Light generating microcapsules for self-healing polymer applications

• US 10,703,834 B2
• Filed: 06/22/2018
• Issued: 07/07/2020
• Est. Priority Date: 06/23/2017
• Status: Active Grant

• Current Assignee: International Business Machines Corporation
• Original Assignee: International Business Machines Corporation
• Inventors: Campbell, Eric J., Czaplewski-Campbell, Sarah K., Kuczynski, Joseph, Tofil, Timothy J.
• Primary Examiner(s): Wax, Robert A
• Assistant Examiner(s): Al-Awadi, Danah
• Application Number:
  US16/015,753
• Publication Number:
  US 20180371123A1
• Time in Patent Office: 746 Days
• Field of Search: None
• CPC Class Codes: A61K 9/5094 Microcapsules containing magnetic carrier material, e.g. ferrite for drug targeting
• CPC Class Codes: B01J 13/04 by physical processes, e.g. drying, spraying
• CPC Class Codes: B01J 13/14 Polymerisation; cross-linking
• CPC Class Codes: B01J 13/22 Coating
• CPC Class Codes: C07D 321/00 Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
• CPC Class Codes: C08F 2/48 by ultraviolet or visible light
• CPC Class Codes: C08F 20/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 20/18 with acrylic or methacrylic acids
• CPC Class Codes: C09B 6/00 Anthracene dyes not provided for above

Abstract

A self-healing polymeric material includes a polymeric matrix material, a plurality of monomer mixture microcapsules dispersed in the polymeric matrix material, and a plurality of light generating microcapsules dispersed in the polymeric matrix material. Each monomer mixture microcapsule encapsulates a mixture of materials that includes monomers and a photoinitiator. Each light generating microcapsule encapsulates multiple reactants that undergo a chemiluminescent reaction. The chemiluminescent reaction generates a photon having a wavelength within a particular emission range that is consistent with an absorption range of the photoinitiator.

Claims

1. A process of utilizing chemiluminescence for polymeric self-healing, the process comprising:

dispersing a monomer mixture microcapsule in a polymeric matrix material, the monomer mixture microcapsule encapsulating a mixture of materials that includes monomers and a photoinitiator; and

dispersing a light generating microcapsule in the polymeric matrix material, the light generating microcapsule encapsulating multiple reactants that undergo a chemiluminescent reaction, wherein the chemiluminescent reaction generates a photon having a wavelength within a particular emission range that is consistent with an absorption range of the photoinitiator,

wherein the monomer mixture microcapsule is adapted to rupture to cause migration of the mixture of materials into a crack in the polymeric matrix material, and

wherein the light generating microcapsule is adapted to cause the multiple reactants to undergo the chemiluminescent reaction within the light generating microcapsule in response to application of a compressive force.

2. The process of claim 1, wherein the light generating microcapsule includes an inner wall and an outer wall, wherein application of the compressive force causes the inner wall to rupture, thereby causing the multiple reactants to mix and undergo the chemiluminescent reaction,

wherein the outer wall remains intact after application of the compressive force, thereby preventing a reaction product of the chemiluminescent reaction from contacting the polymeric matrix material, and

wherein the chemiluminescent reaction includes excitation of a dye from a ground state to an excited state and subsequent release of the photon upon relaxation from the excited state to the ground state.

3. The process of claim 1, wherein the light generating microcapsule includes a multiple-compartment microcapsule that comprises:

a first compartment that contains a first reactant of the multiple reactants;

a second compartment that contains a second reactant of the multiple reactants; and

an isolating structure separating the first compartment from the second compartment, the isolating structure adapted to rupture in response to application of the compressive force to cause the first reactant and the second reactant to undergo the chemiluminescent reaction.

4. The process of claim 3, wherein the multiple-compartment microcapsule includes a shell-in-shell microcapsule comprising an inner shell contained within an outer shell, wherein the inner shell is the isolating structure and encapsulates the first compartment, wherein the outer shell encapsulates the second compartment, and wherein the chemiluminescent reaction occurs without rupture of the outer shell.

5. The process of claim 4, wherein the outer shell comprises a polymer, and the outer shell has a transmittance value of at least 90% for the wavelength within the particular emission range.

6. The process of claim 5, wherein the polymer comprises gelatin, arabic gum, shellac, lac, starch, dextrin, wax, rosin, sodium alginate, zein, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl ethyl cellulose, polyolefins, polystyrenes, polyethers, polyesters, polyureas, polyethylene glycol, polyamides, polyimides, urea-formaldehydes, polyurethane, polyacrylate, epoxy resins, and combinations thereof.

7. An in-situ light generation process comprising:

forming an article of manufacture that includes a self-healing polymeric material, the self-healing polymeric material comprising;

a polymeric matrix material;

a plurality of monomer mixture microcapsules dispersed in the polymeric matrix material, each monomer mixture microcapsule of the plurality of monomer mixture microcapsules encapsulating a mixture of materials that includes monomers and a photoinitiator; and

a plurality of light generating microcapsules dispersed in the polymeric matrix material, each light generating microcapsule of the plurality of light generating microcapsules encapsulating multiple reactants that undergo a chemiluminescent reaction within the respective light generating microcapsule in response to application of a compressive force, the chemiluminescent reaction generating a photon having a wavelength within a particular emission range that is consistent with an absorption range of the photoinitiator; and

exposing the article of manufacture to an environment that results in formation of a crack in the polymeric matrix material, the crack causing microcapsule rupture of a monomer mixture microcapsule of the plurality of monomer mixture microcapsules, the microcapsule rupture resulting in migration of the mixture of materials into the crack,

wherein the chemiluminescent reaction within the light generating microcapsule generates sufficient light to cause the photoinitiator to initiate a polymerization reaction of the monomers within the crack, the polymerization reaction resulting in formation of a polymeric material that seals the crack.

8. The in-situ light generation process of claim 7, wherein the polymerization reaction includes a free radical polymerization reaction, and wherein the photoinitiator includes a free radical initiator.

9. The in-situ light generation process of claim 7, wherein the chemiluminescent reaction includes excitation of a dye from a ground state to an excited state and subsequent release of the photon upon relaxation from the excited state to the ground state.

10. The in-situ light generation process of claim 9, wherein a chemical reaction of a diphenyl oxalate molecule with a hydrogen peroxide molecule results in formation of a 1,2-dioxetanedione molecule, and wherein excitation of the dye is caused by energy released during decomposition of a 1,2-dioxetanedione molecule.

11. A process of forming a self-healing polymeric material, the process comprising:

forming a monomer mixture microcapsule encapsulating a mixture of materials that includes monomers and a photoinitiator;

forming a light generating microcapsule encapsulating multiple reactants that undergo a chemiluminescent reaction, the chemiluminescent reaction generating a photon having a wavelength within a particular emission range that is consistent with an absorption range of the photoinitiator, wherein the light generating microcapsule is adapted to cause the multiple reactants to undergo the chemiluminescent reaction within the light generating microcapsule in response to application of a compressive force; and

dispersing the monomer mixture microcapsule and the light generating microcapsule in a polymeric matrix material to form a self-healing polymeric material.

12. The process of claim 11, wherein forming the light generating microcapsule comprises:

encapsulating a first set of reactants of the multiple reactants within an inner shell of a shell-in-shell microcapsule, the inner shell to isolate the first set of reactants from a second set of reactants of the multiple reactants; and

encapsulating the second set of reactants within an outer shell of the shell-in-shell microcapsule, wherein the outer shell is adapted to resist rupturing in response to application of a compressive force that is great enough to rupture the inner shell.

13. The process of claim 12, wherein the chemiluminescent reaction occurs without rupture of the light generating microcapsules, and wherein the chemiluminescent reaction includes excitation of a dye from a ground state to an excited state and subsequent release of the photon upon relaxation from the excited state to the ground state.

14. The process of claim 13, wherein the first set of reactants includes a mixture of the dye and diphenyl oxalate, and wherein the second set of reactants includes an oxidant.

15. The process of claim 14, wherein the oxidant includes hydrogen peroxide (H₂O₂).

16. The process of claim 14, wherein the dye includes 9,10-diphenylanthracene.

17. The process of claim 12, wherein the outer shell comprises a polymer, and

wherein the outer shell has a transmittance value of at least 90% for the wavelength within the particular emission range.

18. The process of claim 17, wherein the polymer comprises gelatin, arabic gum, shellac, lac, starch, dextrin, wax, rosin, sodium alginate, zein, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl ethyl cellulose, polyolefins, polystyrenes, polyethers, polyesters, polyureas, polyethylene glycol, polyamides, polyimides, urea-formaldehydes, polyurethane, polyacrylate, epoxy resins, and combinations thereof.

19. The process of claim 11, wherein the monomers include acrylate monomers.

20. The process of claim 11, wherein the photoinitiator is a free radical initiator.