US3033797A - Self-luminous paints - Google Patents
Self-luminous paints Download PDFInfo
- Publication number
- US3033797A US3033797A US653733A US65373357A US3033797A US 3033797 A US3033797 A US 3033797A US 653733 A US653733 A US 653733A US 65373357 A US65373357 A US 65373357A US 3033797 A US3033797 A US 3033797A
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- US
- United States
- Prior art keywords
- paint
- tritiated
- plastic
- self
- resins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003973 paint Substances 0.000 title claims description 85
- 229920003023 plastic Polymers 0.000 claims description 43
- 239000004033 plastic Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- 229920000180 alkyd Polymers 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 229940071826 hydroxyethyl cellulose Drugs 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 claims 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 30
- 229910052722 tritium Inorganic materials 0.000 description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 27
- 239000011230 binding agent Substances 0.000 description 26
- 229910052705 radium Inorganic materials 0.000 description 15
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 15
- 239000003607 modifier Substances 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 12
- 230000005855 radiation Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000002285 radioactive effect Effects 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 229920002689 polyvinyl acetate Polymers 0.000 description 7
- 239000011118 polyvinyl acetate Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 6
- 229940072049 amyl acetate Drugs 0.000 description 5
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 239000005087 Radium paint Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- -1 manganese activated phosphor Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 235000015096 spirit Nutrition 0.000 description 3
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005250 beta ray Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012857 radioactive material Substances 0.000 description 2
- 150000003256 radium compounds Chemical class 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005533 tritiation Methods 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- ARIWANIATODDMH-AWEZNQCLSA-N 1-lauroyl-sn-glycerol Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)CO ARIWANIATODDMH-AWEZNQCLSA-N 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- YMCIVAPEOZDEGH-UHFFFAOYSA-N 5-chloro-2,3-dihydro-1h-indole Chemical compound ClC1=CC=C2NCCC2=C1 YMCIVAPEOZDEGH-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- MQKXWEJVDDRQKK-UHFFFAOYSA-N bis(6-methylheptyl) butanedioate Chemical compound CC(C)CCCCCOC(=O)CCC(=O)OCCCCCC(C)C MQKXWEJVDDRQKK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- PCYQQSKDZQTOQG-NXEZZACHSA-N dibutyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCCCOC(=O)[C@H](O)[C@@H](O)C(=O)OCCCC PCYQQSKDZQTOQG-NXEZZACHSA-N 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- MOQRZWSWPNIGMP-UHFFFAOYSA-N pentyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCC MOQRZWSWPNIGMP-UHFFFAOYSA-N 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000005258 radioactive decay Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/04—Luminescent, e.g. electroluminescent, chemiluminescent materials containing natural or artificial radioactive elements or unspecified radioactive elements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
Definitions
- This invention relates to a self-luminous paint and more particularly to a self-luminous paint comprising the radioactive isotope tritium.
- a further disadvantage of radium paints lies in the fact that the alpha particles emitted by radium are capable of destroying the phosphorescent quality of the phosphor crystals in the paint, so that a radium paint loses about one-half of its original brightness each year following compounding of the paint. Thus there is a limited useful period for any radium paint.
- a luminous watch, clock or instrument dial which is several years old will be found to havelost most of its original luminosity.
- Another specific object of this invention is to provide a self-luminous paint which can be prepared and used without hazard to personnel and which can be applied by brushing, dipping or silk screening, as desired.
- Another object of the present invention is to provide a self-luminous paint comprising a predetermined amount of phosphor particles of predetermined size and tritiated hydrogenous paint vehicle which is substantially nonvolatile. 7
- a self-luminous paint comprising an intimate mixture of a pigment which is a phosphorescent'material, a tritiated vehicle, the vehicle comprising either a substantially nonvolatile hydrogenous plastic binder alone or a plastic binder combined with an hydrogenous substantially nonvolatile paint modifier such as a plasticizer, and a solvent for the vehicle.
- the number of phosphor particles per centimeter length 3.6 X l0 /4.7 7.7 X 10 j
- the distance between phosphor particle surfaces is 1.3 10-' minus 1.0x l0- or This thickness of plastic is less than one twenty-fifth the range of tritium beta rays in the plastic, so that an appreciable fraction of beta radiation Will strike phosphor particles, exciting them to luminescence.
- Average diameter of phosphor particles is 10 microns (.001 cm.).
- the average distance between phosphor particles surfaces is 03x10" cm. This corresponds to a plastic thickness nearly one-half the range of tritium beta rays in the plastic. In such 'a case it has been found that approximately 90% of the beta energy will be expended in the plastic, resulting in'poor luminous eificiency.
- Zinc orthosilicate manganese activated phosphor is available in 1 and 2 micron average diameter, and has-been found to be eminently suitable for use in formulating a tritium self-luminous paint.
- a silicate phosphor is preferred to a sulfide phosphor inasmuch as it is more resistant to the deleterious action of moisture and high energy radiations.
- a blue paint can be made by using calcium magnesium silicate: titanium activated.
- a green paint results from using zinc orthosilicate: manganese activated.
- a yellow paint can be prepared using zinc cadmium sulfide: silver activated.
- a red paint can be made with zinc phosphate: manganese activated.
- an orange paint can be obtained using zinc cadmium sulfide: silver activated.
- a self-luminous paint comprises a phosphor, a vehicle, a solvent and a source of radioactive energy for exciting the phosphor to luminescence.
- vehicle excludes the volatile components of an ordinary paint and includes not only the plastic binder but the plastic binder in combination with any other modifying agent as, for example, a plasticizer, which is compatible with the binder and is non-volatile.
- the tritium is chemically combined in the vehicle, either by tritiation of the plastic hinder or by tritiation of the plasticizer or other nonvolatile hydrogenous modifying agent included in the vehicle as defined herein.
- the vehicle of the paint may comprise a tritiated plastic.
- tritiated polyvinyl acetate can be used as the plastic binder component of the vehicle of a self-luminous paint.
- This plastic is prepared first as a monomer, vinyl acetate, by the following reactions, and the monomer subsequently polymerized to polyvinyl acetate:
- Tritium oxide produced by reaction (1) is continuously removed by freezing into a small tube attached to the flask. After completion of reaction (1) the palladium thimble is cooled andunreacted tritium gas is collected on powdered uramum.
- Tritiated water contained in said tube is transferred by freezing into a flask containing ten millimoles of acetic anhydride. When the transfer is complete the contents of the flask are warmed to room temperature, and reaction 2) proceeds rapidly to completion, forming tritiated glacial-acetic acid. Tritiated glacial acetic acid reacts with acetylene according to reaction (3) in the presence of a mercuric salt catalyst. The product, tritiated vinyl acetate, is purified by distillation, allowed to polymerize into polyvinyl acetate, then dissolved in amyl acetate. Specific activity of the material prepared by this series of reactions is, 60 curies per millimole of vinyl acetate, which can be reduced to any desired specific activity by addition of inactive polyvinyl acetate solution in amyl acetate.
- the catalyst is removed from solution by filtration, and ethyl acetate is evaporated from the filtrate by a stream of nitrogen.
- the residue, tritiated diisooctyl succinate, is dissolved in a suitable high-boiling solvent such as xylene, and stored in solution.
- This material functions as a plasticizer to modify the characteristic of a paint.
- Self-luminous paints may be formulated using a tritiated plastic hinder or a non-tritiated plastic binder in conjunction with a tritiated paint modifier, an example of which is tritiated plasticizer. Following are two examples illustrating how such a paint may be prepared.
- a self-luminous paint comprising a tritiated binder can be prepared according to the following procedure.
- the amyl acetate functions as a solvent or thinner. This mixture is milled gently for 10 minutes until the mixture is homogeneous.
- tritiated polyvinyl acetate (1 millimole of material prepared as previously described) is added to the paint mixture and dispersed homogeneously by stirring. 15 grams of a non-radioactive plasticizer, such as dioctyl phthalate, is added if a high initial paint film flexibility is required.
- a non-radioactive plasticizer such as dioctyl phthalate
- the resultant mixture constitutes a self-luminous paint which can be made more viscous by evaporation of amyl acetate or less viscous by addition of more amyl acetate, depending upon the method by which the paint is to be applied.
- a self-luminous paint comprising a phosphor, and a vehicle therefor comprising a non-tritiated plastic binder and a tritiated plasticizer for the binder can be prepared as follows.
- a mixture of 45 grams of zinc orthosilicate: manganese activated phosphor having an average particle diameter between 1 and 2 microns is stirred together with 5 grams of aluminum stearate into a solution comprising 33 grams of Acryloid F-lO (manufactured by Rohm & Haas (30., Philadelphia, Pa.) and 25 grams of mineral spirits.
- Acryloid F-lO is a solution of acrylic resin dissolved in mineral spirits. The additional 25 grams of mineral spirits acts to thin the resin. This mixture is milled gently for 10 minutes until homogeneous.
- a solution of tritiated plasticizer, diisooctyl succinate-HS, containing 60 curies of tritium and prepared as previously described is added to the paint to make it self-luminous.
- the radioactive compound must be homogeneously dispersed throughout the paint and this is accomplished by stirring. The viscosity is increased by evaporating the solvent and is decreased by adding solvent.
- the brightness'of the self-luminous coatings with this paint can be increased by increasing the number of curies of tritiated plasticizer which is added. Similarly the brightness can be decreased by decreasing the number of curies added. The brightness is also dependent upon the coating thickness up to thicknesses of about 20 milligrams persquare centimeter.
- plastic binders which can be tritiated to produce a self-luminous paint: acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxyethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins, vinyl resins, polyvinyl resins, polyvinyl alcohol.
- plastics may comprise all or part of the vehicle of the paint, excluding the volatile constituents thereof.
- plasticizers which can be tritiated for the purposes of the present invention: dioctyl adipate, diisooctyl azelate, polyethyleneglycol dibenzoate, tri-n-butyl citrate, glycerol tributyrate, glycerol monolaurate, arnyl oleate, di-n-octyl phthalate, dibutyl sebacate, amyl stearate, dibutyl succinate, dibutyl tartrate.
- the paint comprise a non-volatile hydrogenous material which may function either as a binder or as a paint modifier and which is tritiated.
- Tritiating the paint modifier is just as eifective as tritiating the plastic binder.
- a self-luminous tritium paint is eflicient only if the tritiated compound is homogeneously dispersed throughout the paint. Because a plasticizer or other paint modifier must be compatible with the plastic binder, it readily disperses uniformly throughout the binder. Accordingly, if the paint modifier is tritiated the radioactivity will be uniformly distributed in the paint.
- Tritium and tritium paints have many advantages over radium and radium paints.
- One of the advantages of using tritium is that it is especially suitable as a radiation source for exciting phosphors. It has very low penetrating power, the beta radiation emitted therefrom having a penetration power of about 0.8 milligram per square centimeter. In most plastics this corresponds to a linear range of approximately 8 (10- cm. In addition it is readily available at a relatively low cost.
- Tritium is about 100,000 times less hazardous than radium if absorbed by the human body and no expensive shielding is required in preparing, handling and using the paint.
- the beta radiations from tritium do not result in phosphor destruction so that the rate of loss of brightness of tritiated paints is essentially the same as the rate of radioactive decay of tritium, about 6% per year.
- tritium paints can be made in various colors more efiectively than radium paints. If it is desired to make a self-luminous paint in a color other than the conventional green but with the same brightness, it would be necessary, due to the human eyes lower response to colors other than green, to increase the concentration of radioactivity in the paint. However, when this is done with radium, it is found that the rate of destruction of the phosphor by the radium is increased tremendously, resulting in an unstable paint having a short useful life.
- tritium paints Another advantage of tritium paints resides in their adaptability to application by silk screening. Due to the hazards of its radiations, radium paint must be handled in small concentrations. Thus, for example, it is the practice to silk screen only one clock dial at a time.
- the radioactive material is a component part of the paint vehicle. Because the plastic binder and the paint modifier, either of which may be modified, are non-volatile, there is no loss of radioactivity to the atomsphere. In this connection it is to be noted that if the plastic binder is tritiated, it must not be in the monomer state since monomers generally are volatile. The plastic binder, if tritiated, must be at least partly polymerized so as to have low volatility. It is recognized that where the paint modifier is tritiated, the plastic binder may be in a volatile state since evaporation of binder will not produce any loss of radioactivity, the tritiated modifier being non-volatile.
- the embodiments of the present invention will comprise a plastic binder which is at least partially polymerized, that is, in a non-volatile state, regardless of whether the binder or the paint modifier is tritiated, and a solvent or thinner for the binder.
- a self-luminous paint consisting essentially of an inorganic phosphorescent material in particle form and a tritiated hydrogenous nonvolatile polymerized organic plastic dispersed uniformly in a volatile solvent for said plastic, said plastic selected from the group consisting of acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxy-ethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins and vinyl resins, the average distance between adjacent phosphorescent particles being less than about 3 microns when said solvent is removed.
- a composition of matter consisting essentially of an inorganic phosphorescent material in particle form embedded in a tritiated organic polymer plastic, said plastic selected from the group consisting of acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxy-ethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins and vinyl resins, the average distance between adjacent phosphorescent particles being less than about 3 microns.
- a self-luminous paint consisting essentially of an inorganic phosphorescent material in particle form dispersed in a tritiated organic plastic selected from the group consisting of acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxyethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins and vinyl resins, the average distance between adjacent phosphorescent particles being less than about 3 microns.
Description
United States Patent 3,033,797 Patented May 8, 1962 3,033,797. SELF-LUMIN US PAINTS Felix R. De Leo, Needham, and Edward Shapiro, Newton, Mass, assignors, by mesne assignments, to Luminous Products Corp., Boston, Mass a corporation of Massachusetts No Drawing. Filed Apr. 19, 1957, Ser. No. 653,733 3 Claims. (Cl. 252-3011) This invention relates to a self-luminous paint and more particularly to a self-luminous paint comprising the radioactive isotope tritium.
Heretotore self-luminous paints have been made using as the exciting agent a compound of radium. Generally the radium compound is in intimate admixture with the phosphor crystals and is not an integral part of the paint vehicle. Unfortunately radium is a particularly dangerous form of radioactive material since when ingested by the body, it has a tendency to lodge in the bony structurewith its radiations causing serious damage to surrounding tissue. In addition, radium and its radioactive descendants emit penetrating gamma radiation which results in continual radiation doses to those who are eX- posed to it as, for example, workers Who apply radium self-luminous paints to watch, clock and instrument dials. A further disadvantage of radium paints lies in the fact that the alpha particles emitted by radium are capable of destroying the phosphorescent quality of the phosphor crystals in the paint, so that a radium paint loses about one-half of its original brightness each year following compounding of the paint. Thus there is a limited useful period for any radium paint. A luminous watch, clock or instrument dial which is several years old will be found to havelost most of its original luminosity.
Because of these and other disadvantages, efforts have been made to produce self-luminous paints superior to radium paints.
Accordingly it is the purpose of this invention to provide a self-luminous paint which avoids the aforementioned difiiculties common to radium paints.
In particular it is the object of this invention to provide a selfrluminous paint in which the radioactive isotope tritium is used to furnishthe energy forexcitation of the phosphor to produce luminescence, thereby eliminating radium with all of its concomitant disadvantages.
Another specific object of this invention is to provide a self-luminous paint which can be prepared and used without hazard to personnel and which can be applied by brushing, dipping or silk screening, as desired.
Another object of the present invention is to provide a self-luminous paint comprising a predetermined amount of phosphor particles of predetermined size and tritiated hydrogenous paint vehicle which is substantially nonvolatile. 7
Other objects and many of the attendant advantages of the present invention willrbecome' more apparent as reference is had to the following detailed description.
By the present invention it is proposed to provide a self-luminous paint comprising an intimate mixture of a pigment which is a phosphorescent'material, a tritiated vehicle, the vehicle comprising either a substantially nonvolatile hydrogenous plastic binder alone or a plastic binder combined with an hydrogenous substantially nonvolatile paint modifier such as a plasticizer, and a solvent for the vehicle.
' In developing this invention it has been determined that the choice of phosphor is determined by two factors: (1) the efficiencyof conversion of beta-ray energy to visible light, and (2) the size of the phosphor particles. The first factor is believed to. be obvious. The second factor can be demonstrated as follows:
Assume a paint mixture which upon drying contains 100 grams of phosphor dispersed uniformly throughout 100 grams of tritiated plastic, the phosphor and plastic having the following physical characteristics: a
( 1) Density of plastic -L- 1.25 grams/cmfi. (2) Density of phosphor 4.00 grams/cm. (3) Volume of plastic 100/ 1.25:80 cmfi. (4) Volume of phosphor l00/4.0=2S cm. (5) Volume of paint 105 cm.
Number of phosphor particles in the length of a cube is (4.8 10 =3.6X10 The number of phosphor particles per centimeter length 3.6 X l0 /4.7=7.7 X 10 j The average distance between the centers of individual particles is l/7.7 10 =l.3 X10 cm.
' Since the average diameter of the phosphor particles is 1.0x 10- cm., the distance between phosphor particle surfaces is 1.3 10-' minus 1.0x l0- or This thickness of plastic is less than one twenty-fifth the range of tritium beta rays in the plastic, so that an appreciable fraction of beta radiation Will strike phosphor particles, exciting them to luminescence.
' Case B:
Average diameter of phosphor particles is 10 microns (.001 cm.).
By calculations analogous to the foregoing, it will be found that the average distance between phosphor particles surfaces is 03x10" cm. This corresponds to a plastic thickness nearly one-half the range of tritium beta rays in the plastic. In such 'a case it has been found that approximately 90% of the beta energy will be expended in the plastic, resulting in'poor luminous eificiency.
From extensive research'it has been discovered that for a given amount of radioactivity best results are obtained when the phosphor particles have a maximum average size in the range of 1 to 2 microns. At the same concentration of radioactivity, increasing thesize of the particles to 3 microns gives satisfactory results, although the efficiency is somewhat lower than with particles of 2 microns. Above 3 microns the efiiciency drops rapidly, but the loss in efiiciency due to the increase in phosphor particle size can be compensated for by increasing the concentration of radioactivity As pointed out more fully hereinafter,
. increasing the-concentration of tritium does not increase the rate of loss of brightness. Accordingly, particle sizes up to approximately 10 micronsaverage diameter may be used if the concentration of tritium is also increased. However, in view of the relatively high cost of tritium, it is more economical to use particles having a maximum diameter of 3 microns or less because of the markedly greater efiiciency that results. Of course particles smaller than 1 micron will give even better results. Unfortunately smaller particles having good efficiency of conversion of beta-ray energy to visible light are not available commercially.
Fortunately there are various phosphors available in the desired sizes. Zinc orthosilicate: manganese activated phosphor is available in 1 and 2 micron average diameter, and has-been found to be eminently suitable for use in formulating a tritium self-luminous paint. A silicate phosphor is preferred to a sulfide phosphor inasmuch as it is more resistant to the deleterious action of moisture and high energy radiations. This choice, however, is not to rule out the use of other phosphors such as 1) zinc sulphide: copper; (2) zinc sulphide: silver; (3) zinc cadmium sulfide: copper; or other types such as zinc orthogermanate when these are available as eflicient phosphors with small 1 to 3 (and preferably 1 to 2) micron diameters.
The choice of phosphor will determine the color of the paint. A blue paint can be made by using calcium magnesium silicate: titanium activated. A green paint results from using zinc orthosilicate: manganese activated. A yellow paint can be prepared using zinc cadmium sulfide: silver activated. A red paint can be made with zinc phosphate: manganese activated. Similarly, an orange paint can be obtained using zinc cadmium sulfide: silver activated.
Speaking generally a self-luminous paint comprises a phosphor, a vehicle, a solvent and a source of radioactive energy for exciting the phosphor to luminescence. As used herein the term vehicle excludes the volatile components of an ordinary paint and includes not only the plastic binder but the plastic binder in combination with any other modifying agent as, for example, a plasticizer, which is compatible with the binder and is non-volatile. In the present invention the tritium is chemically combined in the vehicle, either by tritiation of the plastic hinder or by tritiation of the plasticizer or other nonvolatile hydrogenous modifying agent included in the vehicle as defined herein.
Preparation of Tritiated Plastic Binder The vehicle of the paint may comprise a tritiated plastic. Thus, for example, tritiated polyvinyl acetate can be used as the plastic binder component of the vehicle of a self-luminous paint. This plastic is prepared first as a monomer, vinyl acetate, by the following reactions, and the monomer subsequently polymerized to polyvinyl acetate:
Ten millimoles of tritium gas (10 millimoles=60 milligrams=600 curies) is allowed to react slowly with oxygen in the presence of a palladium catalyst by allowing tritium gas to diffuse through a heated palladium thimble into a flask containing oxygen. Tritium oxide produced by reaction (1) is continuously removed by freezing into a small tube attached to the flask. After completion of reaction (1) the palladium thimble is cooled andunreacted tritium gas is collected on powdered uramum.
Tritiated water contained in said tube is transferred by freezing into a flask containing ten millimoles of acetic anhydride. When the transfer is complete the contents of the flask are warmed to room temperature, and reaction 2) proceeds rapidly to completion, forming tritiated glacial-acetic acid. Tritiated glacial acetic acid reacts with acetylene according to reaction (3) in the presence of a mercuric salt catalyst. The product, tritiated vinyl acetate, is purified by distillation, allowed to polymerize into polyvinyl acetate, then dissolved in amyl acetate. specific activity of the material prepared by this series of reactions is, 60 curies per millimole of vinyl acetate, which can be reduced to any desired specific activity by addition of inactive polyvinyl acetate solution in amyl acetate.
Preparation of a Tritiated Paint Modifier Ten" millimoles of diisooctyl maleate weighing 3.40 grams is dissolved in120 ml. of ethyl acetate contained in The a pressure flask. 300 milligrams of pre-reduced 30% palladium on charcoal catalyst is added to the solution. 20 millimoles of tritium gas (1200 curies) is added to the flask and the contents of the flask including the tritium are shaken until no further takeup of tritium is observed as measured on a mercury manometer. The unreacted tritium (about 600 curies) is collected in a reservoir for future use. The catalyst is removed from solution by filtration, and ethyl acetate is evaporated from the filtrate by a stream of nitrogen. The residue, tritiated diisooctyl succinate, is dissolved in a suitable high-boiling solvent such as xylene, and stored in solution. This material functions as a plasticizer to modify the characteristic of a paint.
Self-luminous paints may be formulated using a tritiated plastic hinder or a non-tritiated plastic binder in conjunction with a tritiated paint modifier, an example of which is tritiated plasticizer. Following are two examples illustrating how such a paint may be prepared.
Preparation of a Self-Luminous Paint Using a T ritiated Plastic Binder A self-luminous paint comprising a tritiated binder can be prepared according to the following procedure. A mixture of 45 grams of zinc orthosilicate; manganese activated phosphor, having an average particle diameter of l to 2 microns, is'mixed together with 5 grams of aluminum stearate in a solution of 50 grams of polyvinyl acetate (not radioactive) in grams of amyl acetate. The amyl acetate functions as a solvent or thinner. This mixture is milled gently for 10 minutes until the mixture is homogeneous. 60 curies of tritiated polyvinyl acetate (1 millimole of material prepared as previously described) is added to the paint mixture and dispersed homogeneously by stirring. 15 grams of a non-radioactive plasticizer, such as dioctyl phthalate, is added if a high initial paint film flexibility is required. The resultant mixture constitutes a self-luminous paint which can be made more viscous by evaporation of amyl acetate or less viscous by addition of more amyl acetate, depending upon the method by which the paint is to be applied.
The brightness of a given thickness of coating Will depend upon the amount of radioactive polyvinyl acetate added per gram of paint. It will also depend upon the coating thickness for thicknesses up to about 20 milligrams/cm? Preparation of a Self-Lumin0us Paint Using a T ritiated Paint Modifier A self-luminous paint comprising a phosphor, and a vehicle therefor comprising a non-tritiated plastic binder and a tritiated plasticizer for the binder can be prepared as follows. A mixture of 45 grams of zinc orthosilicate: manganese activated phosphor having an average particle diameter between 1 and 2 microns is stirred together with 5 grams of aluminum stearate into a solution comprising 33 grams of Acryloid F-lO (manufactured by Rohm & Haas (30., Philadelphia, Pa.) and 25 grams of mineral spirits. Acryloid F-lO is a solution of acrylic resin dissolved in mineral spirits. The additional 25 grams of mineral spirits acts to thin the resin. This mixture is milled gently for 10 minutes until homogeneous. A solution of tritiated plasticizer, diisooctyl succinate-HS, containing 60 curies of tritium and prepared as previously described is added to the paint to make it self-luminous. The radioactive compound must be homogeneously dispersed throughout the paint and this is accomplished by stirring. The viscosity is increased by evaporating the solvent and is decreased by adding solvent.
The brightness'of the self-luminous coatings with this paint can be increased by increasing the number of curies of tritiated plasticizer which is added. Similarly the brightness can be decreased by decreasing the number of curies added. The brightness is also dependent upon the coating thickness up to thicknesses of about 20 milligrams persquare centimeter.
One of the advantages of the present invention resides in the fact that it can be applied to paints comprising various plastic binders and paint modifiers. Following is a list of plastic binders which can be tritiated to produce a self-luminous paint: acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxyethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins, vinyl resins, polyvinyl resins, polyvinyl alcohol.
The foregoing plastics may comprise all or part of the vehicle of the paint, excluding the volatile constituents thereof. Following is a list of plasticizers which can be tritiated for the purposes of the present invention: dioctyl adipate, diisooctyl azelate, polyethyleneglycol dibenzoate, tri-n-butyl citrate, glycerol tributyrate, glycerol monolaurate, arnyl oleate, di-n-octyl phthalate, dibutyl sebacate, amyl stearate, dibutyl succinate, dibutyl tartrate.
The foregoing list of plastics and plasticizers is not to be construed as limiting the invention but are presented by way of example only. The primary requisite of this invention is that the paint comprise a non-volatile hydrogenous material which may function either as a binder or as a paint modifier and which is tritiated.
Tritiating the paint modifier is just as eifective as tritiating the plastic binder. A self-luminous tritium paint is eflicient only if the tritiated compound is homogeneously dispersed throughout the paint. Because a plasticizer or other paint modifier must be compatible with the plastic binder, it readily disperses uniformly throughout the binder. Accordingly, if the paint modifier is tritiated the radioactivity will be uniformly distributed in the paint.
Tritium and tritium paints have many advantages over radium and radium paints. One of the advantages of using tritium is that it is especially suitable as a radiation source for exciting phosphors. It has very low penetrating power, the beta radiation emitted therefrom having a penetration power of about 0.8 milligram per square centimeter. In most plastics this corresponds to a linear range of approximately 8 (10- cm. In addition it is readily available at a relatively low cost. Tritium is about 100,000 times less hazardous than radium if absorbed by the human body and no expensive shielding is required in preparing, handling and using the paint. Moreover, the beta radiations from tritium do not result in phosphor destruction so that the rate of loss of brightness of tritiated paints is essentially the same as the rate of radioactive decay of tritium, about 6% per year.
Another advantage of tritium paints is that they can be made in various colors more efiectively than radium paints. If it is desired to make a self-luminous paint in a color other than the conventional green but with the same brightness, it would be necessary, due to the human eyes lower response to colors other than green, to increase the concentration of radioactivity in the paint. However, when this is done with radium, it is found that the rate of destruction of the phosphor by the radium is increased tremendously, resulting in an unstable paint having a short useful life.
In the case of tritium, however, no such adverse result is produced. When the concentration of tritium is increased, the rate of loss of brightness remains substantially the same. Hence paints in colors other than green in brightnesses perceptible to the human eye are possible under the present invention. Similarly, it is possible to increase the brightness of green tritium paints by adding more radioactivity without affecting the stability thereof. By the present invention it is possible to produce green paints having a brightness to 30 times as great as those paints employing radium compounds, and still not in-,
crease the rate of loss of brightness. 7
Another advantage of tritium paints resides in their adaptability to application by silk screening. Due to the hazards of its radiations, radium paint must be handled in small concentrations. Thus, for example, it is the practice to silk screen only one clock dial at a time.
Naturally this increases the cost of manufacturing the dial. With tritium there is no such danger and it is possible to silk screen clock dials in quantity without hazard to personnel. This saving in time reduces the cost of producing clock dials.
Still a further advantage of the present invention is that the radioactive material is a component part of the paint vehicle. Because the plastic binder and the paint modifier, either of which may be modified, are non-volatile, there is no loss of radioactivity to the atomsphere. In this connection it is to be noted that if the plastic binder is tritiated, it must not be in the monomer state since monomers generally are volatile. The plastic binder, if tritiated, must be at least partly polymerized so as to have low volatility. It is recognized that where the paint modifier is tritiated, the plastic binder may be in a volatile state since evaporation of binder will not produce any loss of radioactivity, the tritiated modifier being non-volatile. Nevertheless, the loss of any binder at all is to be avoided for reasons of economy. Accordingly, in practice the embodiments of the present invention will comprise a plastic binder which is at least partially polymerized, that is, in a non-volatile state, regardless of whether the binder or the paint modifier is tritiated, and a solvent or thinner for the binder.
Obviously many modifications and variations of the present invention are possible in the light of the above teachings. Therefore, it is to be understood that the invention is not limited in its application to the details specifically described hereinabove and that within the scope of the appended claims it may be practiced otherwise than as specifically described.
We claim:
I. A self-luminous paint consisting essentially of an inorganic phosphorescent material in particle form and a tritiated hydrogenous nonvolatile polymerized organic plastic dispersed uniformly in a volatile solvent for said plastic, said plastic selected from the group consisting of acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxy-ethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins and vinyl resins, the average distance between adjacent phosphorescent particles being less than about 3 microns when said solvent is removed.
2. A composition of matter consisting essentially of an inorganic phosphorescent material in particle form embedded in a tritiated organic polymer plastic, said plastic selected from the group consisting of acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxy-ethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins and vinyl resins, the average distance between adjacent phosphorescent particles being less than about 3 microns.
3. A self-luminous paint consisting essentially of an inorganic phosphorescent material in particle form dispersed in a tritiated organic plastic selected from the group consisting of acrylic resins, alkyd resins, cellulose acetate, ethyl cellulose, hydroxyethyl cellulose, phenol formaldehyde resins, polyester resins, polystyrene resins, urea formaldehyde resins and vinyl resins, the average distance between adjacent phosphorescent particles being less than about 3 microns.
References Cited in the file of this patent UNITED STATES PATENTS 2,039,734 Meder May 5, 1936 2,749,251 Shapiro June 5, 1956 FOREIGN PATENTS 646,414 Great Britain Nov. 22, 1950 OTHER REFERENCES Luminous and Fluorescent Paints, by Dept. of Comm. Nat. Bureau of Standards, Sept. 9, 1942; Circular Letter LC 703 and 678.
Claims (1)
1. A SELF-LUMINOUS PAINT CONSISTING ESSENTIALLY OF AN INORGANIC PHOSPHORESCENT MATERIAL IN PARTICLE FORM AND A TRITIATED HYDROGENOUS NON-VOLATILE POLYMERIZED ORGANIC PLASTIC DISPERSED UNIFORMLY IN A VOLATILE SOLVENT FOR SAID PLASTIC, SAID PLASTIC SELECTED FROM THE GROUP CONSISTING OF ACRYLIC RESINS, ALKYD RESISNS, CELLULOSE ACETATE, ETHYL CELLULOSE, HYDROXY-ETHYL CELLULOSE, PHENOL FORMALDEHYDE RESINS, POLYESTER RESINS, POLYSTYRENE RESISNS, UREA FORMALDEHYDE RESINS AND VINYL RESINS, THE AVERAGE DISTANCE BETWEEN ADJACENT PHOSPHORESCENT PARTICLES BEING LESS THAN ABOUT 3 MICRONS WHEN SAID SOLVENT IS REMOVED.
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US653733A US3033797A (en) | 1957-04-19 | 1957-04-19 | Self-luminous paints |
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US653733A US3033797A (en) | 1957-04-19 | 1957-04-19 | Self-luminous paints |
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Cited By (16)
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---|---|---|---|---|
US3147243A (en) * | 1960-08-08 | 1964-09-01 | Continental Oil Co | Radioactive polymers |
US3238139A (en) * | 1960-04-26 | 1966-03-01 | Trilux Lenze Gmbh & Co Kg | Method of making a tritiated selfluminescent body |
US3325420A (en) * | 1964-04-15 | 1967-06-13 | Westo Gmbh Fabrik Fur Chemisch | Tritium-activated luminous pigments |
US3342743A (en) * | 1965-03-19 | 1967-09-19 | Lab For Electronics Inc | Process of preparing a zinc sulfide powder coated with tritiated polystyrene |
US3366573A (en) * | 1965-10-24 | 1968-01-30 | Canrad Prec Ind Inc | Coated phosphor having radioisotope dispersed therein and method of preparation |
US3436242A (en) * | 1964-10-19 | 1969-04-01 | Fluckinger & Cie | Method of making luminescent dial with resin and fluorescent top layer |
US4889660A (en) * | 1987-12-24 | 1989-12-26 | Battelle Memorial Institute | Radioluminescent light sources, tritium containing polymers, and methods for producing the same |
EP0387624A1 (en) * | 1989-03-03 | 1990-09-19 | E.F. Johnson Company | Light emitting polymer electrical energy source |
US5100968A (en) * | 1987-12-24 | 1992-03-31 | Battelle Memorial Institute | Tritium containing polymers having a polymer backbone substantially void of tritium |
US5124610A (en) * | 1989-03-03 | 1992-06-23 | E. F. Johnson Company | Tritiated light emitting polymer electrical energy source |
US5235232A (en) * | 1989-03-03 | 1993-08-10 | E. F. Johnson Company | Adjustable-output electrical energy source using light-emitting polymer |
US5237233A (en) * | 1989-03-03 | 1993-08-17 | E. F. Johnson Company | Optoelectronic active circuit element |
US20040238802A1 (en) * | 2003-05-26 | 2004-12-02 | Tomio Inoue | Combustion promoting material |
US20040238782A1 (en) * | 2003-05-26 | 2004-12-02 | Tomio Inoue | Electric characteristic modifying material |
US20050217782A1 (en) * | 2004-04-06 | 2005-10-06 | Giorgio Agostini | Self-luminescent pneumatic tire |
US20130040765A1 (en) * | 2011-08-08 | 2013-02-14 | Teno DeMont Myles | Luminous attachable basketball training device |
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GB646414A (en) * | 1946-05-31 | 1950-11-22 | Egyesuelt Izzolampa | Improvements in and relating to fluorescent luminous bodies |
US2749251A (en) * | 1953-10-29 | 1956-06-05 | Tracerlab Inc | Source of luminosity |
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US2039734A (en) * | 1932-03-01 | 1936-05-05 | Ig Farbenindustrie Ag | New compositions of matter containing luminous substances |
GB646414A (en) * | 1946-05-31 | 1950-11-22 | Egyesuelt Izzolampa | Improvements in and relating to fluorescent luminous bodies |
US2749251A (en) * | 1953-10-29 | 1956-06-05 | Tracerlab Inc | Source of luminosity |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3238139A (en) * | 1960-04-26 | 1966-03-01 | Trilux Lenze Gmbh & Co Kg | Method of making a tritiated selfluminescent body |
US3147243A (en) * | 1960-08-08 | 1964-09-01 | Continental Oil Co | Radioactive polymers |
US3325420A (en) * | 1964-04-15 | 1967-06-13 | Westo Gmbh Fabrik Fur Chemisch | Tritium-activated luminous pigments |
US3436242A (en) * | 1964-10-19 | 1969-04-01 | Fluckinger & Cie | Method of making luminescent dial with resin and fluorescent top layer |
US3342743A (en) * | 1965-03-19 | 1967-09-19 | Lab For Electronics Inc | Process of preparing a zinc sulfide powder coated with tritiated polystyrene |
US3366573A (en) * | 1965-10-24 | 1968-01-30 | Canrad Prec Ind Inc | Coated phosphor having radioisotope dispersed therein and method of preparation |
US4889660A (en) * | 1987-12-24 | 1989-12-26 | Battelle Memorial Institute | Radioluminescent light sources, tritium containing polymers, and methods for producing the same |
US5100968A (en) * | 1987-12-24 | 1992-03-31 | Battelle Memorial Institute | Tritium containing polymers having a polymer backbone substantially void of tritium |
WO1990010938A1 (en) * | 1989-03-03 | 1990-09-20 | E.F. Johnson Company | Light emitting polymer electrical energy source |
US5008579A (en) * | 1989-03-03 | 1991-04-16 | E. F. Johnson Co. | Light emitting polymer electrical energy source |
EP0387624A1 (en) * | 1989-03-03 | 1990-09-19 | E.F. Johnson Company | Light emitting polymer electrical energy source |
US5124610A (en) * | 1989-03-03 | 1992-06-23 | E. F. Johnson Company | Tritiated light emitting polymer electrical energy source |
US5235232A (en) * | 1989-03-03 | 1993-08-10 | E. F. Johnson Company | Adjustable-output electrical energy source using light-emitting polymer |
US5237233A (en) * | 1989-03-03 | 1993-08-17 | E. F. Johnson Company | Optoelectronic active circuit element |
US20040238802A1 (en) * | 2003-05-26 | 2004-12-02 | Tomio Inoue | Combustion promoting material |
US20040238782A1 (en) * | 2003-05-26 | 2004-12-02 | Tomio Inoue | Electric characteristic modifying material |
US20050217782A1 (en) * | 2004-04-06 | 2005-10-06 | Giorgio Agostini | Self-luminescent pneumatic tire |
US7234498B2 (en) | 2004-04-06 | 2007-06-26 | The Goodyear Tire & Rubber Company | Self-luminescent pneumatic tire |
US20130040765A1 (en) * | 2011-08-08 | 2013-02-14 | Teno DeMont Myles | Luminous attachable basketball training device |
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