US20080107888A1 - Self-Repairing, Reinforced Matrix Materials - Google Patents

Self-Repairing, Reinforced Matrix Materials Download PDF

Info

Publication number
US20080107888A1
US20080107888A1 US11932806 US93280607A US2008107888A1 US 20080107888 A1 US20080107888 A1 US 20080107888A1 US 11932806 US11932806 US 11932806 US 93280607 A US93280607 A US 93280607A US 2008107888 A1 US2008107888 A1 US 2008107888A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
matrix
fibers
fiber
materials
invention
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11932806
Inventor
Carolyn Dry
Original Assignee
Dry Carolyn M
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16Auto-repairing or self-sealing arrangements or agents
    • B29C73/22Auto-repairing or self-sealing arrangements or agents the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/48Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with macromolecular fillers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS, SLAG, OR MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B17/00Details of, or accessories for, apparatus for shaping the material; Auxiliary measures taken in connection with such shaping
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/14Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/18Layered products comprising a layer of metal comprising iron or steel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10807Making layered products containing glass and synthetic resin layers; apparatus therefor
    • B32B17/10963Making layered products containing glass and synthetic resin layers; apparatus therefor specially adapted for repairing the layered products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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 structural features of a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0048Fibrous materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0048Fibrous materials
    • C04B20/0056Hollow or porous fibres
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10Coating or impregnating
    • C04B20/1018Coating or impregnating with organic materials
    • C04B20/1022Non-macromolecular compounds
    • C04B20/1025Fats; Fatty oils; Ester type waxes; Higher fatty acids; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/002Water
    • C04B22/006Water released by a chemical reaction, e.g. polymer condensation
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0003Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof containing continuous channels, e.g. of the "dead-end" type or obtained by pushing bars in the green ceramic product
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0092Temporary binders, mortars or concrete, i.e. materials intended to be destroyed or removed after hardening, e.g. by acid dissolution
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02Selection of the hardening environment
    • C04B40/0263Hardening promoted by a rise in temperature
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0633Chemical separation of ingredients, e.g. slowly soluble activator
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0641Mechanical separation of ingredients, e.g. accelerator in breakable microcapsules
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0675Mortars activated by rain, percolating or sucked-up water; Self-healing mortars or concrete
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/241Preventing premature crosslinking by physical separation of components, e.g. encapsulation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K7/00Use of ingredients characterised by shape
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C47/00Making alloys containing metallic or non-metallic fibres or filaments
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C47/00Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02Pretreatment of the fibres or filaments
    • C22C47/04Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16Auto-repairing or self-sealing arrangements or agents
    • B29C73/163Sealing compositions or agents, e.g. combined with propellant agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/033 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/40Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554Wear resistance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/762Self-repairing, self-healing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2603/00Vanes, blades, propellers, rotors with blades
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00Vehicles
    • B32B2605/18Aircraft
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0067Function or property of ingredients for mortars, concrete or artificial stone the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72Repairing or restoring existing buildings or building materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5284Hollow fibers, e.g. nanotubes
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249971Preformed hollow element-containing
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249994Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249994Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y10T428/249995Constituent is in liquid form
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249994Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y10T428/249995Constituent is in liquid form
    • Y10T428/249997Encapsulated liquid

Abstract

Self-repairing, fiber reinforced matrix materials include a matrix material including inorganic as well as organic matrices. Disposed within the matrix are hollow fibers having a selectively releasable modifying agent contained therein. The hollow fibers may be inorganic or organic and of any desired length, wall thickness or cross-sectional configuration. The modifying agent is selected from materials capable of beneficially modifying the matrix fiber composite after curing. The modifying agents are selectively released into the surrounding matrix in use in response to a predetermined stimulus be it internal or externally applied. The hollow fibers may be closed off or even coated to provide a way to keep the modifying agent in the fibers until the appropriate time for selective release occurs. Self-repair, smart fiber matrix composite materials capable of repairing microcracks, releasing corrosion inhibitors or permeability modifiers are described as preferred embodiments in concrete and polymer based shaped articles.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • [0001]
    This is a continuation of application of Ser. No. 11/278,631, filed Apr. 4, 2006 which is a continuation of application Ser. No. 10/376,906, filed Feb. 28, 2003, U.S. Pat. No. 7,022,179, which is a continuation of application Ser. No. 09/447,894, filed Nov. 23, 1999, U.S. Pat. No. 6,261,360, which is in turn a continuation of Ser. No. 08/918,630, filed Aug. 22, 1997, now U.S. Pat. No. 5,989,334, which is in turn a continuation of application Ser. No. 08,537,228, filed Sep. 29, 1995, now U.S. Pat. No. 5,660,624, which is in turn a continuation of application Ser. No. 08/189,665, filed Feb. 1, 1994, abandoned, which is in turn a continuation-in-part of U.S. Ser. No. 08/174,751, filed Dec. 29, 1993, now U.S. Pat. No. 5,575,841, which is in turn a continuation of U.S. Ser. No. 07/540,191, filed Jun. 19, 1990 abandoned.
  • BACKGROUND OF THE INVENTION
  • [0002]
    The present invention generally relates to matrix materials for use in a wide variety of end use fields and applications. More particularly, the invention relates to new and improved self-repairing, settable or curable matrix material systems containing so-called smart-release fiber reinforcements, alone or in combination with other reinforcement. My prior parent application, Ser. No. 540,191, filed Jun. 19, 1990, describes the new and improved inorganic and organic matrix composites employing concrete matrix systems and asphalt matrix systems as illustrative embodiments. That prior application describes smart-release hollow fiber additives in settable construction materials and thermoplastic matrices, such as asphalt. This application is being filed to describe other embodiments of the smart-release matrix composite materials generally described in my earlier application and to provide additional examples of end use applications to which these new and improved compositions, articles and methods may be specially adapted and used.
  • [0003]
    Cement is a fine, gray powder consisting of alumina, lime, silica and iron oxide which sets to a hard material after mixture with water. Cement, along with sand and stone aggregate, make up concrete, the most widely used building material in the world. Steel reinforcing bars (rebars) are commonly added to the interior of concrete for additional strength.
  • [0004]
    There are many reasons for the popularity of concrete. It is relatively inexpensive, capable of taking on the shape of a mold, has exceptionally high compression strength and is very durable when not exposed to repeated freeze-thaw cycles. However, as a building or construction material, concrete, whether it is reinforced or not, is not without some shortcomings. One major drawback of concrete is that it is relatively low in tensile strength. In other words, it has little ability to bend. Concrete also has little impact resistance and is frequently brittle. A third major drawback is that its durability is significantly reduced when it is used in applications which require it to be exposed to repeated freeze-thaw cycles in the presence of water. Concrete is relatively porous and water is able to permeate the material. Freezing and thawing with the accompanying expansion and contraction of the water, forms cracks in the concrete. Furthermore, if salt is also present in the environment, it dissolves in the water and permeates into the concrete where it is capable of inducing corrosion in any of the rebars or other metallic reinforcements present.
  • [0005]
    Various techniques have been suggested in the past for overcoming these drawbacks. The addition of fibers to concrete has improved its tensile strength but has decreased its compression strength. Providing exterior coatings on the outer surfaces of the concrete has reduced water permeation, but it is a time-consuming additional step and has little, if any, effect on the lasting strength of the concrete. The addition of modifying agents as freely-mixed additives into a concrete mixture before setting has also been tried. These efforts have met with generally unsatisfactory results. Attempts to add modifying agents in the form of micronodules or prills have also been tried. Frequently, the prills are designed to be heat melted to cause release of the modifying agent into the matrix after setting of the materials. These designs require the application of heat to release the beneficial additive into the matrix after cure. Moreover, the melted, permeated agents leave behind voids in the concrete which weakens the overall structure under load. Accordingly, a demand still exists for an improved concrete matrix material having greater tensile strength, greater durability and comparable or improved compression strength.
  • [0006]
    In addition to cementitious building materials, the use of polymer composites as structural materials has grown tremendously in recent years. Polymer composite materials have advantages over steel or concrete including good durability, vibration damping, energy absorption, electromagnetic transparency, toughness, control of stiffness, high stiffness to weight ratios, lower overall weight and lower transportation cost. These polymer matrix materials comprise a continuous polymer phase with a fiber reinforcement therein. Some polymer composite materials are three times stronger than steel and five times lighter. They have heretofore been generally more expensive but their use may, in the long term, be economical because of their greatly reduced life cycle costs. Europeans have made bridges completely of specialty polymer matrix composite materials. The polymer composite materials may be used as rebars, tensioning cables, in bonded sheets, wraps, decks, supports, beams or as the primary structures for bridges, decks or buildings. Structures made from polymer matrix materials are especially effective in aggressive environments or are well adapted for building structures where electromagnetic transparency may be needed for highways, radar installations and hospitals.
  • [0007]
    As used herein, matrix composite materials may refer to generally any continuous matrix phase whether it comprises a settable construction material such as cementitious materials or a thermoplastic material such as asphalt materials, as well as, other synthetic or natural high polymer materials, ceramics, metals and other alloy materials. The matrix composite materials include various fiber reinforcements therein distributed throughout the matrix or placed at desired locations within the continuous phase. The matrix composite materials may be fabricated as large building structures and load bearing shaped articles, or they may be molded or machined as small parts for specialty uses. For example, the matrix material may comprise a thin sheet or web of material in the form of a foil, wrap, tape, patch or in strip form. As presently used in this specification, the term matrix composite material does not necessarily refer to large civil engineering structures such as highways and bridges.
  • [0008]
    In connection with the polymer and/or metal or ceramic matrix composite materials, as well as, in the settable building materials such as concrete materials, special problems cause structures made from these materials to become aged or damaged in use. More particularly, special structural defects arise in use including microcracking, fiber debonding, matrix delamination, fiber breakage, and fiber corrosion, to name but a few. Any one of these microscopic and macroscopic phenomena may lead to failures which alter the strength, stiffness, dimensional stability and life span of the materials. Microcracks, for example, may lead to major structural damage and environmental degradation. The microcracks may grow into larger cracks with time and cause overall material fatigue so that the material deteriorates in long-term use.
  • [0009]
    Advanced matrix composites used in structural applications are susceptible to damage on both the macro- and microscopic levels. Typical macroscopic damage to composite laminates involves delaminations and destruction of the material due to impact. On the micrographic scale, damage usually involves matrix microcracking and/or debonding at the fiber/matrix interface. Internal damage such as matrix microcracking alters the mechanical properties of shaped articles made therefrom such as strength, stiffness and dimensional stability depending on the material type and the laminate structure. Thermal, electrical and acoustical properties such as conductance, resistance and attenuation have also been shown to change as matrix cracks initiate. Microcracks act as sites for environmental degradation as well as for nucleation of microcracks. Thus, microcracks can ultimately lead to overall material degradation and reduced performance.
  • [0010]
    Moreover, prior studies have shown that microcracks cause both fiber and matrix dominated properties of the overall composite to be effected. Fiber dominated properties such as tensile strength and fatigue life may be reduced due to redistribution of loads caused by matrix damages. Matrix dominated properties on the other hand such as compressive residual strength may also be influenced by the amount of matrix damage. The impact responses of toughened polymer matrix composites have been studied and it has been shown that matrix cracking precedes delamination which, in turn, precedes fiber fracture. Tough matrices which can reduce or prevent matrix cracking tend to delay the onset of delamination which results in an improved strength composite and longer lasting composite material.
  • [0011]
    Repair of damages is a major problem when these matrix composite materials are employed in large-scale construction or advanced structures. Macroscale damage due to delamination, microcracking or impacts may be visually detected and can be repaired in the field by hand. Microscale damage occurring within the matrix is likely to go undetected and the damage which results from this type of breakdown may be difficult to detect and very difficult to repair.
  • [0012]
    In order to overcome the shortcomings of the prior art construction and polymer, ceramic or metal matrix composite materials, it is an object of the present invention to provide new and improved smart structural composite materials having a self-healing capability whenever and wherever cracks are generated.
  • [0013]
    It is another object of the present invention to provide new and improved composite materials including self-repairing reinforcing fibers capable of releasing chemical agents into the local microscopic domains of the matrix to repair matrix microcracks and rebond damaged interfaces between fibers and matrices.
  • [0014]
    It is a further object of the present invention to provide a new and improved structural material.
  • [0015]
    It is another object of the present invention to provide a new and improved cementitious material.
  • [0016]
    It is still a further object of the present invention to provide a new and improved cementitious or other construction composite material having greater durability and greater tensile strength.
  • [0017]
    It is still another object of the present invention to provide a new and improved matrix composite materials containing smart self-repairing fiber reinforcement containing repair chemicals therein which may be released by the smart fibers as needed in response to an external stimulus, and optionally which may be refilled with additional repair chemicals as needed in the field.
  • SUMMARY OF THE INVENTION
  • [0018]
    In accordance with these and other objects, the present invention provides new and improved shaped articles comprising:
  • [0019]
    a cured matrix material having a plurality of hollow fibers dispersed therein, the hollow fibers having a selectively releasable modifying agent contained therein, means for maintaining the modifying agent within the fibers until selectively released and means for permitting selective release of the modifying agent from the hollow fibers into the matrix material in response to at least one predetermined external stimulus. In accordance with this invention the shaped articles are matrix composite materials of varying size and end use applications. The cured matrix materials have within them smart fibers capable of delivering repair chemicals into the matrix wherever and whenever they are needed.
  • [0020]
    The present invention also provides a new and improved method for providing shaped articles having long-term durability and environmental degradation resistance comprising the steps of providing a curable matrix composition, distributing a plurality of hollow fibers therein in desired manner so that the hollow fibers are disposed within the matrix material in a desired predetermined distribution. The hollow fibers are filled with a selectively releasable modifying agent therein which is not released during the mixing or distributing step. The fibers are structured so that the modifying agents stay within the interior spaces or cavities of the fibers within the matrix until the matrix is cured or set. After curing, the modifying agents are selectively released from the fibers by application or action of at least one predetermined external stimulus.
  • [0021]
    In a preferred embodiment, the method of providing an improved durability shaped article comprises providing a cured matrix material containing smart self repair fibers reinforcement therein.
  • [0022]
    The principles of the present invention are applicable to space age polymer, metal and/or ceramic structural matrix composite materials as well as more conventional cementitious settable or curable building or construction materials.
  • [0023]
    Other objects and advantages will become apparent from the following Detailed Description of the Preferred Embodiments, taken in conjunction with the Drawings in which:
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0024]
    FIGS. 1 a-1 f are schematic views of the new and improved self-repairing fiber reinforced matrix composite material in accordance with the present invention, illustrating a smart matrix repair sequence of load-induced cracking, modifying chemical release and subsequent rebonding and repair of the fiber and matrix;
  • [0025]
    FIGS. 2 a-2 e are schematic views of the new and improved self-repairing fiber reinforced matrix composite material in accordance with this invention, illustrating a smart matrix repair sequence of salt or pH change penetration into the matrix adjacent a smart fiber wrapped rebar reinforcement causing dissolution of the pH sensitive coating, thereby releasing anticorrosion modifying agents in the domain or vicinity of the rebar to prevent corrosion of the rebar;
  • [0026]
    FIGS. 3 a-3 c are schematic views of the new and improved self-repairing fiber reinforced matrix composite material in accordance with this invention, illustrating a smart matrix repair sequence of freeze/thaw protection including freeze induced release of antifreeze from the fibers to provide an antifreeze-containing matrix to reduce freeze/thaw damage;
  • [0027]
    FIG. 4 is a schematic view of the new and improved smart fiber reinforced matrix composite material in accordance with the present invention, illustrating a release, repair mechanism in which the fiber is debonded from the coating and matrix in response to an applied load to release the modifying agent from the uncoated fiber pores;
  • [0028]
    FIG. 5 is a schematic view of a smart fiber reinforced matrix composite material in accordance with this invention, illustrating a release, repair mechanism in which an applied load causes dimensional changes in the fiber promoting release of modifier from the fiber into the matrix;
  • [0029]
    FIGS. 6 a and 6 b are schematic views of a new and improved matrix composite material in accordance with this invention, illustrating release and repair from twisted fiber bundles, whereby compressive loading causes unlocking of the twisted fiber bundles to release modifying agent into the adjacent matrix;
  • [0030]
    FIG. 7 is a schematic view of a new and improved self-repairing fiber reinforced matrix composite material and system in accordance with the preferred embodiment of this invention, whereby a smart fiber disposed within the matrix may be refilled with replacement modifier as needed by drawing modifier into the fibers using a vacuum pump;
  • [0031]
    FIG. 8 is a schematic view of a fiber reinforced matrix composite material in accordance with another preferred embodiment of the invention, illustrating a matrix containing a network of interconnected smart fibers into which additional modifying chemicals may be added from the exterior of the matrix in use;
  • [0032]
    FIG. 9 is a schematic view of the new and improved matrix composite material in accordance with this invention, illustrating a light activated release mechanism employing lasers;
  • [0033]
    FIG. 10 is a schematic view of the new and improved self-repairing matrix composite material in accordance with this invention, illustrating a hydrostatic pressure induced release and repair mechanism;
  • [0034]
    FIG. 11 is a schematic view of a smart fiber reinforced matrix composite material wherein the modifying agents are released from the fibers by acoustic excitation;
  • [0035]
    FIG. 12 is a schematic view of a smart fiber reinforced matrix composite material of this invention, illustrating seismic or low frequency wave-induced modifying agent release mechanism;
  • [0036]
    FIGS. 13 a and 13 e are schematic views comparing the corrosion of rebars possible with conventional cement rebar-reinforced matrices of the prior art shown in FIG. 13 a with the corrosion prevention provided by the new and improved smart fiber matrices of this invention shown in FIG. 13 e;
  • [0037]
    FIGS. 13 b and 13 f are schematic views illustrating a comparison of the permeability of prior matrices shown in FIG. 13 b with the impermeability produced by the smart matrix permeability modification agent release mechanisms in accordance with this invention shown in FIG. 13 f;
  • [0038]
    FIG. 13 c schematically illustrates the internal cracking problems associated with prior art freeze/thaw damage to prior art matrices shown in FIG. 13 c in comparison with the antifreeze containing smart matrix composite in accordance with this invention shown in FIG. 13 g;
  • [0039]
    FIGS. 13 d and 13 h illustrate the load-induced cracking schematically illustrated for a prior art matrix shown in FIG. 13 d in comparison with the internally released crack prevention and filling smart fiber matrices in accordance with the present invention shown in FIG. 13 h;
  • [0040]
    FIG. 14 is a schematic view of a new and improved smart fiber having a notched wall configuration;
  • [0041]
    FIG. 15 is a schematic view of a new and improved smart fiber having a bulging spheroidal portion and along its cross-sectional configuration;
  • [0042]
    FIG. 16 is a schematic view of a V-shaped smart hollow fiber in accordance with this invention;
  • [0043]
    FIG. 17 is a schematic view of a double lumen smart fiber tubing in accordance with this invention;
  • [0044]
    FIG. 18 is a U-shaped smart fiber tubing in accordance with this invention;
  • [0045]
    FIG. 19 is a schematic view of an alternate smart fiber configuration including an A-shaped tapering enlarged area along the length thereof;
  • [0046]
    FIG. 20 illustrates a coaxial concentric assembly of a polypropylene inner hollow fiber surrounded by an outer brittle glass fiber in accordance with a preferred embodiment;
  • [0047]
    FIG. 21 is a schematic view of a new and improved anticorrosion composite matrix in accordance with this invention, illustrating the use of redundant protective features to provide an enhanced anticorrosion reinforced concrete member;
  • [0048]
    FIGS. 22 a-22 d are schematic views illustrating the use of specialty piezoelectric smart repair fibers to provide selective release and repair of ionically charged ion modifying agents in response to compressive loading;
  • [0049]
    FIG. 23 a is a schematic view of an alternate embodiment of a self-repairing fiber reinforced matrix composite material in accordance with this invention, illustrating the use of a smart matrix repair fiber wrapped rebar in combination with an impermeable barrier layer equipped with sensors to detect changes in moisture, voltage or chloride iron concentration within the matrix;
  • [0050]
    FIG. 23 b is a schematic view of a preferred embodiment similar to FIG. 23 a wherein the impermeable barrier is employed as an electric charge applicator to permit an applied electrical signal to cause a release of anticorrosion chemicals within the matrix adjacent a rebar;
  • [0051]
    FIG. 23 c is a schematic view of the alternate embodiment similar to FIGS. 23 a and 23 b wherein a separate water barrier layer is employed as a first line of defense in combination with the hollow smart fibers in accordance with this invention, which in turn contains water binding hydroscopic chemical agent such as Zypex™, or the like;
  • [0052]
    FIG. 23 d illustrates a special embodiment employing a separate electrode barrier adjacent a rebar wrapped with the smart fibers which act to create a galvanic cell to release a water scavenging hydroscopic chemical when moisture intrusion is detected;
  • [0053]
    FIG. 23 e is an alternate embodiment of the type shown in FIG. 23 d wherein the electrode adjacent to the rebar is capable of causing smart fiber release of charged zinc ions to coat the rebar in an electroplating operation to prevent corrosion of the rebar once the ingress of water or moisture is detected;
  • [0054]
    FIGS. 24 a and 24 b schematically illustrate an alternate embodiment of the present invention wherein the smart fibers comprise a twisted pair of fibers embedded in the matrix as shown in FIG. 24 a and wherein changes in load on the matrix cause chemicals to be released from the twisted pair of fibers as shown in FIG. 24 b and illustrating that the twisted pair of fibers may comprise optical fibers;
  • [0055]
    FIGS. 25 a and 25 b illustrate a schematic view of an alternate embodiment of a new and improved matrix in accordance with this invention, including an outer glass tube smart fiber having an optical fiber therein as well as a modifying adhesive chemical as shown in FIG. 25 b and illustrating the release of adhesive due to cracking or maintaining the optical fiber in an intact condition as shown in FIG. 25 b;
  • [0056]
    FIGS. 26 a and 26 b illustrate another preferred alternate embodiment of the invention, schematically illustrating an optical fiber which itself is used as the smart fiber containing repair chemical therein and having an optical fiber cladding layer along the periphery thereof as shown in FIG. 26 a and showing in FIG. 26 b schematically the change in light transmission properties caused by breakage of the outer glass fiber and leakage of the repair chemical to indicate that a fracture and release and repair have occurred;
  • [0057]
    FIGS. 27 a and 27 b show another alternate embodiment of this invention wherein the smart repair fiber comprises an assembly of an outer glass tube and an inner metal fiber member in an optical fiber and an adhesive modifying chemical therein as shown in FIG. 27 a, which in response to an applied cracking load ruptures the glass fiber to repair the crack while maintaining the optical fiber in an altered, but undamaged condition as shown in FIG. 27 b;
  • [0058]
    FIGS. 28 a-28 c illustrate schematically optical fiber/smart fiber reinforcements for concrete matrices and demonstrate that the release, repair mechanisms may change the refracturing index transmission properties of the fluid so that the repair fiber itself may indicate the fact of rupturing repair and may also indicate the volume of the cracks filled;
  • [0059]
    FIGS. 29 a and 29 b illustrate an alternate aspect of this preferred embodiment wherein septums or Bragg optical gratings may be positioned at desired locations along the length of the smart repair optical fiber as shown in FIG. 29 a, which may aid in indicating the location of cracks along the length of the fiber within the matrix as shown in FIG. 29 b;
  • [0060]
    FIGS. 30 a-30 d illustrate a schematic view of an alternate embodiment wherein a smart fiber reinforcement comprises an optical fiber filled with a repair chemical employing mirrors as shown in FIG. 30 a to assist in locating where a crack damage has occurred as shown in FIG. 30 b and showing repair and rebonding of the repair chemical into the vicinity of the crack in FIG. 30 c and further showing in FIG. 30 d the optional replenishment of the repair chemical from an outside source using a vacuum pump.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • [0061]
    In accordance with the present invention, new and improved shaped articles comprise curable, settable, cross-linkable and/or hardenable matrix materials. The matrix material comprises a continuous phase and is a material that may be shaped to form a three-dimensional shaped article adapted for a particular use. Matrix materials can include any curable, settable or hardenable materials used in construction, building, roofing, roadway, aircraft, automotive, marine, appliances, transportation and/or biomedical fields for making shaped articles. Typically these materials will be moldable or castable to form shaped objects or may be laminated or assembled into finished products. The matrix materials may be inorganic or organic in nature and may include by way of illustration: cement, concrete, sintered fly ash or bottom ash/phosphoric acid mixtures, ceramic including, for example, silicon oxide, titanium oxide, silicon nitride, and metals such as aluminum, steel or other metal alloys, carbon, graphite, asphalt, thermoplastic polymers, thermosetting polymers, thermoplastic elastomers, crosslinkable polymers, curable polymer resin systems and hydroxyapatite. Illustrative thermoplastic polymers include polyolefins, polyesters, polycarbonates, polyacrylates, polyarylates, polyamides, polyimides, polyaramides, polyurethanes, foaming polyurethane compositions and any other thermoplastic polymers used as engineering thermoplastics for making shaped articles. Thermosetting and crosslinkable polymers and curable resin systems may include, for example, one and two part epoxies, phenolformaldehyde resins and other thermosetting and crosslinkable polymers. Thermoplastic elastomers can include rubbery polymers and copolymers including, for example without limitation, styrenebutadiene, rubber, neoprene, SEBS, NBR, and EPDM rubbers and the like. Viscoelastic materials and various latex materials may also be used. The matrix materials may also comprise sinterable ceramic materials including hydroxyapatites, as well as, other ceramic materials such as silicas, titanium, carbides, oxides and alumina. The matrix materials may also comprise metal matrices including aluminum, iron, lead, copper, steel, bronze, phosphor bronze, brass and other alloys, as well as biomimetic systems like bone matrices formed of various calcium salts, as well as other organic and inorganic materials.
  • [0062]
    The matrix materials in accordance with this invention are processable to form shaped articles by molding, casting, sintering, laminating, machining, extruding, or other material fabrication method useful with the matrix material selected. The size and configuration of the finished shaped article produced is essentially unlimited including various small machined parts to very large engineering construction panels for use in building roadway and transportation applications. The matrix materials may be cured by means of catalysts, crosslinkers, radiation, heat, moisture, cooling or by any means used in this art for setting up, hardening, rigidifying, curing, setting or shaping these matrix materials to form shaped articles or objects.
  • [0063]
    The new and improved shaped articles of this invention additionally comprise hollow fibers having interior spaces therein for containing selectively releasable modifying agents. The hollow fiber materials may include inorganic fibers or organic fibers. Illustrative inorganic fibers include, without limitation: fiberglass fibers, cement fibers, asphalt fibers, hydroxyapatite fibers, glass fibers, ceramic fibers, metal fibers, and the like. Illustrative organic fibers that may be used as the hollow fiber component may include, without limitation: polyolefin fibers, polyester fibers, polyamide fibers, polyaramide fibers, polyimide fibers, carbon fibers, graphite fibers, cellulose fibers, nitrocellulose fibers, hydrocarbon fibers Goretex™ fibers, Kevlar™ fibers, and the like, to name but a few.
  • [0064]
    The fibers may be bundled, woven or loose. They may be held or engaged together with flexible web materials. They may comprise twisted pairs and additionally may include concentric structures of one or more fibers. The sidewalls of the fibers are typically rupturable or porous to permit the discharge or exiting of the modifying agent into the surrounding cured composite matrix material. The fibers may come in different shapes, volumes, and wall thicknesses. They may be generally notched, have periodic enlargements or bulges, V-shaped, double or multiple lumens, U-shaped, or they may comprise combinations of one or more different types of fibers. For example, double walled fibers are particularly useful for two-part modifying compositions such as epoxies. Doubled fibers including a metallic inside fiber and a glass outer sheath fiber are useful where bending of the metal fiber assists in breaking the glass carrier fiber. Additionally, assembled structures of polypropylene hollow porous fibers disposed inside a glass outer fiber might be used to permit a first break and release of modifying material to occur with the glass fiber and thereafter a secondary break and release of the polypropylene fiber at a later date to provide a specially long-term profile modification to the shaped matrix composites. The smart-release fibers may also be paired or include other specialty fibers such as piezoelectric fibers or optical sensor fibers for providing special monitoring, metering and diagnostic capabilities. Some of these specialty composites will be more particularly described hereinafter. The fibers may also be woven together into a web so that they may be wrapped as an organized bundle around rebars or the like. Although fiber materials are preferred, other container-like smart release structures or vessels may be provided for special end uses. For example, in relatively large structural parts it may be useful to add the repair chemicals in large flat balloons or bags layered or laid up within the matrix or layers of matrix. It should be apparent to those skilled in this art that for certain end uses, small release vessels having a shape somewhat different from hollow fibers for performing the same smart release functions may be employed. In addition, the fibers may be relatively small, chopped or comminuted fibers having lengths of less than about one inch and diameters of less than about 100 microns. The fibers and matrices may be readily used in usual shaping processes such as in an injection molding operations or the like.
  • [0065]
    In accordance with this invention, the hollow fibers include certain internal modifying agents which are-selectively releasable from the fibers in response to the application of certain predetermined external stimuli. The modifying agents include agents which will modify the performance characteristics of the cured shaped article matrix materials in use. By way of illustration, the modifying agent may include polymerizable monomers such as methyl methacrylates, styrene or other polymerizable starting materials. They may additionally include two part epoxies wherein an epoxy precursor material is disposed in one fiber or in one lumen of a double lumen fiber and the amine or other cross-linking agent is disposed in an adjacent fiber or in the other lumen of the double lumen fiber. Other curable polymerizable monomers may also be employed.
  • [0066]
    Another modifying agent which may be used herein includes a sealant used to prevent water permeability and ingress or egress of water or other liquid materials to and from the cured matrix composite. Illustrative examples for cement may include oily sealants to prevent ingress of water such as linseed oil or other known sealant materials.
  • [0067]
    Another important modifying agent for both cementitious and polymer matrices include adhesives which cure in situ to repair microcracks within the matrix in use. Illustrative adhesives include one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer's glue and others known to those skilled in the art. The adhesives may bond matrix to matrix, fiber to fiber, as well as fiber to matrix.
  • [0068]
    Certain water barriers are particularly useful modifying agents for cementitious matrices. These may include special Zypex™ brand sodium silicate additives as well as siloxane and silica additives known as Salt Guard™ and the like.
  • [0069]
    Another modifying agent useful in the shaped articles of this invention includes anticorrosion agents such as calcium nitrite. These are particularly useful in cementitious matrices employing rebar reinforcements or steel mesh reinforcements.
  • [0070]
    Another example of a modifying agent which may be disposed in the interior of the hollow fibers for use herein includes antifreeze material such as polypropylene glycol.
  • [0071]
    Fiber protectors may also be used as the modifying agents which can be materials which protect the fibers themselves within the matrix material. An example of this includes pH modifiers for protecting fiberglass in highly alkaline environments.
  • [0072]
    Still another class of modifying agents particularly useful in polymer matrices are solvents which permits solvent action to actually repair microcracking damage locally at a cracking site or possibly to dissolve the matrix or fibers or both to permit them to re-form at a later time.
  • [0073]
    In addition to solvents, other curable monomers and co-monomers may also serve this repair function. pH modification agents may also be used as the modifying agents, either alkali or acidic agents, which may be placed in the interior of the fibers only to be released by an appropriate pH changes in the matrix. Other additives may include flame retardant agents. Visco-elastic polymers may also be used as modifiers.
  • [0074]
    In accordance with this invention, means are provided for maintaining the modifying agent within the hollow fibers. The modifying agents may be physically trapped by, for example, drawing liquid additives into the interior of the fibers and retaining them therein by capillary action or by closing off the ends of the fibers. For brittle fibers, sealing of the ends by heat or pressure may be one method for maintaining the modifying agents therein. Moreover, specialty coatings may be used, which will selectively degrade upon the occurrence of a particular external stimulus. Illustrative examples might include heat sensitive coatings, pH sensitive coatings, ion sensitive coatings, and the like. These coatings are effective to close off the pores of the hollow fiber walls or the ends of the fibers to prevent premature leakage of the modifying agent until the intended time. Illustrative coatings may include waxes, low molecular weight hydrocarbon oils and coating polymers to name but a few.
  • [0075]
    In accordance with the present invention, means for permitting selective release of the modifying agent in response to the external stimulus may be provided. Illustrative examples include the selectively removable or dissolvable coatings which give way to permit leakage of the modifying agent in response to, for example, stimuli such as heating, cooling, loading, impacting, cracking, water infusion, chloride infusion, alkalinity changes, acidity changes, acoustic excitation, low frequency wave excitations, hydrostatic pressure, rolling pressure, light sensitivity or laser excitation, or the like. Electrical currents, voltages, electrorheological excitation, radiation, or other energetic stimuli may also be employed or effective to permit or cause selective release of the modifying agent or agents from the fibers.
  • [0076]
    In accordance with this invention, the selective release of the modifier occurs in the matrix when and where it is required and may lead to improved toughness, strength, ductility, brittleness, permeability, fire retardancy, stiffness, dimensional stability, modulus of elasticity, fatigue, impact resistance, and other improved properties. Specially important in accordance with this invention is the ability to repair small microcracks forming in the reinforced matrix composites. The selective release of the modifying agent may be chosen to be effective to rebond the fibers to the matrix, to repair the fibers themselves, to improve or restore the matrix to fiber interface, to repair delaminations, and to repair microcracks in the matrix itself which may repair or overcome cracking or corrosion induced dimensional weaknesses and ultimately reduced durability for the shaped articles.
  • [0077]
    As has been mentioned above, the shaped articles in accordance with this invention may be used for a number of applications, both large and small. Large construction applications are particularly preferred, particularly those used in harsh environments or for outdoor use. Illustrative end use applications for the new and improved shaped articles in accordance with this invention include, for example without limitation, structural sandwich panels, exterior applied insulation panels, fire panels, construction building blocks, cements, concretes, fireproof doors, panels, walls, hazardous waste containment vessels, engines, concrete building blocks, roadways, bridges, dams, engines, road surfaces, roofing blocks, roofing shingles, decks for parking garages, and other building structures and columns. Other construction applications might include the use of these shaped, cured, smart-release composites in bridges, post-tensioning cables, road decks, road deck overlays, aircraft body components, including fuselages, wings and tip design, machined parts, helicopter blades as well as the aforementioned roofing structures.
  • [0078]
    The shaped articles of this invention might also be useful in biomedical applications as bone replacements as prosthetic devices and as biomedical adhesives. More particularly, shaped articles of this invention may be used to form self-growing structures. In accordance with this aspect of the invention, the goal is to create a ceramic resembling bone which is an organic-inorganic composite created at low temperature due to the presence of organisms. Bone is made up of an oriented matrix which is secreted by bone forming cells referred to as osteoblasts. In natural bone, organic matrices are made up of structural molecules which serve as a scaffolding and which are laid down in very precise, oriented pattern of fibrils into and onto which inorganic crystalline phases form. The formation of the first crystals of inorganic salts of calcium phosphate are often referred to as initiation or nucleation which occurs along nucleation sites which appear at regular intervals along the organic scaffolding, usually collagen laid down by osteoblasts. Once nucleation has occurred, the next major process involves the continuation of crystalline growth from these nucleation sites outward along the fabric of the organic matrix and eventually between the molecules which serve as scaffolding. As crystal growth continues and forms against inorganic matrix, there is a loss of organic components which are designed to reserve space in the matrix forever expanding the inorganic phase.
  • [0079]
    In accordance with this biological models, the present invention may be employed to provided a self-growing structure something like bone, wherein the hollow pores polymer fibers may release chemicals and act as an organic template on which to form a strong structural bone-like composite. This self-growing structure might be used for structural materials as well as for computer chips or for prosthetic devices. More particularly, just as ligaments or tendons have been used as natural matrices to form bone materials, these polymer tubes or fibers are used in accordance with the present invention to concentrate bone-like substances. The fibers are hollow and have porous walls. In accordance with this invention chemicals are released from the hollow fibers, particularly polymeric materials which are designed to cause targeted release of water in an inorganic matrix to form a structural network of calcium phosphate materials. Instead of using collagen gels to form a backbone network, in accordance with this invention, a matrix material including inorganic cementitious salts and a first polymer reactant may be provided which includes hollow fiber materials including a condensable or cross-linkable moiety reactive with polymer. Under appropriate conditions, release of the co-reactant from the fibers causes a condensation reaction of the matrix polymer in which water is produced. The water byproduct of the condensation reaction is used to hydrate cement to build up a structural backbone along the fiber regions.
  • [0080]
    In accordance with another aspect of the invention, a hollow porous polymer fiber material may be placed in a calcium phosphate material matrix in which a polymer powder monomer is present. A cross-linking monomer is then released from the fibers into the matrix. The ensuing condensation polymerization reaction releases water, which then hydrates the calcium phosphate materials. Xypex or other cement crystallizing initiator materials may carry the hydration reaction away from the polymer fiber scaffolding within the inorganic matrix. The structural make-up of these materials may be designed to resist stresses by including piezoelectric fibers within the matrix. Lines of force may be generated by prestressing or stressing the piezoelectric polymer fibers along which charged cementitious ions will migrate. This will cause the polymer matrix to rearrange and the composite prestressing forces therefore will generate an appropriate microstructure within the material.
  • [0081]
    Also in accordance with this aspect of the invention, self-healing may be accomplished by leaving some of the original fibers void or by adding additional fibers designed with specialty repair chemicals for repairing the system. Hollow porous fibers may be used to deliver repair chemicals at a later time if damage such as cracking occurs. Repair chemicals, either present as an adjuvant fiber additive or added to hollow fibers from the outside, may be used to improve the visco-elasticity of the entire component as desired.
  • [0082]
    In accordance with this invention, materials may be developed for application in self-repairing materials for use in facings, coatings and membranes. In accordance with this aspect of the invention, the new and improved fiber-containing matrix materials may be provided in the form of paints, membranes, roofing materials, or the like, including self-repairing liquids within the fibers. The materials may be provided in the form of wraps for buildings, bridges, roads, or the like, including webs or fabrics of smart fibers disposed within the matrix. Repair chemicals may repair cracks in the wrap itself or also seep into and repair adjacent structures to which the wrap is adhered to improve the overall structural performance over time. Specialty wraps including solar collecting fibers might also be added to the exterior of previously existing outdoor structures.
  • [0083]
    Another biological or biomedical application for the new and improved shaped articles of this invention might include smart-release bandages, artificial skin materials, poultices, bandaids and the like which include smart fibers which release healing chemicals or healing promoting chemicals by upon movement of the patient or by application of another stimulus, such as for example, a heating pad, or the like. The smart fibers used in these bandage applications might include such release chemicals as oxygen releasing chemicals, moisturizers, aloe vera, antibiotics, anti-inflammatants, analgesics, non-stick agents or the like.
  • [0084]
    Another illustrative use of the shaped articles of this invention might be polymer matrices including smart fibers therein which may be made to include dissolving chemicals which ultimately assist in de-naturing, degrading or destroying the polymeric structures by depolymerization or chemical reaction to improve recyclability of the polymer material.
  • [0085]
    The shaped articles of this invention may also be used in various small shaped article applications including aerospace applications, pipe repair, engine pistons, rubber matrices, water-borne paints and coatings, rubber gasket materials and other seals and in woven fabrics. For example, in fabrics the fibers may contain a fabric glue to repair small tears or abrasions of the fabric. Hard self-repairing shaped articles, such as silicon nitride fibers in carbon-alumina matrices for pistons might be used. Metal matrices that may be employed include metals and alloys such as alumina as well as foamed metals. The fibers for these metallic composites may include adhesive materials or corrosion resistant materials to help repair the matrices or other desirable smart release additives.
  • [0086]
    The new and improved smart fibers of the present may be disposed within large cross-sectional areas or sections of a matrix prior to cure which may thereafter be used to release curing agents from several positions disposed throughout the curable matrix simultaneously to speed up or assist in the curing of large cross-section polymer articles. Similarly, natural fibers such as wheat straws or the like may be added to concrete or adobe matrices to stabilize the composites so that they do not crumble or flow in use.
  • [0087]
    In a related application, the new and improved smart matrix materials may be used to perform road repair and pothole repair. In connection with this aspect, smart release fiber-containing uncured material may be added to a pothole. An agitation or pressure may be used to release curative agents from the interior of fibers provided in the matrix material to promote adhesion and curing of the pothole repair mass to the substrate road surface. Additional fibers may be provided, containing repair adhesives which release in response to tire pressure, to further strengthen and reinforce the pothole patch in use.
  • [0088]
    Another highway application of the present invention includes the use of smart release fibers to add phosphorescent chemicals to concrete or asphalt matrices. Phosphorescent roads may clearly demarcate the road or highway surface from non-road driving surfaces at night without the need for street lights or other markers or reflectors. The smart matrix materials would permit renewed release of phosphorescent agents into the road surface, as the layers of the road surface are worn away by highway traffic. A continually replenishing supply of chemicals that could absorb sunlight during the day and re-emit it as phosphorescent light in the evening hours would be provided.
  • [0089]
    In accordance with another aspect of this invention, the shaped articles may include hollow and continuous matrix formed into a shaped article and having hollow fibers therein which permit visual inspection of the structural part in use. The use of hollow, air-filled fibers permits persons to actually look into and see inside the matrix to see cracks near the fibers. These hollow fibers also permit exterior introduction of chemicals to be performed to add chemicals to a previously cured matrix.
  • [0090]
    Hollow or filled fibers may be provided with dyes or other sensing or sensible materials to identify the presence of structural stresses or weaknesses and also the locations of these stresses in large structural articles. For example, release of dyed materials from fibers may permit the dye to migrate to the surface to indicate a structural compromise or repair need in a highway, bridge, or the like. Specialty dyes such as X-ray sensitive dyes may be added to help diagnose a small micro-structural repair problem. More particularly, if the dye is leaked into the matrix in use due to structural damage, periodic diagnostic teams may test with high energy beams shined into the matrix. The interactive dye would signal back after excitation in a detectable manner so that the need for attention or repair would be revealed. Piezoelectric fibers may also be used to evaluate the state of the matrix. Remote sensing of eddy currents or electrical or magnetic fields generated about the fibers in response to pressures or stress may be detected in a matrix in these ways.
  • [0091]
    Still another application for the shaped articles of this invention can include non-biological but biomimetic materials wherein a polymer matrix containing crystallizable mineral elements such as alumina alkoxide may be provided. A condensation reactive element or ingredient provided inside the smart fibers may be released on application of appropriate external stimulus from the smart fibers within the matrix containing the alumina crystals. The by-product water of the condensation reaction in this case may be used to cause alumina crystals to grow at specified locations within the shaped article.
  • [0092]
    Another special useful application of the shaped articles in accordance with this invention is as a containment structures for radioactive or chemical waste materials. In accordance with this aspect, fibers provided with chemically sensitive coatings or radiation sensitive coatings may be provided which are adapted to release scavenger compounds when radiation or chemical waste is detected. The compounds will then migrate from the fibers into the matrix to scavenge and render harmless radioactive or chemical materials leaking into the containment vessels to prevent them from being discharged from the containment area into the environment. Alternatively, permeability modifying agents may be released from the coated fibers to boost the impermeability of the containment vessel to water-borne contaminants.
  • [0093]
    The new and improved shaped articles of this invention may be employed to form self-repairing impact resistance layers in laminated materials and structures. For example, a clear, transparent polymer matrix containing adhesive filled glass fibers may be used as an interlayer between two safety glass or polymer sheets. Impact fracture of a base sheet will cause local release of repair adhesive from the interlayer to control fragmentation and rebond cracked or fractured sections of a laminate.
  • [0094]
    As has been mentioned above, various means may be provided to force the repair chemicals out of the fibers. Chemicals may be pumped into hollow fibers from the outside or propellant gases may be injected into previously filled fibers to which external access has been provided to force the chemicals out. Other methods to promote repair chemical release may include electrical, magnetic, and chemical means which alter the shape, permeability or coating integrity of the fibers. Shape memory alloy materials may be used as the fiber or these materials may be used in the fiber to squeeze the fiber and thereby pump the chemicals out. Fibers which change their shape in response to applied light or magnetic forces or fields may also be used to discharge the chemicals as desired.
  • [0095]
    The smart release shaped articles and materials in accordance with the present invention may be used throughout building structures to provide earthquake proof buildings which can withstand seismic activity with reduced hazard and damage. This is accomplished by preventing flying debris from being created and by supporting building structures in matrices adapted to visco-elastically respond to seismic vibration.
  • [0096]
    Because the beneficial improvements provided by the new composition, articles and methods of this invention may be useful for broad range of applications, it is difficult to specifically enumerate each of them. The present invention will be further illustrated by several specific end use applications provided to further illustrate the improvements provided by the present invention.
  • [0097]
    Referring now to FIGS. 1 a-1 f, the new and improved self-repairing fiber reinforced matrix composite and its operation in the field is shown. As depicted in FIG. 1, a hollow fiber containing an adhesive modifying agent and coated with a thin coating material is dispersed within a settable or curable matrix material which may be either a polymer or cementitious material. As shown in FIG. 1 b, a loading applied to a shaped article causes strains within the matrix, which in turn cause the fiber to break and the matrix to crack. This causes the modifying chemical agent disposed within the hollow fiber to be released into the vicinity of the crack in the matrix as shown in FIG. 1 b. The modifying agent flows and fills the void as shown in FIG. 1 e and eventually cures to rebond the fiber to the matrix and to repair the fiber to itself as shown in FIG. 1 f. This schematically illustrates the modified fiber concept of the present invention.
  • [0098]
    Referring now to FIGS. 2 a-2 e, a similar smart fiber repair embodiment is depicted wherein the smart hollow fibers contain anticorrosive modifying agent and are coated with fibers which are pH sensitive. These smart fibers are disposed within the matrix adjacent the rebar reinforcement by selectively positioning them adjacent the rebar as the matrix is poured into the concrete mold or the rebar can actually be wrapped with the hollow fibers which have been previously banded together as a web or tape. In accordance with this matrix composite construction, the anticorrosion filled smart fibers are disposed immediately adjacent the rebars. The anticorrosive chemical compounds are not released to protect the rebars unless or until the exchange has occurred in the vicinity of the rebar, either due to chloride iron infiltration or carbon dioxide intrusion. The advance of corrosive chemicals breaks down the pH versus sensitive coating on the smart fiber, releasing the protective anticorrosive agent to protect the rebar from corrosion by the environmental chemicals found in FIGS. 2 c-2 e.
  • [0099]
    Referring now to FIGS. 3 a-3 c, the smart fiber matrix is shown in operation in plain and in antifreeze modifying agent disposed within the hollow fibers. A water-based antifreeze expands as it cools to force its way out of the pores in the hollow fiber, thereby dislodging the coating, if present, and permitting the antifreeze to exit into the local environment of the matrix. As shown in FIGS. 3 b-3 c, the release of the antifreeze into the matrix lowers the freezing temperature of moisture in the materials within the matrix preventing freeze/thaw damage from occurring to the matrix.
  • [0100]
    Referring now to FIG. 4, a debonding of a coated fiber is shown as a mechanism for releasing the modifying agent contained within the smart fiber into adjacent areas of the matrix. This can occur, for example, where there is coating applied to the smart fiber to retain the modifying agent within the fiber interior as a higher affinity for the surrounding matrix in a cured state than to the fiber. Accordingly, debonding of the fiber from its coating allows the pores to become open to permit chemical release.
  • [0101]
    Referring now to FIG. 5, there is illustrated in the embodiment wherein modifying agent release is caused by torting, twisting or other load changes which cause a dimensional change in the shape of the hollow fiber, which in turn forces the modifying agent out into the surrounding matrix. These torting, twisting or other loads placed on the fiber may cause local debonding of the fiber from its coating, permitting release as shown in FIG. 4 or a mechanical forcing of the contents of the fiber through the pores, which in turn causes dislodgment of the coating may also occur.
  • [0102]
    Referring now to FIGS. 6 a and 6 b, the application of the compressive load on a twisted fiber bundle can cause debonding of the coating from the twisted fibers forcing fluid contained within the hollow spaces of the fiber through the fiber pores and into the surrounding matrix.
  • [0103]
    Referring now to FIG. 7, a preferred embodiment of the present invention includes providing the smart hollow fiber reinforcement within a matrix so that end portions of the fiber are accessible from the exterior of the matrix to permit additional modifying agents to be supplied into the fibers of the matrix. As depicted therein, a reservoir of modifying agent may be placed in the fiber and a vacuum pump may be attached to the opposed ends to draw the modifying agent into the fibers to replenish any leaked materials therein.
  • [0104]
    FIG. 8 is an extension of the concept described and schematically illustrated in FIG. 7 wherein a series of hollow smart fiber reinforcements are arranged in a continuous network to permit the additional chemicals to be added from the outside throughout the entire matrix.
  • [0105]
    Referring now to FIG. 9, other mechanisms may be employed for dislodging or releasing the modifying agent into the surrounding matrix at a selected time after curing, such as, by example, using laser energy to cause an aneurysm to form in the fiber which permits leakage.
  • [0106]
    Referring to FIG. 10, hydrostatic pressures may also cause the fiber diameter to be locally reduced, causing an exiting of the modifying agent into the surrounding matrix.
  • [0107]
    FIG. 11 shows an embodiment wherein acoustic excitation is employed as the means for releasing the modifying agent from the fiber.
  • [0108]
    FIG. 12 is an alternate embodiment wherein waves of low frequency such as seismic waves may pass through the matrix in such a manner as to cause debonding of the fiber from a coating or uncoated fibers may cause the modifying agent to exit from pores disposed within the fiber matrix disposed within the hollow fiber.
  • [0109]
    FIGS. 13 a through 13 h demonstrate in a side-by-side comparison the ability of the smart fiber reinforced matrix composite materials prepared in accordance with this invention to prevent environmental distress and aging frequently encountered by prior art composite materials. A comparison of FIGS. 13 a and 13 e shows that the modifying agent in FIG. 13 a is an entire corrosion agent to prevent corrosion of the rebars and in that case calcium nitrite is preferred.
  • [0110]
    In FIGS. 13 b and 13 f the permeability of the matrix may be controlled by setting up a polymerized polymer within the matrix as shown in FIG. 13 f to prevent permeability. This may be effected in several ways, and in one preferred embodiment, polymerizable components are freely mixed within the concrete which require only the exposure to a liquid catalyst to cause them to set up into an impermeable barrier. FIGS. 13 c and 13 g illustrate the release of antifreeze materials in FIG. 13 g to prevent freeze/thaw and to brittleness and cracking due to ice crystals formation within the matrix from occurring. Finally, FIGS. 13 d and 13 h illustrate the development of local microcracks due to local loading which may be locally repaired by release of repairing adhesives as in FIG. 13 h to fill cracks or voids and rebond fibers and matrices adjacent microcracks to prevent major microscopic failures from occurring.
  • [0111]
    In accordance with this invention, the smart fiber hollow fibers used to make the smart fiber reinforcements in accordance with this invention may have any desired configuration. As illustrated in FIGS. 14 through 20, a wide variety of cross-sectional configurations may be employed, as well as multi-lumen tubes and multiple concentric tube assemblies may be employed.
  • [0112]
    Referring now to FIG. 21, the new and improved smart fiber matrix composite materials in accordance with this invention may be used in connection with other matrix protecting practices to provide redundant protection against environmental damage. As depicted in FIG. 21, a cementitious matrix including rebars may include surface coatings and sealants to prevent the ingress of harmful environmental liquids. Calcium nitrite anticorrosion chemicals may be freely mixed within the cement and the smart fiber reinforcements may be disposed immediately adjacent the rebar containing additional anticorrosive modifying agents in accordance with this invention for release as needed when the concentration of corrosion chemicals get sufficiently high to stimulate their release.
  • [0113]
    Referring now to FIGS. 22 a through 22 d, there is depicted a special embodiment of the present invention wherein the notion of smart fiber release and repair is coupled with specialty fibers. As depicted in FIG. 22 a through 22 d, the smart fiber itself comprises a piezoelectric fiber into which a liquid chemical is first applied or deposited by providing an electric current to the piezoelectric components of the fiber. The modifying chemicals accretes within and on the surfaces of the web of fibers making up the solid piezoelectric cylinders, which in turn hollow fibers which may be placed and disposed within the matrix. In accordance with these embodiments the modifying agents are released from the piezoelectric fibers by the application of service load stresses on the matrix. These generate electrical charges in the piezoelectric fibers due to their piezoelectric character. The electrical charges cause positive ions to move from inside the porous fibers into the surrounding matrix. Negative ionic materials located in the matrix may also be drawn into or attracted to the piezoelectric hollow fiber. In this way repair can be done by dispersing charged ions into the matrix or may through by selectively drawing undesired materials into the fibers to remove them and causing damage to the matrix.
  • [0114]
    Referring now to FIGS. 23 a through 23 d, another specialty application for the smart fiber reinforced matrix materials in accordance with this invention is shown, which include an impermeable barrier equipped with smart sensors in addition to a hollow fiber wrapped rebar composite in accordance with this invention. The impermeable barrier may be connected to sensor equipment shown as a feedback loop capable of detecting ingress of moisture, changes in voltage or changes in chloride iron concentration,
  • [0115]
    As shown in FIG. 23 b, once the ingress of moisture is sensed at the impermeable barrier layer, an electrical signal may be sent through the inner barrier layer, causing discharge or migration of cations from the middle layer towards the rebar, which causes a coating on the smart fiber to be broken down to permit release of the modifying agent contained therein of anticorrosion chemicals into the immediate vicinity of the-rebar to prevent corrosion.
  • [0116]
    As depicted in FIG. 23 c, the hollow smart fibers in accordance with this invention are disposed in a region bounded by the barrier layer on one side and the rebar on the other to provide redundant backup protection to the rebar to prevent corrosion. More particularly, the hollow fibers contain water binding chemicals which effectively remove the damaging water from reaching the rebar in that intermediate region, thereby preventing corrosion.
  • [0117]
    In FIG. 23 d, an alternate aspect is provided wherein the barrier is electrified to provide a galvanic cell in the immediate region between the barrier layer and the rebar. A counter galvanic cell is created about the hollow middle fibers which contain a modifying chemical inside the buffer zone, which in turn can release moisture binding hydroscopic chemicals in response to application of electrical charges or may release anticorrosive chemicals. In accordance with FIG. 23 e, the hollow fibers disposed within the barrier buffer zone may include zinc ions which will migrate and coat the rebar in a galvanizing or electric lading action by application of the voltage between the barrier and rebar.
  • [0118]
    Referring now to FIGS. 24 and 24 b, another specialty embodiment of the invention includes the use of optical fibers as the self-repairing fiber which in turn contains a modifying chemical which may be positioned within the matrix. Twisted pair fibers, for example, may be used as shown in FIGS. 24 a and 24 b. In response to the application of applied loads, the optical fibers may be changed in their transmission properties indicating a break or leak in the matrix and may in turn be caused to discharge their internal modifying agent into the surrounding matrix to, for example, repair a microcrack as shown in FIG. 24 d.
  • [0119]
    FIGS. 25 a and 25 b depict a similar embodiment involving the use of glass hollow fibers as surrounding hollow fibers for containing adhesive repair modifying agents and for housing an optical fiber therein. As shown in FIG. 25 b, microcracking of the matrix causes release of the repair adhesive locally within the matrix to prevent further cracking and breaking which might damage the optical fiber and its transmission capability.
  • [0120]
    Referring now to FIGS. 26 a and 26 b, a different use of optical fibers as the smart fibers in a matrix composite in accordance with this invention is shown. More particularly, a cladded optical fiber having an interior cavity filled with an adhesive repair chemical is provided in a surrounding polymer or cement matrix. The light transmission of the intact fiber is of a given value. Once applied, loads are caused cracking and bending of the matrix as shown in FIG. 26 b which will cause bending of the fibers decreasing the amount of light transmitted therethrough.
  • [0121]
    Referring now to FIGS. 27 a and 27 b, another glass fiber embodiment is shown wherein an assembly including an outer hollow glass tube filled with adhesive modifying agent and including an optical fiber therein and a middle fiber therein provide a special matrix composite. As shown in FIG. 27 b, in response to an applied load, the middle fiber bending assist in breaking the outer glass tube to thereby release the repairing adhesive to the matrix. The optical fiber polymer may be bent or stretched and light lost to cladding coating on the fiber may be detected outside the matrix to determine bending of the fibers and possible microcracking therein.
  • [0122]
    Referring now to FIGS. 28 a through 28 c, another use-of an optical fiber for forming the smart repair fibers in accordance with this invention illustrates reliance on release of the repair chemicals within the optical fiber to change the optical characteristics to indicate that microcracking has occurred wherein the change in volume of the repair material can indicate the volume cracks that needed to be filled and the change in refracturing index of light transmitted through the fiber may also give an indication of the volume of the cracks that have been filled in accordance with this invention.
  • [0123]
    Referring now to FIGS. 29 a and 29 b, a plurality of septums or brag optical gradings may be positioned along the modifying agent filled optical fiber in accordance with this invention to permit the diagnostic detection of the location of cracks by noticing changes in the refracturing index located between gradings. FIGS. 29 a and 29 b illustrate a further preferred embodiment employing optical fibers as the hollow fiber component of the smart matrix materials in accordance with this invention. The elongate optical fiber is subdivided into longitudinal segments by dividers or septums over brag optical gradings which maintain the optical transmission characteristics along the fiber when filled with the chemical modifying agents. As depicted in FIG. 29 b, in the event of a breakage and leaking of the repair chemical into the adjacent matrix, the dividers or septums limit the quantity of fluid loss to a local segment only. The change in optical characteristics in that local segment will still serve to identify the location of the crack, while preventing an overall loss in all of the fiber fluid contents.
  • [0124]
    Referring to FIGS. 30 a-30 d, still another optical fiber hollow fiber embodiment of this invention is depicted employing fibers of predetermined longitudinal length or dimension having a mirror end well at one end thereof and having repair chemical disposed therein. Checks on the integrity of the optical fiber segment can be made by intermittently sending an optical pulse along the short length of the fiber and bouncing it off the mirror and comparing the reflected intensity to the transmitted intensity to determine whether or not there has been a change along the length of the fiber. By placing a mirror intermediate the length of a row of fiber, the fiber sensing the optical sensing test could be performed from either end and in that manner the location of the break on one side of the mirror or the other could be determined.
  • [0125]
    Referring now to FIG. 30 c, the new and improved smart matrix material is shown in a rebonded condition wherein the interior modifying agent, in this case an adhesive, has leached into the surrounding matrix to repair crack, to bond the matrix to itself, and to bond the coating to the matrix and the coating to the fiber. This restores the overall integrity of the composite, and in some cases, may lead to actual increases in overall strength and performance for the rebond material.
  • [0126]
    FIG. 30 d illustrates the exterior refilling design in accordance with the preferred embodiment for vacuum pump refilling of a broken optical fiber to repair or restore optical transmission service therealong.
  • [0127]
    In accordance with the present invention, other embodiments for using the self-repairing fiber reinforcement smart matrix composite matrix materials described herein will be readily apparent to those skilled in this art. For example, employing ceramic matrices such as a hydroxyapatite ceramic minerals and reinforcing hollow fibers containing bio-compatible crack repairing adhesives may be used in joint replacements or as shaped articles for prosthetic devices. In this manner, biomedical embodiments for the smart matrix composite materials possessing the self-repair properties may be used to provide improved or extended fuselage to prosthetic devices and bone replacements. Stress load fractures occurring within the artificial bone or joint segment will self-repair in accordance with the principles of this invention.
  • [0128]
    In still another embodiment of the present invention, the overall matrices may be used in building applications to provide some seismic resistance or earthquake-proof properties to the structures. More particularly, the response of a solid matrix material containing rigid-filled fibers or liquid-filled fibers may vary in response to seismic waves. Rheological fluids and electrorheological fluids are known which are stiff in one condition, and thereafter upon application of electrical current, may become fluid or liquid. These fillings within reinforcing fibers may be intentionally changed periods of seismic activity in response to, for example, a sensor switch to liquefy or fluidize building structures to better withstand seismic vibration activity without causing brittleness. In the liquefied electrorheological state, the overall matrix composite may be better able to withstand energy vibration than might be encountered in the solid rigid composite structure.
  • [0129]
    In still another aspect of the invention, it is known that alkali reactions are sometimes caused within cementitious matrix materials when aggregate reacts with matrix causes an expansion of the aggregate against the matrix. This causes internal stresses to develop within the matrix composite or shaped article, which usually appears as cracks within the matrix. The use of the smart fibers in accordance with the present invention containing adhesives will repair some of these cracks. In addition, instead of adhesives these smart fibers may be filled with pH modification agents such as acidic agents to neutralize the alkali reaction. In addition, fibers filled with the alkali reaction inhibiting acidic modifying agent may be used in combination with the matrix repair adhesive filled smart fibers in accordance with this invention.
  • [0130]
    In accordance with this invention, the matrix selected may vary, for example, Ribtec™ mats of stainless steel fibers may be slurry infiltrated with cement, hollow fibers for repair may be included. Under loading, the mat causes the cement to form microcracks, which in accordance with this invention releases the repair adhesives into the matrix to provide a repaired high toughness composite material. Depending on the matrix selected, different fiber properties may be desired, for example, in rigid matrix materials such as cementitious set materials or Sintrex ceramic materials more flexible fibers may be desirable, whereas in polymer matrices having inherent elasticity or flexibility, more rigid fibers such as glass or metal fibers may be desired. In addition, it may be desired to use fibers which become brittle over time. Fibers may be connected to each other with flexible parts to ensure that they do not break prematurely during mixing or compounding. Furthermore, chemicals which survive the long periods of time and which survive repeated temperature variations may also be used as the modifying agents. Although several different matrix materials have been disclosed or suggested herein, others may still be used by those skilled in this art. Although a number of different kinds of fibers have also been described, still other fibers might also be used by those skilled in this art in accordance with the principles of this invention. Different modifying agents and different mechanisms for selective release of the modifying agent in response to an external stimuli or internal stresses caused by other external occurrences might also be developed and designed by those skilled in the art given the principles provided herein. Accordingly, all such obvious modifications may be made herein without departing from the scope and spirit of the present invention as defined by the appended claims.

Claims (24)

  1. 1. An article comprising a cured composite matrix material having a modifying agent in at least one hollow release vessel, wherein the modifying agent is capable of beneficially modifying the composite matrix material in response to a stimulus, wherein the cured matrix is a coating and the coating material is an anticorrosion material over metal.
  2. 2. The article of claim 1, wherein the hollow release vessel is a hollow particle.
  3. 3. The article of claim 1 wherein the coating material has more than one release vessel.
  4. 4. The article of claim 3 wherein an anticorrosion material and an anti-cracking material are in the release vessels.
  5. 5. The article of claim 4 wherein the vessels have a diameter of less than 100 microns.
  6. 6. The article of claim 3 wherein the modifying agent is also a dye.
  7. 7. The article of claim 3 wherein the release vessels comprise fiberglass, cement, asphalt, hydroxyapatite, glass, ceramic, metal, polyolefin, polyester, polycarbonate, polyacrylate, polyarylate, polyamide, polyimide, polyaramide, polyurethane, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, or piezoelectric material.
  8. 8. A corrosion protective coating composition, comprising:
    a) a coating matrix, and
    b) a plurality of hollow vessels within the coating matrix, the vessels containing therein a modifying chemical comprising a self repairing component and a corrosion inhibitor.
  9. 9. The corrosion protective coating composition of claim 8 wherein the corrosion inhibitor is calcium nitrate.
  10. 10. The corrosion protective coating composition of claim 8 comprising an epoxy precursor and a amine crosslinking agent.
  11. 11. The corrosion protective coating composition of claim 8 wherein the coating matrix comprises at least one of polyolefin, polyester, polyamide, polyaramid, polyimide, carbon, graphite, cellulose, nitrocellulose, polysiloxane, epoxy, hydrocarbon, polytetrafluoroethylene, polyurethane, aramid, polypropylene, and elastomer, one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer's glue, amines, polysiloxanes, one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, sealant, siloxane, silica additives, calcium nitrate, polyprolylene glycol, amines and other crosslinkers, epoxy precursers, polymerizable monomers such as methyl methacrylates, styrene, acids, bases, solvents, cement, fly ash, bottom ash, phosphoric acid, ceramic, silicon oxide, titanium oxide, silicon nitride, metals, aluminum, steel, metal alloys, asphalt, thermoplastic polymers, thermosetting polymers, thermoplastic elastomers, crosslinkable polymers, curable polymer resin systems, hydroxyapatite, thermoplastic polymers, polyolefins, polyesters, polycarbonates, polyacrylates, polyarylates, polyamides, polyimides, polyaramides, polyurethanes, foaming polyurethanes, crosslinkable polymers, curable resin systems, phenolformaldehyde resins, rubbery polymers, butadiene, rubber, neoprene, SEBS, NBR, and EPDM rubbers, viscoelastic materials, latexes, sinterable ceramics, hydroxyapatites, silicas, titanium, carbides, oxides, alumina, iron, lead, copper, bronze, phosphor bronze, brass bronze, and calcium salts.
  12. 12. The corrosion protective coating composition of claim 8 wherein the plurality of vessels includes walls comprising a frangible material having structural integrity.
  13. 13. The corrosion protective coating composition of claim 12 wherein the frangible vessles are glass, cellulose, polymeric, fiberglass, cement, asphalt, hydroxyapatite, glass, ceramic, metal, polyolefin, polyester, polycarbonate, polyacrylate, polyarylate, polyamide, polyimide, polyaramide, polyurethane, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, or piezoelectric material.
  14. 14. The corrosion protective coating composition of claim 13 wherein the vessels have a diameter of less than 100 microns.
  15. 15. A corrosion protective coating composition, comprising:
    (a) a coating matrix;
    (b) a plurality of vessels containing a corrosion inhibitor, and
    (c) a plurality of vessels containing a self repairing modifying agent, the plurality of vessels being distributed throughout the matrix.
  16. 16. The corrosion protective coating composition of claim 15 further comprising a plurality of vessels containing a dye.
  17. 17. The corrosion protective coating composition of claim 15 wherein the coating matrix is selected from the group consisting of epoxy resins, polyester resins, polyurethane resins, resins, resins, acrylic resins and nylon.
  18. 18. The corrosion protective coating of claim 15 wherein the plurality of vessels includes walls comprising a frangible material having structural integrity.
  19. 19. The corrosion protective coating composition of claim 18 wherein the frangible material comprises at least one of glass, cellulose, polymeric, fiberglass, cement, asphalt, hydroxyapatite, glass, ceramic, metal, polyolefin, polyester, polycarbonate, polyacrylate, polyarylate, polyamide, polyimide, polyaramide, polyurethane, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, shape memory alloy, magnetostrictive, and piezoelectric material.
  20. 20. The corrosion protective coating composition of claim 15 wherein the vessels have a diameter of less than 100 microns.
  21. 21. A corrosion protective layer, comprising:
    (a) a resin matrix, and
    (b) a plurality of frangible vessels dispersed in the resin matrix, the vessels containing a fluid modifying agent to effect repair of the protective layer when damaged.
  22. 22. The corrosion protective layer of claim 21 wherein the modifying agent composition comprises a corrosion inhibitor and a repair agent.
  23. 23. The corrosion protective layer of claim 22 wherein the repair agent is a dye marker.
  24. 24. The corrosion protective layer of claim 21 wherein the resin matrix comprises at least one of polyolefin, polyester, polyamide, polyaramid, polyimide, carbon, graphite, hydrocarbon, aramid, polypropylene, and elastomer, latex, one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer's glue, acids, bases, solvents, polysiloxanes, and amines.
US11932806 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials Abandoned US20080107888A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US54019190 true 1990-06-19 1990-06-19
US08174751 US5575841A (en) 1990-06-19 1993-12-29 Cementitious materials
US18966594 true 1994-02-01 1994-02-01
US08537228 US5660624A (en) 1990-06-19 1995-09-29 Self-repairing, reinforced matrix materials
US08918630 US5989334A (en) 1990-06-19 1997-08-22 Self-repairing, reinforced matrix materials
US09447894 US6261360B1 (en) 1990-06-19 1999-11-23 Self-repairing, reinforced matrix materials
US10376906 US7022179B1 (en) 1990-06-19 2003-02-28 Self-repairing, reinforced matrix materials
US11278631 US20060169180A1 (en) 1990-06-19 2006-04-04 Self-repairing, reinforced matrix materials
US11932806 US20080107888A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11932806 US20080107888A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US11278631 Continuation US20060169180A1 (en) 1990-06-19 2006-04-04 Self-repairing, reinforced matrix materials

Publications (1)

Publication Number Publication Date
US20080107888A1 true true US20080107888A1 (en) 2008-05-08

Family

ID=27558638

Family Applications (8)

Application Number Title Priority Date Filing Date
US09907378 Expired - Fee Related US6527849B2 (en) 1990-06-19 2001-07-17 Self-repairing, reinforced matrix materials
US11278631 Abandoned US20060169180A1 (en) 1990-06-19 2006-04-04 Self-repairing, reinforced matrix materials
US11932899 Abandoned US20080047472A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932836 Abandoned US20080057296A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932857 Abandoned US20080050612A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932720 Abandoned US20080053338A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932882 Abandoned US20080058445A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932806 Abandoned US20080107888A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials

Family Applications Before (7)

Application Number Title Priority Date Filing Date
US09907378 Expired - Fee Related US6527849B2 (en) 1990-06-19 2001-07-17 Self-repairing, reinforced matrix materials
US11278631 Abandoned US20060169180A1 (en) 1990-06-19 2006-04-04 Self-repairing, reinforced matrix materials
US11932899 Abandoned US20080047472A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932836 Abandoned US20080057296A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932857 Abandoned US20080050612A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932720 Abandoned US20080053338A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials
US11932882 Abandoned US20080058445A1 (en) 1990-06-19 2007-10-31 Self-Repairing, Reinforced Matrix Materials

Country Status (1)

Country Link
US (8) US6527849B2 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080261027A1 (en) * 2007-04-17 2008-10-23 The Regents Of The University Of Michigan Engineered self healing cementitious composites
US20090199947A1 (en) * 2005-10-11 2009-08-13 Commissariat A L'energie Atomique Solid Joint Obtained by Heat Projection
US20100276895A1 (en) * 2009-04-29 2010-11-04 Rolls-Royce Plc Seal arrangement and a method of repairing a seal arrangement
US20110003159A1 (en) * 2008-12-23 2011-01-06 Patrick Mather Self-healing product
US20110173971A1 (en) * 2010-01-15 2011-07-21 Syracuse University Stimuli-responsive product
US20120196373A1 (en) * 2010-06-25 2012-08-02 The Board Of Trustees Of The University Of Illinois System For Visual Indication Of Mechanical Damage
US9720156B1 (en) * 2012-06-11 2017-08-01 Michael P. Ross Sensored fiber reinforced polymer grate

Families Citing this family (90)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6527849B2 (en) * 1990-06-19 2003-03-04 Carolyn M. Dry Self-repairing, reinforced matrix materials
US6518330B2 (en) * 2001-02-13 2003-02-11 Board Of Trustees Of University Of Illinois Multifunctional autonomically healing composite material
US7108914B2 (en) * 2002-07-15 2006-09-19 Motorola, Inc. Self-healing polymer compositions
US20040226620A1 (en) * 2002-09-26 2004-11-18 Daniel Therriault Microcapillary networks
US7185468B2 (en) 2002-10-31 2007-03-06 Jeld-Wen, Inc. Multi-layered fire door and method for making the same
JP3852395B2 (en) * 2002-11-06 2006-11-29 東亞合成株式会社 Curing determining agent for 2-cyanoacrylate and curing determination method
US7285306B1 (en) * 2003-04-18 2007-10-23 United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Process for self-repair of insulation material
EP1625280A2 (en) 2003-05-14 2006-02-15 Services Petroliers Schlumberger Compositions and methods for treating lost circulation
US8469095B2 (en) * 2003-05-14 2013-06-25 Schlumberger Technology Corporation Self adaptive cement systems
US7586233B2 (en) * 2003-05-23 2009-09-08 Virginia Tech Intellectual Properties, Inc. Ferroelastic ceramic-reinforced metal matrix composites
US7126257B2 (en) * 2003-05-23 2006-10-24 Virginia Tech Intellectual Properties, Inc. Piezoelectric ceramic-reinforced metal matrix composites
US20040242095A1 (en) * 2003-05-27 2004-12-02 Amit Prakash Composites reinforced by wire net or mesh for lightweight, strength and stiffness
US7067169B2 (en) * 2003-06-04 2006-06-27 Chemat Technology Inc. Coated implants and methods of coating
DE102004004251A1 (en) * 2004-01-21 2005-08-18 Klaus Dr. Rennebeck fiber arrangement
US9206344B2 (en) 2007-05-10 2015-12-08 Halliburton Energy Services, Inc. Sealant compositions and methods utilizing nano-particles
US8476203B2 (en) 2007-05-10 2013-07-02 Halliburton Energy Services, Inc. Cement compositions comprising sub-micron alumina and associated methods
US8586512B2 (en) 2007-05-10 2013-11-19 Halliburton Energy Services, Inc. Cement compositions and methods utilizing nano-clay
US8685903B2 (en) 2007-05-10 2014-04-01 Halliburton Energy Services, Inc. Lost circulation compositions and associated methods
US9199879B2 (en) 2007-05-10 2015-12-01 Halliburton Energy Serives, Inc. Well treatment compositions and methods utilizing nano-particles
JP2007534865A (en) * 2004-04-21 2007-11-29 ジェルドウィン インコーポレイテッド Fiber-reinforced composite, and building structure including a fiber-reinforced composite
US20070110979A1 (en) * 2004-04-21 2007-05-17 Jeld-Wen, Inc. Fiber-reinforced composite fire door
US7566747B2 (en) 2004-05-07 2009-07-28 The Board Of Trustees Of The University Of Illinois Wax particles for protection of activators, and multifunctional autonomically healing composite materials
US7647682B2 (en) * 2004-06-17 2010-01-19 Adams Marve D Motor mount repair system and methods therefor
KR100609989B1 (en) * 2004-12-08 2006-08-08 제일모직주식회사 Composition for Artificial Marble Having a Korean Traditional Mulberry Paper Pattern and Delicate Hue
US7244500B2 (en) * 2005-02-15 2007-07-17 United States Of America As Represented By The Secretary Of The Army Smart coating system
US7612152B2 (en) 2005-05-06 2009-11-03 The Board Of Trustees Of The University Of Illinois Self-healing polymers
US7445834B2 (en) * 2005-06-10 2008-11-04 Morin Brian G Polypropylene fiber for reinforcement of matrix materials
GB0513498D0 (en) * 2005-06-30 2006-03-29 Bae Systems Plc Fibre materials
EP1901911B1 (en) * 2005-06-30 2009-03-25 BAE Systems plc Auto-repairing fibre materials and repair methods
US7811666B2 (en) * 2005-07-01 2010-10-12 Carolyn Dry Multiple function, self-repairing composites with special adhesives
US7585764B2 (en) * 2005-08-09 2009-09-08 International Business Machines Corporation VIA bottom contact and method of manufacturing same
US7607484B2 (en) * 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles and methods of use
US7607482B2 (en) * 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and swellable particles
WO2007038410A3 (en) * 2005-09-27 2008-01-10 Chemimage Corp Liquid crystal filter with tunable rejection band
CN101340935B (en) * 2005-11-14 2013-05-08 拜奥美特3i有限责任公司 Deposition of discrete nanoparticles on an implant surface
EP1973972A2 (en) 2006-01-05 2008-10-01 The Board Of Trustees Of The University Of Illinois Self-healing coating system
US7758313B2 (en) * 2006-02-13 2010-07-20 General Electric Company Carbon-glass-hybrid spar for wind turbine rotorblades
US7569625B2 (en) * 2006-06-02 2009-08-04 The Board Of Trustees Of The University Of Illinois Self-healing elastomer system
CN101541915A (en) 2006-09-20 2009-09-23 普拉德研究及开发股份有限公司 Cementing composition comprising within un-reacted cement
US7417796B2 (en) * 2006-09-29 2008-08-26 Chemimage Corporation Wavelength discrimination filter for infrared wavelengths
US7916764B2 (en) * 2006-10-25 2011-03-29 Coherent, Inc. Output power control for harmonic-generating laser
US9512351B2 (en) 2007-05-10 2016-12-06 Halliburton Energy Services, Inc. Well treatment fluids and methods utilizing nano-particles
US20090020212A1 (en) * 2007-05-18 2009-01-22 Anthony Cacace Smart composites and method of use thereof
US20080299391A1 (en) * 2007-05-31 2008-12-04 White Scott R Capsules, methods for making capsules, and self-healing composites including the same
US20090181254A1 (en) * 2008-01-15 2009-07-16 The Board Of Trustees Of The University Of Illinois Multi-capsule system and its use for encapsulating active agents
JP5806466B2 (en) 2008-01-28 2015-11-10 バイオメット・3アイ・エルエルシー Implant surface with improved hydrophilic
GB0806921D0 (en) * 2008-04-16 2008-05-21 Airbus Uk Ltd Composite laminate with self-healing layer
US20090285866A1 (en) * 2008-05-13 2009-11-19 Afriat Isabelle R Self-healing polymer compositions
US7617870B1 (en) 2008-05-14 2009-11-17 Halliburton Energy Services, Inc. Extended cement compositions comprising oil-swellable particles and associated methods
CN101289300B (en) * 2008-05-20 2012-03-21 倪卓 Self-repair concrete using polyurethane high molecule microcapsule and method of manufacture
US20100083790A1 (en) * 2008-10-06 2010-04-08 Graney Jon P Flywheel device
EP2202280A1 (en) * 2008-11-24 2010-06-30 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Corrosion inhibting coatings controllable by electromagnetic irradiation and methods for corrosion inhibition using the same
US7934554B2 (en) * 2009-02-03 2011-05-03 Halliburton Energy Services, Inc. Methods and compositions comprising a dual oil/water-swellable particle
ES2361433B1 (en) * 2009-11-12 2012-04-04 Lisardo Gonz�?Lez Abelleira Reinforced concrete structure.
US8545650B2 (en) * 2009-12-08 2013-10-01 The Boeing Company Method of repairing a composite structure
US8641418B2 (en) 2010-03-29 2014-02-04 Biomet 3I, Llc Titanium nano-scale etching on an implant surface
CA2795426C (en) * 2010-04-16 2017-11-28 Cidra Corporate Services Inc. Non-chemical air entrained admix
EP2404975A1 (en) 2010-04-20 2012-01-11 Services Pétroliers Schlumberger Composition for well cementing comprising a compounded elastomer swelling additive
EP2404884A1 (en) 2010-05-19 2012-01-11 Services Pétroliers Schlumberger Compositions and methods for well treatment
WO2011163587A1 (en) * 2010-06-25 2011-12-29 Board Of Governors For Higher Education,State Of Rhode Island And Providence Plantations Self-mending composites incorporating encapsulated mending agents
US20110143082A1 (en) * 2010-06-29 2011-06-16 General Electric Company Ply drops modifications for composite laminate materials and related methods
EP2450417B1 (en) 2010-08-17 2016-05-18 Services Pétroliers Schlumberger Self-repairing cements
CN101954119B (en) * 2010-09-10 2013-08-21 北京化工大学 Method for preparing light-cured bone repair material from double bond-containing siloxane coated and modified hydroxyapatite
CN101966349B (en) * 2010-09-10 2013-09-18 北京化工大学 Method for preparing photo-curable bone repairing material from epoxy group-containing siloxane-clad modified hydroxyapatite
KR20130115254A (en) 2010-09-14 2013-10-21 파워 트리 코포레이션 Composite flywheel
EP2518034B1 (en) 2011-02-11 2015-01-07 Services Pétroliers Schlumberger Use of asphaltite-mineral particles in self-adaptive cement for cementing well bores in subterranean formations
EP2487141B1 (en) 2011-02-11 2015-08-05 Services Pétroliers Schlumberger Self-adaptive cements
EP2502889B1 (en) * 2011-03-21 2014-10-29 Knauf Gips KG Self-healing construction material
US8974594B2 (en) 2011-03-29 2015-03-10 Empire Technology Development Llc Microcapsule corrosion control in reinforced concrete
JP5604590B2 (en) * 2011-05-25 2014-10-08 帝人株式会社 Conjugate
EP2551093B1 (en) 2011-07-28 2014-01-01 EADS Deutschland GmbH Healable composite materials based on reversible binder systems
US8685513B1 (en) 2012-02-29 2014-04-01 Carolyn M. Dry Inflatable articles comprising a self-repairing laminate
US9694629B1 (en) 2012-02-29 2017-07-04 Carolyn Dry Self-repairing inflatable articles incorporating an integrated self-repair system
US9131995B2 (en) 2012-03-20 2015-09-15 Biomet 3I, Llc Surface treatment for an implant surface
US20130319859A1 (en) * 2012-05-31 2013-12-05 The University Of Akron Electrorheological fluids incorporated into polymeric articles and tires
FR2993896B1 (en) * 2012-07-26 2014-08-22 Snecma Method for bonding and debonding between two parts using an adhesive filler
WO2014120321A3 (en) * 2012-11-14 2014-11-06 Ndsu Research Foundation Self-healing nanofibers, composites and methods for manufacturing
EP2951256A1 (en) 2013-02-01 2015-12-09 Carolyn M. Dry Adhesive beads
US9605162B2 (en) 2013-03-15 2017-03-28 Honda Motor Co., Ltd. Corrosion inhibiting compositions and methods of making and using
US9816189B2 (en) 2013-03-15 2017-11-14 Honda Motor Co., Ltd. Corrosion inhibiting compositions and coatings including the same
WO2015021347A9 (en) * 2013-08-08 2015-04-02 Henkel US IP LLC A wear resistant composite
CN103487333B (en) * 2013-10-11 2015-06-17 东南大学 Asphalt mixture self-healing capability evaluating method
ES2571482T3 (en) * 2014-01-08 2016-05-25 Kone Corp Cable for an elevator, elevator and method
KR20160000995A (en) 2014-06-26 2016-01-06 홍영근 Self-healing asphalt containing microcapsules
US9683816B2 (en) 2014-09-08 2017-06-20 Carolyn Dry Self-repairing armor
CN104883092B (en) * 2015-06-19 2017-02-01 清华大学 One kind of cement-based materials with a pressure passage generation packaging structure
CN105111689B (en) * 2015-07-02 2017-07-21 苏州科技学院 Nano self-repair method for preparing a conductive polymer material and
WO2017087792A1 (en) * 2015-11-20 2017-05-26 Sentek Instrument, Llc Method and apparatus for distributed sensing
CN105891029A (en) * 2016-06-30 2016-08-24 哈尔滨工业大学 Pitch fatigue performance evaluation method based on fracture mechanic theory
CN106149545A (en) * 2016-08-04 2016-11-23 浙江工业大学 Intelligent self-monitoring and self-repairing memory alloy composite beam

Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179600A (en) * 1960-03-10 1965-04-20 Ncr Co Minute color-forming capsules and record material provided with such
US3274401A (en) * 1961-11-20 1966-09-20 Thompson Ramo Wooldridge Inc Self-repairing and self-sustaining system
US3423491A (en) * 1964-09-02 1969-01-21 Dow Chemical Co Permselective hollow fibers and method of making
US3475188A (en) * 1965-09-29 1969-10-28 Steetley Refractory Brick Co Refractory compositions
US3505244A (en) * 1965-04-30 1970-04-07 Union Carbide Corp Encapsulated corrosion inhibitor
US3607591A (en) * 1969-04-22 1971-09-21 Stevens & Co Inc J P Temperature adaptable fabrics
US3647557A (en) * 1970-08-19 1972-03-07 Du Pont Hollow gas permeable fiber vented sealed galvanic cells
US3704264A (en) * 1970-12-16 1972-11-28 Loctite Corp Encapsulation of monomeric materials
US3913666A (en) * 1972-03-20 1975-10-21 Peter Bayliss Heat resistant wall construction
US4109033A (en) * 1975-06-06 1978-08-22 Blankenhorn Paul R Process for impregnating concrete with polymers
US4183890A (en) * 1977-11-30 1980-01-15 Monsanto Company Method of cutting hollow filaments embedded in resinous mass
US4272898A (en) * 1976-03-11 1981-06-16 Tansill Horace A Resin-coated fiber mass containing catalyst-filled hollow fibers
US4587279A (en) * 1984-08-31 1986-05-06 University Of Dayton Cementitious building material incorporating end-capped polyethylene glycol as a phase change material
US4733989A (en) * 1984-11-29 1988-03-29 American Colloid Company Self-healing bentonite sheet material composite drainage structure
US4780205A (en) * 1984-10-30 1988-10-25 Teijin Limited Permselective hollow fiber membrane, process for the preparation thereof, method and apparatus for plasma components separation
US4810573A (en) * 1984-11-29 1989-03-07 American Colloid Company Self-healing bentonite sheet material composite article
US4908238A (en) * 1984-07-02 1990-03-13 The United States Of America As Represented By The Secretary Of Agriculture Temperature adaptable textile fibers and method of preparing same
US4961790A (en) * 1989-05-19 1990-10-09 Fritz Chemical Company Concrete admixture device and method of using same
US4978563A (en) * 1986-04-17 1990-12-18 Sandels Claes M C Self repairing elastic bodies
US5232769A (en) * 1989-08-01 1993-08-03 Kanebo, Ltd. Microcapsule, treating liquids containing the same, and textile structure having microcapsules adhering thereto
US5561173A (en) * 1990-06-19 1996-10-01 Carolyn M. Dry Self-repairing, reinforced matrix materials
US5575841A (en) * 1990-06-19 1996-11-19 Carolyn M. Dry Cementitious materials
US5803963A (en) * 1990-06-19 1998-09-08 Dry; Carolyn M. Smart-fiber-reinforced matrix composites
US5851291A (en) * 1996-07-31 1998-12-22 Poterala; Robert J. Chemical foaming machine and mixing apparatus
US5965266A (en) * 1995-03-28 1999-10-12 Societe Nationale D'etude Et De Construction De Moteurs D'aviation Composite material protected against oxidation by a self-healing matrix, and a method of manufacturing it
US6039288A (en) * 1997-03-10 2000-03-21 Telair International Gmbh Floor unit
US6527849B2 (en) * 1990-06-19 2003-03-04 Carolyn M. Dry Self-repairing, reinforced matrix materials
US6766817B2 (en) * 2001-07-25 2004-07-27 Tubarc Technologies, Llc Fluid conduction utilizing a reversible unsaturated siphon with tubarc porosity action
US7022179B1 (en) * 1990-06-19 2006-04-04 Dry Carolyn M Self-repairing, reinforced matrix materials

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US350783A (en) * 1886-10-12 tarbutt
US3069288A (en) * 1959-08-06 1962-12-18 Gen Electric Self-repairing coatings for metal
US3503783A (en) * 1965-07-12 1970-03-31 Minnesota Mining & Mfg Process of forming metal coating on filled microcapsules
DE1629621C2 (en) * 1966-01-26 1974-06-06 G. Siempelkamp & Co, 4150 Krefeld
US3803485A (en) * 1970-02-16 1974-04-09 Battelle Development Corp Indicating coating for locating fatigue cracks
US4086386A (en) * 1976-10-12 1978-04-25 Dayco Corporation Smash-recoverable printing blanket
JPS585529A (en) 1981-06-30 1983-01-12 Bando Chem Ind Ltd No-oiling bearing
JPS5813229A (en) 1981-07-14 1983-01-25 Bando Chem Ind Ltd Oilless bearing
JPS5813227A (en) 1981-07-14 1983-01-25 Bando Chem Ind Ltd Oilless bearing
JPS5992961A (en) 1982-09-28 1984-05-29 Diamond Shamrock Corp Cement fixation retardant composition
US4513053A (en) * 1983-06-13 1985-04-23 Pennwalt Corporation Encapsulated phase change thermal energy storage materials and process
US4505953A (en) * 1983-02-16 1985-03-19 Pennwalt Corporation Method for preparing encapsulated phase change materials
US4504402A (en) * 1983-06-13 1985-03-12 Pennwalt Corporation Encapsulated phase change thermal energy _storage materials
US4851291A (en) * 1986-06-19 1989-07-25 The United States Of America As Represented By The Secretary Of Agriculture Temperature adaptable textile fibers and method of preparing same
JPH01108262A (en) 1987-10-22 1989-04-25 Sumitomo Electric Ind Ltd Oil-containing resin composition for sliding
JPH01113436A (en) 1987-10-26 1989-05-02 Shinichi Cho Preparation of synthetic resin pellet containing microcapsulated additive in high concentration
JPH02145383A (en) 1988-11-28 1990-06-04 Kanzaki Paper Mfg Co Ltd Temperature sensitive microcapsule containing volatile substance
US5538735A (en) * 1993-02-19 1996-07-23 Ahn; Sam S. Method of making a drug delivery system using hollow fibers
US5534289A (en) * 1995-01-03 1996-07-09 Competitive Technologies Inc. Structural crack monitoring technique
US6075072A (en) * 1998-03-13 2000-06-13 3M Innovative Properties Company Latent coating for metal surface repair
GB9916157D0 (en) * 1999-07-10 1999-09-08 British Aerospace Method for manufacturing a filled hollow fibre composite mate rial
US6653151B2 (en) * 1999-07-30 2003-11-25 Large Scale Proteomics Corporation Dry deposition of materials for microarrays using matrix displacement
US6890561B1 (en) * 1999-08-19 2005-05-10 Bio Dar Ltd. Microencapsulated and controlled-release formulations of isoflavone from enriched fractions of soy and other plants
US6746984B2 (en) * 1999-12-08 2004-06-08 Pentax Corporation Image-forming medium coated with microcapsule layer for forming image
US6257849B1 (en) * 2000-04-12 2001-07-10 Scott Wu Manual air pump having selectable high pressure and high pressure modes
US6579827B2 (en) * 2000-04-28 2003-06-17 Pentax Corporation Multi-color image-forming medium
JP2002087896A (en) * 2000-09-12 2002-03-27 Mitsubishi Heavy Ind Ltd Self-repairing high heat resistant and oxidation resistant coating film, and laminated body
US6808461B2 (en) * 2001-06-22 2004-10-26 Acushnet Company Golf ball compositions with microencapsulated healing agent
US6794472B2 (en) * 2001-06-22 2004-09-21 Acushnet Company Self healing polymers in sports equipment
US7157102B1 (en) * 2002-05-31 2007-01-02 Biotek, Inc. Multi-layered microcapsules and method of preparing same
US7108914B2 (en) * 2002-07-15 2006-09-19 Motorola, Inc. Self-healing polymer compositions
US7192993B1 (en) * 2003-03-04 2007-03-20 The United States Of America As Represented By The Secretary Of The Army Self-healing coating and microcapsules to make same
US8114517B2 (en) * 2004-07-30 2012-02-14 Battelle Memorial Institute Micronetworks, microchannels/cylinders and the process for making the same
US7342057B2 (en) * 2004-08-24 2008-03-11 United States Of America As Represented By The Secretary Of The Army Self-healing coatings using microcapsules to suppress lead dust

Patent Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179600A (en) * 1960-03-10 1965-04-20 Ncr Co Minute color-forming capsules and record material provided with such
US3274401A (en) * 1961-11-20 1966-09-20 Thompson Ramo Wooldridge Inc Self-repairing and self-sustaining system
US3423491A (en) * 1964-09-02 1969-01-21 Dow Chemical Co Permselective hollow fibers and method of making
US3505244A (en) * 1965-04-30 1970-04-07 Union Carbide Corp Encapsulated corrosion inhibitor
US3475188A (en) * 1965-09-29 1969-10-28 Steetley Refractory Brick Co Refractory compositions
US3607591A (en) * 1969-04-22 1971-09-21 Stevens & Co Inc J P Temperature adaptable fabrics
US3647557A (en) * 1970-08-19 1972-03-07 Du Pont Hollow gas permeable fiber vented sealed galvanic cells
US3704264A (en) * 1970-12-16 1972-11-28 Loctite Corp Encapsulation of monomeric materials
US3913666A (en) * 1972-03-20 1975-10-21 Peter Bayliss Heat resistant wall construction
US4109033A (en) * 1975-06-06 1978-08-22 Blankenhorn Paul R Process for impregnating concrete with polymers
US4272898A (en) * 1976-03-11 1981-06-16 Tansill Horace A Resin-coated fiber mass containing catalyst-filled hollow fibers
US4183890A (en) * 1977-11-30 1980-01-15 Monsanto Company Method of cutting hollow filaments embedded in resinous mass
US4908238A (en) * 1984-07-02 1990-03-13 The United States Of America As Represented By The Secretary Of Agriculture Temperature adaptable textile fibers and method of preparing same
US4587279A (en) * 1984-08-31 1986-05-06 University Of Dayton Cementitious building material incorporating end-capped polyethylene glycol as a phase change material
US4780205A (en) * 1984-10-30 1988-10-25 Teijin Limited Permselective hollow fiber membrane, process for the preparation thereof, method and apparatus for plasma components separation
US4733989A (en) * 1984-11-29 1988-03-29 American Colloid Company Self-healing bentonite sheet material composite drainage structure
US4810573A (en) * 1984-11-29 1989-03-07 American Colloid Company Self-healing bentonite sheet material composite article
US4978563A (en) * 1986-04-17 1990-12-18 Sandels Claes M C Self repairing elastic bodies
US4961790A (en) * 1989-05-19 1990-10-09 Fritz Chemical Company Concrete admixture device and method of using same
US5232769A (en) * 1989-08-01 1993-08-03 Kanebo, Ltd. Microcapsule, treating liquids containing the same, and textile structure having microcapsules adhering thereto
US6261360B1 (en) * 1990-06-19 2001-07-17 Carolyn M. Dry Self-repairing, reinforced matrix materials
US5575841A (en) * 1990-06-19 1996-11-19 Carolyn M. Dry Cementitious materials
US5660624A (en) * 1990-06-19 1997-08-26 Dry; Carolyn M. Self-repairing, reinforced matrix materials
US5803963A (en) * 1990-06-19 1998-09-08 Dry; Carolyn M. Smart-fiber-reinforced matrix composites
US7022179B1 (en) * 1990-06-19 2006-04-04 Dry Carolyn M Self-repairing, reinforced matrix materials
US6527849B2 (en) * 1990-06-19 2003-03-04 Carolyn M. Dry Self-repairing, reinforced matrix materials
US5561173A (en) * 1990-06-19 1996-10-01 Carolyn M. Dry Self-repairing, reinforced matrix materials
US5989334A (en) * 1990-06-19 1999-11-23 Dry; Carolyn M. Self-repairing, reinforced matrix materials
US5965266A (en) * 1995-03-28 1999-10-12 Societe Nationale D'etude Et De Construction De Moteurs D'aviation Composite material protected against oxidation by a self-healing matrix, and a method of manufacturing it
US5851291A (en) * 1996-07-31 1998-12-22 Poterala; Robert J. Chemical foaming machine and mixing apparatus
US6039288A (en) * 1997-03-10 2000-03-21 Telair International Gmbh Floor unit
US6766817B2 (en) * 2001-07-25 2004-07-27 Tubarc Technologies, Llc Fluid conduction utilizing a reversible unsaturated siphon with tubarc porosity action
US6918404B2 (en) * 2001-07-25 2005-07-19 Tubarc Technologies, Llc Irrigation and drainage based on hydrodynamic unsaturated fluid flow
US7066586B2 (en) * 2001-07-25 2006-06-27 Tubarc Technologies, Llc Ink refill and recharging system

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8431254B2 (en) * 2005-10-11 2013-04-30 Commissariat A L'energie Atomique Solid joint obtained by heat projection
US20090199947A1 (en) * 2005-10-11 2009-08-13 Commissariat A L'energie Atomique Solid Joint Obtained by Heat Projection
US7572501B2 (en) * 2007-04-17 2009-08-11 The Regents Of The University Of Michigan Engineered self healing cementitious composites
US20080261027A1 (en) * 2007-04-17 2008-10-23 The Regents Of The University Of Michigan Engineered self healing cementitious composites
US20110003159A1 (en) * 2008-12-23 2011-01-06 Patrick Mather Self-healing product
US9533469B2 (en) 2008-12-23 2017-01-03 Syracuse University Self-healing product
US20100276895A1 (en) * 2009-04-29 2010-11-04 Rolls-Royce Plc Seal arrangement and a method of repairing a seal arrangement
US9121350B2 (en) 2009-04-29 2015-09-01 Rolls-Royce Plc Seal arrangement and a method of repairing a seal arrangement
US8408557B2 (en) * 2009-04-29 2013-04-02 Rolls-Royce Plc Seal arrangement and a method of repairing a seal arrangement
US8683798B2 (en) 2010-01-15 2014-04-01 Syracuse University Stimuli-responsive product
US20110173971A1 (en) * 2010-01-15 2011-07-21 Syracuse University Stimuli-responsive product
US8846404B2 (en) * 2010-06-25 2014-09-30 Board Of Trustees Of The University Of Illinois System for visual indication of mechanical damage
US20120196373A1 (en) * 2010-06-25 2012-08-02 The Board Of Trustees Of The University Of Illinois System For Visual Indication Of Mechanical Damage
US9720156B1 (en) * 2012-06-11 2017-08-01 Michael P. Ross Sensored fiber reinforced polymer grate

Also Published As

Publication number Publication date Type
US20010050032A1 (en) 2001-12-13 application
US20080057296A1 (en) 2008-03-06 application
US6527849B2 (en) 2003-03-04 grant
US20080047472A1 (en) 2008-02-28 application
US20060169180A1 (en) 2006-08-03 application
US20080050612A1 (en) 2008-02-28 application
US20080053338A1 (en) 2008-03-06 application
US20080058445A1 (en) 2008-03-06 application

Similar Documents

Publication Publication Date Title
Li Engineered cementitious composites-tailored composites through micromechanical modeling
Hollaway et al. Progress in the technique of upgrading metallic structures with advanced polymer composites
Wu et al. A review: Self-healing in cementitious materials and engineered cementitious composite as a self-healing material
Toutanji et al. The effect of surface preparation on the bond interface between FRP sheets and concrete members
Tavakkolizadeh et al. Strengthening of steel-concrete composite girders using carbon fiber reinforced polymers sheets
Aıtcin The durability characteristics of high performance concrete: a review
Karbhari et al. Use of composites for 21st century civil infrastructure
Bisby Fire behaviour of fibre-reinforced polymer (FRP) reinforced or confined concrete
Micelli et al. Durability of FRP rods for concrete structures
US5573348A (en) Structural members
US5925449A (en) Method for bonding fiber reinforcement on concrete and steel structures and resultant products
Bilotta et al. Bond efficiency of EBR and NSM FRP systems for strengthening concrete members
US20040025465A1 (en) Inorganic matrix-fabric system and method
Michaluk et al. Flexural behavior of one-way concrete slabs reinforced by fiber reinforced plastic reinforcements
Kardon Polymer-modified concrete
Hollaway et al. Strengthening of reinforced concrete structures: Using externally-bonded FRP composites in structural and civil engineering
Hollaway A review of the present and future utilisation of FRP composites in the civil infrastructure with reference to their important in-service properties
US4714507A (en) Surface coating agent and method for using the same in civil and construction engineering
Sim et al. Characteristics of basalt fiber as a strengthening material for concrete structures
Lee et al. Interfacial bond strength of glass fiber reinforced polymer bars in high-strength concrete
US5803963A (en) Smart-fiber-reinforced matrix composites
Tavakkolizadeh et al. Repair of damaged steel-concrete composite girders using carbon fiber-reinforced polymer sheets
US7811666B2 (en) Multiple function, self-repairing composites with special adhesives
Bisby et al. Fire endurance of fiber-reinforced polymer-confined concrete columns
Ahmed et al. A review on durability properties of strain hardening fibre reinforced cementitious composites (SHFRCC)