JP6341458B2 - Lightweight, weldable and formable composite material with peel resistance - Google Patents

Description

(Request for profit on the filing date)
The present invention was filed on US Provisional Patent Application No. 13 / 027,423 filed on February 15, 2011, 61 / 371,360 filed on August 6, 2010, and filed on August 27, 2010. No. 61 / 377,599, and 61 / 387,164, filed on Sep. 28, 2010, are hereby incorporated by reference herein in their entirety.

   The present invention relates generally to a composite material comprising a fiber-filled polymeric material and a layer of fiber-filled polymeric material, and more particularly to a sandwich composite comprising a layer of fiber-filled polymeric material and a metal layer.

  Lightweight composites that balance high stiffness, high toughness, and low weight are used in many applications that require low flexibility and can benefit from lighter parts. . Transportation is one industry that requires such materials, for example, as part of a vehicle or for the object to be transported (such as a container).

  Because of the ever-present need to reduce the weight of transport vehicles and objects being transported, and the need for alternatives to other lightweight materials and traditional steel, the industry has decided to use composite materials, and especially sandwich composite materials. investigated. Earlier applications filed by the inventors describe such efforts in detail.

  Unfortunately, the performance requirements commonly imposed on many commercial applications create competing design tensions. A material that meets one need (eg, stampability) may not necessarily meet another need, such as weldability. Thus, up to this inventor's achievement, no material has yet been adopted that can meet various needs in a commercially viable manner. Efforts to use sandwich composites have been unsuccessful due to the complications that often arise due to the lack of highly integrated bonding between layers and long-term corrosion resistance. Of course, when added to the needs of stamping and weldability, many of the above materials were excluded from viable candidates. Therefore, up to this achievement of the present inventor, despite the great efforts to date in the prior art, it does not require a huge cash investment for those who incorporate conventional steel into a finished product. There remains a need for improved composites, such as sandwich composites, that can replace steel. Similarly, there is still a need for stampable materials. In addition, there is still a need for materials that can be welded, and in particular that can be welded using conventional welding techniques and / or instruments. Exhibit long-term durability characteristics, such as one of both corrosion resistance or peel resistance (eg, peel resistance under normal use conditions such as normal use conditions for automobile vehicles), and long term (eg 3 There still exists a need for materials that can withstand the above conditions without delamination of the composite layer over 5, 10 years). In addition, a polymer base that can be used alone or in combination with other materials, such as layered materials, exhibiting excellent processability, durability, electrical characteristics (eg, charge dissipation characteristics), or any combination thereof There is also a need for a composite mass.

  In addition, there remains a need for a weldable lightweight composite having a polymer layer with improved weldability (ie, having a large processing window to obtain an acceptable joint). . Weldability is the maximum current and acceptable welding that produces an acceptable weld while other conditions such as welding pressure and welding time are preferably kept constant at values that result in the best welding. May be measured by the difference between the minimum current producing Weldability is the maximum welding time that produces an acceptable weld, while other conditions such as welding pressure and welding current are preferably kept constant at values that result in the best welding. May be measured by the difference between the minimum current producing the weld).

  The present invention in various aspects meets some or all of the above needs, and certain material combinations have excellent drawability and are weldable (and using conventional techniques and / or instruments) And is predicted based on the unexpected and surprising recognition that it can provide composite materials, such as sandwich composites, that normally resist delamination in the face of conditions that cause delamination The Thus, in many conventional applications where a steel substitute can be effectively used as a temporary material instead of steel, the materials herein and other teachings are effective in realizing the steel substitute. It is. Thus, manufacturers are expected to be able to use this material in manufacturing operations without having to acquire new equipment or other capital investments. The resulting article can also be significantly reduced in weight.

  Various aspects are disclosed herein, and the teachings of one aspect may be used in combination with the teachings of other aspects, as will be appreciated from the description below.

  In a general sense, the present teachings contemplate a composite material that includes at least one second thermoplastic polymer that is different from at least the first thermoplastic polymer and the first thermoplastic polymer. A polymer-based matrix comprising a mixture of and a metal fiber mass distributed throughout the matrix to form a composite mass comprising the polymer-based matrix, the metal fiber mass comprising at least one common Includes a plurality of metal fibers optionally having a planar surface and is present at a concentration of greater than about 3% by volume, based on the total volume of the composite mass.

  The present teachings also consider one or any combination of the following features in this summary of the invention, such as those described throughout the following detailed description. Illustratively, the at least one first thermoplastic polymer may comprise at least one polyolefinic polymer (eg, linear low density polyethylene), and the at least one second polymer is an ethylene-octene copolymer. An elastomer such as The polymer-based matrix may comprise a polymer capable of crosslinking. For example, the polymer-based matrix includes a polymer that can be cross-linked by application of an external stimulus selected from radiation (eg, ultraviolet radiation and / or infrared radiation), moisture, heat, or any combination thereof. The relative weight and / or ratio of the first thermoplastic polymer to the second thermoplastic polymer may vary from about 1: 1 to about 10: 1. More preferably from about 2: 1 to about 5: 1.

  The composite mass may be attached to a substrate such as a metal plate (eg, it is sandwiched between opposing metal plates), and the substrate or metal plate before and after being attached to the composite mass resists corrosion. To this end, one or more coatings (e.g., including zinc, phosphate, or both) may be coated on the opposing major surface of the metal plate, the substrate metal or any sheet metal being Aluminum, steel (mechanical strength features consistent with grades such as high strength steel (eg, having a yield strength of about 240 MPa or more, about 300 MPa or more, about 400 MPa or more, about 450 MPa or more, about 500 MPa or more, or about 550 or more; About 340 MPa or more, about 450 MPa or more, about 500 MPa or more, about 500 MPa or more, greater than about 600 MPa, or Steel having a maximum tensile strength of about 650 or more; or both), or nickel, manganese, copper, niobium, vanadium, chromium, molybdenum, titanium, calcium, one or more rare earth elements, zirconium, Nitrogen or steel containing an alloy component selected from any combination).

  The metal fiber mass may include a plurality of composite coated fibers to resist corrosion, e.g., the plurality of fibers are coated with a composite to define a sacrificial anode, resulting in resistance to resistance. Corrosivity is provided to the metal to which the composite mass is attached by fibers 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. The mass of metal fibers may include aluminum fibers, zinc fibers, magnesium fibers, or any combination thereof, and / or the fibers are at least partially by aluminum, zinc, magnesium, or any combination thereof. It may be coated. The mass of metal fibers includes a plurality of fibers in the shape of ribbons. For example, a metal fiber may have two or more surfaces that are generally flat, and the metal fiber may have a cross section that is generally perpendicular to the longitudinal direction of the fiber, including the straight side, May be generally polygonal (eg, generally rectangular), and the metal fibers may have a cross-section that includes width and thickness, with a width to thickness ratio of about 20: 1 to about 1: 1.

  The resulting composite material may exhibit superior properties that make it suitable as a steel substitute in many applications. For example, after a composite mass has been subjected to a peel test under DIN 11339, the composite exhibits a significant amount of cohesive failure (eg, at least about 40%, 50%, 60% or more, etc.) About 25% or more of cohesive failure), and may be well bonded to any metal layer. The composite mass is exposed to a lap shear testing under DIN 11465 so that the composite exhibits a significant amount of cohesive failure (eg, at least about 40%, 50%, 60% About 25% or more cohesive failure, such as% or more), and may be sufficiently bonded to any metal layer.

  It is clear from the above that one of the unique and unexpected features of the present invention is that excellent bond strength is achieved, and such excellent peel resistance is used in large amounts of composite mass. Or even in the absence of a significant amount of any polar polymer (eg, could be 30%, 20%, 10%, 5%, or 1% by weight) May be achievable. Furthermore, the above bond strength of the polymer matrix composite mass is not compromised, in fact, due to the presence of fibers inside the polymer matrix composite mass, by the phosphated and / or galvanized steel sheet, Or it is unexpected and surprising that both can be enhanced. For example, sandwiched between ordinary carbon, uncoated steel, composites described herein including fibers, and composites that may also include a phosphatized and / or galvanized steel layer as a sandwich layer. It is believed that the latter can surprisingly achieve a 2 or 3 fold increase in peel strength when tested according to DIN 11339 as compared to sandwich composites containing polymers without fiber.

  The yield strength of the sandwich composite formed using the composite material may be about 100 MPa or more. The tensile strength of the sandwich composite formed using the composite material of the present teachings may be about 160 MPa or more. The composite may be in the form of a sandwich composite having a thickness of about 0.4 mm or greater, such that the composite mass has a thickness that is at least about 30% of the total thickness of the sandwich composite. It may be a thing.

  Welded articles are also possible using the present teachings described herein. For example, the shape, size, concentration, and type of metal fibers may include a weld stack comprising a composite material as taught herein and a galvanized steel sheet having approximately the same thickness as a lightweight composite material. ) Shows a static contact resistance of 0.0020Ω or less as measured using a compressive force of about 500 lbs applied by two axially aligned electrodes each having an electrode surface diameter of 4.8 mm As selected. As a further example, the shape, size, concentration, and type of metal fibers are selected such that the lightweight composite has a static contact resistance ratio of about 0.01 or less, wherein the static contact resistance ratio is: (Ii) a first weld stack having a static contact resistance of a first weld stack comprising the composite material according to any one of claims 1 to 23 and a steel plate having substantially the same thickness as the lightweight composite material; Is the ratio to the static contact resistance of a second weld stack of two identical steels as in, the static contact resistance being aligned in two axial directions, each having an electrode surface diameter of 4.8 mm. Measured using a compressive force of about 500 lbs (about 2224 Nt) applied by the applied electrode.

  The teachings herein also contemplate a method of making an article, the method plastically deforming a composite material of the present teachings to a draw ratio of at least about 1.5 (eg, in a stamping operation). Welding the composite material (eg, using the same welding conditions conventionally used to weld two bodies of conventional galvanized steel without the need to use special welding parameters), or , May include both. The present teachings also contemplate articles using the taught composite materials and / or made from the taught methods. The use of the material in or as part of a motor vehicle part is likewise considered.

Other attributes of the composite material of the present teachings may include one or more of the following. The flexural modulus of the composite material may be at least about 200 GPa as measured by ASTM D790. Since a sufficiently high concentration of the filled polymeric layer, the density of the composite material is less than or equal to about 0.8d _m (d _m is the weight average density of any metal plate that is employed in combination with the mass of composite material ). Any surface of the metal layer can be galvanized, such as electrogalvanized technology, phosphorylated to include a phosphate-containing layer, or any combination thereof to withstand corrosion (composite It may be processed on one or more surfaces (before forming the material).

  The metal fibers may be formed of scrap and / or starting material derived from either or both of the first or second metal layers (eg, chopped pieces that do not have a coating thereon) The strips or chopped pieces of starting material), or the metal fibers may comprise steel fibers and fibers of another metal having a melting temperature lower than the melting temperature of the steel fibers.

  If more than one polymer is used, one of the polymers may have a tensile modulus as measured by ASTM D638, i.e., greater than about 25%, which is different from the tensile modulus of another polymer. One polymer may have a water absorption as measured by ASTM D570, that is, about 25% or more different from the water absorption of another polymer. One polymer may be about 5 ° C. or higher, unlike the thermal deflection temperature as measured by ASTM D648, ie, the thermal deflection temperature of another polymer. One or more polymers may be substantially free of oxygen and nitrogen atoms. One or more polymers may include a total concentration of oxygen and nitrogen atoms based on a total weight percent of the polymer that is less than the total concentration of oxygen and nitrogen atoms in the other polymer.

  At least one of the polymers used may be a polyamide. At least one of the polymers used may be an ionomer. At least one of the polymers may be a copolymer. The ratio of tensile modulus, such as between two of the polymers, may be 1.25: 1 or higher. The weight or volume ratio of one polymer to the other polymer may vary from about 10:90 to about 90:10. One of the polymers may include a grafted polyolefin, such as a polyolefin grafted with maleic anhydride.

  The teachings herein may further be characterized by the composite being one or any combination of the following features: the lightweight composite may have a static contact resistance of 0.0017Ω or less; The lightweight composite may have a static contact resistance of about 0.0015Ω or less; the lightweight composite has a static contact resistance greater than that of galvanized steel of the same thickness. The lightweight composite may have a static contact resistance that is at least 100% greater than the static contact resistance of galvanized steel having the same thickness; the lightweight composite may have zinc having the same thickness May have a static contact resistance that is at least 200% greater than the static contact resistance of the plated steel; the lightweight composite is at least 400% greater than the static contact resistance of the galvanized steel having the same thickness May have static contact resistance The lightweight composite may have a static contact resistance of about 0.0001 Ω or greater, the lightweight composite may have a current range of about 1.5 kA or greater; the lightweight composite is about 2.1 kA A light weight composite may have a current range greater than about 2.1 kA; a light weight composite may have a current range greater than about 2.5 kA; a light weight composite is the same A light current composite may have a current range that is at least about 0.5 kA greater than the current range of steel of the same thickness; The lightweight composite may have a current range that is greater than or equal to about 1.0 kA than the current range of steel of the same thickness.

The concentration of metal fibers may be from about 10 volume percent to about 25 volume percent, based on the total volume of filled polymer material, and the concentration of metal fibers is about 12 based on the total volume of filled polymer material. may be from percent by volume to about 23 percent by volume, the metal fibers may have an average cross-sectional area of about 0.0009Mm ² or more, the cross-sectional area is measured in a direction perpendicular to the length of the fibers, metal The fibers may have an average cross-sectional area of about 0.0025 mm ² or more, the cross-sectional area being measured in a direction perpendicular to the fiber length, and the metal fibers being generally rectangular in the direction perpendicular to the fiber length. The rectangular cross-section may be characterized by a thickness and a width that is at least as long as the thickness, with a ratio of width to thickness of about 20 or less.

  Another aspect of the teaching is i) applying pressure to the weld stack, ii) passing a first welding current while applying pressure, wherein the first welding current is about 0.8 kA or less. A step, iii) considering a step comprising ramping the welding current incrementally, gradually or continuously over an up slope time until the welding current reaches a second welding current; The welding current of 2 is at least about 0.5 kA higher than the first welding current, the upslope time is about 0.01 seconds or more, and the weld stack includes a composite material and 1 each comprising at least one metal layer. The composite material includes two metal layers and one or more polymer layers at least partially disposed between the two metal layers, the polymer layer comprising one or more polymers. Including one or more polymer layers By weight of metal fibers, and the total volume of the one or more polymer layers is about 30% or more of the total volume of the composite material. Preferably, the step includes maintaining the welding current at the second welding current for at least 0.06 seconds.

1A represents a composite material having a polymer layer and a metal layer, and 1B represents a composite material having a polymer core layer placed between two metal layers. 1 is a schematic diagram of an exemplary process for monitoring a polymer or composite material. Fig. 3 is a photomicrograph of a typical metal fiber that may be used in the core layer. 2 is a photomicrograph of a typical core layer containing metal fibers and polymer. 2 is a photomicrograph of a typical lightweight composite that includes two metal layers, metal fibers, and a polymer. Weld button size (in mm) and welding current (in kA) for lightweight composites welded to galvannealed metal having a welding current range of 2.0 kA or more (eg, about 3.0 kA) It is a curve which shows the relationship. For lightweight composites welded to uncoated deep drawn quality steel having a welding current range of about 2.0 kA or more (eg, about 2.8 kA), the welding button size (in mm) and welding current (in mm) It is a graph which shows the relationship (in the unit of kA). For lightweight composites welded to galvannealed metal having a welding current range of about 1.5 kA or more (eg, about 1.7 kA), welding button size (in mm) and welding current (in kA) ). For lightweight composites welded to hot-dip galvanized and coated metal having a welding current range of about 1.5 kA or more (eg, about 2.0 kA), welding button size (in mm) and welding current It is a graph which shows the relationship (in the unit of kA).

  In general, the materials described herein use filled polymeric materials, as described, and in particular materials that include a metallic fiber phase distributed in a polymer matrix. In general, the composite materials described herein employ at least two layers, one of which is a polymer material (eg, fiber filled polymer layer) filled as described above (eg, fiber filled polymer layer). It is in). In particular, the material herein is a composite comprising a sandwich structure, in accordance with which the polymer layer filled with fibers is sandwiched between two or more other layers. The materials described herein also contemplate sandwich construction precursors, for example, a first layer that is attached such that the filled polymer layer has an exposed outer surface. The second layer may then be attached to the filled polymer layer. The present invention also contemplates raw material composites (eg, in pellets, plates, or other shapes) that include polymeric materials filled with fibers in accordance with the present teachings. As illustrated, the materials described herein are suitable for use in deformation operations (eg, relatively high strain rate forming operations such as stamping), welding operations, or both. Shows a unique, surprising and attractive combination of features. For example, as can be seen from the present teachings, the filled polymer layer is designed to be multiphasic. At least one phase (eg, filling) provides a conductive flow path, is plastically deformable, and strain hardens when exposed to stresses that induce plastic deformation. In addition, the polymer phase binds well to another material (metal layer such as a metal plate) where the processing of the composite material for welding and / or deformation (e.g. deformation by stamping etc.) does not result in delamination of the composite material It ’s like that. The polymer phase may be exposed to other chemical baths when exposed to a coating operation (e.g., an electrostatic coating bath commonly found in sheet metal coating operations, or other baths to provide corrosion resistance). It may be resistant to degradation when exposed).

  The composite material of the present invention may have surprisingly superior weldability using electrical resistance weldability, despite the inclusion of polymers with generally poor electrical conductivity. For example, the process window for obtaining an acceptable weld may generally be wide. As used herein, an acceptable weld may be a weld having a button-sized diameter that is about 95% or more of the diameter of the electrode used to make the weld. As described herein, the composite material may have a processing window for welding that is wider than steel of the same thickness (eg, galvannealed steel).

  The present invention in various aspects utilizes unique combinations of materials that lead to attractive composites, especially laminated composites. The laminate may be drawn (eg, deep drawn), welded, or otherwise used in a manner similar to sheet material disclosed in the prior art, such as steel plates (eg, stainless steel and / or low carbon steel). Both may be done. In general, the present invention utilizes a multiphase composite material in which the material is selected and used to provide overall weldability, or both. In addition, the material can be used in conventional techniques because the resulting lamination relates to, among other things, the process of providing a decorative or functional surface treatment (eg, coating, plating, or otherwise). It may be such that it can be processed in the same way as surrounded by the disclosed thin wall.

  For example, certain preferred combinations of materials herein include two layers located on the sides of the core material, the latter being preferably a filled polymeric material. The filled polymer material preferably comprises at least one polymer, which polymer comprises a thermoplastic polymer, consists essentially of a thermoplastic polymer, consists entirely of a thermoplastic polymer, or otherwise One has the characteristic that it can generally be processed as a thermoplastic polymer. The filled polymeric material comprises a filled layer, preferably a phase having a filled material, wherein the filled material comprises or consists essentially of a fiber phase, in particular a fiber phase such as an elongated metal fiber phase. Completely consisting of the fiber phase. Because the phases as described above are well positioned and / or distributed (eg, wrapped, knitted, lined, entangled, or any combination thereof) and used in sufficient amounts, the polymer A conductive network of at least a portion of the filled polymer material is realized even if it is generally not conductive. Particularly preferred rectangular fiber phases themselves may exhibit elongation (either individual fibers or the whole mass or both) and, in some cases, strain hardening.

  Of course, references to “layers” herein do not necessarily require individual or separate pieces of material. For example, a layered composite includes one sheet of material that is folded on itself to define two layers of material, despite sharing a common edge between the filled polymeric materials. May still be within the scope of the present teachings.

  Turning now more specifically to the teachings herein, in a first aspect, at least one layer (eg, a metal layer such as a metal surface layer) and at least one polymer layer are provided. Including composite materials made from adjacent dissimilar materials, which can be formed into molded panels (eg, stressed to cause (at a relatively fast rate) plastic strain of the material) Can be stamped or otherwise cold formed on a press). The composite material may be a composite laminate including one metal layer and one polymer layer, or may include one or more other layers. For example, the composite material may be a laminate comprising one metal layer placed between two polymer layers, or a laminate comprising a polymer layer sandwiched between at least two opposing metal layers. As indicated, a particularly preferred approach assumes this latter structure, which may function as a predecessor for the latter structure. In such an example, a method of forming a sandwich structure includes adding a layer to a predecessor to form a sandwich structure, adding a first predecessor to a second precursor to form a sandwich structure Steps or both may be included.

  An example of a composite laminate (10) having one metal layer (14) and one polymer layer (16) is shown in FIG. 1A. The sandwich (12) is placed between the first metal layer (14), the second metal layer (14 ′), and the first and second metal layers, as illustrated in FIG. 1B. A polymer layer (16) (eg, a polymer core layer). Referring to FIGS. 1A and 1B, the polymer layer (16) includes at least one polymer (eg, a thermoplastic polymer) (18) and one fiber (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 have a length and orientation that extends from one surface of the polymer layer to the opposite surface of the polymer layer. However, it will be appreciated that other fiber lengths and orientations are within the scope of the present invention. For example, the fraction of fibers (eg, metal fibers) that extend between two opposing faces of the polymer layer may be less than 20%, less than 10%, less than 5%, or less than 1%. The fibers shown in FIGS. 1A and 1B are generally straight fibers. It will be appreciated from the teachings herein that preferred fibers are generally not straight. Preferred fibers have one or more curvatures along the length of the fibers, generally have curvilinear characteristics, or both.

  As noted above, in addition to the multi-layer structure that is a composite, another aspect of the present invention includes a thermoplastic polymer and fibers (eg, metal fibers) that can be subsequently sandwiched between two metal layers. Considerable predecessor polymer layer sheet material (ie, a single polymer layer).

  Yet another aspect of the present invention contemplates a precursor polymer feedstock comprising polymer and fiber. Such polymer raw materials can be molded into a polymer layer (eg, into a sheet) as a single material or by dilution with one or more additional materials (eg, one or more additional polymers) ( For example, it may be molded or extruded). As such, the precursor polymer raw material may include some or all of the components in the polymer layer of the composite material. Preferably, the polymer raw material includes almost all of the fibers for the polymer layer.

  In use, the composite may be deformed (eg, formed by a stamping process, etc.), attached to another structure (eg, steel or another composite material), or both. A preferred approach is to use the process of welding the composite of the present invention to another structure. The molded panel may be connected to other parts as required by techniques other than welding such as using an adhesive or a brazing process. In both cases, composite materials (eg, laminates or sandwich plates) can be formed by inexpensive stamping methods, but surprisingly, there are no limitations previously encountered in the art. By virtue of its unique characteristics, the composite material is very attractive for a variety of applications that conventionally use a regular unitary metal plate, such as in the body panels currently used in the transportation (eg, automotive) industry. It is a candidate.

  One particular feature of the present invention is the specific choice of polymer (eg, thermoplastic polymer) and metal fibers, as well as new formable composite materials (eg, sandwiches or laminates) for inexpensive stamping operations. To incorporate metal fibers and optional particles, and other optional fillers into the polymer matrix. Another novelty is that the stampable sandwich is a resistance weld (eg spot weld, seam weld, flash weld, projection weld or upset weld), energy beam weld (eg laser beam, electron beam, or Laser hybrid welding), gas welding (eg, oxyfuel welding using a gas such as oxyacetylene), arc welding (eg, gas metal arc welding, MIG welding, or shielded metal arc welding) It may be joined by conventional welding techniques. Preferred joining techniques include high speed welding techniques such as resistance spot welding and laser welding.

Various features of formable / stampable materials, test methods as described above, test criteria, defect descriptions, and description of the formation process are described in the following publications, all cited: Is incorporated herein by:
M.M. Weiss, M.M. E. Dingle, B.D. F. Rolfe, and P.R. D. Hodgson, "The Influence of Temperature on the Forming Behavior of Metal / Polymer Laminates in Sheet Metal Forming", Journal of Engineering Materials and Technology, October 2007, Volume 129, Issue 4, pp. 530-537.
D. Mohr and G.M. Straza, “Development of Formable All-Metal Sandwich Sheets for Automatic Applications”, Advanced Engineering Materials, Volume 7. 4, 2005, pp. 243-246.
J. et al. K. Kim and T.K. X. Yu, “Forming And Failure Behaviour Of Coated, Laminated And Sandwiched Sheet Metals: A Review”, Journal of Materials ol. 33-42.
K. J. et al. Kim, D.D. Kim, S.M. H. Choi. K. Chung, K.K. S. Shin, F .; Barlat, K.M. H. Oh, J .; R. Youn, "Formability of AA5182 polypropylene / AA5182 Sandwich Sheet, Journal of Materials Processing Technology, Volume 139, Number 139 p.
Trevor William Cline and Athina Markaki US Pat. No. 6,764,772 (filed Oct. 3, 2001, issued Jul. 20, 2004).
Frank Gissinger and Thierry Gheysens, filed Mar. 4, 1993, U.S. Pat. No. 5,347,099, issued on Sep. 13, 1994, “Method And Device For The Electric Of Sul.
Straza George CP, International Patent Application Publication (PCT): WO2007062061, “Formed Metal Core Sandwich Structure Method And System For Making Same”, date of publication: 5/31, 7/200.
Howard R.M. N. , Strain Hardening of Thermoplastics, Macromolecules 1993, 26, 5860-5869.
The International Patent Publication No. published on February 25, 2010. WO20 0/021899 (by Mizrahi)
US patent application no. 61 / 290,384 (by Mizrahi)
US patent application no. 61 / 089,704 (by Mizrahi)
US patent application no. 61/181, 511 (by Mizrahi)
US Patent Application Publication No. US2010 / 0040902A1, published on February 18, 2010, by Mizrahi.
<Material>

  As an example, the use of polymer layer fiber fillers is believed to facilitate composite fabrication, and surprisingly low levels can be used herein to achieve beneficial results. Surprisingly, the selection and combination of materials taught herein makes available less metal per unit volume than conventional metal structures of similar shape (eg, metal plates), while , Still showing comparable properties and characteristics. Problems faced by those skilled in the art with unexpected material combinations are avoided. In this respect, some behavioral properties of the material that can be predicted are surprisingly avoided and are advantageously used in the resulting composite, or both. The resulting laminates are therefore offered as attractive candidates that are temporary substitutes for existing materials, for example, to refresh equipment or significantly change processing conditions. It can be used instead of a steel plate, without requiring significant investment in the source.

<Polymer layer>
The polymer layer may generally comprise or consist essentially of a filled polymer (eg, a thermoplastic polymer filled with reinforcing fibers such as metal fibers). As such, it is generally a packed polymeric material composite mass, the polymeric material composite mass having a polymer matrix and a mass of fibers distributed throughout the polymer matrix.

  The filled polymer material used in the polymer layer is preferably a material that is generally characterized as being relatively rigid and relatively strong, has a relatively high elongation at break, and high strain hardening Having characteristics and being light weight, or any combination thereof, for example, described in International Patent Application Publication No. WO2010 / 021899 published February 25, 2010 by Mizrahi, in its entirety Is incorporated herein by reference.

  Preferably, at least some of the polymers of the filled polymeric material are thermoplastic, but are thermoset polymers, especially treated as thermoplastic, but may be cured thermoset polymers; Alternatively, the thermosetting polymer can be included. Preferably, at least 50 wt% (if not 100%, preferably at least 60 wt%, 70 wt%, 80 wt%, 90 wt%, or even 95 wt% if not 100%) of the polymer used in the filled polymeric material is It is a plastic polymer.

  The filled polymer material may also have electrical conduction properties (eg, the filled polymer material may be a conductor) so that the conductive passage is provided through the filled polymer and the composite material is a second material such as a metal plate. Can be welded to the structure. The electrical conductivity properties of the polymer core material are dispersed in the polymer in an amount having at least a percolation concentration, as described, for example, in International Patent Application Publication No. WO2010 / 021899 published February 25, 2010 by Mizrahi. Can be achieved through the use of metal fibers and optional metal or carbon black particulates. Filled polymeric materials and composite materials of the present teachings are disclosed in Mizrachi, published in International Patent Application Publication No. WO2010 / 021899 published on Feb. 25, 2010, with the disclosed technique schedule or It may be weldable using other welding schedules. For example, the material may allow for a more economical weld that is faster, requires less energy, or both.

  Filled polymer materials (eg, polymers of filled polymer materials) are known in polymer compound technology, described in Mizrahi, International Patent Application Publication No. WO2010 / 021899, published February 25, 2010, One or more known additives may further be included. For example, filled polymeric materials are described in US Pat. No. 3,784,509 (Dotson et al., January 8, 1974, see, for example, substituted imides described in column 1, line 59 to column 4, line 64), U.S. Pat. No. 3,868,388 (Dotson et al., Feb. 25, 1975, see, for example, halogenated bisimides described in column 1, line 23 to column 3, line 39), U.S. Pat. 903,109 (see Dotson et al., September 2, 1975, eg, substituted imides described in column 1, line 46 to column 4, line 50), US Pat. No. 3,915,930 ( Dotson et al., Oct. 28, 1975, see, for example, the halogenated bisimides described in column 1, line 27 to column 3, line 40), and US Pat. No. 3,953,397 (Dot on et al., April 27, 1976, column 1, line 4 to column 2, column 28, the reaction product of brominated imide and benzoyl chloride). Each may include a flame retardant compound, each of which is incorporated herein by reference in its entirety.

  The filled polymeric material may be free of plasticizers or other relatively low molecular weight materials that will volatilize (eg, during a resistance welding process). When used, the concentration of plasticizer or other relatively low molecular weight material is preferably about 3% by weight, based on the total weight of the filled polymer material (eg, the filled polymer material does not separate from a metal layer into a thin layer). Less than, more preferably less than about 0.5% by weight, and most preferably less than about 0.1% by weight.

It is also possible that the teachings herein contemplate the process of selecting materials, processing conditions, or both, so that during processing, peeling of the filled polymeric material from the metal layer substantially or Completely avoided (eg, exfoliation is caused by an increase in vapor pressure at the interface between the filled polymer material and the metal layer sufficient to cause exfoliation).
<Polymer>

With more attention to certain examples of polymers used herein, the polymer used in the filled polymer material preferably comprises a thermoplastic polymer, the thermoplastic polymer having a temperature greater than about 50 ° C. High (preferably higher than about 80 ° C., more preferably higher than about 100 ° C., even more preferably higher than about 120 ° C., more preferably higher than about 160 ° C., more preferably higher than 180 ° C. And most preferably higher than about 205 ° C.) either the peak melting temperature (as measured according to ASTM D3418-08) or the glass transition temperature (as measured according to ASTM D3418-08). Have. The thermoplastic polymer has a peak melting temperature, a glass transition point, or both, and is less than about 300 ° C, less than about 250 ° C, less than about 150 ° C, or less than about 100 ° C. The thermoplastic polymer can be at least partially crystalline at room temperature, or substantially completely glassy at room temperature. Suitable polymers (eg, suitable thermoplastic polymers) have the following tensile properties (measured according to ASTM D638-08 at a nominal strain rate of 0.1 s ⁻¹ ), greater than about 30 MPa (eg, about Greater than 750 MPa, or greater than about 950 MPa) tensile modulus (eg, Young's modulus), engineering tensile strength (ie, σ _e ), true tensile strength (ie, σ _t , where σ _t = (1 + ε _e ) σ _e , Where ε _e is the engineering load), or both, greater than about 8 MPa (eg, greater than about 25 MPa, greater than about 60 MPa, even greater than about 80 MPa); or at least about 20% (Eg, at least about 50%, at least about 90%, or at least about 300%) One or any combination of plastic elongation at break; elongation at break; Unless otherwise specified, the term “tensile strength” refers to engineering tensile strength.

  The polymer may have strain hardening properties such as those described in Mizrahi, International Patent Application Publication No. WO 2010/021899 published on Feb. 25, 2010 (eg, relatively high strain hardening modulus, relatively low estimate). Preferred yield stress or both). As such, strain hardening properties are measured by Howard R., which is incorporated herein in its entirety. N, “Strain Hardening of Thermoplastics, Macromolecules, 1993, 26, 5860-5869”.

  Examples of thermoplastic polymers that can be used in the polymer layer include polyolefins such as polyethylene (such as linear low density polyethylene) and polypropylene, and acetal copolymers, polyamides, polyamide copolymers, polyimides, polyesters such as polyethylene terephthalate and poly Butylene terephthalate), polycarbonate, thermoplastic polyurethane, thermoplastic polyether-ester copolymer (thermoplastic elastomer-ether-ester material described in ASTM D 6835-08, incorporated herein by reference), acrylonitrile butadiene Styrene copolymer, polystyrene, at least 60% by weight α-olefin and at least one additional monomer (at least 80% by weight ethylene Copolymers containing ethylene copolymer and the like) containing a copolymer containing one of these polymers, ionomers containing any of these polymers, or blends of these polymers or, any combination thereof. As can be seen from the above features, the one or more polymers can be an elastomer, such as a thermoplastic elastomer.

  The filled polymeric material preferably comprises, or consists essentially of, one or more polymers that adhere to the metal fibers, metal layers, or both Thus, it has sufficient adhesive force with respect to a metal. For example, the filled polymeric material may comprise or consist essentially of one or more polymers having a sufficient concentration of polar groups such that the polymer adheres to the metal fibers, the metal layer, or both.

  Of course, it is surprising that generally non-polar groups, including polymers, can be used as the dominant polymer component, and satisfactory adhesion results can be obtained, as the teaching assists in other parts. It can be. In particular, good resistance to delamination is achieved in the absence of use in the main amount of composite mass or in substantial amounts of any polar polymer (eg potentially 30%, 20%, 10% by weight). Even a lack of 5% by weight, or even 1% by weight) can be achieved.

  Furthermore, the bonding force between the polymer matrix composite masses is not compromised, in fact by the presence of fibers in the polymer matrix composite mass, by the use of phosphated and / or galvanized steel sheets, or It is unexpected and surprising that both can be enhanced. For example, a sandwich-like composite containing polymer without planar carbon and fibers sandwiched between uncoated steel, and containing and galvanized and / or phosphated When compared to the composites described herein, which can include an additional steel layer as a sandwich layer, the latter surprisingly has an increase in peel strength of 2x or even 3x when tested according to DIN 11339, for example. I am convinced that I was able to achieve it. Such a result may be possible through the use of polymers having polar groups, polymers not containing polar groups, or both. One approach is to use a mixture of thermoplastic polymers (eg, polyolefins such as linear low density polyethylene) and elastomers (eg, thermoplastic elastomers such as ethylene-containing copolymers), ionomers, or both.

  The filled polymer material can be stamped at a low temperature (eg, at a temperature of about −30 ° C. at about −30 ° C. so that the composite material can be stamped in a high speed stamping operation, so that it does not break or both. Ductile, which may include one or more commonly ductile polymers (eg, elastomers such as thermoplastic elastomers) that are ductile when impact treated (at a temperature of 40 ° C. or both). Can be composed of one or more generally ductile polymers, or can consist essentially of one or more generally ductile polymers. By way of example, generally ductile polymers include polymers having a glass transition temperature of about −25 ° C. or lower, −30 ° C. or lower, −35 ° C. or lower, −40 ° C. or lower, or −45 ° C. or lower. . Without limitation, the glass transition temperature of generally ductile polymers can be about −100 ° C. or higher. The ductile polymer is a semi-crystalline polymer having a crystallinity of about 90% or less, about 80% or less, about 70% or less, about 60% or less, about 50% or less, or about 40% or less. It can be. Such polymers are characterized by having a high tensile elongation, preferably about 50% or more, more preferably 80% or more, and most preferably about 110% or more, as measured by AST D638.

  As described herein, in various aspects of the invention, the composite material is subjected to one or more electrical resistance welding operations. The welding operation decomposes the polymer into low molecular weight compounds (ie, compounds that volatilize at a temperature of about 200 ° C. or about 300 ° C.) and volatilizes the low molecular weight compounds (perhaps within the compound that causes exfoliation, It will be appreciated that high temperatures can be generated near the weld that cause internal pressure) or both. As such, the polymer can be selected so that the polymer degrades significantly during the welding operation to produce low molecular weight compounds. The polymer can be selected such that the concentration of the low molecular weight compound, if any, is sufficiently low. As a result, the filled polymer material does not delaminate from the metal layer during resistance welding operations. Further, the composite material is preferably substantially free or completely free of polymers or other compounds that, when heated in a welding operation, produce compounds capable of decomposing metals such as metals in the metal layer. .

  Preferred polymers are particularly humid (eg, about 90% relative humidity, about 95% relative humidity, higher), hot (eg, about 25 ° C, about 40 ° C, or about 60 ° C). ), Corrode (eg, salt spray containing about 5% by weight sodium chloride), or reduce the corrosion of metal fibers, metal layers, or both in an environment of any combination thereof, or prevent. For example, the polymer can adhere to the metal and prevent water from coming into contact with the surface of the metal. As such, the filled polymer composition is about 8 wt% or less, preferably about 3 wt% or less, more preferably about 1 wt% or less, even more preferably about 0.2 wt% or less, and most preferably May comprise or consist essentially of one or more polymers having an equilibrium water concentration of about 0.05% by weight or less (eg, measured at about 25 ° C. at about 90% relative humidity). obtain. The filled polymer material is substantially free or completely free of polymers that corrode metals. If a polymer that corrodes metal is used, the polymer is preferably blended with one or more additives, one or more additional polymers, or both, so that metal corrosion is reduced, or Is substantially prevented.

  A single thermoplastic polymer may provide one or more desired characteristics for the filled thermoplastic composition or lightweight composite, such as the characteristics described herein. As such, the thermoplastic polymer can consist essentially of a single thermoplastic polymer. However, to achieve one or more features, to reduce costs, or both, use a blend or mixture of thermoplastic polymers, or multiple layers containing one or more different thermoplastic polymers It may be desirable to use further. The filled thermoplastic composition may comprise at least a) a first thermoplastic polymer, and ii) a second thermoplastic polymer that is different from the first thermoplastic polymer. For example, a filled thermoplastic composition may include a first thermoplastic polymer having one or any combination of the following characteristics, and a second thermoplastic polymer: one first thermoplastic polymer The second thermoplastic polymer may be substantially free of oxygen and nitrogen atoms; the second thermoplastic polymer may be substantially free of oxygen atoms, one or more nitrogen atoms, or both; The total concentration of oxygen atoms and nitrogen atoms based on the total weight percent of the polymer below the total concentration of oxygen atoms and nitrogen atoms in the first thermoplastic polymer (preferably the first thermoplastic polymer And the difference between the total concentration of oxygen and nitrogen atoms in the second thermoplastic polymer is about 2 wt% or more, more preferably about 4 wt% or more, even more preferably about 10 wt% or more, and most About 20 wt% or more Mashiku). As measured in accordance with AST D638, the second thermoplastic polymer can have a modulus of elasticity of elasticity, that is, it differs from that of the first thermoplastic polymer by about 15% or more (preferably about 25% or more, more preferably about 50% or more, and most preferably about 70% or more). The second thermoplastic polymer has a water absorption as measured by ASTM D570, i.e., is different from the water absorption of the first thermoplastic polymer by about 15% or more (preferably different by about 25% or more, more preferably about 50 %, And most preferably about 70% or more). The second thermoplastic polymer has a softening point such as a heat distortion temperature as measured according to ASTM D648, ie, differs from the heat distortion temperature of the first thermoplastic polymer by about 5 ° C. or more (preferably about 15 ° C. or more). Different, more preferably about 25 ° C. or more, even more preferably about 35 ° C. or more, and most preferably about 50 ° C. or more). Surprisingly, said mixture comprising a first thermoplastic polymer and a second thermoplastic polymer can result in a material having properties not found in a single thermoplastic polymer.

Preferred polyolefins for use in any of the embodiments herein are polypropylene homopolymers (eg, isotactic polypropylene homopolymers), polypropylene copolymers (eg, random polypropylene copolymers, impact polypropylene copolymers, Or other polypropylene copolymers containing isotactic polypropylene), polyethylene homopolymers (eg, high density polyethylene, or other polyethylene having a density greater than about 0.94 g / cm ³ ; linear low density polyethylene (e.g., about having a density below the density of high density polyethylene, such as 0.93 g / cm less than ^3), or others), polyethylene copolymers (e.g., preferably at least about 0% ethylene, more preferably at least 80 wt.% Ethylene), including any blend or any combination thereof, of these polymers. Polypropylene homopolymer and polypropylene copolymer may be substantially free of atactic polypropylene. When present, the concentration of atactic polypropylene in the polypropylene is preferably less than about 10% by weight. Suitable polypropylene copolymers and polyethylene copolymers include copolymers, which copolymers consist essentially of one or more α-olefins (eg at least 98% by weight) or are composed entirely. Other polypropylene and polyethylene copolymers that may be used include copolymers comprising one or more comonomers selected from the group comprising acrylate, vinyl acetate, acrylic acid or any combination thereof. The comonomer concentration may be less than about 40 wt%, preferably less than about 25 wt%, more preferably less than about 20 wt%, and most preferably less than about 15 wt%, based on the total weight of the copolymer. . Exemplary polyethylene copolymers that may be used are ethylene-co-vinyl acetate (ie, “EVA”, eg, containing less than about 20% by weight acetic acid), ethylene-co-methyl methacrylate (ie, EMA), ethylene- Co-acrylic acid, or any combination thereof.

  Polyamides are polymers that generally have one or more repeating units that contain amide groups along the backbone of the polymer chain. For example, the polyamide can be a reaction product of a diamine and a diacid. Other examples of polyamides include simple polyamides. In general, a single polyamide is formed by a ring-opening reaction. Exemplary polyamides formed from diamines and diacids can include polyamides (eg, polyamides) that contain the reaction product of a diamine and either adipic acid or terephthalic acid. Exemplary unitary polyamides include polyamide 6 and poly (p-benzamide). The polyamide can be a homopolymer, a copolymer, or a mixture thereof. Preferred polyamide homopolymers that can be used in the present invention are polyamide 3, polyamide 4, polyamide 5, polyamide 6, polyamide 6T, polyamide 66, polyamide 610, polyamide 612, polyamide 69, polyamide 7, polyamide 77, polyamide 8, Polyamide 9, polyamide 10, polyamide 11, polyamide 12 and polyamide 91 are included. Copolymers comprising any of the polyamides described above can also be used. The polyamide copolymer can be a random copolymer, a block copolymer, or a combination thereof. Examples of polyamide copolymers include polymers having a plurality of different amides (ie, polyamide-polyamide copolymers), polyester amide copolymers, polyether ester amide copolymers, polycarbonate ester amides, or any combination thereof.

  The polyamide-polyamide copolymer may comprise two or more of the polyamides described herein for the polyamide homopolymer. Preferred polyamide-polyamide copolymers include polyamide 6 and polyamide 66, polyamide 610, or any combination. For example, the polyamide-polyamide copolymer can consist essentially of 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 consists essentially of two or more polyamides selected from the group consisting of polyamide 6, polyamide 66, polyamide 69 and polyamide 610. Examples of such copolymers include polyamide 6/66, polyamide 6/69 and polyamide 6/66/610. A particularly preferred polyamide-polyamide copolymer is a polyamide 6/66 copolymer. The concentration of polyamide 66 in the polyamide 6/66 copolymer is about 90 wt% or less, preferably about 70 wt% or less, more preferably about 60 wt% or less, and most preferably about 50 wt%, based on the total weight of the copolymer. % Or less. The concentration of polyamide 6 in the polyamide 6/66 copolymer is about 10 wt% or more, preferably about 30 wt% or more, more preferably about 40 wt% or more, and most preferably about 50 wt%, based on the total weight of the copolymer. % Or more. Another particularly preferred polyamide-polyamide copolymer is a random or block copolymer of polyamide 6 and polyamide 69. A polyamide copolymer (ie, a copolymer comprising one or more amide monomers) may comprise a polyether such as an aliphatic ether or an aromatic ether.

  If used, the polyamide copolymer can be used alone or as a mixture with one or more additional thermoplastics. The polyamide copolymer can be a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or any combination thereof. Without limitation, the polyamide copolymer may include polyamide 6, polyamide 6,9, or both. For example, the polyamide copolymer can be a copolymer and comprises polyamide 6 at a concentration of about 1% or more, preferably about 5% or more, more preferably about 10% or more, and most preferably about 20% or more. . If used, the concentration of polyamide 6 in the copolymer may be about 99% or less, preferably about 95% or less, even more preferably about 90% or less, and most preferably about 80% or less. . The polyamide copolymer can be a copolymer and comprises polyamide 6,9 in a concentration of about 1 wt% or more, preferably about 5 wt% or more, more preferably about 10 wt% or more, and most preferably about 20 wt% or more. If used, the concentration of polyamide 6,9 in the copolymer is about 99% or less, preferably about 95% or less, even more preferably about 90% or less, and most preferably about 80% or less. possible. Particularly preferred polyamide copolymers comprise polyamide 6 and polyamide 6,9 or consist essentially of polyamide 6 and polyamide 6,9. The polyamide copolymer can be blended with one or more polyamide homopolymers. Without limitation, polyamide homopolymers that can be used include or consist essentially of polyamide 6, polyamide 6,6, polyamide 6,9, or any combination thereof. Such a blend can have a sufficient amount of polyamide copolymer so that the filled polymer layer has good tenacity, good moldability, or both. Such blends can have a sufficient amount of polyamide homopolymer so that the filled polymeric material has a high heat distortion temperature, generally a low price, or both. The weight ratio of polyamide homopolymer to polyamide copolymer can be about 1:99 or more, about 5:95 or more, about 10:90 or more, about 30:70 or more, or about 50:50 or more. The weight ratio of polyamide homopolymer to polyamide copolymer can be about 99: 1 or less, about 95: 1 or less, about 90:10 or less, about 80:20 or less, or about 70:30 or less. A particularly preferred blend of polyamide homopolymer and polyamide copolymer is a blend of polyamide 6 and polyamide 6 / 6,9 copolymer (eg, a ratio of about 30:70 to about 70:30).

  Polyethers that can be used in polyamide copolymers can be formed by polymerization of diols such as glycols (eg, comprising one or more additional monomers). Exemplary glycols that may be used include propylene glycol, ethylene glycol, tetramethylene glycol, butylene glycol, or any combination thereof. Any of the above copolymers can be block copolymers comprising relatively soft blocks and relatively hard blocks. The ratio of the modulus of elasticity of the relatively hard block to the relatively hard block is greater than about 1.1, preferably greater than about 2, and more preferably greater than about 10. The relatively hard block may comprise or consist essentially of one or more aromatic amides, one or more semi-aromatic amides or one or more aliphatic amides. The relatively soft block may include polyesters such as the polyesters described above (eg, aliphatic polyesters), polycarbonates (eg, aliphatic polycarbonates), polyethers (eg, aliphatic polyethers), or any combination thereof. The amide copolymer can include a first monomer (eg, a first amide monomer) and a second monomer, both of which are each greater than about 5% by weight, preferably about 5%, based on the total weight of the copolymer. It independently has a concentration greater than 20% by weight, more preferably greater than about 30% by weight, and most preferably greater than about 40% by weight. The concentration of the first monomer, the second monomer, or both is less than about 95 wt%, preferably less than about 80 wt%, more preferably less than about 70 wt%, and most preferably, based on the total weight of the copolymer May be less than about 60% by weight. The mixed concentration of the first monomer and the second monomer is greater than about 50 wt%, preferably greater than about 75 wt%, more preferably greater than about 90 wt%, based on the total weight of the copolymer; And most preferably greater than about 95% by weight.

  Polyamide copolymers can be characterized as thermoplastic elastomers having a relatively low melting temperature, a relatively low modulus of elasticity, or both. For example, the copolymer can have a relatively low melting temperature compared to the highest melting temperature of any of the homopolymers consisting essentially of one of the monomers of the copolymer. For example, the copolymer can have a relatively low modulus of elasticity compared to the highest modulus of elasticity of any of the homopolymers consisting essentially of one of the monomers of the copolymer. Preferred polyamide copolymers or other polymeric materials for use herein are less than about 220 ° C. (preferably less than about 190 ° C., more preferably less than about 170 ° C. as measured by ASTM D3418-08. And a melting point of most preferably less than about 150 ° C; greater than about 60 ° C as measured by ASTM D3418-08 (preferably greater than about 80 ° C, preferably greater than about 100 ° C, and A melting point of most preferably less than about 110 ° C; less than about 2.5 GPa (preferably less than about 1.2 GPa, more preferably less than about 800 MPa, and most preferably less than about 500 MPa, as measured by ASTM D638-08 ) Elastic modulus; as measured by ASTM D638-08 Modulus of elasticity greater than 50 MPa (preferably greater than about 100 MPa, more preferably greater than about 200 MPa); greater than about 50% (preferably greater than about 90%, more preferably greater than about as measured by ASTM D638-08) Characterized by fracture strain (over 300%); or a combination thereof.

  The teaching herein is that a combination of two or more polymers can be used, at least one of which can be a polyolefin, such as a linear low density polyethylene. The polymer exhibits a tensile strength of at least about 50 MPa, more preferably at least about 60 MPa (per ASTM D882-10), and an ultimate elongation (per ASTM D882-10) of at least about 500%, more preferably at least about 600%. Can do. Examples of commercially available polyolefins are: HIFOR® LT74104 from Westlake Chemical; Dowlex ™ 2553, 2045G, 2517 from Dow Chemical Company; GS710060 of Equistar Petrothene Select; ) 7109; or may include SABIC's SABIC LLDPE 726 series.

  Suitable ionomer mixtures of ionic compounds and copolymers containing polar and non-polar monomers. Suitable non-polar monomers that may be used in the ionomer copolymer include α-olefins, such as α-olefins having from 2 to about 20 carbon atoms (eg, from about 2 to about 8 carbon atoms). Exemplary non-polar monomers that can be used herein with copolymers (with or without ionomers) can include ethylene, propylene, 1-butene, 1-hexene, and 1-octene, or any combination thereof. . Suitable polar monomers include monomers that have ionic groups upon polymerization. Without limitation, examples of polar monomers that can be used in the copolymers herein (with or without ionomers) include acids such as acids having from about 2 to about 20 carbon atoms (eg, ethacrylic acid). The concentration of any polar monomer herein is less than about 40 wt%, preferably less than about 25 wt%, and more preferably about 20 wt%, based on the total weight of the ionomer (with or without ionomer) Can be less. The concentration of polar monomer in the ionomer can be about 1% or more, about 2% or more, about 3% or more, about 5% or more, about 7% or more, or about 10% or more. Suitable ionic compounds for any ionomer herein can include compounds containing one or more alkaline earth metals, one or more alkaline earth metals, or both. Without limitation, the ionic compound may include sodium, potassium, lithium, calcium, magnesium, or any combination thereof. Particularly preferred ionic compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. By way of example, commercially available ionomers include SURLYN® poly (ethylene-co-methacrylic acid) ionomer and NAFION® perfluorosulfonic acid ionomer. An example of a generally non-polar polymer (eg, alone or as part of a mixture of polymers) that can be used herein is an ethylene-octene copolymer. Suitable nonpolar polymers are at least about 7.5, more preferably at least 9.0 ultimate tensile strength (MPa) per AST D638-08, at least about 700, and more preferably at least 800 per ASTM D638-08. % Ultimate tensile elongation, at least about 13, and more preferably at least about 15 (1% secant), and at least about 12 and more preferably about 14 (2% secant) per ASTM D790-10 (MPa). Examples of commercially available polymers are Mitsui Chemicals' Tafmer® A-0550S, ExxonMobil's Exact ™ 9071, Dow Chemical Company's Engage ™ 8150, or Dow Chemical Company's Trademark Company trademark. ) 9007.

  If used, the ionomer or non-polar polymer as described above can be used alone or as a mixture with one or more additional polymers, such as one or more additional thermoplastics. For example, ionomers can be used in a mixture comprising one or more polyolefins.

Exemplary polyolefins that can be used in any of the embodiments herein, or optionally mixed with ionomers, are homopolymers and greater than or equal to about 50% by weight having about 2 to 10 carbons. Copolymers containing α-olefins are included. Preferred polyolefins for mixing with the ionomer include polyolefins having about 50% by weight or more of ethylene, propylene, butane or hexane. More preferred polyolefins for blending with the ionomer include polyolefins having about 50% by weight or more of ethylene or propylene. The concentration of α-olefin in the polyolefin (eg, ethylene or propylene concentration) is preferably about 60 wt% or more, more preferably about 70 wt% or more, and even more preferably about 80 wt%, based on the total weight of the polyolefin. % By weight, and most preferably about 90% by weight or more. Preferred polyolefins include polyolefins consisting essentially of one or more α-olefins. For example, the concentration of the one or more α-olefins can be about 90% or more, about 95% or more, about 98% or more, about 99% or more, or 99.9%, based on the total weight of the polyolefin. % Or more. Without limitation, polyolefins used in blends with ionomers are high density polyethylene (eg, having a density of about 0.945 to about 0.990 g / cm ³ ), low density polyethylene, linear low density polyethylene (eg, , about 0.915 to copolymers having a density of about 0.930 g / cm ^3), medium density polyethylene (e.g., about 0.930 to copolymers having a density of about 0.945 g / cm ^3), very low density polyethylene ( For example, having a density of about 0.900 to about 0.915 g / cm ³ ), polyethylene plastomer (eg, about 0.860 to about 0.900 g / cm ³ , preferably about 0.870 to about 0.895 g). Copolymer having a density of / cm ³ ), isotactic polypropylene homopolymer, about 5% by weight or more Or includes an isotactic polypropylene copolymer having a degree of crystallinity, impact polypropylene, a polypropylene block copolymer comprising one or more blocks of isotactic polypropylene, a mixture thereof, or any combination thereof Or essentially.

  Examples of other polyolefins that are suitable for use herein, such as for optional blending or other mixing with other polymers (eg, with elastomers, ionomers, or otherwise) include i) about 60 wt% or more α-olefin; and ii) one or more monomers selected from the group consisting of vinyl acetate, methyl acrylate, butyl acrylate, acrylic acid, methyl methacrylate, methacrylic acid and any combination thereof A copolymer comprising or consisting essentially of. The mixture of ionomer and polyolefin can contain a sufficient amount of ionomer so that the polymer adheres to the metal layer, the metal fiber, or both. The weight ratio of ionomer to polyolefin can be about 1:99 or more, about 3:97 or more, about 5:95 or more, about 10:90 or more, or about 20:80 or more. The weight ratio of ionomer to polyolefin can be 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.

  Suitable polyurethanes include thermoplastics formed by polymerizing one or more diisocyanates and one or more diols. Preferred polyurethanes comprise a thermoplastic formed by polymerizing one or more diisocyanates and two or more diols. The polyurethane can be a thermoplastic polyurethane elastomer, such as one comprising a first polymer block containing a first diol and a second polymer block comprising a second diol, wherein the first block is The block is a relatively hard block (eg, has a relatively high modulus), and the second block is a relatively soft block (eg, has a lower modulus than a relatively hard block). The concentration of the relatively hard block and the relatively soft block is each independently greater than about 5%, preferably greater than about 10%, and more preferably about 20%, based on the total weight of the copolymer. It can exceed% by weight. The concentration of the relatively hard block and the relatively soft block are each independently less than about 95% by weight, preferably less than about 90% by weight, and more preferably about 20% by weight, based on the total weight of the copolymer. Can be less. The total concentration of relatively hard blocks and relatively soft blocks is greater than about 60% by weight, preferably greater than about 80% by weight, more preferably greater than about 95% by weight, based on the total weight of the polymer. And most preferably the amount may exceed about 98% by weight. Commercially available thermoplastic polyurethanes (TPU) that can be used are ESTANE® brand TPU available from Lubrizol Corporation, ELASOLAN ™ brand available from BASF, DESMOPAN available from Bayer ( Includes registered trademark brand TPU.

  The thermoplastic polymers are preferably relatively long chain polymers so that they are greater than about 20,000, preferably greater than about 60,000, and most preferably greater than about 140,000. Can have an average molecular weight. They can be unplasticized, plasticized, elastomer modified, or without elastomer. The semicrystalline polymer is greater than about 10% by weight, preferably greater than about 20% by weight, more preferably greater than about 35% by weight, even more preferably greater than about 45% by weight, and most preferably about 55% by weight. May have a degree of crystallinity of greater than%. The semi-crystalline polymer may have a crystallinity of less than about 90% by weight, preferably less than about 85% by weight, more preferably less than about 80% by weight, and most preferably less than about 68% by weight. The crystalline quality of a thermoplastic polymer can be measured using differential scanning calorimetry by measuring the heat of fusion and comparing the heat of fusion with the heat of fusion known in the art for a particular polymer.

  The polymer of the filled polymeric material is also of a graft polymer (eg, a grafted polyolefin such as an isotactic polypropylene homopolymer or copolymer or a polyethylene homopolymer or copolymer) that is grafted with a polar molecule such as maleic anhydride. Up to about 10% by weight can be included. The concentration of the grafted compound can be about 0.01% by weight or more based on the total weight of the grafted polymer. A particularly preferred grafted polymer comprises about 0.1% to about 3% by weight maleic anhydride.

  The thermoplastic polymer is a substantially amorphous polymer (eg, less than about 10% by weight, preferably less than about 5% by weight, as measured by differential scanning calorimetry at a rate of about 10 ° C./min, and most Preferably a polymer having less than about 1% by weight of crystalline). For example, the thermoplastic polymer is greater than 50 ° C, preferably greater than 120 ° C, more preferably greater than 160 ° C, even more preferably 180 ° C, as measured by dynamic mechanical analysis at a rate of about 1 Hz. It may comprise a substantially amorphous polymer having a glass transition temperature above ° C and most preferably above 205 ° C. Exemplary amorphous polymers can include polystyrene-containing polymers, polycarbonate-containing polymers, acrylonitrile-containing polymers, and combinations thereof.

  Without limitation, examples of styrene containing copolymers that can be used in the filled polymer material are described in International Patent Application Publication No. WO 2010/021899 published by Mizrahi on February 25, 2010.

As will be appreciated from the teachings herein, the polymer layer may use an elastomer having one or both of the following properties in place of or in addition to any thermoplastic polymer: : Relatively low modulus of elasticity at 100% elongation (eg, less than about 3 MPa, preferably less than about 2 MPa), relatively high elongation at break (eg, greater than about 110%, preferably greater than about 150%), both Both were measured by ASTM D638-08 at a nominal distortion of about 0.1 s- ¹ . Examples of elastomers that can be used are described in International Patent Application Publication No. WO2010 / 021899 published by Mizrahi on February 25, 2010.

  It is possible that one or more polymers can be used in any embodiment of the teachings herein that are crosslinkable or cross-linked. The polymer can be a thermosetting material or monomer, or other precursor of a thermosetting material. The polymer can be an epoxy based rubber, urethane or some other suitable material. One or more materials can be used to enable crosslinking in response to a stimulus, such as heat, radiation (eg, ultraviolet and / or infrared), moisture, or any combination thereof (and crosslinking is used). obtain).

Although it is possible that a specific amount of epoxy can be used, the polymer of the filled polymeric material is preferably an epoxy, or other brittle polymer (eg, ASTM D638- with a nominal strain of about 0.1 s ^−1. Polymer having an elongation at break of less than about 20%, as measured by 08), or both. When present, the concentration of epoxy, other brittle polymer, or both is preferably less than about 20% by volume, more preferably less than about 10% by volume, more preferably about 5%, based on the total volume of the filled polymeric material. Less than volume percent, and most preferably less than about 2 volume percent.

  In one particularly preferred embodiment of the present invention, the filled polymeric material is one or more polyamide copolymers, one or more thermoplastic polyurethanes, one or more thermoplastic polyether ester copolymers, one or more ionomers or any of its Includes combinations. The polyamide copolymer can be any of the polyamide copolymers described herein. Preferred polyamide copolymers include polyamide-polyamide copolymers, polyesteramide copolymers, polyetheresteramides, polycarbonate-esteramide copolymers, or any combination thereof. Any of the thermoplastics can be random copolymers or block copolymers. Some of the thermoplastics can be thermoplastic elastomers. By way of example, the filled polymeric material may be a polyester-amide thermoplastic elastomer, a polyetheresteramide thermoplastic elastomer, a polycarbonate-esteramide thermoplastic elastomer, a polyetherester thermoplastic elastomer, an amide block copolymer thermoplastic elastomer, or any of its Combinations can be included. The filled polymeric material can optionally include one or more polymers, but the polymers are not copolymers. For example, the filled polymeric material can include one or more polyamide homopolymers. Particularly preferred polyamide homopolymers include polyamide 6 and polyamide 6,6. If used, the concentration of one or more polyamide homopolymers is preferably relatively low (eg, compared to the concentration of one or more copolymers). If present, the concentration of the one or more polyamide homopolymers is preferably about 50 wt% or less, more preferably about 40 wt% or less, even more preferably, based on the total weight of the polymer in the filled polymer material. About 30% or less, and most preferably about 25% or less.

  In general, filled polymeric materials including polar polymers can have sufficient attractive force between the polar polymer and the metal fiber, resulting in a functionalized improvement in adhesion between the thermoplastic and the metal fiber. No polymer is required. As such, the filled polymeric material may be substantially free or completely free of polymers having maleic anhydride, acrylic acid, acrylate, acetic acid, or any combination thereof. For example, the filled polymer may be substantially free or completely free of maleic acid graft polymer. If used, the concentration of the polymer having maleic anhydride, acrylic acid, acrylate, acetic acid or any combination in the filled polymer material is preferably about 20 weights based on the total weight of the polymer in the filled polymer material. % Or less, more preferably about 10% or less, even more preferably about 5% or less, even more preferably about 1% or less, and most preferably about 0.1% or less. As an example, in general, polar polymers include acetal homopolymers or copolymers, polyamide homopolymers or copolymers, polyimide homopolymers or copolymers, polyester homopolymers or copolymers, polycarbonate homopolymers or copolymers, and any combination thereof. Including. Filled polymeric materials that generally comprise a polar polymer may be substantially free or completely free of polyolefin homopolymers and copolymers comprising about 50% by weight of one or more olefins. If used, the total concentration of polyolefin homopolymer and optional copolymer comprising about 50% by weight of one or more olefins is preferably about 30% or less, preferably based on the total weight of the polymer in the filled polymer material. May be about 20% or less, more preferably about 10% or less, even more preferably about 5% or less, and most preferably about 1% or less.

  The life cycle use of the composite material can include heating the composite material to a sufficiently high temperature so that the metal can be recovered. As such, the polymer can be heated to a temperature at which it burns or is thermally degraded. Preferred polymers for use in composite materials are those that do not form toxic compounds (eg, toxic gases or carcinogenic compounds) during combustion or otherwise pyrolysis (eg, temperatures above about 600 ° C.). Including.

<Filler>
Filled polymeric materials (eg, filled thermoplastic polymer layers) contain one or more fillers. The filler can be a reinforcing filler such as a fiber, and in particular a metal fiber. Metal fillers (eg, metal fibers) that may be used are described in International Patent Application Publication No. WO 2010 / O21899 published by Mizrahi on February 25, 2010. For example, the metal fibers that can be used in the present invention include steel (eg, low carbon steel, stainless steel, etc.), aluminum, magnesium, titanium, copper, metal containing at least 40 wt% copper, at least 40 wt% iron. Including fibers formed from metals such as other alloys including, other alloys including at least 40 wt% aluminum, other alloys including at least 40 wt% titanium, and any combination thereof. The metal fibers comprise or consist essentially of carbon steel, such as steel having no more than about 10 wt% chromium, no more than about 7 wt% chromium, or no more than about 3 wt% chromium.

  The metal fibers can have a sufficiently low melting or liquidus temperature, so that during the process of welding (such as electrical resistance spot welding), the area between the welding tips before one or both of the metal layers melts. Some or all of the inner metal layer is at least partially melted (eg, completely melted). The electrical resistivity of the filled polymer material can be higher than the electrical resistivity of the metal layer (eg, about 10 times higher, or about 100 times higher), so that the metal fibers are melted before the metal layer begins to melt. Begin to. The welding process may use a process that sufficiently cools the weld tip, so that the metal fibers melt before the metal layer begins to melt. As such, the metal fiber is a metal (eg, steel) that has a melting or liquidus temperature below, or the same as or greater than the melting or liquidus temperature of the first metal layer, the second metal layer, or both. Or may consist essentially of.

  The filled polymeric material may comprise non-metallic conductive fibers such as those described in published International Patent Application Publication No. WO 2010/021899 published by Mizrahi on February 25, 2010.

  Metal fibers or other fillers used in the filled polymer material can preferably reduce or eliminate corrosion of the metal layer. In one approach, one or more of the metal fibers or other fillers in the metal fibers or filled polymeric material can have a relatively high galvanic activity. For example, the metal fibers or other fillers in the metal fibers or filled polymer material are metals used on one or preferably both surfaces of the metal layer that contacts or faces the filled polymer material (opposite material). May have higher galvanic activity. As such, it may be desirable for the filled polymeric material to be substantially free or completely free of fillers having low galvanic activity. As an example, this approach to reducing the corrosion of the composite material may use a filled polymeric material that is substantially free or completely free of carbon black. The one or more fillers having a relatively high galvanic activity is a metal layer of about 0.05 V or more, more preferably about 0.1 V or more, more preferably about 0.2 V or more, and most preferably about 0.25 V or more. It preferably has a higher anodization index. The one or more fillers having a relatively high galvanic activity can be any known art material having a higher galvanic activity than the metal layer. By way of example, such fillers can include one or more zinc-containing materials, one or more magnesium-containing materials, one or more aluminum-containing materials, or any combination thereof. Where the second filler is a sacrificial filler, the one or more fillers can include a first filler and a second filler that has more galvanic activity than the first filler. When the filled polymer material includes a first filler and a sacrificial filler, the first filler is preferably a metal fiber. The sacrificial filler may have a relatively high total surface area (ie, all of the sacrificial filler particles) compared to the surface area of the metal layer, the total surface area of the first filler, or preferably both. For example, the ratio of the total surface area of the sacrificial filler to the surface area of the metal layer can be about 1.5 or higher, preferably about 3 or higher, more preferably about 10 or higher, and most preferably about 50 or higher. When the filled polymeric material includes a first filler and a sacrificial filler, the first filler can have a surface 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 that has a galvanic activity that is greater than the galvanic activity of the surface of the metal layer, the first filler may function as a sacrificial filler. As such, the second sacrificial filler may not be necessary and the one filled with polymer may be substantially free or completely free of the second sacrificial filler.

  Some or all of the metal fibers may be provided with cathodic protection on one or more metal layers of the composite material. For example, the metal fibers can include fibers that are formed of or coated with a material having a standard electrochemical reduction potential below the standard electrochemical reduction potential of the first metal layer, the second metal layer, or both. In general, metals having a low standard electrochemical reduction potential include metals having a standard electrochemical reduction potential below that of steel (eg, SAE carbon steel 1015). Metals that generally have a low standard electrochemical reduction potential include aluminum, zinc and magnesium. As such, some or all of the metal fibers can include or essentially include aluminum, zinc, magnesium, alloys thereof, or any combination thereof. Particularly preferred fibers for cathodic protection are zinc fibers. Some or all of the metal fibers may be coated and / or plated metal (eg, steel), such as by electrocoating, electroplating, or a process that includes one or more steps of both. May be included. For example, the metal can be coated by a galvanizing process. The metal fiber can be coated on one or more of its sides, or all of its sides can be coated. Without limitation, the fibers can be coated by spraying, dipping (eg, by hot dipping). As an example, metal fibers can be prepared from sheets or foils coated (eg, by spraying or dipping) on one or two surfaces, and then cut into narrow strips or ribbons. As such, the metal fibers can have one or two coated surfaces. As another example, after being formed into fibers, the fibers can be coated so that all sides of the fibers are coated. As yet another example, continuous filaments can be coated and then interrupted into the fiber so that all sides of the fiber except the ends are coated. The coating suitably includes a metal selected from aluminum, zinc, magnesium, alloys thereof, or any combination thereof. As such, the metal fiber may comprise one or more coating layers of metal including aluminum, zinc, magnesium, alloys thereof, or any combination thereof, and aluminum, zinc, magnesium, alloys thereof, or any combination thereof. One or more substrate layers may be included. Particularly preferred coated metal fibers comprise a coating layer having a standard electrochemical reduction potential below the standard electrochemical reduction potential of the composite metal layer (eg, the first metal layer, the second metal layer, or both). Including. Particularly preferred coated fibers are those that are coated with a layer comprising zinc or a zinc alloy.

  When utilized, fibers that provide cathodic protection can be exposed to a corrosive environment for a long time (eg, by mist spraying of saline (eg, containing about 5% by weight sodium chloride) for about 200 hours or longer (eg, A sufficient amount, size, surface area, or those such that corrosion of the surface of the metal layer (for example, the surface facing the polymer layer) during (at about 40 ° C.) is reduced or substantially eliminated Can be provided in any combination.

The metal fibers preferably have a dimension and distribution of dimensions as described in International Patent Application Publication WO 2010/021899, issued February 25, 2010. Without limitation, the metal fibers may have a weight average length (L _avg ) greater than about 1 mm, preferably greater than about 2 mm, and most preferably greater than about 4 mm. Suitable fibers are less than about 200 mm, preferably less than about 55 mm, more preferably about 30 mm, and most preferably have an _{L avg} of less than about 25 mm. The weight average diameter of the fibers can be greater than about 0.1 μm, more preferably greater than about 1.0 μm, and most preferably greater than about 4 μm. The weight average diameter of the fibers can be less than about 300 μm, preferably less than about 50 μm, more preferably less than about 40 μm, and most preferably less than about 30 μm.

  The metal fibers can have any shape. Preferably, the metal fiber is a curve. For example, generally straight metal fibers can be used. More preferably, the metal fibers are not straight fibers along the length of the fibers. By way of example, a non-straight metal fiber can have one or more bends, can have generally arcuate characteristics, can have a generally helical shape, or can have any combination thereof. Metal fibers that are initially straight preferably become non-linear fibers (as described above) when combined with a thermoplastic polymer.

  The cross section of the metal fiber, perpendicular to the fiber length, can have any geometric shape. For example, the cross-section can have one or more sides that are generally arcuate, one or more sides that are generally straight, or any combination thereof. As an example, the metal fiber may have a polygonal, annular, elliptical, star, semi-annular, or other cross-section.

  In one embodiment of the present invention, the metal fibers preferably have one or more generally flat surfaces, such as a generally flat surface in the machine direction of the fibers. Without being bound by theory, metal fibers having a generally flat surface can provide a conductive material that is lighter in weight compared to filled polymer materials and / or materials in which the metal fibers generally have a cylindrical shape. It is believed that it can be increased. The cross section of the metal fiber, which is in the transverse direction of the fiber (ie, perpendicular to the length of the fiber), can have one or more general lengths. For example, the cross-section of the transverse metal fibers can have four or more general lengths, two or more parallel sides, or both. Without limitation, the metal fibers may have a cross section that is a general rectangle, a general parallelogram, a general polygon with four or more sides, or a general square. It will be appreciated that the metal fibers can have a cross-section that is generally elliptical, such as an ellipse having an aspect ratio of about 3 or more, preferably about 5 or more, and more preferably about 7 or more. Let's go. The cross-section of the transverse metal fibers can be characterized by width (ie, longest dimension) and thickness (eg, thinnest dimension and / or direction perpendicular to the width). The ratio of width to fiber thickness can be about 1 or more, about 2 or more, or about 3 or more. The ratio of width to fiber thickness can be about 30 or less, about 20 or less, or about 15 or less. Exemplary fibers are prepared by cutting metal foil (eg, having a thickness that is approximately the thickness of the fiber) and making small ribbons (eg, the spacing between cuts can be the width of the fiber). Fiber. The metal fibers can be prepared from an integral metal foil or from a metal foil having one or more coatings (eg, coatings on both large surfaces), such as a coating that provides cathodic protection. It will be appreciated from the teachings of the specification.

Metal fibers have a length greater than the width and thickness. The weight average length of the metal fibers is preferably about 200 μm or more, more preferably about 500 μm or more, even more preferably about 800 μm or more, and most preferably about 1 mm or more. It will be appreciated that the metal fibers have a weight average length of about 10 mm or greater, or are generally continuous. For applications requiring spot welding, the metal fibers are preferably less than the diameter of the welding tip typically used for spot welding so that the metal fibers can flow more easily away from the weld during the welding process. It has a certain weight average length. For example, the metal fibers can have a weight average length of 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 fiber aspect can be evaluated by dividing the fiber length by (4A _T / TT) ^1/2 , where _AT is the cross-sectional area of the fiber in the transverse direction. The fiber aspect ratio can be about 5 or more, about 10 or more, about 20 or more, or about 50 or more. The aspect ratio of the fibers can be about 10,000 or less, about 1,000 or less, or about 200 or less. It will be appreciated from the teachings herein that metal fibers having aspect ratios greater than 10,000 can be utilized.

  When used in a polymer layer between two metal layers, the metal fibers exist as a mass of fibers. Metal fiber masses can be interconnected. Metal fiber clumps can be tangled. The fiber mass can form a mechanical interlocking mechanism (ie, two or more fibers can be mechanically coupled). The metal fiber mass preferably spans the thickness of the polymer layer so that the majority of the fibers (eg, a network of metal fibers) electrically connect the two metal layers. A single metal fiber can span the thickness of the polymer layer, but preferably no metal fiber spans the thickness of the polymer layer. When the metal fibers are spread across the thickness of the polymer layer, the fraction of the fibers spreading in the thickness is preferably about 0.4 or less, more preferably about 0.20 or less, even more preferably about 0.10 or less, More preferably it is about 0.04 or less, and most preferably about 0.001 or less. The fibers in the fiber mass are preferably arranged in an unordered arrangement. For example, the maximum number of neighboring metal fibers arranged in a generally arranged arrangement is less than about 100, preferably less than about 50, more preferably less than about 20, even more preferably less than about 10, and most preferably Can be less than about 5. More preferably, the fiber mass is generally arranged in a random arrangement. The individual metal fibers that contact the surface of one of the metal layers are preferably free of planar contact. As such, the composite material can be characterized as having little or no planar contact between the metal fibers and the metal layer. The fibers that contact the metal surface preferably have line contact, point contact, or a combination thereof. If any of the metal fibers contact the metal layer over most of the length of the metal fiber, some of the metal fibers will contact one of the metal layers, but may have little contact . As such, the large fraction of metal fibers has a significant portion that does not contact the metal layer or at least does not contact the metal layer. The fraction of metal fibers that contact the metal layer along at least half the length of the fibers is preferably about 0.3 or less, more preferably about 0.2 or less, even more preferably about 0.1 or less, and even more Preferably it is about 0.04 or less, and most preferably about 0.01 or less.

  The metal fibers are preferably sufficiently thin and present in a thickness sufficient for many fibers to be arranged between the surface of the layers. For example, the average number of fibers that are parallel to the thickness direction of the polymer layer and intersect the line through the polymer layer is preferably about 3 or more, more preferably about 5 or more, more preferably about 10 or more. , And most preferably 20 or more. Without being bound by theory, it is believed that many metal fibers advantageously allow for more uniform deformation of the material, such as during the stamping process.

  The concentration of metal fibers is preferably greater than about 1% by volume, more preferably greater than about 3% by volume, even more preferably greater than about 5% by volume, and even more preferably, based on the total volume of the filled polymeric material. Greater than about 7% by volume, even more preferably greater than about 10% by volume, and most preferably greater than about 12% by volume. The metal fibers are less than about 60% by volume, preferably less than about 50% by volume, more preferably less than about 35% by volume, even more preferably less than about 33% by volume, and most preferably less than about 30% by volume (eg, about Present in the filled polymeric material at a concentration of less than 25% by volume, or less than about 20, 10 or 5% by volume. For example, the amount of fiber can be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% by volume, based on the total volume of the filled polymeric material. It can be in the range bounded by 9% or 10% by volume, or their values (such as from about 1% to about 6%). The composites herein can surprisingly be able to use metal fiber concentrations that are substantially lower than the amount of particulate filler needed to achieve similar weld properties. In addition, fibers and materials are selected so that better welding operations can be realized with relatively low concentrations of metal fibers compared to the same composite material with higher concentrations of metal fibers. It is also possible. For example, the use of a filled polymer material having about 10% by volume metal fibers results in a composite material having superior welding properties compared to those made with filled polymer materials having a higher concentration of metal fibers. This is surprising.

  The thermoplastic polymeric material is greater than about 40% by volume, preferably greater than about 65% by volume, more preferably greater than about 67% by volume, even more preferably greater than about 70% by volume, and most preferably about 75% by volume. % (Eg, at least about 80 volume%, at least about 90 volume%, or at least about 95 volume%) in the filled polymeric material.

  The volume ratio of polymer (eg, thermoplastic polymer) to fiber (eg, metal fiber) is preferably greater than about 2.2: 1, more preferably greater than about 2.5: 1, and most preferably Greater than about 3: 1. The volume ratio of polymer (eg, thermoplastic polymer) to fiber (eg, metal fiber) is preferably less than about 99: 1, more preferably less than about 33: 1, even more preferably less than about 19: 1, and most preferably Less than about 9: 1 (eg, less than about 7: 1).

  Any core material in the sandwich composites herein can include pores or cavities, or be substantially free of pores or cavities. Preferably, the concentration of pores or cavities in the filled polymer material is less than about 25%, more preferably less than about 10%, even more preferably less than about 5% by volume, based on the total volume of the filled polymer material. , And most preferably less than about 2% by volume (eg, less than about 1% by volume).

  The fibers (e.g., conductive fibers such as metal fibers) are preferably greater than about 40% by volume, more preferably greater than about 70% by volume, and most preferably about approximately, based on the total volume of filler in the filled polymeric material. It is present at a concentration greater than 80% by volume (eg, greater than about 90% by volume, or greater than about 95% by volume). The combined volume of polymer (eg, thermoplastic polymer) and metal fibers is preferably at least about 90% by volume, more preferably at least about 95% by volume, and most preferably about 98% by volume.

  Metal fibers can be used for strain hardening of polymer structures by utilizing electrical conductivity for welding, reinforcement, or fibers that allow the metal to provide better strain hardening properties to the polymer core. One or any combination of reinforcements is provided. As such, the stretchable elongation (at break) of the metal fiber is preferably greater than about 5%, more preferably greater than about 30%, and most preferably about 60% as measured by ASTM A370-03a. Greater than%.

  The materials herein can be utilized in combination with fibers, metal particles. The metal particles can be spherical, elongated, or any shape other than a fiber shape. Metal particles that can be used include those described in International Patent Application Publication WO 2010/021899, issued February 25, 2010. The fibers (eg, metal fibers) or the combination of fibers and metal particles is preferably less than about 30% by volume of the total polymer layer (more preferably less than about 25% by volume and most preferably less than about 20% by volume). In a polymer matrix at a volume concentration of (eg, randomly dispersed). Where metal particles are utilized, the ratio of the volume of fibers (eg, metal fibers) to the volume of metal particles in the filled polymeric material layer is greater than about 1:30, preferably greater than about 1: 1, and Most preferably it may be greater than about 2: 1.

  In one aspect of the present invention, the metal particles, metal fibers, or both, pulverize scrap and / or scrap as described in Mizrahi, International Patent Application Publication WO 2010/021899, issued February 25, 2010. It can be obtained by the process. Scraps and / or scrap may be derived from the metal plate used to make the sandwich composites herein. Thus, to the extent that the metal plate is coated or otherwise processed to withstand corrosion, scrap and / or scrap can also include the coating or treatment. The fibers can thus be in the form of finely divided or otherwise shredded, phosphated and / or galvanized steel, which can be high strength steel.

  Particularly preferred metal fibers that may optionally be used with one or more other fibers are generally rectangular cross-sections in a direction perpendicular to the length, a weight average thickness of about 10 to 70 μm, and about 40 to about 200 μm. Carbon steel having a weight average width and a weight average length of about 0.8 to about 5 mm. Surprisingly, this metal fiber is large compared to the same composite material (eg, greater than about 50%, or (About 100% or more) It can be used in a composite material having conductivity in the thickness direction.

  With reference to FIG. 3, the metal fiber (20 ″) may have a longitudinal cross-section including one, two, or more generally straight sides (such as a generally rectangular cross-section). . The length of the metal fibers can have a generally straight region, a generally arcuate region, or both. The metal fibers are of sufficient length, have sufficient curvature (eg, along the length of the fiber), and can be present in a sufficient amount or any combination thereof, so that the entangled fibers A lump is formed.

  FIG. 4 is an exemplary photomicrograph of a section of the core layer (16) comprising metal fibers (20) and polymer (18). As shown in FIG. 4, the fibers can overlap sufficiently so that current can be conducted through the core layer. For example, the conductivity of the core layer may be sufficient so that the composite material can be welded using electrical resistance welding.

  FIG. 5 illustrates an edge of an exemplary composite material that includes metal fibers (20 ') having a general rectangular cross-section in a direction that intersects the longitudinal direction of the fibers. The core layer comprises a mass of tangled metal fibers (20 ') and a polymer (18') sandwiched between two metal layers (14 ").

  As can be seen, the metal fibers are preferably selected so that the composite material generally has good weld characteristics. For example, the concentration of 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, or any combination thereof is generally determined by the composite material. It can be selected to have a good weld treatment window, generally high conductivity, generally high static contact resistance, or any combination thereof. A generally superior weld processing window may be characterized, for example, by a high welding current range, a high welding time range, or both.

  In addition to the fillers described above, one or more conventional fillers disclosed in the art can also be utilized herein in their art-disclosed ratios, examples of which are , Mica, wollastonite, nanoclay, calcium carbonate, silicate, and the like.

<Test method for measuring welding current range>
The current range for the test material shall be measured by welding a stack of test material sheets and a controllable monolithic steel (such as a piece of galvanized steel) having the same thickness as the test material sheets. Can do. Welding can be performed using two electrodes. The electrode for the test material has a face diameter d. The electrode for the steel sheet of adjustable steel may be equal to or greater than d. The welding time and welding pressure are fixed and can be predetermined, such as from a standard welding schedule for the material. The weld button size can be measured by separating two sheets. The measurement is started by selecting a current that creates a weld button of 0.95d or greater. Thereafter, the welding current gradually decreases until the welding button becomes less than d. Thereafter, the welding current is increased until a poor weld is obtained. The minimum current that produces an acceptable weld (eg, a weld having a weld button size of at least 0.95d) is the minimum weld current. At high welding currents, poor welds can be indicated by metal ejection, sheet metal sticking, loud weld popping noise, or any other combination thereof. The highest current that makes an acceptable weld is the maximum welding current. The welding current range is the difference between the maximum welding current and the initial welding current. As an example, the welding current range 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 diameter of the electrode on the composite material can be about 3.8 mm and the thickness of the electrode on the galvanized steel can be about 4.8 mm. A compressive force of about 610 psi can be applied. The welding conditions may include an intermediate frequency DC welding current having a frequency of about 1,000 Hz, an up slope time of about 50 milliseconds, and a welding time of about 200 milliseconds. The material preferably has a width of about 25 mm and a thickness of 25 mm or 75 mm.

  When welded to a single piece of steel having the same thickness as the composite material, the welding current range for the composite material, lc, is preferably the current of the single piece of steel having the same thickness as the composite material. The range is greater than lm. The ratio of lc to lm is preferably about 1.1 or higher, more preferably about 1.2 or higher, even more preferably about 1.3 or higher, even more preferably about 1.4 or higher, and most preferably about 1 .5 or more. The current range of the composite material, lc, is preferably about 1.5 kA or more, more preferably about 1.7 kA or more, even more preferably about 1.9 kA or more, even more preferably about 2.1 kA or more, even more preferably About 2.3 kA or more, and most preferably about 2.5 kA or more. FIG. 6 illustrates the welding current range for a composite material having a surprisingly high welding current range.

<Test method for measuring static contact resistance>
Static contact resistance is a composite sheet and a stack of cold rolled steel sheets having a thickness of about 0.8 mm (preferably having a face diameter of about 4.8 mm) between the two classes of I-RWNA electrodes Apply a force of about 500 psi for about 45 seconds or more without welding the two sheets, and measure the average resistance of the weld stack for 5 seconds after the time for the resistance to stabilize. A stable resistance can be determined by a resistance change of less than 2% per second, less than 1% per second, or less than 0.5% per second. Preferably, the static contact resistance can be measured using a thin plate having a thickness of about 0.8 mm, a width of about 25 mm, and a length of about 25 mm or about 75 mm. However, thin plates having other thicknesses, lengths, and widths can be used.

  The static contact resistance of the composite material is preferably about 0.0020Ω or less, more preferably about 0.0017Ω or less, even more preferably about 0.0015Ω or less, even more preferably about 0.0012Ω or less, and most preferably about It is 0.0008Ω or less.

  Without being bound by theory, it is believed that having a higher static contact resistance than monolithic steel helps to achieve and increase a high welding current range. Therefore, the ratio of the static contact resistance of the composite to the static contact resistance of steel (eg, cold rolled steel, galvanized steel, galvanized steel, or any combination thereof) is preferably about 1 or more, more preferably Is about 1.2 or higher, even more preferably about 1.5 or higher, even more preferably about 2 or higher, even more preferably about 3 or higher, even more preferably about 4 or higher, even more preferably about 5 or higher, and Most preferably, it is about 10 or more. It will be appreciated that if the static contact resistance is too high, the composite will be difficult to pass current and therefore may not be easily welded. Therefore, the ratio of the static contact resistance of the composite to the static contact resistance of steel (eg, cold rolled steel, galvanized steel, galvanized steel, or any combination thereof) is preferably about 1000 or less, more preferably Is about 300 or less, even more preferably about 100 or less, even more preferably about 75 or less, and most preferably about 40 or less.

<Metal layer>
As discussed, it is foreseen that the composites herein may utilize a sandwich structure where the polymer core mass is located on opposite sides by spaced layers. For example, the structure herein includes two sheets (eg, metal plates) having a metal fiber reinforced polymer core material disposed between the sheets, preferably in contact with the sheets. obtain. The sandwich metal layer (eg, the first metal layer and the second metal layer) is in the form of a foil or thin plate or a layer having equal or unequal thickness (eg, average thickness) across the layer, It can be made from a suitable material (eg, metal). Each metal layer generally has a constant thickness or may have a different thickness. Each face metal on each side is made of a material having the same or different properties and can be made of the same or different metals. If the metal surfaces are made of unequal thickness metal plates, the materials have different properties or have different metals. The composite material may have markings or other means of identifying and distinguishing different metal surfaces. The layers may be the same or different in configuration, size (eg, thickness, width, volume, or otherwise), shape, or other characteristics compared to each other. The metal layer may have a surface treatment to help resist corrosion (eg, coating with zinc, phosphorus, or both). Thus, before or after making a composite with a filled polymer layer, one or more metal layers can be galvanized, phosphatized, or both.

  Examples of metal layers that can be utilized are described in International Patent Application Publication No. WO2010 / 021899, issued February 25, 2010 by Mizrahi.

  The ability to down gauge steel sheets using high-strength steel in panel applications, such as automotive panel applications, is generally not limited by the strength of the steel, but by the bending modulus of the steel. Is done. Surprisingly, the filled polymer layer provides sufficient stiffness to the flexural modulus of the composite material to allow further down gauge. As such, a particularly preferred steel for use in one or more metal layers (eg, the first metal layer, the second metal layer, or both) of the composite material is a high strength steel. Without limitation, the high strength steel may have a yield strength of about 280 MPa or more, preferably about 280 MPa or more, more preferably about 320 MPa or more, and most preferably about 340 MPa or more. The high strength steel can have a yield strength of about 600 MPa or less. Without limitation, the high strength steel may have a tensile strength of about 340 MPa or more, preferably about 370 MPa or more, more preferably about 400 MPa or more, even more preferably about 430 MPa, and most preferably about 450 MPa or more. The high strength steel can have a tensile strength of about 800 MPa or less.

  The first metal layer, the second metal layer, or both may comprise a sufficient amount of high strength steel such that the flexural modulus of the composite is at least about 200 GPa as measured by ASTM D790; Here, the concentration of the filled polymer layer is sufficiently high so that the density of the composite material is about 0.8 dm or less, and dm is the weight average density of the first metal layer and the second metal layer. Surprisingly, the composite material is about 100 MPa or higher (preferably about 120 MPa or higher, more preferably about 140 MPa or higher, even more preferably about 170 MPa or higher, even more preferably about 200 MPa or higher, and most preferably about 240 MPa or higher). Or about 160 MPa or more (preferably about 200 MPa or more, more preferably about 220 MPa or more, even more preferably about 250 MPa or more, even more preferably about 270 MPa or more, even more preferably about 290 MPa or more, and most preferably Can have one or both of the properties of high tensile strength (about 310 MPa or more).

  Preferred metal layers generally have a uniform thickness such that the properties of the composite material do not change in the periodic pattern or the like. For example, in a 100 mm × 100 mm section of the metal layer, the difference between the highest and lowest thickness divided by the average thickness is about 20% or less, about 10% or less, or about 5% or less. obtain. One or both of the metal surfaces are preferably relatively thick so that when preparing and / or processing the composite material, the metal surfaces do not wrinkle, tear or otherwise form. 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, even more preferably at least about 0.15 mm, and most preferably at least about 0.18 mm. is there. The lamina may have a thickness of less than about 3 mm, preferably less than about 1.5 mm, more preferably less than about 1 mm, and most preferably less than about 0.5 mm. For example, the composite material may comprise at least one Class A or Class B surface, preferably at least one A (eg, after a stamping process, welding process, electrodeposition coating process, painting process, or any combination thereof). It can be used in automotive panels that require a grade surface. The composite material may have a first surface that is a Class A surface and a second surface that is not a Class A surface. The Class A surface has a first metal surface surface having a relatively high thickness and a first thickness having a relatively low thickness (eg, at least about 20% or at least about 40% less than the thickness of the first metal surface). It may optionally have a surface that is not a class A surface, which may be a two-metal surface. In general, the ratio of the thickness (eg, average thickness) of the first metal layer to the thickness of the second metal layer is about 0.2 to about 5, preferably 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 may be in the form of a multi-layer sheet (eg, a sandwich structure comprising a sheet of material such as metal that sandwiches a core of filled polymeric material). The sheet is less than about 30 mm, preferably less than about 10 mm, preferably about 4 mm, and most preferably less than about 2 mm; and preferably greater than about 0.1 mm, more preferably greater than about 0.3 mm, and most preferably May have a total average thickness greater than about 0.7 mm. The composite material generally has a uniform thickness, or the composite material can have a different thickness (eg, a random or periodic change in one or more directions). For example, the change in thickness is such that the standard deviation of thickness is less than about 10% of the average thickness. The standard deviation in thickness is preferably less than about 5% of the average thickness, more preferably less than about 2% of the average thickness, and most preferably less than about 1% of the average thickness.

  The thickness of the filled polymer layer may be greater than about 10%, 20%, 30%, 40%, or more of the total thickness of the composite material. The volume of the filled polymer layer may be about 10%, 20%, 30%, 40%, or more of the total volume of the composite material. Preferably, more than 50% of the volume of the composite material is a filled polymer material. The concentration of the filled polymer material is more preferably greater than about 60% by volume, more preferably greater than about 70% by volume, based on the total volume of the composite material. The concentration of the filled polymer material is typically less than 92% by volume, based on the total volume of the composite; however, higher concentrations are particularly high for composites that are relatively thick (eg, about 1.5 mm Having a greater thickness).

  The total thickness of the outer layers (eg, metal layers) of the sandwich composite structures herein can be less than about 70% of the total thickness of the composite material. The total thickness of the metal layer is preferably less than about 50%, more preferably less than about 40%, and most preferably less than about 30% of the total thickness of the composite material. The total thickness of the outer layer (eg, metal layer) may be greater than about 5%, preferably greater than about 10%, and more preferably greater than about 20% of the total thickness of the composite material.

  The polymer core is preferably in contact with at least a portion of the surface of an adjacent layer (eg, one or more metal layers) facing the core layer (directly or via a primer and / or adhesive layer). Indirectly). Preferably, the area of contact is at least about 30%, more preferably at least about 50%, and most preferably at least about 70% of the total area of the surface of the adjacent layer facing the polymer core layer. If a primer or adhesive layer is utilized, the thickness is preferably sufficiently low that it does not affect the electrical properties of the composite material. When utilized, the ratio between the thickness of the primer and / or adhesive layer and the thickness of the polymer core layer is preferably 0.30 or less, more preferably about 0.20 or less, and even more preferably about 0.00. 10 or less, even more preferably about 0.05 or less, and most preferably about 0.02 or less. Two adjacent metal layers are preferably not substantially in contact with each other. When the surface of the first metal layer is in contact with the second metal layer, the ratio of the contact area to the surface area of the first metal layer is preferably about 0.3 or less, more preferably about 0.1 or less, More preferably about 0.05 or less, even more preferably about 0.02 or less, and most preferably about 0.01 or less.

  The composite material may include a number of polymer core layers. For example, the composite material may include one or more core layers that include adhesion to adhere to a metal layer, a different core layer, or both.

  The composite material may have a relatively high stiffness to density ratio, such as that described in International Patent Application Publication No. WO2010 / 021899, issued February 25, 2010 by Mizrahi.

<Process for preparing filled polymer layer and composite>
The process of preparing the filled polymer material and the composite material may utilize the process described in International Patent Application Publication No. WO2010 / 021899, issued February 25, 2010 by Mizrahi.

  The composite material is bonded to at least one adjacent layer (eg, a metal-like sheet), preferably sandwiched between two layers (eg, two metal layers) and bonded to one or both layers. Can be prepared using a process that results in a filled polymeric material (eg, a core layer). The process may include one or any combination of heating, cooling, deformation (eg, molding by stamping, etc.), or bonding steps to arrive at the final desired editorial. At least one or all of the adjacent layers (eg, metal layers) may be in the form of a roll sheet, forging, casting, formed structure, extruded layer, sintered layer, or any combination thereof. It is foreseen that it can be provided.

The sheet can be heated to a temperature greater than about 90 ° C. (eg, greater than about 130 ° C. or greater than about 180 ° C.). Preferably, the sheet is heated to a temperature above about T _min , where T _min is the highest glass transition temperature (T _g ) and melting temperature (T _m ) of the thermoplastic of the filled polymer material. The metal sheet, the filled polymeric material, or both can be heated to the highest temperature at which the polymer (eg, thermoplastic polymer) undergoes significant degradation. The thermoplastic polymer can be heated to a temperature preferably less than about 350 ° C., more preferably to a temperature less than about 300 ° C. The heated polymer can be mixed with metal fibers and any additional fillers. A heated polymer (eg, a thermoplastic polymer) can be extruded as a sheet layer. The sheet layer can be extruded directly between the metal surfaces, or can later be placed between the metal surfaces in a process or separate steps. The process can include one or more steps of drying the polymer so that the concentration of water in the polymer is lower than a predetermined maximum moisture concentration. The step of drying the polymer can occur before, during, or after the step of heating the polymer. The process may include one or more steps of storing the polymer, polymer core layer, or composite material in a low humidity environment so that the concentration of water in the polymer is greater than a predetermined maximum moisture concentration. Is also kept low.

  The polymer core layer may be a homogeneous layer or may include multiple underlayers. For example, the filled polymeric material may include an adhesive layer such as that described in International Patent Application Publication No. WO2010 / 021899, issued February 25, 2010 by Mizrahi.

  The process of making a composite material also includes heating one or more metal layers, applying pressure to the layers, a polymer (eg, a thermoplastic polymer, or a thermoplastic polymer combined with metal fibers and optional fillers). One or more of the following steps: annealing the composite sheet (eg, at a temperature greater than the melting temperature of any thermoplastic polymer in the material). The process of producing a filled polymeric material (eg, a core layer for a sandwich composite herein) includes contacting the fiber and at least a portion of a polymer (eg, a thermoplastic polymer), the fiber and at least a portion of the polymer. Blending steps may be included, or both. The process of forming the polymer layer may be a continuous process or a batch process. Preferably the process is a continuous process. The blending or contacting step may include heating the polymer to a maximum temperature greater than about 90 ° C, greater than about 140 ° C, greater than about 170 ° C, or greater than about 190 ° C. The blending or contacting step can include heating the polymer to a maximum temperature of less than about 350 ° C, less than about 300 ° C, less than about 280 ° C, less than about 270 ° C, or less than about 250 ° C.

A suitable process is that at least some of the polymers of the filled polymeric material are above about 80 ° C, preferably above about 120 ° C, more preferably above about 180 ° C, and even more preferably above about 210 ° C. And, most preferably, one or more steps of applying pressure when under a temperature greater than about 230 ° C. may be utilized. The step of applying pressure is greater than about 0.01 MPa, preferably greater than about 0.1 MPa, more preferably greater than about 0.5 MPa, even more preferably greater than about 1 MPa, and most preferably greater than about 2 MPa. Pressure can be utilized. The maximum pressure during the step of applying pressure can be less than about 200 MPa, preferably less than about 100 MPa, more preferably less than about 40 MPa, and most preferably less than about 25 MPa. The process may also include cooling the composite material (eg, to a temperature below T _min , preferably below the melting temperature of the polymer of the filled polymer material, more preferably below about 50 ° C.).

  The composite material is or may include a laminate, such as that described in International Patent Application Publication No. WO 2010/021899, issued February 25, 2010 by Mizrahi.

  Preventing water (liquid, gas, or solid) from contacting the polymeric material, resulting in a low moisture content in the polymeric material and no corrosion of the filler in the polymeric material, or both. desirable. As such, the process of preparing the composite material may include one or more steps that sufficiently protect the edges of the composite material from contact with liquids or gases. For example, the coating or protective layer may span one or more (or preferably all) polymer layers (core layer), one or more (or preferably all) composite edges that can be sealed, or any combination thereof. Can be placed. If utilized, the coating or protective layer disposed over the edges of the polymer layer preferably comprises one or more materials that have a relatively low permeability to moisture compared to the polymer of the filled polymer material. Any material that has a relatively low permeability to moisture can be used. Without limitation, the low permeability material may comprise polyethylene vinyl alcohol or a copolymer layer thereof, a polyolefin homopolymer layer, or a copolymer consisting essentially of one or more olefins, or any combination thereof. The coating or protective layer can be permanently applied to the polymer layer, to the metal layer, or both. Alternatively, a coating or protective layer can be used temporarily. For example, the coating or protective layer may be removed before one or more forming steps, before one or more welding steps, before one or more electrodeposition coating steps, or before one or more painting steps. . Any edge of the composite material can be sealed using any method known in the art that forms one or more sealed spaces between the metal layers. As an example, the metal layers can be welded together near the edges. The metal layers can be welded together along the entire circumference of the composite material.

  One or more processes for monitoring part quality may be utilized during or after assembly of the polymer layer or composite component. The monitoring process aims to ensure bond integrity between two or more layers, to ensure proper dispersion of the fibers, to detect surface anomalies (cracking, dirt, wrinkles, roughness, etc.), voids The thickness distribution of one or any combination of layers of the composite (eg, average thickness, intermediate thickness, thickness variation, minimum thickness, maximum thickness, or any combination thereof) ) For any purpose, or any combination thereof.

  One approach may include monitoring a component (eg, a polymer material or a composite material) with one or more probes. Monitoring can be done optically (to detect surface defects, to measure thickness or thickness distribution, such as by infrared metrology, temperature, or any combination thereof). It can be done by measuring the response of the component to one or more external stimuli. For example, conductivity, resistivity, impedance, or some other electrical property can be measured in response to one or more applied electrical stimuli. For example, the probe can be used to measure (continuously and / or substantially simultaneously) electrical properties at one or more locations on a part in response to electrical stimulation. Magnetic features can be monitored in a similar manner. The stimulus is a magnetic field and the response may be a mechanical response, an electrical response, a magnetic response, or any combination thereof. Monitoring can be done audibly (eg, using a probe or other source of sound waves, such as ultrasound). Auditory measurements can be used to detect voids, cracks, component distribution, and the like.

  An assembly suitable for monitoring is one or more electrical probe sources (eg, a general carrier (probe array) that is essentially spread over the part for quality assessment or translated across the part to obtain measurements. A plurality of probes), and at least one processor for receiving signals from the probes. The processor compares the signal with a range of predicted values of the measured part, and the measured value is outside of the predicted range or otherwise included within a certain predetermined range When a signal is transmitted, an operation such as a signal transmission process can be performed. FIG. 2 shows an embodiment of the system.

  A layered workpiece of the present teachings (eg, a stack of metal layers (14) (14 ') sandwiching a polymer layer (16) containing metal fibers) is assembled. After the layers are joined, a stimulus is applied to one or more of the metal layers (14) (14 '), the polymer layer (16), or any combination thereof (eg, by an electrical source (102) Applied electrical stimulation). Electrical stimulation can be transmitted to one or more metal layers using one or more wires (110) or other means of electrical communication.

  One or more probes (104) may be carried by the carrier (106) and will measure the response of the workpiece to the stimulus. The probe may be on one or both sides of the workpiece. The measured response is signaled to the processor (108), which may also be under control or other signaling communication with a stimulus source (eg, electrical source (102)). .

  It will be appreciated that the monitoring process described herein can also be used for monitoring polymeric materials (eg, pellets, sheets or other samples of polymeric materials).

<Molding process>
The composite material of the present invention may plastically deform the material and include steps of stamping, roll forming, bending, forging, punching, stretching, winding, some other metalwork, or any combination thereof. Exposed to a suitable molding process, such as a process. A preferred molding process is a process that includes stamping the composite material. The stamping process can occur at or near ambient temperature. For example, the temperature of the composite material during stamping can be less than about 65 ° C, preferably less than about 45 ° C, and more preferably less than about 38 ° C. The molding process can include stretching the region of the composite material to various stretch ratios. In one aspect of the invention, the composite material is subjected to a process of stretching to a relatively high stretch ratio that is free of cracks, wrinkles, or twists. For example, the composite material is subjected to a stretching process so that at least some of the composite material is stretched to a stretch ratio greater than 1.2. Desirably, the composite material can be stretched and is greater than about 1.5, preferably greater than about 1.7, more preferably greater than about 2.1, and most preferably greater than about 2.5. It can be stretched to the maximum stretch ratio. The limit point at which cracks in the stretch ratio occur is described in Weiss et al. (M. Weiss, M. E. Dingle, B. F. Rolfe, and P. D. Hodgson, "The Influence of Temperature on the Forming Behavior of Metal / Polymer Laminates in Sheet Metal Forming", Journal of Engineering Materials and Technology , (October 2007), Volume 129, Issue 4, pp. 534-535), and measured using a circular cup drawing test, these references Are incorporated herein by reference. The forming process may include applying pressure to a die die (eg, a die die having a hardness greater than the hardness of the metal fibers as measured by a Mole hardness scale) in contact with the composite material.

  Suitable molding processes that may be utilized include those described in International Patent Application Publication No. WO2010 / 021899, issued February 25, 2010 by Mizrahi.

  After forming the composite material, the process may include one or more steps that protect the edges of the composite material to reduce moisture penetration into the filled polymeric material. Any of the foregoing steps for protecting the edges of the composite material can be used.

<Characteristics of composite material>
The polymer layer, the composite material, or both are low springback angles, relatively low electrical resistivity, excellent, such as those described in International Patent Application Publication WO2010 / 021899 issued February 25, 2010 by Mizrahi Weldability (eg, using resistance welding), relatively low thermal conductivity, relatively low acoustic transmission, or any combination thereof.

Preferably, the filled thermoplastic material, composite material, or both are weldable (eg, using resistance welding techniques such as spot welding, seam welding, flash welding, projection welding, or upset welding). Possible), has a relatively low electrical resistance. Thus, the teachings herein also consider one or more steps of welding the composite materials taught herein. The electrical resistance of the composite material in the thickness direction can be described by the sum of the electrical resistance of the metal layer and the core layer. Typically, the electrical resistance of the metal layer is much less than the electrical resistance of the core layer, so that the electrical resistance of the composite material can be evaluated by the electrical resistance of the core layer. Specific resistance (eg, specific resistance measured in the thickness direction (perpendicular to the plane of the sheet)) is measured using AC modulation and is measured from voltage drop, V, and current, I :
Specific resistance = (V / I) (A / t)
Here, A is the area of the sheet, and t is the thickness of the sheet. The resistivity of the composite material, core layer, or both (in the thickness direction of conduction) is relatively low (eg, the composite material, core layer, or both are less than about 100,000 Ω · cm, preferably about Less than 10,000 Ω · cm, more preferably less than about 3,000 Ω · cm, and most preferably less than about 1,000 Ω · cm).

  The composite material is welded to the unitary steel sheet by resistance welding technology, using a welding schedule where the composite material is generally the same as the welding schedule for welding two unitary steels of the same thickness. It can have a sufficiently low electrical resistivity that it can. For example, the electrical resistivity in the thickness direction is about 100 Ω · cm or less, preferably about 10 Ω · cm or less, more preferably about 1 Ω · cm or less, even more preferably about 0.15 Ω · cm or less, and even more preferably It can be about 0.1 Ω · cm or less, and most preferably about 0.075 Ω · cm or less.

  The composite material may be welded using any welding process known to those skilled in the art of welding metals. The welding process is described in International Patent Application Publication No. WO 2010/021899, US Patent Application No. 61 / 290,384, filed on Dec. 28, 2009 by Mizrahi, issued February 25, 2010 by Mizrahi. One or more steps, devices, or processes may be included, both of which are hereby incorporated by reference in their entirety for all purposes.

  Preferred composite materials have relatively good corrosion resistance. The composite material is preferably characterized by the rate of corrosion of the metal layer facing the core layer, the surface of the core layer comprising polymer and metal filler, ie the metal filler in the core layer is replaced with the polymer of the core layer Except that the rate of corrosion of the surface of the metal layer facing the core layer of the same composite material is lower (more preferably at least less than 50%). For example, the composite material has a rate of corrosion of the surface of the metal layer facing the core layer, and the core layer includes a sacrificial filler, ie, the same composite except that the sacrificial filler is replaced with the core layer polymer. Less than the rate of corrosion of the surface of the metal layer facing the core layer of material. The rate of corrosion in water is measured by placing a sample of a composite material having a predefined dimension in a water bath at a predefined corrosion test temperature for a predefined corrosion test time, and measuring the amount of corrosion on the surface. Can be determined. The rate of corrosion in salt water is determined by placing a sample of composite material having a predefined dimension in a salt water bath having a predefined salt concentration at a predefined corrosion test temperature for a predefined corrosion test time and surface It can be determined by measuring the amount of corrosion above. Without limitation, the corrosion test temperature can be about 40 ° C. and the corrosion test time can be about 168 hours.

  Weld joints made using the various composite materials described herein are composites such as those described in International Patent Application Publication No. WO 2010/021899, published February 25, 2010 by Mizrahi. It is possible to show microstructural deformations throughout the material.

<Welding of composite materials>
When the composite material is welded to one or more integral metal materials (eg, a steel material such as a steel plate) (eg, spot welding), the process includes a first electrode that contacts the composite material and a second electrode that contacts the integral metal. Electrodes can be used. The first electrode and the second electrode can be the same or different. Preferably, the first electrode and the second electrode are different. Surprisingly, if the first electrode has a diameter that is less than the diameter of the second electrode, both metal layers of the composite material are more easily welded to a unitary metal material. Without being bound by theory, it is believed that the use of smaller diameter electrodes to contact the composite material will result in a more even heat distribution and / or more efficient removal of the polymer from the weld area or both. It has been. Most preferably, the first electrode has a diameter that is sufficiently smaller than the diameter of the second electrode so that both the first metal layer and the second metal layer are welded during the spot welding process. The The ratio of the diameter of the second electrode to the diameter of the first electrode is preferably about 1.02 or greater, more preferably about 1.06 or greater, even more preferably about 1.12 or greater, and most preferably about 1.2 or more. 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 integral metal materials. For example, the metallic fiber can be welded to a steel material selected from the group consisting of uncoated steel, hot dip galvanized steel, galvanized steel, or any combination thereof. Shape, size, concentration and type can be selected. In a particularly preferred embodiment of the present invention, the composite material may be composed of two or more different integral steels (two or more coated steels) without having to change the welding time, electrode force, welding time, or weld tip size. Non-steel, hot dip galvanized steel, or galvannealed steel) two or more integral steels with different thicknesses (one material has approximately the same thickness as the composite material and another material is With an overall high welding current range (as described hereinabove), with respect to (having a thickness of about 1.5 times or more than the composite material), or both. Thus, without having to change the welding conditions, the composite material can be welded to a surprisingly wide variety of materials and has a surprisingly wide range of thicknesses. Some changes to the welding conditions can be sought, but because of the wide welding current range, these changes can be greatly reduced over other materials.

  As an example, FIGS. 7, 8 and 9 illustrate the measurement of the welding current range for a composite material of the present invention welded to uncoated steel, galvannealed steel and hot dip galvanized steel, respectively. 7, 8 and 9 are graphs showing the welding button size according to the welding current. An acceptable or good weld may be a weld that has i) a weld button size that is greater than about 95% of the weld electrode diameter, ii) does not eject any metal, or both. For example, if an electrode diameter of about 3.8 mm is used to contact the composite material, a good weld can have a weld button size of about 3.6 mm or greater. FIGS. 7, 8 and 9 illustrate composite materials having a welding current range of about 1.5 or greater (eg, about 1.7 or greater). FIG. 7 illustrates that when welding a composite material to a first steel (eg, uncoated steel), an excellent weld can be obtained with welding currents ranging from about 6.4 kA to about 9.2 kA. To do. FIG. 8 illustrates that when welding composite materials to different steels (eg, galvannealed steel), excellent welds can be obtained with welding currents of about 7.75 kA to about 9.45 kA. FIG. 9 illustrates that when welding a composite material to another steel (eg, hot dip galvanized steel), an excellent weld can be obtained with a welding current of about 7.35 kA to about 9.35 kA. Initially, all three materials give an overall high welding current range. The current overlap (ie, overlapping weld current ranges) that results in a good weld is then generally high. For example, composite materials create superior welds with these three materials at about 7.8 kA to about 9.2 kA, with overlapping weld current ranges of about 1.4 kA or more.

  The composite material of the present invention can be used in any number of applications that require one or any combination of the properties described herein, including, but not limited to, a relatively low density, Includes relatively low thermal conductivity, relatively high stiffness to density ratio, or relatively low sound transmission. Exemplary applications that may utilize the composite material of the present invention may include applications associated with automobiles and other transportation, applications associated with building structures, and applications associated with electrical equipment. Composite materials include automotive panels, truck panels, bus panels, containers (eg containers used for shipping), train vehicles panels, jet panels, tubes (eg bicycle tubes), motorcycle panels (E.g. cowling or fairing), trailer panels, panels on recreational vehicles, panels on snowmobiles, automotive bumper fascias, spoilers, wheel well liners, aerodynamic ground effects, air dams, containers, Bed liner, divider wall, appliance housing, vehicle filler door, vehicle bumper, decorative insert, duct, handrail, storage partition door (Storage components), housings of electronic devices (cell phones, computers, cameras, tablet computers, music or video players, etc.), consoles, air inlets, battery housings, lattices, wheel wells, seat pans, etc. Can be used in applications. Composite materials include exterior trim elements, flashing, gutter, shingles, walls, flooring, countertops, cabinet fading, windows Frames, door frames, paneling, vents, ducts, blanking, framework studies, shelves, plumbing fixtures, sinks, shower pans, bathtubs, enclosures, etc. It can be used as a building structure material. An exemplary application is a vehicle body panel (e.g., a skin of a vehicle body such as an automobile). Automotive panels that can use the composite materials described herein include front quarter panels, rear quarter panels, door panels, hood panels, roof panels, or others. The automotive panel may have a Class A, Class B, or Class C surface, preferably a Class A or Class B surface, and more preferably a Class A surface. The composite material herein may also include one or more decorative exterior surfaces, or veneers such as metal veneer, wood veneer, polymer veneer, or otherwise. The outer surface may have a texture, color, or other appearance as a facing layer. For example, the outer layer of iron may be colored to assume a copper color, bronze color, brass color, gold color or some other color.

  The composite materials of the present invention may be used in processes that include coating a composite material, such as an electrodeposition coating process, a painting process, a powder coating process, or any combination thereof. When utilized, the coating process may include one or more steps to clean or otherwise prepare the surface, one or more steps to heat or bake the coating (eg, about 100 ° C. or higher, preferably about 120 ° C. or higher). Temperature), or any combination thereof. The coating may be applied by any conventional means, such as by a dipping process, a spraying process, or a process that utilizes an application tool such as a roller or brush. Thus, preferably, the composite material is free of components (eg, low molecular weight components) that leach out and contaminate the coating process bath, such as the electrocoat process bath. Similarly, the methods herein include one or more coating steps that are free of contamination of the bath by the components of the composite.

  Composite materials (eg, stamped parts formed of composite materials) can be used in assemblies that require the composite material to be coupled to one or more other materials or parts. For example, a composite material may be mechanically connected to another part using a fixture, or chemically connected to another part using an adhesive, an adhesion promoter (eg, a primer), or both. obtain. Other means of coupling include welding, brazing, and soldering. One or any combination of these linking methods can be used.

  As previously discussed, high quality lamination with peel resistance during use is possible according to the teachings herein. The resulting composite material may exhibit excellent properties that make it suitable as a steel substitute in many applications. For example, when a composite mass is subjected to a peel test under DIN 11339, the composite may have a significant amount of cohesive failure (eg, greater than about 25%, at least about 40%, 50%, 60% or more It can be well bonded to any metal layer so as to exhibit high cohesive failure. When the composite mass is subjected to a lap shear test under DIN 11465 as a result, the composite has a significant amount of cohesive failure (eg, greater than about 25%, at least about 40%, 50%, 60% Or fully bonded to any metal layer so as to exhibit a higher cohesive failure). As can be seen, reference to cohesive failure generally refers to failure that would occur within the polymer matrix, as opposed to adhesive failure that would occur between the polymer matrix and the adjacent metal layer. Thus, a large amount of cohesive failure reflects the strength of the bond between the polymer matrix and one or both of the metal layers of the sandwich composite that exceeds the internal strength of the polymer matrix material.

  Preferably, the composite material does not delaminate (eg, the metal layer does not delaminate from the core layer) during processing of the composite material to form the component or assembly or during use of the component. As such, the composite material preferably does not delaminate during the stamping operation, during the coupling operation (eg, during the welding operation), or both.

  Another aspect of the present invention contemplates a method for recycling, recycling, or both of used parts made using the present invention. One approach envisions providing a part having the composite structure taught herein and subjecting the part to a process of separating hydrocarbon compounds from the metal material (eg, by a high temperature heating process). Either or both of the hydrocarbon compound or the metal material can be recovered and reused. Another approach is to crush the composite material or otherwise recycle it by forming particles from the composite material, and the components of the core material of the composite material (composite material as described herein) Assuming that the particles are optionally provided.

EXAMPLES It should be understood that the configuration of the following examples can vary by about ± 20% and give similar results (eg, within about ± 20%). In addition, other materials taught herein can be substituted for those described and similar results are considered.

<Example 1>
The core material for the lightweight composite is about 45 g of polyamide 6 and about 72 g of stainless steel fibers having an average diameter of about 3 to 10 μm and an average length of about 2 to 4 mm at a speed of about 20 rpm. Prepared by melt mixing in a Brabender Plastograph mixer at 260 ° C. Polyamide 6 has a density of about 1.142g / cm ^3, the steel has a density of about 7.9 g / cm ^3. After mixing for about 60 minutes, the mixture is removed from the Brabender mixer. One skilled in the art will appreciate that longer or preferably shorter mixing times may be used (eg, less than about 30 minutes, less than about 20 minutes, less than about 10 minutes or even less than about 5 minutes). . Further, such mixing times can be used for other polymers of the present teachings. When prepared in this manner, Example 1 comprises about 18.8% by volume steel fibers and about 81.2% by volume polyamide 6 and has a density of about 2.41 g / cm ³ .

<Example 2>
The core material is prepared using the same method as Example 1 except that the weight of the stainless steel fibers is about 102 g and the weight of polyamide 6 is about 40 g. When prepared in this manner, the mixture comprises about 26.9% by volume steel fibers and about 73.1% by volume polyamide 6 and has a density of about 2.962 g / cm ³ .

<Example 3>
The core material is prepared using the same method as Example 1 except that the weight of the stainless steel fibers is about 35.4 g and the weight of the polyamide 6 is about 50.6 g. When prepared in this manner, the mixture comprises 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>
The core material is prepared using the same method as Example 1 except that no stainless steel fibers are used and about 53 g of polyamide 6 is mixed in a Brabender plastograph mixer. Comparative Example 5 has a density of about 1.142 g / cm ³ .

<Comparative Examples 5 to 6>
The composite material is prepared by compression molding a sandwich panel comprising two steel plates, each of the two steel plates having a thickness of about 0.20 mm, a length of about 74.2 mm, and a width of about 124.2 mm. And the polyamide 12 is placed between the metal plates without metal fibers. The steel sheet is made of No. 5 temper (aluminum killed) low carbon steel that meets AISA 1008 and ASTM A109 standards. As shown in Table 1, the core material thickness for Comparative Examples 5 and 6 is about 0.30 mm and about 0.44 mm, respectively. Comparative Examples 5 and 6 are compression molded using an indentation mold at a temperature of about 250 ° C. and a load of about 12000 kg. The overall density of the composite panel is about 32-46% by weight lower than the density of the steel used in the steel plate. The thickness-thickness electrical resistivity of Comparative Examples 5 and 6 is greater than 1 × 10 ¹⁰ Ω · cm, indicating that these panels have insulating properties. Although a stamping process is possible, attempts to weld Comparative Examples 5 and 6 to an integral steel panel result in a structure that is not welded together. These samples fail the weld test in that the weld is weaker than the panels being welded together.

<Examples 7 to 8>
Examples 7 and 8 use the method described in Comparative Example 7, except that a core material comprising about 26.9% by volume steel fibers and about 73.1% by volume polyamide 12 is used. And a composite material prepared by compression molding a sandwich panel. The steel fibers in the core material have an average diameter of about 3-10 μm and an average length of about 2-4 mm, and are mixed with polyamide 12 in a Brabender Plastograph mixer at about 260 ° C. The thickness of the core material is about 0.40 mm and about 0.57 mm for Examples 7 and 8, respectively. These samples are illustrated in Table 2. The overall density of the composite panel is about 29-36% by weight lower than the density of steel. These composite panels are welded to a steel plate having a thickness of about 0.8 mm using AC resistance welding (spot welding). A good weld (ie, a weld that provides a weld button when the weld panel is separated by force because it is stronger than the panel being welded) has a weld of about 9.7 kA at a pressure of about 600 psi. Obtained using current and 8 welding cycles. These conditions are lower than those required to weld two integral sheets of 0.8 mm thick steel (12.9 kA, 15 welding cycles, 600 psi pressure). Each weld cycle is about 1/60 second, and the welding parameters are about 1 cycle (ie about 1/60 second) slope, about 10 cycles (ie about 1/6 second) hold time, and about 1 second. Including squeezing time.

<Examples 9 to 10>
Examples 12 and 13 are the methods described with respect to Comparative Examples 5-6, except that a core material comprising about 20.2 volume percent steel fibers and about 79.8 volume percent polyamide 12 is used. And a composite material prepared by compression molding a sandwich panel. The steel fibers in the core material have an average diameter of about 3 to 10 μm and an average length of about 2 to 4 mm and are mixed with polyamide 12 in a Brabender Plastograph mixer at about 260 ° C. The core material thickness is about 0.37 and about 0.55 mm for Examples 9 and 10, respectively. These samples are illustrated in Table 2. The overall density of the composite panel is about 31-41% by weight lower than that of steel. These composite panels are welded to a steel sheet having a thickness of about 0.8 mm using AC resistance welding (spot welding). A good weld is obtained using a welding current of about 9.7 kA and 8 welding cycles at a pressure of about 600 psi.

  The stiffness and density of Example 9 and the integral steel sheet of the same steel used in the metal layer of Example 9 both have a thickness of about 0.87 mm, which are measured in the thickness direction. Example 9 is expected to have a higher stiffness to density ratio than an integral sheet of steel.

<Example 11>
The composite sample of Example 11 is prepared by compression molding a sandwich panel using the method described with respect to Comparative Example 5, except that Example 3 is used for the core material. The composite panel sample is welded to a steel plate having a thickness of about 0.8 mm using AC resistance welding (spot welding). A good weld is obtained using a welding current of about 9.7 kA and 8 welding cycles at a pressure of about 600 psi.

<Examples 12 to 14>
Examples 12 to 14 are pure polymers and mixtures of stainless steel fibers and polymers prepared using the method of Example 1. Examples 12 through 14 are prepared using polyamide 6 with about 0 wt%, about 3 wt%, and about 10 wt% stainless steel fibers with respect to Examples 12, 13 and 14, respectively. The tensile modulus of the core material of Example 12 is about 3.3 GPa. When steel fibers are added at a concentration of about 3% by weight (Example 13), the tensile modulus increases by over 17% to about 3.9 GPa. When steel fibers are added at a concentration of about 10% by weight (Example 14), the tensile modulus increases by over 100% to about 7.3 GPa. The polyamide is replaced with a copolyamide and the concentration of stainless steel fibers is about 0%, about 3%, and about 10% by weight for Examples 15, 16 and 17, respectively. The tensile modulus of the core material of Example 15 is about 700 MPa. When steel fibers are added at a concentration of about 3% by weight (Example 16), the tensile modulus increases by 50% or more to about 1160 MPa. When steel fibers are added at a concentration of about 10% by weight (Example 17), the tensile modulus increases by over 200% to about 2280 MPa. Thus, in general, this and other embodiments of the invention taught herein are preferably more than the tensile modulus of filled polymeric materials (eg, core layer materials) that do not include steel fibers but have the same composite. Characterized by a tensile modulus of the filled polymeric material (eg, core layer material) comprising steel fibers, at least 15%, more preferably at least 50% or more, even more preferably at least about 100%, most preferably at least about 200% larger Attached.

<Examples 15 to 20>
Examples 15-20 are prepared by mixing steel fibers and thermoplastics in a Brabender mixer using the polymer and steel fiber concentrations shown in Table 3. The composite material is then prepared by molding a sandwich having a 0.4 mm fiber-filled thermoplastic layer between two 0.2 mm thick steel plates. The plate thickness electrical resistivity of the composite material was measured using AC modulation and is shown in Table 3. All of the thermoplastics filled with the composite material have a relatively low electrical resistivity, and all of the unfilled thermoplastics have a relatively high electrical resistivity.

<Example 21>
The filled thermoplastic is about 15% by volume low carbon steel fiber having a diameter of about 4 to about 40 μm and a length of about 1 to about 10 mm, about 50% by weight polyamide 6 and about 50% by weight. About 85% by volume copolyamide of polyamide 6,9 (modulus of elasticity of about 300 MPa measured according to ISO 527-2, melting point of about 130 ° C. measured according to ISO 11357, and measured according to ISO 527-3 A copolymer characterized by an elongation at break of about 900%). The filled thermoplastic material is mixed at a temperature of about 190 ° C to about 250 ° C. Thereafter, the filled thermoplastic is placed between two low carbon steels, each having a thickness of about 0.2 mm. The material is then compressed at a temperature of about 220 ° C. to about 230 ° C. and a pressure of about 1 to about 22 MPa. The composite material has a core thickness of filled thermoplastic material of about 0.4 mm. The composite material is stamped in a high speed stamping operation with a drawing ratio greater than about 3, and no cracks or other surface defects are observed. After stamping, the surface of the composite material is relatively smooth compared to the surface of an integral low carbon steel sample having the same overall thickness and stamped under the same conditions. The composite material is then subjected to a typical e-coat process and painted with a primer and black paint. The painted surface has a smooth finish with no pitting, orange peeling and other visible surface defects. The painted surface is characterized as a Class A finish. The surface of the painted composite material is smoother than the surface of a similarly treated monolithic sample of low carbon steel having a thickness of about 0.8 mm.

<Example 22>
The composite material is prepared using the same materials, composites and methods as Example 21, except that the fiber is replaced with a low carbon fiber having a generally rectangular cross section in a direction perpendicular to the length of the fiber. Is done. The fibers have an average length of about 2.3 mm. The average cross-sectional area of the fiber is about 0.0045 mm ² . The ratio of width to fiber thickness is about 2 to 8. The composite material has a thickness of about 0.8 mm. The composite material is stacked with a sample of cold rolled steel having a thickness of about 0.8 mm. The stack is placed on a spot welding machine between a pair of welding tips having a diameter of about 13 mm. A force of about 2.2 kNt is applied to the welding tip. The resistance of the composite material in the thickness direction is measured while being subjected to a force of 2.2 kNt. When measured in this way, the electrical resistivity of the composite material of Example 22 is about 0.1Ω or less. When welded using a typical welding scheme for two sheets of cold rolled steel having a thickness of about 0.8 mm, the composite material is welded to the cold rolled steel and is larger than the diameter of the weld tip. Create a weld button with a diameter. No extra heating, extra welding cycles, and no extra current are required to create a better weld in Example 22.

<Example 22B>
Example 22B is identical to Example 22 except that the concentration of metal fibers in the filled polymer material is increased by about 20 volume percent and the concentration of polymer is decreased by about 80 volume percent. The composite material of Example 22B is welded to a piece of galvanized steel having a thickness of about 0.8 mm. An electrode with a surface diameter of about 3.8 mm is used on the side of the weld stack with the composite material, and an electrode with a surface diameter of about 4.8 mm is used on the side with the galvanized steel. A force of about 610 lBs is applied to the weld stack by the electrodes. The material is welded using a medium frequency DC weld having a frequency of about 1,000 Hertz. Each weld is made on a sample having a width of about 25 mm and a length of about 75 mm. The welding time is constant at about 200 milliseconds. Welding is done using welding currents ranging from about 8.8 kA to over 13 kA. The weld button size on the composite plate is measured after welding is complete. The welding button size and the welding current for each welding sample (46) are shown in diagram 30 in FIG. At the low welding current provided by region (44), the weld button size is less than 95% of the diameter of the electrode (36) used in the face of the composite material during the welding process. With the intermediate welding current exemplified by region (40), the button size is greater than 95% of the diameter of electrode (36). With the welding current exemplified by region (42), metal discharge and / or loud popping noise is produced and the resulting weld is unacceptable. The minimum welding current (34) to obtain an acceptable weld is about 10 kA for Example 22B. The maximum welding current (32) to obtain 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). When measured in this way, the welding current range for Example 22B is about 3.0 kA. For comparison, the welding current range is for a welding stack consisting of two integral sheets of galvanized steel, each having a thickness of about 0.8 mm measured in the same way, about 1 Determined to be less than 3 kA. Surprisingly, the composite material of Example 22B is easier to weld than galvanized steel as measured by its higher welding current range (ie, has a wider processing window for welding). ).

<Example 22C>
The welding current range is measured for a weld stack consisting of two integral galvannealed steels, each having a thickness of about 0.8 mm similarly measured, and determined to be less than about 1.3 kA. Is done. The welding current range is measured using the same method as for Example 228. Surprisingly, the composite material of Example 228 is easier to weld than galvanized steel, as measured in its higher welding current range (eg, compared to Example 22C). (Ie having a wider processing window for welding).

<Example 22D>
Example 22D is a composite with the same composition, filled thermoplastic polymer, and structure as Example 228. Except that the load on the weld is about 2.76 kN (about 600 lb), the upslope time is about 50 milliseconds, the welding time is about 300 milliseconds, and the initial welding current is about 8-9 kA The welding current range of Example 220 is measured using the same conditions as Example 228. The welding current range is first measured on a weld stock consisting of the composite material of Example 220 and an uncoated deep drawn quality steel (Le., 000) having a thickness of about 1.2 mm. . The weld button size is measured at different welding currents as shown in FIG. An excellent weld, characterized by i) a button size diameter of about 3.6 mm or more, and ii) no discharge of metal, has a welding current of about 6.4 kA to about 9.2 kA. Sometimes obtained. The welding current range is determined to be about 2.8 kA to weld Example 22D to a 1.2 mm thick uncoated DDW.

  Next, a weld stack consisting of composite material and 0.8 mm thick galvanized steel is prepared and welded using the same conditions as for uncoated DOC steel. Surprisingly, excellent welds are obtained without changing the upslope time, welding time, initial welding current, or load on the welding tip. The weld button is measured at different welding currents as shown in FIG. An excellent weld, characterized by i) a button size diameter of about 3.6 mm or greater, and ii) no discharge of metal, has a welding current of about 7.75 kA to about 9.45 kA. Sometimes obtained. The welding current range is determined to weld the composite material of Example 22D to 0.8 mm thick galvanized steel.

  The composite material of Example 22D is also welded to hot dip galvanized steel (Le., HOG) having a thickness of about 1.5 mm. A weld stack made of composite material and a 1.5 mm thick HDG are prepared and welded using the same conditions as for uncoated DDQ steel. Surprisingly, excellent welds are obtained without changing the upslope time, welding time, initial welding current, or load on the welding tip. The weld button is measured at different welding currents as shown in FIG. An excellent weld, characterized by i) a button size diameter of about 3.6 mm or more, and ii) no discharge of metal, when the welding current is about 7.35 kA to 9.35 kA Is obtained. The welding current range is determined to be about 2.0 kA to weld the composite material of Example 220 to a 1.5 mm thick HOG.

  Surprisingly, the same welding conditions can be used to weld the composite material to different types of steel (eg, 000, HOG, or galvanized steel). Furthermore, the composite material can be welded to steel (Le, 0.8 mm to 0.8 mm × 187% = 1.5 mm) with a thickness that varies by about 87% without changing the welding conditions. It is amazing to be. It is also surprising that for different types of steel and different thickness steels, welding to composite materials is characterized by an overall wide welding current range.

<Example 23>
The composite material is that of Example 21, except that the steel sheet is replaced with a 0.2 mm thick high strength steel having a yield strength of about 359 MPa, a tensile strength of about 460 MPa, and an elongation of about 22%. Prepared using the same materials, composites and methods. The composite material is expected to have a yield strength of about 193 MPa, a tensile strength of about 253 MPa, and an elongation of about 22%. The density of the composite is expected to be about 34% lower than a single sheet of low carbon steel having the same thickness (about 0.8 mm). The composite material is expected to have a yield strength that is about 50 MPa or more than the yield strength of an integral sheet of low carbon steel having the same thickness. The composite material is expected to have a tensile strength that is at least about 90% of the tensile strength of a single sheet of low carbon steel having the same thickness. The composite is expected to have a flexural modulus that is at least about 85% of the flexural modulus of an integral sheet of low carbon steel having the same thickness.

  As used herein, unless otherwise specified, the teachings may exclude any component of a category (list) from the category and / or exclude any component of a Markush classification from the category. Assume that you get.

  Unless otherwise specified, any numerical value set forth herein is high from one unit step low value, assuming there is a separation of at least two units between any low value and any high value. Includes all values up to the value. By way of example, if the amount of a component, a property or a value of a process that can be changed, eg temperature, pressure, time, etc. is stated, eg 1 to 90, preferably 20 to 80, more preferably 30 to 70 For example, intermediate range values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 are within the scope of the teachings herein. Similarly, individual intermediate values are also within the scope of the teachings of the present invention. For values that are less than 1, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 as appropriate. These are just examples of what is specifically specified, and all possible combinations of numerical values between the lowest and highest values listed are expressly described in this application in a similar manner. Shall be considered. As will be appreciated, the teachings of quantities expressed herein as “parts by weight” consider the same ranges expressed in terms of weight percent. Accordingly, expressions in the detailed description of the invention, in terms of the “x” parts by weight of the resulting polymer blend composition, are similarly enumerated for x in weight percent of the resulting polymer blend composition. Taking into account the teachings on the range of quantities.

  Unless otherwise specified, all ranges include both endpoints and all numbers between endpoints. The use of “about” or “approximately” in relation to a range also applies to both ends of the range. Thus, “about 20 to 30” is intended to range from “about 20 to about 30” and includes at least the designated endpoint.

  The disclosures of all articles and citations, including patent applications and publications, are incorporated by reference for all purposes. The term “consisting essentially of” describing a combination is intended to include the specified element, component, component or process, such element, component, component or process being the basis of said combination and Does not substantially affect new features. The term “comprising or including” for describing a combination of an element, component, component, or process described herein consists of, or consists essentially of, an element, component, component, or process. Consider an embodiment that even consists of:

  Multiple elements, components, components or processes may be provided by a single integrated element, component, component or process. Alternatively, one integrated element, component, component or process may be divided into separate multiple elements, components, components or processes. The disclosure of “a” or “an” to describe an element, component, component or process is not intended to exclude an additional element, component component or process. References in this specification to elements or metals belonging to a specific class refer to copyrighted Periodic Table of the Elements, published in 1989 by CRC Press, Inc. Any reference to a classification (Group or Groups) should be taken to be a classification (Group or Groups) reflected in this Periodic Table of the Elements, using the IUPAC system to number the classifications. To do.

  As used herein, the terms “polymer” and “polymerization” are generic and are either the more specific cases of “homopolymer and copolymer” and “homopolymerization and copolymerization”, respectively. Or both can be included.

  The above description is intended to be illustrative and non-limiting. Many examples and many applications in addition to the provided examples will be apparent to those skilled in the art after reading the above description. The scope of the invention should, therefore, be determined not with reference to the above description, but should be determined with reference to the appended claims along with the full scope of equivalents to which such claims are entitled. is there. The disclosures of all articles and citations, including patent applications and publications, are incorporated by reference for all purposes. Abbreviations in the following claims of any aspect of the subject matter disclosed herein do not disclaim such subject matter, and the inventor deems such subject matter to be the subject of the inventive subject matter disclosed. It should not be considered part of it.

Claims (1)

A composite material for welding ,
A first metal plate, a second metal plate, and an extrudate of filled polymer material attached to the first metal plate;
The filled polymer material is
a)
i) a first thermoplastic polymer, and
ii) a polymer-based matrix comprising a blend of a second thermoplastic polymer that, unlike the first thermoplastic polymer, is an elastomer, an ionomer, or both;
b) to form a filled polymer material comprising a polymer-based matrix, comprising a mass of metal fibers distributed throughout the polymer-based matrix;
The mass of metal fibers is present from about 3% to about 25% by volume, based on the total volume of the filled polymer material, generally extending in the thickness of the filled polymer material and comprising a plurality of metal fibers;
The metal fibers are steel fibers, have a weight average length of about 0.5 mm to about 7 mm, have a ribbon fiber shape with a generally rectangular cross section, and a ratio of width to thickness. There about 2 about 20, and are entangled with each other, the composite material for welding.