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WO1982000527A1 - Solution de liquide radiochromique - Google Patents

Solution de liquide radiochromique Download PDF

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Publication number
WO1982000527A1
WO1982000527A1 PCT/US1981/000920 US8100920W WO8200527A1 WO 1982000527 A1 WO1982000527 A1 WO 1982000527A1 US 8100920 W US8100920 W US 8100920W WO 8200527 A1 WO8200527 A1 WO 8200527A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
dye
cyanide
acid
solvent
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.)
Ceased
Application number
PCT/US1981/000920
Other languages
English (en)
Inventor
Corp Bicron
J Noakes
R Culp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Ceramics and Plastics Inc
Original Assignee
Bicron Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bicron Corp filed Critical Bicron Corp
Priority to JP50264581A priority Critical patent/JPS58501091A/ja
Priority to DE19813152187 priority patent/DE3152187A1/de
Publication of WO1982000527A1 publication Critical patent/WO1982000527A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/02—Dosimeters
    • G01T1/04—Chemical dosimeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/48—Photometry, e.g. photographic exposure meter using chemical effects
    • G01J1/50—Photometry, e.g. photographic exposure meter using chemical effects using change in colour of an indicator, e.g. actinometer

Definitions

  • This invention relates to a radiochromic liquid solution which is particularly sensitive to radiation from wave lengths of between .005 Angstroms and 3900 Angstroms and which, upon exposure to such radiation, responds by permanently changing from a clear solution to a colored solution.
  • the above wave lengths include ultraviolet radiation, gamma ray radiation, and X-ray radiation.
  • One device measures ultraviolet radiation and provides a color indicator for use when a person has been exposed to too much sunlight, as disclosed in U.S. Patent 3,449,572.
  • Other devices measure, by color indicators, the exposure to gamma ray and X-ray radiation for persons who work around equipment which emits such radiation, as disclosed in U.S. Patents 2,848,625; 3,657,538; and 3,899,677.
  • Still other devices measure the exposure to nuclear radiation, as disclosed in U.S. Patents 3,461,288 and 4,001,587.
  • a "rad” is a unit of absorbed radiation dosage equal to the delivery of .01 joules per kilogram of human body material.
  • a dosage of 1000 rads is lethal.
  • a dosage of 600 rads can be lethal to perhaps fifty per cent of the population exposed to the dosage.
  • a dosage of 200 rads is not lethal. It is obviously important to be able to measure these various dosages accurately, and there are such devices, but they are laboratory-type instruments which require a special reader or which require a special power supply to charge them and keep them charged.
  • the object of the present invention is to provide a radiochromic liquid which responds to radiation from ultraviolet wave lengths and below, including X-rays and gamma rays, which is particularly sensitive to low exposures of radiation from such wave lengths and which does not require a separate reader or power supply.
  • a radiochromic liquid which responds to radiation from ultraviolet wave lengths and below, including X-rays and gamma rays, which is particularly sensitive to low exposures of radiation from such wave lengths and which does not require a separate reader or power supply.
  • the leucocyanide dyes come as a crystalline powder and are described in U.S. Patents 2,441,561; 2,528,496; 2,676,887; and 2,877,167. They can be dissolved in a monomer and then polymerized into a solid plastic or they can be dissolved in a suitable liquid medium and kept in solution. In either event, when they are exposed to ultraviolet or ionizing radiation, they change from the clear or "leuco" state into the colored state. In suitable conditions, the change is permanent. Even the crystalline powder will change color when exposed to ultraviolet or ionizing radiation, but it does' this more slowly than when dissolved in solution or suitably incorporated into a polymer.
  • the leucocyanide dyes for use in the present invention can be any hydrophobic, substituted aminotriphenyl methane leucocyanide dye. We prefer blue, violet, or green dyesbecause those colors can be discerned by most persons, that is, fewer persons are color-blind to them.
  • the preferred dyes are: pararosaniline cyanide hexa(hydroxyethyl) pararosaniline cyanide new fuchsin cyanide crystal violet cyanide.
  • Suitable dyes are: malachite green cyanide brilliant blue cyanide methyl green cyanide helvetia green cyanide seto-glaucine cyanide.
  • leucocyanide dyes for use in accordance with the present invention may be represented by the following basic formula:
  • the R groups may be one of a hydrogen atom, an alkyl group of less tham eight carbon atoms, such as methyl, ethyl, propyl, or butyl groups, or a hydroxyethyl group.
  • the R groups may be the same or may be different in the positions shown in the formula. Also, the amino groups in the para position on the phenyl groups can be replaced by a hydrogen atom.
  • the dyes are dissolved in a polar solvent, which should be clear so that when the dye is dissolved, the solution is clear or at least has a minimum of background coloration.
  • the solvent should be free of hydroxy groups.
  • solvents with relatively high polarities of at least about 5 deBye units The higher polarity solvents facilitate dissolving greater amounts of dye therein. Also, they seem to enhance the sensitivity of the dye in the color Change reaction.
  • the solvents should stay liquid down to below at least about 20° C. , and should not boil or vaporize at temperatures below about 80° C. Cost and availability are other obvious considerations.
  • the concentration of the dye in the polar solvent should be at least about 1 to 25 per cent by weight, and preferably about 1 to 10 per cent by weight, which in most instances is approaching or about at the saturation point. We prefer, and try to obtain, relatively high concentrations of dye in the polar solvent.
  • the compounding and formulation must take place in a room which is filtered to keep out ultraviolet light and all other wave lengths of less than 4000 Angstroms.
  • the dye solution must also be kept in containers which filter out ultraviolet light. Preferably, the solution is bubbled with nitrogen. Means must be found to facilitate dissolution of the dyes in the solvent, because you are approaching the satura tion limits of the dye in the solvent.
  • the dyes cannot be heated in order to dissolve them in the solvent because the heat activates them and they tend to change to their colored state. They therefore have to be dissolved in the solvent in amounts which approach their saturation point by ultrasonic vibration.
  • the powdered dye is poured into a beaker of sol vent and the beaker subjected to ultrasonic vibration until, by visual inspection, one may determine that all of the dye has been dissolved in the solvent.
  • Suitable polar solvents are: triethyl phosphate; dimethyl sulfoxfde; dimethyl formamide; vinyl pyrollidone; tributyl phosphate; trioctyl phosphate; and trichloroethyl phosphate.
  • the preferred organic acid sensitizers and stabilizers are: acetic acid; citric acid; carboxylic and benzoic acid.
  • Other acids which we contemplate using in addition to those already mentioned are: tartaric acid phthalic acid salicylic acid maleic acid.
  • the organic acids should dissolve in the solvent in which they are employed, and should be free of water.
  • the amount of the organic acid should be enough to make the solution slightly acidic with a pH of 5 to 7 and stabilize the color change.
  • the above was irradiated with ultraviolet radiation from a hydrogen continuum lamp for 60 seconds.
  • the liquid changed to a deep red color.
  • a wave shifting and concentration of radiant energy takes place so that, in this combination, a smaller amount of dye becomes just about as effective as a larger amount in the combination of the foregoing examples.
  • the aromatic solvent absorbs X-ray and gamma ray radiation, and emits radiation at around 3000 Angstrom wave lengths.
  • the fluor picks up the emissions from the aromatic solvent and emits photon energy in the 3000-3800 Angstrom wave length range, which is a range to which the leucocyanide dyes are very sensitive. These photons, in turn, are absorbed by the leucocyanide dye in the polar solution to change its color.
  • Suitable fluors are those which absorb radiation at around 3000 Angstroms and emit at around 3850 Angstroms.
  • Suitable fluors are the various oligophenylenes, oxazoles, thiazoles, or oxadiazoles with two to six or more benzene rings such as PPO, PBD, PBBO, NPO, and NOPON and the like, in which P is used for phenyl, N for naphthyl, B for biphenyl, O for oxazole, and D for the oxadiazole group.
  • Suitable aromatic solvents are those which absorb radiation below 20Q0 Angstroms and emit at around 3000 Angstroms.
  • the fluor is dissolved in the arc ⁇ atic solvent in amounts approaching the saturation point so as not to exceed the saturation point when mixed with the polar solvent.
  • the mixed solution was then exposed to gamma rays from a cobalt 60 source to provide a total exposure of 100 rads.
  • Example I The solution changed to a pale blue color determined by unaided visual observation.
  • the color approached the intensity of that of Example I, which contained about twice the amount of dye.
  • a polar solvent which also has an aromatic ring in it which responds to X-ray and gamma ray radiation like the aromatic solvent previously disclosed.
  • This solvent may be Idded a leucocyanide dye, an organic acid, and a fluor.
  • Polar aromatic solvents for hydrophobic leucocyanide dyes possessing one or more aromatic groups may be a compound such as triphenyl phosphate.
  • the compounds used in accordance with our invention should be free of impurities.
  • the dyes in particular, should be pure. Impurities in the dyes will give objectionable background coloration or flush. While the commercially available solvents, organic acids and secondary fluors are usually relatively pure and can often be used as is without additional purification, the purity of the ingredients in the system must be kept in mind. In working with these materials, one can never tell when an impurity will act as a screener or otherwise upset the response of the system.
  • solutions made in accordance with our invention respond to two general classes of radiation, namely, ultraviolet radiation, and radiation from gamma rays and X-rays and the like at the lower end of the spectrum which is also ionizing radiation.
  • ultraviolet radiation starts at 3900 Angstroms and goes down to 100 Angstroms.
  • the ionizing radiation is in the range of from about 300 Angstroms down to .005 Angstroms.
  • Radiochromic solutions made in accordance with the present invention respond to photons or wave lengths between .005 Angstroms up to 3900 Angstroms by changing color, as is well known. For gamma and X-rays, these solutions respond to exposures of from about 20 rads up to 1000 rads. For ultraviolet, the threshold of response is in the range of about 5 millijoules per square centimeter. The response to radiation is cumulative. If a person receives 100 rads one day and 300 rads the next day, the radiochromic dye solutions of the present invention give a response of 400 rads. In other words, radiochromic solutions made in accordance with the present invention respond in proportion to the integrated intensity of the exposure.
  • radiochromic liquids of our invention can be incorporated in dosimeters and carried about by persons working with X-rays or gamma radiation. They can be made up in sealed ampoules with tissue or bone equivalencies and placed on or within a critical area of the human body in order to determine precise dosage for radiation therapy. They can be used by persons with sensitive skin working in bright sunlight who wish to avoid excessive exposure to ultraviolet radiation. They can be attached to foodstuffs to record sterilizing radiation. Troops exposed to nuclear radiation can carry simple dosimeters having a solution made in accordance with our invention and, by noting color change alone in the field, will be able to estimate their exposure.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Molecular Biology (AREA)
  • Measurement Of Radiation (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Color Printing (AREA)

Abstract

Solution d'une teinture de leucocyanure dans un solvant clair, polaire a laquelle on ajoute suffisamment d'acide organique pour rendre la solution au moins legerement acide, ce qui la rend sensible a de petites doses de radiation ionisante et ultraviolette, et repondant en changeant constamment de couleur. Jusqu'a la moitie de la solution, en poids, peut etre remplacee par une seconde solution d'un solvant aromatique et d'un fluor organique. Une autre modification de l'invention est une solution d'une teinture de leucocyanure dans un solvant clair, polaire ayant un groupe aromatique, un compose fluore organique et suffisamment d'acide organique pour rendre la solution au moins legerement acide.
PCT/US1981/000920 1980-07-25 1981-07-06 Solution de liquide radiochromique Ceased WO1982000527A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP50264581A JPS58501091A (ja) 1980-07-25 1981-07-06 放射線着色性溶液
DE19813152187 DE3152187A1 (de) 1980-07-25 1981-07-06 Radiochromic liquid solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17225080A 1980-07-25 1980-07-25
US172250800725 1980-07-25

Publications (1)

Publication Number Publication Date
WO1982000527A1 true WO1982000527A1 (fr) 1982-02-18

Family

ID=22626911

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1981/000920 Ceased WO1982000527A1 (fr) 1980-07-25 1981-07-06 Solution de liquide radiochromique

Country Status (4)

Country Link
FR (1) FR2487526B1 (fr)
GB (1) GB2101460B (fr)
SE (1) SE8201863L (fr)
WO (1) WO1982000527A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0618462A3 (fr) * 1993-03-31 1995-03-29 Autotype Int Ltd Détection de rayons gamma.

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441561A (en) * 1943-07-23 1948-05-18 Chalkley Lyman Photochemical preparation of stable dyes
US2528496A (en) * 1946-04-30 1950-11-07 Chalkley Lyman Photosensitive leucocyanide composition
US2664511A (en) * 1949-11-01 1953-12-29 Patterson Moos & Company Inc Dosimeter
US2676887A (en) * 1950-11-03 1954-04-27 Chalkley Lyman Photochemical process and product
US2844465A (en) * 1954-03-17 1958-07-22 Chalkley Lyman Photographic process
US2877166A (en) * 1957-04-02 1959-03-10 Chalkley Lyman Dye cyanides and photosensitive compositions containing same
US2877167A (en) * 1957-06-19 1959-03-10 Chalkley Lyman Hydrophilic cyanide of para-amino triphenylmethane dyes
US2877169A (en) * 1957-07-05 1959-03-10 Chalkley Lyman Hydrophilic dye cyanides-hydroxyalkyl compounds
US3010908A (en) * 1959-12-30 1961-11-28 Broderick Edward Fluorescent plastic scintillators
US3068178A (en) * 1959-10-14 1962-12-11 Leonard E Ravich Scintillator solution enhancers
US3226233A (en) * 1960-06-13 1965-12-28 Miehle Goss Dexter Inc Photosensitive compositions containing leucocyanides of triphenylmethane dyes
US3666683A (en) * 1969-06-09 1972-05-30 Erwin Maeder Scintillation counting composition containing oxdiazole
US3710109A (en) * 1970-05-27 1973-01-09 L Chalkley Precision dosimetry of high energy radiation

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441561A (en) * 1943-07-23 1948-05-18 Chalkley Lyman Photochemical preparation of stable dyes
US2528496A (en) * 1946-04-30 1950-11-07 Chalkley Lyman Photosensitive leucocyanide composition
US2664511A (en) * 1949-11-01 1953-12-29 Patterson Moos & Company Inc Dosimeter
US2676887A (en) * 1950-11-03 1954-04-27 Chalkley Lyman Photochemical process and product
US2844465A (en) * 1954-03-17 1958-07-22 Chalkley Lyman Photographic process
US2877166A (en) * 1957-04-02 1959-03-10 Chalkley Lyman Dye cyanides and photosensitive compositions containing same
US2877167A (en) * 1957-06-19 1959-03-10 Chalkley Lyman Hydrophilic cyanide of para-amino triphenylmethane dyes
US2877169A (en) * 1957-07-05 1959-03-10 Chalkley Lyman Hydrophilic dye cyanides-hydroxyalkyl compounds
US3068178A (en) * 1959-10-14 1962-12-11 Leonard E Ravich Scintillator solution enhancers
US3010908A (en) * 1959-12-30 1961-11-28 Broderick Edward Fluorescent plastic scintillators
US3226233A (en) * 1960-06-13 1965-12-28 Miehle Goss Dexter Inc Photosensitive compositions containing leucocyanides of triphenylmethane dyes
US3666683A (en) * 1969-06-09 1972-05-30 Erwin Maeder Scintillation counting composition containing oxdiazole
US3710109A (en) * 1970-05-27 1973-01-09 L Chalkley Precision dosimetry of high energy radiation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RADIAT. PHYS. CHEM., volume 9, no. 4-6, issued 1977, Humpherys, K.C., et al, pages 737-747 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0618462A3 (fr) * 1993-03-31 1995-03-29 Autotype Int Ltd Détection de rayons gamma.

Also Published As

Publication number Publication date
FR2487526A1 (fr) 1982-01-29
SE8201863L (sv) 1982-03-24
FR2487526B1 (fr) 1985-08-02
GB2101460B (en) 1984-08-01
GB2101460A (en) 1983-01-12

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