The invention is directed to chemically and thermally-stable structural core materials comprising compressed foamed polyester strands and methods for their preparation. The invention is also directed to structural sandwich composites constructed from such core materials and methods for their preparation.
Structural sandwich composites—which are sandwich-like arrangements of a relatively low-density core material bonded between comparatively thin, high-strength and high-stiffness skins—are used in a wide variety of applications that require lightweight, yet structurally strong materials. To name but a few applications, structural sandwich composites are used in boating, construction, aviation, rapid transit, and recreational vehicles. Structural sandwich composites are useful because of their high strength and low weight per unit area. When bonded between skins, the low-density core provides a large strength and stiffness enhancement over the skins alone, but adds only a comparatively small weight. To illustrate the benefits of structural sandwich composite construction, consider that dividing a material (e.g., aluminum or fiberglass) into two skins and bonding a core material that is twice the original material's thickness in between them, results in a composite having a stiffness 7 times greater and a strength 3.5 times greater than the original material's while having a density only 1.03 times that of the original material. A
How well a sandwiched core material functions in real-world applications can be predicted from laboratory measurements of its compression strength and modulus, tensile strength and modulus, and shear strength and modulus.
The properties of the core material are of great importance. Desirable properties include high strength, low density, rigidity, high chemical and heat resistance, and low cost. The most common core materials are wood, honeycomb structures, and foams comprising both thermoplastic and thermosetting compositions. Wood core materials suffer from variations in properties and are susceptible to fungal decay, especially in marine use. Honeycomb cores are of an open structure, i.e., comprised of contiguous, connected, and/or interlocked cells, and are typically constructed from rigid materials, such as thermoplastics, fiberglass, aluminum, and stainless steel. While honeycomb-core materials provide strong, high-quality, chemically resistant composites, they are difficult to manufacture. The connected nature of the cells precludes composite manufacture by vacuum-mediated resin techniques because the vacuum draws the resin into the individual cells. Furthermore, honeycomb cores are not suitable for marine applications because a crack in the composite skin can lead to the entire composite filling with water. Closed-cell thermoplastic or thermosetting foams avoid some of these problems, but generally are thermally and chemically sensitive; thus, their composites cannot be used in certain higher-temperature applications. A further disadvantage of thermoplastic- or thermosetting-foam core materials is that certain resin-type adhesives can significantly degrade them, both chemically and via the heat evolved during the cure process.
Skins can be attached to core materials by a variety of methods. One of the most popular methods, because of the high shear strength of the resulting composite, is bonding the skins to the core with a resin (the resin-cure method). The resin-cure method provides structural sandwich composites with excellent skin-core adhesion and delamination resistance. In the resin-cure method, an uncured resin is applied to the contacting surfaces, the core and the skins are contacted, and bonding results upon resin cure. Often, a reinforcing material such as a glass-fiber fabric or mat is combined with the uncured resin to improve strength and stiffness in the resulting joint. During resin cure, substantial heat is generated.
Vacuum-bagging and vacuum-injection-molding techniques are used commercially to introduce the resin between the skins and suitable cores see, for example, U.S. Pat. No. 6,159,414 (issued May 18, 1999); U.S. Pat. No. 5,316,462 (issued May 31, 1994); and U.S. Pat. No. 5,834,082 (issued Nov. 10, 1998). In this process, vacuum is used to draw the uncured resin between the core and skin. Advantageously, the vacuum removes resin fumes as well as shields the uncured resin from air.
With some core materials, however, such as honeycomb structures, vacuum-mediated resin application is difficult or impossible. And unfortunately, in these cases, open-air resin application is proscribed because the hazardous resin fumes are not contained and resin curing can be inhibited by air and moisture. Thus, thermoplastic or thermosetting foams are ideal in that they do not suffer from the biodegradability of wood cores and are amenable to vacuum-mediated resin application. But a serious drawback with thermoplastic- or thermosetting-foam cores is that the heat evolved during resin cure and the chemically corrosive properties of the resin can degrade them, resulting in weaker composites.
Thermoplastic polyester resins, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) that have been pre-treated with branching agents (hereinafter “branched polyesters”) yield closed-cell foams having excellent strength and mechanical properties, low density, and high chemical and thermal resistance. The branching agents, which have multiple chemical-reaction sites, function by chemically condensing two or more polyester chains (“branching”). This branching gives the pre-foam polyester melt viscoelastic properties more suitable for foaming, leading to higher quality foams. Polyester foams, prepared from branched polyesters, such as branched polyethylene terephthalate, have been disclosed in U.S. Pat. No. 5,000,991 (issued Mar. 19, 1991); U.S. Pat. No. 5,229,432 (issued Jul. 20, 1993); U.S. Pat. No. 5,340,846 (issued Aug. 23, 1994); U.S. Pat. No. 5,362,763 (issued Nov. 8, 1994); U.S. Pat. No. 5,422,381 (issued Jun. 6, 1995); U.S. Pat. No. 5,679,295 (Oct. 21, 1997); U.S. Pat. No. 5,681,865 (Oct. 28, 1997); U.S. Pat. No. 6,342,173 (issued Jan. 29, 2002), each of which eight patents are hereby incorporated by reference herein. These foams are closed-cell structures with low densities, excellent mechanical properties, and high thermal and chemical resistance. Regrettably, because the process used for their manufacture leads to irregular surfaces, such foams make mediocre to poor core materials. The irregular surfaces promote weak bonding to the composite skin and wide cell-size distribution and, therefore, poor mechanical properties. To explain more fully, polyesters are generally foamed by extruding a pressurized mixture of a branched-polyester melt and a volatile, organic expanding or “blowing agent” through an annular or slit die. Upon entering ambient pressure, the blowing agent evaporates and the polyester foams. This process suffers in that if the die opening size surpasses a critical limit, extruder pressure cannot be maintained. Furthermore, as the die opening is enlarged to the size required for use as a core material, blowing-agent evaporation throughout the material becomes non-uniform leading to erratic cell-size distribution, oversized cells, and an irregular surface.
Coalesced-strand polyester foams are more suitable as core materials because they can be produced in thicker size with a uniform distribution of small cells. Coalesced-strand polyester foams are disclosed in U.S. Pat. No. 5,475,037 (issued Dec. 12, 1995). Generally, coalesced-strand thermoplastic foams are prepared by melting a thermoplastic resin, mixing the melt with a blowing agent, and extruding the resulting gel through a multi-orifice die. The orifices are so arranged such that some contact between adjacent strands occurs during foaming, and the contacting strand surfaces adhere to one another resulting in a coalesced-strand structure. These strand foams, however, are not used as core materials. Tenacious, tough thermoplastic resins such as polypropylene or polyethylene which generally exhibit lower stiffness, may be advantageously used for some applications, such as shock absorbers (see, e.g., U.S. Pat. No. 6,213,540 (issued Apr. 10, 2001)) but they offer poor performance as composite core materials for which high strength and stiffness are desirable.
In view of the above, there is a need for low-density closed-cell core materials that are rigid, strong, chemically and thermally resistant, and amenable to vacuum-mediated resin application.
The invention provides high-strength, chemically and thermally stable, closed-cell foams, useful as core materials in composites. The core materials of the invention comprise multiple foamed polyester strands, compressed together (or shaped) to form a unitary, closed cell foam displaying anisotropic properties.
A further feature of core materials of the invention is that, although they are manufactured by extruding through a multi-orifice die, there are substantially no voids in between the strands (no inter-strand voids). This is a result of the special shaping process and shaping apparatus described in more detail herein. The shaping process can be adjusted to completely remove the strand appearance of the core material. That is, if the core material is cut perpendicular to the strand direction, strands are no longer visible to the human eye. The strands have coalesced to a degree wherein the core material appears to be completely unitary. Thus, to the human eye, the core materials of the invention appear identical to a conventional foam board manufactured by extruding through a single-orifice, standard slot die. However, the core materials of the invention display improved properties over conventional slot-die produced foam boards. And, in contrast to such conventional foam boards, the core materials of the invention are significantly anisotropic in character and have an unusual cell size distribution. The cell-size distribution of core materials of the invention defines a plurality of “discrete volumes”, running parallel to the strand direction. These “discrete volumes” comprise an interior section running parallel to the strand direction and a “jacket” surrounding the “interior section of the discrete volume”. The “interior section of the discrete volume” has closed cells of average cell size relatively larger than the average cell size of the cells in the surrounding “jacket”. In other words, the average-cell diameter is smaller where the strands have intersected and merged than at the original strand's interior. This can be described as a pseudo honeycomb structure.
Because of their high thermal and chemical resistance, the core materials of the invention are amenable to vacuum-mediated resin bonding to composite skins to provide lightweight, high-strength, buoyant, and watertight structural sandwich composites suitable for use in a variety of applications, such as construction, boats, ships, and other marine applications, aviation, rapid transit, and recreational vehicles. In fact, the core materials of the invention are compatible with just about all resins, and can accept high molding temperatures and pressures. They can be processed with nearly all composite fabrication techniques including contact molding, vacuum bagging, resin infusion, autoclave, RTM, match metal molding, pre-preg and others.
In one embodiment, the invention is directed to a method for making a composite comprising: extruding a foamable gel comprising a blowing agent and a foamable polyester through a multi-orifice die to give a plurality of strands; foaming the strands to form a multi-stranded foamed article; shaping the multi-stranded foamed article to give a core material; and bonding the core material to one or more structural skins.
In another embodiment, the invention is directed to a composite comprising a foamed polyester core material bonded to one or more structural skins, wherein the core material comprises a plurality of discrete volumes, each discrete volume comprising an interior section and a corresponding jacket, wherein the average cell size in the interior section is larger than the average cell size in the jacket.
In still another embodiment, the invention relates to a composite comprising a foamed polyester core material bonded to one or more structural skins, wherein the core material comprises a plurality of foamed strands, wherein there are substantially no inter-strand voids.
In yet one more embodiment, the invention is directed to a composite comprising a foamed polyester core material bonded to one or more structural skins, wherein the core material is anisotropic.
In another embodiment, the invention relates to a core material comprising foamed polyester, wherein the foamed polyester comprises a plurality of discrete volumes, each discrete volume comprising an interior section and a corresponding jacket, wherein the average cell size in the interior section is larger than the average cell size in the jacket. Preferably, the core material is anisotropic.
These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where:
The core materials of the invention may be prepared as follows. A foamable polyester, of suitable melt rheology, is heated above its melt point to form a polyester melt. The heated mixture is pressurized in an extruder and a blowing agent is blended into the melt to form a foamable gel. During blowing-agent addition and mixing, the pressure is maintained above the blowing agent's equilibrium vapor pressure at the operating temperature of the foamable gel. The gel is cooled and extruded through a multi-orifice die of desired design. Upon entering ambient pressure, the blowing agent boils and expands thereby foaming the strands. As the strands foam, they coalesce resulting in multi-stranded polyester foam. At this point, the foam has voids or channels running parallel to the strands. The voids are removed by compressing the foam in a special shaping process. Temperatures, pressures, and extrusion rates will depend upon the specific polyester, additives, blowing agents, equipment, die design, and on the properties desired in the final foam product. The core materials of the invention may be bonded to skins to form composites by well-known methods in the art, such as vacuum-mediated resin application.
As used herein, the phrase “structural sandwich composite” means an article comprising a core material integrally bonded to one or more structural skins. Preferably a “structural sandwich composite” means a sandwich-like article comprising a core material integrally bonded between structural skins. The phrase “Integrally bonded” means that the skin is bonded to the core material substantially throughout the skin's entire contact area. A “structural sandwich composite of the invention” means a structural sandwich composite comprising a core material of the invention. Examples of suitable structural skins include, but are not limited to, thermoplastic polymers and thermosetting polymers, optionally reinforced with glass fibers, metallic fibers, inorganic fibers, or carbon fibers; wood; inorganic materials, such as fiberglass; and metallic materials, such as aluminum and stainless steel and many others, which are well known to those of skill in the art.
As used herein, the phrase “core materials of the invention” means a foamed article prepared by extruding a melt comprising a foamable polyester and one or more blowing agents through a multi-orifice die, according to the methods described more fully herein, to give a multi-stranded foamed core material. Preferably, the coalesced multi-stranded foamed core material is further compressed (via shaping) to remove substantially all the voids between the individual strands. Thus, the multi-stranded foamed core material is transformed via shaping into a unitary closed-cell structure, wherein certain foam-cell walls (those corresponding to the surface where the exterior of the strands were compressed together during shaping) are of increased (generally double) thickness over those of the strand interior. The strand density of the multi-stranded foamed core material prior to shaping will govern the relative number of cells having such increased thickness. Such a structure is referred to herein as a “compressed-strand structure” gives the core materials of the invention advantageous structural and mechanical properties over traditional foam core materials.
As used herein, the phrase “pre-shaped core material” means a “core material of the invention” prior to its being shaped by a shaper of the invention, which shaper and shaping process is more fully described in Section 5.3.2 below. In some cases, pre-shaped core materials of the invention may have gaps or air pockets between the strands. The shaping process, which results in a “shaped core material of the invention”, compresses the strands thereby removing the gaps or air pockets. Preferably, core materials of the invention are shaped.
As used herein, the phrase “strand direction” means the axis along which a core material of the invention was extruded during production. This is an important reference point since, in some cases, the strand character of core materials of the invention is not visible to strand compression and merger during the special shaping disclosed herein (see Section 5.3.2 below). The “strand direction” influences the anisotropic physical properties of core materials of the invention. For example, the core materials of the invention exhibit greater compressive strength in the “strand direction”. This is discussed more fully in Section 5.4.2 below.
The phrase “end-strand direction” is used in reference to composites of the invention wherein the composite's skins are bonded to a core material of the invention perpendicular to the strand direction. In such circumstances, the “end-strand direction” means a direction or axis perpendicular to the strand direction (therefore, also parallel to the composite skins).
The phrase “longitudinal direction” is used in reference to composites of the invention wherein the composite's skins are bonded to a core material of the invention such that the skins are parallel to the strand direction. In such circumstances, the “longitudinal direction” means a direction or axis parallel to the strand direction.
The phrase “transverse direction” is used in reference to composites of the invention wherein the composite's skins are bonded to a core material of the invention such that the skins are parallel to the strand direction. In such circumstances, the “transverse direction” means a direction or axis perpendicular to the strand direction.
As used herein, the phrases “foamable polyester” or “foamable-polyester resin” mean any thermoplastic or thermoplastic mixture comprising polyester, a branched polyester, a polyester co-polymer, or a branch polyester co-polymer that can be effectively foamed to yield a core material of the invention.
As used herein, the phrase “polyester co-polymer” means a polyester prepared, according to well-known methods, by co-polymerizing an ester monomer and one or more other monomers.
As used herein, the phrase “branched polyester” means a polyester or a polyester co-polymer that has been condensed with one or more branching agents. Preferably, branched polyesters are foamable.
Although polyesters have excellent chemical and thermal stability and structural properties, foaming is often difficult due to their melt rheology (e.g., low melt strength and low melt viscosity). In some cases, this can be overcome by using special processing equipment. But the more common way to improve polyester foaming characteristics is to alter the melt rheology by pre-treating them with branching agents, for example, polyfunctional carboxylic acids, polyfunctional anhydrides, and polyhydroxyl compounds according to well-known methods.
Preferably, foamable polyester resins in the invention have a crystallinity of from about 5% to about 100%, more preferably, of from about 10% to about 60%, most preferably, of from about 25% to about 45%, and even more preferably, of from about 28% to about 39%, as measured by differential scanning calorimetry.
Preferably, foamable polyester resins have the following melt rheology and properties: (1) a melt strength of from about 1 to about 60 centinewtons, preferably, of from about 5 to about 30 centinewtons; (2) a melt viscosity of from about 30,000 to about 500,000 poises, preferably, of from about 200,000 to about 300,000; and (3) an inherent viscosity of from about 0.5 to about 1.95 dl/g, preferably, of from about 0.7 to about 1.2 dl/g.
The crystallinity of foamable polyester resins for use in the invention may be measured by differential scanning calorimetry. This involves absorbed-energy measurement as a polyester-resin sample is heated to and beyond its crystalline melting point. The crystallinity is defined as the ratio of the energy absorbed per unit mass to the theoretical heat of fusion. For polyethylene terephthalate resin, the theoretical heat of fusion is 26.9 kJ/g-mole of repeat units, or more conveniently 140 Joules per gram of resin. 3 B. W
As is well known in the art, a differential scanning calorimeter can measure very small quantities of energy that are absorbed or released from a sample material. In a typical procedure, a 5 mg to 10 mg polyester resin sample is sealed in an aluminum pan and placed in the calorimeter's sample cell. Typically, the sample is purged with an inert gas, such as nitrogen to preclude sample oxidation. Then, the sample temperature is ramped, for example, 10° C. per minute while the differential scanning calorimeter measures the energy absorbed or released. The enthalpy of melting or heat of fusion is determined automatically by the differential scanning calorimeter with software that integrates the area under the melting peak. For quality assurance, the foamable polyester's crystallinity should be measured by differential scanning calorimetry prior to foaming. For references relating to differential scanning calorimetry, see Dole et al., 20 J. C
The melt strength may be measured according to the procedure set forth in American Society for Testing and Materials (“ASTM”) D3835 “Standard Test Method for Determination of Properties of Polymeric Materials by Means of a Capillary Rheometer” measured at 280° C. This test method describes measurement of the rheologic properties of polymeric materials at various temperatures and shear rates common to processing equipment. It covers measurement of melt viscosity, sensitivity, or stability of melt viscosity with respect to temperature and polymer dwell time in the rheometer, die swell ratio (polymer memory), and shear sensitivity when extruding under constant rate or stress. The techniques described permit the characterization of materials that exhibit both stable and unstable melt viscosity properties. Other suitable methods are set forth in U.S. Pat. No. 5,362,763 (issued Nov. 8, 1994); U.S. Pat. No. 6,350,822 (issued Feb. 26, 2002); or U.S. Pat. No. 6,251,319 (issued Jun. 26, 2001) which patents are hereby incorporated by reference herein using, a Rheotens Melt Strength Tester, Type 010.1, supplied by Gottfert Werkstoff-Prufinaschinen Gmbh of Buchen, Germany. This test involves drawing an extruded strand of polymer vertically into the nip between two counter-rotating nip rollers using piston rate of 0.2 mm/sec. The strand is extended using a Brabender Plasticorder single screw extruder of screw diameter 19 mm and length to diameter ratio (L/D) of 25. The extruded material exits through a right angle capillary die of length 30 mm and 1 mm diameter at a rate of 0.030 cc/sec to a length of 41.9 mm at 270° C. The strand is then stretched at a constant acceleration while measuring the elongation. The temperature profile used was uniform along the length of the barrel of the extruder and the die and was set at 280° C. The nip rollers are mounted on a balance arm, which allows the force in the drawing strand to be measured. The velocity of the nip rolls is increased at a uniform acceleration rate. As the test proceeds, the force increases until eventually the strand breaks. The force at breakage is termed the “melt strength”.
The melt viscosity may be measured according to the procedure set forth in ASTM D4440-01 “Standard Test Method for Plastics: Dynamic Mechanical Properties: Melt Rheology”, hereby incorporated by reference herein. ASTM test procedures are compiled, reviewed, and published by the American Society for Testing and Materials, which is a voluntary standards development organization operating out of West Conshohocken, Pa. This test method describes the use of dynamic mechanical instrumentation for gathering and reporting the rheologic properties of thermoplastic resins. It may be used as a test method for determining the complex viscosity and significant viscoelastic characteristics of polyester thermoplastics as a function of frequency, strain amplitude, temperature, and time. Rheometric calculations from data obtained by ASTM D4440-01 may be performed according to ASTM D4065-01 “Standard Practice for Plastics: Dynamic Mechanical Properties: Determination and Report of Procedures”, hereby incorporated by reference herein. This report recites laboratory practice for determining dynamic mechanical properties of specimens subjected to various oscillatory deformations on a variety of instruments of the type commonly called dynamic mechanical analyzers or dynamic thermomechanical analyzers.
The inherent viscosity may be measured according to ASTM Test Method D4603-96 “Standard Test Method for Determining Inherent Viscosity of Poly(Ethylene Terephthalate) (PET) by Glass Capillary Viscometer”, hereby incorporated by reference herein (see e.g., U.S. Pat. No. 5,422,381, hereby incorporated by reference herein). This test method is for the determination of the inherent viscosity of polyethylene terephthalate soluble at 0.50% concentration in a 60/40 phenol/1,1,2,2-tetrachloroethane solution by means of a glass capillary viscometer. Some highly crystalline forms of polyethylene terephthalate may not be soluble in this solvent mixture and will require a different procedure The inherent viscosity values obtained by this test method are comparable with those obtained using differential viscometry described in ASTM Test Method D5225-98 “Standard Test Method for Measuring Solution Viscosity of Polymers with a Differential Viscometer”, hereby incorporated by reference herein.
Polyesters that are foamable or can be converted to foamable polyesters are suitable for use in the invention. Preferably, the polyester is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate (PBT), more preferably, polyethylene terephthalate. The polymer's molecular weight is not critical, generally molecular weights of 100,000 D to 1,000,000 D are suitable depending on the polymer type.
Preferred polyesters include, but are not limited to, foamable polyesters derived from reaction of aromatic dicarboxylic acid and a dihydric alcohol, such as those polyesters described in U.S. Pat. No. 5,110,844 (issued May 5, 1992), hereby incorporated by reference herein. Specific examples of preferred foamable polyesters include, but are not limited to, foamable polyethylene terephthalate (PET), foamable polybutylene terephthalate (PBT), foamable polyethylene naphthalate (PEN), foamable copolymers of PET, foamable copolymers of PBT, foamable copolymers of PEN, foamable liquid-crystalline polyesters.
Foamable blends of polyesters and other thermoplastics are also suitable for use in the invention. Suitable blends include foamable polyester/polycarbonate blends as described in U.S. Pat. No. 4,833,174 (issued May 23, 1989) and U.S. Pat. No. 4,462,947 (issued Jul. 31, 1984), both of which are hereby incorporated herein by reference. Suitable blends also include foamable polyester/polyolefin blends as described in U.S. Pat. No. 4,981,631 (issued Jan. 1, 1991) and U.S. Pat. No. 5,128,202 (issued Jul. 7, 1992), both of which are hereby incorporated by reference herein. Suitable polyolefins include, but are not limited to, those listed in column 4, line 33 through column 4, line 35 of U.S. Pat. No. 4,981,631, which disclosure is hereby incorporated by reference herein.
Foamable co-polymers of polyesters and other thermoplastics are also suitable for use in the invention. Suitable polyester co-polymers include, but are not limited to, those listed in column 3, line 3 through column 4, line 41 of U.S. Pat. No. 5,475,037 (issued Dec. 12, 1995), which disclosure is hereby incorporated by reference herein and poly-2-hydroxy-6-naphthoic acid and polynaphthalene terephthalate, which is a copolymer of 2,6-dihydroxynaphthalene and terephthalic acid.
Polyesters for use in the invention are readily available commercially or can be synthesized by well-known literature methods, for example see, G
Suitable procedures for preparing foamable polyesters by condensing polyesters with branching agents are disclosed in U.S. Pat. No. 3,553,157 (issued Jan. 5, 1971), U.S. Pat. No. 4,132,707 (issued Jan. 2, 1979); U.S. Pat. No. 4,145,466 (issued Mar. 20, 1979); U.S. Pat. No. 4,462,947 (issued Jul. 31, 1984); U.S. Pat. No. 4,999,388 (issued Mar. 12, 1991); U.S. Pat. No. 5,000,991 (issued Mar. 19, 1991); U.S. Pat. No. 5,110,844 (issued May 5, 1992); U.S. Pat. No. 5,128,383 (issued Jul. 7, 1992); U.S. Pat. No. 5,134,028 (issued Jul. 28, 1992); U.S. Pat. No. 5,288,764 (issued Feb. 22, 1994); U.S. Pat. No. 5,362,763 (issued Nov. 8, 1994); U.S. Pat. No. 5,422,381 (issued Jun. 6, 1995); U.S. Pat. No. 5,482,977 (issued Jan. 9, 1996); U.S. Pat. No. 5,696,176 (issued Dec. 9, 1997); U.S. Pat. No. 5,229,432 (issued Jul. 20, 1993); and U.S. Pat. No. 6,350,822 (issued Feb. 26, 2002), all of which are hereby incorporated by reference herein.
Suitable polyfunctional carboxylic acid branching agents have three or more carboxylic acid functions per molecule and include, but are not limited to, trimesic acid; pyromellitic acid; benzophenonetetracarboxylic acid; 2,3,6,7-napthalenetetracarboxylic acid; 1,2,5,6-napthalenetetracarboxylic acid; 1,2,3,4-cyclobutanetetracarboxylic acid; tetrahydrofuran-2,3,4,5-tetracarboxylic acid; 2,2-bis(3,4-dicarboxyphenyl)propane; and 3,3′, 4,4′-biphenyltetracarboxylic acid. Such branching agents are commercially available or prepared by well-known methods.
Suitable polyhydroxyl compounds and equivalents (i.e., a compound that can be converted in situ to a polyhydroxy alcohol, e.g., esters of polyhydroxyl compounds) have at least three hydroxyl groups or hydroxyl-group equivalents per molecule and include, but are not limited to, glycerol; trimethylolpropane; trimethylolethane; pentaerythritol, dipentaerythritol, tripentaerythritol, and esters thereof; 1,2,6-hexanetriol; sorbitol; glycerol tripropylate; glycerol tribenzoate; 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane; tris(2-hydroxyethyl)isocyanurate; ethylene oxide; and propylene oxide. Polymers or copolymers having polyhydroxyl groups are also suitable and include, but are not limited to, poly(ethylene-co-vinyl alcohol) and poly(ethylene-co-vinyl acetate). Preferably, the polyhydroxyl compound is pentaerythritol, dipentaerythritol, tripentaerythritol, or an ester thereof; trimethylolpropane; trimethylolethane; glycerol; or any mixture thereof. Such branching agents are commercially available or prepared by well-known methods.
Polyfunctional acid anhydride branching agents are the most preferred class of branching agents for preparing suitable foamable polyesters. Suitable polyfunctional acid anhydride branching agents have at least one anhydride group and one or more additional carboxylic, hydroxyl, or anhydride groups per molecule and include, but not limited to, pyromellitic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride; benzophenonetetracarboxylic acid dianhydride; diphenylsulfone tetracarboxylic dianhydride; bis(3,4-dicarboxyphenyl)ether dianhydride; bis(3,4-dicarboxyphenyl)thioether dianhydride; bisphenol-A bisether dianhydride; 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 2,3,6,7-napthalenetetracarboxylic acid dianhydride; bis(3,4-dicarboxyphenyl)sulfone dianhydride; 1,2,5,6-napthalenetetracarboxylic acid dianhydride; 2,2′, 3,3′-biphenyltetracarboxylic acid dianhydride; hydroquinone bisether dianhydride; 3,4,9,10-perylene tetracarboxylic acid dianhydride; tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride; 3,3′, 4,4′-biphenyltetracarboxylic acid dianhydride; and 4,4′-oxydiphthalic dianhydride. Polymers or copolymers containing an acid anhydride component are also suitable. Preferred polyfunctional acid anhydride branching agents are pyromellitic dianhydride; 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride; and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, more preferably, pyromellitic dianhydride. The preferred polyfunctional acid anhydride branching agent is pyromellitic dianhydride, which is commercially available, for example, from Aldrich.
Mixtures of polyfunctional carboxylic acids, polyhydroxyl compounds; and/or polyfunctional acid anhydrides, are also suitable branching agents, for example, a mixture comprising a polyhydroxyl alcohol and a polyfunctional acid anhydride.
Well-known methods can be used in the initial, multi-stranded foaming process to produce coalesced multi-stranded foamed articles, which are precursors to the unitary core materials of the invention. Such procedures are described in detail in U.S. Pat. No. 3,573,152 (issued Mar. 30, 1971); U.S. Pat. No. 4,122,047 (issued Oct. 24, 1978); U.S. Pat. No. 4,462,947 (issued Jul. 31, 1984); U.S. Pat. No. 4,824,720 (Apr. 25, 1989); U.S. Pat. No. 4,833,174 (issued May 23, 1989); U.S. Pat. No. 4,981,631 (Jan. 1, 1991); U.S. Pat. No. 5,246,976 (issued Sep. 21, 1993); U.S. Pat. No. 5,254,400 (issued Oct. 19, 1993); U.S. Pat. No. 5,340,846 (issued Aug. 23, 1994); U.S. Pat. No. 5,360,829 (Nov. 1, 1994); U.S. Pat. No. 5,362,763 (issued Nov. 8, 1994); U.S. Pat. No. 5,391,582 (issued Feb. 21, 1995); U.S. Pat. No. 5,399,595 (Mar. 21, 1995); U.S. Pat. No. 5,422,381 (issued Jun. 6, 1995); U.S. Pat. No. 5,458,832 (issued Oct. 17, 1995); U.S. Pat. No. 5,527,573 (issued Jun. 18, 1996); U.S. Pat. No. 6,197,233 (Mar. 6, 2001); U.S. Pat. No. 6,213,540 (Apr. 10, 2001); and U.S. Pat. No. 6,350,822 (issued Feb. 26, 2002), all of which are hereby incorporated herein by reference.
A typical process is outlined in
An alternative foaming extrusion process, which is well known in the art, employs tandem extruders. According to this process, the polyester and other components are mixed, melted, pressurized, and homogenized with the blowing agent(s) in a first extruder, as described above, resulting in the foamable gel. The foamable gel is transferred by means of a conventional transfer tube or static mixer, optionally assisted by a gear-type melt pump, to the feed section of the second extruder, which conveys the foamable gel to the die and adjusts the temperature and pressure necessary for optimum foaming. Typically, the two extruders are of different sizes. The well-known tandem-extruder process allows excellent control of process variables. See e.g., J
The special shaping process described below serves three functions: (a) to compress the pre-shaped core material's coalesced strands and eliminate inter-strand voids between and running parallel to the strands; (b) To mold the core material of the invention to the desired shape; and (c) to provide the core material with a smooth surface. The shaper of the invention basically comprises a shaping conduit of specified shape, having an entrance, an exit, and a length, with the conduit's top having a degree of decline, while the angle of the sides and bottom remain straight (i.e., the sides and bottom are fixed in a parallel relationship). As the recently extruded multi-stranded core material is forced or pulled through the shaper, it is compressed. The compression removes the inter-strand voids resulting in the high-strength core materials of the invention (see
In any case, in next step of
As shown in
Preferably, the feed mixture comprises foamable polyester and the other additives if they will be used. Preferably, a nucleating agent is included in the feed mixture to promote even evaporation of the blowing agent, thereby controlling the size and number of cells and cell-size distribution. Nucleating agents are well known in the art. Suitable nucleating agents include, but are not limited to, inorganic substances, such as calcium carbonate, talc, clay, titanium oxide, silica, barium sulfate, diatomaceous earth, and carbon dioxide that is generated by including a mixture of a basic salt (e.g., sodium-, potassium-, or ammonium carbonate or bicarbonate) and an inorganic or organic acid (e.g., boric acid, citric acid, and tartaric acid) in the feed material. Finely pulverized inorganic substances, such as calcium carbonate and talc are preferred. The particle size of nucleating agent is from 0.1 to 20 microns, preferably, from 1 to 3 microns. Preferably, the nucleating agent is present in an amount of from about 0.01% to about 5% by weight of polyester, more preferably, of from about 0.1% to about 3% by weight. In general, more nucleating agent gives a smaller average cell diameter. If the amount exceeds 5% by weight, agglomeration or insufficient dispersion of nucleating substance occurs, which results in over-expanded cells and often cell collapse. On the other hand, if the nucleating agent is present in an amount of less than about 0.01% by weight, the nucleating action is negligible.
In another embodiment, the polyester can be non-foamable polyester having one or more branching agents included as an additive to render the polyester foamable in situ. Upon feed-mixture heating and melting, the polyester and branching agent react, in situ, to give foamable polyester, which is extruded as above. Such a process is described in U.S. Pat. No. 5,340,846 (issued Aug. 23, 1994) and U.S. Pat. No. 6,254,977, (issued Jul. 3, 2001) both of which are hereby incorporated by reference herein.
Optionally, the feed mixture may comprise further additives, as well known in the art, depending on the desired properties of the core material. Examples of other additives include, but are not limited to reclaim polymer generated in manufacturing, flame retardants, colorants or pigments, anti-static agents, antioxidants, ultraviolet ray absorbents, and reinforcement by short fibers, etc.
The blowing agents suitable for use in the invention generally have a boiling point temperature range of about −90° C. to about 130° C. Suitable blowing agents include, but are not limited to, aliphatic hydrocarbons, such as octane, heptane, hexane, cyclohexane, pentane, cyclopentane, isopentane, neo-pentane, isobutane, butane, propane, and ethane; alcohols, such as methanol, ethanol, isopropanol, and butanol; non-fully chlorinated chlorohydrocarbons, partially or fully fluorinated fluorohydrocarbons, and non-fully halogenated fluorochlorohydrocarbons, such as 1-chloro-1,1-fluoroethane; 1,1,1,2-tetrafluoroethane (HFC 134a); 1,1-difluoroethane (HFC 152a); 1-chloro-1,1-difluoroethane (HCFC 142b); 1,1,1,3,3-pentafluorobutane (HFC-365mfc); 1,1,1,3,3-pentafluoropropane (HFC-245fa); gases, such as carbon dioxide, argon, and nitrogen; and compounds that decompose in situ to release a blowing-agent gas, such as azobisformamide or azodicarbonamide. Preferably, the blowing agent is hexane, carbon dioxide, or 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane.
The amount of blowing agent depends on the desired foam density and such amounts are readily determined by well-known methods, such as those described in U.S. Pat. No. 5,681,865 (issued Oct. 28, 1997), hereby incorporated herein by reference. The amount of blowing agent should not exceed an amount that causes separation between the polyester melt and blowing agent in the extruder, that is exceeds the solubility of said blowing agent in the melt at operating temperatures The preferred amount of blowing agent is of from about 0.5% by weight to about 15% by weight of the feed mixture, more preferably, of from about 1% to about 5%, most preferably, of from about 1% to about 3%. Mixtures of blowing agents can be employed, such as the mixtures described in U.S. Pat. No. 5,679,295 (issued Oct. 21, 1997) according to the procedure described therein, hereby incorporated by reference herein. For example, the following combination of blowing agents could be used: (1) of from about 50 mole percent to about 99.9 mole percent of a first blowing agent having a boiling temperature at STP (Standard Temperature and Pressure) of greater than 310° K, such as heptane, octane, or cyclopentane; (2) of from about 0.1 mole percent to about 50 mole percent of a second blowing agent having a boiling temperature at STP of less than 310° K, such as butane, tetrafluoroethane, carbon dioxide, or pentane.
Foam strands that exit from the orifice generally expand to about 3 to about 6 times the orifice diameter depending on the density, thus the ratio of total orifice cross-sectional area to that of the interior of the die just ahead of the orifice-containing faceplate should be less than 10 percent, more preferably, less than 5 percent.
The die plate comprises a plurality of orifices, in the shape of holes, slits, or any other desired shape, such as square saw tooth or triangular saw tooth wave pattern. The size of the holes can be calculated based on a method described in U.S. Pat. No. 6,197,233 (issued Mar. 6, 2001), hereby incorporated by reference herein. The ratio of the theoretical diameter of an individual strand to the distance between the orifices is, preferably, greater than or equal to 1, more preferably, greater or equal to 1.2. The theoretical diameter of each strand can be calculated based on the foam volume expansion and extrusion-direction speed of the product. The foam volume can be calculated from mass balance and foaming temperature. The orifice size and overall open area are determined also by considering extrude throughput and foaming pressure. The big overall open area can increase throughput and foam cross section area, but reduce the die pressure and cause foaming in die. The only limitation on special arrangement of the die orifices is that contact and coalescence of adjacent strands or profiles after extrusion from the die faceplate must be achieved.
Merely by way of example, a suitable die plate has the following construction: a diameter of orifice is about 1.5 mm, wherein the orifices are arranged in a triangular pattern with a distance of about 6.5 mm between the center of the orifices. In another embodiment, a preferred die-faceplate pattern comprises evenly spaced circular orifices of a diameter of from about 0.8 mm to about 4 mm, preferably, of from about 1.5 mm to about, more preferably, of from about 1 mm to about 2 mm. For example, a suitable die is a circular carbon steel plate of a diameter of 165 mm comprising about 34 equally spaced circular-shaped holes, contained in an area of 7 cm×2 cm, arranged in four rows, wherein the holes are about 0.065 inches (1.65 mm) in diameter and spaced approximately 0.25 inches (6.35 mm) between the centers. In another example, a suitable die is a circular carbon steel plate of a diameter of 165 mm comprising about 34 equally spaced circular-shaped holes, contained in an area of 7 cm×2 cm, arranged in four rows, wherein the holes are about 0.052 inches (1.32 mm) in diameter and spaced approximately 0.25 inches (6.35 mm) between the centers. In yet another example, a suitable die is a circular carbon steel plate of a diameter of 165 mm comprising about 78 equally spaced circular-shaped holes contained in an area of 10 cm×2.5 cm arranged in five rows, wherein the holes are about 0.065 inches (1.62 mm) in diameter and spaced approximately 0.25 inches (6.35 mm) between the centers. Special alloys of more highly conductive metals, such as beryllium-copper, and having heat-transfer fluid passages or electric heaters, would be advantageous in the precise control of temperature of the die faceplate.
Core materials of the invention are chemically and thermally stable by virtue of the polyesters from which they are derived. Furthermore, by virtue of the preparation methods described herein, the core materials of the invention are low-density, relatively small-cell sized, closed-cell foams, of uniform cell size with a low open-cell count. The core materials of the invention are further characterized by excellent mechanical properties, such as high compression strength and compression modulus, high shear strength and shear modulus, and high tensile strength and tensile modulus. Strength refers to the maximum load per unit of area transverse to the loading direction, that the material can resist. Modulus is precise measurement of how much deformation the material will exhibit under a given load. High modulus means that the structure deforms relatively little under large applied forces.
As discussed above, in the shaping process, as the recently extruded multi-stranded core material is forced or pulled through the shaper; it is compressed, thereby removing the inter-strand voids, such that the core materials of the invention appear to be unitary (the strand structure is not visible to the human eye). The properties, however, of the unitary polyester core materials of the invention are much improved over traditional unitary block foams produced by extruding through a single-aperture die or unshaped multi-stranded foams. The origins of these improved properties, such as strength, are not fully understood, but may be due to the change in cell-size distribution that accompanies extrusion and shaping of multi-stranded polyester foams. Upon extrusion and prior to shaping, the core material comprises a multitude of coalesced foamed strands having inter-strand voids running parallel to the strand direction. Upon shaping, the inter-strand voids are removed, and the core materials of the invention often appear unitary, although, in some cases, the strand intersections can be seen.
Surprisingly, however, a plurality of “discrete volumes”, running parallel to the length of the core material results. These “discrete volumes” comprise an “interior section” running parallel the strand-direction and a “jacket” surrounding the “interior section of the discrete volume”. This interior section has closed cells of average cell size relatively larger than the average cell size of the cells in the surrounding “jacket”. In other words, the average-cell diameter is smaller where the strands have intersected and merged than at the original strand's interior. Accordingly, as used herein, the phrase “interior section of the discrete volume” means a section within a core material of the invention running in the strand direction that is surrounded by a “jacket”. For example, the “jacket” could be a donut shaped cylindrical volume and the interior section of the discrete volume a cylindrical core inside the cylindrical donut. It follows that the sum value of the volume of the “interior section of the discrete volume” and the volume of the “jacket” equals the “discrete volume”, which discrete volume approximates the volume of the corresponding strand before shaping.
Where the interior section of the discrete volume approximates a cylinder shape, such a cylinder has a cross-sectional area of π(x)(½d)2 where “d” is the diameter of the discrete volume. Preferably “x” is a value of from about 0.99 to about 0.01, more preferably, of from about 0.95 to about 0.5, even more preferably, of from about 0.90 to about 0.75. The volume and shape of the “jacket” surrounding the “interior section of the discrete volume” is the difference between the discrete volume and the volume of the interior section of the discrete volume. Suitable extrapolations can be made by one of skill in the art when the interior section does not approximate a cylinder. Preferably, the average cell diameter of cells in the jacket of the discrete volume is of from about 5% to about 98% of the average cell diameter of cells in the interior section of the discrete volume, more preferably, of from about 20% to about 80%, even more preferably, of from about 30% to about 70%. This inter-strand cell-size distribution can be viewed by any suitable technique, such as optical microscope techniques so as to distinguish cell diameters within the plurality of discrete volumes.
The core materials of the invention are significantly anisotropic in character; meaning that they exhibit different physical properties depending upon which axis (direction) the property is measured. For example, the core materials of the invention exhibit different shear properties, tensile properties, and compressive properties depending upon the axis along which the property was measured. This character is related to the fact that the core materials of the invention are derived from compressed strands. Although the strand character of the core materials of the invention may not be visible, the anisotropic character is readily apparent through standard testing, for example, testing for differences in shear properties versus applied-force direction, tensile properties versus applied-force direction, and compressive properties versus applied-force direction. For example, in a core material of the invention, the shear strength in the end-strand direction differs from the shear strength in the transverse direction, which both differ from the shear strength in the longitudinal direction.
In core materials of the invention, the shear strength differs, the shear modulus differs, and the shear elongation at break differs depending on the relationship between the applied-force direction and the strand direction. Preferably the shear strength difference ranges from about 10% to about 400% higher in the end-strand over the transverse direction, more preferably, from about 20% to about 200%, even more preferably, from about 40% to about 150%. Preferably, the shear modulus difference ranges from about 10% to about 400% higher in the end-strand over the transverse direction, more preferably, from about 20% to about 200%, even more preferably, from about 40% to about 150%. Preferably the shear elongation at break point difference ranges from about 10% to about 600% higher in the end-strand over the transverse direction, more preferably, from about 20% to about 400% even more preferably, from about 50% to about 200%.
In core materials of the invention, the tensile strength differs and the tensile modulus differs depending on the relationship between the applied-force direction and the strand direction. Preferably the tensile strength difference ranges from about 100% to about 3000% higher in the end-strand over the transverse direction, more preferably, from about 500% to about 2000%, even more preferably, from about 800% to about 1100%. Preferably the tensile modulus difference ranges from about 100% to about 3000% higher in the end-strand over the transverse direction, more preferably, from about 500% to about 2000%, even more preferably, from about 900% to about 1500%.
In core materials of the invention, the compressive strength differs and the compressive modulus differs depending on the relationship between the applied-force direction and the strand direction. Preferably the compressive strength difference ranges from about 50% to about 1000% higher in the end-strand over the transverse direction, more preferably, from about 100% to about 500%, even more preferably, from about 120% to about 300%. Preferably the compression modulus difference ranges from about 10% to about 500% higher in the end-strand over the transverse direction, more preferably, from about 20% to about 200%, even more preferably, from about 30% to about 100%.
The core materials of the invention are characterized by low density, preferably, of from about 1 kg/m3 to about 400 kg/m3, more preferably, of from about 50 kg/m3 to about 300 kg/m3, and most preferably, of from about 60 kg/m3 to about 250 kg/m3 as measured according to ASTM Test Method D1622-98 “Standard Test Method for Apparent Density of Rigid Cellular Plastics”, hereby incorporated by reference herein. This publication sets forth procedures for the determination of both the apparent overall density and the apparent core density of cellular plastics.
The core materials of the invention are characterized by small average cell size, preferably, of from about 0.05 mm to about 1.5 mm, more preferably, of from about 0.1 mm to about 0.5 mm, as measured according to ASTM Test Method D3576-98 “Standard Test Method for Cell Size of Rigid Cellular Plastics”, hereby incorporated by reference herein. This publication sets forth methods for determination of the apparent cell size of rigid cellular plastics by counting the number of cell-wall intersections in a specified distance. Procedure A requires the preparation of a thin slice, not more than one half the average cell diameter in thickness, that is mechanically stable. For most rigid cellular plastics this limits the test method to materials with an average cell size of at least 0.2 mm. Procedure B is intended for use with materials whose friable nature makes it difficult to obtain a thin slice for viewing.
The core materials of the invention are characterized by a low open-cell content, preferably, of from about 5 to about 20, more preferably, of from about 5 to about 10 as measured according to ASTM Test Method D2856-94 (1998) “Standard Test Method for Open-Cell Content of Rigid Cellular Plastics by the Air Pycnometer”, hereby incorporated by reference herein. Cellular plastics are composed of the membranes or walls of polymer separating small cavities or cells. These cells may be interconnecting (open cell), non-connecting (closed cell), or any combination of these types. This test method determines numerical values for open cells. It is a porosity determination, measuring the accessible cellular volume of a material. The volume occupied by closed cells is considered to include cell walls. This test method consists of three procedures: procedure A, designed to correct for cells opened during sample preparation, by measuring cell diameter, calculating, and allowing for surface volume; procedure B, designed to correct for cells opened in sample preparation, by cutting and exposing new surface area equal to the surface area of the original sample dimension; and procedure C, which does not correct for cells opened during sample preparation and gives good accuracy on predominantly highly open-celled materials. The accuracy decreases as the closed-cell content increases and as the cell size increases.
High compression strength and medium compression modulus in the strand direction characterize the core materials of the invention. For example, core materials of the invention, preferably, have a compression strength of from about 0.20 Mpa to about 1.5 Mpa, more preferably, of from about 1.0 to about 1.5 Mpa at a density of 80 kg/m3. At a density of 140 kg/m3, preferably, the core materials have a compression strength of from about 0.8 Mpa to about 2.5 Mpa, more preferably, of from about 1.5 Mpa to about 2.5 Mpa. Preferably, core materials of the invention have a compression modulus of from about 10 Mpa to about 30 Mpa, more preferably, of from about 15 Mpa to about 25 Mpa at a density of 80 kg/m3. At a density of 140 kg/m3, preferably, the core materials have a compression modulus of from about 25 Mpa to about 65 Mpa, more preferably, of from about 45 Mpa to about 55 Mpa. Compression properties can be measured according to the procedure set forth in ASTM Test Method C365-00 “Standard Test Method for Flatwise Compressive Properties of Sandwich Cores”, hereby incorporated by reference herein. This publication describes determination of the compressive strength and modulus of composite cores. These properties are usually determined for design purposes, in a direction normal to the plane of facings as the core would be placed in a structural sandwich construction. The test procedures pertain to compression in this direction in particular, but also can be applied with possible minor variations to determining compressive properties in other directions.
The core materials of the invention are characterized by medium tensile strength and high tensile modulus. Tensile strength of the core material provides and indication of its composite's resistance to skin buckling upon edgewise loading. For example, core materials of the invention, preferably, have a tensile strength of from about 0.5 Mpa to about 2.5 Mpa, more preferably, of from about 1 Mpa to about 2 Mpa at a density of 80 kg/m3. At a density of 140 kg/m3, the core materials, preferably, have a tensile strength of from about 1.5 Mpa to about 3.5 Mpa, more preferably, of from about 2 Mpa to about 3 Mpa. Preferably, core materials of the invention have a tensile modulus of from about 50 Mpa to about 200 Mpa, more preferably, of from about 100 Mpa to about 150 Mpa at a density of 80 kg/m3. At a density of 140 kg/m3, the core materials, preferably, have a tensile modulus of from about 100 Mpa to about 300 Mpa, more preferably, of from about 150 Mpa to about 250 Mpa. The tensile strength and modulus can be measured according to the procedure set forth in ASTM Test Method C297-94 “Standard Test Method for Flatwise Tensile Strength of Sandwich Constructions”, hereby incorporated by reference herein. This publication illustrates the determination of the core flatwise tension strength, or the bond between core and facings of an assembled sandwich panel. The test consists of subjecting a sandwich construction to a tensile load normal to the plane of the sandwich, such load being transmitted to the sandwich through thick loading blocks bonded to the sandwich facings or directly to the core.
The core materials of the invention are characterized by medium shear strength and high shear modulus. For example, core materials of the invention, preferably, have a shear strength of from about 0.3 MPa to about 1.5 Mpa, more preferably, of from about 0.6 MPa to about 1.2 Mpa at a density of 80 kg/m3. At a density of 140 kg/m3, the core materials, preferably, have a shear strength of from about 0.5 MPa to about 3 Mpa, more preferably, of from about 1 Mpa to about 2 Mpa. Preferably, core materials of the invention have a shear modulus of from about 10 to about 35, more preferably, of from about 20 MPa to about 30 MPa at a density of 80 kg/m3. At a density of 140 kg/m3, the core materials, preferably, have a shear modulus of from about 20 Mpa to about 60 MPa, more preferably, of from about 30 MPa to about 50 Mpa. The shear strength and modulus can be measured according to the procedure set forth in ASTM Test Method C273-00e1 “Standard Test Method for Shear Properties of Sandwich Core Materials”. This publication illustrates the determination of shear properties of sandwich construction core materials associated with shear distortion of planes parallel to the facings. It describes determination of shear strength parallel to the plane of the sandwich, and the shear modulus associated with strains in a plane normal to the facings. The test may be conducted on core materials bonded directly to the loading plates or the sandwich facings bonded to the plates.
Composites of the invention can be prepared according to well-known methods by integrally bonding the core materials of the invention to standard composite skins. Examples of such methods are described in U.S. Pat. No. 6,206,669 (issued Mar. 27, 2001); U.S. Pat. No. 6,156,146 (issued Dec. 5, 2000); U.S. Pat. No. 6,117,519 (issued Sep. 12, 2000); U.S. Pat. No. 6,013,213 (issued Jan. 11, 2000); U.S. Pat. No. 5,916,672 (issued Jun. 29, 1999); U.S. Pat. No. 5,904,972 (issued May 18, 1999); U.S. Pat. No. 5,580,502 (issued Dec. 3, 1996); and U.S. Pat. No. 5,316,462 (May 31, 1994), all of which are hereby incorporated by reference herein. Just about any composite skin suitable for use with thermoplastic foam cores can be used. Such composite skins are commercially available, for example, from M. C. Gill (El Monte, Calif.), DFI Pultrude Composites, Inc. (Erlanger, Ky.); and Gordon Plastics (Montrose, Calif.). Examples of suitable composite skins include, but are not limited to, thermoplastic polymers and thermosetting polymers, optionally reinforced with glass fibers, metallic fibers, inorganic fibers, or carbon fibers; wood; inorganic materials, such as fiberglass; and metallic materials, such as aluminum and stainless steel and many others, which are well known to those of skill in the art. The composites can be built up in layers. When building composites in layers one or more structural skins can comprise another structural sandwich composite.
A preferred composite-manufacture method is resin infusion molding, which comprises vacuum suction to pull liquid resin into a dry lay up (composite skins and core materials) with almost no hazardous-vapor emissions. The chemically and thermally resistant core materials of the invention are especially suited to such processing.
In some applications where it is necessary that the core of the laminate be conformed to a curved surface, such as a boat hull or a cylindrical storage tank, the core materials of the invention can be processed into a contourable blankets or web-like structures, wherein the core material of the invention is divided into an array of smaller blocks or tiles. Such a blanket may be adhered to a fabric scrim or common carrier whereby the blanket can be conformed to a contoured surface. A process for producing contourable blankets from foamed articles is disclosed in U.S. Pat. No. 5,798,160 (issued Aug. 25, 1998), hereby incorporated herein by reference. The contourable blanket structures are thereafter bonded to skins to form contoured composite materials of the invention.
To produce contourable core materials of the invention, several standard slabs are stacked and bonded together by thermal fusion or by a suitable adhesive to create a large multi-slab block. The block is then sliced transversely in parallel planes normal to the lines of adhesive to yield a plurality of panels. A saw can be used for slicing. Each panel is composed of a series of interconnected foam-plastic sections derived from respective slabs of the block whereby the density of the sections is evenly distributed throughout the panel and the mechanical properties of the panel are therefore predictable and satisfy structural laminate criteria.
In the basic process for producing composite materials of the invention, the core materials of the invention (in rigid, contourable-blanket form, or any other form) and skins are laid up in a tool while dry then a vacuum bag is placed over the lay up and sealed to the tool. Resin is introduced via a resin inlet and distributed throughout the laminate. The pressure differential provides the driving force for infusing the resin into the lay up. The procedure is described in detail in U.S. Pat. No. 4,902,215 (issued Feb. 20, 1990); U.S. Pat. No. 5,052,906 (issued Oct. 1, 1991); U.S. Pat. No. 5,721,034 (issued Feb. 24, 198); U.S. Pat. No. 5,904,972 (issued May 18, 1999); U.S. Pat. No. 5,958,325 (issued Sep. 28, 1999); and U.S. Pat. No. 6,159,414 (issued Dec. 12, 2000), all of which are hereby incorporated herein by reference. Vacuum-bag lay-up products are commercially available, for example, from Airtech International (Carson, Calif.); Hawkeye Enterprises (Los Angeles, Calif.); National Aerospace Supply Co. (San Elemente, Calif.); Richmond Aircraft Supply (Norwalk, Calif.) and Taconic, Process Materials Division (Santa Maria, Calif.). Resins for bonding the skins to the core materials of the invention are commercially available, for example, from Aircraft Spruce & Specialty Company (Corona, Calif.); CMI/Composite Materials Inc. (Santa Fe Springs); E. V. Roberts (Culver City, Calif.); Gougen Brothers, Inc. (Bay City, Mich.); and National Aerospace Supply Co. (San Elemente, Calif.).
A mixture of polyethylene terephthalate resin (COBIFOAM 0, purchased from M&G Polymers, Patrica, Italy) having an intrinsic viscosity of 1.25 dl/g; and a melting point of 251° C. and nucleating agent was dried for 5 hours at 330° F. (165° C.) by a dehumidified dryer. The mixture was charged into a two-stage extruder having a 2.5″ (6.35 cm) single-screw, length to diameter of 44 to 1, with a SMR melt cooler heated to a temperature of 280° C.; and pressurized to 10 Mpa, a polyethylene terephthalate melt. Blowing agent (3 weight percent of the total weight of the melt) was injected by a injection pump and the mixture homogenized in the extruder by mixing section, static mixer and SMR melt cooler to give a foamable gel. The temperature was reduced to 250-255° C. at a pressure of 3.5-5.0 Mpa and the foamable gel was extruded through a rectangular multi-orifice die plate that was fastened on the die body, which the other end of the die body was attached to the melt cooler. The extrusion rate was 20 kg/hr. The die plate was 7.0 cm×2.0 cm and comprised 34 equally spaced circular-shaped holes arranged in four rows. The holes were approximately 0.065 inches (1.65 mm) in diameter and spaced approximately 0.25 inches (6.35 mm) between the centers.
The following parameter values were used in the extrusion.
The resulting coalesced multi-stranded pre-shaped core material was conveyed through a shaper of the invention, constructed of aluminum plate, having a width of 7 cm and a length of 30 cm. The ratio of the opening area to the parallel cross-sectional area was 2.3. The first 2.5 cm range of shaper has a 12° angle of decline so that the expanded strands can be squeezed and compressed into foam board without voids between strands. The distance of the cap plate to the bottom of shaper was adjusted from 3 cm to 4 cm based on output of extrusion and speed of take off equipment.
The resulting core material of the invention had a cross section of 7 cm by 3.4 cm; uniform cell size (<0.2 mm); no voids between the strands; and a foam density of 5.4 pcf (86.5 kg/m3) pounds per cubic foot. The core material so produced had the following characteristics:
The procedure of Example 1 was followed using 4 weight percent blowing agent and a die plate of 7.0 cm×2.0 cm comprising 34 holes each of 0.052 inches (1.32 mm) in diameter. The holes and rows were equally spaced at approximately 0.25 inches (6.35 mm) between the centers. The coalesced multi-stranded pre-shaped core material was shaped as described in Example 1. The resulting core material of the invention had a cross section of 2.75 inches (7.0 cm) by 1.45 inches (3.68 cm); uniform cell size (<0.3 mm); no voids between the strands; and a foam density of 4.7 pounds per cubic foot (75 kg/m3). The core material so produced had the following characteristics:
The procedure of Example 1 was followed, with 0.15 weight percent talc as a nucleating agent and 2 weight percent blowing agent. The resulting core material of the invention had a cross-section of 7.0 cm by 3.18 cm; a uniform cell size (<0.2 mm); no voids between the strands; and a foam density of 7.56 pounds per cubic foot (121 kg/m3). The core material so produced had the following characteristics:
Using the procedure of Example 1, a foamable gel comprising a mixture of polyethylene terephthalate polyester resin (CRYSTAR 5067, available from Du Pont Polyester) having a melting point of 251° C. and 1.5 weight percent 1,1,1,2-tetrafluoroethane (HFC R134a) as a blowing agent was cooled to a temperature of 255° C. and extruded through the die plate. The SMR melt cooler was not used. The die plate was connected directly to the end of extruder; was 10 cm×2.5 cm; and comprised 78 equally spaced circular-shaped holes arranged in five rows. The holes were about 0.065 inches (1.65 mm) in diameter and spaced about 0.25 inches (6.35 mm) between their centers.
The resulting coalesced multi-stranded pre-shaped core material was conveyed through an aluminum-plate shaper of the invention having a width of 11 cm and a length of 30 cm. The ratio of the opening area to the parallel cross-sectional area was 1.6. The first 2.5 cm range of shaper has a 12° angle of decline so that the expanded strands can be squeezed and compressed into foam plank without voids between strands. The distance of the cap plate to the bottom of shaper was adjusted from 3 cm to 4 cm based on output of extrusion and speed of take off equipment.
The resulting core material of the invention had a cross section of 4.4 inches (11.2 cm) by 1.35 inches (3.4 cm), a uniform cell size (<0.01 mm), and no voids between the strands. The density was 9.5 pounds per cubic foot (152 kg/m3). The core material so produced had the following characteristics:
A mixture of polyethylene terephthalate resin (COBIFOAM 0, purchased from M&G Polymers, Patrica, Italy) having an intrinsic viscosity of 1.25 dl/g and a melting point of 251° C. and talc powder 0.3 weight %, was dried for 6 hours at 165° C. by a dehumidified dryer. The mixture was charged into a co-rotating twin-screw extruder, model BC 132 PET-F (BC Foam, Volpiano, Italy) equipped with a melt cooler and homogenizer. The extruder screw was 13.2 cm in diameter and 220 cm in length. The mixture was heated in the extruder to a temperature of 285° C. and pressurized to 5 Mpa, then 1,1-difluoroethane (R 152 A) (1.4 weight percent of the total weight of the melt) was introduced via an injection pump. The mixture was homogenized to give a foamable gel. The temperature of the foamable gel was reduced to about 250-255° C. and the pressure was adjusted to about 3.5-4.0 Mpa. The foamable gel was extruded at a rate of 180 kg/hr through a multi-orifice die plate of 42 cm×5 cm comprising 580 equally spaced circular-shaped holes arranged in eight rows. The holes were approximately 1.65 mm in diameter and spaced approximately 6.35 mm between centers.
The following parameter values were used in the extrusion:
The resulting coalesced multi-stranded pre-shaped core material was conveyed through an aluminum-plate shaper of the invention having a width of 43 cm and a length of 30 cm. The ratio of the opening area to the parallel cross-sectional area was 1.6. The first 2.5 cm range of shaper has a 12° angle of decline so that the expanded strands can be squeezed and compressed to remove inter-strand voids. The distance of the cap plate to the bottom of shaper was adjusted from 5 cm to 6 cm based on output of extrusion and speed of take off equipment.
The resulting core material of the invention has a cross section of 42 cm by 5.7 cm; uniform cell size (<0.2 mm); no voids between the strands; and a foam density of 135 kg/m3. The core material so produced had the following characteristics:
The procedure of Example 5 above was followed using 0.5 weight percent nitrogen as blowing agent. The resulting core material of the invention had a cross section of 40 cm by 3.80 cm; uniform cell size (<0.1 mm); no voids between the strands; and a foam density of 350-400 kg/m3.
The core material so produced had the following characteristics:
The procedure of Example 1 was followed except that: (1) the shaping process and shaper of Example 4 was used; (2) 0.3 weight percent talc was included in the foamable gel as a nucleating agent; and (3) 0.9 weight percent CO2 was included in the foamable gel as the blowing agent. The resulting core material of the invention had a cross-section of 420 cm×2.3 cm, a uniform cell size (<0.2 mm); no voids between the strands; and a foam density of 125 kg/m3. The core material so produced had the following characteristics:
Materials of the Invention
This Example demonstrates the pronounced anisotropic properties of core materials of the invention. Samples were selected from a density range of about 80 kg/m3 to about 150 kg/m3. The PET core materials of the invention were prepared according to Example 1 and had an average cell size 0.1 mm and an open-cell content <10%. Test samples were prepared by binding core materials of the invention (7 cm by 3.5 cm planks) into a block then cutting ½″ panels in the grain direction according to the procedure set forth in U.S. Pat. No. 4,536,427 (issued Aug. 20, 1985), hereby incorporated by reference herein. The test samples were cut from the block as end-strand panels or as flat-strand panel as appropriate depending on whether the test would be performed by applying force in the end-strand, transverse, or longitudinal directions.
The shear tests were conducted according to the procedure set forth in ASTM C-273 as discussed in Section 5.4.8 above. The results are shown in
The tensile tests were conducted according to the procedure set forth in ASTM C297-94 as discussed in Section 5.4.7 above. The results are shown in
The compression tests were conducted according to the procedure set forth in ASTM C365-00 as discussed in Section 5.4.6 above. The results are shown in
In sum, this example demonstrates that the core materials of the invention are significantly anisotropic in character.
This Example compares the shear properties of PET core materials of the invention against those of standard PET foam boards produced by extruding foamable PET through a conventional, rectangular slot die (“conventional PET foam boards”). The shear properties of the PET core materials of the invention were tested in the longitudinal direction.
The conventional foam boards and core materials of the invention used in this Example ranged in density from about 80 kg/m3 to about 215 kg/m3. Test sample of core materials of the invention were prepared as in Example 8 (6″×2.5″×0.5″), and the conventional PET foam boards (also 6″×2.5″×0.5″) can be obtained from M&G Polymers, Patrica, Italy. Both the conventional foam boards and the core materials of the invention had an average cell size of about 0.1 mm and an open-cell content of about <10%. The shear tests were conducted according to the procedure set forth in ASTM C-273 as discussed in Section 5.4.8 above.
The results are shown in
These graphs show: (1) that the shear strength of the PET core materials of the invention are about 50% higher than that of conventional foam boards over the entire density range; (2) the core materials of the invention have a higher shear modulus by about 25%-85% over that of the conventional foam boards over the density range; and (3) the shear elongation at break of core materials of the invention is about 100%-200% higher than that of the conventional foam boards over the density range. This Example illustrates that the core materials of the invention are far superior to conventional foam boards comprising the same composition.
Although the present invention has been described in considerable detail with reference to certain preferred embodiments and versions, other versions and embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the versions and embodiments expressly disclosed herein. The references discussed in Background Section 2 are not admitted to be prior art with respect to the invention.
Number | Name | Date | Kind |
---|---|---|---|
3413387 | Ohsol | Nov 1968 | A |
3467570 | Baxter et al. | Sep 1969 | A |
3573152 | Wiley et al. | Mar 1971 | A |
3674719 | Jenkins | Jul 1972 | A |
3720572 | Soda et al. | Mar 1973 | A |
3723586 | Foster et al. | Mar 1973 | A |
3830604 | Korpela | Aug 1974 | A |
3839268 | Kilian | Oct 1974 | A |
3857914 | Aishima et al. | Dec 1974 | A |
3861977 | Wiley | Jan 1975 | A |
3954365 | Barth et al. | May 1976 | A |
3954555 | Kole et al. | May 1976 | A |
3954928 | Omori et al. | May 1976 | A |
3980513 | Omori et al. | Sep 1976 | A |
3993721 | Soda et al. | Nov 1976 | A |
4032275 | Schwab et al. | Jun 1977 | A |
4073842 | Smith | Feb 1978 | A |
4074960 | Dockray et al. | Feb 1978 | A |
4192839 | Hayashi et al. | Mar 1980 | A |
4221621 | Seki et al. | Sep 1980 | A |
4224264 | Ort et al. | Sep 1980 | A |
4284596 | Inokuchi et al. | Aug 1981 | A |
4312960 | Ort et al. | Jan 1982 | A |
4361453 | Gagliani et al. | Nov 1982 | A |
4369261 | Gagliani et al. | Jan 1983 | A |
4394461 | Stott | Jul 1983 | A |
4401612 | Nehmey et al. | Aug 1983 | A |
4409165 | Kim | Oct 1983 | A |
4419309 | Krutchen | Dec 1983 | A |
4431752 | Oswitch | Feb 1984 | A |
4438058 | Tanaka | Mar 1984 | A |
4438223 | Hunter | Mar 1984 | A |
4440704 | Bussey, Jr. | Apr 1984 | A |
4440876 | Mazzola et al. | Apr 1984 | A |
4454087 | Hayashi et al. | Jun 1984 | A |
4456571 | Johnson | Jun 1984 | A |
4462947 | Huggard | Jul 1984 | A |
4464484 | Yoshimura et al. | Aug 1984 | A |
4465649 | Johnson | Aug 1984 | A |
4465792 | Carr et al. | Aug 1984 | A |
4469651 | Hahn et al. | Sep 1984 | A |
4470938 | Johnson | Sep 1984 | A |
4479914 | Baumrucker | Oct 1984 | A |
4486369 | Schafler et al. | Dec 1984 | A |
4491554 | Hamel et al. | Jan 1985 | A |
4508669 | Iwai et al. | Apr 1985 | A |
4520137 | Hamel et al. | May 1985 | A |
4522954 | Ive | Jun 1985 | A |
4525440 | Barnette et al. | Jun 1985 | A |
4525485 | Maeda et al. | Jun 1985 | A |
4532094 | Wu et al. | Jul 1985 | A |
4536427 | Kohn | Aug 1985 | A |
4548775 | Hayashi et al. | Oct 1985 | A |
4550123 | Lopatin et al. | Oct 1985 | A |
4562022 | Li et al. | Dec 1985 | A |
4579874 | Krutchen | Apr 1986 | A |
4579878 | Krutchen et al. | Apr 1986 | A |
4600727 | Pastorino | Jul 1986 | A |
4606873 | Biglione et al. | Aug 1986 | A |
4613627 | Sherman et al. | Sep 1986 | A |
4665105 | Krutchen et al. | May 1987 | A |
4693856 | Rubens et al. | Sep 1987 | A |
4728472 | Windley et al. | Mar 1988 | A |
4730009 | Soredal | Mar 1988 | A |
4753762 | Li et al. | Jun 1988 | A |
4755408 | Noel | Jul 1988 | A |
4801484 | Yao et al. | Jan 1989 | A |
4810440 | Yoshida et al. | Mar 1989 | A |
4824720 | Malone | Apr 1989 | A |
4837060 | Bambara et al. | Jun 1989 | A |
4843109 | Bailey et al. | Jun 1989 | A |
4858629 | Cundari | Aug 1989 | A |
4865786 | Shibukawa et al. | Sep 1989 | A |
4879078 | Antoon, Jr. | Nov 1989 | A |
4917845 | Cohn | Apr 1990 | A |
4923654 | Freeland | May 1990 | A |
4942092 | Takabayashi et al. | Jul 1990 | A |
4980389 | Hill et al. | Dec 1990 | A |
4990542 | Motani et al. | Feb 1991 | A |
5000991 | Hayashi et al. | Mar 1991 | A |
5023009 | Merchant | Jun 1991 | A |
5023010 | Merchant | Jun 1991 | A |
5064559 | Merchant et al. | Nov 1991 | A |
5071884 | Malone | Dec 1991 | A |
5080823 | Arnaud et al. | Jan 1992 | A |
5082608 | Karabedian et al. | Jan 1992 | A |
5086083 | Franklin et al. | Feb 1992 | A |
5089187 | Aptel et al. | Feb 1992 | A |
5089193 | Behrens et al. | Feb 1992 | A |
5096638 | Meyke | Mar 1992 | A |
5098595 | Merchant | Mar 1992 | A |
5100572 | Merchant | Mar 1992 | A |
5109029 | Malone | Apr 1992 | A |
5122316 | Saatchi et al. | Jun 1992 | A |
5124095 | Gianni et al. | Jun 1992 | A |
5124097 | Malone | Jun 1992 | A |
5124098 | Vischer | Jun 1992 | A |
5128079 | Damle et al. | Jul 1992 | A |
5133913 | Miyakawa et al. | Jul 1992 | A |
5134028 | Hayashi et al. | Jul 1992 | A |
5140052 | Franklin | Aug 1992 | A |
5141530 | Jensvold et al. | Aug 1992 | A |
5151229 | Burns | Sep 1992 | A |
5160674 | Colton et al. | Nov 1992 | A |
5182040 | Bartlett et al. | Jan 1993 | A |
5185111 | Lazar | Feb 1993 | A |
5188748 | Arnaud et al. | Feb 1993 | A |
5202069 | Pontiff | Apr 1993 | A |
5206082 | Malone | Apr 1993 | A |
5221492 | Bartlett | Jun 1993 | A |
5223545 | Kumar | Jun 1993 | A |
5229432 | Muschiatti | Jul 1993 | A |
5234640 | Amano et al. | Aug 1993 | A |
5234963 | Garcia et al. | Aug 1993 | A |
5240634 | Merchant | Aug 1993 | A |
5246976 | Pontiff | Sep 1993 | A |
5250579 | Smits et al. | Oct 1993 | A |
5254400 | Bonner, Jr. et al. | Oct 1993 | A |
5262444 | Rusincovitch et al. | Nov 1993 | A |
5266251 | Jensen | Nov 1993 | A |
5271886 | Collom et al. | Dec 1993 | A |
5277852 | Spydevold | Jan 1994 | A |
5278196 | Robin et al. | Jan 1994 | A |
5288764 | Rotter et al. | Feb 1994 | A |
5310513 | Yamamoto et al. | May 1994 | A |
5314925 | Burnell et al. | May 1994 | A |
5314927 | Kondo et al. | May 1994 | A |
5317033 | Motani et al. | May 1994 | A |
5317044 | Mooney et al. | May 1994 | A |
5321052 | Taka et al. | Jun 1994 | A |
5328650 | Ingram et al. | Jul 1994 | A |
5334336 | Franz et al. | Aug 1994 | A |
5348985 | Pearce et al. | Sep 1994 | A |
5358675 | Campbell et al. | Oct 1994 | A |
5360829 | Kawabe et al. | Nov 1994 | A |
5362763 | Al Ghatta et al. | Nov 1994 | A |
5368794 | Ou | Nov 1994 | A |
5373026 | Bartz et al. | Dec 1994 | A |
5384203 | Apfel | Jan 1995 | A |
5387617 | Hedstrand et al. | Feb 1995 | A |
5389319 | Hayashi et al. | Feb 1995 | A |
5391582 | Muschiatti et al. | Feb 1995 | A |
5391694 | Duh et al. | Feb 1995 | A |
5397807 | Hitchcock et al. | Mar 1995 | A |
5399595 | Sublett et al. | Mar 1995 | A |
5405563 | Hayashi et al. | Apr 1995 | A |
5407966 | Ebert et al. | Apr 1995 | A |
5409962 | Bartlett et al. | Apr 1995 | A |
5411683 | Shah | May 1995 | A |
5411689 | Lee et al. | May 1995 | A |
5422381 | Al Ghatta et al. | Jun 1995 | A |
5424016 | Kolosowski | Jun 1995 | A |
5458832 | Kabumoto et al. | Oct 1995 | A |
5468430 | Ekiner et al. | Nov 1995 | A |
5474695 | Macaudiere et al. | Dec 1995 | A |
5475035 | Park et al. | Dec 1995 | A |
5475037 | Park et al. | Dec 1995 | A |
5482977 | McConnell et al. | Jan 1996 | A |
5500173 | Dugan | Mar 1996 | A |
5507982 | Brotz | Apr 1996 | A |
5508316 | Nakamura et al. | Apr 1996 | A |
5514192 | Grigsby, Jr. | May 1996 | A |
5523036 | Luke et al. | Jun 1996 | A |
5527573 | Park et al. | Jun 1996 | A |
5531944 | Frisch | Jul 1996 | A |
5565497 | Godbey et al. | Oct 1996 | A |
5567370 | Deseke et al. | Oct 1996 | A |
5569421 | Grone | Oct 1996 | A |
5580503 | Hall, III et al. | Dec 1996 | A |
5601753 | Omure et al. | Feb 1997 | A |
5603873 | Ingram et al. | Feb 1997 | A |
5605937 | Knaus | Feb 1997 | A |
5618853 | Vonken et al. | Apr 1997 | A |
5648017 | Bartlett et al. | Jul 1997 | A |
5667740 | Spydevold | Sep 1997 | A |
5670102 | Perman et al. | Sep 1997 | A |
5679295 | Harfmann | Oct 1997 | A |
5681501 | Minor | Oct 1997 | A |
5681865 | Harfmann | Oct 1997 | A |
5696176 | Khemani et al. | Dec 1997 | A |
5700407 | Branger | Dec 1997 | A |
5707571 | Reedy | Jan 1998 | A |
5707573 | Biesenberger et al. | Jan 1998 | A |
5710186 | Chaudhary | Jan 1998 | A |
5710189 | Brandt | Jan 1998 | A |
5723510 | Kabumoto et al. | Mar 1998 | A |
5730894 | Minor | Mar 1998 | A |
5733472 | Minor et al. | Mar 1998 | A |
5753157 | Hall, III et al. | May 1998 | A |
5753161 | Lightle et al. | May 1998 | A |
5762818 | Minor et al. | Jun 1998 | A |
5776990 | Hedrick et al. | Jul 1998 | A |
5780539 | Tung | Jul 1998 | A |
5783610 | Fukushima et al. | Jul 1998 | A |
5786398 | Hulls et al. | Jul 1998 | A |
5798063 | Bender et al. | Aug 1998 | A |
5798160 | Kohn | Aug 1998 | A |
5804112 | Greene | Sep 1998 | A |
5811038 | Mitchell | Sep 1998 | A |
5811164 | Mitchell | Sep 1998 | A |
5823669 | Jones | Oct 1998 | A |
5830393 | Nishikawa et al. | Nov 1998 | A |
5833782 | Crane et al. | Nov 1998 | A |
5833894 | Lanzani et al. | Nov 1998 | A |
5833896 | Jacobs et al. | Nov 1998 | A |
5840212 | Doerge | Nov 1998 | A |
5847012 | Shalaby et al. | Dec 1998 | A |
5847017 | Brandt | Dec 1998 | A |
5854294 | Hirosawa et al. | Dec 1998 | A |
5866053 | Park et al. | Feb 1999 | A |
5889064 | Herrmann | Mar 1999 | A |
5902529 | Ishikawa et al. | May 1999 | A |
5904972 | Tunis, III et al. | May 1999 | A |
5912279 | Hammel et al. | Jun 1999 | A |
5922782 | Khemani | Jul 1999 | A |
5925450 | Karabedian et al. | Jul 1999 | A |
5938874 | Palomo et al. | Aug 1999 | A |
5955511 | Handa et al. | Sep 1999 | A |
5958164 | Ishiwatari et al. | Sep 1999 | A |
5977195 | Craig et al. | Nov 1999 | A |
5980795 | Klotzer et al. | Nov 1999 | A |
5985190 | Harfmann | Nov 1999 | A |
5994418 | Weiser et al. | Nov 1999 | A |
6005013 | Suh et al. | Dec 1999 | A |
6005014 | Blackwell et al. | Dec 1999 | A |
6007890 | DeBlander | Dec 1999 | A |
6013194 | Minor | Jan 2000 | A |
6015516 | Chung et al. | Jan 2000 | A |
6020393 | Khemani | Feb 2000 | A |
6031011 | Tapscott | Feb 2000 | A |
6033748 | Dunning et al. | Mar 2000 | A |
6051174 | Park et al. | Apr 2000 | A |
6054500 | Ghatta et al. | Apr 2000 | A |
6057379 | Choi et al. | May 2000 | A |
6063316 | Harfmann | May 2000 | A |
6066680 | Cope | May 2000 | A |
6071580 | Bland et al. | Jun 2000 | A |
6080798 | Handa et al. | Jun 2000 | A |
6080799 | Kruecke et al. | Jun 2000 | A |
6093350 | Sadinski | Jul 2000 | A |
6093750 | Craig et al. | Jul 2000 | A |
6103152 | Gehlsen et al. | Aug 2000 | A |
6110983 | Tokoro et al. | Aug 2000 | A |
6130261 | Harfmann | Oct 2000 | A |
6153293 | Dahl et al. | Nov 2000 | A |
6159414 | Tunis et al. | Dec 2000 | A |
6165308 | Chen et al. | Dec 2000 | A |
6169122 | Blizard et al. | Jan 2001 | B1 |
6172127 | Choi et al. | Jan 2001 | B1 |
6172128 | Lau et al. | Jan 2001 | B1 |
6197233 | Mason et al. | Mar 2001 | B1 |
6210788 | Cuypers | Apr 2001 | B1 |
6213540 | Tusim et al. | Apr 2001 | B1 |
6228897 | Daly et al. | May 2001 | B1 |
6232354 | Tan | May 2001 | B1 |
6241220 | Blackwell et al. | Jun 2001 | B1 |
6258864 | Dalton et al. | Jul 2001 | B1 |
6284810 | Burnham et al. | Sep 2001 | B1 |
6291539 | Kreiser et al. | Sep 2001 | B1 |
6294115 | Blizard et al. | Sep 2001 | B1 |
6294116 | Shih et al. | Sep 2001 | B1 |
6306320 | Flautt et al. | Oct 2001 | B1 |
6306921 | Al Ghatta et al. | Oct 2001 | B1 |
6315931 | Bruning et al. | Nov 2001 | B1 |
6328916 | Nishikawa et al. | Dec 2001 | B1 |
6334970 | Kuroda et al. | Jan 2002 | B1 |
6339109 | Day et al. | Jan 2002 | B1 |
6342173 | Harfmann | Jan 2002 | B1 |
6361724 | Maeda et al. | Mar 2002 | B1 |
6844055 | Grinshpun et al. | Jan 2005 | B1 |
20010018121 | Okamoto et al. | Aug 2001 | A1 |
20010023510 | Masubuchi | Sep 2001 | A1 |
20010031794 | Yamamoto et al. | Oct 2001 | A1 |
20010033040 | Cardona et al. | Oct 2001 | A1 |
20010051693 | Seo et al. | Dec 2001 | A1 |
20020008076 | Bartholomew | Jan 2002 | A1 |
20020017734 | Sugihara et al. | Feb 2002 | A1 |
20020024165 | Xu | Feb 2002 | A1 |
20020036363 | Kuroda et al. | Mar 2002 | A1 |
Number | Date | Country |
---|---|---|
2116940 | Aug 1972 | DE |
279668 | Aug 1988 | EP |
407252724 | Oct 1995 | JP |
411152363 | Jun 1999 | JP |
411166066 | Jun 1999 | JP |
02000052397 | Feb 2000 | JP |
0200345019 | Dec 2000 | JP |
02001096599 | Apr 2001 | JP |
02001347535 | Dec 2001 | JP |
Number | Date | Country | |
---|---|---|---|
20040001946 A1 | Jan 2004 | US |