Patent Grant
9233526
The invention relates to multi-layered composite materials and methods for making multi-layered composite materials having good adhesion between the layers. The composite materials generally include metal layers and a polymeric core layer interposed between the metal layers. The adhesion between the layers may be improved by treating a surface of the metal layer, dispersing a filler (e.g., a filler having a high aspect ratio, such as a flake or fiber) into the polymeric core layer, or both.
The adhesion between polyolefins and aluminum has long be recognized as being poor due to the generally hydrophobic characteristic of polyolefins. For example, the adhesion between polyethylene and aluminum is generally low and for nearly all applications, an improvement in the adhesion of the polyolefin and aluminum is required. Various approaches have been employed to improve the adhesion between aluminum and polyolefins. These include treating the surface of either the polymer or the aluminum, using an adhesive coating or primer, and adding functional groups to the polymer. Examples of these approaches are described in U.S. Pat. Nos. 3,035,953, 3,470,056, and 3,635,938, and in U.S. Patent Application Publication No. US 2011/0129887 A1, and in Hjertberg et al., “Functional Group Efficiency in Adhesion between Polyethylene and Aluminum”, J. of Applied Polymer Science, Vol. 37, 1287-97 (1989), the contents of which are all incorporated herein by reference.
These approaches require the use of special polymers, additional layers of material between the polymer and the aluminum, or special treatments steps, which can be costly, affect the performance of the composite, alter the physical properties of the material. Furthermore, some of these approaches only provide marginal improvements in adhesion.
There continues to be a need for new composite materials and new methods for producing the composite materials having good adhesion between an aluminum layer and a polyolefin layer. For example there is a need for such materials that does not rely on the use of a functionalized polymer, does not rely on the use of polymeric coating, or both.
The adhesion between a polymer layer and a metal layer of a multi-layered composite material may be improved by a process including a step of pre-treating a surface of the metal layer prior to contacting the metal surface with the polymer layer, and by including filler particles in the polymer layer. Using this approach, it is possible to increase the peel strength by about 10% or more, by about 20% or more, by about 40% or more, or by about 100% or more, compared with an otherwise identical composite material that does not include both of these features.
One aspect of the invention is directed at a process for preparing a composite material comprising the steps of: contacting a surface of a metal foil with a metal phosphate for cleaning the surface, for coating the surface, or both; contacting the surface of the metal foil with a filled polymeric core material: and adhering the filled polymeric core material to the surface of the metal foil using heat, pressure, or both; wherein the filled polymeric core material includes about 2 volume percent to about 50 volume percent metal particles; and about 50 volume percent to about 98 volume percent of one or more polyolefin resins, wherein the polyolefin resin includes about 65 weight percent of an α-olefin.
Another aspect of the invention is directed at a process for preparing a composite material comprising the steps of: contacting a surface of a metal foil with a solution including a fluoride, for sealing the surface, rinsing the surface, or both; contacting the surface with a filled polymeric core material; and adhering the filled polymeric core material to the surface of the metal foil using heat, pressure, or both; wherein the filled polymeric core material includes about 2 volume percent to about 50 volume percent metal fibers; and about 50 volume percent to about 98 volume percent of one or more polyolefin resins, wherein the polyolefin resin includes about 65 weight percent of an α-olefin.
Another aspect of the invention is directed at a composite material prepared using a method according to the teachings herein.
Yet another aspect of the invention is directed at a process for preparing a composite material comprising: (i) one or more steps of pretreating an aluminum foil selected from the group consisting of (a) washing the surface of the aluminum foil with an alkaline solution; (b) washing the surface of the aluminum foil with an acid solution; (c) contacting a surface of the aluminum foil with a metal salt; and (d) contacting a surface of the aluminum foil with a solution including a fluoride; (ii) contacting the surface with a filled polymeric core material; and (iii) adhering the filled polymeric core material to the surface of the aluminum foil using heat, pressure, or both; wherein the filled polymeric core material includes about 2 volume percent to about 50 volume percent metal fibers; and about 50 volume percent to about 98 volume percent of one or more polyolefin resins, wherein the polyolefin resin includes about 65 weight percent of an α-olefin.
This application claims priority to U.S. Provisional Patent Application 61/679,229 entitled Composites Having Improved Interlayer Adhesion and Methods Thereof, filed on Aug. 3, 2012 by Chadwick Lee Van Sweden, which is incorporated herein by reference in its entirety.
The composite materials according to the teachings herein include a polymeric layer, such as a polymeric core layer, having a surface that faces a metal layer. The composite material may be a laminate, such as a laminate having a single metal layer, or the composite material may be a sandwich material including a polymeric core layer interposed between two metal layers. Although the composite may include additional layers, preferred composite materials consist essentially of, or consist entirely of the metal layer(s) and a single polymeric layer. For example, the composite material have two layers including a single metal skin layer or the composite material may have three layers including two metal skin layers with the polymeric core layer sandwiched between the skin layers. Such a composite material may be used in applications, such as transportation applications, where weight reduction from a polymeric core layer is desirable. These composite materials according to the teachings herein also have good forming capabilities so that they can be stamped, similar to the stamping of a monolithic sheet of steel. Examples of sandwich composite materials that offer weight reductions relative to monolithic sheets of steel and having good forming capabilities are described in U.S. Patent Application Publications US2010/0040902 A1 (by Mizrahi, published on Feb. 18, 2010), US 2011/0188927 A1 (by Mizrahi, published on Aug. 4, 2011), US 2011/0200816 A1 (by Mizrahi et al., published on Aug. 18, 2011), and PCT Patent Application Publication WO 2012/010115 A1 (by Mizrahi et al., published on Feb. 9, 2012) each incorporated herein by reference in their entirety.
Improvements in the adhesion between a surface of a polymeric layer and a surface of a metal layer have been achieved by i) employing filler particles, such as filler particles having an aspect ratio of about 10 or more in the polymeric layer; ii) pre-treating the surface of the metal layer prior to contacting with the polymeric layer; or both. In particular, it may be beneficial to employ both i) the filler particles having an aspect ratio of about 10 or more in the polymeric layer and ii) a step of pre-treating the surface of the metal layer to achieve adhesion results superior to that obtained by employing ether i) or ii) alone.
The composite material according to the teachings herein may include one or more features of the cross-section of the multi-layered composite material 10 illustrated in
The composite material may be provided in any shape. For example, the composite material 10 may be in the form of a sheet 40 such as illustrated in
The adhesion between the core layer and the metal layers 14 may be evaluated using a T-peel test. Features that may be employed in the preparation of the test specimens for a T-peel test are illustrated in
It will be appreciated that a plurality of specimen may be prepared at that same time, such as illustrated in
The process for preparing the T-peel specimen generally includes heating and pressing process 70, such as illustrated in
The orientation of the test specimen for the T-peel test is shown in
The metal layers may be made of a suitable material (e.g., metal, or metal alloy) in the form of foils or sheets or other layers having equal or unequal thickness (e.g., average thickness) across the layer. Each metal layer may have a generally constant thickness or may have a thickness that varies. In the composite material including two or more metal layers, one or two metal layers may be on outside faces of the composite material (i.e., the composite material may have one or more face metals). The face metal on each side of a composite may be made of materials having the same or different properties and be made of the same or different metals. If the metal faces are made of metal layers of different thickness, metal to having different properties, or metal layers having different metals, the composite material have a marking or other means of identifying and distinguishing the different metal faces. The metal layers may be the same or different in composition, size (e.g., thickness, width, length, volume, or otherwise), shape, or other features, relative to each other layer. The metal layer and the polymeric layer preferably have substantially the same width or length, and more preferably have the same width and length.
Examples of metal layers that may be employed are described in described in international Patent Application Publication WO 2010/021899 (published on Feb. 25, 2010 by Mizrahi), see for example paragraphs 082-091, and US Patent Application Publication US 2011/0200816 A1 (published on Aug. 18, 2011 by Mizrahi et al.), see for example paragraphs 81-87, both incorporated herein by reference.
One exemplary metal layer is an aluminum foil. As used herein, an aluminum foil is a foil that includes at least 30 wt. % aluminum atoms, based on the total weight of the foil. The concentration of aluminum in the foil preferably is about 40 wt. % or more, more preferably about 50 wt. % or more, even more preferably about 70 wt. % or more, even more preferably about 80 wt. % or more, and most preferably about 90 wt. % or more, based on the total weight of the foil. The aluminum foil may be essentially pure aluminum or may be an alloy including aluminum atoms a concentration of about 99% or less, or about 95% or less, based on the total weight of the alloy.
Preferred metal layers are foils have a generally uniform thickness along the width direction. Preferred metal layers are foils have a generally uniform thickness along the length direction. A foil having generally uniform thickness may have a thickness range (i.e., difference between maximum thickness and minimum thickness), a standard deviation of thickness, or both, that is about 10% or less of the average thickness, about 5% or less of the average thickness, or about 2% or less of the average thickness.
The thickness of the metal layer should be sufficiently low so that the weight of the composite material is reduced relative to a monolithic metal material. For example, the ratio of the thickness of one metal layers to the total thickness of the composite may be about 40% or less, about 30% or less, about 20% or less, or about 15% or less. The ratio of the total thickness of all of the metal layers to the total thickness of the composite may be about 80% or less, about 60% or less, about 50% or less, about 40% or less, or about 30% or less. The total thicknesses of all of the metal layers is typically about 2 mm or less, about 1 mm or less, about 0.7 mm or less, or about 0.4 mm or less. It will be appreciated that the metal layers of the composite material according to the teachings herein may also have a total thickness greater than about 2 mm.
The thickness of the metal layer should be sufficiently high so that the layer does not tear or otherwise fail during processing or use. For example the ratio of the thickness of the metal layer to the total thickness of the composite may be about 1% or more, about 2% or more, about 3% or more, about 5% or more, about 10% or more, or about 15% or more. The total thicknesses of all of the metal layers is typically about 0.05 mm or more, about 0.10 mm or more, about 0.15 mm or more, about 0.20 mm or more, about 0.25 mm or more, about 0.30 mm or more. It will be appreciated that the metal layers of the composite material according to the teachings herein may also have a total thickness less than about 0.05 mm.
The surface of the metal layer that contacts the polymeric layer may be free of any polymeric coating (e.g., prior to contacting the metal layer and the polymeric layer). The surface of the metal layer that contacts the polymeric layer may be free of any primer or adhesive.
The composite material includes one or more polymeric layers having a density less than the density of the metal layer so that the composite material is relatively light weight compared with the metal of the metal layer. The polymeric layer (e.g., the polymeric core layer) preferably is a layer in the composite material that contacts one or two metal layers. For example the polymeric core layer may be a layer that substantially, or entirely fills the volume between two stacked and spaced apart metal layers.
The polymeric core layer preferably includes a filled polymeric material. The filled polymeric material includes, consists essentially of, or consists entirely of one or more polymers resins and one or more fillers. The concentration of the filler in the filled polymeric material may be sufficiently high so that the adhesion between the polymeric layer is increased compared to a composite material having a polymeric core layer of the same thickness and same polymer(s) with the same metal layers. The concentration of the filler in the filled polymeric material may be sufficiently high so that the composite can pass an electric current. The concentration of the filler in the filled polymeric material may be sufficiently high so that the composite material can be passed through an electro-coating process without fouling any solutions employed in the elecro-coating process with the polymer resin of the filled polymeric material.
In various aspects of the invention, it may be desirable for the filled polymeric material to be an electrically insulating layer. As such, the concentration of the filler (e.g., the metal fiber) may be sufficiently low so that the filled polymeric layer does not generally pass an electric current, across its thickness. For example, the filled polymeric layer may have an electrical resistivity of about 1,000 Ω·cm or more, about 104 Ω·cm or more, about 105 Ω·cm or more, about 5×105 Ω·cm or more, about 106 Ω·cm or more, or about 107 Ω·cm or more. For example, the concentration of the filler may be i) sufficiently high so that the adhesion between the metal layer and the polymer layer is increased and/or the composite material is capable of being electro-coated without fouling any solution in the elecro-coating process; and ii) sufficiently low so that the filled polymeric material does not pass an electric current.
The polymer resin includes one or more polymers and optionally includes one or more additives. The additives, if employed may be provided with the polymer, or may be added in one or more compounding steps. The filled polymeric material, the polymer and the additives may include one or more of the features of the polymers and additives described in International Patent Application Publication WO 2010/021899 (published on Feb. 25, 2010 by Mizrahi), see for example paragraphs 15-22, 29-51, and 85-91, and US Patent Application Publication US 2011/0200816 A1 (published on Aug. 18, 2011 by Mizrahi et al.) see for example paragraphs 27-51 and 88, both incorporated herein by reference.
The polymer resin, the filled polymeric material (e.g., the polymer of the filled polymeric material), or both, may optionally include one or more additives known to the polymer compounding art, such as described in International Patent Application Publication WO 2010/021899 (published on Feb. 25, 2010 by Mizrahi). For example, the filled polymeric material, the polymer resin, or both, may include halogenated flame retardant compounds disclosed in U.S. Pat. No. 3,784,509 (Dotson et. al., Jan. 8, 1974, see for example the substituted imides described in column 1, line 59 through column 4, line 64), U.S. Pat. No. 3,868,388 (Dotson et al. Feb. 25, 1975, see for example the halogenated bisimides described in column 1, line 23 through column 3, line 39); U.S. Pat. No. 3,903,109 (Dotson et al. Sep. 2, 1975, see for example the substituted imides described in column 1, line 46 through column 4, line 50); U.S. Pat. No. 3,915,930 (Dotson et al. Oct. 28, 1975, see for example halogenated bisimides described in column 1, line 27 through column 3, line 40); and U.S. Pat. No. 3,953,397 (Dotson et al. Apr. 27, 1976, see for example the reaction products of a brominated imide and a benzoyl chloride described in column 1, line 4 through column 2, line 28), each of which is incorporated by reference in its entirety. The polymer resin, the filled polymeric material or both, may include one or more additives to improve the drawing (e.g., stamping) of the composite material. The polymer resin, the filled polymeric material or both may include one or more additives for controlling (e.g., increasing or decreasing) the shrinkage of the filled polymeric material when the filled polymeric material is cooled from a melt state to a solid state. The polymer may be substantially free of, or entirely free of additives that reduce the adhesion between the polymer and a metallic layer (e.g., an aluminum layer).
The filled polymeric material, the polymer resin, or both, may be free of a plasticizer or other relatively low molecular weight materials which may become volatilized (e.g., during a resistance welding process). If employed, the concentration of plasticizer or other generally low molecular weight materials (e.g., having a molecular weight of about 200 or less) preferably is less than about 3 wt. %, more preferably less than about 0.5 wt. %, and most preferably less than about 0.1 wt. % based on the total weight of the filled polymeric material, based on the total weight of the polymer resin, or both.
The polymer resin preferably includes one or more polyolefin polymers. For example the polymer resin may include, consist essentially of, or consist entirely of polyolefin polymers and optionally one or more additives. The total concentration of the additives and the polyolefin polymers in the polymer resin may be about 90 wt. % or more, about 92 wt. % or more, about 94 wt. % or more, about 96 wt. % or more, about 98 wt. % or more, or about 100 wt. %, based on the total weight of the polymer resin.
As used herein, a polyolefin polymer is a polymer that consists essentially of, or consists entirely of one or more olefins. The concentration of the one or more olefins preferably is about 95 wt. % or more, more preferably about 98 wt. % or more, even more preferably about 99 wt. % or more, even more preferably about 99.5 wt. % or more, even more preferably about 99.9 wt. % or more, and most preferably about 99.96 wt. % or more, based on the total weight of the polyolefin polymer. The concentration of the one or more olefins may be about 100%, or may be about 99.99% or less, based on the total weight of the polyolefin polymer. Preferred olefins that may be employed in the polyolefin polymer include α-olefins having from 2 to 20 carbon atoms. For example, the polyolefin polymer may include, consist, essentially of, or consist entirely of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. The polyolefin polymer may be classified based on the primary monomer the monomer that is present in the highest concentration in units of weight percent). For example, the polyolefin polymer may be a polyethylene, a polypropylene, a polybutene, or a polyhexene, where the primary monomer is respectively ethylene, propylene, butane, and hexene. The primary monomer preferably is present at a concentration of about 50 wt. %, or more, more preferably about 60 wt. % or more, even more preferably about 65 wt. % or more, even more preferably about 70 wt. % or more, and most preferably about 75 wt. % or more. Particularly preferred polyolefin polymers include polyethylene homopolymers, polyethylene copolymers, polypropylene homopolymers, and polypropylene copolymers. The total concentration of ethylene, propylene, butane, hexene and octene in the polyolefin polymer is preferably is about 95 wt. % or more, more preferably about 98 wt. % or more, even more preferably about 99 wt. % or more, even more preferably about 99.5 wt. % or more, even more preferably about 99.9 wt. % or more, and most preferably about 9996 wt. % or more, based on the total weight of the polyolefin polymer.
The polyolefin polymer may be prepared by any suitable polymerization process. Particularly preferred polyolefin polymers are polymerized using a Ziegler-Natta catalyst or a single site catalyst, such as a metallocene catalyst.
The polymer (e.g., the polyolefin polymer) may be a homopolymer or a copolymer. The polymer (e.g., the polyolefin polymer) preferably is a thermoplastic polymer having a final melting point of about 70° C. or more. The polymer (e.g., the polyolefin polymer) may be a thermoplastic polymer having a crystallinity of about 5% or more, about 10% or more, about 15% or more, about 20% or more, or about 25% or more. The polymer (e.g., the polyolefin polymer) may be a thermoplastic polymer having a crystallinity of about 75% or less, about 70% or less, or about 60% or less. Crystallinity of the polymer may be measured using differential scanning calorimetry by measuring the heat of fusion and comparing it to art known heat of fusion for the specific polymer (e.g., having the same polymer crystals).
The thermoplastic polymer may be selected so that it includes relatively long chains, such that they may have a number average molecular weight greater than about 20,000, preferably greeter than about 60,000, and most preferably greater than about 140,000.
The polymer preferably is selected so that it has a melt index sufficiently high so that the polymer can be processed using extrusion equipment. Preferred polymers have a flow rate of about 0.05 g/10 min or more, about 0.1 g/10 min or more, or about 0.3 g/10 min or more as measured according to ASTM D1238 at 190° C./2.16 kg. The polymer preferably has a melt index sufficiently low so that the polymer has good mechanical properties. Preferred polymers have a melt flow rate of about 1000 g/10 min or less, about 200 g/10 mm or less, about 50 g/10 min or less, about 20 g/10 min or less, or about 4 g/10 min or less as measured according to ASTM D1238 at 190° C./2.16 kg.
The polymer may include a polyolefin plastomer. The polyolefin plastomer may include, consist essentially of, or consist entirely of two or more α-olefins having 2 to 20 carbon atoms. For example, the polyolefin plastomer may include a first α-olefin having 2 or 3 carbon atoms, and a second α-olefin having more carbon atoms than the first α-olefin. Preferred second α-olefins include butene, hexene, and octene. Suitable α-olefins may have one or more double bonds. Preferred α-olefins have exactly one double bond. The first α-olefin and the second α-olefin preferably have exactly one double bond. The concentration of α-olefins having more than one double bond preferably is about 15 wt. % or less, more preferably about 5 wt. % or less, even more preferably about 2 wt. % or less, even more preferably about 1 wt. % or less, and most preferably about 0.3 wt. % or less, based on the total weight of the plastomer. The concentration of α-olefins having more than one double bond may be 0, or may be about 0.1 wt. % or more. The concentration of the α-olefins having one exactly one double bond (e.g., the concentration of the first α-olefin and the second α-olefin) preferably is about 85 wt. % or more, more preferably about 95 wt. % or more, more preferably about 98 wt. % or more, even more preferably about 99 wt. % or more, based on the total weight of the polyolefin plastomer. The concentration of α-olefins having exactly one double may be 100 wt. % or may be about 99.9 wt. % or less. The polyolefin plastomer may be an ethylene plastomer including about 50 wt. % or more ethylene monomer. The polyolefin plastomer may be a propylene plastomer including about 50 wt. % or more propylene monomer. Preferably the second monomer is present at a concentration of about 20 wt. %, more preferably about 30 wt. % or more. Preferred polyolefin plastomer have a melting temperature of about 50° C. or more, about 60° C. or more, or about 70° C. or more. Preferred polyolefin plastomers have a melting temperature of about 110° C. or less, about 105° C. or less, about 100° C. or less, about 95° C. or less, or about 90° C. or less. Preferred polyolefin plastomers have a crystallinity of about 1% or more, about 2% or more or about 5% or more. The crystallinity of the polyefin plastomer preferably is about 35% or less, more preferably about 25% or less, and most preferably about 20% or less. Examples of polyolefin plastomers that may be employed include EXACT, commercially available from ExxonMobil Chemical Company, and ENGAGE available from Dow Chemical Company.
The filled polymeric material includes one or more particulate fillers. The filled polymeric material preferably includes a sufficient concentration of particulate filler so that the peel strength of the filled polymeric material and the metal layer is increased. For example, the filled polymeric material may include a sufficient concentration of particulate filler so that when used as a core material between two metal layers that have been pretreated according to the teachings herein, the peel strength is about 25% or more greater than the peel strength when no filler particles are employed in the filled polymeric material. Preferred particulate fillers are fillers having a generally high aspect ratio, such as an aspect ratio of about 10 or more.
Examples of particulate fillers having a high aspect ratio include fillers having particle shapes that are fibers, or plates. Fibers have one dimension, (e.g., a length), that is substantially greater in distance than the dimensions in the other directions (e.g., directions orthogonal to the length, such as width and thickness, or diameter). The fibers may be straight or bent. If the fibers are bent, the length of the fiber is defined by the curvilinear distance in the long direction. Plates have two or more dimension (e.g., a length and a width, or a diameter) that are substantially greater in distance than a third dimension (e.g., in a direction orthogonal to the first two dimensions, such as a thickness). The plate may be flat or may have curvature. If the plat has curvature, it may have only regions with concave curvature, only regions with convex curvature, or both regions with concave curvature and regions with convex curvature. The plate like particle may have a regular shape such as a geometric. For example the plate shaped filler particles may be flakes that have curvature and an irregular shape. The aspect ratio may be defined by the ratio of the length of the particle filler (e.g., fiber, plate, or otherwise) to the thickness of the particulate filler. Particularly preferred particulate fillers are characterized as having an aspect ratio of about 10 or more, more preferably about 20 or more, even more preferably about 30 or more, more preferably about 50 or more, and most preferably about 100 or more.
The particulate filler may have a relatively high stiffness compared to the polymer of the filled polymeric material so that the stiffness of the filled polymeric material is increased. For example, the ratio of the modulus of the particulate filler to the modulus of the polymer may be about 1.3 or more, about 2 or more, about 5 or more, about 10 or more, or about 30 or more.
Preferred particulate fillers are sufficiently ductile so that they can deform without fracturing, such as during a step of forming the composite material and/or during use of the composite material. For example, preferred particulate fillers are not brittle at temperatures between −40° C. and 120° C., such that they can be strained by about 5% or more, by about 10% or more, or by about 15% or more, in a tensile mode at a rate of about 25 mm/min. If any brittle particulate filler is employed in the filled polymeric material, they preferably are present at a concentration of about 25 weight percent or less, more preferably about 10 weight percent or less, and most preferably about 4 weight percent or less, based on the total weight of the particulate fillers in the filled polymeric material. The filled polymeric material preferably is substantially (e.g., about 2 weight percent or less, or about 1 weight percent or less) or entirely free of brittle particulate fillers.
The particulate filler may be of any suitable material that results in composites with generally good adhesion between the filled polymeric material and the metal layers. For example, the particulate filler may be a metal, a polymer, or a mineral filler. The particulate filler may be organic or inorganic. The particulate filler may be made of any of the materials described hereinbefore for the metal layers. Preferred particulate fillers are metallic and may be the same or different metal as the metal layers.
Examples of particulate fillers that may be employed include the metallic fillers (e.g., metallic fibers) described in paragraphs 064-081 of International Patent Application Publication WO 2010/021899 (published on Feb. 25, 2010 by Mizrahi), and paragraphs 52-70, FIGS. 2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H, 2I, 2J, 3, and 4 of U.S. Patent Application Publication 2011/0188927 (published Aug. 4, 2011 by Mizrahi), and paragraphs 66-88 of U.S. Patent Application Publication 2011/0200816 (published Aug. 18, 2011 by Mizrahi), all incorporated herein by reference.
A particularly preferred particulate filler is a fiber or plate (e.g., flake) including or consisting substantially of aluminum.
The concentration of the particulate filler may be sufficiently high so that the adhesion between the metal layer and the core layer (e.g., a layer of the filled polymeric material) is increased. For example, the concentration of the particulate filler may be about 1 volume % or more, about 2 volume % or more, about 4 volume % or more, about 6 volume % or more, about or 8 volume % or more, based on the total volume of the filled polymeric material. Preferably the concentration of the particulate filler is sufficiently low so that the density of the composite material is reduced or minimized. The concentration of the particulate filler may be about 50 volume % or less, about 40 volume % or less, about 30 volume % or less, about 22 volume % or less, about 16 volume % or less, about 10 volume % or less, or about 9 volume % or less, based on the total volume of the filled polymeric material.
The particulate filler may have a longest dimension which is characterized by the weight average length, Lavg. The weight average length may be greater than about 0.5 mm, more preferably greater than about 1 mm, and most preferably greater than about 2 mm. Suitable particles may have an Lavg of less than about 100 mm, preferably less than about 35 mm, more preferably less than about 25 mm, and most preferably less than about 15 mm.
The particulate filler may have a smallest dimension which is characterized by the weight average thickness. The weight average thickness of the particulate filler (e.g., fiber or plates) may 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 thickness of the particulate filler may be less than about 300 μm, preferably less than about 50 μm, even more preferably less than about 40 μm, and most preferably less than about 30 μm.
The particulate filler may have any shape. For example, the particulate filler particle may be plate-like particles 30 having two opposing faces that are generally planar, such as shown in
The particulate preferably has a high surface area to volume ratio so that small concentrations of particulate filler may be employed while maintaining generally high contact area between the filler and the polymer. The ratio of surface area to the volume of the particulate filler preferably is about 5 mm−1 or more, more preferably about 10 mm−1 or more, even more preferably about 15 mm−1 or more, and most preferably about 20 mm−1 or more.
The cross-sectional area of the fibers in the plane transverse to the longitudinal axis preferably is about 1×10−6 mm2 or more, more preferably about 1×10−5 mm2 or more, even more preferably about 8×10−5 mm2 or more, even more preferably about 1×10−4 mm2 or more, and most preferably about 4×10−4 mm2 or more. The cross-sectional area of the fibers in the plane transverse to the longitudinal axis preferably is about 2.5×10−3 mm2 or less, more preferably about 1×10−3 mm2 or less, even more preferably about 2.5×10−3 mm2 or less, and most preferably about 1×10−3 mm2 or less.
The particulate filler may have a substantially constant thickness across its length, across it width, or both. A major surface of the particulate filler may be smooth (i.e., generally free of texture), or may have a texture. For example a ribbon-like fiber may have both major surfaces that are smooth, both major surfaces that are textured, or one major surface that is textured and one major surface that is smooth.
The particulate filler preferably has a weighted average thickness of about 1 μm or more, about 5 μm or more, about 15 μm or more, or about 20 μm or more. The particulate filler preferably has a weight average thickness of about 200 μm or less, about 100 μm or less, about 80 μm or less, about 70 μm or less, or about 60 μm or less.
The particulate filler may include or consist essentially of metal fibers having one or any combination of the features described herein. The weight average length of the metal fibers preferably is about 0.4 mm or more, more preferably about 0.6 mm or more, and most preferably about 0.8 mm or more. The weight average length of the metal fiber preferably is about 20 mm or less, more preferably about 10 mm or less, even more preferably about 7 mm or less, and most preferably about 5 mm or less.
The particulate filler is preferably sufficiently thin and present in a sufficient concentration so that many fibers are arranged between the surfaces of the layer. For example, the average number of particles that intersect a line parallel to the thickness direction of the filled polymeric layer and going through the polymeric layer preferably is about 3 or more, more preferably about 5 or more, more preferably about 10 or more, and most preferably about 20 or more. Without being bound by theory, it is believed that a large number of particles advantageously improves the apparent adhesion between the filled polymeric material and the metal layers (e.g., as measured by the peel test).
The total concentration of the polymer and the filler (e.g., the particulate filler) in the filled polymeric layer preferably is about 80 volume % or more, more preferably about 95% or more, even more preferably about 98% or more (e.g., about 100%), based on the total volume of the volume of the filled polymeric material. The filled polymeric material may be substantially or even entirely free of voids. The concentration of voids, if present, preferably is about 10 volume % or less, more preferably about 2 volume % or less, and most preferably about 2 volume % or less, based on the total volume of the filled polymeric material and/or based on the total volume between the metal layers.
The volume ratio of the polymer (e.g., the thermoplastic polymer) to the particulate filler (e.g., the metallic fibers) is preferably about 2.5:1 or more, more preferably about 3:1 or more, and most preferably about 4:1 or more. The volume ratio of the polymer (e.g., the thermoplastic polymer) to the particulate filler (e.g., the metallic fibers) is preferably about 99:1 or less, more preferably about 33:1 or less, even more preferably about 19:1 or less, even more preferably about 9:1 or less, and most preferably about 7:1 or less.
The particulate filler (e.g., the metallic fiber) preferably is present at a concentration greater than about 40 volume %, more preferably greater than about 70 volume %, and most preferably greater than about 80% (e.g., greater than about 90 volume %, or even greater than about 95 volume %) based on the total volume of the filler in the filled polymeric material.
The particulate filler (e.g., the metallic fibers) preferably is dispersed (e.g., randomly dispersed) in the polymeric matrix at a volumetric concentration of less than about 30% (more preferably less than about 25%, and most preferably less than about 20%) by volume of the total polymeric layer).
The process for preparing the filled polymeric material and the composite material may employ a process including one or any combination of the steps and/or features described in International Patent Application Publication WO 2010/021899 (published on Feb. 25, 2010 by Mizrahi), see for example paragraphs 092-107; and US Patent Application Publication 2011/0200816 A1 (published on Aug. 18, 2011 by Mizrahi et al), see for examples paragraphs 102-114, both incorporated herein by reference.
The composite material may be prepared using a process that results in the filled polymeric material (e.g., core layer) being bonded to at least one adjoining layer (e.g., a metallic sheet) and preferably being interposed between two layers (e.g., two metallic layers) and bonded to one or both layers. The process may include one or any combination of steps of heating, cooling, deforming (e.g., forming, such as by stamping), or bonding, in order to arrive at a final desired article. It is envisioned that at least one, or even all of the adjoining layers (e.g., metallic layers) may be provided in the form of a rolled sheet, a forging, a casting, a formed structure, an extruded layer, a sintered layer, or any combination thereof.
Preferably, the process includes one or more steps of pretreating a surface of the metal layer to be contacted with the filled polymeric material. For example, the face of each of the two metal layers that will be in contact with the filled polymeric material may be exposed to one or more steps of pretreating the surface. It will be appreciated that one or more steps of the pretreatment may additionally be applied to surfaces that will not contact the filled polymeric material. For example, it may be advantageous to expose all of the surfaces of one or both metal layers (e.g., metal foils) to some or all of the pretreatment steps so that the metal layer has generally uniform surface treatments.
The pretreating steps may include one or any combination of the following steps: one or more steps of washing the metal surface, one or more steps of applying a cleaner and/or coater to the metal surface, one or more steps of sealing the metal surface, or one or more steps of rinsing the metal surface.
The step of washing the metal surface may include one or more steps of contacting the surface of the metal with water, contacting the surface of the metal with a water solution, contacting the surface of the metal with a solvent, or any combination thereof. Preferred water solutions include alkaline solutions and acid solutions. The alkaline solution may include a solution of a metal hydroxide in water. The concentration of the metal hydroxide preferably is sufficiently high so that the pH of the solution is about 8 or more, about 9 or more, about 10 or more, or about 11 or more. The alkaline solution may have a pH of about 14 or less, about 13 or less, or about 12 or less. Suitable acid solutions include an acid that is soluble in water. The concentration of the acid may be sufficiently high so that the pH of the solution is about 6 or less, about 5 or less, about 4 or less, or about 3 or less. The acid solution may have a sufficiently low pH so that the acid solution is capable of etching the surface of the metal. Acid solutions that do not etch the surface of the metal may also be employed. Following a step of contacting the surface of the metal with an alkaline solution or an acid solution, the metal surface may be further washed with water, with a neutralizer, or with water that includes a neutralizer.
The step of contacting the surface of the metal with a cleaner/coater may include a step of contacting a surface of the metal with a solution including a metal salt. The metal salt may include a halide, a nitrate, a nitrite, a phosphate, a phosphate, a sulfate, a sulfide, or any combination thereof. A particularly preferred metal salt is a metal phosphate. The metal phosphate may be any metal phosphate useful for cleaning the metal. Examples of the metal phosphates that may be employed alone or in any combination include zinc phosphate, manganese phosphate, or iron phosphate. A preferred metal phosphate is zinc phosphate. For example, the step of washing may include contacting the metal surface with a solution including CHEMFOS® 700 NR zinc phosphate, commercially available from PPG. The process preferably includes a plurality of steps of contacting the metal surface with a cleaner/coater. The process may include one or more steps of rinsing between two steps of contacting the metal surface with a cleaner/coater.
The step of sealing may include a step of contacting the metal surface with a solution including a halide. For example, the solution may include a bromide, a chloride, a fluoride, or any combination thereof. Preferred sealing steps include a step of contacting the metal surface with a solution including a fluoride. The solution for the sealing step preferably is free of chromium atoms (e.g., free of chrome). By way of example, the step of sealing may employ a sealer solution that includes a chromium free, fluoride sealer such as CHEMSEAL® 59 commercially available from PPG.
The process may de one or more steps of rinsing the surface of the metal layer. A rinsing step may include a titanated activated rinse, a step of rinsing a phosphate, a step or rinsing a sealant, or any combination thereof. A step of rinsing may apply water, one or me more organic solvents or any combination thereof. A preferred rinse includes or consists essentially deionized water.
The step of pretreating the surface of the metal preferably is free of a step of e-coating the surface. The step of pretreating the surface of the metal preferably is free of a step of coating the surface with a polymer prior to contacting the surface with the filled polymeric material.
One or more, or even all of the aforementioned pretreating steps may be particularly useful in a composite material that includes aluminum metal layers and a filled polymeric material including a fibers and a polymer (e.g., a polyolefin).
The sheets (e.g., after the one or more pretreating steps) may be heated to a temperature greater than about 90° C. (e.g. greater than about 130° C., or greater than about 180° C.). Preferably, the sheets are heated to a temperature greater than about Tmin, where Tmin is the highest glass transition temperature (Tg) and melting temperature (Tm) of the thermoplastic of the filled polymeric material. The metallic sheets, the filled polymeric material, or both may heated to a maximum temperature above which the polymer (e.g., the thermoplastic polymer) may undergo significant degradation. The thermoplastic polymer may be heated to a temperature preferably less than about 350° C., more preferably less than about 300° C. The heated polymer may be mixed with the metallic fiber, and with any additional fillers. The heated polymer (e.g., thermoplastic polymer) may be extruded as a sheet layer. The sheet layer may be extruded directly between the metal faces, or placed between the metal faces later in the process or in a separate step. The process may include one or more steps of drying the polymer so that the concentration of water in the polymer is below a predetermined maximum moisture concentration. A step of drying the polymer may occur before, during, or after a step of heating the polymer. The process may include one or more steps of storing a polymer, a polymeric core layer, or a composite material in low humidity environment so that the concentration of water in the polymer is maintained below a predetermined maximum moisture concentration. When the filled polymeric material contacts the surface of the metal layer (e.g., the aluminum foil), the temperature of the polymer may be about (Tm−30° C.) or more, about (Tm−20° C.), about Tm−10° C. or more, or about Tm or more, where Tm is the melting temperature of the polymer.
The surface pretreatment 90 of a surface (i.e., at least surfaces 16 and/or 18) of the metal layer 12, 14 may include one or any combination of the steps illustrated in
The polymeric core layer may be a homogeneous layer or may comprise a plurality of sublayers. Preferably the polymeric core layer is a homogeneous layer (i.e., a layer of the filled polymeric material) and is free of any separate adhesive layers.
The process for fabricating the composite material may also include one or more steps of heating one or more metal layers, applying pressure to the layers, calendaring a polymer (e.g., a thermoplastic polymer or the thermoplastic polymer compounded with the metallic fiber and the optional fillers), and annealing the composite sheet (e.g., at a temperature greater than melting temperature of any thermoplastic polymer in the material).
The process for preparing the filled polymeric material (e.g., a core layer for the sandwich composites herein) may include a step of contacting the fiber and at least a portion of the polymer (e.g., thermoplastic polymer), blending the fiber and at least a portion of the polymer, or both. The process of forming the polymeric 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 may include heating the polymer to a maximum temperature 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.
The process may employ one or more steps of applying pressure when at least some of the polymer of the filled polymeric material is at a temperature greater than about 80° C., preferably greater than about 120° C., more preferably greater than about 180° C., even more preferably greater than about 210° C., and most preferably greater than about 230° C. The step of applying pressure may employ a maximum pressure 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. The maximum pressure during the step of applying pressure may 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 a step of cooling the composite material (e.g., to a temperature below Tmin, preferably below the melting temperature of polymer of the filled polymeric material, and more preferably below about 50° C.).
The process for preparing a metal surface may include a step of cleaning the metal surface with isopropyl alcohol 26 such as illustrated in
Preparation and testing test specimen may employ one or any combination of the features illustrated in
The core layer herein may employ metal flakes, according to the teachings herein. For example, the core layer may include aluminum flakes such as illustrated in
Adhesion testing is performed on specimens that are prepared by placing a sheet of a polymeric core material between two strips of aluminum. Each aluminum strip has a width of 32 mm, a thickness of about 1.3 mm, and a length of about 152 mm. The specimen is placed in a heated press at a temperature sufficiently high so that the polymer can melt. A temperature of 460° F. was chosen for this study. However, it will be appreciated that higher or lower temperatures may be used depending on the characteristics (such as melting temperature, preheating time, and decomposition temperature of the polymer). Shims having the same thickness are placed in the press and a compressive force is applied while the material is heated. A preheating time of about 5 minutes without the compressive force is used. It will be appreciated that the preheating time may be shorter or longer depending on the thermal characteristics (e.g., melting properties and decomposition properties) of the polymer and the press temperature. After the preheating, a force of 30 tons is applied. The specimens are removed from the mold. Any polymer that has flowed from the core is trimmed and the polymer is cooled at ambient conditions (e.g., about 25° C.) in air. The resulting specimen has a thickness that is nearly equal to the thickness of the shim. The shim may act as a stop to control the thickness.
The specimen is tested using a T-peel test, as illustrated in
In Example 1 and Example 3, the core polymeric material includes about 20 volume percent aluminum fibers (aluminum alloy 5056) and about 80 volume percent of one or more polyethylene copolymers. The polyethylene copolymer includes at least 65 wt. % ethylene. In Example 2, the core polymeric material does not include any metallic fibers and only includes the polyethylene copolymer. The same polyethylene copolymer is used in Examples 1, 2, and 3. The same type of aluminum fibers, having the same distribution of fiber lengths and formed of the same grade of aluminum are used in Examples 1 and 3.
Examples 1 and 2 are prepared by pretreating the aluminum surfaces of the foil that later contact the polymeric core material. The pretreating is performed prior to placing the polymeric core material between the two aluminum sheets. The pretreating step includes (1) washing the surfaces of the aluminum with an alkaline solution; (2) contacting a surface of the aluminum with a metal phosphate for cleaning the surface, coating the surface, or both; and (3) rinsing the surface of the aluminum. The rinsing of the surface is performed using a solution including CHEMSEAL® 59 sealer commercially available from PPG Industrial Coatings. Although other solutions may be employed in the rinsing step, the rinsing step preferably employs a solution that is chrome-free, a solution that includes a fluoride, or both (i.e., a solution including fluoride that is chrome-free).
Example 3 is prepared with a pretreating step consisting essentially of wiping the surface with isopropyl alcohol. The pretreating of the aluminum in Example 3 does not employ any of the pretreating steps described above for Examples 1 and 2.
In Examples 1, 2, and 3, the pretreatment of the aluminum surface does not include a step of contacting a surface of the aluminum with a polymer or a polymerizable material.
The preparation and peel test results for Examples 1-3 are summarized in Table 1.
As used herein, unless otherwise stated, the teachings envision that any member of a genus (list) may be excluded from the genus; and/or any member of a Markush grouping may be excluded from the grouping.
Unless otherwise stated, any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component, a property, or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that intermediate range values such as (for example, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within the teachings of this specification. Likewise, individual intermediate values are also within the present teachings. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. As can be seen, the teaching of amounts expressed as “parts by weight” herein also contemplates the same ranges expressed in terms of percent by weight. Thus, an expression in the Detailed Description of the Invention of a range in terms of at “‘x’ parts by weight of the resulting polymeric blend composition” also contemplates a teaching of ranges of same recited amount of “x” in percent by weight of the resulting polymeric blend composition.
Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of “about” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to 30” is intended to cover “about 20 to about 30”, inclusive of at least the specified endpoints.
The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The to “consisting essentially of” to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms “comprising” or “including” to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist or even consist essentially of the elements, ingredients, components or steps.
Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated elements, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of “a” or “one” to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps. All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
As used herein the terms “polymer” and “polymerization” are generic, and can include either or both of the more specific cases of “homo-” and copolymer” and “homo- and copolymerization”, respectively.
It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments as well as many applications besides the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the invention should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor should it be regarded that the inventors did not consider such subject matter to be part of the disclosed inventive subject matter.
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