iron envelope (203), so providing a composite wire having a diameter in the range of 5 to 15 mm duringstep 23. - This composite wire (204) is alternatingly reduced with several ε (e.g. ε1, ε2) higher than 0.5, e.g. 1.5 and than annealed at a temperature in the range of 800 to 1100° C., E.g. 1030° C. This heat treatment takes 0.05 to 5 minutes, e.g. 2 minutes. These steps are represented as
step 24. Afinal reduction 25 reduces the composite diameter with E being higher than 4.5. Thisfinal reduction 25 provides the final diameter to the composite wire. Finally the matrix and enveloping material is removed (26) by pickling with an acid, e.g. nitric acid. Stainless steel fibers (205) with a diameter in the range of e.g. 6 to 15 μm are obtained, which have an Cu-diffusion of less than 1 at % over a depth of 100 nm over the whole surface of the fibers. - It is obvious for a person skilled in the art, that deformability and limited number of inclusions in the stainless steel wires may further positively influence the deformability of the composite wire. The stainless steel fibers as subject of the invention have improved fracture strength and strain at fracture, as compared to similar presently known stainless steel fibers.
- In Table II underneath, and in FIG. 3, examples of fracture strength, strain at fracture and the standard deviation on these properties, measured on stainless steel fibers as subject of the invention (sample301 a, 301 b and 301 c), and on presently known stainless steel fibers, out of AISI 302 alloy (sample 302 a and 302 b) or AISI 316L alloy (sample 303 a and 303 b) are provided.
TABLE II Fracture strength Strain at fracture Fiber equiv. Standard Standard Diameter Value deviation deviation sample (μm) (MPa) (MPa) Value (%) (%) 301a 8 2229 94 1.5 0.08 301b 8 2269 113 1.4 0.09 301c 11 2106 126 1.4 0.09 302a 8 1553 360 0.9 0.21 302b 11 1842 238 1.1 0.15 303a 8 1115 339 0.8 0.25 303b 12 1539 195 1.1 0.16 - The fracture strength (
horizontal axis 310 in FIG. 3) of the stainless steel fibers as subject of the invention is more than 2000 MPa having a standard deviation of less than 180 MPa. The strain at fracture (invertical axis 320 in FIG. 3) of the stainless steel fibers as subject of the invention is more than 1.1% meanwhile having a standard deviation of less than 0.15%. It is clear that these values are significantly different from the values for fracture strength, strain at fracture and standard deviation on these parameters, as in presently knownfibers - FIG. 4 shows schematically the ESD or EMI-
shielding layer 400 of a plastic article as subject of the invention. The ESD or EMI-shielding layer 400 of the plastic article comprises apolymer matrix 401 and a plurality of stainless steel fibers 402 as subject of the invention, being identical as the fibers of which the composition of the alloy is given in Table I. The stainless steel fibers in the ESD or EMI-shielding layer of the plastic article have an average length L of more than 0.5 mm. L is measured by making the average length of L1 to Ln, n being a statistically representative number of fibers in the ESD or EMI-shielding layer of the plastic article. - The thickness T of the ESD or EMI-shielding layer of the article is the average thickness of the ESD or EMI-shielding layer of the plastic article, obtained by making the average of t1 to Tm, wherein m is statistically representative number of thickness measurements over the ESD or EMI-shielding layer surface, excluding possible apertures in the surface of the ESD or EMI-shielding layer.
- Eight embodiments of the ESD or EMI-shielding layer of plastic articles, being sheets with substantially equal thickness T were provided using PA12 as polymer matrix and stainless steel fibers as subject of the invention.
Thickness of the ESD or EMI- shielding % vol of layer stainless Sample of plastic steel ID article fibers; A A1 1 mm 0.25 % vol A2 1 mm 0.5 % vol A3 1 mm 1 % vol A4 1 mm 1.5% vol B B1 3 mm 0.25% vol B2 3 mm 0.5% vol B3 3 mm 1% vol B4 3 mm 1.5% vol - Identical reference ESD or EMI-shielding layers of plastic articles were made, using presently known and generally applies stainless steel fibers of type AISI302.
Thickness of the ESD or EMI- shielding % vol of layer stainless Sample of plastic steel ID article fibers; Aref A1ref 1 mm 0.25 % vol A2ref 1 mm 0.5 % vol A3ref 1 mm 1 % vol A4ref 1 mm 1.5% vol Bref B1ref 3 mm 0.25% vol B2ref 3 mm 0.5% vol B3ref 3 mm 1% vol B4ref 3 mm 1.5% vol - All sheets were tested on shielding effectiveness at 1 GHz (TEM-t cell) and 0.4 GHz (H-t cell). In FIG. 5, the shielding effectiveness (ordinate) in function of the volume percentage (abscissa) of the stainless steel fibers is shown.
- It was found that in comparison with presently known AISI302 stainless steel fibers, the amount of stainless steel fibers may be reduced with 33% when using stainless steel fibers as subject of the invention, providing the same shielding effectiveness, especially when more than 0.5 vol % stainless steel fibers are used in the ESD or EMI-shielding layer of the plastic article.
- the ESD or EMI-shielding layer of the plastic article as shown in FIG. 4, was obtained by injection molding of a master batch, comprising pallets of polyamide12 and grains as subject of the invention, comprising 75% vol stainless steel fibers as subject of the invention, and 25% vol PVA-polymer. These grains were obtained by cutting a thread having the same constitution, into lengths of 5 mm.
Claims (42)
1. A plastic article comprising:
at least one of an ESD layer and EMI-shielding layer having a polymer matrix and stainless steel fibers obtained by the bundled drawing of stainless steel wires wherein said stainless steel fibers having an equivalent diameter being more than 0.5 μm, said equivalent diameter being less than 100 μm, said stainless steel fibers having a composition comprising iron and the following components expressed in percent by weight:
C≦0.05%,
Mn≦5%,
Si≦2%,
8≦Ni≦12%,
15%≦Cr≦20%,
Mo≦3%,
Cu<4%
N<0.05%,
S<0.03%,
P<0.05%.
2. A plastic article according to claim 1 , whereby said composition satisfies the following relationship:
MI=551−462×(C %+N %)−9.2×Si %−20×Mn %−13.7×Cr %−29×(Ni %+Cu %)−18.5×Mo %, said MI≦−40.
3. A plastic article according to claim 2 , said MI≦−55.
4. A plastic article according to claim 1 , wherein the volume of said stainless steel fibers is more than or equal to 0.1% volume of said plastic article.
5. A plastic article according to claim 1 , wherein the volume of said stainless steel fibers is less than or equal to 5 vol % of said plastic article.
6. A plastic article according to claim 5 , wherein the volume of said stainless steel fibers is less than or equal to 2.5 vol % of said plastic article.
7. A plastic article according to claim 6 , wherein the volume of said stainless steel fibers is less than or equal to 1.5 vol % of said plastic article.
8. A plastic article according to claim 7 , wherein the volume of said stainless steel fibers is less than or equal to 1 vol % of said plastic article.
9. A plastic article according to claim 1 , wherein said plastic article has a thickness T, said T being less than or equal to 5 mm.
10. A plastic article according to claim 9 , wherein T is less than or equal to 3 mm.
11. A plastic article according to claim 10 , wherein T is less than or equal to 1 mm.
12. A plastic article according to claim 1 , wherein said polymer matrix is a thermo-set polymer.
13. A plastic article according to claim 1 , wherein said polymer matrix is a thermoplastic polymer.
14. A plastic article according to claim 1 , wherein said polymer matrix is chosen out of the group consisting of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyethylene napthalate (PEN), polybuteen terephthalate (PBT) polyvinylchloride (PVC), polyamide (PA), polyester (PES), polyimide (PI), polycarbonate (PC), styrene acrilonitryl (SAN), acrylonitril-butadiene-styrene (ABS), thermoplastic polyurethane (TPU), thermoplastic polyolefins (TPO), thermoplastic copolyetheresters, copolymers of these polymers or a mixture of these polymers.
15. A plastic article according to claim 1 , wherein said plastic article has a shielding effectiveness of more than 5 dB.
16. A plastic article according to claim 1 , wherein said plastic article has a shielding effectiveness of more than 20 dB.
17. A plastic article according to claim 1 , wherein said plastic article has a shielding effectiveness of more than 30 dB.
18. A plastic article according to claim 7 , wherein said plastic article has a shielding effectiveness of more than 5 dB.
19. A plastic article according to claim 7 , wherein said plastic article has a shielding effectiveness of more than 20 dB.
20. A plastic article according to claim 7 , wherein said plastic article has a shielding effectiveness of more than 30 dB.
21. A plastic article according to claim 10 , wherein said plastic article has a shielding effectiveness of more than 5 dB.
22. A plastic article according to claim 10 , wherein said plastic article has a shielding effectiveness of more than 20 dB.
23. A plastic article according to claim 10 , wherein said plastic article has a shielding effectiveness of more than 30 dB.
24. A plastic article according to claim 1 , said stainless steel fibers having a fracture strength, said fracture strength having a standard deviation of less than 180 MPa.
25. A plastic article according to claim 1 , said stainless steel fibers having a strain at fracture, said strain at fracture having a standard deviation of less than 0.15%.
26. A plastic article according to claim 25 , said fracture strength being more than 2000 MPa.
27. A plastic article according to claim 25 , said strain at fracture being more than 1%.
28. A plastic article according to claim 1 , whereby the diffusion of the individual elements of the matrix material, used on said stainless steel wires during said bundled drawing, is limited to less than 1 at % at a depth of 100 nm below the surface of said stainless steel fibers.
29. A plastic article according to claim 28 , whereby said matrix material comprises a metal or a metal alloy.
30. A plastic article according to claim 29 , whereby said metal or metal alloy comprises copper, iron or a copper or iron alloy.
31. A thread comprising an impregnating resin and stainless steel fibers obtained by the bundled drawing of stainless steel wires wherein said stainless steel fibers having an equivalent diameter being more than 0.5 μm, said equivalent diameter being less than 100 μm, said stainless steel fibers having a composition comprising iron and the following components expressed in percent by weight:
C≦0.05%,
Mn≦5%,
Si≦2%,
8≦Ni≦12%,
15%≦Cr≦20%
Mo≦3%,
Cu≦4%
N≦0.05%,
S≦0.03%,
P≦0.05%.
32. A thread according to claim 31 , whereby said composition satisfies the following relationship:
MI=551−462×(C %+N %)−9.2×Si %−20×Mn %−13.7×Cr %−29×(Ni %+Cu %)−18.5×Mo %, said MI≦−40.
33. A thread according to claim 32 , said MI≦−55.
34. A thread according to claim 31 , wherein said impregnating resin provides between 1% vol and 99% vol of said tread.
35. A thread according to claim 31 , wherein said impregnating resin is polyvinylalcohol (PVA), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinylchloride (PVC), polyester (PES), polyacrylate, polymethacrylate or a copolymer of these polymers.
36. A grain comprising an impregnating resin and stainless steel fibers obtained by the bundled drawing of stainless steel wires wherein said stainless steel fibers having an equivalent diameter being more than 0.5 μm, said equivalent diameter being less than 100 μm, said stainless steel fibers having a composition comprising iron and the following components expressed in percent by weight:
C≦0.05%,
Mn≦5%,
Si≦2%,
8≦Ni≦12%,
15%≦Cr≦20%
Mo≦3%,
Cu≦4%
N≦0.05%,
S≦0.03%,
P≦0.05%.
37. A grain according to claim 36 , whereby said composition satisfies the following relationship:
MI=551−462×(C %+N %)−9.2×Si %−20×Mn %−13.7×Cr %−29×(Ni %+Cu %)−18.5×Mo %, said MI≦−40.
38. A grain according to claim 37 , said MI≦−55.
39. A grain according to claim 36 , wherein said impregnating resin provides between 1% vol and 99% vol of said tread.
40. A grain according to claim 36 , wherein said grain having a length ranging between 0.5 mm and 12 mm.
41. A grain according to claim 36 , wherein said grain having a length ranging between 3 mm and 6 mm.
42. A grain according to claim 36 , wherein said impregnating resin is polyvinylalcohol (PVA), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinylchloride (PVC), polyester (PES), polyacrylate, polymethacrylate or a copolymer of these polymers.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01202775.1 | 2001-07-20 | ||
EP01202775 | 2001-07-20 |
Related Parent Applications (2)
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PCT/EP2002/007269 Continuation-In-Part WO2003010353A1 (en) | 2001-07-20 | 2002-07-02 | Bundle drawn stainless steel fibers |
US10/482,379 Continuation-In-Part US7166174B2 (en) | 2001-07-20 | 2002-07-02 | Bundle drawn stainless steel fibers |
Publications (1)
Publication Number | Publication Date |
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US20040247848A1 true US20040247848A1 (en) | 2004-12-09 |
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US10/482,379 Expired - Lifetime US7166174B2 (en) | 2001-07-20 | 2002-07-02 | Bundle drawn stainless steel fibers |
US10/771,276 Abandoned US20040247848A1 (en) | 2001-07-20 | 2004-02-04 | Plastic article comprising bundle drawn stainless steel fibers |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US10/482,379 Expired - Lifetime US7166174B2 (en) | 2001-07-20 | 2002-07-02 | Bundle drawn stainless steel fibers |
Country Status (9)
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---|---|
US (2) | US7166174B2 (en) |
EP (1) | EP1412549B1 (en) |
JP (1) | JP4068556B2 (en) |
CN (1) | CN1276989C (en) |
AT (1) | ATE524573T1 (en) |
DK (1) | DK1412549T3 (en) |
ES (1) | ES2373709T3 (en) |
PT (1) | PT1412549E (en) |
WO (1) | WO2003010353A1 (en) |
Cited By (3)
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US20040265576A1 (en) * | 2001-07-20 | 2004-12-30 | Stefaan De Bondt | Bundle drawn stainless steel fibers |
WO2006128741A1 (en) * | 2005-06-02 | 2006-12-07 | Nv Bekaert Sa | Polymer emi housing comprising conductive fibre |
US20140045400A1 (en) * | 2011-04-26 | 2014-02-13 | Nv Bekaert Sa | Steel fiber reinforced composites |
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CN107552588B (en) * | 2017-08-22 | 2020-01-07 | 北京中远科健科技有限公司 | Continuous microfiber separation process for improving radiation resistance of metal |
US20210072146A1 (en) * | 2019-09-05 | 2021-03-11 | Chevron U.S.A. Inc. | Flexible pipe armor wire monitoring system and method |
CN111021116B (en) * | 2019-12-27 | 2021-10-19 | 江阴法尔胜泓昇不锈钢制品有限公司 | Production process of corrosion-resistant stainless steel wire rope for woven mesh |
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---|---|---|---|---|
US20040265576A1 (en) * | 2001-07-20 | 2004-12-30 | Stefaan De Bondt | Bundle drawn stainless steel fibers |
US7166174B2 (en) * | 2001-07-20 | 2007-01-23 | Nv Bekaert Sa | Bundle drawn stainless steel fibers |
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US20080248230A1 (en) * | 2005-06-02 | 2008-10-09 | Nv Bekaert Sa | Polymer Emi Housing Comprising Conductive Fibre |
US20140045400A1 (en) * | 2011-04-26 | 2014-02-13 | Nv Bekaert Sa | Steel fiber reinforced composites |
Also Published As
Publication number | Publication date |
---|---|
ES2373709T3 (en) | 2012-02-08 |
JP2004536230A (en) | 2004-12-02 |
ATE524573T1 (en) | 2011-09-15 |
EP1412549A1 (en) | 2004-04-28 |
US20040265576A1 (en) | 2004-12-30 |
EP1412549B1 (en) | 2011-09-14 |
PT1412549E (en) | 2011-12-22 |
DK1412549T3 (en) | 2011-12-05 |
JP4068556B2 (en) | 2008-03-26 |
CN1276989C (en) | 2006-09-27 |
US7166174B2 (en) | 2007-01-23 |
WO2003010353A1 (en) | 2003-02-06 |
CN1535324A (en) | 2004-10-06 |
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