# US 9,519,066 B2 · Photonic polymer multilayers for colorimetric radiation sensing > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,519,066 B2 - Document ID: US9519066B2 - Status: Granted - Kind: B2 - Application number: 14/924,912 - Filed: 2015-10-28 - Published: 2016-09-01 - Granted: 2016-12-13 - Earliest claimed: 2014-10-29 - Assignees: University of Massachusetts - Applicants: The University of Massachusetts - Inventors: Ryan Hayward; Maria Chiappelli - Web page: https://patentgrep.com/patent/US9519066B2 ## CPC - G01T 1/06: Glass dosimeters {using colour change; including plastic dosimeters} - C08L 33/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen - C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen - G01T 1/04: Chemical dosimeters (G01T1/06, G01T1/08 take precedence) - G01T: MEASUREMENT OF NUCLEAR OR X-RADIATION (radiation analysis of materials, mass spectrometry G01N23/00; tubes for determining the presence, intensity, density or energy of radiation or particles H01J47/00) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) ## Abstract A radiation sensor includes a substrate and a polymer multilayer film including alternating layers of a high refractive index polymer and a low refractive index polymer. The high refractive index polymer and the low refractive index polymer each comprise repeat units derived from a photo-crosslinkable monomer. The radiation sensors are useful in preparing various articles, including wearable patches, packaging materials, labels, and window panes. Also described is a method of detecting radiation using the radiation sensors. ## Claims ### Claim 1 A radiation sensor comprising, a substrate; a polymer multilayer film comprising alternating layers of a high refractive index polymer and a low refractive index polymer; wherein the high refractive index polymer comprises repeat units derived from a first photo-crosslinkable monomer; and wherein the low refractive index polymer consists of repeat units derived from a second photo-crosslinkable monomer and at least one monomer selected from the group consisting of C1-12 alkyl (meth)acrylates, C1-12 aryl (meth)acrylates, macromeric (meth)acrylates, (meth)acrylic acids, alpha olefins, vinyl esters, vinyl alkyl ethers, styrenic monomers, fluorinated monomers, and combinations thereof. ### Claim 2 (depends on 1) The radiation sensor of claim 1, wherein the substrate is glass. ### Claim 3 (depends on 1) The radiation sensor of claim 1, wherein the substrate is a flexible substrate. ### Claim 4 (depends on 3) The radiation sensor of claim 3, wherein the flexible substrate is a poly(ethylene terephthalate) substrate. ### Claim 5 (depends on 1) The radiation sensor of claim 1, wherein the polymer multilayer film comprises at least 2 to 50 alternating layers. ### Claim 6 (depends on 1) The radiation sensor of claim 1, wherein the high refractive index polymer layers and the low refractive index polymer layers each independently have thicknesses of 0.01 to 0.2 micrometers. ### Claim 7 (depends on 1) The radiation sensor of claim 1, wherein the high refractive index polymer has a refractive index greater than 1.5. ### Claim 8 (depends on 1) The radiation sensor of claim 1, wherein the high refractive index polymer further comprises repeat units derived from para-methylstyrene. ### Claim 9 (depends on 1) The radiation sensor of claim 1, wherein the low refractive index polymer has a refractive index less than or equal to 1.5. ### Claim 10 (depends on 1) The radiation sensor of claim 1, wherein the low refractive index polymer consists of repeat units derived from a photo-crosslinkable monomer and at least one monomer selected from the group consisting of oligoethylene glycol methacrylate, methyl methacrylate, and combinations thereof. ### Claim 11 (depends on 1) The radiation sensor of claim 1, wherein the first and second photo-crosslinkable monomers each comprise a benzophenone group. ### Claim 12 (depends on 1) The radiation sensor of claim 1, wherein the high refractive index polymer comprises 1 to 10 mole percent of the first photo-crosslinkable monomer, and the low refractive index polymer comprises 1 to 10 mole percent of the second photo-crosslinkable monomer. ### Claim 13 (depends on 1) The radiation sensor of claim 1, wherein the substrate is glass; the high refractive index polymer comprises repeat units derived from para-methylstyrene and a first photo-crosslinkable monomer; the low refractive index polymer consists of repeat units derived from a second photo-crosslinkable monomer and at least one monomer selected from the group consisting of oligoethylene glycol methacrylate, methyl methacrylate, and combinations thereof; and the first and second photo-crosslinkable monomers each comprise a benzophenone group. ### Claim 14 (depends on 1) The radiation sensor of claim 1, wherein the support substrate is a flexible support substrate comprising poly(ethylene terephthalate); the high refractive index polymer comprises repeat units derived from para-methylstyrene and a photo-crosslinkable monomer; the low refractive index polymer consists of repeat units derived from a photo-crosslinkable monomer and at least one monomer selected from the group consisting of oligoethylene glycol methacrylate, methyl methacrylate, or a combination thereof; and the first and second photo-crosslinkable monomers each comprise a benzophenone group. ### Claim 15 (depends on 1) The radiation sensor of claim 1, wherein the low refractive index polymer consists of repeat units derived from oligoethylene glycol methacrylate and the second photo-crosslinkable monomer comprising a benzophenone group; and wherein a 5 to 300 nanometer blue shift in the wavelength of reflected light of an irradiated region of the sensor occurs upon swelling the low refractive index polymer layers following exposure to a dose of ionizing radiation of greater than 0 to 400 kilogray. ### Claim 16 (depends on 1) The radiation sensor of claim 1, wherein the low refractive index polymer consists of repeat units derived from methyl methacrylate and the first photo-crosslinkable monomer comprising a benzophenone group; and wherein a 5 to 300 nanometer red shift in the wavelength of reflected light of an irradiated region of the sensor occurs upon swelling the low refractive index polymer layers following exposure to a dose of ionizing radiation of greater than 0 to 400 kilogray. ### Claim 17 An article comprising a radiation sensor, the radiation sensor comprising, a substrate; a polymer multilayer film comprising alternating layers of a high refractive index polymer and a low refractive index polymer; wherein the high refractive index polymer comprises repeat units derived from a first photo-crosslinkable monomer; and wherein the low refractive index polymer consists of repeat units derived from a second photo-crosslinkable monomer and at least one monomer selected from the group consisting of C1-12 alkyl (meth)acrylates, C1-12 aryl (meth)acrylates, macromeric (meth)acrylates, (meth)acrylic acids, alpha olefins, vinyl esters, vinyl alkyl ethers, styrenic monomers, fluorinated monomers, and combinations thereof; wherein the article is a wearable patch, a packaging material, a label, or a window pane. ### Claim 18 A method of detecting radiation, the method comprising, exposing to ionizing radiation a radiation sensor comprising, a substrate; a polymer multilayer film comprising alternating layers of a high refractive index polymer and a low refractive index polymer; wherein the high refractive index polymer comprises repeat units derived from a first photo-crosslinkable monomer; and wherein the low refractive index polymer consists of repeat units derived from a second photo-crosslinkable monomer and at least one monomer selected from the group consisting of C1-12 alkyl (meth)acrylates, C1-12 aryl (meth)acrylates, macromeric (meth)acrylates, (meth)acrylic acids, alpha olefins, vinyl esters, vinyl alkyl ethers, styrenic monomers, fluorinated monomers, and combinations thereof; immersing the sensor in a solvent to swell the low refractive index layers; and monitoring the sensor for a change in color resulting from exposure to a dose of ionizing radiation. ### Claim 19 (depends on 18) The method of claim 18, wherein the dose of ionizing radiation is greater than 0 to 400 kilogray. ### Claim 20 (depends on 18) The method of claim 18, wherein the high refractive index polymer comprises repeat units derived from para-methylstyrene and a photo-crosslinkable monomer comprising benzophenone; the low refractive index polymer comprises repeat units derived from oligoethylene glycol methacrylate, methyl methacrylate, or a combination thereof and a photo-crosslinkable monomer comprising benzophenone; the solvent comprises ethanol; and the change in color is a shift in the wavelength of reflected light of about 5 to 300 nanometers.