US20050027078A1 - Method and chemistry for automatic self-joining of failures in polymers - Google Patents
Method and chemistry for automatic self-joining of failures in polymers Download PDFInfo
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- US20050027078A1 US20050027078A1 US10/631,374 US63137403A US2005027078A1 US 20050027078 A1 US20050027078 A1 US 20050027078A1 US 63137403 A US63137403 A US 63137403A US 2005027078 A1 US2005027078 A1 US 2005027078A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/225—Correcting or repairing of printed circuits
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing 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
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing 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
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/22—Auto-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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1163—Chemical reaction, e.g. heating solder by exothermic reaction
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/284—Applying non-metallic protective coatings for encapsulating mounted components
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/303—Surface mounted components, e.g. affixing before soldering, aligning means, spacing means
- H05K3/305—Affixing by adhesive
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
- Y10T428/2985—Solid-walled microcapsule from synthetic polymer
Definitions
- This invention relates generally to repair of failures in polymers. More specifically this invention relates to the chemistry to form cross-links within a material failure to chemically bond opposing faces of the failure.
- Polymeric materials tend to fail or degrade due to mechanical fatigue, mechanical impact, oxidative aging due to radiation or impurities, thermal fatigue, chemical degradation, or a combination of these processes.
- the degradation can lead to embrittlement of the polymer, among other adverse effects.
- the embrittlement and associated cracking can advance to the point of product failure, which creates replacement costs.
- Mechanical fatigue and mechanical stress, such as that caused by dropping the object, can also lead to cracks that eventually cause failure.
- Thermoplastic and thermoset polymer systems used in products can be particularly susceptible to these failure modalities.
- PCB printed circuit board
- other degradation processes such as redox reactions or chemical diffusion, can be expected in organic semi-conductors and in electrically conductive polymers (which degrade their characteristics).
- Polymeric based paints are also subject to cracking due to environmental exposure causing degradation. Any polymer components used in the structure of equipment, such as airplanes or trains will be subject to long term degradation described above.
- microcapsules containing a healing agent in a polymer matrix.
- the healing agent enclosed in the microcapsules is dicyclopentadiene (DCPD).
- DCPD dicyclopentadiene
- a ruthenium polymerization agent, corresponding to CAS No. 172222-30-9, is dispersed in the polymer matrix.
- the healing agent is functionally active in the presence of moisture and air (oxygen source).
- the healing agent is released from the ruptured microcapsules and contacts the fracture surfaces.
- the healing agent also comes into contact with a polymerization agent dispersed in the polymer matrix to the extent the dispersed polymerization agent is located in the direct vicinity of the fracture and released healing agent.
- the healing agent contacts the self-healing agent, the healing agent is polymerized, resulting in filling of the crack planes of the fracture. This filling arrests fracture propagation and reduces the compliance of the post-fractured matrix material.
- One aspect of the present invention provides a self-joining polymer composition, comprising a polymer, a plurality of amine pendant groups attached to the polymer and a plurality of microcapsules of flowable polymerizable material dispersed in the polymer where the microcapsules of flowable polymerizable material include microcapsules and flowable polymerizable material inside the microcapsules.
- the microcapsules are effective for rupturing with a failure of the polymer and the flowable polymerizable material cross-links with the reactable pendant groups upon rupture of the microcapsules.
- Another aspect of the present invention is a method for healing a failure in a composite member, where the method includes providing a composite member comprising a polymer, a plurality of reactable pendant groups attached to the polymer, and a plurality of microcapsules containing a flowable polymerizing agent dispersed throughout the polymer. The method also includes rupturing at least one of the plurality of microcapsules responsive to a failure in a region of the composite member. The method further provides releasing the flowable polymerizing agent responsive to the rupturing and cross-linking the flowable polymerizing agent with the plurality of reactable pendant groups in the failure region.
- a third aspect of the present invention is an article of manufacture comprising a self-joining polymer composition, where the self-joining polymer composition comprises a polymer, a plurality of reactable pendant groups attached to the polymer and a plurality of microcapsules containing a flowable polymerizable material dispersed in the polymer, the microcapsules effective for rupturing with a failure of the polymer wherein the flowable polymerizable material cross-links with the reactable pendant groups to join the failure.
- FIGS. 1 and 2 illustrate schematically, a material with a failure at two stages of propagation in accordance with various embodiments of the invention
- FIG. 3 illustrates schematically the material of FIG. 2 wherein the failure has been self-joined, in accordance with various embodiments of the invention
- FIG. 4 illustrates an enlargement of the self-joined failure of FIG. 3 ;
- FIG. 5 illustrates a chemical structure of a polymerizing agent, in accordance with a first embodiment of the invention
- FIG. 6 illustrates a chemical structure of a first amine pendant group, in accordance with a first embodiment of the invention
- FIG. 7 illustrates a chemical structure of a first amine pendant group chemically bonded with the polymerizing agent in accordance with a first embodiment of the invention.
- FIG. 8 illustrates the chemical structure of FIG. 7 chemically bonded to a second amine pendant group, in accordance with a first embodiment of the invention.
- FIG. 1 illustrates schematically, a self-joining polymer composition 20 comprised of a polymer 21 , which has a plurality of amine pendant groups 31 and a plurality of microcapsules 40 containing flowable polymerizable material 50 dispersed throughout the polymer 21 .
- the flowable polymerizable material 50 can be formed from short and long chain dianhydrides and mixtures thereof.
- the polymer 21 may be epoxies, thermoset, thermoplastic, elastomeric, and mixtures thereof.
- a failure 60 is illustrated as the failure begins to propagate into the self-joining polymer composition 20 .
- a failure refers to a crack or a loss of functionality created by a loss of cohesion in the self-joining polymer composition 20 .
- a failure has a first face 61 and a second face 62 , which opposes the first face 61 .
- These faces may be rough or smooth surfaces.
- the faces may include a plurality of surfaces or faces. The discussion herein will be limited to two faces although the concept applies to more than two faces.
- Amine pendant groups 32 dangling from the first face 61 are those amine pendant groups 31 dispersed throughout the polymer 21 , which are exposed on the first face 61 of the failure 60 as the failure propagates into the self-joining polymer composition 20 .
- the amine pendant groups 32 are reactable with flowable polymerizable material 50 .
- Amine pendant groups 33 dangling from the second face 62 are those amine pendant groups 31 dispersed throughout the polymer 21 which are exposed on the second face 62 of the failure 60 as the failure propagates into the self-joining polymer composition 20 .
- the amine pendant groups 33 are also reactable with flowable polymerizable material 50 .
- FIG. 2 illustrates the self-joining polymer composition 20 of FIG. 1 at a later time, when the failure 60 has propagated deeper into the self-joining polymer composition 20 .
- the failure 60 has a first face 61 and a second face 62 , which opposes the first face 61 .
- Amine pendant groups 32 dangling from the first face 61 are those amine pendant groups 31 dispersed throughout the polymer 21 , which are exposed on the first face 61 of the failure 60 as the failure propagates into the self-joining polymer composition 20 .
- the amine pendant groups 32 are reactable with flowable polymerizable material 50 and 51 .
- Amine pendant groups 33 dangling from the second face 62 are those amine pendant groups 31 dispersed throughout the polymer 21 which are exposed on the second face 62 of the failure 60 as the failure 60 propagates into the self-joining polymer composition 20 .
- the amine pendant groups 33 are also reactable with flowable polymerizable material 50 and 51 .
- FIG. 2 illustrates a moment in time when the failure has intersected with one of the microcapsules 40 containing flowable polymerizable material 50 .
- the microcapsule 40 can be designed to rupture upon intersection with a failure 60 as described in detail in commonly assigned U.S. patent application Ser. No. 10/195,858 filed Jul. 15, 2002 entitled “Self-Healing Polymer Compositions.”
- the microcapsule shell may be comprised of several materials metal oxide, silica, silicate, carbon, polymer, and mixtures thereof.
- the released flowable polymerizable material 51 from ruptured microcapsule 41 flows through the ruptured microcapsule opening 42 in the microcapsule 41 shell into the failure 60 .
- Microcapsules 40 containing flowable polymerizable material 50 embedded in the self-joining polymer composition 20 which have not intersected with the fracture 60 , will remain intact.
- FIG. 3 illustrates a moment in time after the released flowable polymerizable material 51 from ruptured microcapsule 41 , which flowed through the ruptured microcapsule opening 42 in the microcapsule 41 shell into the failure 60 , has bonded with the amine pendant groups 32 dangling from the first face 61 and the amine pendant groups 33 dangling from the second face 62 .
- the self-joining polymer composition 20 comprised of a polymer 21 , has a plurality of amine pendant groups 31 and a plurality of microcapsules 40 containing flowable polymerizable material 50 dispersed throughout the polymer.
- the released flowable polymerizable material 51 FIG.
- a first end (see FIG. 5 and FIG. 7 ) of the released flowable polymerizable material 51 can bond with a reactable first face 61 dangling amine pendant group 34 before a second end (see FIG. 5 and FIG. 8 ) of the released flowable polymerizable material 51 bonds with a reactable second face 62 dangling amine pendant group 35 .
- the second end (see FIG. 5 and FIG. 8 ) of the released flowable polymerizable material 51 can bond with a second face 62 dangling amine pendant group 35 before the first end (see FIG. 5 and FIG.
- the released flowable polymerizable material 51 bonds with a first face 61 dangling amine pendant group 34 . Or, both bonds can occur simultaneously. Since the released flowable polymerizable material 51 is a symmetric molecule the distinction between first and second end of the released flowable polymerizable material 51 is only brought out to describe the bonding events.
- FIG. 4 illustrates schematically, an expanded view of the self-joined failure 63 , after the first end (see FIG. 5 and FIG. 7 ) of the reacted polymerizable material 53 has bonded with a first face 61 dangling amine pendant group 34 and the second end (see FIG. 5 and FIG. 8 ) of the released flowable polymerizable material 51 bonds with a second face 62 dangling amine pendant group 35 to form a cross-linked region 64 within the repaired or self-joined failure 63 .
- the cross-link region will form a mesh-like web based on a link comprised of amine pendant group 34 , bonded polymerizable material 53 and amine pendant group 35 .
- the flowable polymerizable material 50 which flowed from the ruptured microcapsule 41 through the ruptured microcapsule opening 42 is now the reacted polymerizable material 53 .
- FIG. 5 illustrates the chemical structure for the formula of an exemplary polymerizing agent 50 in which O represents oxygen, C represents carbon and R represents a group of connecting atoms or chemical groups, typically several methylene groups, intended to give the polymerizing agent 50 lateral range for bonding crack faces 61 and 62 (see FIG. 1 ) as described below.
- This is the chemical structure of released flowable polymerizable material 51 .
- FIG. 6 illustrates the chemical structure of an exemplary amine pendant group 31 , which can be dispersed throughout the polymer 21 along with the plurality of microcapsules 40 containing flowable polymerizable material 50 to form the self-joining polymer composition 20 as illustrated in the previous figures.
- R′ and R′′ represent either H atoms or different segments of the polymer 21 backbone with at least one of which comprising a segment of the polymer 21 backbone on the first face 61 of the failure 60 to which the pendant amine group 32 is attached while N and H represent nitrogen and hydrogen respectively.
- the amine functionality represented in FIG. 6 may be a part of the polymer composition 21 or the polymer composition 21 may be deliberately modified prior to formation of self-joining polymer composition 20 .
- FIGS. 7 and 8 Chemical reactions described in FIGS. 7 and 8 are presented in the normal equation where the molecules, which will react, are shown to the left of the arrow and the chemical structure upon reaction is illustrated to the right of the arrow.
- a first bonding event is illustrated in FIG. 7 .
- One reactant is a reactable pendant amine group 32 bonded to two polymer backbones R′ and R′′ of first face 61 at the nitrogen atom.
- the other reactant is released flowable polymerizable material 51 .
- the segments labeled 34 and 52 show the chemical structure of the pendant amine group 34 attached to face one 61 two polymer backbones R′ and R′′ and the first bonded polymerizable material 52 after the bonding reaction indicated by the arrow.
- Nitrogen atom 69 of the amine pendant group attached to polymerizable material 51 is now attached to the carbon atom 70 while the hydrogen 66 from the amine pendant group is attached to the oxygen atom 65 of released flowable polymerizable material 51 .
- the aforementioned reaction has formed an amide and a carboxylic acid from the acid anhydride reaction with the amine.
- the second bonding event is illustrated in FIG. 8 .
- the resultant chemical structure from the bonding illustrated in FIG. 7 and comprised of amine pendant group 34 and first bonded polymerizable material 52 is one reactant.
- the second face 62 dangling amine pendant group 33 attached to second face 62 of the failure 60 at polymer backbones R′′′ and R′′′′ is the other reactant in the bonding event illustrated in FIG. 8 .
- the resultant link comprised of segments illustrated by amine pendant group 34 and bonded polymerizable material 53 and amine pendant group 35 . This bonding event illustrated in FIG.
- FIGS. 7 and 8 are meant to illustrate only one of many possible chemical bonding structures operable to form self-joining bonds 64 ( FIG. 4 ) between a first face 61 and a second face 62 of a polymeric failure 60 ( FIG. 4 ).
- a manufactured article will be able to prevent cracks from propagating, allowing for a longer lifetime for the article.
- Structures can be manufactured from composite materials comprising the self-joining polymer composition 20 of FIG. 1 .
- Such structures such as aerospace vehicles, automotive parts, including body structures, sporting equipment and other structures requiring lightweight, high strength materials, will be self joining if a crack were to start from stresses on the structure and will have an extended lifetime.
- Examples of other joining methods include formation of esters from anhydrides and alcohol polymer pendant groups, formation of esters from carboxylic acids and alcohol polymer pendant groups, formation of amides from carboxylic acids and amine pendant groups, formation of amides from amines and anhydride polymer pendant groups, formation of amides from amines and carboxylic acid polymer pendant groups, formation of esters from alcohols and anhydride polymer pendant groups, formation of esters from alcohols and carboxylic acid polymer pendant groups.
Abstract
Description
- This invention relates generally to repair of failures in polymers. More specifically this invention relates to the chemistry to form cross-links within a material failure to chemically bond opposing faces of the failure.
- Polymeric materials tend to fail or degrade due to mechanical fatigue, mechanical impact, oxidative aging due to radiation or impurities, thermal fatigue, chemical degradation, or a combination of these processes. The degradation can lead to embrittlement of the polymer, among other adverse effects. The embrittlement and associated cracking can advance to the point of product failure, which creates replacement costs. Mechanical fatigue and mechanical stress, such as that caused by dropping the object, can also lead to cracks that eventually cause failure. Thermoplastic and thermoset polymer systems used in products can be particularly susceptible to these failure modalities.
- This problem is a great concern because of the widespread and intensive use in modern society of polymers in product components. For instance, polymers have a significant importance and presence in the electronics industry. Examples of applications include printed circuit board (PCB) laminates, housings, enclosures, adhesives, die attach, component packaging, and organic semi-conductors. In addition to the above-mentioned failure modes, other degradation processes, such as redox reactions or chemical diffusion, can be expected in organic semi-conductors and in electrically conductive polymers (which degrade their characteristics). Polymeric based paints are also subject to cracking due to environmental exposure causing degradation. Any polymer components used in the structure of equipment, such as airplanes or trains will be subject to long term degradation described above.
- Traditional approaches to increasing the reliability of polymeric-based components and products have included a focus on suitable design enhancements and the use of incrementally improved plastics. Recently, a significant increase in the availability of so-called ‘smart” materials has occurred, which relates to materials that can sense impending failure and facilitate appropriate corrective measures to prevent extensive damage. Alternatively, if the damage has already occurred, some new material systems can purportedly self-heal the damaged structure. See, e.g., Chen, et al., “A Thermally Re-Mendable Cross-Linked Polymeric Material,” Science, Vol. 295, March 2002, pp. 1698-1702.
- One recently developed process intended to impart self-healing capability to a polymer involves the incorporation of microcapsules containing a healing agent in a polymer matrix. White, S. R., et al., Nature, “Autonomic Healing of Polymer Composites,” 409, 794-797 (2001). The healing agent enclosed in the microcapsules is dicyclopentadiene (DCPD). A ruthenium polymerization agent, corresponding to CAS No. 172222-30-9, is dispersed in the polymer matrix. The healing agent is functionally active in the presence of moisture and air (oxygen source). When a fracture occurring in the polymer matrix propagates in close proximity of the microcapsules, the associated stresses caused by the fracture rupture the microcapsules. As a consequence, the healing agent is released from the ruptured microcapsules and contacts the fracture surfaces. The healing agent also comes into contact with a polymerization agent dispersed in the polymer matrix to the extent the dispersed polymerization agent is located in the direct vicinity of the fracture and released healing agent. When the polymerization agent contacts the self-healing agent, the healing agent is polymerized, resulting in filling of the crack planes of the fracture. This filling arrests fracture propagation and reduces the compliance of the post-fractured matrix material.
- U.S. Pat. No. 6,518,330 B2 by S. R. White et al., describes a self healing polymer material, which relies upon rupture of microcapsules on contact with a fracture surface exposing a polymerizer to a catalyst. The reacting material within the crack fills the crack and adheres the crack faces together.
- It is desirable, therefore, to provide a method for automatic repair of polymer failures that overcomes these and other disadvantages.
- One aspect of the present invention provides a self-joining polymer composition, comprising a polymer, a plurality of amine pendant groups attached to the polymer and a plurality of microcapsules of flowable polymerizable material dispersed in the polymer where the microcapsules of flowable polymerizable material include microcapsules and flowable polymerizable material inside the microcapsules. The microcapsules are effective for rupturing with a failure of the polymer and the flowable polymerizable material cross-links with the reactable pendant groups upon rupture of the microcapsules.
- Another aspect of the present invention is a method for healing a failure in a composite member, where the method includes providing a composite member comprising a polymer, a plurality of reactable pendant groups attached to the polymer, and a plurality of microcapsules containing a flowable polymerizing agent dispersed throughout the polymer. The method also includes rupturing at least one of the plurality of microcapsules responsive to a failure in a region of the composite member. The method further provides releasing the flowable polymerizing agent responsive to the rupturing and cross-linking the flowable polymerizing agent with the plurality of reactable pendant groups in the failure region.
- A third aspect of the present invention is an article of manufacture comprising a self-joining polymer composition, where the self-joining polymer composition comprises a polymer, a plurality of reactable pendant groups attached to the polymer and a plurality of microcapsules containing a flowable polymerizable material dispersed in the polymer, the microcapsules effective for rupturing with a failure of the polymer wherein the flowable polymerizable material cross-links with the reactable pendant groups to join the failure.
- The foregoing device and method as well as features and advantages of the present invention will become further apparent from the following detailed description of the presently preferred embodiments, read in conjunction with the accompanying drawings. The detailed description and drawings are merely illustrative of the present invention rather than limiting, the scope of the present invention being defined by the appended claims and equivalents thereof.
- The present invention is illustrated by way of example and not limitation in the accompanying figures, in which like references indicate similar elements, and in which:
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FIGS. 1 and 2 illustrate schematically, a material with a failure at two stages of propagation in accordance with various embodiments of the invention; -
FIG. 3 illustrates schematically the material ofFIG. 2 wherein the failure has been self-joined, in accordance with various embodiments of the invention; -
FIG. 4 illustrates an enlargement of the self-joined failure ofFIG. 3 ; -
FIG. 5 illustrates a chemical structure of a polymerizing agent, in accordance with a first embodiment of the invention; -
FIG. 6 illustrates a chemical structure of a first amine pendant group, in accordance with a first embodiment of the invention; -
FIG. 7 illustrates a chemical structure of a first amine pendant group chemically bonded with the polymerizing agent in accordance with a first embodiment of the invention; and -
FIG. 8 illustrates the chemical structure ofFIG. 7 chemically bonded to a second amine pendant group, in accordance with a first embodiment of the invention. - The present description relates to an exemplary embodiment of this invention and examples of other embodiments.
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FIG. 1 illustrates schematically, a self-joiningpolymer composition 20 comprised of apolymer 21, which has a plurality ofamine pendant groups 31 and a plurality ofmicrocapsules 40 containing flowablepolymerizable material 50 dispersed throughout thepolymer 21. The flowablepolymerizable material 50 can be formed from short and long chain dianhydrides and mixtures thereof. Thepolymer 21 may be epoxies, thermoset, thermoplastic, elastomeric, and mixtures thereof. InFIG. 1 , afailure 60 is illustrated as the failure begins to propagate into the self-joiningpolymer composition 20. As used herein, a failure refers to a crack or a loss of functionality created by a loss of cohesion in the self-joiningpolymer composition 20. Typically, a failure has afirst face 61 and asecond face 62, which opposes thefirst face 61. These faces may be rough or smooth surfaces. The faces may include a plurality of surfaces or faces. The discussion herein will be limited to two faces although the concept applies to more than two faces. -
Amine pendant groups 32 dangling from thefirst face 61 are thoseamine pendant groups 31 dispersed throughout thepolymer 21, which are exposed on thefirst face 61 of thefailure 60 as the failure propagates into the self-joiningpolymer composition 20. Theamine pendant groups 32 are reactable with flowablepolymerizable material 50.Amine pendant groups 33 dangling from thesecond face 62 are thoseamine pendant groups 31 dispersed throughout thepolymer 21 which are exposed on thesecond face 62 of thefailure 60 as the failure propagates into the self-joiningpolymer composition 20. Theamine pendant groups 33 are also reactable with flowablepolymerizable material 50. -
FIG. 2 illustrates the self-joiningpolymer composition 20 ofFIG. 1 at a later time, when thefailure 60 has propagated deeper into the self-joiningpolymer composition 20. Thefailure 60 has afirst face 61 and asecond face 62, which opposes thefirst face 61.Amine pendant groups 32 dangling from thefirst face 61 are thoseamine pendant groups 31 dispersed throughout thepolymer 21, which are exposed on thefirst face 61 of thefailure 60 as the failure propagates into the self-joiningpolymer composition 20. Theamine pendant groups 32 are reactable with flowablepolymerizable material Amine pendant groups 33 dangling from thesecond face 62 are thoseamine pendant groups 31 dispersed throughout thepolymer 21 which are exposed on thesecond face 62 of thefailure 60 as thefailure 60 propagates into the self-joiningpolymer composition 20. Theamine pendant groups 33 are also reactable with flowablepolymerizable material -
FIG. 2 illustrates a moment in time when the failure has intersected with one of themicrocapsules 40 containing flowablepolymerizable material 50. Themicrocapsule 40 can be designed to rupture upon intersection with afailure 60 as described in detail in commonly assigned U.S. patent application Ser. No. 10/195,858 filed Jul. 15, 2002 entitled “Self-Healing Polymer Compositions.” The microcapsule shell may be comprised of several materials metal oxide, silica, silicate, carbon, polymer, and mixtures thereof. The released flowablepolymerizable material 51 from rupturedmicrocapsule 41 flows through the rupturedmicrocapsule opening 42 in themicrocapsule 41 shell into thefailure 60.Microcapsules 40 containing flowablepolymerizable material 50 embedded in the self-joiningpolymer composition 20, which have not intersected with thefracture 60, will remain intact. -
FIG. 3 illustrates a moment in time after the released flowablepolymerizable material 51 from rupturedmicrocapsule 41, which flowed through the rupturedmicrocapsule opening 42 in themicrocapsule 41 shell into thefailure 60, has bonded with theamine pendant groups 32 dangling from thefirst face 61 and theamine pendant groups 33 dangling from thesecond face 62. As inFIG. 1 and 2, the self-joiningpolymer composition 20 comprised of apolymer 21, has a plurality ofamine pendant groups 31 and a plurality ofmicrocapsules 40 containing flowablepolymerizable material 50 dispersed throughout the polymer. As illustrated inFIG. 3 , the released flowable polymerizable material 51 (FIG. 2 ) has bonded to the reactablefirst face 61 dangling amine pendant groups 32 (FIG. 2 ) to form a reactedgroup 34 and the reactablesecond face 62 dangling amine pendant groups 33 (FIG. 2 ) to form a reactedgroup 35. Reactedgroup 34 and reactedgroup 35 are bonded to reactedpolymerizable material 53. The failure 60 (FIG. 2 ) is now a self-joinedfailure 63. - The sequence of the bonding is variable, leading to the same result. A first end (see
FIG. 5 andFIG. 7 ) of the released flowablepolymerizable material 51 can bond with a reactablefirst face 61 danglingamine pendant group 34 before a second end (seeFIG. 5 andFIG. 8 ) of the released flowablepolymerizable material 51 bonds with a reactablesecond face 62 danglingamine pendant group 35. Or, the second end (seeFIG. 5 andFIG. 8 ) of the released flowablepolymerizable material 51 can bond with asecond face 62 danglingamine pendant group 35 before the first end (seeFIG. 5 andFIG. 8 ) of the released flowablepolymerizable material 51 bonds with afirst face 61 danglingamine pendant group 34. Or, both bonds can occur simultaneously. Since the released flowablepolymerizable material 51 is a symmetric molecule the distinction between first and second end of the released flowablepolymerizable material 51 is only brought out to describe the bonding events. -
FIG. 4 illustrates schematically, an expanded view of the self-joinedfailure 63, after the first end (seeFIG. 5 andFIG. 7 ) of the reactedpolymerizable material 53 has bonded with afirst face 61 danglingamine pendant group 34 and the second end (seeFIG. 5 andFIG. 8 ) of the released flowablepolymerizable material 51 bonds with asecond face 62 danglingamine pendant group 35 to form across-linked region 64 within the repaired or self-joinedfailure 63. The cross-link region will form a mesh-like web based on a link comprised ofamine pendant group 34, bondedpolymerizable material 53 andamine pendant group 35. The flowablepolymerizable material 50 which flowed from the rupturedmicrocapsule 41 through the rupturedmicrocapsule opening 42 is now the reactedpolymerizable material 53. -
FIG. 5 illustrates the chemical structure for the formula of anexemplary polymerizing agent 50 in which O represents oxygen, C represents carbon and R represents a group of connecting atoms or chemical groups, typically several methylene groups, intended to give the polymerizingagent 50 lateral range for bonding crack faces 61 and 62 (seeFIG. 1 ) as described below. This is the chemical structure of released flowablepolymerizable material 51. -
FIG. 6 illustrates the chemical structure of an exemplaryamine pendant group 31, which can be dispersed throughout thepolymer 21 along with the plurality ofmicrocapsules 40 containing flowablepolymerizable material 50 to form the self-joiningpolymer composition 20 as illustrated in the previous figures. R′ and R″ represent either H atoms or different segments of thepolymer 21 backbone with at least one of which comprising a segment of thepolymer 21 backbone on thefirst face 61 of thefailure 60 to which thependant amine group 32 is attached while N and H represent nitrogen and hydrogen respectively. It should be noted that the amine functionality represented inFIG. 6 may be a part of thepolymer composition 21 or thepolymer composition 21 may be deliberately modified prior to formation of self-joiningpolymer composition 20. - Chemical reactions described in
FIGS. 7 and 8 are presented in the normal equation where the molecules, which will react, are shown to the left of the arrow and the chemical structure upon reaction is illustrated to the right of the arrow. - A first bonding event is illustrated in
FIG. 7 . One reactant is a reactablependant amine group 32 bonded to two polymer backbones R′ and R″ offirst face 61 at the nitrogen atom. The other reactant is released flowablepolymerizable material 51. The segments labeled 34 and 52 show the chemical structure of thependant amine group 34 attached to face one 61 two polymer backbones R′ and R″ and the first bondedpolymerizable material 52 after the bonding reaction indicated by the arrow.Nitrogen atom 69 of the amine pendant group attached topolymerizable material 51 is now attached to thecarbon atom 70 while thehydrogen 66 from the amine pendant group is attached to theoxygen atom 65 of released flowablepolymerizable material 51. One skilled in the art will appreciate that the aforementioned reaction has formed an amide and a carboxylic acid from the acid anhydride reaction with the amine. - The second bonding event is illustrated in
FIG. 8 . The resultant chemical structure from the bonding illustrated inFIG. 7 and comprised ofamine pendant group 34 and first bondedpolymerizable material 52 is one reactant. Thesecond face 62 danglingamine pendant group 33 attached tosecond face 62 of thefailure 60 at polymer backbones R′″ and R″″ is the other reactant in the bonding event illustrated inFIG. 8 . After the chemical bonding illustrated by the arrow the resultant link comprised of segments illustrated byamine pendant group 34 and bondedpolymerizable material 53 andamine pendant group 35. This bonding event illustrated inFIG. 8 was due tooxygen 67 of the first bondedpolymerizable material 52 being bonded to thehydrogen atom 68 of theamine pendant group 33 and thecarbon atom 72 of first bondedpolymerizable material 52 being bonded to thenitrogen atom 71 of theamine pendant group 33. One skilled in the art will appreciate that the aforementioned reaction has formed an amide and a carboxylic acid from the acid anhydride reaction with the amine. Within thefailure 60, there are a plurality of such links formed, creating a net of chemical bonds between thefirst face 61 and thesecond face 62. - The described bonding is only one of many possible manners in which bonds can be established to form a cross-linking between face one 61 and face two 62 of
failure 60. The illustrated embodiments ofFIGS. 7 and 8 are meant to illustrate only one of many possible chemical bonding structures operable to form self-joining bonds 64 (FIG. 4 ) between afirst face 61 and asecond face 62 of a polymeric failure 60 (FIG. 4 ). By manufacturing articles from the described materials a manufactured article will be able to prevent cracks from propagating, allowing for a longer lifetime for the article. Structures can be manufactured from composite materials comprising the self-joiningpolymer composition 20 ofFIG. 1 . Such structures, such as aerospace vehicles, automotive parts, including body structures, sporting equipment and other structures requiring lightweight, high strength materials, will be self joining if a crack were to start from stresses on the structure and will have an extended lifetime. - Examples of other joining methods include formation of esters from anhydrides and alcohol polymer pendant groups, formation of esters from carboxylic acids and alcohol polymer pendant groups, formation of amides from carboxylic acids and amine pendant groups, formation of amides from amines and anhydride polymer pendant groups, formation of amides from amines and carboxylic acid polymer pendant groups, formation of esters from alcohols and anhydride polymer pendant groups, formation of esters from alcohols and carboxylic acid polymer pendant groups.
- These illustrative embodiments are not intended to be exhaustive of all possibilities or to limit what materials can be used for the aforementioned purpose. There is, therefore, a multiplicity of other possible combinations and embodiments. By using what is shown and described herein, an automated self-joining of failures in polymers is possible, where the material strength upon self-joining is equivalent to the material strength of the original polymer prior to any failures. Those having ordinary skill in the art will therefore appreciate the benefit of employing an embodiment of this automated self-joining of failures in polymer compositions in a variety of devices, components and equipment comprised of polymers.
Claims (22)
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US10/631,374 US6858660B1 (en) | 2003-07-31 | 2003-07-31 | Method and chemistry for automatic self-joining of failures in polymers |
PCT/US2004/025732 WO2005012368A2 (en) | 2003-07-31 | 2004-07-27 | Method and chemistry for automatic self-joining of failures in polymers |
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US10/631,374 US6858660B1 (en) | 2003-07-31 | 2003-07-31 | Method and chemistry for automatic self-joining of failures in polymers |
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Cited By (5)
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US20070087198A1 (en) * | 2005-07-01 | 2007-04-19 | Carolyn Dry | Multiple function, self-repairing composites with special adhesives |
US8685513B1 (en) | 2012-02-29 | 2014-04-01 | Carolyn M. Dry | Inflatable articles comprising a self-repairing laminate |
US8753924B2 (en) | 2012-03-08 | 2014-06-17 | Texas Instruments Incorporated | Grown carbon nanotube die attach structures, articles, devices, and processes for making them |
US9694629B1 (en) | 2012-02-29 | 2017-07-04 | Carolyn Dry | Self-repairing inflatable articles incorporating an integrated self-repair system |
US11543322B2 (en) * | 2020-05-01 | 2023-01-03 | Globalfoundries U.S. Inc. | Crack identification in IC chip package using encapsulated liquid penetrant contrast agent |
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US8735463B2 (en) | 2007-05-31 | 2014-05-27 | Creighton University | Self-healing dental composites and related methods |
US8088015B2 (en) * | 2007-11-01 | 2012-01-03 | Gkn Driveline North America, Inc. | Self-repairing boot for a constant velocity joint |
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US8683798B2 (en) * | 2010-01-15 | 2014-04-01 | Syracuse University | Stimuli-responsive product |
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Cited By (10)
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US20070087198A1 (en) * | 2005-07-01 | 2007-04-19 | Carolyn Dry | Multiple function, self-repairing composites with special adhesives |
US7811666B2 (en) | 2005-07-01 | 2010-10-12 | Carolyn Dry | Multiple function, self-repairing composites with special adhesives |
US20100308276A1 (en) * | 2005-07-01 | 2010-12-09 | Carolyn Dry | Multiple function, self-repairing composites with special adhesives |
US8721959B2 (en) | 2005-07-01 | 2014-05-13 | Carolyn Dry | Multiple function, self-repairing composites with special adhesives |
US8685513B1 (en) | 2012-02-29 | 2014-04-01 | Carolyn M. Dry | Inflatable articles comprising a self-repairing laminate |
US8877309B1 (en) | 2012-02-29 | 2014-11-04 | Carolyn M. Dry | Self-repairing inflatable articles |
US9694629B1 (en) | 2012-02-29 | 2017-07-04 | Carolyn Dry | Self-repairing inflatable articles incorporating an integrated self-repair system |
US10011149B2 (en) | 2012-02-29 | 2018-07-03 | Carolyn M. Dry | Self-repairing inflatable articles |
US8753924B2 (en) | 2012-03-08 | 2014-06-17 | Texas Instruments Incorporated | Grown carbon nanotube die attach structures, articles, devices, and processes for making them |
US11543322B2 (en) * | 2020-05-01 | 2023-01-03 | Globalfoundries U.S. Inc. | Crack identification in IC chip package using encapsulated liquid penetrant contrast agent |
Also Published As
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WO2005012368A3 (en) | 2005-06-16 |
US6858660B1 (en) | 2005-02-22 |
WO2005012368A2 (en) | 2005-02-10 |
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