WO1996004132A1 - Syntactic foam sheet material - Google Patents
Syntactic foam sheet material Download PDFInfo
- Publication number
- WO1996004132A1 WO1996004132A1 PCT/US1995/009977 US9509977W WO9604132A1 WO 1996004132 A1 WO1996004132 A1 WO 1996004132A1 US 9509977 W US9509977 W US 9509977W WO 9604132 A1 WO9604132 A1 WO 9604132A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- microspheres
- resin
- mixture
- layer
- syntactic foam
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
- B29C70/086—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
- B29C70/66—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler comprising hollow constituents, e.g. syntactic foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/001—Producing wall or panel-like structures, e.g. for hulls, fuselages, or buildings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/04—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the partial melting of at least one layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/046—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/08—Glass
- B32B2315/085—Glass fiber cloth or fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2361/00—Phenoplast, aminoplast
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/06—Molding microballoons and binder
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/07—Binding and molding cellular particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
- Y10T156/1043—Subsequent to assembly
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
- Y10T428/249972—Resin or rubber element
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
- Y10T428/249974—Metal- or silicon-containing element
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/647—Including a foamed layer or component
- Y10T442/652—Nonwoven fabric is coated, impregnated, or autogenously bonded
- Y10T442/653—Including particulate material other than fiber
Definitions
- This invention is generally related to a syntactic foam core material and a method of forming same, and, more particularly, to a syntactic foam core made of a mixture of hollow ceramic microspheres and a dry resin powder intermixed therewith.
- the hollow microspheres are joined together by heating the mixture to integrate the combination as a foam core material usable for example as a core for composite laminates, having preselectable strength, density and weight properties engineered therein.
- Syntactic foam layers and products have been conventionally made by intermixing glass microspheres with a heated liquid binding resin, and at times including reinforcing elements such as fibers.
- the use of resin in a fluid state heated to effect a cure results in a considerable release of fumes and liquid vapors which can interrupt or destroy the integrity of the material and often must be treated as environmentally objectionable.
- heat curing or setting of heated powdered resin in a mixture with microspheres results in little effluent of fumes or liquid vapor.
- phenolic resins for example, during heating to a liquid phase and curing give off vapors in a considerable amount whereas dry phenolic powders during heat curing give off little vapor.
- resin in a fluid condition is less adaptable to providing a syntactic foam microsphere mixture capable of the wide range of light densities
- a number of product properties can be imparted to a product by use of a reactive resin in powdered form that cannot be accomplished with resin in a liquid form.
- the bulk density of powdered resin is much less than the bulk density of solid resin of the same composition or liquid formed of the resin by heating it to a melted condition.
- An important advantage of using powdered resin mixed with ceramic microspheres to form a syntactic foam layer according to the present invention is that the bulk density of the final product can be the same as that of the initial compacted mixture.
- the powdered resin is converted to melted droplets which can flow over and join the microspheres of the mixture sacs may be aided by an adhesion promoting coating, for example a coupling agent, on the microspheres.
- the mixture is thus in a sense coalesced into a mass which upon hardening provides a light weight solid foam layer.
- the foam layer includes closed voids containing evolved gas and air.
- the bulk density of syntactic foam material as in the present invention can be half that of a conventional material made from liquid resin with intermixed microspheres.
- the present invention eliminates the problems of high viscosity when many microspheres are added to a liquid resin, and eliminates the process problem of getting microspheres (which tend to float) wetted out and incorporated into a liquid resin. It has been found that finer powder resins function much more effectively to produce the desired results than coarse powders. When the powders included are too coarse, the melting and dispersion of the material between the microspheres become more difficult and are much less effective in providing a uniformly integrated syntactic foam product.
- the mixture can be heated by a number of techniques including induction heating with high frequency energy or conductive heating such as with heated platens on opposite major surfaces of the layer of microspheres and resin powder.
- induction heating with high frequency energy or conductive heating
- a skin layer can be formed at the surfaces of the foam.
- a layer of separator material a material which will not bond or unite with the syntactic foam layer, is provided between each of the platen surfaces and the surfaces of the microsphere mixture.
- the mixture can be compacted by bringing the heating platens closer together to establish a predetermined thickness.
- the thickness can be established by placing spacer members of the predetermined desired thickness between the platens which will limit the closeness to which the platens can be moved and thereby establish the desired thickness of the product produced.
- the spacers can also function to limit the area over which the microsphere-resin powder mixture can spread. In other words, they can be used to confine the area of the mixture, such as in a tray, to establish the predetermined dimensions of the product to be produced.
- the invention is used to form a stratum or core for structural laminate panels, but variations of the mixture of glass microspheres and resin powder can be engineered for a wide range of products as well, such as flooring, ducts, and three dimensional products useable for aircraft, trucks, automobiles, ships, boats, industrial tanks and the like.
- the desired light weight and strength properties of the foam are attained in part by utilizing microspheres or bubbles, preferably hollow ceramic microspheres such as of glass commercially available in various diameters and wall thicknesses.
- the microsphere diameters and wall thicknesses are selected to impart specific predeterminable shear and compression strengths as well as desired weights and densities when integrated with the resin intermixed therewith.
- the powdered resin intermixed with the microspheres or bubbles is of substantially finer dimension than the bubbles thereby enabling thorough distribution of the powder and filling of the interstices between the bubbles.
- thermosetting resin refers to heat processing to a fluid then to a more stable hardened or set condition, but to facilitate description of the invention also refers herein to hardening of thermoplastic resins to a set condition upon cooling after being heated to a fluid condition according to the concepts of the present invention.
- the bubbles of the mass may be of different sizes which permits their close compaction into an intimate mass for strength, while the finer resin powder fills the interstices more readily to effect an inter-bonding of the bubbles and resin.
- the amount of resin incorporated in the core can be just sufficient to effect the desired inter-bonded relation between components of the mixture, which with a light concentration of the powder in the mixture can result in the cured syntactic layer being porous and permeable. More desirably, however, for most applications the concentration of powder in the mixture is such that the cured integrated mass is substantially impermeable to moisture beside having high shear and compression strengths.
- the foam mixture can optionally include reinforcing elements such as glass or carbon fibers or fibers of other high strength material.
- the fibers may be incorporated in the mixture as individual fibers, as bundles of chopped strands, or as continuous filaments in nonwoven mats or woven fabrics.
- Other reinforcing elements such as honeycomb structures can also be incorporated in the core material as well.
- An object of the invention is to provide a mixture of components for formation of a syntactic foam material capable of being engineered and manufactured economically into products having a wide range of predeterminable structural properties.
- Another more specific object of the invention is to provide a basic, easily processed, economically producible, light weight core material capable of providing structural properties in layer form adaptable to use in sandwich structure composites.
- a feature of the invention is that the combination of powdered phenolic material and glass microspheres gives off little or no volatiles or fumes during cure.
- the mixture can, within a wide range, be pre-engineered for a desired density, shear strength, compression strength, low flammability and low smoke and high moisture resistance while at the same time being capable of production at a low cost.
- a further feature is that a syntactic foam core layer for laminar structures can be produced with no reduction in thickness dimension of the layer during heat processing.
- Strength and density of the sheet can be modified by appropriate selection of the size and wall thickness of commercially available microspheres and the size and type of powder resin particles.
- the microspheres can be provided with a coating of a coupling agent such as silane to facilitate their coverage and inter-bonding by the melted resin powder.
- a coupling agent such as silane to facilitate their coverage and inter-bonding by the melted resin powder.
- the resin powders are of finer size than the small microspheres and fit in the interstices of the mass of microspheres to effect an inter-bonding upon heating and hardening. As the amount of resin present increases as part of the mixture the greater the weight of the microsphere foam product becomes.
- the process of producing the syntactic sheet or core material involves first combining the microspheres and powdered resin.
- the combination is preferably deposited as a layer on a base having a release agent or commercial release film over its surface to prevent bonding to the final foam product.
- the base also is provided with boundary means to define the dimensions of the product.
- the combination is first vibrated for thorough intermixture of the resin powder in the microsphere interstices, and the mixture is then heated to melt the resin particles for inter-bonding with the microspheres.
- pressure is not necessary to effect the inter- bonding of microspheres and resin, pressure can be applied to the mixture as an assist in effecting its compaction when a more dense product is desired.
- Such compaction of the mixture can be effected by bringing the overlying and underlying heated platens to a preselected spacing for a desired thickness of the layer.
- the thickness of a given deposited layer as well as its density and mechanical properties of the final product can thus be predetermined.
- structural reinforcement elements such as fibers (hollow or solid) or fiber bundles can also be selectively included.
- Other reinforcements for example can be mats of random reinforcing fibers or reinforcing fiber fabrics, both woven and non-woven, rods, glass flakes and honeycomb structures which in appropriate locations can improve mechanical properties such as shear strength and shear modulus of the sheet product.
- Resin in powder form such as can be formed by grinding down solid resin, is selected for its fineness to fill the interstices of the microspheres which can be accomplished more readily than with coarser powders.
- the powders are also selected for their chemical reactivity and heat softenable adhesive affinity for the glass microspheres. They can also be selected for low flame and smoke properties. In this regard, the invention is quite versatile in permitting trial and error establishment of the engineered properties desired.
- the resulting syntactic foam product is corrosion resistant, electrically and thermally relatively non- conductive, non-magnetic, electromagnetically transparent, light weight, much less than the weight of steel, has high strength and dimensional stability, and is adaptable to providing a wide range of physical and mechanical properties.
- any of a number of reactive resin powders may be used to provide the specific desired properties including, but not limited to, phenolic resins aforementioned as well as epoxy and epoxy-modified phenolic resin, polyester resin powders, polyurethane, and polyphenylene sulphide.
- powder resin from waste dust collection devices such as in a resin manufacturing plant, can be used in the present invention. Disposal of these waste materials is particularly an environmental problem because they are most frequently reactive powders. -The present invention is thus additionally advantageous in that it can frequently eliminate environmental problems by providing a value-added use for waste materials.
- Figure 1 is a broken away perspective view of a syntactic foam core made according to the concepts of the present invention
- Figure 2A is an illustration representative of a magnified broken away view of a portion of the product of Figure 1 as taken on line 2-2 illustrating a mixture of hollow microspheres of different sizes and cured resin powder intermixed therewith;
- Figure 2B is an illustration representative of a magnified broken away view of a product like that of Figure 2A including bundles of reinforcing fibers;
- Figure 3 is a representation of a layer of the mixture of the invention in a vibrating tray
- Figure 4 is a schematic illustration of a layer of syntactic core material of the present invention in a press for heat cure and selective pressurization of the material of the present invention to an integrated condition;
- Figure 5 is a schematic perspective view of a laminate product having top and bottom surface layers shown with an inbetween core layer of syntactic foam material of the present invention
- Figure 6 is a schematic illustration of a laminate including a core material of the present invention faced with opposite surface layers in a press in which the assembly can be heat cured and selectively pressurized to an integrated condition;
- Figure 7 is a broken away perspective view of syntactic core material of the present invention including reinforcing elements in the form of fiber bundles distributed through the resin-microsphere structure;
- Figure 8 is a schematic illustration of a portion of a continuous production line for producing a syntactic foam material according to the principles of the present invention.
- the beginning material of this invention is a particle mixture of hollow ceramic microspheres, preferably of glass, which are frequently referred to conventionally as bubbles, and resin powder of diameter finer than the microspheres which is heat softenable and curable or hardenable to effect inter-bonding of the mass into an integrated form.
- the beginning mixture may also include reinforcing elements such as chopped strands forming dispersed bundles of reinforcing fibers such as of glass or carbon.
- the powdered resin can be a thermosetting resin powder such as phenolic powders or powders of a high temperature thermoplastic resin such as polyphenylene sulfide reactor powder so that upon the mixture being heated, the mass of resin powders will soften and flow to effect the desired inter-bonding of the particles of the mass.
- a thermosetting resin powder such as phenolic powders or powders of a high temperature thermoplastic resin such as polyphenylene sulfide reactor powder
- a coating of an adhesion promoting material can be provided on the microspheres, such as a silane coating, to facilitate wet out of the microspheres which results in better adhesion.
- an adhesion enhancing material and the resin powder or a catalyst might be included in a thermosetting powdered resin.
- the resin is a phenolic resin
- a catalyst such as hexamethylenetetramine can be included which can be cured in an oven at a temperature in the order of 350 degrees F.
- the resin powder can be present in the mass of microspheres in an amount just adequate to effect the desired inter-bonding but at the high end of the volume spectrum can be present in an amount more than that which is adequate to fill interstices in the microsphere mass to form a solid integrated material of the mass.
- a range of densities of the microsphere mixture can thus be provided dependent upon the amount of resin incorporated therein.
- the melted resin flows over the surface of the microspheres into their points of close proximity so that upon solidification the microspheres are solidly fused together leaving a generally predeterminable amount of void space inbetween.
- a syntactic foam product of predeterminable density can be produced.
- the volume of resin powder is less than or just fills the interstices of the layer of microspheres, the density of the mass can be maintained fixed throughout the heat processing to the final product .
- the amount of powdered resin added to the hollow microsphere mass fills the entire void space between the microspheres in its dry unheated state, after melting of the powder voids between microspheres will still result because of the lower bulk density of the powder resin.
- the amount of resin powder by bulk volume is about 26%, upon contraction to a melted state, in a perfectly packed mass, an internal void space of about 13 to 17% in the final product results.
- the amount of powdered resin originally added to the mixture is less than about 26% for a theoretically perfectly packed mass of microspheres, such amount being just adequate to effect coverage and joinder of the microspheres, the void space remaining would be greater than 17% and result in a still lighter density syntactic foam.
- Inter-bonding of particles can be effected by mere deposition of the mixture lightly packed as a layer without application of pressure and mere supply of curing heat thereto such as by contact of a hot platen surface to one side thereof. It has been found desirable, however, to selectively apply pressure for compaction of the mass mixture to provide a desired density and thickness in the final product.
- the product as herein described is a planar core material for sandwich structure laminates, the concept of the invention lends itself to forming layers of different thicknesses in different regions as well as to form products of three dimensional shapes such as by deposition on a curved surface or in an intricately shaped mold type heating unit with or without the presence of surface layers of a laminate product.
- Figure 1 shows a heat cured syntactic foam sheet 10 formed of microspheres and resin to which surface skins or surface panel layers can be supplied to form a structural laminate.
- the thickness of the layer can be selected to provide the desired physical and mechanical properties of the finished composite laminate sandwich structure.
- Figure 2A shows a portion of the body 10 of the syntactic foam material of Figure 1 as taken on line 2-0 after being heated and set illustrating in detail the base particles of the integrated product wherein hollow microspheres 11, 12 and 13 of three different sizes with resin 14, originally in powdered condition, intermixed therewith as they appear in the cured body or sheet with voids 19 distributed therethrough.
- the resin powder used in forming the sheet product is of much finer size than the microspheres and is present in an amount adequate to effect the desired inter-bonding of the microspheres but, in some products of the invention, the resin powder is present in an amount selected to establish a predetermined bulk density as well as the desired shear and compression strengths of the sheet product which results and at the same time leaving open voids 19 within the body.
- Figure 2B illustrates a syntactic foam material like that of Figure 2A with glass fiber bundles 15 distributed therethrough to impart a greater shear strength to the core sheet to permit formation of higher strength laminate structures.
- Figure 3 is representative of a mixture 16 of microspheres and resin powder in a tray 17 mounted on a vibrator 18 typically at about 600 vibrations per minute for about 10-15 seconds to thoroughly intermix the components of the mixture prior to being heated.
- the tray 17 is made to provide the desired peripheral dimensions of the syntactic layer and thickness of boundary members for insertion in a heating unit.
- the tray 17 is provided with a layer of separator material at its bottom to avoid bonding of the mixture thereto and permit removal of the core material after heating to a resin melt stage and hardening.
- An overlayer of separator material is also provided over the top surface prior to insertion in a press type heating unit.
- Figure 4 illustrates a heating press 20 on pedestals 22 in which the syntactic foam core sheet 10 of Figure 1 can be produced having a base platen 24 and a moveable upper platen 21 both of which can be heated with the mixture of microspheres and resin located within a confined space determined by boundary members 28 of predetermined thickness and location in the press which determine the thickness to which the upper platen 21 can press the uncured mass as well as the boundary dimensions of the sheet 10 which finally results.
- the upper platen 21 can be lowered on guide rods 23 to a level of the thickness of the boundary members 28 and the mass of microspheres and resin particles can be deposited within the confines of the boundary members 28 to provide the degree of compaction which will result in the desired density of the final core sheet 10 determined by trial and error in forming the foam material.
- Figure 5 shows a laminate 40 incorporating a syntactic core 30 of the invention having panels or sheets 41 at its base and 42 over its upper surface.
- the lower and upper surfaces 41 and 42 respectively can be resin panels or metal sheets bonded to the core 30 as a sandwich structure designed to have the strength properties as determined by calculation and trial and error construction of the structure.
- the lower and upper panels 41 and 42 respectively can be bonded together with the core 30 of the type described in relation to Figure 1 by separate bonding of the faces to the core 30 after the core 30 has been cured as in a press 20 illustrated in Figure 6.
- the surface sheets can also be bonded to the core in a press as shown in Figure 6 wherein the lower panel 41 and upper panel 42 are placed in the press over the core material 40 as it is being heated to a cured condition.
- Boundary members 48 on opposite sides of the composite determine the thickness to which the upper platen 21 can press the combination. If one or both of the surface sheets are of pre-impregnated skin in an uncured condition, they can be combined with the syntactic foam core 40 while it is in an uncured state and the combination can then be cured in one cycle to effect a cure of both the skin layers as the core layer is being cured.
- both skin layers 41 and 42 can be subjected to a partial cure, such as by being brought to a B-stage cure prior to combination with the uncured core material and then in a single cycle of final cure the complete assembly can be cured.
- a partial cure such as by being brought to a B-stage cure prior to combination with the uncured core material and then in a single cycle of final cure the complete assembly can be cured.
- the assembly can be shaped in a die or mold positioned in the press to provide a desired shape for the final product.
- both surface layers 41 and 42 sandwitching the core can be made of sheet molding compound (SMC) layers in which the final cure is accomplished under heat and pressure.
- SMC sheet molding compound
- the sheet molding compound being an entrapped jell material will become solidified under heat and pressure when cured to provide the final surface layers.
- an uncured prepreg layer on one side of the core and a sheet molding compound layer can be assembled on the other side of the core as the outer layers of the laminate either before or while the laminate cure is effected.
- FIG 7 illustrates another form of the invention in which the syntactic foam layer 60 includes additional reinforcing elements such as glass fibers or carbon fibers in individual form or as chopped strand bundles or in the form of continuous strand mats or stacked non-woven or woven fabrics.
- foam material can be made substantially as represented in Figure 4.
- Figure 8 illustrates a continuous conveyor line rocess for production of syntactic foam sheet material according to the invention in which glass microspheres and resin powder, and optionally reinforcing elements, are introduced into a hopper 72 to which the components are supplied in continuously metered form or in batch form in predetermined percentage amounts by weight or volume to produce a mixture 71.
- the mixture 71 is supplied from the hopper through an end spout 73 to a conveyor belt 74 over an underlying vibrator 76 by which the mixture is sufficiently agitated to effect uniform distribution of the resin, and any included reinforcing elements uniformly throughout the mass of microspheres.
- the vibrated mixture then is conveyed by the continuously moving conveyor belt 74 having associated moveable side walls 75 on opposite edges of the conveyor belt which move in unison therewith to limit the breadth of distribution of the mixture deposited on the conveyor.
- the side walls 75 might optionally be stationary side walls but are preferably arranged to move in unison with the conveyor as a raised edge confining the particulate mixture to the width of the belt.
- the conveyor belt 74 is made of a high-temperature flexible material such as a high-temperature polymer material or can be a flexible metal belt such as a steel band.
- the conveyor with the uncured syntactic foam material deposited thereon is passed through a curing oven 77 having an overlying belt 78 arranged to mate with the conveyor belt 74 to compact the foam material 70 to the thickness determined by the height of the side walls 75 as 04132 PC17US95/09977
- the temperature and the rate of movement of the conveyor belt 74 through the oven are selected to provide the cure cycle matching the material 71 supplied from the hopper 72 by way of the channel 73.
- Both the conveyor belt 74 and the overlying belt 78 are surfaced with a separator material to avoid sticking or bonding of the foam material to the belts during the cure cycle.
- a continuous sheet of syntactic foam material moves from the oven 77 it is passed onto a secondary conveyor 81 where the length of the sheet is determined by cutting it with means such as a chopper 79.
- cutting means such as a saw, a laser, or a water jet cutter may be used to provide a syntactic foam sheet 80 meeting predetermined desired length specifications.
- Microspheres of glass included to lighten the weight of the foam material can have a bulk density in the order of 0.2 pounds per cubic foot.
- the density of the solid resin in contrast would be about 80 pounds per cubic foot.
- a final product can be made in a density range of from 6 to 45 pounds per cubic foot.
- the sheet material can be made to any thickness such as in the range of from about 1/16 inch to 6 inches or more.
- a mixture including phenolic resin as the matrix binder and a catalyst therefor along with the microspheres and additional reinforcing elements can be cured at a temperature in the order of 325-350 degrees F. with the heating surface in contact with the mixture for a period in the order of 10 minutes. No post cure of the product has been found necessary.
- the resulting foam material is formed practically without volitization of any components.
- the resin powder during heating goes through a transition stage in which it is in a semi-sticky liquid stage which ultimately becomes solid in consolidated relation with the glass microspheres and reinforcing elements.
- the foam character of the material results from the voids provided by both the hollow microspheres and the voids left by reason of melting of the powdered resin which solidifies to a much lesser volume than the bulk powdered resin.
- a syntactic foam product having a density of about 6 pounds can be formed in a cycle time in the range of 10-15 minutes.
- the upper platen can be closed slowly to compact the mixture without rupturing the microspheres.
- syntactic foam cores of different densities which have been made according to the present invention:
- the resin particle size in each of the above examples was in the order of 20 microns. A particle size of 50 microns is judged to be the upper desireable limit of the resin powder for satisfactory production of a foam according to the invention. The finer the resin powder the better the product properties that are attained, down to as low as one micron size particle.
- the glass bubbles in each of the examples above had a US 80 mesh particle size (177 microns) .
- the resin powder can be a reactive resin such as is produced as a waste byproduct from powdered resin coating materials.
- the small diameter dust powder collected as waste in a powdered coating production facility and which is usually air borne and collected as waste during manufacture of the powdered coating has been found to be excellent in providing syntactic foam according to the present invention.
- the reinforcement material for the syntactic foam layer is provided in the form of carbon fiber or glass fiber mats or high strength glass fiber mats or hollow glass fiber mats to increase the flex strength of the composite, a mat of sufficient thickness can be provided so that the resin powder and microspheres can be deposited and sifted into the mat by agitation.
- Such a process can provide a foam which when cured has improved physical and mechanical properties compared to a three component foam sheet which includes chopped fibers only as reinforcing elements.
- any number of skin materials can be bonded or molded to the core so made, including composite resin sheets of different material or metal sheets such as aluminum sheets.
- a layer of the mixture of basic components that is the bubbles, reinforcing media and powdered resin along with its catalyst if it is a thermosetting resin, can be pre-heated to a sticky integrated conformable stage which can then be draped over a three dimensional form for a final cure or hardening to the three dimensional article of desired shape.
- Microwave energy can be utilized for pre-heating and for cure of such a product, whether in planar or three dimensional form.
- the three dimensional shaping can result from use of a mold or tray having a contoured three dimensional shape in which the mold or tray is filled with a mixture of the powdered resin, reinforcing elements and glass microspheres which are pre-heated to a prepreg sticky condition and then further shaped into the three dimensional form.
- the foam material can be cured into a thick block or a thick layer which can be machined or passed through a router for a desired three dimensional shape.
- the core is desirably engineered so that in actual use when stressed to the breaking point a non-preferential rupture will occur either in the core or a face of the composite.
- the face sheet strength and the core strength be substantially equal against rupture in the stressed sandwich structure.
- the rupture strength of the composite or flexural modulus has been determined in the order of 4.3 million psi. If the thickness of the composite is set, then the core shear strength and the face modulus can be determined in order to engineer the product for the maximum strength which it must sustain.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95929401A EP0772516A4 (en) | 1994-07-29 | 1995-07-27 | Syntactic foam sheet material |
MX9700745A MX9700745A (en) | 1994-07-29 | 1995-07-27 | Syntactic foam sheet material. |
AU32770/95A AU708635B2 (en) | 1994-07-29 | 1995-07-27 | Syntactic foam sheet material |
KR1019970700731A KR970704573A (en) | 1994-07-29 | 1995-07-27 | Syntactic foam sheet material |
JP8506806A JPH10503801A (en) | 1994-07-29 | 1995-07-27 | Syntactic foam sheet material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/282,371 US5587231A (en) | 1994-07-29 | 1994-07-29 | Syntactic foam core material and method of manufacture |
US08/282,371 | 1994-07-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996004132A1 true WO1996004132A1 (en) | 1996-02-15 |
Family
ID=23081216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/009977 WO1996004132A1 (en) | 1994-07-29 | 1995-07-27 | Syntactic foam sheet material |
Country Status (8)
Country | Link |
---|---|
US (2) | US5587231A (en) |
EP (1) | EP0772516A4 (en) |
JP (1) | JPH10503801A (en) |
KR (1) | KR970704573A (en) |
AU (1) | AU708635B2 (en) |
CA (1) | CA2196164A1 (en) |
MX (1) | MX9700745A (en) |
WO (1) | WO1996004132A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003080330A1 (en) * | 2002-03-26 | 2003-10-02 | Basf Aktiengesellschaft | Composite elements |
WO2017162827A1 (en) * | 2016-03-23 | 2017-09-28 | Sandvik Tps Zweigniederlassung Der Sandvik Materials Technology Deutschland Gmbh | Structural body and method for the production thereof |
WO2019038291A1 (en) * | 2017-08-22 | 2019-02-28 | Eco - Technilin Sas | Material with a sandwich-type structure to be thermocompressed and manufacturing methods thereof |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USD953709S1 (en) | 1985-08-29 | 2022-06-07 | Puma SE | Shoe |
USD855953S1 (en) | 2017-09-14 | 2019-08-13 | Puma SE | Shoe sole element |
US5773121A (en) * | 1994-07-29 | 1998-06-30 | Isorca Inc. | Syntactic foam core incorporating honeycomb structure for composites |
KR19980703761A (en) * | 1996-02-13 | 1998-12-05 | 캣츠 스티븐 지. | Syntactic Foam Core Materials for Composite Structural Materials |
JP3876491B2 (en) * | 1997-02-27 | 2007-01-31 | 三菱電機株式会社 | Vacuum insulation panel, method for manufacturing the same, and refrigerator using the same |
US6043769A (en) * | 1997-07-23 | 2000-03-28 | Cuming Microware Corporation | Radar absorber and method of manufacture |
US6451231B1 (en) | 1997-08-21 | 2002-09-17 | Henkel Corporation | Method of forming a high performance structural foam for stiffening parts |
US6068915A (en) | 1997-11-06 | 2000-05-30 | Mcdonnell Douglas Corporation | Thermosetting syntactic foams and their preparation |
US6032300A (en) | 1998-09-22 | 2000-03-07 | Brock Usa, Llc | Protective padding for sports gear |
US6231961B1 (en) * | 1998-12-09 | 2001-05-15 | Henry Sperber | Layered structures comprising particles, a dry binder and a foamable substance |
US6171688B1 (en) * | 1999-02-08 | 2001-01-09 | Board Of Trustees Operating Michigan State University | Material and method for the preparation thereof |
US7037865B1 (en) * | 2000-08-08 | 2006-05-02 | Moldite, Inc. | Composite materials |
US7662468B2 (en) | 2000-10-06 | 2010-02-16 | Brock Usa, Llc | Composite materials made from pretreated, adhesive coated beads |
US6649002B2 (en) * | 2000-11-09 | 2003-11-18 | Patent Holding Company | Method of manufacturing articles utilizing a composite material having a high density of small particles in a matrix material |
FR2885144B1 (en) * | 2005-04-27 | 2007-06-15 | Saint Gobain Vetrotex | FIBROUS STRUCTURE BONDED LOAD |
TW200812793A (en) * | 2006-09-13 | 2008-03-16 | Tiong Liong Ind Co Ltd | Foam laminated material made of a number of materials |
US8623265B2 (en) * | 2007-02-06 | 2014-01-07 | World Properties, Inc. | Conductive polymer foams, method of manufacture, and articles thereof |
US20090226696A1 (en) * | 2008-02-06 | 2009-09-10 | World Properties, Inc. | Conductive Polymer Foams, Method of Manufacture, And Uses Thereof |
DE112008000327T5 (en) * | 2007-02-06 | 2009-12-31 | World Properties, Inc., Lincolnwood | Conductive polymer foams, manufacturing processes and applications thereof |
ITUD20070117A1 (en) * | 2007-06-27 | 2008-12-28 | Design Manufactoring S P A In | AIRCRAFT COMPONENT AND PROCEDURE FOR ITS REALIZATION |
US20090149284A1 (en) * | 2007-12-11 | 2009-06-11 | Isaac Garcia | Hockey Stick Blade Having Fiber-Reinforced High Density Foam Core |
US8110132B2 (en) * | 2008-02-13 | 2012-02-07 | James Hardie Technology Limited | Process and machine for manufacturing lap siding and the product made thereby |
US7824591B2 (en) | 2008-03-14 | 2010-11-02 | Bauer Hockey, Inc. | Method of forming hockey blade with wrapped, stitched core |
US9802369B2 (en) | 2008-03-14 | 2017-10-31 | Bauer Hockey, Llc | Epoxy core with expandable microspheres |
CN102112534A (en) * | 2008-08-05 | 2011-06-29 | 环球产权公司 | Conductive polymer foams, method of manufacture, and articles thereof |
FR2939077B1 (en) | 2008-12-03 | 2013-01-11 | Ateca | MATERIAL OF AME. |
US20110104473A1 (en) * | 2009-06-01 | 2011-05-05 | Tippur Hareesh V | Light weight interpenetrating phase composite foam and methods for making and using the same |
US8815408B1 (en) | 2009-12-08 | 2014-08-26 | Imaging Systems Technology, Inc. | Metal syntactic foam |
EP2335899A1 (en) * | 2009-12-17 | 2011-06-22 | EUROCOPTER DEUTSCHLAND GmbH | A method of fabricating an improved mold core and a mold core obtained by said method |
JP2013515840A (en) * | 2009-12-29 | 2013-05-09 | ロジャース コーポレーション | Conductive polymer foam, its production method and use |
US8251174B2 (en) * | 2010-03-26 | 2012-08-28 | Spirit Aerosystems, Inc. | Method for bonding honeycomb cores |
US8677599B2 (en) | 2010-09-20 | 2014-03-25 | Bauer Hockey, Inc. | Blade constructs and methods of forming blade constructs |
JP5829279B2 (en) * | 2011-09-20 | 2015-12-09 | 住友理工株式会社 | Urethane foam molding and method for producing the same |
US20130251924A1 (en) * | 2012-03-21 | 2013-09-26 | Majdi Haddad | Macrosphere carbon fiber reduction |
WO2014031169A1 (en) * | 2012-08-24 | 2014-02-27 | The Uab Research Foundation | Modular shelters comprising composite panels |
JP2016171636A (en) * | 2015-03-11 | 2016-09-23 | ファナック株式会社 | Stator and manufacturing method of the same |
EP3307978B1 (en) * | 2015-06-12 | 2020-04-01 | 3M Innovative Properties Company | Buoyancy module and method of making such a module |
NL2016945B1 (en) * | 2016-06-10 | 2018-01-24 | Lantor Bv | Flexible core for machine processing or production of composite parts or materials |
US10226099B2 (en) | 2016-08-26 | 2019-03-12 | Reebok International Limited | Soles for sports shoes |
USD850766S1 (en) | 2017-01-17 | 2019-06-11 | Puma SE | Shoe sole element |
USD975417S1 (en) | 2017-09-14 | 2023-01-17 | Puma SE | Shoe |
CN108202486B (en) * | 2018-03-13 | 2023-05-16 | 远东电缆有限公司 | Composite core production line and production process thereof |
US11832684B2 (en) * | 2018-04-27 | 2023-12-05 | Puma SE | Shoe, in particular a sports shoe |
IT201800010223A1 (en) * | 2018-11-09 | 2020-05-09 | Persico Spa | PRODUCTION PROCESS OF A COMPOSITE PRODUCT |
WO2021039722A1 (en) * | 2019-08-27 | 2021-03-04 | 株式会社イノアックコーポレーション | Fiber-reinforced-resin composite molded article and method for producing same, antibacterial composite molded article and method for producing same, antibacterial fiber-reinforced-resin composite molded article and method for producing same, and fiber-reinforced-resin laminated molded article and method for producing same |
CN116496540A (en) * | 2023-05-25 | 2023-07-28 | 大连理工大学 | Magnetized solid buoyancy material adopting novel foaming agent and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4144372A (en) * | 1975-01-29 | 1979-03-13 | Minnesota Mining And Manufacturing Company | Low-density space-filling sheet material |
US5219629A (en) * | 1988-11-23 | 1993-06-15 | Chemical & Polymer Technology, Inc. | Laminates, panels and methods for making them |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2806509A (en) * | 1956-06-11 | 1957-09-17 | Goodyear Aircraft Corp | Sandwich structures |
US2985411A (en) * | 1957-06-25 | 1961-05-23 | Jr Baxter C Madden | Structural element having sphericallike filling |
US3429955A (en) * | 1965-09-23 | 1969-02-25 | Pittsburgh Corning Corp | Method of making a shaped article from coated multicellular glass nodules |
US3855160A (en) * | 1970-10-27 | 1974-12-17 | Leben Utility Co | Thermosetting foamable resinous composition |
JPS515836B1 (en) * | 1971-06-30 | 1976-02-23 | ||
JPS5634864B2 (en) * | 1973-05-30 | 1981-08-13 | ||
US4025686A (en) * | 1975-06-26 | 1977-05-24 | Owens-Corning Fiberglas Corporation | Molded composite article and method for making the article |
US4095008A (en) * | 1975-08-13 | 1978-06-13 | Rogers Corporation | Syntactic foam matrix board |
US4193829A (en) * | 1977-03-16 | 1980-03-18 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Process for the manufacture of low density bis-maleimide-carbon microballoon composites |
FR2386409A2 (en) * | 1977-04-05 | 1978-11-03 | Saunier Jean Pierre | Cellular thermosetting resin prods. mfr. - for construction elements imparting heat- and sound-insulating properties, and flame-resistance |
US4132755A (en) * | 1977-07-22 | 1979-01-02 | Jay Johnson | Process for manufacturing resin-impregnated, reinforced articles without the presence of resin fumes |
US4201823A (en) * | 1977-12-29 | 1980-05-06 | Rohm And Haas Company | Method for making fiber reinforced articles |
US4178406A (en) * | 1977-12-29 | 1979-12-11 | Rohm And Haas Company | Three-layered fiberglass construction |
US4447565A (en) * | 1981-12-07 | 1984-05-08 | The United States Of America As Represented By The United States Department Of Energy | Method and composition for molding low density desiccant syntactic foam articles |
DE3424474A1 (en) * | 1984-02-08 | 1986-01-16 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING A LIGHT MATERIAL |
JPS61246237A (en) * | 1985-04-25 | 1986-11-01 | Sumitomo Deyurezu Kk | Production of phenolic resin composite foam |
FR2586215B1 (en) * | 1985-08-13 | 1988-09-02 | Hutchinson | THERMAL INSULATION MATERIAL OF THE SYNTACTIC TYPE, MACHINE AND METHOD FOR THE PRODUCTION THEREOF, AND INSULATION MEANS COMPRISING SUCH A MATERIAL |
GB8702847D0 (en) * | 1987-02-09 | 1987-03-18 | Ici Plc | Shaping of syntactic foam |
US4861649A (en) * | 1987-11-02 | 1989-08-29 | Browne James M | Impact resistent composites |
US5034256A (en) * | 1989-08-28 | 1991-07-23 | United Technologies Corporation | Closeout configuration for honeycomb core composite sandwich panels |
JPH06157808A (en) * | 1992-11-25 | 1994-06-07 | Yokohama Rubber Co Ltd:The | Production of syntactic foam |
-
1994
- 1994-07-29 US US08/282,371 patent/US5587231A/en not_active Expired - Fee Related
-
1995
- 1995-07-27 CA CA002196164A patent/CA2196164A1/en not_active Abandoned
- 1995-07-27 MX MX9700745A patent/MX9700745A/en not_active IP Right Cessation
- 1995-07-27 KR KR1019970700731A patent/KR970704573A/en not_active Application Discontinuation
- 1995-07-27 AU AU32770/95A patent/AU708635B2/en not_active Ceased
- 1995-07-27 JP JP8506806A patent/JPH10503801A/en active Pending
- 1995-07-27 WO PCT/US1995/009977 patent/WO1996004132A1/en not_active Application Discontinuation
- 1995-07-27 EP EP95929401A patent/EP0772516A4/en not_active Withdrawn
-
1996
- 1996-06-03 US US08/655,083 patent/US5846357A/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4144372A (en) * | 1975-01-29 | 1979-03-13 | Minnesota Mining And Manufacturing Company | Low-density space-filling sheet material |
US5219629A (en) * | 1988-11-23 | 1993-06-15 | Chemical & Polymer Technology, Inc. | Laminates, panels and methods for making them |
Non-Patent Citations (1)
Title |
---|
See also references of EP0772516A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003080330A1 (en) * | 2002-03-26 | 2003-10-02 | Basf Aktiengesellschaft | Composite elements |
CN100393508C (en) * | 2002-03-26 | 2008-06-11 | 巴斯福股份公司 | Composite elements |
WO2017162827A1 (en) * | 2016-03-23 | 2017-09-28 | Sandvik Tps Zweigniederlassung Der Sandvik Materials Technology Deutschland Gmbh | Structural body and method for the production thereof |
WO2019038291A1 (en) * | 2017-08-22 | 2019-02-28 | Eco - Technilin Sas | Material with a sandwich-type structure to be thermocompressed and manufacturing methods thereof |
FR3070306A1 (en) * | 2017-08-22 | 2019-03-01 | Eco - Technilin Sas | THERMOCOMPRIMER SANDWICH-TYPE STRUCTURE MATERIAL AND METHODS OF MANUFACTURING THE SAME |
Also Published As
Publication number | Publication date |
---|---|
KR970704573A (en) | 1997-09-06 |
US5587231A (en) | 1996-12-24 |
CA2196164A1 (en) | 1996-02-15 |
US5846357A (en) | 1998-12-08 |
MX9700745A (en) | 1997-09-30 |
AU3277095A (en) | 1996-03-04 |
AU708635B2 (en) | 1999-08-12 |
EP0772516A4 (en) | 1998-11-25 |
JPH10503801A (en) | 1998-04-07 |
EP0772516A1 (en) | 1997-05-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5846357A (en) | Method of making syntactic foam core material | |
US5888642A (en) | Syntactic foam core material for composite structures | |
US5773121A (en) | Syntactic foam core incorporating honeycomb structure for composites | |
JPH02141211A (en) | Molded form composed of foamed substance board and manufacture thereof | |
CN85100805A (en) | Improvement to fibre reinforced moulded plastics articles | |
WO2018001642A1 (en) | Moulding composite panels | |
Brody et al. | Reactive and non‐reactive binders in glass/vinyl ester composites | |
KR20060088891A (en) | Method for the production of dual-layer slab or board-like articles and slab or board-like articles which can be obtained by the method | |
JPS63209810A (en) | Post forming semimanufacture product | |
WO2018001639A1 (en) | Moulding composite panels | |
Bigg | Manufacturing methods for long fiber reinforced polypropylene sheets and laminates | |
CN108025988B (en) | Method for manufacturing slab | |
JP2002515924A (en) | Syntactic foam core material for composite structures | |
Bader et al. | Processing for laminated structures | |
CN110312612B (en) | Method for manufacturing slab | |
JPS61112642A (en) | Fiber reinforced thermoplastic resin sheet for molding stampand manufacture thereof | |
Martin et al. | Gaughan, RG (Phillips Petroleum Com-pany, Bartlesville, OK, USA) US Pat 4 689 098 (25 August 1987) A composition comprising a met of non-metallic reinforcing fibres and a distribution | |
JPH09248868A (en) | Composite plastic panel and its manufacture | |
JPH04241936A (en) | Preparation of plate-shape composite material having foam core | |
UKPATENTS | Method of manufacturing fibres of ing the properties of glass fibre 1979 | |
JPH04216924A (en) | Manufacture of tubular foam core-sandwich laminate | |
WO2018001641A1 (en) | Moulding composite panels | |
Newkirk et al. | US PATENTS |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LT LU LV MD MG MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG UZ VN |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): KE MW SD SZ UG AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1995929401 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2196164 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1019970700731 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 1995929401 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1019970700731 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1995929401 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1019970700731 Country of ref document: KR |