WO2005118703A1 - Wax particles for protection of activators, and multifunctional autonomically healing composite materials - Google Patents
Wax particles for protection of activators, and multifunctional autonomically healing composite materials Download PDFInfo
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- WO2005118703A1 WO2005118703A1 PCT/US2005/015783 US2005015783W WO2005118703A1 WO 2005118703 A1 WO2005118703 A1 WO 2005118703A1 US 2005015783 W US2005015783 W US 2005015783W WO 2005118703 A1 WO2005118703 A1 WO 2005118703A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
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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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/745—Polymers of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Definitions
- This self-healing system includes a material containing, for example, solid particles of Grubbs' catalyst and capsules containing liquid dicyclopentadiene (DCPD) embedded in an epoxy matrix
- the present invention is a composite material, comprising (i) a polymer, (ii) a polymerizer, (iii) a protected corresponding activator for the polymerizer, and (iv) a plurality of capsules.
- the polymerizer is in the capsules, and the corresponding activator is protected with a corresponding encapsulant for the polymer and the polymerizer.
- the present invention is a composite material, comprising (i) a polymer, (ii) a polymerizer, (iii) microparticels of a protected corresponding catalyst for the polymerizer, and (iv) a plurality of capsules.
- the polymerizer is in the capsules, the corresponding catalyst is protected with a corresponding encapsulant for the polymer and the polymerizer, and the encapsulant comprises wax.
- the present invention is particles, comprising (a) a compound, and (b) a wax, surrounding the compound. The particles are microparticles.
- a polymerizer is a composition that will form a polymer when it comes into contact with a corresponding activator for the polymerizer.
- Examples of polymerizers include monomers of polymers such as styrene, ethylene,
- activator is anything that when contacted or mixed with a polymerizer will form a polymer.
- activators are catalysts, initiators, and native activating moieties.
- a corresponding activator for a polymerizer is an activator that when contacted or mixed with that specific polymerizer will form a polymer.
- a catalyst is a compound or moiety that will cause a polymerizable composition to polymerize, and is not always consumed each time it causes polymerization.
- catalysts include ring opening polymerization (ROMP) catalysts such as Grubbs catalyst.
- a corresponding catalyst for a polymerizer is a catalyst that when contacted or mixed with that specific polymerizer will form a polymer.
- An initiator is a compound that will cause a polymerizable composition to polymerize, and is always consumed at the time it causes polymerization.
- initiators are peroxides (which will form a radical to cause polymerization of an unsaturated monomer); a monomer of a multi-monomer polymer system such as diols, diamines, and epoxide; and amines (which will form a polymer with an epoxide).
- a corresponding initiator for a polymerizer is an initiator that when contacted or mixed with that specific polymerizer will form a polymer.
- a native activating moiety is a moiety of a polymer that when mixed or contacted with a polymerizer will form a polymer, and is always consumed at the time it causes polymerization. Examples of a native activating moiety include an amine moiety (which will form a polymer with an epoxide).
- a water-deactivatible activator, water-deactivatible catalyst, water- deactivatible initiator, and water-deactivatible native activating moiety are each a type of activator, catalyst, initiator and native activating moiety, respectively, that has a reduced ability to form a polymer from a polymerizer after exposure to moisture or water.
- a water-deactivatible corresponding activator, water-deactivatible corresponding catalyst, water- deactivatible corresponding initiator, and water-deactivatible corresponding native activating moiety are each a type of corresponding activator, corresponding catalyst, corresponding initiator and corresponding native activating moiety, respectively, that has a reduced ability to form a polymer from a polymerizer after exposure to moisture or water.
- water- deactivatible activators include WCI 6 , M0CI 5 and Et 2 AICI.
- a compound is a molecule that contains at most 100 repeating units. This is in contrast to a polymer, which contains more than 100 repeating units.
- a capsule is a hollow closed object having an aspect ratio of 1 :1 to 1 :10, that may contain a solid, liquid, gas, or combinations thereof.
- the aspect ratio of an object is the ratio of the shortest axis to the longest axis; these axes need not be perpendicular.
- a capsule may have any shape that falls within this aspect ratio, such as a sphere, a toroid, or an irregular ameboid shape.
- the surface of a capsule may have any texture, for example rough or smooth.
- An encapsulant is a material that will dissolve in a polymerizer and will protect an activator from reaction with materials used to form a polymer.
- a corresponding encapsulant for a polymer and for a polymerizer will protect an activator from reaction with materials used to form that specific polymer and will dissolve in that specific polymerizer.
- Paraffin is an example of an encapsulant.
- a microparticle is a particle with an average diameter of at most 500 micrometers.
- Figure 1A illustrates a self-healing material using unprotected Grubbs' catalyst.
- Figure 1 B illustrates a self-healing material with an activator embedded in a microparticle of an encapsulant.
- Figure 2A is a photograph of a sections of epoxy samples cut to -300 ⁇ m thick containing 2.5 wt % unprotected Grubbs' catalyst.
- Figure 2A is a photograph of a sections of epoxy samples cut to ⁇ 300 ⁇ m thick containing 5 wt % wax microparticles that contain 5 wt % Grubbs' catalyst.
- Figures 3A and 3B illustrate a virgin and a healed load-displacement curves for the cases of (A) low and (B) high non-linearity of the healed crack growth, 1 wt % of microparticles containing 25 wt % catalyst and 5 wt % of microparticles containing 5 wt % catalyst, respectively.
- Figures 4A and 4B illustrate the dependence of healing efficiency on (A) the amount of catalyst in the microparticles (with 5 wt % microparticle loading in the epoxy) and (B) the way the catalyst loading in the wax and the microparticle loading in the epoxy are balanced to maintain an overall catalyst concentration of 0.25 wt %; each point is the average of three trials, and the error bars indicate ⁇ one standard deviation.
- the present invention makes use of the discovery that activators that are protected by an encapsulant allows for the used of activators that might not otherwise be possible, since with being protected they would de-activate while the polymer is being formed. Furthermore, when the activator is protected, significantly less is need to produce an otherwise similar self- healing material. These low loading levels may also improve the physical properties of the polymer before any self-healing takes place.
- the present invention includes a composite material, containing capsules 4 and a protected activator 2 in a polymer 6, as shown in Figure 1 B.
- the capsules contain a polymerizer.
- the activator is not a corresponding native activating moiety for the polymerizer, and more preferably the activator is a corresponding initiator, or most preferably a corresponding catalyst, for the polymerizer.
- the activator is protected by a corresponding encapsulant for the polymer and the polymerizer, and more preferably the encapsulant is a wax.
- the composite is the same, or similar, to the composite of U.S. Patent
- the activator is a protected activator.
- a native activating moiety may also be used as the activator.
- the protected activator may be produced by a variety of methods. For example, a liquid containing the encapsulant may be formed, and powder or small particles of the activator may then be dispersed into the liquid. Then the encapsulant is solidified. Particles, preferably microparticles, of the protected activator are formed. It is these particles that are added to the polymer while it is being formed. In this way, the activator is protected from the substances used to form the polymer.
- the activator may be added, and then the system cooled.
- the solid protected activator may then be ground up to form particles.
- the encapsulant may be dissolved in a solvent to form a solution, mixed with the activator, the solvent removed, and again the solid mixture ground up to form particles.
- the molten mixture, or solution may be formed into particles using the methods described in U.S. Patent No. 6,669,961 , incorporated herein by reference.
- the liquid mixture may be poured into a solvent in which both the encapsulant and the activator are insoluble, and then formed into a suspension by rapid stirring; cooling with rapid stirring solidifies the encapsulant, to form particles, more preferably microparticles, of the protected activator.
- a surfactant is included.
- a wax may be used as the encapsulant, and bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride (first generation Grubbs' catalyst) 9 may be used as the activator.
- the wax- protected catalyst microparticles may be synthesized by pouring a mixture of the molten wax and into a hot, rapidly-stirred, aqueous solution of poly(ethylene-co-maleic anhydride) (EMA). The resulting suspension of molten wax droplets may then be rapidly cooled with the addition of cold water to solidify the wax. The wax microparticles can be filtered, dried, and sifted to give a coarse powder. When this was carried out, microscopy shows that catalyst particles are suspended in the colorless wax giving the microparticles a speckled appearance, but this heterogeneity was not apparent to the unaided eye.
- EMA poly(ethylene-co-maleic anhydride)
- a model system of wax without Grubbs' catalyst shows that the average size of the microparticles can be easily controlled by the rate of stirring. For example, with stirring rates of 450, 900, and 1500 RPM, the average diameters of collected wax microparticles were 150, 90, and 50 ⁇ m, respectively. The size distributions are large, but through the use of sieves, narrower size ranges can be isolated.
- the EMA is included as a surfactant to facilitate the formation of a suspension. In the absence of EMA, the average particle size is increased by more than a factor of three, and excessive non- spherical wax debris is formed.
- the encapsulant may be formed by the reaction of two or more compounds, such as a polymer, then a solution or liquid containing compounds may be formed, the activator mixed in, and then the reaction of the compounds forms the protected activator. Again, the solid may be ground up to form particles.
- the encapsulant is soluble in the polymerizer, and solid at room temperature. Examples of encapsulants are polymers and waxes. Waxes include waxy polymers. Waxes are water insoluble, organic materials that are solid or semi-solid at room temperature and usually of lower density than water, and typically can be melted above room temperature to form a liquid.
- Preferred waxes include any naturally occurring and synthetic waxes, wax esters, and greases that generally have a melting temperature of 30° C or more with a melting range of less than 10° C and are usually non-reactive with the reagents or solvents to which they are exposed.
- waxes are esters of various long-chain (fatty) alcohols and long-chain acids, preferably where at least one member of the ester has 10 or more carbon atoms, including various unsaturated and branched chain types and also those esters of glycerols and sterols.
- certain free alcohols or acids have wax-like properties of melting temperature and inertness.
- saturated fatty acids examples include capric, lauric, myristic, palmitic, margaric, stearic, arachidic, behenic, tetracosanic, lignoceric, cerotic, and melissic.
- unsaturated fatty acids examples include tiglic, hypogaeic, gaidic, physetoleic, elaidic, oleic, isooleic, erudic, brassidic, and isoerudic.
- fatty alcohols examples include octadecyl, carnaubyl, ceryl, melissyl, and phytol.
- esters of these and other fatty acids with any suitable fatty alcohols, or sterols such as cholesterol, or glycerols.
- suitable fatty alcohols or sterols
- Other examples are natural or suitably modified or derivatized waxes such as various plant derived waxes, greases and oils including carnauba wax, cranberry wax, ouricuri wax, candelilla wax, raphia wax, apple, cotton and cactus waxes; waxes (including greases) produced by bacteria (e.g. cetyl stearate); fungi, protozoa and algae; various invertebrate waxes and greases including insect waxes such as beeswaxes (e.g.
- triacontyl palmitate, palmatyl palmitate), and Coccus sp. derived waxes e.g. lac, cochineal and Chinese insect
- other animal fats e.g. triglycerides
- waxes including spermaceti (e.g. cetyl palmitate), lanolin and wool grease.
- spermaceti e.g. cetyl palmitate
- lanolin lanolin
- wool grease also included are various derivatives, extracts, and combinations of these materials.
- waxes are many natural or synthetic hydrocarbons such as white waxes, paraffins, ceresins, vaselines, silicon greases and waxes, polychlorinated or polyfluorinated hydrocarbons, aromatic hydrocarbons (such as naphthalene and durene (1 ,2,4,5- tetramethylbenzene)), polyether waxes and polyester waxes.
- Waxy polymers are polymers that have wax-like chemical or physical properties alone or when combined with other waxes. Examples of wax-like polymers are polyethylenes and polypropylenes.
- synthetic rubbers such as isoprene polymers, hydrogenated rubber, butadiene polymers, chloroprene polymers and butyl polymers.
- the capsules contain a polymerizer.
- the polymerizer contains a polymerizable compound such as a monomer or prepolymer, and may optionally contain other ingredients, such as other monomers and/or prepolymers, stabilizers, solvents, viscosity modifiers such as polymers, odorants, colorant and dyes, blowing agents, antioxidants, and co-catalysts.
- the polymerizer is a liquid at room temperatue.
- the activator is a catalyst or an initiator.
- polymerizable compounds are cyclic olefins, preferably containing 4-50 carbon atoms and optionally containing heteratoms, such as DCPD, substituted DCPDs, norbornene, substituted norbornene, cyclooctadiene, and substituted cyclooctadiene.
- Corresponding catalysts for these are ring opening metathesis polymerization (ROMP) catalysts such as Schrock catalysts 14 ' 15 .
- Another example of polymerizable compounds are lactones such as caprolactone, and lactams, that when polymerized will form polyesters and nylons, respectively.
- Corresponding catalysts for these are cyclic ester polymerization catalysts and cyclic amide polymerization catalysts, such as scandium triflate.
- a polymerizer may contain a polymerizable compound and one part of a two-part catalyst, with a corresponding initiator being the other part of the two-part catalyst.
- the polymerizable compound may be a cyclic olefin; one part of a two-part catalyst may be a tungsten compound, such as an organoammonium tungstate, an organoarsonium tungstate, or an organophosphonium tungstate; or a molybdenum compound, such as organoammonium molybdate, an organoarsonium molybdate, or an organophosphonium molybdate.
- tungsten compound such as an organoammonium tungstate, an organoarsonium tungstate, or an organophosphonium tungstate
- a molybdenum compound such as organoammonium molybdate, an organoarsonium molybdate, or an organophosphonium molybdate.
- the second part of the two-part catalyst may be an alkyl aluminum compound, such as an alkoxyalkylaluminum halide, an aryloxyalkylaluminum halide, or a metaloxyalkylaluminum halide in which the metal in the compound is tin, lead, or aluminum; or an organic tin compound, such as a tetraalkyltin, a trialkyltin hydride, or a triaryltin hydride.
- the polymerizable compound may be unsaturated compounds such as acrylates; acrylic acids; alkyl acrylates; alkyl acrylic acids; styrenes; isoprene; and butadiene.
- atom transfer radical polymerization may be used, with one of the two components being mixed with the polymerizable compound and the other acting as the initiator: one component being an organohalide such as 1-chloro-1- phenylethane, and the other component could be a copper(l) source such as copper(l) bipyridyl complex.
- one component could be a peroxide such as benzoyl peroxide, and the other component could be a nitroxo precursor such as 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO).
- the polymerizable material may for example be a compound containing both an isocyanate group and a hydroxyl group, or two different compounds, one compound containing at least two isocyanate groups and the other compound containing at least two hydroxyl groups.
- This carbon dioxide can provide for the creation of expanded polyurethane foam; optionally the polymerizer may contain a blowing agent, for example a volatile liquid such as dichloromethane.
- condensation polymerization may be used, with one of the two components being mixed with the polymerizable compound and the other acting as the initiator: for example, one component could be an alkyltin compound such as stannous 2-ethylhexanoate, and the other component could be a tertiary amine such as diazabicyclo[2.2.2]octane (DABCO).
- DABCO diazabicyclo[2.2.2]octane
- the polymer contains both capsules and a corresponding activator for the polymerizer.
- a set of capsules may be present that contain one or more additional ingredients, such as stabilizers, solvents, viscosity modifiers such as polymers, odorants, colorant and dyes, blowing agents, antioxidants, and co-catalysts.
- the capsules have an average diameter of 10 nm to 1 mm, more preferably 30-500 ⁇ m, most preferably to 50-300 ⁇ m.
- the capsules have an aspect ratio of 1 :1 to 1 :10, preferably 1 :1 to 1 :5, more preferably 1 :1 to 1 :3, and even more preferably 1 :1 to 1 :2, and most preferably 1 :1 to 1 :1.5.
- the wall thickness of the capsules is preferably 100 nm to 3 ⁇ m. The selection of capsule walls thickness depends on the polymer in the composite. For example, capsule walls that are too thick will not rupture when a crack approaches, while capsules with very thin walls will break during processing.
- the adhesion between the capsules and the polymer of the composite influences whether the capsules will rupture or debond in the presence of an approaching crack.
- various silane coupling agents may be used. Typically, these are compounds of the formula R-SiX 3 Where R is preferably a reactive group
- Examples include silane coupling agents available from DOW CORNING (with reactive group following the name in parentheses): Z6020 (Diamino); Z6030 (Methacrylate); Z6032 (Styrylamine Cationic); Z6040 (Epoxy); and Z6075 (Vinyl).
- DOW CORNING with reactive group following the name in parentheses
- Z6020 Diamino
- Z6030 Metal-acrylate
- Z6032 Styrylamine Cationic
- Z6040 Epoxy
- Z6075 Vinyl
- urea-formaldehyde capsules may be washed in a solution of Silane Z6020 or Z6040 and hexane (1 :20 wt.) followed by adding Silane Z6032 to the polymer (1 % wt.).
- Capsules may be made by a variety of techniques, and from a variety of materials, such as those described in Microencapsulation: Methods and Industrial Applications Ed. Benita, Simon Marcel Dekker, New York, 1996; Microencapsulation: Processes and Applications Ed. Vandegaer, J. Plenum Press, New York, 1974; and Microcapsule Processing and Technology
- Examples of materials from which the capsules may be made, and the techniques for making them include: urea-formaldehyde, formed by in situ polymerization; gelatin, formed by complex coacervation; polyurea, formed by the reaction of isocyanates with a diamine or a triamine, depending on the degree of crosslinking desired (the extent of crosslinking also determines the brittleness of the capsule);and polyamide, formed by the use of a suitable acid chloride and a water soluble triamine.
- the polymer may be any polymeric material into which the capsules may be dispersed.
- Examples include polyamides such as nylons; polyesters such as poly(ethylene terephthalate) and polycaprolactone; polycarbonates; polyethers such as epoxides; polyimides such as polypyromellitimide (for example KAPTAN); phenol-formaldehyde resins (for example BAKELITE); amine-formaldehyde resins such as a melamine resin; polysulfones; poly(acrylonitrile-butadiene-styrene) (ABS); polyurethanes; polyolefins such as polyethylene, polystyrene, polyacrylonitrile, polyvinyls, polyvinyl chloride, poly(DCPD) and poly(methyl methacrylate); polysilanes such as poly(carborane-siloxane); and polyphosphazenes.
- polyamides such as nylons
- polyesters such as poly(ethylene terephthalate) and polycaprolactone
- polycarbonates
- the capsules and protected activator may be dispersed into the polymer by forming the polymer around the capsules and activator, such as by polymerizing monomer to form the polymer with the capsules and activator mixed into the monomer.
- the polymer may be first formed, and then the capsules and protected activator mixed in.
- the polymer may be dissolved in a solvent and the capsules and protected activator mixed into the solution, followed by removal of the solvent.
- other components may be added to the polymer, such as fibers, fillers, adhesion modifiers, blowing agents, anti-oxidants, colorants and dyes, and fragrances.
- the vial containing the wax and the catalyst was submerged in the same 82 °C water bath. After 10 min, the wax had melted and the aqueous solution had reached 65-70 °C. The vial with the molten wax was shaken to disperse the catalyst. The vial was then opened (in air), and the wax was poured into the aqueous solution. After 2 min, cold water (600 mL, 0 °C) was quickly added, and the stirring was stopped. The microparticles were collected by filtration and dried under vacuum.
- the reactivity of the wax-embedded catalyst was quantified by using in situ 1 H NMR to measure the ROMP kinetics of endo-DCPD in the presence of the microparticles. 10
- the rate constant for ROMP of DCPD measured for a sample prepared with Grubbs' catalyst obtained from the wax microparticles was 0.0162 s "1 .
- An analogous control sample prepared with unprotected Grubbs' catalyst had a rate constant of 0.0179 s "1 , which shows that the process of embedding the catalyst in wax microparticles only reduces the reactivity by 9%. This small reduction in rate shows that the brief exposure of the catalyst to heat and air only mildly affects its reactivity.
- the measured rate constant does not change significantly from that of the original microparticles. Because this recycling process can be done without loss of reactivity, microparticles that fall outside the desired size range can be reformed with useful diameters, thus avoiding the costly waste of catalyst.
- the wax greatly increases the resistance of the catalyst to ethylenediamine (EDA).
- EDA ethylenediamine
- NMR samples were prepared using the non-volatile catalyst and wax residues, and the kinetics of ROMP of DCPD using the exposed catalyst were measured.
- the wax preserved 69% of the catalyst's reactivity while the unprotected catalyst showed no reactivity. Because of its low volatility, DETA could not be used in a similar experiment, but the wax appears to similarly protect the catalyst from
- FIG. 2A shows a sample of epoxy containing unprotected catalyst (2.5 wt %), and the micrograph shows that the catalyst tends to form rather large particles with relatively large separations.
- Figure 2B shows a similar sample with 5 wt % wax microparticles.
- the sample has only 0.25 wt % overall loading of Grubbs' catalyst, which is an order of magnitiude lower than the sample in Figure 2A.
- the wax microparticles are well distributed throughout the sample giving a much higher sectional density of catalyst particles even with a much lower overall catalyst loading.
- the catalyst will also be more evenly distributed across the crack plane of a fractured sample, and this uniformity facilitates healing by delivering catalyst to the DCPD on the entire crack plane rather than only to localized areas near scarce catalyst particles.
- strain energy (Jc) at crack propagation is a better measure of healing ability than stress-intensity ( ic) at fracture (which was used in our previous reports), and the healed critical strain energy is dependent on both the critical load for the crack to propagate (Pc) and the extent of non-linearity captured by the parameter ⁇ increasing either of these terms increases healing.
- healing efficiency is a measure of recovery of the strain energy prior to crack propagation, the greater resistance to crack growth in the healed material after the start of propagation yields a total energy to sample failure that is greater than the brittle failure of the virgin material. Therefore, the healing efficiencies calculated using critical strain energy may underestimate the full recovery effect of self-healing.
- Figure 4A shows how healing efficiencies vary with the amount of catalyst included in the wax microparticles. As expected, the samples with the largest amounts of catalyst gave the best healing efficiencies (93%), but even with the lowest attempted catalyst loading good healing (59%) was observed. In this series, the loading of microparticles in the epoxy is held constant at 5 wt %. If it is assumed that the non-linearity in this system results from wax being incorporated into the polyDCPD, the relatively constant values for ⁇ in this series are likely due to the nearly constant amount of wax in each sample. The data in Figure 4A show that an overall catalyst loading of 0.25 wt % (i.e.
Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP05804808A EP1751224A1 (en) | 2004-05-07 | 2005-05-06 | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
CA002565969A CA2565969A1 (en) | 2004-05-07 | 2005-05-06 | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
JP2007511617A JP2007536410A (en) | 2004-05-07 | 2005-05-06 | Wax particles to protect activators and multifunctional autonomous repair composites |
Applications Claiming Priority (2)
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US10/840,937 US7566747B2 (en) | 2004-05-07 | 2004-05-07 | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
US10/840,937 | 2004-05-07 |
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WO2005118703A1 true WO2005118703A1 (en) | 2005-12-15 |
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PCT/US2005/015783 WO2005118703A1 (en) | 2004-05-07 | 2005-05-06 | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
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US (1) | US7566747B2 (en) |
EP (1) | EP1751224A1 (en) |
JP (1) | JP2007536410A (en) |
KR (1) | KR20070011575A (en) |
CN (1) | CN1950441A (en) |
CA (1) | CA2565969A1 (en) |
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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 |
US7612152B2 (en) | 2005-05-06 | 2009-11-03 | The Board Of Trustees Of The University Of Illinois | Self-healing polymers |
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Also Published As
Publication number | Publication date |
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JP2007536410A (en) | 2007-12-13 |
KR20070011575A (en) | 2007-01-24 |
CA2565969A1 (en) | 2005-12-15 |
US7566747B2 (en) | 2009-07-28 |
US20050250878A1 (en) | 2005-11-10 |
CN1950441A (en) | 2007-04-18 |
EP1751224A1 (en) | 2007-02-14 |
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