KR20190003998A - Delamination resistant, weldable and formable light weight composites - Google Patents

Abstract

The present invention is directed to a lightweight composite material (10, 12) comprising a polymer layer of a filled polymeric material (16) comprising a thermoplastic polymer (18) and a metal fiber (20) and a metal layer (14). The polymer layer comprises a filled polymeric material 16. The composite material of the present invention can be molded at room temperature using a conventional stamping apparatus. The composite material of the present invention can be welded to other metal materials using conventional welding techniques. The composite shows resistance to peeling.

Description

DELIVERY RESISTANT, WELDABLE AND FORMABLE LIGHT WEIGHT COMPOSITES < RTI ID = 0.0 >

The present invention relates to a sandwich composite comprising a fiber-filled polymeric material, a composite material comprising a fiber-filled polymeric material layer, and in particular a fiber-filled polymeric material layer and a metal layer.

Lightweight composites with high stiffness, high toughness, and good balance of low weight are used in many applications requiring low flexibility and reduced weight. The transport sector can be used in industries where such materials are necessary, for example, in automotive parts or in objects to be transported (e.g. containers).

The need for materials replacing other lightweight materials and conventional steel materials as well as vehicles, vehicles and objects to be transported has created an industry that develops new composite materials, particularly sandwich composites. Such efforts are described in prior applications by the present inventors.

Unfortunately, performance requirements that are emphasized for many commercial applications limit design. Materials that meet one condition (e.g., stampability) do not match other conditions, such as weldability. Thus, until the work of the inventors of the present invention, materials meeting various commercial demands have never been used. Efforts to use sandwich composites have been successful, but the bond between the layers is not perfect and the long-term corrosion resistance is not high. Of course, when stampability and weldability are required at the same time, many such materials are excluded from the candidates. Thus, despite the great efforts of the prior art, there is still a need for improved composites, such as sandwich composites, which can replace conventional rigid materials without incurring too much cost to include the material in the finished product do. There is also a demand for materials that can be stamped. There is also a need for materials that can be welded, in particular, those that can be welded with conventional welding techniques and / or devices. It is also possible to obtain a long term durability characteristic, for example, resistance to abrasion or peel resistance (e.g., resistance to peeling under general service conditions, for example, general service conditions of an automobile, 3, 5, 10, years or more) of the composite material layer). It is also possible to use a polymer-substrate which can be used alone or in combination with other materials, such as a laminated material, which exhibits excellent processing characteristics, durability, electrical properties (e.g., charge dissipation properties) Lt; / RTI >

There remains a need for a weldable lightweight composite comprising a polymer layer with improved weldability (i. E., Having a larger processing window to obtain an acceptable weld). The weldability is fixed in the welding current range (i.e., the difference between the maximum current and the minimum current to form an acceptable weld, the other conditions, for example, the welding pressure and the welding time, ). ≪ / RTI > The weldability is fixed in the welding time range (i.e., the difference between the maximum time and the minimum time to form an acceptable weld, other conditions, for example, welding pressure and welding current, ). ≪ / RTI >

The present invention relates to a steel sheet which satisfies some or all of the above conditions with a combination of unique materials, exhibits excellent stretchability and is capable of welding (which can be welded also by using a conventional technique and apparatus) , ≪ / RTI > for example, a sandwich composite. Such effective materials can be effectively used for various steel applications by replacing steel. Therefore, the materials of the present invention can be used in the manufacturing process without investing in new equipment or other costs. The manufactured products can also be weight-reduced.

Hereinafter, the present invention will be described in detail.

The composite material comprises at least one first thermoplastic polymer; And one or more second thermoplastic polymers different from the first thermoplastic polymer; And a plurality of metal fibers having at least one generally flat surface, wherein the polymer matrix is present at a concentration of at least about 3 vol% based on the total volume of the composite mass, and wherein the polymer is distributed throughout the matrix, And a lump of metal fibers forming a matrix of the substrate and a filled polymeric material composite mass.

The features of the present invention are explained in detail in the summary part of the invention and the concrete means for carrying out the following invention.

The one or more first thermoplastic polymers may comprise one or more polyolefinic polymers (e.g., linear low density polyethylene); The at least one second polymer comprises an elastomer, for example, an ethylene-octene copolymer. The polymer-based matrix may comprise a crosslinkable polymer. For example, the polymer-based matrix comprises a polymer that is crosslinkable by external stimuli selected from radiation (e.g., ultraviolet radiation and / or infrared radiation), moisture, heat, or a combination thereof. The relative weight and / or ratio of the first thermoplastic polymer to the second thermoplastic polymer is from about 1: 1 to about 10: 1, more preferably from about 2: 1 to about 5: 1.

The composite agglomerates may be attached to a substrate, e.g., a metal sheet (e.g., sandwiched between opposed metal sheets); The base or metal sheet may be coated with one or more coatings (e. G., Zinc, phosphate, or both) to improve corrosion resistance before or after the major surface of the sheet is adhered to the composite lump. The base metal or sheet may be made of aluminum, steel (e.g., high strength steel (e.g., having a mechanical strength in accordance with the rating, for example, a yield strength of at least about 240 MPa, at least about 300 MPa, at least about 400 MPa, at least about 450 MPa, A steel having a maximum strength of at least about 550 MPa, a maximum strength of at least about 340 MPa, at least about 450 MPa, at least about 500 MPa, at least about 500 MPa, at least about 600 MPa, or at least about 650; or both) Molybdenum, titanium, calcium, one or more rare earth elements, zirconium, nitrogen, or a combination thereof.

The agglomerates of the metal fibers may comprise a plurality of fibers coated with a composition for improving corrosion resistance; For example, the plurality of fibers can be coated with a composition defining the sacrificial anode so that the fibers are adhered to the composite mass due to having a standard electrochemical reduction potential that is less than the standard electrochemical reduction potential of the metal to which the composite mass is attached Corrosion resistance is provided to the metal. Agglomerates of metal fibers may include aluminum fibers, zinc fibers, magnesium fibers, or combinations thereof; And / or the fibers may be at least partially coated with aluminum, zinc, magnesium, or combinations thereof. The mass of metal fibers includes a plurality of fibers in the form of a ribbon. For example, the metal fibers may have two or more surfaces that are generally flat; The metal fiber has a cross-section crossing the longitudinal direction of the fiber; The cross section of the metal fibers may be generally polygonal (e.g., generally rectangular); The metal fibers may have a cross-section including width and thickness, wherein the ratio of width to thickness is from about 20: 1 to about 1: 1.

The resulting composite material exhibits excellent properties to replace steel in various applications. For example, the composite agglomerates are sufficiently bonded to the metal layer that a significant amount of cohesive failure (e. G., At least about 25%, such as about 40%, 50%, 60% Destruction). In the superposition shear test under DIN 11465, the composite is subjected to a significant amount of cohesive failure (for example, at least about 25%, for example, at least about 40%, 50%, 60% Cohesive failure).

As described above, according to the present invention, it is possible to provide a polymer having excellent bonding strength and excellent bonding strength without using a large amount or a substantial amount of polar polymer (for example, 30%, 20%, 10%, 5% A composite mass showing excellent peeling resistance can be obtained. In addition, the bond strength between the polymer matrix composite masses is not reduced unexpectedly, and is actually enhanced by the fibers present in the polymer matrix composite mass, by the use of phosphate treatment and / or galvanized steel sheets, or both . For example, a sandwich composite comprising a polymer and sandwiched between ordinary carbon steels that does not include fibers and is uncoated and a composite of the present invention, i. E., Fibers, and includes a phosphate treatment and / or galvanized steel layer as a sandwich layer , The latter peel strength was improved by a factor of two or three when tested according to DIN 11339, for example.

The yield strength of sandwich composites using composites is greater than about 100 MPa. The tensile strength of a sandwich composite using a composite material is greater than about 160 MPa. The composite may be a sandwich composite having a thickness of about 0.4 mm or more, and the composite lump thickness is at least about 30% of the total thickness of the sandwich composite.

It is also possible to produce a welded product according to the invention. For example, the shape, size, and shape of the metal fibers are selected such that the galvanized steel sheet having a thickness approximately equal to the weld stack and lightweight composite comprised of the composite exhibits an electrostatic contact resistance of less than or equal to about 0.0020 ohms . The electrostatic contact resistance is measured by applying a force of about 500 lb between two electrodes placed side by side with a diameter of about 4.8 mm. In embodiments, the shape, size concentration and shape of the metal fibers are selected such that the ratio of electrostatic contact resistances of the lightweight composite is about 0.01 or greater, wherein the electrostatic contact resistivity ratio is: (i) (Ii) the electrostatic contact resistance of a second weld stack consisting of the same two steel sheets as the first weld stack, and (ii) the electrostatic contact resistance of a steel sheet having a thickness approximately equal to the first weld stack and lightweight composite comprised. The electrostatic contact resistance is measured by applying a force of about 500 lb between two electrodes placed side by side with a diameter of about 4.8 mm.

The present invention can also include a method of making a product, which method comprises modifying the composite material to an elongation of at least about 1.5 (e.g., a high speed stamping operation), or welding the composite material to a weld Using conventional welding conditions used to weld conventional hot-dip galvanized steel to each other without use), or both. The present invention also encompasses articles comprising composite materials prepared by the method. The use of the material as an automobile part, and the product.

Other properties of the composite material are as follows. And a modulus of elasticity of the composite material is approximately 200GPa minimum measured according to ASTM D790, the concentration of the filled polymeric layer is sufficiently high density of the composite material is greater than about 0.8 d _m, where d _m is a metal sheet used in the composite loaf Lt; / RTI > The surface of the metal layer may be coated with one or more surfaces (prior to compounding) by galvanizing, e.g., electro-galvanizing techniques; Phosphate treatment to include a phosphate containing layer; Electrostatic coating; Or a combination thereof, may be a treatment for an internal formula.

The metal fibers may be formed of scrap and / or starting material (e.g., uncoated, scrap strips or scrap strips of starting material) derived from one or both of the first or second metal layers Or; The metal fibers may include steel fibers and other metals having a melting point lower than the melting point of the steel fibers.

When two or more polymers are used, the tensile modulus of one polymer measured according to ASTM D638 is at least about 25% and is different from the tensile modulus of another polymer. One polymer has a water absorption rate measured according to ASTM D570 of at least about 25% and is different from the water absorption rate of the other polymer. The heat distortion temperature measured according to ASTM D648 of one polymer is at least about 5 DEG C and is different from the heat distortion temperature of the other polymer. The one or more polymers do not substantially contain oxygen and nitrogen atoms. The total concentration of oxygen and nitrogen atoms based on the total weight of the polymer of the at least one polymer is less than the total concentration of oxygen and nitrogen atoms of the other polymer.

The one or more polymers used may be polyamides. The one or more polymers used may be ionomers. The one or more polymers may be co-polymers. The ratio of the tensile modulus between the two polymers may be 1.25: 1 or more. The weight or volume ratio of one polymer to the other is from about 10:90 to about 90:10. One of the polymers may comprise a grafted polyolefin, for example a polyolefin grafted with maleic anhydride.

The composite of the present invention has one or more of the following properties: the electrostatic contact resistance of the lightweight composite is less than or equal to about 0.0017 ohms; The electrostatic contact resistance of the lightweight composite is about 0.0015 Ω or less; The electrostatic contact resistance of lightweight composites may be greater than the electrostatic contact resistance of galvanized steel of the same thickness; The electrostatic contact resistance of lightweight composites may be greater than 100% of the electrostatic contact resistance of galvanized steel of the same thickness; The electrostatic contact resistance of lightweight composites may be greater than 20% of the electrostatic contact resistance of galvanized steel of the same thickness; The electrostatic contact resistance of lightweight composites may be greater than 400% of the electrostatic contact resistance of galvanized steel of the same thickness. The lightweight composite may have an electrostatic contact resistance of about 0.0001? Or more; Lightweight composites can have a current range of about 1.5 kA or more; Lightweight composites can have a current range of about 2.1 kA or more; The lightweight composite may have a current range of about 2.5 kA or more; The lightweight composite may have a current range greater than the current range of steel of the same thickness; The lightweight composite may have a current range greater than about 0.5 kA above the current range of steel of the same thickness; The lightweight composite may have a current range greater than about 1.0 kA above the current range of steel of the same thickness.

The concentration of the metal fibers may be from about 10% by volume to about 25% by volume based on the total volume of the charged polymeric material; The concentration of the metal fibers may be from about 12% by volume to about 23% by volume based on the total volume of the charged polymeric material; The cross-sectional area of the metal fibers across the longitudinal axis is greater than about 0.0009 mm < 2 >; The cross-sectional area of the metal fibers across the longitudinal axis is at least about 0.0025 mm < 2 >; The metal fibers have a generally rectangular cross-section across the longitudinal axis; Or rectangular cross section is specified by thickness and width and the ratio of width to thickness is about 20 or less.

The present invention also relates to a process for the preparation of a weld stack comprising: i) applying pressure to a weld stack; ii) adding an initial welding current of about 0.8 kA or less to the weld stack while applying pressure; and iii) continuously increasing the welding current so that the welding current takes 0.01 second or more until reaching a second welding current which is higher than the first welding current by about 0.5 kA or more. Wherein the weld stack may comprise a component comprising a composite material, one or more additional components each comprising one or more metal layers; Wherein the composite material comprises two metal layers; And at least one polymer layer sandwiched between two metal layers, wherein the polymer layer may contain one or more polymers, the polymer layer may comprise one or more metal fibers, and the total volume of one or more polymer layers Is at least 30% of the total volume of the composite material. Preferably, the process includes stopping the welding current for a second welding current for at least 0.06 seconds.

The composite material of the present invention can be effectively used in various steel applications by replacing steel. Therefore, the materials of the present invention can be used in the manufacturing process without investing in new equipment or other costs. The manufactured products can also be weight-reduced.

1A shows a composite material having a polymer layer and a metal layer.
1B shows a composite material having a polymer core layer sandwiched between two metal layers.
2 is a diagram showing a process of observing a polymer material or a composite material.
3 is a macrograph showing the metal fibers that can be used for the core layer.
4 is a macrograph showing a core layer comprising metal fibers and a polymer.
Figure 5 is a macrograph showing a lightweight composite comprising two metal layers, metal fibers, and a polymer.
Figure 6 shows the relationship between the welding button size (in mm) and the welding current (in kA) for a lightweight composite material welded to a galvanized metal having a welding current range of about 2.0 kA or more (e.g., about 3.0 kA) Fig.
Figure 7 shows the welding button size (in mm) and the welding current (in units of kA) for a lightweight composite material welded to an unplated deep-drawn steel plate having a welding current range of about 2.0 kA or more (e.g., about 2.8 kA) ). ≪ / RTI >
8 shows the relationship between the welding button size (in mm) and the welding current (in kA) for a lightweight composite material welded to a galvanized metal having a welding current range of about 1.5 kA or more (e.g., about 1.7 kA) Fig.
Figure 9 shows the welding button size (in mm) and the welding current (in units of kA) for a lightweight composite material welded to an unplated deep-drawn steel sheet having a welding current range of about 1.5 kA or greater (e.g., about 2.0 kA) ). ≪ / RTI >

In general, the materials of the present invention include the following filled polymeric materials, particularly metal fiber phases distributed in polymer matrices. Generally, the composite material of the present invention uses two or more layers, one of which is a filled (e.g., fiber filled) polymeric material (e.g., a fiber-filled polymeric layer therein) . In particular, the material of the present invention is a composite comprising a sandwich structure, wherein the fiber-filled polymer layer is sandwiched between two or more different layers. The material of the present invention also includes a sandwich structure precursor, e. G., A polymer layer filled with a polymer layer packed on the first layer exposed to the outside. The second layer may then be attached to the filled polymer layer. The present invention also includes a raw composition (e.g. in the form of pellets, sheets, etc.) comprising a fiber-filled polymeric material according to the invention. The material of the present invention exhibits various unique and excellent properties and is a material suitable for a deforming operation (for example, a relatively high strain forming operation such as stamping), a welding operation, or both. That is, the packed polymer layer is designed to have multiple phases. One or more phases (e. G., Fillers) may provide a conductive path and strain harden when subjected to stresses that induce plastic deformation, while allowing for plastic deformation. In addition, the polymeric phase can be attached to other materials (e.g., metal layers, e.g., steel sheets) and used for composite (e.g., stamping) . The polymer phase is not decomposed during operation (e.g., a chemical plating bath, such as an electrostatic coating bath or other plating bath that imparts general corrosion resistance to sheet metal coatings).

The composite material of the present invention exhibits excellent weldability in spite of the fact that it generally contains a polymer having low electrical conductivity, and is capable of electric resistance welding. For example, the size of the processing window for obtaining acceptable welds is generally wide. In the present invention, an acceptable weld may have a weld button size of at least about 95% of the weld electrode diameter. In the present invention, the composite material may have a wider processing window for welding than steel (e.g., galvanized steel) of the same thickness.

The present invention provides attractive composites, particularly laminate composites, with a unique combination of materials. For example, the laminate can be drawn (e.g., deep drawn), welded, or both in a manner similar to known sheet materials, such as sheet metal (e.g., stainless steel and / or low carbon steel) In general, the present invention uses a variety of composite materials, wherein the material is selected to impart stretchability, weldability, or both. The material can also be produced by processing the resulting laminate into a thin, (E. G., Coating, plating, etc.) so that it can be applied to the surface of the substrate.

For example, a particularly preferred combination of materials may comprise two layers with a core, and the core is preferably a filled polymeric material. The filled polymer comprises a material, preferably one or more polymers, and the polymer comprises or consists of a thermoplastic polymer or other material that is generally processable as a thermoplastic polymer. The filled polymeric material preferably comprises a filler phase, and preferably the filler has a filler which comprises or consists of a fiber phase, in particular an elongated, long fiber phase, for example, a thin and long metal fiber phase . Such an image may be sufficiently located or distributed (e.g., wrapped, twisted, arranged side by side, puckered, or a combination thereof) and used in a sufficient volume so that when the polymer itself is generally non- Thereby forming a network for imparting electrical conductivity to the substrate. A particularly preferred slender filler phase is stretched by itself (individual fibers or whole) and is strain hardenable.

As used herein, " layer " does not require a clearly distinguished material. For example, a layered composite may be folded into a single sheet of material to form two layers of the material, to share common edges and to place the filled polymeric material therebetween .

A first feature of the present invention is a composite material made of a layer in which dissimilar materials are combined and comprises at least one layer (e.g. a metal layer, for example a metal surface layer) and at least one polymer layer, (E. G., Cold stamping on a stamping or press machine with stress causing elastic deformation) to form a panel. The composite material may include one metal layer and one polymer layer, or may be a composite laminate further comprising one or more other layers. For example, a laminate with a metal layer sandwiched between two polymer layers, or a laminate in which a polymer layer is sandwiched between two or more opposing metal layers. A particularly preferred structure is the latter, and the former structure can be used as a precursor for the latter. The method of forming such a sandwich structure may include the steps of applying a layer to the precursor to form a sandwich structure, applying the first precursor to the second precursor to form a sandwich structure, or both.

An example of a composite laminate 10 having a metal layer 14 and a polymer layer 16 is shown in Fig. 1B, the sandwich 12 includes a first metal layer 14, a second metal layer 14 ', and a polymer layer 16 sandwiched between the first and second metal layers (e.g., , A polymer core layer). 1A and 1B, the polymer layer 16 comprises at least one polymer (e.g., a thermoplastic polymer) 18 and fibers 20. The polymer layer 16 and the first metal layer 14 may have a common surface 22. As shown in FIGS. 1A and 1B, some or all of the fibers may extend in length and direction from one surface of the polymer layer to the opposite surface. However, other fiber lengths and orientations are also included within the scope of the present invention. For example, the fraction of fibers (e.g., metal fibers) extending between the opposing faces of the polymer layer is 20% or less, 10% or less, 5% or less, or 1% or less. The fibers shown in Figs. 1A and 1B are generally straight fibers. Preferred fibers are not generally straight fibers. Preferred fibers are fibers with at least one bend along their length.

As described above, in addition to composites, multi-layer structures, the present invention relates to a precursor polymer layer sheet material (i.e., a polymer layer single layer) comprising a thermoplastic polymer and a fiber (e.g., a metal fiber) It can be sandwiched between two metal layers.

The present invention also relates to a precursor polymer raw material comprising a polymer and a fiber. Such polymeric raw materials are formed (e.g., compressed or extruded) into a polymeric layer (e.g., sheet) with a single material or with at least one additional material (e.g., one or more addition polymers). The precursor polymeric material May comprise some or all of the polymeric layer components of the composite material. Preferably, the precursor polymeric material comprises substantially all of the fibers for the polymeric layer.

In use, the composite can be deformed (e.g., by molding, e.g., stamping), attached to other structures (e.g., steel or other composite material), or both. A preferred method is to use the step of welding the composite of the present invention to another structure. The molded panel may be bonded to other components, if desired, using techniques other than welding, such as adhesives, brazing processes, and the like. In both cases, the composite material (e.g., laminate or sandwich sheet) could be molded by a low-cost stamping method and surprisingly could be free from the limitations encountered in the known art. This property of the composite material makes it a very attractive candidate for application areas using regular single metal sheets, for example, body panels used in the transportation (e.g., automotive) industry.

A feature of the present invention is the ability to select a particular polymer (e.g., a thermoplastic polymer) and metal fibers, add metal fibers and optional particles and any other filler to the polymer matrix to form a new (E. G., A sandwich or laminate structure). ≪ / RTI > Other features include but are not limited to resistance welding (e.g., spot welding, seam welding, spark welding, protrusion welding, or upset welding), energy beam welding (e.g. laser beam, electron beam or laser hybrid welding) (For example, oxygen fuel welding using a gas such as oxyacetylene), arc welding (e.g., gas metal arc welding, metal inert gas welding, or shielded metal arc welding) To provide a stampable sandwich. Preferred joining techniques include high speed welding techniques such as resistance spot welding and laser welding.

Various formable / stampable materials, test methods, test ranges, welding processes and features, and detailed molding processes are disclosed in the following references:

M. Weiss, ME Dingle, BF Rolfe, and PD Hodgson, "Influence of Temperature on the Forming Behavior of Metal / Polymer Laminates in Sheet Metal Forming", October 2007, Volume 129, Issue 4, pp . 530-537.

D. Mohr and G. Straza, " Development of Formable All-Metal Snidwitch Sheets for Automotive Applications " 4, 2005, pp. 243-246.

J. K. Kim and T. X. Yu, "Forming And Failure Behavior Of Coated, Laminated And Sandwiched Sheet Metals: A Review", Volume 63, No.1-3, 1997, pp. 33-42.

K.J. Kim, D. Kim, S.H. Choi, K. Chung, K.S. Shin, F. Barlat, K.H. Oh, J.R. Youn, " Formability of AA5182 / Polypropylene / AA5182 Sandwitch Sheet, Journal of Material Processing Technology, Volume 1, 20 August 2003, pp. 1-7. Trevor William Clyne and Athina Markaki US Patent Number 6,764,772 filed Oct 31, 2001, issued Jul 20, 2004).

Frank Gissinger and Thierry Gheysens, U.S. Pat. Patent Number 5,347,099, Filed Mar 4, 1993, Issued Sep 13, 1994, " Method And Device For The Electric Welding Of Sheets Of Multilayer Structure ".

Straza George C P, International Patent Application Publication (PCT): WO2007062061, "Formed Metal Core Sandwitch Structure And Method And System For Making Same" Publication date: May 31, 2007.

Haward R. N., Strain Hardening of Thermoplastics, Macromolecules 1993, 26, 5860-5869.

International Patent Publication No. WO 2010/021899 (published on Feb. 25, 2010, Mizrahi).

U.S. Patent Application No. 61 / 290,384 (2009,12,28 application, Mizrahi).

U.S. Patent Application No. 61 / 089,704 (2008, 8,18 application, Mizrahi).

U.S. Patent Application No. 61 / 181,511 (2009, 5,27 application, Mizrahi).

U.S. Patent Publication No. US2010 / 0040902A1, 2010, 2, 18 disclosed in Mizrahi.

material

For example, the use of a fiber filler in the polymer layer facilitates composite fabrication and surprisingly low levels can be used to obtain excellent results. Surprisingly, with the selection and combination of materials, comparable properties and properties can be exhibited while using less metal per unit volume than common metal structures (e.g. sheet metal) of the same type. Those skilled in the art have generally not been able to foresee the combination of such materials and have been avoided. In this respect, surprisingly, some behavioral properties of the material, which is expected to be avoided, were used excellently in the composite. Thus, the resulting laminate can be used as an alternative to conventional materials, for example, instead of a steel sheet, with a light weight as compared to a steel material, without rework or special process conditions. material

The polymer layer

The polymer layer can generally consist of a filled polymer, or a filled polymer (e. G., A thermoplastic polymer filled with reinforcing fibers, e. G., Metal fibers). Generally, it is a packed polymeric material composite mass consisting of a polymeric matrix and a fiber mass distributed in the matrix.

The filled polymeric material for use in the polymeric layer is preferably generally relatively hard, relatively strong, has a relatively high elongation at break, has high strain hardening properties, is lightweight, or a combination thereof, Is disclosed in the patent application publication publication WO 2010/021899 (published on February 25, 2010), which is hereby incorporated by reference.

Preferably, at least a portion of the polymer of the charged polymeric material is thermoplastic, but may comprise a thermosetting polymer, particularly a thermosetting processable thermosetting polymer. Preferably, at least 50 wt.% (More preferably at least 70 wt.%, 80 wt.%, 90 wt.% Or 95 wt.% Or more) of the polymer used in the filled polymeric material is a thermoplastic polymer.

The filled polymeric material may be electrically conductive (e.g., the filled polymeric material may be an electrical conductor) to provide a conductive path through the filled polymeric layer and to allow the composite material to be well welded to other structures, . The electrical conductivity of the polymer cores can be controlled by the use of metal fibers and any metal or carbon dispersed in the polymer in an amount having at least a permeation concentration as described, for example, in International Patent Application Publication WO 2010/021899 (published Feb. 25, 2010) Black particles. The filled polymeric materials and composites of the present invention can be welded by known welding schedules or other welding schedules, and such welding schedules are disclosed in International Patent Application Publication No. WO 2010/021899 (published February 25, 2010) It is posted. For example, materials enable a more economical welding schedule that is faster, less energy consuming, or both.

The filled polymeric material (e.g., a polymer of charged polymeric material) may additionally include one or more additives known in polymer blending technology, such as those disclosed in International Patent Application Publication No. WO 2010/021899 (Feb. 25, 2010 Which may be incorporated by reference herein. For example, the charged polymeric material may be a halogenated U.S. Pat. No. 3,784,509 (January 8, 1974, eg, substituted imides, column 1, line 59 to column 4, line 64, 3,868,388 (February 25, 1975, for example, halogenated bisimides, column 1, line 23, column 3, line 39); No. 3,903,109 (September 2, 1975, for example, substituted imides posted at column 1, line 46 through column 4, line 50); No. 3,915,930 (Oct. 28, 1975, for example, halogenated bisimide, column 1, line 27 to column 3, line 40); And the flame retardant compounds disclosed in U.S. 3,953,397 (April 27, 1976, for example, the reaction product of brominated imide and benzoyl chloride, column 1, line 4 to column 2, line 28) have.

The filled polymeric material may not include a plasticizer or a relatively low molecular weight material that can volatilize (e.g., during a resistance welding process). If used, the concentration of the plasticiser or relatively low molecular weight material is preferably less than or equal to 3% by weight, based on the total weight of the polymeric material loaded (e.g., so that the filled polymeric material is not stripped from the metal layer) Is preferably 0.5% by weight or less, and most preferably 0.1% by weight or less.

The invention also relates to a process for preparing a polymeric material, wherein the polymeric material charged during the process is substantially or completely peeled from the metal layer (for example, by peeling caused by the vapor pressure of the space between the charged polymeric material and the metal layer) And selecting both of them.

polymer

As a specific example of the polymer of the present invention, the polymer for use in the filled polymer material preferably has a temperature of about 50 캜 (preferably 80 캜 or higher, more preferably 100 캜 or higher, more preferably 120 캜, (Measured according to ASTM D3418-08) or glass transition temperature (measured according to ASTM D3418-08) of greater than or equal to 160 DEG C, more preferably greater than or equal to 180 DEG C, and most preferably greater than or equal to 205 DEG C ). ≪ / RTI > The thermoplastic polymer may have a peak melting point, a glass transition temperature, or both, and is 300 ° C or lower, 250 ° C or lower, 150 ° C or lower, or 100 ° C or lower. They are at least partially crystalline or substantially vitreous at room temperature. Suitable polymers (e.g., suitable thermoplastic polymers) are specified by one or more of the following tensile properties (as measured at a nominal strain rate of about 0.1 s ^-1 according to ASTM D638-08): tensile modulus (e.g., ) Greater than or equal to about 30 MPa, (e.g., greater than or equal to about 750 MPa, or greater than or equal to about 950 MPa); (I.e., σ _e ), true tensile strength (ie, σ _t , σ _t = (1 + ε _e ) σ _e , where σ _e is the nominal tensile strength), or both of about 8 MPa or more At least about 25 MPa, at least about 60 MPa, or at least about 80 MPa); Or at least about 20% (e.g., at least about 50%, at least about 90%, at least about 300%) of elongation at break. Unless otherwise specified in the present invention, tensile strength means nominal tensile strength.

The polymer preferably has a strain hardening property (e.g., a relatively high strain hardening rate, a relatively low extrapolative yield strength, or both), for example, in International Patent Application Publication No. WO 2010/021899 Publicly available), for example, as published in paragraph 052-063. Such strain hardening properties are measured by the method published in Haward RN, Strain hardening of Plastics, Macromolecules 1993, 26, 5860-5869.

Examples of thermoplastic polymers for use in the polymer layer include polyolefins (e.g., polyethylene (e.g., linear low density polyethylene) and polypropylene), acetal copolymers, polyamides, polyamide copolymers, polyimides, Thermoplastic polyether-ester copolymers (e.g., thermoplastic elastomeric ether-ester materials as disclosed in ASTM D 6835-08), acrylics, such as acrylonitrile-butadiene- (For example, an ethylene copolymer containing at least 80% by weight of ethylene), polystyrene, at least 60% by weight of an alpha olefin and at least one addition monomer, a copolymer comprising these polymers, Ionomers comprising these polymers, blends of these polymers, There is a combination thereof. The at least one polymer may be an elastomer, for example, a thermoplastic elastomer.

The filled polymeric material preferably comprises one or more polymers that are capable of fully adhering to the metal, such that the polymer is attached to the metal fiber, metal layer, or both. For example, the charged polymeric material includes at least one polymer having a sufficient concentration of polar groups, such that the polymer is attached to the metal fiber, metal layer, or both.

Of course, satisfactory adhesion results can be obtained even if a polymer containing a non-polar group is generally used as the main polymer component. In particular, a composite exhibiting excellent bonding strength and excellent peel resistance without using a large amount or a substantial amount of polar polymer (for example, 30%, 20%, 10%, 5% You can get a lump.

In addition, the bond strength between the polymer matrix composite masses is not reduced unexpectedly, and is actually enhanced by the fibers present in the polymer matrix composite mass, by the use of phosphate treatment and / or galvanized steel sheets, or both . For example, a sandwich composite comprising a polymer and sandwiched between ordinary carbon steels that does not include fibers and is uncoated and a composite of the present invention, i. E., Fibers, and includes a phosphate treatment and / or galvanized steel layer as a sandwich layer , The latter peel strength was improved by a factor of two or three when tested according to DIN 11339, for example. Such a result can be obtained by using a polymer having a polar group, a polymer having no polar group, or both. It is also possible to use mixtures of thermoplastic polymers (for example polyolefins, for example linear low density polyethylene) and elastomers (for example thermoplastic elastomers such as ethylene-containing copolymers), ionomers, Do.

The filled polymeric material can be made from one or more generally flexible polymers (e.g., elastomers, e.g., thermoplastic elastomers) that are flexible at low temperatures (e.g., about -30 캜, about -40 캜, or both) The composite material can be stamped at high speed, and the composite material does not break at -30 캜 or -40 캜, or both. For example, generally, a soft polymer includes polymers having a glass transition temperature of about -25 占 폚 or lower, about -30 占 폚 or lower, about -35 占 폚 or lower, about -40 占 폚 or lower, or about -45 占 폚 or lower. Generally, the glass transition temperature of the flexible polymer is about -100 ° C or higher. The ductile polymer may be a semi-crystalline polymer having a crystallinity of up to about 90 wt%, up to about 80 wt%, up to about 70 wt%, up to about 60 wt%, up to about 50 wt%, or up to about 40 wt% . Such polymers have a high tensile elongation, preferably at least about 50%, more preferably at least about 80%, and most preferably at least about 110%, as measured by ASTM D638.

The composite material of the present invention is subject to one or more electrical resistance welding operations. Such a welding operation can volatilize low molecular weight compounds (e.g., the compound can volatize at about 200 占 폚, or about 300 占 폚) at a high temperature at which the polymer can decompose into a low molecular weight compound Pressure may be added to cause peeling). Therefore, the polymer is selected so as not to decompose during the welding operation to produce low molecular weight compounds. The polymer is selected so that its concentration is sufficiently low even in the presence of low molecular weight compounds so that the charged polymeric material is not stripped from the metal layer during resistance welding. Further, the composite material preferably contains substantially no or no metal, for example, a metal decomposing compound when heated by a welding operation.

Preferred polymers include, but are not limited to, humid environments (e.g., about 90% relative humidity, about 95% relative humidity, and above), hot environments (e.g., about 25C, about 40C, (E. G., A saline spray comprising about 5 wt.% Sodium chloride), or combinations thereof, to prevent or reduce corrosion of metal, e. For example, the polymer is attached to the metal to prevent the metal surface from coming into contact with moisture. Thus, the filled polymer composition may have an equilibrium moisture content (e.g., measured at about 25 DEG C, at about 90% relative humidity) of about 8 wt% or less, preferably about 3 wt% or less, Or less, more preferably about 0.2 wt% or less, and most preferably about 0.05 wt% or less. The filled polymeric material does not contain any or substantially no polymer that corrodes the metal. When a metal corroding polymer is used, the polymer is preferably used in combination with one or more additives, one or more additional polymers, or both to reduce or prevent metal corrosion.

A single thermoplastic polymer can provide desirable properties for a filled thermoplastic composition or lightweight composite material, for example, such properties are disclosed herein. The thermoplastic polymer may thus consist of a single thermoplastic polymer. However, it is also possible to use a mixture or blend of thermoplastic polymers for obtaining one or more properties, cost savings, or both, or a plurality of layers comprising other thermoplastic polymers. The filled thermoplastic composition may comprise i) a first thermoplastic polymer and ii) a second thermoplastic polymer different from the first thermoplastic polymer. For example, the filled thermoplastic composition may comprise a first thermoplastic polymer and a second thermoplastic polymer having one or more of the following properties: the first thermoplastic polymer comprises at least one oxygen atom, at least one nitrogen atom, or both ; The second thermoplastic polymer does not substantially contain oxygen and nitrogen atoms; The total concentration of oxygen and nitrogen atoms in the second thermoplastic polymer is less than the total concentration of oxygen and nitrogen atoms in the first thermoplastic polymer, based on the total weight percent of the polymer (preferably, the first thermoplastic polymer and the second thermoplastic polymer Is at least about 2% by weight, more preferably at least about 4% by weight, more preferably at least about 10% by weight, and most preferably at least about 20% by weight. The tensile modulus of the second thermoplastic polymer is at least about 15% different (preferably at least about 25% different, more preferably at least about 50% different from the tensile modulus of the first thermoplastic polymer, as measured according to ASTM D638, Most preferably by about 70% or more). The moisture absorption rate of the second thermoplastic polymer differs from the water absorption rate of the first thermoplastic polymer by about 15% (preferably by at least about 25%, more preferably at least about 50% Most preferably by about 70% or more). The softening point of the second thermoplastic polymer, e.g., the heat deflection temperature, differs from the thermal deflection temperature of the first thermoplastic polymer by about 5 DEG C, as measured according to ASTM D648 (preferably at least about 15 DEG C, and more preferably about More preferably at least about 25 占 폚, more preferably at least about 35 占 폚, most preferably at least about 50 占 폚. Surprisingly, a mixture comprising the first thermoplastic polymer and the second thermoplastic polymer produces a material having properties not found in a single thermoplastic polymer.

Preferred polyolefins for use in the present invention are polypropylene homopolymers (e.g., isotactic polypropylene homopolymers), polypropylene copolymers (e.g., random polypropylene copolymers, impact polypropylene copolymers, or isotactic (E.g., other polypropylene copolymers including polypropylene), polyethylene homopolymers (e.g., high density polyethylene, or other polyethylene having a density of at least 0.94 g / cm3), polyethylene copolymers (e.g., By weight or more of ethylene, more preferably 80% by weight or more of ethylene), a low density polyethylene, a blend of these polymers, or a combination thereof. The polypropylene homopolymer and the polypropylene copolymer do not substantially contain an atactic polypropylene. If included, the concentration of the atactic polypropylene in the polypropylene is preferably less than or equal to 10% by weight. The copolymer may be substantially (e.g., greater than 98 weight percent) or fully composed of a copolymer (e. G., A polypropylene copolymer or a polyethylene copolymer) with one or more alpha olefins. More preferred polyolefins are high density polyethylene (e.g., polyethylene having a density of at least 0.945 g / cm3, such as 0.945 to 0.990 g / cm3 or 0.945 to 0.960 g / cm3), low density polyethylene (e.g., (E.g., polyethylene having a density of 0.945 g / cm 3 or less including a sufficient concentration of side chains of 15 carbon atoms or more), linear low density polyethylene (e.g., a copolymer having a density of 0.915 to 0.930 g / cm 3), medium density polyethylene (For example, a copolymer having a density of 0.930 to 0.945 g / cm 3), a very low density polyethylene (e.g., a copolymer having a density of 0.900 to 0.915 g / cm 3), a polyethylene plastomer An isotactic polypropylene homopolymer, an isotactic polypropylene copolymer (e. G., A copolymer having a crystallinity of at least 5% by weight), < RTI ID = 0.0 & Propylene, and an isotactic poly one or more blocks of polypropylene block copolymer, a mixture thereof, including the propylene, or a combination thereof. More preferred polyolefins are low density polyethylene, linear low density polyethylene, ultra low density polyethylene, or a combination thereof. Other polyolefins may include copolymers of one or more monomers that are not olefins and one or more olefins. For example, the other polyolefin may comprise one or more alpha olefins (e. G., Greater than or equal to 60% by weight alpha olefins) and ii) one or more alpha olefins, such as, for example, acrylates (e. G., Methyl acrylate, butyl acrylate, Substantially or completely composed of at least one polar comonomer selected from the group consisting of vinyl acetate, acrylic acid (e.g., acrylic acid, methacrylic acid, or both), methyl methacrylate, ≪ / RTI > The concentration of the comonomer is up to 40 wt%, preferably up to 25 wt%, more preferably up to 20 wt%, and most preferably up to 15 wt%, based on the total weight of the copolymer. Examples of polyethylene copolymers include ethylene-co-vinyl acetate (i.e. EVA containing 20% by weight or less of vinyl acetate), ethylene-co-methyl acrylate (i.e., EMA), ethylene- ≪ / RTI > or combinations thereof. Examples of alpha olefins include ethylene, propylene, butene, hexene, octene, or combinations thereof.

Polyamides useful in the present invention are polymers comprising at least one amide group repeat unit in the main chain of the polymer. For example, polyamides are reactants of diamines and diacids. Other examples of polyamides include polyamides of a single source. Generally, the polyamide of a single raw material is formed by a ring opening reaction. An example of a polyamide which is a reaction product of a diamine and a dicarboxylic acid is a polyamide (for example, nylon) in which adipic acid and terephthalic acid are reacted with a diamine. Examples of single raw polyamides include nylon 6, and poly (p-benzamide). The nylon may be a homopolymer, a copolymer, or a mixture thereof. Preferred polyamide homopolymers for use in the present invention include polyamides such as nylon 3, nylon 4, nylon 5, nylon 6, nylon 6T, nylon 66, nylon 610, nylon 612, nylon 69, nylon 7, nylon 77, nylon 8, Nylon 10, nylon 11, nylon 12, and nylon 91. The polyamide-containing copolymer may also be used. The polyamide copolymer may be a random copolymer, a block copolymer, or a combination thereof. Examples of the polyamide copolymer include a copolymer having a plurality of different amides (i.e., a polyamide-polyamide copolymer), a polyester amide copolymer, a polyether ester amide copolymer, a polycarbonate-ester amide, .

The polyamide-polyamide copolymer is one that contains two or more polyamides published relative to the polyamide homopolymer. Preferred polyamide-polyamide copolymers include polyamide 6 and polyamide 66, polyamide 610, or combinations thereof. For example, the polyamide-polyamide copolymer may comprise two or more polyamides selected from the group consisting of polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 612, and polyamide 12 . More preferably, the polyamide-polyamide copolymer is composed of two or more polyamides selected from the group consisting of polyamide 6, polyamide 66, polyamide 69, and polyamide 610. Examples of such copolymers are polyamide 6/66, polyamide 6/69, and polyamide 6/66/610. Particularly preferred polyamide-polyamide copolymers are polyamide 6/66 copolymers. The concentration of polyamide 66 in the polyamide 6/66 copolymer is up to about 90% by weight, preferably up to about 70% by weight, more preferably up to about 60% by weight, most preferably up to about 60% Is about 50% by weight or less. The concentration of polyamide 66 in the polyamide 6/66 copolymer is at least about 10% by weight, preferably at least about 30% by weight, more preferably at least about 40% by weight, most preferably at least about 10% by weight, Is at least about 50% by weight. Other particularly preferred polyamide-polyamide copolymers are random or block copolymers of polyamide 6 and polyamide 69. Polyamide copolymers (i.e., copolymers comprising one or more amide monomers) may include polyethers, such as aliphatic or aromatic ethers.

The polyether used in the polyamide copolymer can be formed by the polymerization of a diol, for example a glycol (e.g. with one or more additional monomers). Examples of glycols include propylene glycol, ethylene glycol, tetramethylene glycol, butylene glycol, or combinations thereof. The copolymer may be a block copolymer comprising a relatively soft block and a relatively hard block. The elastic modulus ratio of the relatively soft block relative to the relatively hard block is at least about 1.1, preferably at least about 2, more preferably at least about 10. The relatively hard block may comprise at least one aromatic amide, at least one semi-aromatic amide, or at least one aliphatic amide. A relatively soft block may be formed of a polyester, such as a polyester (e.g., an aliphatic polyester), a polycarbonate (e.g., an aliphatic polycarbonate), a polyether (e.g., an aliphatic polyether) As shown in FIG. The amide copolymer may comprise a first monomer (e.g., a first amide monomer) and a second monomer, each of which is independently at least about 5% by weight, preferably at least about 20% by weight, based on the total weight of the copolymer By weight, more preferably at least about 30% by weight, and most preferably at least about 40% by weight. The combined concentration of the first monomer and the second monomer is less than or equal to about 95 wt%, preferably less than or equal to about 80 wt%, more preferably less than or equal to about 70 wt%, and most preferably less than or equal to about 60 wt% % Or less. The combined concentration of the first monomer and the second monomer is at least about 50 wt%, preferably at least about 75 wt%, more preferably at least 90 wt%, and most preferably at least about 95 wt%, based on the total weight of the copolymer, Or more.

The polyamide copolymer is characterized by a thermoplastic elastomer having a relatively low melting point, a relatively low modulus of elasticity, or both. For example, the copolymer has a relatively low melting point relative to the highest melting point of the homopolymer consisting solely of one monomer of the copolymer. For example, the copolymer has a relatively low modulus of elasticity compared to the highest modulus of a single polymer consisting solely of one monomer of the copolymer. Preferred polyamide copolymers have a melting point of 220 占 폚 or less (preferably 190 占 폚 or less, more preferably 170 占 폚 or less, most preferably 150 占 폚 or less) measured according to ASTM D3418-08; 60 DEG C or higher (preferably 80 DEG C or higher, more preferably 100 DEG C or higher, and most preferably 110 DEG C or higher); The elastic modulus measured according to ASTM D638-08 is 2.5 GPa or less (preferably 1.2 GPa or less, more preferably 800 MPa or less, and most preferably 500 MPa or less); 50 MPa (preferably 100 MPa or more, more preferably 200 MPa or more; breaking strain measured according to ASTM D638-08 is 50% or more (preferably 90% or more, more preferably 300% or more) It is a combination.

In the present invention, combinations of the above polymers can be used, and at least one of them is a polyolefin, for example, a linear low density polyethylene. The polymer has a maximum strength of at least about 50 MPa, more preferably at least about 60 MPa (according to ASTM D882-10), a maximum elongation of at least about 500%, and more preferably at least about 600% . Examples of commercial polyolefins include HIFOR LT74104 (Westlake Chemical); Dowlex ^TM 2553, 2045G, 2517 (The Dow Chemical Company); Equistar Petrothene Select GS710060; MarFlex 7109 (Chevron Phillips); Or SABIC LLDPE 726 series (SABIC).

A preferred ionomer is a mixture of an ionic compound and a copolymer comprising a polar monomer and a non-polar monomer. The non-polar monomers used in the copolymer of the ionomer may include alpha olefins, for example olefins of from about 2 to about 20 carbon atoms (e.g., from about 2 to about 8 carbon atoms). Examples of non-polar monomers include ethylene, propylene, 1-butene, 1-hexene, and 1-octene, or combinations thereof. Suitable polar monomers include monomers having an ionic group at the time of polymerization. Examples of polar monomers for use in the copolymer of the ionomer include acids, for example, acids of from about 2 to about 20 carbon atoms (e.g., methacrylic acid, ethacrylic acid). The concentration of the polar monomer in the copolymer of the ionomer is no more than about 40 wt%, preferably no more than about 25 wt%, more preferably no more than about 20 wt%, based on the weight of the ionomer. The concentration of the polar monomer in the copolymer of the ionomer may be at least 1 wt%, at least about 2 wt%, at least about 3 wt%, at least about 5 wt%, at least about 7 wt%, or at least about 10 wt% Or more. In ionic compounds suitable for ionomers, polar monomers may comprise one or more alkali metals, one or more alkaline earth metals, or both. The ionic compound may include sodium, potassium, lithium, calcium, magnesium, or combinations thereof. Particularly preferred ionic compounds are sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. For example, commercial ionomers include SURLYN poly (ethylene-co-methacrylic acid) ionomers and NAFION perfluorosulfonate ionomers. In general, examples of non-polar polymers (e.g., alone or as part of a polymer mixture) include ethylene-octene copolymers. Suitable non-polar polymers have a maximum strength (MPa) of ASTM D638-08 of at least about 7.5, more preferably at least about 9.0, a maximum elongation (%) of ASTM D638-08 of at least about 700, and more preferably at least about (MPa) of about 13 or more, more preferably about 15 or more, (2% secant), and more preferably about 14 or more, of a bending elastic modulus (MPa) of about 800 to 800 ASTM D790-10 Or more. Commercially available polymers include Tafmer A-0550S (Mitsui Chemicals), Exact 9071 (ExxonMobil), Engage ^TM 8150 (The Dow Chemical Company), or Infuse 9007 (The Dow Chemical Company).

If used, the ionomer or non-polar polymer may be used alone or as a mixture with one or more additional polymers, for example, one or more additional thermoplastic polymers. For example, the ionomer used in the mixture comprises at least one polyolefin.

Polyolefins which may be used in the examples or optionally mixed with the ionomer are homopolymers and copolymers comprising at least about 50% by weight of alpha olefins having from about 2 to about 10 carbons. Preferred polyolefins for mixing with the ionomer are those containing at least about 50% by weight of ethylene, propylene, butane, or hexane. More preferred polyolefins for mixing with the ionomer are those containing about 50% by weight or more of ethylene, or propylene. The concentration of alpha olefins in the polyolefin (e.g., the concentration of ethylene or propylene) is preferably at least about 60% by weight, more preferably at least about 70% by weight, more preferably at least about 80% by weight, %, And most preferably at least about 90 wt%. A preferred polyolefin is a polyolefin consisting solely of one or more alpha olefins. For example, the concentration of the one or more alpha olefins is at least about 90 weight percent, at least about 95 weight percent, at least about 98 weight percent, at least about 99 weight percent, or at least about 99.9 weight percent, based on the total weight of the polyolefin. The ionomer is mixed with the polyolefin is high-density polyethylene (e. G., A density of about 0.945 to about 0.990g / cm ^3), low density polyethylene, linear low density polyethylene (e.g., copolymers of from about 0.915 to about 0.930g / cm ³ density ), Medium density polyethylene (e. G., Density copolymer) of about 0.930 to about 0.945g / cm ^3, for example, polyethylene (for example, a very low density, a density of about 0.900 to about 0.915g / cm ^3), polyethylene plastomer (e. g., a density of about 0.860 to about 0.900g / cm ^3, preferably a copolymer of from about 0.870 to about 0.895g / cm ^3), isotactic polypropylene and isotactic having a single polymer, a crystallinity of at least about 5 wt% Polypropylene copolymers, impact polypropylene, polypropylene block copolymers comprising at least one isotactic polypropylene block, mixtures thereof, or combinations thereof.

Other polyolefins suitable for the present invention, for example, for blending with any blending or other polymer (e.g., elastomer, ionomer, or other polymer) include: i) about 60% or more by weight of an alpha olefin; And ii) at least one monomer selected from vinyl acetate, methyl acrylate, butyl acrylate, acrylic acid, methyl methacrylate, methacrylic acid, and combinations thereof. The mixture of ionomer and polyolefin comprises a sufficient amount of ionomer to allow the polymer to adhere to the metal layer, metal fiber, or both. The weight ratio of ionomer to polyolefin is at least about 1:99, at least about 3:97, at least about 5:95, at least about 10:90, or at least about 20:80. The weight ratio of ionomer to polyolefin is about 99: 1 or less, about 90:10 or less, about 70:30 or less, about 50:50 or less, or about 40:60 or less.

Preferred polyurethanes include thermoplastic polymers formed by the polymerization of one or more diisocyanates with one or more diols. More preferred polyurethanes include thermoplastic polymers formed by polymerization of one or more diisocyanates and two or more diols. The polyurethane comprises a thermoplastic polyurethane elastomer, for example a first polymer block comprising a first diol and a second polymer block comprising a second diol, wherein the first block comprises a relatively rigid block (e.g., Stiffness) and the second block is a relatively soft block (e. G., Has a lower stiffness than a relatively hard block). The concentration of the relatively hard block and the relatively soft block is at least 5 wt%, preferably at least 10 wt%, more preferably at least 20 wt%, based on the total weight of the copolymer, respectively. The concentration of the relatively hard block and the relatively soft block is 95 wt% or less, preferably 90 wt% or less, more preferably 20 wt% or less, based on the total weight of the copolymer, respectively. The total concentration of the relatively hard block and relatively soft block is at least 60 wt%, preferably at least 80 wt%, more preferably at least 95 wt%, and most preferably at least 98 wt%, based on the total weight of the copolymer. Commercial thermoplastic polyurethanes (TPUs) include ESTANE brand TPUs available from Lubrizol, ELASTOLAN brand TPUs available from BASF, and DESMOPAN brand available from Bayer.

The thermoplastic polymer is selected to have a relatively long chain and has a number average molecular weight of 20,000 or more, preferably 60,000 or more, and most preferably 140,000 or more. The plasticizer may or may not be added, may be modified with an elastomer or may not contain an elastomer. The crystallinity of the semi-crystalline polymer is at least 10% by weight, more preferably at least 20% by weight, more preferably at least 35% by weight, more preferably at least 45% by weight and most preferably at least 55% by weight. The crystallinity of the semi-crystalline polymer is 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less and most preferably 68% by weight or less. The crystallinity of the thermoplastic polymer can be measured by measuring the fusing heat with a differential scanning calorimeter and comparing the known fusing heat of the particular polymer.

The polymer of charged polymeric material may contain up to about 10% by weight of polar molecules, such as grafted polymers with maleic anhydride (e.g., grafted polyolefins such as isotactic polypropylene homopolymers or copolymers). The concentration of the grafted compound is at least 0.01% by weight based on the total weight of the grafted polymer. A particularly preferred grafted polymer comprises from about 0.1% to about 3% by weight of maleic anhydride.

The thermoplastic polymer has a crystallinity of at most 10% by weight, preferably at most 5% by weight, most preferably at most 1% by weight, as measured by a differential scanning calorimeter at 10 캜 / Polymer). For example, the thermoplastic polymer may have a glass transition temperature of at least 50 占 폚, preferably at least 120 占 폚, more preferably at least 160 占 폚, more preferably at least 180 占 폚, and most preferably at least 205 占 폚 And may comprise a substantially amorphous polymer having a transition temperature. Examples of amorphous polymers include polystyrene containing polymers, polycarbonate containing polymers, acrylonitrile containing polymers, and combinations thereof.

Examples of styrene-containing copolymers include those used in filled polymeric materials published in International Patent Application Publication No. WO 2010/021899 (published February 25, 2010).

Instead of or in addition to the thermoplastic polymer, the polymer layer may use one or more elastomers having the following properties: a relatively low tensile modulus (e.g., about 3 MPa or less, preferably about 2 MPa or less) at 100% A relatively high tensile elongation at break (e.g., at least about 110%, preferably at least about 150%). Both properties were measured at a nominal strain rate of about 0.1 s < ^-1 > according to ASTM D638-08. Examples of elastomers are those published in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

The one or more polymers used in the present invention are crosslinkable or crosslinked. These may be thermosetting materials or monomers, or precursors of thermosetting materials. They may be epoxy based, rubber, urethane or other suitable materials. One or more other agents that are crosslinked in response to stimulation, for example, heat, radiation (e.g., ultraviolet and / or infrared), moisture, or combinations thereof, may be used.

A small amount of epoxy may be used, but the polymer of the filled polymeric material, preferably substantially epoxy or other fragile polymer (e.g., at a nominal strain rate of about 0.1 s ^-1 measured according to ASTM D638-08 of about 20 % Or less), or both. When used, the concentration of the epoxy, other fragile polymer, or both, is preferably no more than 20% by volume, more preferably no more than 10% by volume, more preferably no more than 5% % Or less, and most preferably 2 volume% or less.

In a particularly preferred example, the filled polymeric material may comprise one or more polyamide copolymers, one or more thermoplastic polyurethanes, one or more thermoplastic polyether-ester copolymers, one or more polyolefins, one or more ionomers, or combinations thereof . As the polyamide copolymer, any of the above-mentioned polyamide copolymers can be used. Preferred polyamide copolymers are polyamide-polyamide copolymers, polyester amide copolymers, polyether ester amides, polycarbonate-ester amide copolymers, or combinations thereof. The thermoplastic polymer may be a random copolymer or a block copolymer. The thermoplastic polymer may be a thermoplastic elastomer. For example, the filled polymeric material includes a polyester amide thermoplastic elastomer, a polyetheresteramide thermoplastic elastomer, a polycarbonate-esteramide thermoplastic elastomer, a polyether-ester thermoplastic elastomer, an amide block copolymer thermoplastic elastomer, or combinations thereof can do. For example, the filled polymeric material may comprise one or more polyamide homopolymers that are not copolymers. Particularly preferred polyamide homopolymers are polyamide 6 and polyamide 6,6. The concentration of the at least one polyamide homopolymer is preferably relatively low (e. G., Relative to the concentration of the one or more copolymers). The concentration of the at least one polyamide homopolymer is preferably less than or equal to 50 wt%, more preferably less than or equal to 40 wt%, more preferably less than or equal to 30 wt%, and most preferably less than or equal to 30 wt%, based on the total weight of the polymer in the filled polymeric material Is not more than 25% by weight.

Generally, a filled polymeric material comprising a polar polymer does not need to have sufficient attraction between the polar polymer and the metal fiber to improve adhesion between the plastic and the metal fiber using a polymer having a functional group. As such, the filled polymeric material does not include polymers that are substantially or completely free of maleic anhydride, acrylic acid, acrylate, acetate, or combinations thereof. For example, the filled polymer does not include a substantially or completely maleinated grafted polymer. When used, the concentration of the polymer with maleic anhydride, acrylic acid, acrylate, acetate, or combinations thereof is preferably less than or equal to 20 weight percent, more preferably less than or equal to 10 weight percent, %, More preferably not more than 5 wt%, more preferably not more than 1 wt%, most preferably not more than 0.1 wt%. For example, in general, the polar polymer may be an acetal homopolymer or copolymer, a polyamide homopolymer or copolymer, a polyimide homopolymer or copolymer, a polyester homopolymer or copolymer, a polycarbonate homopolymer or copolymer, . ≪ / RTI > Generally, a filled polymeric material comprising a polar polymer may be substantially or completely free of a copolymer comprising a polyolefin homopolymer and about 50 weight percent of one or more olefins. When used, the total concentration of the copolymer comprising the polyolefin homopolymer and about 50% by weight of the at least one olefin in the filled polymeric material is up to about 30% by weight, preferably up to about 20% by weight, More preferably about 10% by weight or less, more preferably about 5% by weight or less, and most preferably about 1% by weight or less.

During the use of the composite material, the composite material may be heated to a sufficiently high temperature to deform the metal. Therefore, when the polymer is heated to that temperature, it may be burned or thermally decomposed. Polymers preferred for composite use are polymers that do not generate toxic compounds (e.g., toxic gases and / or carcinogenic compounds) upon combustion or thermal degradation (e.g., at temperatures above about 600 ° C).

filling

The filled polymeric material (e.g., the filled thermoplastic polymeric layer) comprises one or more fillers. The filler may be a reinforcing filler, for example a fiber, especially a metal fiber. A metal filler (for example, metal fiber) disclosed in International Patent Application Publication No. WO 2010/021899 (published on February 25, 2010) can be used. For example, the metal fiber used in the present invention may be a metal such as steel (e.g., low carbon steel, stainless steel, etc.), aluminum, magnesium, titanium, copper, an alloy containing 40 wt% Another alloy containing more than 40% by weight of aluminum, another alloy containing 40% by weight or more of titanium, or a combination of these. The metal fibers may comprise or consist of carbon steel, for example, steel containing less than about 10 weight percent chromium, less than or equal to about 7 weight percent chromium, or less than or equal to about 3 weight percent chromium.

The metal fibers have a sufficiently low melting point so that during welding (e.g., electrical resistance spot welding), some or all of the metal fibers between the welding tips melt at least partially before one or both metal layers are melted (e.g., ). The electrical resistance of the charged polymeric material is higher than the electrical resistance of the metal layer (e.g., about 10 times higher or about 100 times higher) and the metal fibers start to melt before the metal layer begins to melt. The welding process includes a step of sufficiently cooling the welding tip so that the metal fiber melts before the metal layer begins to melt. Thus, the metal fibers may include metals (e.g., steel) having a same or higher weld, lower than the steel contained in the first metal layer, the second metal layer, or both. The filled polymeric material may include other non-metallic conductive fibers, such as those disclosed in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

The filled polymeric material may include metal fibers or other fillers that can prevent or reduce corrosion of the metal layer. One or more of the metal fibers or other fillers in the filled polymeric material has a relatively high galvanic activity. For example, metal fibers or other fillers in the charged polymeric material have a higher galvanic activity than the metal layer (of the composite) used on one, preferably two, sides of the metal layer in contact with the filled polymeric material. As such, the filled polymeric material does not substantially or completely contain a filler having a low galvanic activity. For example, filled polymeric materials that do not substantially or completely contain carbon black can be used to reduce corrosion of the composite material. The at least one filler having a relatively high galvanic activity preferably has a positive electrode index greater than about 0.05 V, more preferably about 0.1 V, more preferably about 0.20 V, and most preferably about 0.25 V greater than the metal layer . The one or more fillers having a relatively high galvanic activity may be a known material having a higher galvanic activity than the metal layer. For example, such fillers include one or more zinc containing materials, one or more magnesium containing materials, one or more aluminum containing materials, or combinations thereof. The one or more fillers may have a first filler and a second filler having a higher galvanic activity than the first filler, wherein the second filler is a sacrificial filler. If the filled polymeric material comprises a first filler and a sacrificial filler, then the first filler is preferably a metal fiber. The sacrificial filler has a relatively high total surface area (i.e., of all sacrificial filler particles) compared to the surface area of the metal layer or the total surface area of the first filler, or both. For example, the ratio of the total surface area of the sacrificial filler to the surface area of the metal layer is at least about 1.5, preferably at least about 3, more preferably at least about 10, and most preferably at least about 50. If the filled polymeric material comprises a first filler and a sacrificial filler, the first filler may have a surface with galvanic activity that is less than, equal to, or greater than the galvanic activity of the surface of the metal layer. If the first filler has a surface with galvanic activity greater than that of the metal layer surface, then the first filler may act as a sacrificial filler. As such, a second sacrificial filler may not be necessary and the filled polymer does not substantially or completely comprise the second sacrificial filler.

Some or all of the metal fibers may provide bipolar protection for one or more metal layers of the composite material. For example, the metal fibers may be coated with or formed from a material having a standard electrochemical reduction potential that is less than the standard electrochemical reduction potential of the first metal layer, the second metal layer, or both. In general, metals with low standard electrochemical reduction potentials include metals having a lower standard electrochemical reduction potential than steel (e.g. SAE carbon steel 1015). In general, metals with low standard electrochemical reduction potential include aluminum, zinc, and magnesium. Thus, some or all of the metal fibers may comprise aluminum, zinc, magnesium, alloys thereof, or combinations thereof. A particularly preferred fiber for anode protection is zinc fiber. Some or all of the metal fibers may be coated with one or more electrical coatings, electroplating, or both, and / or may include plated metals (e.g., steel). For example, the metal may be covered by zinc plating. The metal fibers may be coated with one or more or all sides. The fibers may be covered by spraying, plating (e. G., Hot dip galvanizing) by spraying. For example, the metal fibers can be made from a sheet or foil with one or both sides coated (e.g., by spraying or plating) and cut into narrow strips or ribbons. As another example, after the fiber is formed into a fiber form, it can be coated so that all sides are covered. In another example, continuous filaments are coated and finished with fibers to allow all sides of the fiber to be coated except for the ends. The coating may preferably comprise aluminum, zinc, magnesium, alloys thereof, or combinations thereof. The metal fibers may thus consist of one or more coating layers comprising aluminum, zinc, magnesium, alloys thereof, or combinations thereof and one or more substrate layers that do not comprise aluminum, zinc, magnesium, alloys thereof, have. A particularly preferred coated metal fiber comprises a coating layer having a standard electrochemical reduction potential that is less than the standard electrochemical reduction potential of the metal layer of the composite (e.g., the first metal layer, the second metal layer, or both) . Particularly preferred coated fibers are fibers coated with a layer comprising zinc or a zinc alloy.

The fibers providing the anode protection may be provided to have a sufficient amount, size, surface area, or a combination thereof, to provide a protective barrier against corrosion in a corrosive environment (e.g., at about 40 ° C, in a saline spray (including, for example, about 5 weight percent sodium chloride) The corrosion of the metal layer surface (for example, the surface in contact with the polymer layer) is reduced or eliminated even when exposed for a long period of time (for example, 200 hours or more).

The metal fibers preferably have a size and distribution as described in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010). The weight average length of the metal fibers, L _avg , is at least about 1 mm, more preferably at least about 2 mm, and most preferably at least about 4 mm. The L _avg of suitable fibers is about 200 mm or less, preferably about 55 mm or less, more preferably about 30 mm or less, and most preferably about 25 mm or less. The weight average diameter of the fibers is at least about 0.1 탆, more preferably at least about 1.0 탆, and most preferably at least about 4 탆. The fibers have a weight average diameter of about 300 탆 or less, preferably about 50 탆 or less, more preferably about 40 탆 or less, and most preferably about 30 탆 or less.

The metal fiber may have any shape. The metal fibers may include curved portions. In general, linear metal fibers can be used. More preferably, the metal fibers are not linear fibers along the length direction of the fibers. For example, the metal fibers may not be straight fibers but may include one or more bends, arcs, generally helical shapes, or a combination thereof. The metal fibers may initially be straight, and preferably they may be non-straight fibers (as described above) when combined with a thermoplastic polymer.

 For example, the cross section of the metal fiber perpendicular to the fiber length may have a geometric shape. For example, the cross-section may have one or more faces that are generally straight or generally arcs, or combinations thereof. For example, the metal fibers may have an elliptical, polygonal, star-shaped, semi-circular cross-section.

In one example of the invention, the metal fibers have at least one plane, for example in a direction transverse to the fiber length. This is believed to be due to the fact that metal fibers with flat surfaces generally improve electrical conductivity of filled polymeric materials and / or lightweight composites compared to generally circular metal fibers. The cross-section of the metal fibers in a direction transverse to the fiber length (i.e., perpendicular to the length of the fiber) has at least one generally straight surface. For example, the cross-section of the metal fiber in the transverse direction may have at least four straight sides and at least two parallel sides. The cross section of the metal fibers has, for example, a generally rectangular shape, a generally parallelogram shape, or a generally square cross-section. The metal fibers may be generally elliptical, e.g. having an aspect ratio of about 3 or more, preferably about 5 or more, and more preferably about 7 or more. The cross-section of the metal fibers in the transverse direction is specified by the width (i.e., the longest dimension) and the thickness (e.g., the direction perpendicular to the thinnest dimension and / or width). The width to thickness ratio of the fibers is at least 1, at least about 1.4, at least about 2, or at least about 3. The ratio of fiber width to thickness is less than about 300, less than about 100, less than about 50, or less than about 15. Such a fiber may be subjected to one or more fiber forming steps, for example, a metal foil (e.g. having a thickness that is approximately the thickness of a fiber) to a narrow ribbon strip (e.g., the space between the cuts defining the width of the fiber) And cutting. The metal fiber is made of a single metal foil, or a metal foil having a coating that provides one or more coatings (e.g., coating on two broad sides), for example, zinc plating protection.

The metal fibers have a length greater than the width and thickness. The average length of the metal fibers is preferably at least about 200 占 퐉, more preferably at least about 500 占 퐉, more preferably at least about 800 占 퐉, and most preferably at least about 1 mm. The weight average length of the metal fibers may be about 10 mm or more, or generally continuous. For spot welding, the metal fibers preferably have a weighted average length less than the diameter of the welding tip used for spot welding, so that the metal fibers flow more readily from the welding zone during welding. For example, the weight average length of the metal fibers is about 20 mm or less, about 10 mm or less, about 7 mm or less, about 5 mm or less, about 4 mm or less, or about 3 mm or less. The aspect ratio of the fiber is the length of the fiber divided by (4A _T / Π) ^1/2 , where A _T is the cross-sectional area of the fiber in the direction transverse. The aspect ratio of the fibers is about 5 or more, about 10 or more, about 20 or more, or about 50 or more. The aspect ratio of the fibers is about 10,000 or less, about 1,000 or less, or about 200 or less. Fibers having an aspect ratio of 10,000 or more can also be used.

When used in a polymer between two metal layers, the metal fibers are preferably present as a fiber agglomerate. The metal fiber agglomerates may be connected to each other. The fiber agglomerates can be mechanically engaged (i.e., two or more fibers can be mechanically engaged). The metal fiber agglomerates preferably spread to the thickness of the polymer layer such that the fiber agglomerates (e.g., metal fiber meshes) electrically couple the two metal layers. Although it is possible for the single metal fibers to spread to the thickness of the polymer layer, it is preferred that the metal fibers do not spread to the thickness of the polymer layer. When the metal fibers cross the thickness of the polymer layer, the fiber fraction across the thickness is preferably less than about 0.4, more preferably less than about 0.20, more preferably less than about 0.10, more preferably less than about 0.04, Most preferably about 0.01 or less. The fibers in the fiber agglomerate are preferably arranged irregularly. For example, the maximum number of generally aligned neighboring metal fibers is about 100 or less, preferably about 50 or less, more preferably about 20 or less, more preferably about 10 or less, and most preferably about 5 Or less. More preferably, the fiber agglomerates are generally irregularly arranged. The respective metal fibers contacting the surface of the metal layer preferably do not make planar contact. As such, the composite material is substantially or completely free of surface contact between the metal fibers and the metal layer. The fibers in contact with the metal surface are preferably contacted by line contact, contact, or a combination thereof. Some metal fibers may contact one of the metal layers, but few metal fibers contact a metal layer over a large portion of the length of the metal fibers. As such, many fractions of the metal fibers do not come into contact with the metal layer, or at least the significant portion does not contact the metal layer. The metal fiber fraction contacting the metal layer along more than half of the fiber length is preferably less than about 0.3, more preferably less than about 0.2, more preferably less than about 0.1, more preferably less than about 0.04, Is about 0.01 or less.

The metal fibers are preferably sufficiently thin and of sufficient concentration that many fibers are arranged between the surfaces of the layers. For example, the average number of fibers parallel to the thickness direction of the polymer layer is preferably at least about 3, more preferably at least about 5, more preferably at least about 10, and most preferably at least about 20. Many metal fibers are advantageous for uniform deformation of the material, for example a stamping process.

The concentration of the metal fibers is preferably at least about 1% by volume, more preferably at least about 3% by volume, more preferably at least about 5% by volume, and more preferably at least about 7% by volume, based on the total volume of the charged polymeric material By volume, more preferably at least about 10% by volume, and most preferably at least about 12% by volume. The concentration of the metal fibers in the filled polymeric material is less than or equal to about 60 vol%, preferably less than or equal to about 50 vol%, more preferably less than or equal to about 35 vol%, more preferably less than or equal to about 33 vol% 30 vol% or less (e.g., about 25 vol% or less, or about 20, 10, or 5 vol% or less). For example, the amount of fiber may be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% based on the total volume of the charged polymeric material (E.g., from about 1% to about 6%). It is possible to obtain similar welding characteristics surprisingly using metal fibers of an amount substantially lower than the particle filler. In addition, it is possible to obtain excellent welding performance as compared with a composite material using a metal fiber having a high concentration while using a relatively low concentration of metal fiber by suitably selecting fibers and materials. For example, it is possible to produce a composite material having excellent welding performance compared to a composite material using a high concentration of metal fibers with a filled polymeric material having surprisingly about 10 volume% metal fibers.

The concentration of the thermoplastic polymeric material in the filled polymeric material is at least about 40% by volume, preferably at least about 65% by volume, more preferably at least about 67% by volume, more preferably at least about 70% by volume, (E.g., at least about 80 vol%, at least about 90 vol%, at least about 95 vol%).

The volume ratio of polymer (e.g., thermoplastic polymer) to fiber (e.g., metal fiber) is preferably at least about 2.2: 1, more preferably at least about 2.5: 1, and most preferably at least about 3: 1 to be. The volume ratio of polymer (e.g., thermoplastic polymer) to fiber (e.g., metal fiber) is preferably less than about 99: 1, more preferably less than about 33: 1, more preferably less than about 19: Most preferably about 9: 1 or less (e.g., about 7: 1 or less).

The core material of the sandwich composite may or may not include pores or voids. Preferably, the volume of the pores or voids in the filled polymeric material is less than or equal to about 25 percent by volume, more preferably less than or equal to about 10 percent by volume, more preferably less than or equal to about 5 percent by volume based on the total volume of the charged polymeric material, And most preferably about 2 vol% or less (e.g., about 1 vol% or less).

The fibers (e. G., Conductive fibers, e. G., Metal fibers) are preferably present in the filled polymeric material in an amount of preferably at least about 40 percent by volume, more preferably at least about 70 percent by volume, About 80 vol% or more (e.g., about 90 vol% or more, or about 95 vol% or more).

The total volume of polymer (e.g., thermoplastic polymer) and metal fibers is preferably at least about 90% by volume, more preferably at least about 95% by volume, and most preferably at least about 95% by volume, About 98% by volume.

The metal fibers provide electrical conductivity for welding, strength for reinforcement, or allow the polymer structure using the fibers to be stretched like a metal and impart strain hardening properties to the polymer core. When measured according to ASTM A370-03a, the elongation at break of the metal fiber is preferably at least about 5%, more preferably at least about 30%, and most preferably at least about 60%.

It is also possible to use metal particles together with fibers in the material of the present invention. The metal particles can be any shape other than spherical, elongated, or fibrous. The metal particles are disclosed in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

The combination of fibers (e.g., metal fibers) or fibers and metal particles preferably comprises up to about 30% (more preferably up to about 25%, most preferably up to about 20% (For example, irregularly dispersed). When metal particles are used, the ratio of volume of fibers (e.g., metal fibers) to volume of metal particles in the layer of charged polymeric material is at least about 1:30, preferably at least about 1: 1, 2: 1 or more.

In the present invention, metal particles, metal fibers, or both can be obtained, for example, from scrubbing scraps or scraps published in paragraph 21 of International Patent Application Publication No. WO 2010/021899 (published February 25, 2010) . Debris or scrap may be derived from the metal sheet used to make the sandwich composite of the present invention. Thus, as long as the sheet metal is coated or internally treated, debris or scrap may also include coating or such treatment. Thus, the fibers can be subdivided or finely divided personnel greased and / or galvanized steel, high strength steels.

Particularly preferred metal fibers are metal fibers having optionally one or more other fibers and having a square cross-section perpendicular to the length, generally having a square cross-section (e.g., defining a profile for a generally flat ribbon strip) Carbon steel fibers). The weight average thickness of the metal fibers is about 10 to about 70 mu m, the weight average width is about 40 to about 200 mu m, the weight average length is about 0.8 to about 5 mm, or a combination thereof. Surprisingly, when the metal fibers are used in a composite material, the electrical conductivity in the whole-thickness direction becomes larger (for example, about 50% or more, or about 100 % More than)

In Fig. 3, the metal fibers 20 " have one or more generally straight sides in cross-section in the direction transverse to the longitudinal direction (for example, are generally rectangular cross-sections) The metal fibers may be sufficiently long, bent sufficiently (e.g., along the length of the fibers), in a sufficient amount, or in combinations thereof, to form a fiber agglomerate do.

4 is a micrograph showing the surface of the core layer 16 comprising the metal fibers 20 and the polymer 18. As shown in Fig. 4, the fibers are sufficiently overlapped to transfer an electric current to the core layer. For example, the electrical conductivity of the core layer is sufficient so that the composite material can be welded by electrical resistance welding.

5 is a micrograph showing a composite material comprising a metal fiber 20 'having a generally rectangular cross-section in a direction transverse to the fiber length direction. The core layer is sandwiched between the metal layers 14 ", including the mass of metal fibers 20 ' and the polymer 18 '.

The metal fibers are preferably selected so that the composite material has excellent weld properties. For example, the concentration of the metal fibers, the size of the metal fibers, the amount of contact between the metal fibers, the shape of the metal fibers, the amount of contact between the metal fibers and the metal layer, , Generally high electrical conductivity, generally high electrostatic contact resistance, or a combination thereof. Generally, excellent welding process windows are specified by, for example, a high welding current range, a high welding time range, or both.

In addition to the above fillers, one or more known fillers can be used in known proportions, for example, talc, mica, wollastonite, nano-clay, calcium carbonate, silicate and the like.

Test method for measurement of welding current range

Test method for welding current range

The measurement of the welding process window is the current range (i.e., the welding current range). The welding current range for the test material can be determined by welding a stack of test sheet and a control sheet (for example, galvanized steel sheet) having the same thickness as the test sheet. Welding is performed using two electrodes. The electrode for the test material has a face diameter, d. The electrode for the steel sheet of the control is equal to or greater than d. The welding time and welding pressure are fixed and can be predetermined, for example, from a standard welding schedule for the material. The welding button size is measured by separating the two sheets and is determined by the average diameter of the welding button. The measurement is started by selecting a current that produces a weld button of 0.95 d or more. The welding current then drops sharply until the diameter of the welding button is less than d. The lower limit of the welding current is the lowest current that produces an acceptable weld (e. G. Welding with a welding button size of at least 0.95 d). The welding current increases again until an unacceptable weld is obtained which is characterized by metal release, adhesion of the sheet to the electrode, noisy welding noise, or a combination thereof. The highest current producing an acceptable weld is the upper limit of the welding current. The welding current range is between the upper and lower limits of the welding current. For example, a welding current range measurement can be performed using a composite material having a thickness of about 0.8 mm and a galvanized steel sheet having a thickness of about 0.8 mm. The electrode on the composite has a diameter of about 3.8 mm and the electrode on the galvanized steel sheet has a thickness of about 4.8 mm. A compressive force of about 2713 Nt (e.g., 610 pounds) may be applied. Welding conditions for the welding current range measurement include an intermediate wavelength DC welding current having a wavelength of about 1,000 Hz, a stroke time of about 50 milliseconds, and a welding time of about 200 milliseconds. The material is preferably about 25 mm wide and 25 mm or 75 mm thick. When welded to steel of the same thickness as the composite material, the welding current range lc of the composite material is preferably greater than the current range lm for two steel sheets of the same thickness as the composite material. The ratio of lc to lm is preferably at least about 1.1, more preferably at least about 1.2, more preferably at least about 1.3, even more preferably at least about 1.4, and most preferably at least about 1.5. The current range, lc, of the composite material is preferably at least about 1.5 kA, more preferably at least about 1.7 kA, and even more preferably at least about 1.9. kA, more preferably at least about 2.1 kA, more preferably at least about 2.3 kA, and most preferably at least about 2.5 kA. Figure 6 shows the welding current range for a composite material having a surprisingly high welding current range.

Test method of electrostatic contact resistance (SCR)

The SCR of the material or two material stacks is measured by placing the composite sheet and the stack containing the cold rolled steel sheet with a thickness of about 0.8 mm between two class I - RWNA electrodes with a diameter of about 4.8 mm. Unless otherwise noted, the SCR is measured using a force of about 2220 Nt (about 500 lb) applied by the electrode. During the SCR measurement, the resistance is measured for about 45 seconds from the time the electrode is loaded. The SCR is determined by the average resistance of the material or two material stacks for 5 seconds after the resistance is stable. A stable SCR is determined by a change of less than 2%, less than 1%, less than 0.5% per second. High pressure may be used for SCR measurements of materials having a thickness greater than about 1.2 mm. The SCR of the material is measured using a sample having a thickness of about 0.8 mm, a width of about 25 mm, and a length of about 25 mm or 75 mm. However, samples of different thickness, length, and width may be used.

The SCR of the composite material is preferably about 0.0020 Ω or less, more preferably about 0.0017 Ω or less, more preferably about 0.0015 Ω or less, still more preferably about 0.0012 Ω or less, and most preferably about 0.0008 Ω or less.

Having a larger electrostatic contact resistance than steel of a single material is useful for obtaining a high welding current range. Thus, the ratio of electrostatic contact resistances of the composite to the electrostatic contact resistance of steel (e. G., Cold rolled steel, galvanized steel, or combinations thereof) is preferably at least about 1, more preferably at least about 1.2, Preferably about 1.5 or more, more preferably about 2 or more, more preferably about 3 or more, still more preferably about 4 or more, still more preferably about 5 or more, and most preferably about 10 or more. If the SCR of the composite is too high, the composite will have difficulty passing current and will not be easily welded. Thus, the ratio of electrostatic contact resistances of the composite to the electrostatic contact resistance of steel (e. G., Cold rolled steel, galvanized steel, or combinations thereof) is preferably less than about 1000, more preferably less than about 300, Preferably about 100 or less, more preferably about 75 or less, and most preferably about 40 or less.

Metal layer

As described above, the composite uses a sandwich construction in which a polymer core is sandwiched between opposed layers. For example, the structure includes two sheets (e.g., a metal sheet) and the metal fiber reinforced polymer core is sandwiched between the sheets, preferably in contact with the sheet. The metal layers (e.g., the first metal layer and the second metal layer) of the sandwich structure may be of the same or different thicknesses (e.g., average thickness) along the foil, sheet or layer with a suitable material Lt; / RTI > layer. Each metal layer generally has a constant or varying thickness. The metal on each side is made of the same or different material and is made of the same or different metal. If the metal surface is made of a metal sheet of different thickness, the material may have different properties or have different metals. The composite material may have markings or other means to distinguish the different metal surfaces. The layer may have the same composition or size (e.g., thickness, width, volume, etc.), shape, etc., as the other layers. The metal layer may have a surface treatment (e. G., Coated with zinc, phosphorus, or both) that contributes to corrosion resistance. Before or after fabricating the composite into a filled polymer layer, one or more of the metal layers may be treated with zinc plating, a phosphate treatment, or both.

An example of a metal layer is disclosed in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010), paragraph 082-091. Preferred metal layers include one or more steels.

Down gauging performance of steel for panels, such as those using high strength steels for automotive panels, is generally limited by the flexural modulus of the steel, not by high strength steels. Surprisingly, the filled composite layer provides sufficient stiffness to the flexural modulus of the composite to allow down sizing. For example, high-strength steel can be used as one or more metal layers (first metal layer, second metal layer, or both) of a lightweight composite material. The high-strength steel has a high yield strength of at least about 200 MPa, preferably at least about 320 MPa, more preferably at least 310 MPa. The high strength steel has a yield strength of about 600 MPa or less. The high strength steel has a tensile strength of at least about 340 MPa, preferably at least about 370 MPa, more preferably at least about 400 MPa, more preferably at least about 430 MPa, and most preferably at least about 450 MPa. The high strength steel has a tensile strength of about 800 MPa or less.

The first metal layer, the second metal layer, or both, including a sufficient amount of high strength steel, the elastic modulus of the composite measured according to ASTM D790 is at least about 200 GPa, and the concentration of the filled polymer layer is sufficiently high, density is greater than about 0.8 d _m, where d _m is the weight average density of the first metal layer and second metal layers. Surprisingly, such a composite material has one or two of the following properties: at least about 100 MPa, (preferably at least about 120 MPa, more preferably at least about 140 MPa, more preferably at least about 170 MPa, even more preferably at least about 200 MPa , And most preferably at least about 240 MPa); Or about 160 MPa or higher (preferably about 200 MPa or higher, more preferably about 220 MPa or higher, more preferably about 250 MPa or higher, more preferably about 270 MPa or higher, even more preferably about 290 MPa or higher, and most preferably about 310 MPa or higher) tensile strength.

The preferred metal layer has a generally uniform thickness such that the composite does not change, for example, in a periodic pattern. For example, the difference between the highest thickness and the lowest thickness in a metal cut to 100 mm x 100 mm is about 20% or less, about 10% or less, or about 5% or less by the average thickness.

The one or both metal surfaces are preferably relatively thick, so that the metal surface does not wrinkle, tear, or otherwise suffer defects during fabrication or processing of the composite. Preferably, the thickness of one or both of the metal surfaces is at least about 0.05 mm, more preferably at least about 0.10 mm, more preferably at least about 0.15 mm, and most preferably at least about 0.18 mm. The sheet has a thickness of 3 mm or less, preferably 1.5 mm or less, more preferably 1 mm or less, and most preferably 0.5 mm or less. For example, the composite material may require one or more A or B grade surfaces, preferably one or more A grade surfaces (e.g., after stamping, welding, electrocoating, painting, Can be used in automotive panels. In such a composite, the first surface may be a Class A surface and the second surface may not be a Class A surface. The first metal surface, which is a Class A surface, is relatively thick and optionally has a second metal surface that is not a Class A surface (e.g., about 20% or less than about 40% of the first metal surface thickness) . Generally, the ratio of the thickness (e.g., average thickness) of the first metal layer to the thickness of the second metal layer is from about 0.2 to about 5, preferably from about 0.5 to about 2.0, more preferably from about 0.75 to about 1.33, and most preferably from about 0.91 to about 1.1.

Composite material

The composite material is a sandwich structure comprising a laminated sheet, for example, a filled polymeric material sandwiched between sheets of metal material. The total average thickness of the sheet is about 30 mm or less, preferably about 10 mm or less, more preferably about 4 mm or less, and most preferably about 2 mm or less; Preferably at least about 0.1 mm, more preferably at least about 0.3 mm, and most preferably at least about 0.7 mm. Composite materials generally have a uniform thickness or varying thickness (e.g., irregularly or periodically varying in one or more directions). For example, the thickness variation has a standard deviation of less than about 10% of the average thickness. The standard deviation of the thickness is preferably no more than about 5%, more preferably no more than about 2%, and most preferably no more than about 1% of the average thickness.

The thickness of the filled polymer layer is about 10%, 20%, 30%, 40%, or more of the total composite material thickness. The volume of the filled polymer layer is about 10%, 20%, 30%, 40%, or more of the total volume of the composite material. Preferably, the volume of the filled polymer layer is at least 50% of the total volume of the composite material. The concentration of the charged polymeric material is more preferably at least about 60% by volume, more preferably at least about 70% by volume, based on the total volume of the composite material. The concentration of the charged polymeric material is generally no greater than 92% by volume based on the total volume of the composite material. However, higher concentrations may also be used, especially in relatively thick composites (e.g., having a thickness of at least about 1.5 mm).

The total thickness of the outer layer (e.g., metal layer) of the sandwich composite structure is about 70% or less, preferably about 50% or less, more preferably about 40% or less, most preferably about 30% or less. The total thickness of the outer layer (e.g., metal layer) is at least about 5%, preferably at least about 10%, and more preferably at least about 20% of the total thickness of the composite material.

The polymeric core layer preferably undergoes direct or indirect contact (e.g., primer and / or adhesive layer) with at least a portion of the surface of the bonding layer (e.g., one or more metal layers) facing the core layer. Preferably, the contact area is at least about 30%, more preferably at least about 50%, and most preferably at least about 70% of the total area of the bonding layer surface facing the polymer core layer. If a primer or adhesive layer is used, the thickness should preferably be sufficiently thin so as not to affect the properties of the composite material. When used, the thickness ratio of the primer and / or adhesive layer to the thickness of the polymeric core layer is preferably less than or equal to about 0.30, more preferably less than or equal to about 0.20, more preferably less than or equal to about 0.10, , And most preferably about 0.02 or less. The two adjacent metal layers preferably do not substantially contact each other. When the first metal layer contacts the second metal layer, the ratio of the contact area to the surface area of the first metal layer is preferably less than about 0.3, more preferably less than about 0.1, more preferably less than about 0.05 , More preferably not more than about 0.02, and most preferably not more than about 0.01.

The composite material may comprise a plurality of polymer core layers. For example, the composite material may include one or more core layers, including an adhesive that adheres to a metal layer, another core layer, or both.

For example, as described in International Patent Application Publication WO 2010/021899, a composite material may be relatively stiff compared to a density ratio.

 Processes for preparing filled polymer layers and composites

The manufacturing process of the filled polymeric material and the composite material is carried out by the method described in International Patent Application Publication No. WO 2010/021899 (published on Feb. 25, 2010) paragraph 092-107. (E.g., a core layer) is added to one or more bonding layers (e.g., metal sheets), preferably two layers (e. G., Two Metal layer) and attached to one or both layers. The process goes through at least one of heating, cooling, deforming (e.g., molding, e.g. stamping), or attaching, and arriving at the final product. One or more, or all, bonding layers (e.g., metal layers) may be provided in the form of a rolled sheet, forgings, castings, forming structures, extruded layers, sintered layers, or combinations thereof.

The sheet may be heated to a temperature of 90 占 폚 or higher (e.g., 130 占 폚 or higher, or 180 占 폚 or higher). Preferably, the sheet is about T _min , Where T _min is the maximum glass transition temperature (T _g ) and melting point (T _m ) of the thermoplastic material of the filled polymeric material. The metal sheet, the filled polymeric material, or both, can be heated to an ultra-high temperature at which the polymer (e.g., a thermoplastic polymer) undergoes significant degradation. The thermoplastic polymer may preferably be heated to about 350 캜 or less, more preferably to about 300 캜 or less. The heated polymer may be mixed with metal fibers, and additional fillers. The heated polymer (e.g., a thermoplastic polymer) can be extruded into a sheet layer. The sheet layer may be extruded directly between the metal surfaces, or may be placed between the metal surfaces in a process or in a separate step. The process may include one or more steps of drying the polymer such that the polymer comprises water at or below a predetermined maximum moisture content. The polymer drying step may be performed before, during, or after the heating of the polymer. The process may include one or more steps of keeping the polymer, polymeric core layer, or composite material in a low humidity environment to maintain the moisture concentration of the polymer below a predetermined maximum moisture content.

The polymer core layer may be a uniform layer or may consist of multiple lower layers. For example, the filled polymeric material may include an adhesive layer as described in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

The process of making the composite material may include heating one or more metal layers, applying pressure to the layers, calendering a polymer (e.g., a thermoplastic polymer mixed with a thermoplastic polymer or metal fiber and optional filler), and quenching the composite sheet At least above the melting point of the thermoplastic polymer in the material).

The process of making a filled polymeric material (e.g., a core layer of a sandwich composite) comprises contacting the fibers with at least a portion of a polymer (e.g., a thermoplastic polymer), blending at least a portion of the fibers and polymer, Both. The step of molding the polymer layer is a continuous process or a batch process. Preferably, the process is a continuous process. The blending or contacting step includes heating the polymer to a maximum temperature of at least about 90 占 폚, at least about 140 占 폚, at least about 170 占 폚, or at least about 190 占 폚. The blending or contacting step includes heating the polymer to a maximum temperature of about 350 DEG C or less, about 300 DEG C or less, about 280 DEG C or less, about 270 DEG C or less, or about 250 DEG C or less. .

Process is performed such that the polymer of at least a portion of the charged polymeric material is at a temperature of at least about 80 캜, preferably at least 120 캜, more preferably at least 180 캜, more preferably at least 210 캜, and most preferably at least 230 캜 And may include one or more steps of applying pressure. The pressure application step may use a maximum pressure of 0.01 MPa or higher, preferably 0.1 MPa or higher, more preferably 0.5 MPa or higher, more preferably 1 MPa or higher, and most preferably 2 MPa or higher. The maximum pressure in the pressure applying step is 200 MPa or less, preferably 100 MPa or less, more preferably 40 MPa or less, and most preferably 25 MPa or less. The process may also include cooling the composite material (e.g., T _min Preferably below the melting point of the polymer of charged polymeric material, more preferably below about 50 < 0 > C).

The composite material may include the laminate described in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

It is desirable to reduce the moisture content of the polymeric material to prevent the polymeric material from contacting water (liquid, gas or solid) so that the filler of the polymeric material will not corrode. Thus, the manufacturing process of the composite material may include one or more steps that substantially protect the edge to prevent the composite material from contacting the liquid or gas. For example, a coating or protective layer may be placed on the edge of one or more (or preferably all) polymer layers (core layers), or the edges of one or more (or preferably all) Is performed. When such a method is used, the coating or protective layer provided on the edge of the polymeric layer comprises one or more materials having a relatively low water permeability compared to the polymer of the filled polymeric material. Any material having a relatively low moisture permeability may be used. The low permeability material includes a polyethylene vinyl alcohol or copolymer layer thereof, a polyolefin homopolymer or a copolymer layer comprising at least one olefin, or a combination thereof. The coating or protective layer may be permanently attached to the polymer layer, the metal layer, or both. Alternatively, the coating or protective layer may be used temporarily. For example, the coating or protective layer may be removed before one or more molding steps, before one or more welding steps, before one or more electrical coating steps, or before one or more painting steps. The edges of the composite material can be sealed using known techniques to create at least one enclosed space between the metal layers. For example, the metal layers can be welded together near the edges. The metal layers can be welded together along the entire periphery of the composite material.

And may include one or more steps of monitoring the quality of the parts used during or after the assembly of the polymer layer or components of the composite. Monitoring may include identifying the bond strength between two or more layers, confirming proper dispersion of the fibers of one or more layers of the composite, detecting surface anomalies (e.g., cracks, flaws, wrinkles, roughness, etc.) , A thickness distribution (e.g., average thickness, thickness distribution, minimum thickness, maximum thickness, or a combination thereof), or a combination thereof.

There is also a method of monitoring a part (e.g., a polymeric material or a composite material) using one or more probes. Monitoring may be done optically (e.g., detection of surface defects, measurement of thickness or thickness distribution, temperature by infrared measurement, or a combination thereof). Or by measuring the response of the part to one or more external stimuli. For example, electrical conductivity, electrical resistance, impedance, or other electrical properties are measured in response to applied electrical stimuli. For example, probes can be used to measure electrical properties at one or more sites on the part (sequentially and / or simultaneously to electrical stimulation). The magnetic properties can also be measured in a similar way. The stimulus may be a magnetic field and the response may be a mechanical response, an electrical response, a magnetic response, or a combination thereof. Monitoring may be done acoustically (e.g., using probes or other sound waves, e.g., using ultrasound). Acoustic measurements are used to measure pores, cracks, composition distribution, and so on.

A preferred monitoring device includes one or more probes (e.g., one or more processors that receive signals from a probe and a plurality of probes (also collectively referred to as probe assemblies) on a common carrier across a component for evaluating quality. For example, compares the signal to a range of predicted values for the measured part, and generates a signal when the signal is outside the predicted value range or within a predetermined range. Figure 2 shows an example of such a system.

A stack of workpieces 12 of the present invention (e.g., a laminate in which a polymer layer 16 comprising metal fibers sandwiched between metal layers 14, 14 ') is mounted. After the layers are combined, a stimulus is applied to one or more of the metal layers 14, 14 ', the polymer layer 16, or a combination thereof (e.g., electrical stimulation is applied by the power source 102). Electrical stimulation is delivered to one or more metal layers using electrical communication of one or more wires 110 or other means.

The one or more probes 104 are carried by the carrier 106 and measure the response of the workpiece to the workpiece. The probes can be on one or both sides of the workpiece. The measured response is signaled to the processor 108 and may be in a controlled state or in a different signal communication with the stimulus source (e.g., power source 102).

The monitoring process of the present invention can also be used to monitor polymeric materials (e. G., Samples of pellets, sheets, or other polymeric materials).

Molding process

The composite material of the present invention can be applied to a suitable forming process, for example, a process of tamponally deforming a material, and can be used for stamping, roll forming, bending, forging, perforating, drawing, winding, . ≪ / RTI > A preferred forming process comprises a stamping step of the composite material. The stamping process occurs at or near room temperature. For example, the temperature of the composite material during stamping is about 65 占 폚 or less, preferably about 45 占 폚 or less, and more preferably about 38 占 폚 or less. The forming process may include a step of stretching the area of the composite material at various stretching ratios. In the present invention, the composite material is subjected to a step of stretching at a relatively high stretching ratio without breaking, wrinkling, or buckling. For example, at least some of the composites in the stretching step are stretched at a stretching ratio of 1.2 or more. Preferably, the composite material can be stretched to a maximum draw ratio of at least about 1.5, preferably at least about 1.7, more preferably at least about 2.1, and most preferably at least about 2.5. The cracking limits of the stretching ratio are described in M. Weiss, ME Dingle, BF Rolfe, and PD Hodgson, "Influence of Temperature on the Forming Behavior of Metal / Polymer Laminates in Sheet Metal Forming", October 2007, Volume 129 , Issue 4, pp. 534-535. ≪ / RTI > The forming process includes applying pressure to a die to which the composite contacts (e.g., a die having a hardness greater than the hardness of the metal fiber as measured by a Mohs hardness scale).

Suitable molding balls may include those described in International Patent Application Publication No. WO 2010/021899 (published February 25, 2010).

After molding of the composite material, the process may include one or more steps of protecting the edges of the composite material to prevent transmission of moisture to the filled polymer material. The above-mentioned steps for protecting the edges of the composite material may be used.

Characteristics of Complex

The polymer layer, the composite material, or both can have a low spring back angle, relatively low electrical resistance, good weld performance (e.g., when using resistance welding), relatively low thermal conductivity, relatively low sound transmission, , For example, in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

Preferably, the filled thermoplastic material, composite material, or both are weldable (e.g., can be welded using resistance welding techniques such as spot welding, seam welding, spark welding, projection welding, or upset welding) And has a relatively low electrical resistance. The invention includes one or more steps of welding a composite material. The electrical resistance of the composite is expressed as the sum of the electrical resistances of the metal layer and the core layer. Generally, since the electrical resistance of the metal layer is much smaller than the electrical resistance of the core layer, the electrical resistance of the composite material can be estimated as the electrical resistance of the core layer. The resistance (for example, the resistance measured in the thickness direction with respect to the sheet surface) is measured using AC modulation and is determined from the voltage drop, V, and current, I:

Resistance = (V / I) (A / t)

Where A is the area of the sheet and t is the thickness of the sheet. The resistance (through the thickness direction) of the composite material, the core layer, or both is relatively low (e.g., the resistance of the composite material, core layer (e.g., filled thermoplastic material) Cm, preferably about 10,000 Ω · cm, more preferably about 3,000 Ω · cm or less, and most preferably about 1,000 Ω · cm or less.

Preferably, the electrical resistivity of the composite is sufficiently low so that it can be welded to the substrate using the same welding schedule as welding two steel plates having the same thickness as the composite. For example, the electrical resistance of the filled polymeric material, or composite, through the thickness direction is preferably less than about 100? Cm, less than about 10? Cm, less than about 1? Cm, less than about 0.15? , About 0.1? Cm or less, or about 0.075? Cm or less.

The composite material may be welded using a welding process of conventional metal welding techniques. The welding process may be one or more of the steps, apparatus, or apparatus described in International Patent Application Publication No. WO 2010/021899 (published February 25, 2010), and U.S. Patent Application No. 61 / 290,384 (filed December 28, 2009) Process.

Preferred composite materials have relatively good corrosion resistance. The composite material preferably has a metal layer surface in contact with the core layer of the same composite material except that the corrosion rate of the surface of the metal layer in contact with the core layer containing the additive and the metal filler is replaced by the polymer of the core layer, (More preferably at least 50% lower). For example, the composite material may be a composite material having a surface of the metal layer in contact with the core layer of the same composite material, except that the corrosion rate of the surface of the metal layer in contact with the core layer containing the sacrificial filler is replaced by the polymer of the core layer. It is lower than the corrosion rate. The corrosion rate in water is determined by placing the sample in a bath of predetermined corrosion test temperature and measuring the amount of surface corrosion. The corrosion rate in salt water is determined by placing the salt in a salt bath having a predetermined salt concentration and measuring the amount of surface corrosion at a predetermined corrosion test temperature. The corrosion test temperature may be about 40 占 폚, and the corrosion test time may be about 168 hours, but is not limited thereto.

Weld joints made using the various composites of the present invention exhibit various microstructures along the composite, such as the microstructure posted in International Patent Publication No. WO2010 / 021899 (published Feb. 25, 2010).

Welding of composite materials

When the composite material is spot welded to one or more single metal materials (e.g., a steel material such as a steel sheet), the process may use a second electrode that contacts a single metal with the first electrode contacting the composite material. The first electrode and the second electrode may be the same or different. The first electrode and the second electrode are preferably different. For example, when the diameter of the first electrode is less than the diameter of the second electrode, the two metal layers of the composite material can be more easily welded to a single metal material. It is believed that contacting a smaller diameter electrode to the composite material results in a more balanced thermal distribution and more effectively removes the polymer from the weld zone. Most preferably, the first electrode has a diameter sufficiently smaller than the second electrode so that both the first metal layer and the second metal layer are welded during the spot welding process. The ratio of the diameter of the second electrode to the diameter of the first electrode is preferably at least about 1.02, more preferably at least about 1.06, even more preferably at least about 1.12, and most preferably at least about 1.2. The ratio of the diameter of the second electrode to the diameter of the first electrode is preferably about 5 or less, more preferably about 3 or less, and most preferably about 2 or less.

The composite material of the present invention can preferably be welded to one or more single metal materials. For example, the shape, size, concentration, and shape of the metal fibers may be welded (e.g., spot welded) to a steel sheet selected from a steel sheet without a composite material, a hot dip galvanized steel sheet, a galvanized steel sheet, Lt; / RTI > In a particularly preferred embodiment of the invention, the composite material can be made from two or more different single steel materials (e.g., two or more uncoated steel sheets, hot dip galvanized Steel, or galvanized steel), or a combination of two or more single steel materials having different thicknesses (e.g., one material having approximately the same thickness as the composite material and the second material having a thickness of at least about 1.5 times the thickness of the composite material (E. G., As described above) relative to the source current (i. E. Likewise, composites can be welded to an incredibly diverse range of materials with varying thicknesses without having to change welding conditions. Even if the welding conditions need to be changed slightly, a larger welding current range is allowed for small changes compared to other materials.

For example, Figs. 7, 8 and 9 show the measured welding current ranges for the inventive composite material welded to uncoated steel sheet, galvanized steel sheet, and hot-dip galvanized steel sheet, respectively. Figures 7, 8 and 9 are graphs showing weld button sizes as a function of welding current. Acceptable or superior welds are i) welded button sizes of at least about 95% of the weld electrode diameter, ii) no metal release, or both. For example, when an electrode diameter of about 3.8 mm is used to contact a composite material, an excellent weld may have a weld button size of about 3.6 mm or greater. Figures 7, 8, and 9 show composite materials having a welding current range of about 1.5 or more (e.g., about 1.7 or more). Fig. 7 shows that good welding can be obtained with a welding current of 6.4 kA to 9.2 kA when the composite material is welded to a first steel sheet (for example, an uncoated steel sheet). 8 shows that good welding can be obtained with a welding current of about 7.75 kA to about 9.45 kA when the composite material is welded to another steel sheet (for example, a galvanized steel sheet). Fig. 9 shows that good welding can be obtained with a welding current of about 7.35 kA to about 9.35 kA when the composite material is welded to another steel sheet (for example, a hot dip galvanized steel sheet). First, all three materials generally have a high welding current range. Second, overlapping currents (i.e., overlapping welding current ranges) that result in good welds are generally high. For example, the current range for obtaining good welds with these three materials is about 7.8 kA to about 9.2 kA, and the overlap welding current range is about 1.4 kA or more.

 The composite materials of the present invention, which can be used in various applications, exhibit relatively low density, relatively low thermal conductivity, relatively high stiffness in density, or relatively low sound transmission. The composite materials of the present invention can be used, for example, in automotive and other transportation related applications, building construction related applications, and related devices. Applications for which the composite material may be used include, for example, passenger car panels, truck panels, bus panels, containers (e.g., liners), other panels, airplane panels, cubes (E.g., engine cover or pairing), trailer panel, interior of a door (e.g., inside a car door), roof panel, interior of a car hood, car floor pan, car rear panel, car trunk panel, Inside the car deck lid, a vehicle panel for leisure, a snowmobile panel, an automobile bumper plate, a spoiler, a wheel house liner, a spongy effect or floor effect, a vent wall, a container, a bed liner, (For example, a cellular phone, a computer, a camera, a computer, a music or video storage device, or a music or video recording device) A video player, a door, a console, an air inflow part, a battery housing, a grill, a wheel house, or a seat fan. The composite material can be used as a material for building construction such as exterior trim parts, roofing, troughs, shingles, walls, floors, counter decks, cabinet closures, window frames, door frames, wall panels, vents, plumbing, Tubing anchor, drain, shower pan, bathtub and enclosure. For example, an automobile body panel (e.g., a body exterior skin of a transport mechanism such as a passenger car). Automotive panels that can use composites include front panels, rear panels, door panels, hood panels, and roof panels. The automobile panel may have an A-grade, B-grade or C-grade surface, preferably an A-grade or B-grade surface, more preferably an A-grade surface. The composite material of the present invention may include one or more exterior decorative surfaces or decorations, such as metal decorations, wood decorations, polymer decorations, and the like. The outer surface may have a different texture, color or appearance than the layers facing each other. For example, the steel outer layer may be colored in copper, bronze, brass, gold, or other colors.

The composite material of the present invention can be used in a step including a coating of a composite material, for example, an electrocoating process, a painting process, a powder coating process, a combination thereof, and the like. If used, the coating process may comprise a cleaning or surface preparation step, heating or baking the coating (e.g., at a temperature of at least about 100 캜, preferably at least about 120 캜), or a combination thereof . The coating may be carried out by conventional means, for example, an immersion process, a spray process, or a process using a device such as, for example, a roller or a brush. The composite material preferably does not contain any components that leach out and contaminate the bath of the coating process, e. G., The electrocoating bath (e. G., Low molecular weight components). Likewise, the process of the present invention comprises one or more coating steps free of contamination of the bath due to the composite.

Composite materials (e.g., stamped parts formed of a composite material) can be used in devices that must be bonded to one or more other materials or components. For example, the composite material may be mechanically joined to another component using a fastener, chemically bonded to another component using an adhesive, an adhesion promoter (e.g., a primer), or the like. Other bonding means include welding, brazing, and soldering. One or more of these bonding methods may be used in combination.

As described above, the present invention provides a high strength laminate excellent in resistance to peeling. The resulting composite material exhibits excellent properties that can replace steel in many applications. For example, the composite lumps are attached to the metal layer so that, in the delamination test under DIN 11339, the composite has a significant amount of cohesive failure (e.g., at least about 25%, such as at least about 40%, 50% Further cohesive failure). The composite mass is sufficiently adhered to the metal layer that, in the adhesive joint test under DIN 11465, the composite has a significant amount of cohesive failure (e.g., at least about 25%, such as at least about 40%, 50%, 60% Cohesive failure). Cohesive failure generally refers to failure that occurs within the polymer matrix as opposed to adhesion failure that occurs between the polymer matrix and the bonding metal layer. Thus, a large amount of cohesive failure is that the bond strength of the polymer matrix and one or both of the metal layers of the sandwich composite exceeds the internal strength of the polymer matrix material.

Preferably, the composite material is not peeled off (e.g., the metal layer is not peeled off from the core layer) during processing of the composite into a part or device, or during use of the part. Likewise, the composite material is preferably not peeled off in a stamping operation, a joining operation (e.g., a welding operation), or both.

The present invention also includes a method of recovering parts manufactured using the present invention. One method includes providing a component having a composite structure of the present invention, and separating the hydrocarbon compound from the metal material (e.g., by high temperature heating). The titanium hydrocarbon compound or metal material can be recovered and reused. Another method involves grinding the composite material or forming particles from the composite material, and optionally reusing the particles by providing the composite as a component of the composite (e. G., The composite material).

Example

The compositions of the following examples can vary by about +/- 20% and exhibit similar results (e.g., within about +/- 20%). In addition, the materials of the present invention can be replaced with the above-mentioned other materials and exhibit similar results.

Example 1

A lightweight composite core was prepared by mixing about 45 grams of polyamide 6 and about 72 grams of stainless steel fibers in a Brabender Plastograph mixer at a temperature of 260 DEG C, at a speed of about 20 rpm. Respectively. The diameter of the stainless steel fibers was about 3-10 mu m and the length was about 2-4 mm. The density of polyamide 6 is about 1.142 g / cm ³ and the density of steel is about 7.9 g / cm ³ . After mixing for about 60 minutes, the mixture was removed from the Brabender mixer. Those skilled in the art can adjust the mixing time to be longer or shorter (for example, about 30 minutes or less, about 20 minutes or less, about 10 minutes or less, or about 5 minutes or less). Such a mixing time can also be used for other polymers of the present invention. Prepared in Example 1 is about 18.8 volume% steel fibers and about 81.2% by volume comprises a polyamide 6 and a density of about 2.411g / cm ^3.

Example 2

The core material was prepared in the same manner as in Example 1 except that the core material was made of about 102 g of stainless steel fibers and about 40 g of polyamide 6. The prepared mixture is from about 26.9 volume% steel fibers and about 73.1 volume% of polyamide 6 and a density of about 2.962g / cm ^3.

Example 3

The core material was prepared in the same manner as in Example 1 except that the core material was made of about 35.4 g of stainless steel fibers and about 50.6 g of polyamide 6. The prepared mixture contains about 10% by volume steel fibers and about 90% by volume polyamide 12 and has a density of about 1.816 g / cm ³ .

Comparative Example 4

Approximately 53 grams of polyamide 6 was mixed in a Brabender Plastograph mixer, without using stainless steel fibers, in the same manner as in Example 1. Comparative Example 4 has a density of about 1.142 g / cm ³ .

Comparative Example 5-6

A composite material was prepared by compression molding a sandwich panel comprising two steel sheets having a thickness of about 0.20 mm, a length of about 74.2 mm and a width of about 124.2 mm, and a polyamide 12 having no metal fibers sandwiched between metal plates. The steel plate is made of AISA 1008 and ASTM A109. 5 aluminum-killed low-carbon steel. The core thicknesses of Comparative Examples 5 and 6 were about 0.30 mm and about 0.44 mm, respectively, and are shown in Table 1. Compression molding of Comparative Examples 5 and 6 was carried out in a mold at a load of about 250 ° C and a load of about 12000 kg. The overall density of the composite panel was about 32-46% lower than the steel density used for the steel plate. The total-thickness electrical resistances of Comparative Examples 5 and 6 were not less than ¹ x ¹⁰ < ¹⁰ > Stamping was possible, but Comparative Example 5 and 6 were not welded well in a welding attempt on a single steel sheet. These samples failed weld tests and welds were weaker than panels welded together.

Comparative Example 5 Comparative Example 6 Metal plate 1    material steel steel    Thickness, mm 0.20 0.20 Metal plate 2    material steel steel    Thickness, mm 0.20 0.20 Core material    Thickness, mm 0.30 0.44    Thickness, total volume% 43% 57%    Metal fibers,% by volume of core material 0% 0%    Polyamide 12, volume% 100% 100% Overall density, g / cm ³ 5.37 4.27 Weight reduction,% 32% 46% Core layer resistance, Ω · cm > 10 ¹² > 10 ¹² Welding properties Fail Fail

Examples 7-8

The composite material of Examples 7 and 8 was prepared by compression molding the sandwich panel using the method described in Comparative Examples 5 and 6 except that the core material containing about 26.9 volume% of steel fiber and about 73.1 volume% polyamide 12 was used Respectively. The core steel fibers had an average diameter of about 3-10 μm and an average length of about 2-4 mm and were mixed at a temperature of about 260 ° C. in a polyamide 12 and a Brabender Plastograph mixer. The thicknesses of the core materials of Examples 7 and 8 are about 0.40 mm and about 0.57 mm, respectively. These samples are listed in Table 2. The overall density of the composite panel is about 29-36% lower than the steel density. These composite panels were well welded when subjected to AC resistance welding (spot welding) to a steel sheet about 0.8 mm thick. Good welding was obtained when welding was performed using a welding current of about 9.7 kA and 8 welding cycles at a pressure of about 600 psi (i.e., the welding button was obtained when the welding was stronger than the welding panel and the welding panel was forcibly disconnected). This condition is lower than what is required to weld two sheets of 0.8 mm thick steel sheets (12.9 KA, 15 weld cycles, 600 psi pressure). Each welding cycle is about 1/60 second, and the welding parameters include a slope of about one cycle (i.e., about 1/60 second), a downtime of about 10 cycles (i.e., about 1/6 second) .

Example 7 Example 8 Example 9 Example 10 Metal plate 1    material steel steel steel steel    Thickness, mm 0.20 0.20 0.20 0.20 Metal plate 2    material steel steel steel steel    Thickness, mm 0.20 0.20 0.20 0.20 Core material    Thickness, mm 0.40 0.57 0.37 0.55    Thickness, total volume% 50% 59% 48% 58% Metal fibers,
The volume% 26.9%
26.9%
20.2% 20.2%    Polyamide 12, volume% 73.1% 73.1% 79.8% 79.8% Overall density, g / cm ³ 5.61 5.04 5.43 4.70 Weight reduction,% 29% 36% 31% 41% Core layer resistance,
Ω · cm 910 480 740 500 Welding properties Excellent Excellent Excellent Excellent

EXAMPLES 9-10 Sandwich panels were compression molded using the methods described in Comparative Examples 5 and 6, except that core material comprising about 20.2% by volume of steel fibers and about 79.8% by volume of polyamide 12 was used, Was prepared. The core steel fibers had an average diameter of about 3-10 μm and an average length of about 2-4 mm and were mixed at a temperature of about 260 ° C. in a polyamide 12 and a Brabender Plastograph mixer. The thicknesses of the core materials of Examples 9 and 10 are about 0.37 and about 0.55 mm, respectively. These samples are listed in Table 2. The overall density of the composite panel is about 31-41% by weight lower than the steel density. These composite panels were well welded when subjected to AC resistance welding (spot welding) to a steel sheet about 0.8 mm thick. Good welding was obtained when welding using a welding current of about 9.7 kA and 8 welding cycles with a pressure of about 600 psi.

The stiffness and density of the steel sheet of the same material as that of the steel material used for the metal layers of Example 9 and Example 9, both of which were about 0.87 mm in thickness, were measured in the entire thickness direction. Example 9 exhibited higher rigidity than the steel sheet in comparison with the density.

Example 11

A sandwich panel was compression molded using the method described in Comparative Example 5, except that the core material of Example 3 was used to produce the composite material of Example 11. These composite panel samples were well welded when subjected to AC resistance welding (spot welding) to steel sheets of about 0.8 mm thickness. Good welding was obtained when welding using a welding current of about 9.7 kA and 8 welding cycles with a pressure of about 600 psi.

Examples 12-14

Examples 12-14 are polymers and polymer mixtures comprising stainless steel fibers prepared by the method of Example 1. [ Examples 12-14 were prepared using polyamide 6 with about 0 wt%, about 3 wt%, and about 10 wt% stainless steel fibers, respectively. The tensile modulus of the core material of Example 12 is about 3.3 GPa. When the steel fiber is added at a concentration of about 3 wt% (Example 13), the tensile modulus increases by about 17% to about 3.9 GPa. When the steel fibers are added at about 10 wt% (Example 14), the tensile modulus increases by 100% to about 7.3 GPa. Examples in which the polyamide is replaced by a polyamide copolymer and the concentration of the stainless steel fibers is about 0% by weight, about 3% by weight and about 10% by weight are 15, 16, and 17, respectively. The tensile modulus of the core material of Example 15 is about 700 MPa. When the steel fiber is added at a concentration of about 3% by weight (Example 16), the tensile elastic modulus is increased by 50% or more to about 1160 MPa. When the steel fiber is added at a concentration of about 10% by weight (Example 17), the tensile elastic modulus is increased by 200% or more to about 2280 MPa. Thus, in general and other examples of the present invention, the tensile modulus of a filled polymeric material (e. G., The material of the core layer) comprising metal fibers can be controlled by varying the tensile modulus of the filled polymeric material More preferably at least 50%, more preferably at least about 100%, and most preferably at least about 200%, of the tensile modulus of the core material layer).

Examples 15-20 (electrical resistance)

Examples 15 to 20 were prepared by mixing steel fibers and thermoplastic polymers in a Brabender mixer using the polymer and steel fiber concentrations reported in Table 3. The composite material was prepared by compression molding a sandwich having a 0.4 mm fiber filled thermoplastic polymer layer between two 0.2 mm thick steel sheets. The total-thickness electrical resistance of the composite, measured using AC modulation, is shown in Table 3. Composites with composite filled thermoplastic polymers all exhibited relatively low electrical resistance and composites with uncharged thermoplastic polymers all exhibited relatively high electrical resistance.

Thermoplastic Steel fiber (% by volume) Electrical resistance Ω · cm Example 15 Polyamide 0 > 10 ¹¹ Example 16 Polyamide 26.9 250 Example 17 Polyamide 10 300 Example 18 EVA 0 > 10 ¹¹ Example 19 EVA 3 400 Example 20 Co polyamide 3 600

EVA = ethylene vinyl acetate copolymer

Example 21

The filled thermoplastic material comprises about 15 vol% of low carbon steel fibers of about 4 to about 40 microns in diameter and about 1 to about 10 mm in length and about 85 vol% of a polyamide copolymer (about 50 wt% polyamide 6 and about 50 , A modulus of elasticity of about 300 MPa as measured by ISO 527-2, a melting point of about 130 DEG C as measured by ISO 11357, and a breaking elongation of about 900% as measured by ISO 527-3) . The filled thermoplastic material was mixed at about 190 캜 to about 250 캜. The filled thermoplastic material is placed between two low carbon steel sheets of about 0.2 mm thickness. The material is compressed to a pressure of from about 1 to about 22 MPa at from about 200 [deg.] C to about 230 [deg.] C. The thickness of the core made of the filled thermoplastic material of the composite material is about 0.4 mm. The composite material was spam-punched with a high-speed stamping operation to have an elongation of about 3 or more and no cracks or surface defects were found. After stamping, the surface of the composite material was comparatively smooth compared to a low-carbon steel of a single material stamped with the same thickness and under the same conditions. The composite material was subjected to a common electrocoating process and primer and black paint. The painted surface did not exhibit spotting, peeling, and other visible surface defects. The painted surface showed grade A finish. The surface of the painted composite material was smoother than the surface of a similarly treated low carbon steel single material having a thickness of about 0.8 mm.

Example 22

Composites were prepared by the same materials, compositions and methods as in Example 21, except that the fibers were replaced by low carbon steel fibers having a square cross section in the direction perpendicular to the longitudinal direction. The average length of the fibers is about 2.3 mm. The average cross-sectional area of the fibers is about 0.0045 mm ² . The ratio of the width to the thickness of the fibers is about 2 to 8. The thickness of the composite material is about 0.8 mm. The composite material is stacked with a cold rolled steel sample having a thickness of about 0.8 mm. The stack is placed in a spot welding machine between a pair of welding tips with a diameter of about 13 mm. Apply a force of approximately 2.2 kNt to the welding tip. Under the force of 2.2 kNt, the resistance of the composite in the thickness direction is measured. The electrical resistance of the measured composite material of Example 22 is less than about 0.1 ohm.cm. The thickness produces a weld button with a diameter greater than the diameter of the welding tip when welded with a common welding schedule for two sheets of cold rolled steel sheets of about 0.8 mm. Excellent welding is obtained in Example 22 without the need for additional heating, additional welding cycles, and additional current.

Example 22B

Example 22B is the same as Example 22 except that the concentration of the metal fibers in the filled polymeric material was increased to about 20% by volume and the concentration of the polymer was reduced to about 80% by volume. The composite material of Example 22B is welded to a galvanized steel sheet having a thickness of about 0.8 mm. An electrode with a face-to-face diameter of about 3.8 mm was used for the weld stack with a composite material and an electrode with a face-to-face diameter of about 4.8 mm was used for the galvanized steel sheet. A load of about 610 lbs is applied to the weld stack by the electrode. Materials were welded using intermediate frequency DC welding with a frequency of about 1,000 Hertz. Each weld was performed on a sample having a width of about 25 mm and a length of about 75 mm. The welding time was constant about 200 milliseconds. The welding current range was about 8.8 ka to 13 kA. The size of the weld button of the composite sheet was measured after welding. The size and welding current of the welding button of each welding sample 46 are shown in the graph 30 of Fig. If the region 44 is given a low welding current, the welding button size is no more than 95% of the diameter of the electrode 36 used for the composite material during the welding step. If intermediate welding current is used in zone 40, the button size is at least 95% of the diameter of electrode 36. At high welding currents in zone 42, there was metal release or excessive noise during welding and welding was not possible. The minimum welding current 34 to obtain an acceptable weld is about 10 kA in Example 22B. The maximum welding current 32 for obtaining an acceptable weld is about 13 kA. The difference between the maximum welding current 32 and the minimum welding current 34 is the current range 38. Thus, the measured welding current range is about 3.0 kA in Example 22B. For comparison, the welding current range for weld stacks consisting of two galvanized steel sheets of about 0.8 mm thickness was measured and measured to be less than about 1.3 kA. The welding current range was measured in the same manner as in Example 22B. Surprisingly, the composite of Example 22B has a higher welding current range (e.g., compared to Example 22C), being more susceptible to welding than a galvanized steel (i.e., having a wider processing window for welding).

Example 22D

Example 22D is a composite material having the same composition, filled thermoplastic polymer, and structure as in Example 22B. Example 22D measures the welding current range using the same conditions as in Example 22B, with a load on the welding electrode of about 2.76 kN (about 600 lb), a stroke time of about 50 ms, a welding time of about 300 ms, Use about 8-9 kA. The welding current range is first measured for the composite of Example 22D and for a weld stock consisting of uncoated deep-drawn steel (i.e., DDQ) with a thickness of about 1.2 mm. The welding button size is measured at different welding currents as shown in Fig. Good welding is characterized by i) a weld button size of about 3.6 mm or more in diameter and ii) no metal release at a welding current of about 6.4 kA to about 9.2 kA. The welding current range measured when welding the Example 22D to a 1.2 mm thick uncovered DDQ is about 2.8 kA.

Next, a weld stack composed of a composite material and a 0.8 mm thick galvanized steel sheet is prepared and welded using the same conditions as uncoated DDQ steels. Surprisingly, excellent welding is obtained without any change in the stroke time, the welding time, the initial welding current, or the load on the welding electrode. The welding button size is measured at different welding currents as shown in Fig. Excellent welds are characterized by i) a weld button size of about 3.6 mm or more in diameter and ii) no metal release at a welding current of about 7.75 kA to about 9.45 kA. The welding current range measured when welding the example 22D to a 0.8 mm thick galvanized steel sheet is about 1.7 kA.

The composite of Example 22D is welded to a 1.5 mm thick fused zinc plated steel sheet (i.e., HDG). Welding stacks of composite material and 1.5 mm thick HDG are prepared and welded using the same conditions as uncoated DDQ steels. Surprisingly, excellent welding is obtained without any change in the stroke time, the welding time, the initial welding current, or the load on the welding electrode. The welding button size is measured at different welding currents as shown in Fig. Good welding is characterized by i) a weld button size of about 3.6 mm or greater in diameter and ii) no metal release at a welding current of about 7.35 kA to about 9.35 kA. The welding current range measured when welding the Example 22D to 1.5 mm thick HDG is about 2.0 kA.

Surprisingly, the same welding conditions can be used to weld the composite material to different kinds of steel sheets (e.g., DDQ, HDG, or galvanized steel sheets). It is also surprising to be able to weld steel sheets of various thicknesses varying up to about 87% (i.e., 0.8 mm to 0.8 mm x 187% = 1.5 mm) without changing welding conditions. It is also surprising that for steel sheets having different thicknesses from those of other steel sheet types, welding of the composite material is generally characterized by a large welding current range

Example 23

A composite material was prepared in the same manner as in Example 21 except that the metal sheet was replaced with a 0.2 mm thick high strength steel sheet having a yield strength of about 350 MPa, a tensile strength of about 460 MPa, and a elongation of about 22% . The yield strength of the composite material is predicted to be about 193 MPa, a tensile strength of about 253 MPa, and a elongation of about 22%. The density of the composite material is expected to be about 34% less than a low carbon steel sheet of the same thickness (about 0.8 mm). The yield strength of composite materials is about 50 MPa higher than the yield strength of low carbon steel sheets of the same thickness. The tensile strength of the composite material is predicted to be about 90% or more of the tensile strength of the same thickness low carbon steel sheet. The flexural modulus of the composite material is predicted to be about 85% or more of the flexural modulus of the same thickness low carbon steel sheet.

Unless otherwise noted, it may include members excluded from it or members excluded from the group.

Unless otherwise stated, the numbers recited in the present invention include all values between the minimum and maximum values, and the interval between the maximum and minimum values is at least two units. For example, when referring to the amount and nature of the components, various process conditions such as temperature, pressure, time, and the like, it is preferable to use, for example, 1 to 90, preferably 20 to 80, (For example, 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.). Likewise, each intermediate value is within the scope of the present invention. For values less than or equal to 1, one unit may be considered to be 0.0001, 0.001, 0.01, or 0.1. These are merely examples and all numerical values between the maximum and minimum values should be considered. When expressing amounts in the present invention, " weight parts "Quot; x " parts by weight of the corresponding " b " blend compositions produced, for example.

Unless otherwise noted, all ranges include all numerical values between both endpoints and their endpoints. &Quot; about " or " roughly " refers to a range that is applied to both ends of the range. Thus, from about 20 to about 30 meets about 20 to about 30, and at least the specified endpoint is included.

All documents, including patent applications and public announcements, are used for reference purposes. &Quot; Substantially composed " is intended to encompass an element, component, element or step, and does not affect other elements, components, elements or steps that are fundamental and novel. &Quot; comprising " is intended to encompass any element, component, element, or step consisting essentially of, or consisting of, elements, elements, components or steps.

A plurality of elements, components, elements, or steps may be provided by one element, component, component, or step. Or an element, component, element, or step may be divided into a plurality of elements, components, components, or steps. &Quot; a " or " an " means that an element, element, component, element, or step does not require additional elements, elements, components, or steps. All elements or metals are listed in a particular group of the Periodic Table of the Elements issued by CRC Press, Inc., 1989. The number of a particular group of elements in the periodic table is specified using the IUPAC system.

&Quot; Polymer " and " polymerisation " are generic and include in each case "single and copolymer" and "single and copolymer", respectively.

The specification of the present invention is merely for the purpose of illustrating the present invention, and the present invention is not limited thereto. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Accordingly, the scope of the present invention should not be limited by the above description of the present invention, but is defined by the claims of the present invention and applies to the same scope. All documents and references, patent applications, and public announcements incorporated herein by reference may be disclosed for all purposes. The portion not described in the claims does not mean the renunciation of the right to the portion, nor should it be considered that the inventor has not regarded the object as a part of the present invention.

10, 12: Lightweight composite
14, 14 ': metal layer
16: polymer layer
18: polymer
20: Fiber

Claims (11)

(i) at least one first thermoplastic polymer; And
(ii) at least one second thermoplastic polymer different from the first thermoplastic polymer; (A) and < RTI ID = 0.0 >
(i) a plurality of metal fibers having a cross-section that is defined by one or more straight sides, said cross-sections being perpendicular to the fiber length,
(ii) at a concentration of at least 3 vol% based on the total volume of the composite,
(B) distributed throughout the matrix to form a filled polymeric material composite with the polymeric matrix,
The filled polymeric material composite is sandwiched between opposing metal sheets in thickness;
Wherein the plurality of metal fibers comprise metal fibers that do not extend to the thickness of the filled polymeric material composite. (i) at least one first thermoplastic polymer; And
(ii) at least one second thermoplastic polymer different from the first thermoplastic polymer; (A) and < RTI ID = 0.0 >
(i) a plurality of metal fibers having a cross-section that is defined by one or more straight sides, said cross-sections being perpendicular to the fiber length,
(ii) at a concentration of at least 3 vol% based on the total volume of the composite,
(B) distributed throughout the matrix to form a filled polymeric material composite with the polymeric matrix,
The filled polymeric material composite is attached to the metal sheet with a thickness;
Wherein the plurality of metal fibers comprise metal fibers that do not extend to the thickness of the filled polymeric material composite. 3. The composite material of claim 1 or claim 2, wherein the at least one first thermoplastic polymer is a linear low density polyolefin and the cross-section comprises two parallel sides. 3. A composite material according to claim 1 or 2, wherein the filled polymeric material composite is sandwiched between opposing metal sheets, wherein at least one surface is coated with an anti-corrosive coating. The composite material of Claim 1 or 2, wherein the filled polymeric material composite is sandwiched between opposing metal sheets, the opposite surfaces of which are coated with one or more coatings comprising zinc, phosphate or both. . The composite of claim 1 or 2, wherein the filled polymeric material composite comprises one or more of aluminum, carbon steel or nickel, manganese, copper, niobium, vanadium, chromium, molybdenum, titanium, calcium, one or more rare earth elements, zirconium, ≪ / RTI > wherein the composite material is attached to steel comprising an alloy component selected from a combination of: 3. A composite material according to claim 1 or 2, characterized in that the filled polymeric material composite is sufficiently bonded to the metal layer that the composite in the delamination test according to DIN 11339 exhibits a cohesive failure of at least 40%. 2. The composite material of claim 1, wherein the filled polymeric material composite forms a sandwich composite having a thickness of at least 0.4 mm, and the thickness of the filled polymeric composite is at least 30% of the total thickness of the sandwich composite. A welded article comprising the composite material of claim 1 or 2. A method of making a product comprising the step of welding a sandwich composite formed by sandwiching between metal sheets using the composite material of claim 1 or 2 to a metal. The method of manufacturing a product according to claim 10, comprising plastic-deforming the composite material of any one of claims 1 to 5 at a stretch ratio of 1.5 or more.

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