WO2024028538A1 - A method for determining exposure to nuclear radiation - Google Patents
A method for determining exposure to nuclear radiation Download PDFInfo
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- WO2024028538A1 WO2024028538A1 PCT/FI2023/050449 FI2023050449W WO2024028538A1 WO 2024028538 A1 WO2024028538 A1 WO 2024028538A1 FI 2023050449 W FI2023050449 W FI 2023050449W WO 2024028538 A1 WO2024028538 A1 WO 2024028538A1
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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
- G01T1/10—Luminescent dosimeters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T7/00—Details of radiation-measuring instruments
Definitions
- the present invention relates to a method for determining exposure of a sensor material to nuclear radiation.
- the present invention also relates to a dosimeter.
- Hackmanite which is a variety of sodalite material, is a natural mineral having the chemical formula of Na 8 Al 6 Si 6 O 24 (Cl,S) 2 .
- a synthetic hackmanite-based material can be prepared and these materials can also be called hackmanites.
- Another aim of the invention is to provide a wearable dosimeter or other easily transportable devices for detecting past irradiation.
- a particular aim is also to provide a passive gamma-detector, i.e. one that does not require electronic devices for the detection as such.
- a method for determining exposure of a used sensor material to nuclear radiation comprising - exposing the used sensor material to ultraviolet or X-radiation to induce colouration, - subjecting the used sensor material to a measurement by a device configured to measure visible light to obtain a measured spectrum of reflected, transmitted, or detected light, - using at least one of - a comparison of a calculated ratio of intensity values of the used sensor material and a calculated ratio of intensity values of the sensor material un-exposed to nuclear radiation, wherein the ratios of intensity values are calculated from at least two different points of the measured spectra of reflected, transmitted, or detected light, - a comparison of a difference spectrum of reflected, transmitted or detected light to a baseline, wherein the difference spectrum is calculated as a difference between the measured spectrum of reflected, transmitted or detected light of the used sensor material and the measured spectrum of reflected, transmitted, or detected light of the sensor material un-exposed to nuclear radiation, - determining that the used sensor material has been exposed to
- dosimeter for gamma irradiation comprising as sensor material material represented by formula (I).
- Figure 1 illustrates reflectance spectra of a Na 8 Al 6 Si 6 O 24 (Br,S) 2 . sample exposed to different air kerma values from a 60 Co source.
- Figure 2 illustrates a ratio of two different components in the reflectance spectra of Figure 1.
- Figure 3 illustrates reflectance spectra of a Na 8 Al 6 Si 6 O 24 (Cl,S) 2 sample exposed to a 7- kGy air kerma value from a 60 Co source.
- the present description relates to a method for determining exposure of a used sensor material to nuclear radiation, the method comprising - exposing the used sensor material to ultraviolet or X-radiation to induce colouration, - subjecting the used sensor material to a measurement by a device configured to measure visible light to obtain a measured spectrum of reflected, transmitted, or detected light, - using at least one of - a comparison of a calculated ratio of intensity values of the used sensor material and a calculated ratio of intensity values of the sensor material un-exposed to nuclear radiation, wherein the ratios of intensity values are calculated from at least two different points of the measured spectra of reflected, transmitted, or detected light, - a comparison of a difference spectrum of reflected, transmitted or detected light to a baseline, wherein the difference spectrum is calculated as a difference between the measured spectrum of reflected, transmitted or detected light of the used sensor material and the measured spectrum of reflected, transmitted, or detected light of the sensor material un-exposed to nuclear radiation, - determining that the used sensor material
- the present method thus allows to determine whether the sensor material has been subjected to nuclear radiation or not.
- the method is thus based on the fact that these types of materials, commonly called hackmanites, are permanently altered when exposed to nuclear radiation. Indeed, the structural changes in the hackmanite structure, under the effect of nuclear radiation, result in additional absorption bands in the reflectance spectrum of the material. Thus, the hackmanite’s reflectance spectrum’s shape changes upon exposure to nuclear radiation, and thus the material can also remember previous exposure while still remaining radio- and photochromically fully functional making it a unique memory material.
- This colouration ability has potential use in dosimetry and as nuclear radiation memory proving that hackmanite can be used as an environmentally friendly, non-toxic, low-cost and reusable material for detecting high doses of high-energy radiation.
- the nuclear radiation can be alpha or beta particles, positrons, or gamma radiation.
- the nuclear radiation is gamma radiation.
- hackmanites can thus be used to probe whether the sample has experienced gamma radiation at some point of its life, making it a potential material for defence, space, nuclear facility, and other similar applications. It does not matter whether hackmanite has bleached, since simple UV- or X-ray colouration can be used to reveal the additional colour centre.
- the present method may therefore be used for example for gamma dose mapping in high dose applications as well as a memory material that has the one-of-a-kind ability to remember earlier gamma exposure.
- the method may also be used for monitoring various radiation sources, for example to ensure the radiation is not scattered to areas it should not be directed to, or to use for monitoring the amount of radiation a person is receiving within a given time frame.
- the present method also makes it possible to manufacture a passive gamma radiation detector, where the coloration caused by the radiation can be seen with a naked eye, and electronic devices are only needed for determining the dose level or previous gamma exposure from the detector after exposure, but not during the exposure as such.
- the present method may be used in tenebrescence imaging for dense objects as well as for monitoring food irradiation, sterilisation of food or medical packaging or devices, or similar.
- this memory effect which is shown in the Experimental part, is due to a particular property of hackmanites. Indeed, sodium atoms can move inside the hackmanite and even exit the structure. It is thus presumed that under high-energy radiation such as gamma irradiation a sodium atom is removed from the surrounding of the V Cl leading to a defect that can be noted Na 3 V Cl (i.e. a chlorine vacancy surrounded by three Na atoms).
- the material fulfils the general formula (I).
- the method presented here has an advantage of not requiring batch- specific lookup tables, but only material specific. Batch-specific lookup tables are necessary in other methods exploiting only one component of the visible spectrum due to the fact that the depth of colouration changes from batch to batch. Multicomponent analysis of the spectrum reveals a ratio of different colour centres in the material, which eliminates the requirement of measuring a batch-specific standard series to determine the level of exposure of a sample.
- the term “spectrum” can be used to denote the spectrum of reflected, transmitted or detected light.
- used sensor material denotes a sensor material that has been used, and for which it is typically not known to what radiation (if any) it has been exposed to.
- sensor material denotes the material comprising a material represented by formula (I). Most typically, the used sensor material and the sensor material to which it is compared to are the same material as to their chemical composition of the material of formula (I). They do however not need to be of a same batch, as the property used for this method is independent of the batch and depends only on the chemical composition of the material of formula (I). According to an embodiment, a is a value of 0.0002 – 4, such as 0.001 – 4 or 0.05 – 4.
- the raw materials for preparing the material represented by formula (I) have some impurities, which mean that a is different from 0 (zero) in the material.
- the value of a can thus be for example from 0.0002, 0.0003, 0.0005, 0.0007, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.01, 0.05, 0.1, 0.4, 0.7, 1, 1.5, 2, 2.5, 3, or 3.5 up to 0.0003, 0.0005, 0.0007, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.01, 0.05, 0.1, 0.4, 0.7, 1, 1.5, 2, 2.5, 3, 3.5, or 4.
- the used, bleached sensor material is exposed to ultraviolet or X-radiation to induce colouration.
- the radiant UV exposure can be for example 1 ⁇ 10000 mJ/cm 2 , such as about 200 mJ/cm 2 for inducing the colouration, and the absorbed dose for X-radiation can be in the order of 0.001 ⁇ 1000000 Gy, such as 1 Gy, or alternatively the equivalent dose can be in the order of 0.001 ⁇ 1000000 Sv, such as 0.05 Sv.
- the used sensor material After exposure, the used sensor material is subjected to a measurement by a device configured to measure visible light to obtain a measured spectrum of reflected, transmitted or detected light.
- the device is typically a spectrometer.
- the steps of exposure and measurement as such are known to a person skilled in the art.
- the present method includes two possible ways of detecting or determining whether the used sensor material has been exposed to nuclear radiation. It is possible to use one of the ways or both at the same time.
- One of the ways makes use of ratio of intensity values, the other of difference spectrum of reflected, transmitted, or detected light and a baseline. In the case of ratio of intensity values, these are obtained from the spectrum of spectrum of reflected, transmitted, or detected light. The values are taken at same points of the spectrum, and it is also possible to compare two ranges of values.
- the intensity value can be taken at 550 and 650 nm, or from a range of 530-570 nm and 600- 700 nm.
- the values are thus taken at at least two points, and preferably are taken at several points for increased accuracy of the method.
- the method further comprises determining the amount of radiation to which the used sensor material has been exposed, by comparing the calculated ratio of intensity values of a spectrum of reflected, transmitted, or detected light of the used sensor material, to calculated ratio of intensity values of the sensor material exposed to known amounts of nuclear radiation.
- the method further comprises, prior to exposing the used sensor material to ultraviolet or X-radiation, bleaching the used sensor material of colouration.
- This step is optional if the used sensor material has already been de-coloured but may be required if this is not the case.
- the bleaching may be carried out with heat or white light.
- heat a temperature such as 50 ⁇ 500 0C, for example 200 0C is sufficient.
- white light the luminous exposure needs to be sufficient, such as 100 ⁇ 1000000000 lux seconds.
- information for the sensor material un-exposed to nuclear radiation and optional information for the sensor material exposed to known amounts of nuclear radiation is thus contained in a database.
- the database may comprise at least one of a lookup table and a graph.
- the ratios of intensity values and/or the spectra of reflected, transmitted or detected light and corresponding radiation values, as needed, are given, and are based on measurements and calculations carried out in controlled conditions, i.e. where the amount of radiation used is known.
- the database can, in addition to being a lookup table, also be any other suitable form of data structure.
- the database may be used automatically (i.e. the process may be computerised), or it may be used manually.
- the amount of radiation to which the material has been subjected to can be determined either qualitatively or quantitatively.
- the nuclear radiation may thus have a wavelength from 0.1 zm (zeptometre, i.e.
- 1.0 x 10- 21 m 500 zm, 1 am (attometre, i.e. 1.0 x 10 -18 m), 500 am, 1 fm (femtometre, i.e. 1.0 x 10 -15 m), 500 fm, or 1 pm (picometre, i.e. 1.0 x 10 -12 m) up to 500 zm, 1 fm, 500 fm, 1 pm, or 10 pm.
- the wavelength range of gamma radiation is 1 zm – 10 pm.
- the nuclear radiation can be alpha or beta particles, positrons, or gamma radiation. In particular, the nuclear radiation is gamma radiation.
- dosimeter for gamma irradiation comprising as sensor material a material represented by formula (I).
- This dosimeter is a passive dosimeter, which is thus easy to make and light weight to carry (i.e. can be made for example to a form that can be placed in a pocket).
- dosimeters for alpha and/or beta particle radiation, or positron radiation are also provided.
- the energy of the nuclear radiation which past presence and/or amount can be determined with the present method is for example 1 keV – 1000 TeV, such as 40 keV – 2 MeV.
- the upper limit may even be up to 2000 TeV.
- the sensor material is potentially exposed to said nuclear radiation for a period of time. This period of time the sensor material is exposed to radiation may be up to ten years. For example, this period of time may be up to 5, 10, 15, 30 or 45 minutes, 1, 5, 10, 15 or 20 hours, 1, 5, 10, 15, 20, 25 or 30 days or 1, 5 or 10 years.
- the time is typically dependent on the application the method is used for, i.e.
- the material of formula (I) is an optically active material that is configured to be able to retain radiation exposed thereon, i.e. the material is able to trap therein the radiation that it is exposed to.
- M1’ represents a monovalent monoatomic cation of an alkali metal selected from a group consisting of Na, Li, K, Rb, Cs, and Fr, or any combination of such cations. In another embodiment, M1’ does not represent the monoatomic cation of Na alone.
- M1’ represents a combination of at least two monoatomic cations of different alkali metals selected from a group consisting of Li, Na, K, Rb, Cs, and Fr.
- M1’ represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements.
- the stoichiometric number in M1’ adjusts to keep the overall charge of 8+ for the M1’ +M2’ combination.
- M1’ represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, wherein the combination comprises at most 98 mol-%, at most 95 mol-%, at most 90 mol-%, at most 85 mol-%, at most 80 mol-%, at most 70 mol-%, at most 60 mol-%, at most 50 mol-%, at most 40 mol-% of the monoatomic cation of Na, or at most 30 mol-% of the monoatomic cation of Na, or at most 20 mol-% of the monoatomic cation of Na.
- M1’ represents a monoatomic cation of Li.
- M1’ represents a monoatomic cation of K. In one embodiment, M1’ represents a monoatomic cation of Rb. In one embodiment, M1’ represents a monoatomic cation of Cs. In one embodiment, M1’ represents a monoatomic cation of Fr.
- M2’ represents a divalent monoatomic cation of an alkaline earth metal selected from a group consisting of Be, Mg, Ca, Sr, Ba, and Ra, or any combination of such cations. In one embodiment, M2’ represents a combination of at least two monoatomic cations of different alkaline earth metals selected from Group 2 of the IUPAC periodic table of the elements.
- M’’ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC periodic table of the elements, or any combination of such cations.
- M’’ represents a trivalent monoatomic cation of a transition element selected from any of Groups 3 – 12 of the IUPAC periodic table of the elements, or any combination of such cations.
- M’’ represents a trivalent monoatomic cation of a metal selected from a group consisting of Al and Ga, or a combination of such cations.
- M’’ represents a trivalent monoatomic cation of B.
- M’’ represents a trivalent monoatomic cation of a metal selected from a group consisting of Al and Ga, or a combination of such cations.
- M’’ represents a trivalent monoatomic cation of B.
- M’’ represents a trivalent monoatomic cation of a transition element selected from Period 4 of the IUPAC periodic table of the elements, or any combination of such cations.
- M’’ represents a trivalent monoatomic cation of an element selected from a group consisting of Cr, Mn, Fe, Co, Ni, and Zn, or any combination of such cations.
- M’’’ represents a monoatomic cation of an element selected from a group consisting of Si and Ge, or a combination of such cations.
- X represents an anion of an element selected from a group consisting of F, Cl, Br, I, and At, or any combination of such anions.
- X represents an anion of an element selected from a group consisting of F, Cl, Br, and I, or any combination of such anions.
- X is absent.
- X’ represents an anion of an element selected from a group consisting of O, S, Se, and Te, or any combination of such anions.
- X’ represents an anion of one or more elements selected from a group consisting of O, S, Se, and Te, or any combination of such anions.
- X’ represents a monoatomic or a polyatomic anion of one or more elements selected from a group consisting of O, S, Se, and Te, or any combination of such anions.
- X’ represents an anion of S.
- X’ is (SO 4 ) 2- or other sulphur oxyanion.
- X’ is absent.
- the material is doped with at least one transition metal ion.
- M’’’’ represents a dopant or it is absent.
- M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements, or from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations.
- the dopant may be any element or combination of elements.
- the dopant may for example be an element that does not take part in the functioning of the material.
- the material is represented by formula (I), wherein M’’’’ represents a cation of an element selected from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations.
- M’’’’ represents a cation of an element selected from transition metals of the f-block of the IUPAC periodic table of the elements. In one embodiment, M’’’’ represents a cation of an element selected from transition metals of the d-block of the IUPAC periodic table of the elements. In one embodiment, M’’’’ represents a cation of an element selected from a group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, W, and Zn, or any combination of such cations. In one embodiment, M’’’’ represents a cation of Ti.
- M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements. In one embodiment, M’’’’ represents a cation of an element selected from a group consisting of Yb, Er, Tb, and Eu, or any combination of such cations. In one embodiment, M’’’’ represents a combination of two or more dopant cations. In one embodiment, the material is represented by formula (I), wherein M’’’’’ is absent. In this embodiment, the material is not doped.
- the material represented by the formula (I) comprises M’’’’ in an amount of 0.001 – 10 mol-%, or 0.001 - 5 mol-%, or 0.1 – 5 mol-% based on the total amount of the material.
- the material represented by formula (I) comprises residuals. These residuals originate from the manufacturing process of the material and may be present in an amount of up to 1 mol-% or even more, such as up to 10 mol-%.
- the material represented by formula (I) is selected from a group consisting of: (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cr) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Si 6 O 24 (Cl,
- LiNa 7 Al 6 Si 6 O 24 (Br,S) 2 :Sr where the amount of Sr varies from 0.0004to 6 mol-%, for example from 3 to 6 mol-%.
- Some other suitable ranges are 0.0004 – 0.005 mol-%, 0.0004 – 0.05 mol-%, 0.005 – 0.05 mol-%, 0.05 – 1 mol %, and 0.05 – 3 mol-%.
- the material may also comprise Cu, for example in the amount of 1 mol- %.
- Some suitable materials represented by formula (I) can be selected from a group consisting of: (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cr) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Si 6 O 24 (Br,S
- the material may be synthesised by a reaction according to Norrbo et al. (Norrbo, I.; G ⁇ uchowski, P.; Paturi, P.; Sinkkonen, J.; Lastusaari, M., Persistent Luminescence of Tenebrescent Na 8 Al 6 Si 6 O 24 (Cl,S) 2 : Multifunctional Optical Markers. Inorg. Chem.2015, 54, 7717-7724), which reference is based on Armstrong & Weller (Armstrong, J.A.; Weller, J.A. Structural Observation of Photochromism. Chem. Commun. 2006, 1094- 1096).
- Zeolite A and Na 2 SO 4 as well as LiCl, NaCl, KCl and/or RbCl can be used as the starting materials.
- At least one dopant may be added as an oxide, such as TiO 2 , a chloride, a sulfide, a bromide, or a nitrate.
- the material can be prepared as follows: Zeolite A may first be dried at 500 °C for 1 h. The initial mixture may then be heated at 850 °C in air for e.g.2 h, 5 h, 12 h, 24 h, 36 h, 48 h, or 72 h. The product may then be freely cooled down to room temperature and ground.
- the product may be re-heated at 850 °C for 2 h under a flowing 12 % H 2 + 88 % N 2 atmosphere.
- the as-prepared materials may be washed with water to remove any excess LiCl/NaCl/KCl/RbCl impurities. The purity can be verified with an X-ray powder diffraction measurement.
- the material is prepared in powder form and is typically also used in powder form. The particle size in the powder is typically about 5-10 ⁇ m, as measured by transmission electron microscopy, the area was determined from the pictures with a watershed segmentation algorithm in the ImageJ program.
- the material of the present description is typically non-toxic and non-expensive.
- the method described above may also comprise, at its beginning, arranging the sensor material in a polymer matrix.
- the material can be arranged in a polymer matrix by using tape casting, also known as knife coating or doctor blading.
- Tape casting is a process where a thin sheet of ceramic or metal particle suspension fluid is cast on a substrate.
- the fluid may contain volatile nonaqueous solvents, a dispersant, (a) binder(s) and the dry matter, i.e. the material having formula (I).
- the process may comprise preparing the suspension and applying it onto a surface of a substrate.
- the binder may create a polymer network around the dry matter particles, while the plasticiser may function as a softening agent for the binder.
- the tape When combining these substances, the tape may become resistant against cracking and flaking off when bent.
- the dispersant may be used to de-aggregate the particles and homogenise the suspension.
- the material is arranged in a polymer matrix by mixing the material with the tape casting components. Any suitable and typical tape casting components can be used, as known in the art.
- the tape casting components comprise ethanol Aa, ethyl methyl ketone, triton X-100, benzyl butyl phthalate and polyvinyl butyral.
- the polymer matrix, i.e. tape-casting polymer can comprise one or several different polymers. Any polymer capable to act as an energy converter, i.e.
- the polymer can be a silicone elastomer, benzyl butyl phthalate or polyvinyl butyral or any combination thereof.
- the material according to formula (I) may be attached to a surface for example as a coating or a film.
- the substrate of the plate or detector may comprise or consist of glass or polymer.
- the substrate may comprise or consist of a glass layer or a polymer layer.
- the substrate may comprise (a) further layer(s).
- the substrate may also or alternatively comprise an attachment layer, such as a printing paper, and/or a base layer, such as a cardboard layer, or any other layer(s) where desired or needed.
- the detector may comprise further layers and/or components.
- the detector has the added utility of enabling the use of the material represented by formula (I) as a detector material.
- the detector has a further added utility of making use of an optically active material being non- toxic and non-expensive compared to currently used materials such as Ba(F,Cl,Br,I) 2 :Eu and CsI:Ti.
- the detector provided it has not been exposed to nuclear radiation, has still an added utility of being reusable and recyclable.
- the detector can be reused and recycled, however the effect of exposure to nuclear radiation cannot be deleted, but rather, the material shows a total exposure to nuclear radiation during the life of the detector. Further, the detector can be used for point- of-care analysis without the need of complicated analysis systems.
- the present description further relates to a device, wherein the device comprises a material according to one or more embodiments described in this specification.
- the device is a gamma radiation sensor, a gamma radiation detector, a gamma radiation indicator, a gamma radiation dose indicator, a positron radiation sensor, a positron radiation detector, a positron radiation indicator, a positron radiation dose indicator, an alpha and/or beta particle radiation sensor, an alpha and/or beta particle radiation detector, an alpha and/or beta particle radiation indicator, or an alpha and/or beta particle radiation dose indicator.
- the device is a gamma radiation sensor for gamma radiation therapy, e.g. gamma knife surgery/radiation therapy.
- the device may also be an alpha or beta particle radiation sensor for alpha or beta particle radiation therapy, e.g.
- the device is a sensor or detector in space applications for detection direction or source or intensity or wavelengths of radiation of gamma radiation or direction or source or intensity of alpha and/or beta particle radiation or direction or source or intensity of positron radiation.
- the present method may further be used for monitoring counterfeit goods.
- a small device comprising a known compound of formula (I) as defined above is attached to a goods at its manufacturing site. Should there be suspicion of a counterfeit product being imported for example, the goods may be subject to gamma radiation for a pre-determined amount of time, and the resulting intensity of colour of the light measured. If such intensity of colour differs from what the manufacturer has indicated, it may be concluded that the product is counterfeit.
- One example of using hackmanite in an industrial product line that sterilises foodstuff is as follows. Different hackmanite sample films are irradiated with known doses of gamma radiation and the colouration is measured with a digital camera. These values are used to construct a calibration curve that will be used with this type of hackmanite films. Non-coloured hackmanite films are placed under a gamma radiation source in the product line, and the subsequent colouration is measured again with a digital camera and compared with the calibration curve. A dose distribution map is constructed for the gamma source in the product line, enabling the radiation user to determine the area of lowest acceptable dose.
- compositions were determined using X-ray fluorescence.
- the mixture of powders was ground by hand in an agate mortar and transferred to an alumina crucible and heated at 850 °C in air atmosphere for 2 h and let to cool passively to room temperature.
- the sample was ground and heated to 850 °C in a flowing N 2 /H 2 (88/12 %) atmosphere for 2 h and let to cool passively to room temperature.
- the sample was ground once again to yield the finished end product.
- the hackmanite powders were cast as 80 ⁇ m thick flexible green tapes in order to fix them easily to their positions in the exposure chamber, and also to measure their reflectance spectra easily. X-ray powder diffraction measurements were carried out to establish the samples’ purity.
- the equipment used was a PANalytical Empyrean using CuK ⁇ 1,2 , radiation with wavelengths 1.5406 (K ⁇ 1 ) and 1.5444 ⁇ (K ⁇ 2 ).
- Photochromic activity under UV and X irradiation were tested with a UVP UVLS-24 UV lamp operating with 4 W at 254 nm and a PANalytical Epsilon 1 X-ray fluorescence spectrometer equipped with an Ag tube (K ⁇ emission at ca.22 keV).
- Preliminary irradiation tests were carried out with a number of different nuclides, as shown in Table 1, which gives the predominating energy lines.
- the materials were irradiated free in air in collimated Co-60 gamma ray beam.
- the gamma radiation qualities were established according to ISO standard 4037-1:2019.
- the materials were set up so that the samples were perpendicular to the beam and facing towards the source.
- the doses were controlled by adjusting the samples’ distance from the source and the exposure time.
- Exposure to beta radiation (positrons) was performed by pipetting 18F-water (3 ⁇ l in triplicate) with a measured activity concentration (Veenstra VDC-405 dose calibrator) directly on the film.
- the light source was either a 60 W incandescent light bulb (colour fading measurements) or an Ocean Optics LS-1 Cal calibration lamp (other measurements) directed towards the sample 20 cm away.
- the tenebrescence bleaching spectra and fading curves were compiled from reflectance spectra recorded for a fully coloured sample. The full colouration was obtained by 7000 Gy of Co-60 gamma radiation, 2 h of X-ray exposure in PANalytical Epsilon 1 XRF machine (Ag tube with peak intensity at ca. 22 keV) or 1 min of 254 nm UV irradiation.
- the sample was irradiated with selected wavelengths from a 150 Xe lamp.
- the wavelengths were adjusted using a LOT MSH300 monochromator.
- the bleaching time at each wavelength was 10 min for sample Li, 1 min for sample Br, 1 min for sample Na and 30 s for sample Rb due to material-specific differences in the optical energy needed to induce a visible change in the reflectance spectrum.
- the Raman spectra were recorded using an inVia Qontor confocal Raman microscope (Renishaw, Gloucestershire, UK) using 785 nm continuous wave laser excitation.
- XPS measurements were carried out using Perkin Elmer PHI 5400 ESCA and Thermo Scientific NEXSA XPS systems using Mg and monochromated Al X-ray sources respectively. Measurement time was limited to as low as possible to minimise X-ray-induced sample colouring during the measurement.
- the XPS signal widths were quantified using Gaussian fitting in the Origin 2016 program. Geometry optimisations calculations were performed in periodic boundary condition (PBC) within the density functional theory (DFT) framework.
- PBC periodic boundary condition
- DFT density functional theory
- the global hybrid functional PBE0 was used along with the ab-initio CRYSTAL17 code and localised (Gaussian) basis sets. All-electron double- ⁇ basis sets with polarisation functions were used for Si ([4s3p1d]/(20s12p1d)), Al ([4s3p1d]/(17s9p1d)), O ([3s2p1d]/(10s4p1d)), and Cl ([4s3p1d]/(16s10p1d)), while all-electron triple- ⁇ basis sets with polarisation functions were used for Na ([4s3p1d]/(15s7p1d).
- TD-DFT calculations were done using the Gaussian16 code along with the B3LYP functional on clusters extracted from the geometries optimised in PBC.
- the clusters were embedded in a sphere of pseudopotentials and an array of point charges. These point charges are used to simulate the Madelung potential of the crystal and were obtained through the Ewald package, using a 5 X 5 X 5 supercell. The fitting procedure led to an RMS error lower than 1 ⁇ V on the Ewald potential.
- Results Preliminary tests with gamma, alpha and beta radiation The materials’ purity was first checked with X-ray powder diffraction and then their photochromic activity under UV and X-rays was confirmed as an initial proof of the samples being able to change colour under radiation treatment.
- the reflectance spectra indicate that the reflectance minimum is always centred at around 530 nm, i.e. at the same wavelength obtained previously with UV and X-ray irradiation.
- some sources also induced narrower bands. These bands, observed at ca. 480 and 600 nm, were most prominent in the samples exposed to alpha-emitting nuclides, i.e. Am-241, depleted uranium and Pb-210. These additional bands will be discussed below.
- Figure 1 illustrates reflectance spectra of a Na 8 Al 6 Si 6 O 24 (Br,S) 2 sample exposed to different air kerma values from a 60 Co source, the white reference being a non-exposed, white sample.
- Comparison with X-ray induced photochromism For the comparison of photochromism induced by different radiation types, Na 8 Al 6 Si 6 O 24 (Cl,S) 2 , was again used as an example.
- the absorption spectrum of the colour centre is similar for UV, X-ray and gamma, alpha or beta induced photochromism, i.e. centred around the same wavelength.
- the additional peaks do not have any effect on the perceived colour.
- the optical bleaching spectrum of the gamma-induced colour is very similar to that of X-ray-induced colour.
- the bleaching spectrum shifts by ca.100 nm to 450 nm.
- the fading is single exponential.
- the lifetimes obtained with single exponential fitting are 16.4 ⁇ 0.1 (main peak), 13.5 ⁇ 0.2 (blue side) and 14.8 ⁇ 0.2 min (red side).
- the fading is very similar in all these three ranges.
- the fading curve of the main peak of the gamma-induced colour is clearly not linear when plotted with logarithmic intensity scale, i.e. it is multi-component exponential.
- 14.9 ⁇ 1.8 (30 % amplitude) and 187 ⁇ 67 min (70 %) as the lifetimes for the main peak are obtained.
- the former lifetime is similar to that of UV-induced colouring, and it can be assigned to the same colour centre.
- the main colour centre is similar to what is present in UV- and X-ray- induced photochromism, but with gamma and alpha irradiation there are additional absorbing species that affect the overall energetics of photochromism. The origin of the two additional reflectance signals will be discussed in more detail below.
- Figure 2 illustrates a ratio of two different components in the reflectance spectra of Figure 1 and shows how it is dependent on the irradiation dose.
- Figure 3 illustrates reflectance spectra of a Na 8 Al 6 Si 6 O 24 (Cl,S) 2 sample exposed to a 7- kGy air kerma value from a 60 Co source, the same sample after bleaching and recolouring with 254 nm UV, and also a non-exposed sample coloured with 254 nm UV.
- the Figure clearly shows how the fact that the material has been exposed to gamma radiation has a different reflectance than the material un-exposed to gamma radiation. As shown above, hackmanite’s colour intensity increases with increasing gamma dose.
- compositions of hackmanite Na 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Li,Na) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Na,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Rb,Na) 8 Al 6 Si 6 O 24 (Cl,S) 2 and Na 8 Al 6 Si 6 O 24 (Br,S) 2 were tested. These compositions were chosen to investigate if changing the contents of the beta cage would affect the performance. Once the dose is high enough, a very intense colouring was obtained. The overall colour intensity vs. dose curves were rather similar for each of the studied materials and clearly the overall colour intensity can be calibrated to indicate the radiation dose.
- the hackmanites’ colour becomes visible to the naked eye at doses of 1000 Gy and higher when irradiating with gamma radiation from Co- 60.
- doses 1000 Gy and higher when irradiating with gamma radiation from Co- 60.
- This dose range is clearly much too high than would be feasible for a dosimeter to be used to monitor people’s radiation exposure, since 100 Gy can result to instant death.
- the doses are only in the range of tens or hundreds of cGy to a few Gy.
- the hackmanites’ working range fits very well with that used in food irradiation. It typically employs doses from 1 to 50 kGy, but in many cases the highest allowed dose is less, e.g.150 Gy for potatoes and onions.
Abstract
The present invention relates to a method for determining exposure of a used sensor material to nuclear radiation, the method comprising exposing the used sensor material to ultraviolet or X-radiation to induce colouration, measuring a spectrum of reflected, transmitted, or detected light, and comparing the results to known results to determine that the used sensor material has been exposed to nuclear radiation. The sensor material comprises hackmanites.
Description
A METHOD FOR DETERMINING EXPOSURE TO NUCLEAR RADIATION FIELD The present invention relates to a method for determining exposure of a sensor material to nuclear radiation. The present invention also relates to a dosimeter. BACKGROUND AND OBJECTS Hackmanite, which is a variety of sodalite material, is a natural mineral having the chemical formula of Na8Al6Si6O24(Cl,S)2. A synthetic hackmanite-based material can be prepared and these materials can also be called hackmanites. These synthetic materials are described for example in WO 2017/194825 and WO 2017/194834, and can be used for various devices, such as for detecting and indicating the intensity of a radiation (as described in WO 2019/092309) or for determining the amount of radiation (as described in WO 2019/092308). In the method described in WO 2019/092308, the amount of radiation is determined based on an amount of visible light emitted by a sensor material as a result of being subjected to heat treatment and/or to optical stimulation. It is an aim of the present invention to provide a method for determining whether a material has been exposed to certain types of radiation, especially for gamma radiation. Another aim of the invention is to provide a wearable dosimeter or other easily transportable devices for detecting past irradiation. A particular aim is also to provide a passive gamma-detector, i.e. one that does not require electronic devices for the detection as such. SUMMARY OF THE INVENTION The invention is defined by the features of the independent claims. Some specific embodiments are defined in the dependent claims. According to a first aspect, there is provided a method for determining exposure of a used sensor material to nuclear radiation, the method comprising - exposing the used sensor material to ultraviolet or X-radiation to induce colouration,
- subjecting the used sensor material to a measurement by a device configured to measure visible light to obtain a measured spectrum of reflected, transmitted, or detected light, - using at least one of - a comparison of a calculated ratio of intensity values of the used sensor material and a calculated ratio of intensity values of the sensor material un-exposed to nuclear radiation, wherein the ratios of intensity values are calculated from at least two different points of the measured spectra of reflected, transmitted, or detected light, - a comparison of a difference spectrum of reflected, transmitted or detected light to a baseline, wherein the difference spectrum is calculated as a difference between the measured spectrum of reflected, transmitted or detected light of the used sensor material and the measured spectrum of reflected, transmitted, or detected light of the sensor material un-exposed to nuclear radiation, - determining that the used sensor material has been exposed to nuclear radiation, if - the calculated ratio of intensity values of the used sensor material differs from the ratio of intensity values of the sensor material un-exposed to nuclear radiation, and/or - the difference spectrum differs from the baseline, wherein the sensor material comprises a material represented by formula (I) (M1’ 8-2a M2’ a )(M’’ 14-(4b/3) M’’’ b )O 24 (X 2-dc dX’ n c- ):M’’’’ (I) wherein - M1’ represents a monovalent monoatomic cation of an alkali metal selected from Group 1 of the IUPAC periodic table of the elements, or any combination of such cations; - M2’ represents a divalent monoatomic cation of an alkaline earth metal selected from Group 2 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC periodic table of the elements, or of a transition element selected from any of Groups 3 – 12 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’’ represents a monoatomic cation of an element selected from Group 14 of the IUPAC periodic table of the elements, or any combination of such cations;
- X represents an anion of an element selected from the halogens of Group 17 of the IUPAC periodic table of the elements, or any combination of such anions; - X’ represents an anion of one or more elements selected from the chalcogens of Group 16 of the IUPAC periodic table of the elements, or any combination of such anions; - M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements, or from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations, or wherein M’’’’ is absent; - a is a value of 0 – 4; - b is a value of 1 – 10; - c is a value of 1, 2, 3, or 4; - d is a value of above 0 – 2; and - n is a value of 1, 2, 3, or 4. According to a second aspect, there is provided dosimeter for gamma irradiation, comprising as sensor material material represented by formula (I). BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates reflectance spectra of a Na8Al6Si6O24(Br,S)2. sample exposed to different air kerma values from a 60Co source. Figure 2 illustrates a ratio of two different components in the reflectance spectra of Figure 1. Figure 3 illustrates reflectance spectra of a Na8Al6Si6O24(Cl,S)2 sample exposed to a 7- kGy air kerma value from a 60Co source. DETAILED DESCRIPTION The present description relates to a method for determining exposure of a used sensor material to nuclear radiation, the method comprising - exposing the used sensor material to ultraviolet or X-radiation to induce colouration, - subjecting the used sensor material to a measurement by a device configured to measure visible light to obtain a measured spectrum of reflected, transmitted, or detected light, - using at least one of
- a comparison of a calculated ratio of intensity values of the used sensor material and a calculated ratio of intensity values of the sensor material un-exposed to nuclear radiation, wherein the ratios of intensity values are calculated from at least two different points of the measured spectra of reflected, transmitted, or detected light, - a comparison of a difference spectrum of reflected, transmitted or detected light to a baseline, wherein the difference spectrum is calculated as a difference between the measured spectrum of reflected, transmitted or detected light of the used sensor material and the measured spectrum of reflected, transmitted, or detected light of the sensor material un-exposed to nuclear radiation, - determining that the used sensor material has been exposed to nuclear radiation, if - the calculated ratio of intensity values of the used sensor material differs from the ratio of intensity values of the sensor material un-exposed to nuclear radiation, and/or - the difference spectrum differs from the baseline, wherein the sensor material comprises a material represented by formula (I) (M1’ 8-2a M2’ a )(M’’ 14-(4b/3) M’’’ b )O 24 (X 2-dc dX’ n c- ):M’’’’ (I) wherein - M1’ represents a monovalent monoatomic cation of an alkali metal selected from Group 1 of the IUPAC periodic table of the elements, or any combination of such cations; - M2’ represents a divalent monoatomic cation of an alkaline earth metal selected from Group 2 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC periodic table of the elements, or of a transition element selected from any of Groups 3 – 12 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’’ represents a monoatomic cation of an element selected from Group 14 of the IUPAC periodic table of the elements, or any combination of such cations; - X represents an anion of an element selected from the halogens of Group 17 of the IUPAC periodic table of the elements, or any combination of such anions; - X’ represents an anion of one or more elements selected from the chalcogens of Group 16 of the IUPAC periodic table of the elements, or any combination of such anions;
- M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements, or from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations, or wherein M’’’’ is absent; - a is a value of 0 – 4; - b is a value of 1 – 10; - c is a value of 1, 2, 3, or 4; - d is a value of above 0 – 2; and - n is a value of 1, 2, 3, or 4. The present method thus allows to determine whether the sensor material has been subjected to nuclear radiation or not. As will be apparent below, according to an embodiment it is also possible to use the present method to determine the amount of nuclear radiation. The method is thus based on the fact that these types of materials, commonly called hackmanites, are permanently altered when exposed to nuclear radiation. Indeed, the structural changes in the hackmanite structure, under the effect of nuclear radiation, result in additional absorption bands in the reflectance spectrum of the material. Thus, the hackmanite’s reflectance spectrum’s shape changes upon exposure to nuclear radiation, and thus the material can also remember previous exposure while still remaining radio- and photochromically fully functional making it a unique memory material. This colouration ability has potential use in dosimetry and as nuclear radiation memory proving that hackmanite can be used as an environmentally friendly, non-toxic, low-cost and reusable material for detecting high doses of high-energy radiation. The nuclear radiation can be alpha or beta particles, positrons, or gamma radiation. In particular, the nuclear radiation is gamma radiation. Hackmanites can thus be used to probe whether the sample has experienced gamma radiation at some point of its life, making it a potential material for defence, space, nuclear facility, and other similar applications. It does not matter whether hackmanite has bleached, since simple UV- or X-ray colouration can be used to reveal the additional colour centre. The present method may therefore be used for example for gamma dose mapping in high dose applications as well as a memory material that has the one-of-a-kind ability to remember earlier gamma exposure. The method may also be used for monitoring various radiation sources, for example to ensure the radiation is not scattered to areas it
should not be directed to, or to use for monitoring the amount of radiation a person is receiving within a given time frame. The present method also makes it possible to manufacture a passive gamma radiation detector, where the coloration caused by the radiation can be seen with a naked eye, and electronic devices are only needed for determining the dose level or previous gamma exposure from the detector after exposure, but not during the exposure as such. Furthermore, the present method may be used in tenebrescence imaging for dense objects as well as for monitoring food irradiation, sterilisation of food or medical packaging or devices, or similar. Without wishing to be bound by a theory, it is assumed that this memory effect, which is shown in the Experimental part, is due to a particular property of hackmanites. Indeed, sodium atoms can move inside the hackmanite and even exit the structure. It is thus presumed that under high-energy radiation such as gamma irradiation a sodium atom is removed from the surrounding of the VCl leading to a defect that can be noted Na3VCl (i.e. a chlorine vacancy surrounded by three Na atoms). The comparison of the reflectance spectra of two UV-coloured hackmanite films, one having been exposed to nuclear radiation, the other one not, shows that the material with nuclear radiation exposure in its history has an additional shoulder just above 600 nm. This indicates that the Na3VCl entity created by the nuclear irradiation is permanent. The ability to be coloured and bleached, on the other hand, remained functional without any loss of sensitivity after bleaching and recolouring, even after exposure to nuclear radiation. The hackmanite thus retained its ability to be sustainably used for dose determination and dose mapping. It is believed that the material according to formula (I) is such that the results based on the spectrum of reflected, transmitted or detected light according to the present method are independent of the exact chemical formula of the material, i.e. it is sufficient that the material fulfils the general formula (I). In any case, when comparing the method of determining the amount of exposure to said radiation with other methods, e.g. determining the exposure by measuring the material’s colour intensity, the method presented here has an advantage of not requiring batch- specific lookup tables, but only material specific. Batch-specific lookup tables are necessary in other methods exploiting only one component of the visible spectrum due to
the fact that the depth of colouration changes from batch to batch. Multicomponent analysis of the spectrum reveals a ratio of different colour centres in the material, which eliminates the requirement of measuring a batch-specific standard series to determine the level of exposure of a sample. In the present application, the term “spectrum” can be used to denote the spectrum of reflected, transmitted or detected light. The term “used sensor material” denotes a sensor material that has been used, and for which it is typically not known to what radiation (if any) it has been exposed to. The term “sensor material” denotes the material comprising a material represented by formula (I). Most typically, the used sensor material and the sensor material to which it is compared to are the same material as to their chemical composition of the material of formula (I). They do however not need to be of a same batch, as the property used for this method is independent of the batch and depends only on the chemical composition of the material of formula (I). According to an embodiment, a is a value of 0.0002 – 4, such as 0.001 – 4 or 0.05 – 4. Indeed, typically the raw materials for preparing the material represented by formula (I) have some impurities, which mean that a is different from 0 (zero) in the material. The value of a can thus be for example from 0.0002, 0.0003, 0.0005, 0.0007, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.01, 0.05, 0.1, 0.4, 0.7, 1, 1.5, 2, 2.5, 3, or 3.5 up to 0.0003, 0.0005, 0.0007, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.01, 0.05, 0.1, 0.4, 0.7, 1, 1.5, 2, 2.5, 3, 3.5, or 4. As is illustrated in the Experimental part below, when aiming at a as close to 0 as possible, its value is typically in the range of 0.003 to 0.03, determined using X-ray fluorescence. In the method, the used, bleached sensor material is exposed to ultraviolet or X-radiation to induce colouration. The radiant UV exposure can be for example 1−10000 mJ/cm2, such as about 200 mJ/cm2 for inducing the colouration, and the absorbed dose for X-radiation can be in the order of 0.001−1000000 Gy, such as 1 Gy, or alternatively the equivalent dose can be in the order of 0.001−1000000 Sv, such as 0.05 Sv. After exposure, the used sensor material is subjected to a measurement by a device configured to measure visible light to obtain a measured spectrum of reflected, transmitted or detected light. The device is typically a spectrometer. The steps of exposure and measurement as such are known to a person skilled in the art.
The present method includes two possible ways of detecting or determining whether the used sensor material has been exposed to nuclear radiation. It is possible to use one of the ways or both at the same time. One of the ways makes use of ratio of intensity values, the other of difference spectrum of reflected, transmitted, or detected light and a baseline. In the case of ratio of intensity values, these are obtained from the spectrum of spectrum of reflected, transmitted, or detected light. The values are taken at same points of the spectrum, and it is also possible to compare two ranges of values. For example, the intensity value can be taken at 550 and 650 nm, or from a range of 530-570 nm and 600- 700 nm. The values are thus taken at at least two points, and preferably are taken at several points for increased accuracy of the method. In case the calculated ratio of intensity values of the used sensor material differs from the ratio of intensity values of the sensor material un-exposed to nuclear radiation, the used sensor material has been exposed to nuclear radiation. According to an embodiment, the method further comprises determining the amount of radiation to which the used sensor material has been exposed, by comparing the calculated ratio of intensity values of a spectrum of reflected, transmitted, or detected light of the used sensor material, to calculated ratio of intensity values of the sensor material exposed to known amounts of nuclear radiation. That is, a database has been previously set up with either the given sensor material or any sensor material fulfilling the formula (I), with the material having been exposed to various, known amounts and types of nuclear radiation. By comparison, it is thus possible to also determine the amount of nuclear radiation the used sensor material has been exposed to. It has indeed been noticed that when the amount of nuclear radiation increases, the spectrum becomes broader. In the case of difference spectrum, it is calculated as a difference between the measured spectrum of reflected, transmitted, or detected light of the used sensor material and the measured spectrum of reflected, transmitted, or detected light of the sensor material un- exposed to nuclear radiation. This difference spectrum is then compared to the baseline, and if there is a difference, the used sensor material has been exposed to nuclear radiation. According to an embodiment, the method further comprises, prior to exposing the used sensor material to ultraviolet or X-radiation, bleaching the used sensor material of colouration. This step is optional if the used sensor material has already been de-coloured
but may be required if this is not the case. The bleaching may be carried out with heat or white light. When heat is used, a temperature such as 50−500 ⁰C, for example 200 ⁰C is sufficient. When white light is used, the luminous exposure needs to be sufficient, such as 100−1000000000 lux seconds. According to an embodiment, information for the sensor material un-exposed to nuclear radiation and optional information for the sensor material exposed to known amounts of nuclear radiation is thus contained in a database. The database may comprise at least one of a lookup table and a graph. In such a database, the ratios of intensity values and/or the spectra of reflected, transmitted or detected light and corresponding radiation values, as needed, are given, and are based on measurements and calculations carried out in controlled conditions, i.e. where the amount of radiation used is known. The database can, in addition to being a lookup table, also be any other suitable form of data structure. The database may be used automatically (i.e. the process may be computerised), or it may be used manually. When comparing the calculated ratio and/or the spectrum to the information in the database, the amount of radiation to which the material has been subjected to can be determined either qualitatively or quantitatively. The nuclear radiation may thus have a wavelength from 0.1 zm (zeptometre, i.e. 1.0 x 10- 21 m), 500 zm, 1 am (attometre, i.e. 1.0 x 10-18 m), 500 am, 1 fm (femtometre, i.e. 1.0 x 10-15 m), 500 fm, or 1 pm (picometre, i.e. 1.0 x 10-12 m) up to 500 zm, 1 fm, 500 fm, 1 pm, or 10 pm. For example, the wavelength range of gamma radiation is 1 zm – 10 pm. The nuclear radiation can be alpha or beta particles, positrons, or gamma radiation. In particular, the nuclear radiation is gamma radiation. The radiations which presence can be determined with the above method are used in various applications, for example in medical appliances, diagnostics, medical treatments, cleaning, food manufacturing, disinfection, space applications, defence applications, etc. According to an aspect, there is also provided dosimeter for gamma irradiation, comprising as sensor material a material represented by formula (I). This dosimeter is a passive dosimeter, which is thus easy to make and light weight to carry (i.e. can be made for example to a form that can be placed in a pocket). Similarly, it is possible to manufacture dosimeters for alpha and/or beta particle radiation, or positron radiation.
The energy of the nuclear radiation which past presence and/or amount can be determined with the present method is for example 1 keV – 1000 TeV, such as 40 keV – 2 MeV. The upper limit may even be up to 2000 TeV. In the present method, the sensor material is potentially exposed to said nuclear radiation for a period of time. This period of time the sensor material is exposed to radiation may be up to ten years. For example, this period of time may be up to 5, 10, 15, 30 or 45 minutes, 1, 5, 10, 15 or 20 hours, 1, 5, 10, 15, 20, 25 or 30 days or 1, 5 or 10 years. The time is typically dependent on the application the method is used for, i.e. is it used for example for monitoring the amount of radiation a person is submitted to or to provide a radiation map (as will be explained in more detail below). The material of formula (I) is an optically active material that is configured to be able to retain radiation exposed thereon, i.e. the material is able to trap therein the radiation that it is exposed to. M1’ represents a monovalent monoatomic cation of an alkali metal selected from a group consisting of Na, Li, K, Rb, Cs, and Fr, or any combination of such cations. In another embodiment, M1’ does not represent the monoatomic cation of Na alone. According to an embodiment, M1’ represents a combination of at least two monoatomic cations of different alkali metals selected from a group consisting of Li, Na, K, Rb, Cs, and Fr. In one embodiment, M1’ represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements. When alkaline earth elements are present, the stoichiometric number in M1’ adjusts to keep the overall charge of 8+ for the M1’ +M2’ combination. In one embodiment, M1’ represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, wherein the combination comprises at most 98 mol-%, at most 95 mol-%, at most 90 mol-%, at most 85 mol-%, at most 80 mol-%, at most 70 mol-%, at most 60 mol-%, at most 50 mol-%, at most 40 mol-% of the monoatomic cation of Na, or at most 30 mol-% of the monoatomic cation of Na, or at most 20 mol-% of the monoatomic cation of Na. In a yet further embodiment, M1’ represents a monoatomic cation of Li. In one embodiment, M1’ represents a monoatomic cation of K. In one embodiment, M1’
represents a monoatomic cation of Rb. In one embodiment, M1’ represents a monoatomic cation of Cs. In one embodiment, M1’ represents a monoatomic cation of Fr. M2’ represents a divalent monoatomic cation of an alkaline earth metal selected from a group consisting of Be, Mg, Ca, Sr, Ba, and Ra, or any combination of such cations. In one embodiment, M2’ represents a combination of at least two monoatomic cations of different alkaline earth metals selected from Group 2 of the IUPAC periodic table of the elements. According to an embodiment, M’’ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC periodic table of the elements, or any combination of such cations. According to another embodiment, M’’ represents a trivalent monoatomic cation of a transition element selected from any of Groups 3 – 12 of the IUPAC periodic table of the elements, or any combination of such cations. In one embodiment, M’’ represents a trivalent monoatomic cation of a metal selected from a group consisting of Al and Ga, or a combination of such cations. In one embodiment, M’’ represents a trivalent monoatomic cation of B. In a further embodiment, M’’ represents a trivalent monoatomic cation of a metal selected from a group consisting of Al and Ga, or a combination of such cations. In one embodiment, M’’ represents a trivalent monoatomic cation of B. In one embodiment, M’’ represents a trivalent monoatomic cation of a transition element selected from Period 4 of the IUPAC periodic table of the elements, or any combination of such cations. In one embodiment, M’’ represents a trivalent monoatomic cation of an element selected from a group consisting of Cr, Mn, Fe, Co, Ni, and Zn, or any combination of such cations. In one embodiment, M’’’ represents a monoatomic cation of an element selected from a group consisting of Si and Ge, or a combination of such cations. In one embodiment, X represents an anion of an element selected from a group consisting of F, Cl, Br, I, and At, or any combination of such anions. In one embodiment, X represents an anion of an element selected from a group consisting of F, Cl, Br, and I, or any combination of such anions. In one embodiment, X is absent. In one embodiment, X’ represents an anion of an element selected from a group consisting of O, S, Se, and Te, or any combination of such anions. In one embodiment, X’ represents an anion of one or more elements selected from a group consisting of O, S, Se, and Te, or
any combination of such anions. In one embodiment, X’ represents a monoatomic or a polyatomic anion of one or more elements selected from a group consisting of O, S, Se, and Te, or any combination of such anions. In one embodiment, X’ represents an anion of S. In an embodiment, X’ is (SO4)2- or other sulphur oxyanion. In yet another embodiment X’ is absent. In one embodiment, the material is doped with at least one transition metal ion. M’’’’ represents a dopant or it is absent. According to an embodiment, M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements, or from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations. The dopant may be any element or combination of elements. The dopant may for example be an element that does not take part in the functioning of the material. In one embodiment, the material is represented by formula (I), wherein M’’’’ represents a cation of an element selected from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations. In one embodiment, M’’’’ represents a cation of an element selected from transition metals of the f-block of the IUPAC periodic table of the elements. In one embodiment, M’’’’ represents a cation of an element selected from transition metals of the d-block of the IUPAC periodic table of the elements. In one embodiment, M’’’’ represents a cation of an element selected from a group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, W, and Zn, or any combination of such cations. In one embodiment, M’’’’ represents a cation of Ti. In one embodiment, M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements. In one embodiment, M’’’’ represents a cation of an element selected from a group consisting of Yb, Er, Tb, and Eu, or any combination of such cations. In one embodiment, M’’’’ represents a combination of two or more dopant cations. In one embodiment, the material is represented by formula (I), wherein M’’’’ is absent. In this embodiment, the material is not doped. In one embodiment, the material represented by the formula (I) comprises M’’’’ in an amount of 0.001 – 10 mol-%, or 0.001 - 5 mol-%, or 0.1 – 5 mol-% based on the total amount of the material.
According to a further embodiment, the material represented by formula (I) comprises residuals. These residuals originate from the manufacturing process of the material and may be present in an amount of up to 1 mol-% or even more, such as up to 10 mol-%. In one embodiment, the material represented by formula (I) is selected from a group consisting of: (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cr) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Co) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ni) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cu) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,B) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,B) 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Mn 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Cr 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Fe 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Co 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Ni 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Cu 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 B 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a B 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Ga 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Ga 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 Si 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 (Si,Ge) 6 O 24 (Cl,S) 2 :Ti,
(Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 (Si,Ge) 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8( Al,Cr) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Co) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ni) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cu) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,B) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,B) 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Mn 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Cr 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Fe 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Co 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Ni 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Cu 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 B 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a B 6 Ge 6 O 24 (Cl,S) 2 :Ti, (Li x Na 1-x-y-z K y Rb z ) 8 Ga 6 Ge 6 O 24 (Cl,S) 2 :Ti, and (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Ga 6 Ge 6 O 24 (Cl,S) 2 :Ti, wherein x + y + z ≤ 1, x ≥ 0, y ≥ 0, z ≥ 0, and 0 ≥ a ≥ 4.
Some further suitable materials are LiNa7Al6Si6O24(Br,S)2:Sr, where the amount of Sr varies from 0.0004to 6 mol-%, for example from 3 to 6 mol-%. Some other suitable ranges are 0.0004 – 0.005 mol-%, 0.0004 – 0.05 mol-%, 0.005 – 0.05 mol-%, 0.05 – 1 mol %, and 0.05 – 3 mol-%. The material may also comprise Cu, for example in the amount of 1 mol- %. Some suitable materials represented by formula (I) can be selected from a group consisting of: (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cr) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Co) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ni) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cu) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,B) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,B) 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Mn 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Cr 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Fe 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Co 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Ni 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Cu 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 B 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a B 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Ga 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Ga 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 Si 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 (Si,Ge) 6 O 24 (Br,S) 2 :Sr,
(Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 (Si,Ge) 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8( Al,Cr) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Co) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ni) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cu) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,B) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,B) 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Mn 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Cr 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Fe 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Co 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Ni 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Cu 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 B 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a B 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 Ga 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Ga 6 Ge 6 O 24 (Br,S) 2 :Sr, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cr) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu,
(Li x Na 1-x-y-z K y Rb z ) 8 (Al,Co) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ni) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cu) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,B) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,B) 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Mn 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Cr 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Fe 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Co 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Ni 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Cu 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 B 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a B 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Ga 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Ga 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 Si 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 (Si,Ge) 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 (Si,Ge) 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Al 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Al 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ga) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,Ga) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8( Al,Cr) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Mn) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Fe) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Co) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,Ni) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu,
(Li x Na 1-x-y-z K y Rb z ) 8 (Al,Cu) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 (Al,B) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a (Al,B) 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Mn 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Cr 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Fe 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Co 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Ni 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Cu 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 B 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a B 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, (Li x Na 1-x-y-z K y Rb z ) 8 Ga 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, and (Li x Na 1-x-y-z K y Rb z ) 8-2a (Ca,Mg) a Ga 6 Ge 6 O 24 (Br,S) 2 :Sr,Cu, wherein x + y + z ≤ 1, x ≥ 0, y ≥ 0, z ≥ 0, and 0 ≥ a ≥ 4. The material may be synthesised by a reaction according to Norrbo et al. (Norrbo, I.; Głuchowski, P.; Paturi, P.; Sinkkonen, J.; Lastusaari, M., Persistent Luminescence of Tenebrescent Na8Al6Si6O24(Cl,S)2: Multifunctional Optical Markers. Inorg. Chem.2015, 54, 7717-7724), which reference is based on Armstrong & Weller (Armstrong, J.A.; Weller, J.A. Structural Observation of Photochromism. Chem. Commun. 2006, 1094- 1096). As an example, stoichiometric amounts of Zeolite A and Na2SO4 as well as LiCl, NaCl, KCl and/or RbCl can be used as the starting materials. At least one dopant may be added as an oxide, such as TiO2, a chloride, a sulfide, a bromide, or a nitrate. The material can be prepared as follows: Zeolite A may first be dried at 500 °C for 1 h. The initial mixture may then be heated at 850 °C in air for e.g.2 h, 5 h, 12 h, 24 h, 36 h, 48 h, or 72 h. The product may then be freely cooled down to room temperature and ground. Finally, the product may be re-heated at 850 °C for 2 h under a flowing 12 % H2 + 88 % N2 atmosphere. If needed, the as-prepared materials may be washed with water to remove any
excess LiCl/NaCl/KCl/RbCl impurities. The purity can be verified with an X-ray powder diffraction measurement. The material is prepared in powder form and is typically also used in powder form. The particle size in the powder is typically about 5-10 µm, as measured by transmission electron microscopy, the area was determined from the pictures with a watershed segmentation algorithm in the ImageJ program. The material of the present description is typically non-toxic and non-expensive. The method described above may also comprise, at its beginning, arranging the sensor material in a polymer matrix. According to one embodiment, the material can be arranged in a polymer matrix by using tape casting, also known as knife coating or doctor blading. Tape casting is a process where a thin sheet of ceramic or metal particle suspension fluid is cast on a substrate. The fluid may contain volatile nonaqueous solvents, a dispersant, (a) binder(s) and the dry matter, i.e. the material having formula (I). The process may comprise preparing the suspension and applying it onto a surface of a substrate. The binder may create a polymer network around the dry matter particles, while the plasticiser may function as a softening agent for the binder. When combining these substances, the tape may become resistant against cracking and flaking off when bent. The dispersant may be used to de-aggregate the particles and homogenise the suspension. Thus, according to one embodiment the material is arranged in a polymer matrix by mixing the material with the tape casting components. Any suitable and typical tape casting components can be used, as known in the art. According to one embodiment, the tape casting components comprise ethanol Aa, ethyl methyl ketone, triton X-100, benzyl butyl phthalate and polyvinyl butyral. The polymer matrix, i.e. tape-casting polymer, can comprise one or several different polymers. Any polymer capable to act as an energy converter, i.e. capable to be excited by the optically stimulated luminescence emission, can be used. According to one embodiment, the polymer can be a silicone elastomer, benzyl butyl phthalate or polyvinyl butyral or any combination thereof.
The material, tape-casted in a polymer matrix, thus forms an image detector that can be used as gamma detectors. The material according to formula (I) may be attached to a surface for example as a coating or a film. The substrate of the plate or detector may comprise or consist of glass or polymer. The substrate may comprise or consist of a glass layer or a polymer layer. The substrate may comprise (a) further layer(s). The substrate may also or alternatively comprise an attachment layer, such as a printing paper, and/or a base layer, such as a cardboard layer, or any other layer(s) where desired or needed. The detector may comprise further layers and/or components. The detector has the added utility of enabling the use of the material represented by formula (I) as a detector material. The detector has a further added utility of making use of an optically active material being non- toxic and non-expensive compared to currently used materials such as Ba(F,Cl,Br,I)2:Eu and CsI:Ti. The detector, provided it has not been exposed to nuclear radiation, has still an added utility of being reusable and recyclable. Also, even if the detector has been exposed to nuclear radiation, it can be reused and recycled, however the effect of exposure to nuclear radiation cannot be deleted, but rather, the material shows a total exposure to nuclear radiation during the life of the detector. Further, the detector can be used for point- of-care analysis without the need of complicated analysis systems. The present description further relates to a device, wherein the device comprises a material according to one or more embodiments described in this specification. In one embodiment, the device is a gamma radiation sensor, a gamma radiation detector, a gamma radiation indicator, a gamma radiation dose indicator, a positron radiation sensor, a positron radiation detector, a positron radiation indicator, a positron radiation dose indicator, an alpha and/or beta particle radiation sensor, an alpha and/or beta particle radiation detector, an alpha and/or beta particle radiation indicator, or an alpha and/or beta particle radiation dose indicator. In one embodiment, the device is a gamma radiation sensor for gamma radiation therapy, e.g. gamma knife surgery/radiation therapy. The device may also be an alpha or beta particle radiation sensor for alpha or beta particle radiation therapy, e.g. alpha or beta particle radiation therapy. In one embodiment, the device is a sensor or detector in space applications for detection direction or source or intensity or wavelengths of radiation of gamma radiation or direction
or source or intensity of alpha and/or beta particle radiation or direction or source or intensity of positron radiation. The present method may further be used for monitoring counterfeit goods. In such case, a small device comprising a known compound of formula (I) as defined above is attached to a goods at its manufacturing site. Should there be suspicion of a counterfeit product being imported for example, the goods may be subject to gamma radiation for a pre-determined amount of time, and the resulting intensity of colour of the light measured. If such intensity of colour differs from what the manufacturer has indicated, it may be concluded that the product is counterfeit. One example of using hackmanite in an industrial product line that sterilises foodstuff is as follows. Different hackmanite sample films are irradiated with known doses of gamma radiation and the colouration is measured with a digital camera. These values are used to construct a calibration curve that will be used with this type of hackmanite films. Non- coloured hackmanite films are placed under a gamma radiation source in the product line, and the subsequent colouration is measured again with a digital camera and compared with the calibration curve. A dose distribution map is constructed for the gamma source in the product line, enabling the radiation user to determine the area of lowest acceptable dose. It is to be understood that the embodiments of the invention disclosed are not limited to the particular structures, process steps, or materials disclosed herein, but are extended to equivalents thereof as would be recognised by those ordinarily skilled in the relevant arts. It should also be understood that terminology employed herein is used for the purpose of describing particular embodiments only and is not intended to be limiting. Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the description, numerous specific details are provided, such as examples of lengths, widths, shapes, etc., to provide a thorough understanding of embodiments of the invention. The verbs “to comprise” and “to include” are used in this document as open limitations that neither exclude nor require the existence of also un-recited features. The features recited in dependent claims are mutually freely combinable unless otherwise explicitly stated. Furthermore, it is to be understood that the use of "a" or "an", i.e. a singular form, throughout this document does not exclude a plurality.
In the following Experimental part, concrete examples of use of the material are given to further illustrate the invention. EXPERIMENTAL PART Preparation of the materials All materials were synthesised with a solid-state reaction route using high-temperature furnaces. The starting materials were zeolite A (Sigma Aldrich), NaCl (> 99.5 %, J. T. Baker), Na2SO4 (Merck, > 99 %), LiCl (99 %, Acros), RbCl (≥ 99.0 %, Sigma) and NaBr (J. T. Baker, reagent grade). The samples were prepared by weighing stoichiometric amounts of reagents, i.e. - 0.700 g zeolite A (dried at 500 °C for 1 h), 0.240 g NaCl and 0.0600 g Na2SO4 when producing Na8Al6Si6O24(Cl,S)2, of which the composition was (Na,K,Rb) 7.9949 Ca 0.0026 Al 6 Si 6 O 24 (Cl,S) 2 :Sr (a = 0.0026), the presence of a small amount of Sr being due to impurities in the starting materials or the synthesis oven. - 0.700 g zeolite A, 0.496 g RbCl and 0.0600 g Na2SO4 when producing (Rb,Na)8Al6Si6O24(Cl,S)2, of which the composition was (Na,K,Rb) 7.9938 Ca 0.0031 Al 6 Si 6 O 24 (Cl,S) 2 (a = 0.0031). - 0.700 g zeolite A, 0.0850 g LiCl, 0.1200 g NaCl and 0.0600 g Na2SO4 when producing (Li,Na)8Al6Si6O24(Cl,S)2, of which the composition was (Na,K,Li) 7.9969 Ca 0.0015 Al 6 Si 6 O 24 (Cl,S) 2 :Sr (a = 0.0015), the presence of a small amount of Sr being due to impurities in the starting materials or the synthesis oven. - 0.700 g zeolite A, 0.427 g NaBr and 0.0600 g Na2SO4 when producing Na8Al6Si6O24(Br,S)2, of which the composition was (Na,K) 7.9965 Ca 0.0017 Al 6 Si 6 O 24 (Br,S) 2 (a = 0.0017). - 0.700 g zeolite A, 0.306 g KCl, and 0.0600 g Na2SO4 when producing (Na,K)8Al6Si6O24(Cl,S)2 of which the composition was (Na,K,Rb) 7.9995 Mg 0.0003 Al 6 Si 6 O 24 (Cl,S) 2 (a = 0.0003). The compositions were determined using X-ray fluorescence.
The mixture of powders was ground by hand in an agate mortar and transferred to an alumina crucible and heated at 850 °C in air atmosphere for 2 h and let to cool passively to room temperature. After this, the sample was ground and heated to 850 °C in a flowing N2/H2 (88/12 %) atmosphere for 2 h and let to cool passively to room temperature. Finally, the sample was ground once again to yield the finished end product. The hackmanite powders were cast as 80 µm thick flexible green tapes in order to fix them easily to their positions in the exposure chamber, and also to measure their reflectance spectra easily. X-ray powder diffraction measurements were carried out to establish the samples’ purity. The equipment used was a PANalytical Empyrean using CuKα1,2, radiation with wavelengths 1.5406 (Kα1) and 1.5444 Å (Kα2). Photochromic activity under UV and X irradiation were tested with a UVP UVLS-24 UV lamp operating with 4 W at 254 nm and a PANalytical Epsilon 1 X-ray fluorescence spectrometer equipped with an Ag tube (Kα emission at ca.22 keV). Preliminary irradiation tests were carried out with a number of different nuclides, as shown in Table 1, which gives the predominating energy lines. In the dosimetric tests, the materials were irradiated free in air in collimated Co-60 gamma ray beam. The gamma radiation qualities were established according to ISO standard 4037-1:2019. The materials were set up so that the samples were perpendicular to the beam and facing towards the source. In both the preliminary and dosimetric tests, the doses were controlled by adjusting the samples’ distance from the source and the exposure time. Exposure to beta radiation (positrons) was performed by pipetting 18F-water (3 µl in triplicate) with a measured activity concentration (Veenstra VDC-405 dose calibrator) directly on the film.
Nuclide Radiation Activity (Bq) Energy (keV) Co-60 γ 215·10 3 1173 γ 1333 318
Pb-210 γ 20·10 3 46 β 17 α 3720 Am-241 γ 2·10 3 60 X 12-22 α 5486 U-238 (depleted α n.a. 4198 uranium) F-18 Positrons 2.410 6 634
511 Table 1 (*annihilation photon) All reflectance measurements were carried out with an Avantes AvaSpec ULS2048CL- EVO spectrometer coupled to an Avantes FC-IR600-1-ME-HTX optical fiber. The light source was either a 60 W incandescent light bulb (colour fading measurements) or an Ocean Optics LS-1 Cal calibration lamp (other measurements) directed towards the sample 20 cm away. The tenebrescence bleaching spectra and fading curves were compiled from reflectance spectra recorded for a fully coloured sample. The full colouration was obtained by 7000 Gy of Co-60 gamma radiation, 2 h of X-ray exposure in PANalytical Epsilon 1 XRF machine (Ag tube with peak intensity at ca. 22 keV) or 1 min of 254 nm UV irradiation. For the bleaching spectra, the sample was irradiated with selected wavelengths from a 150 Xe lamp. The wavelengths were adjusted using a LOT MSH300 monochromator. The bleaching time at each wavelength was 10 min for sample Li, 1 min for sample Br, 1 min for sample Na and 30 s for sample Rb due to material-specific differences in the optical energy needed to induce a visible change in the reflectance spectrum.
X-band (9.43 GHz) EPR spectra were recorded on a Magnettech GmbH MS-200 Miniscope high resolution spectrometer equipped with XL Microwave frequency counter (Model 3200) at 77 K by submerging the sealed samples in liquid nitrogen. The spectra were calibrated against diphenyl picryl hydrazyl (DPPH, g = 2.0036). The Raman spectra were recorded using an inVia Qontor confocal Raman microscope (Renishaw, Gloucestershire, UK) using 785 nm continuous wave laser excitation. XPS measurements were carried out using Perkin Elmer PHI 5400 ESCA and Thermo Scientific NEXSA XPS systems using Mg and monochromated Al X-ray sources respectively. Measurement time was limited to as low as possible to minimise X-ray-induced sample colouring during the measurement. The XPS signal widths were quantified using Gaussian fitting in the Origin 2016 program. Geometry optimisations calculations were performed in periodic boundary condition (PBC) within the density functional theory (DFT) framework. The global hybrid functional PBE0 was used along with the ab-initio CRYSTAL17 code and localised (Gaussian) basis sets. All-electron double-ζ basis sets with polarisation functions were used for Si ([4s3p1d]/(20s12p1d)), Al ([4s3p1d]/(17s9p1d)), O ([3s2p1d]/(10s4p1d)), and Cl ([4s3p1d]/(16s10p1d)), while all-electron triple-ζ basis sets with polarisation functions were used for Na ([4s3p1d]/(15s7p1d). To describe the trapped electron in all structures, a basis set was optimised with the 111G(d) structure. The reciprocal space was sampled according to a sublattice with a 12 X 12 X 12 k-points mesh for the geometry optimisation of the bulk system, while a single k-point (the Γ point) was used for the geometry optimisation of the 2 X 2 X 2 supercell. The convergence criterion for the SCF cycle was fixed at 10−7 Ha per unit cell. When considering the formation of a sodium vacancy (Na4VCl -> Na3VCl) the resulting loss of electroneutrality was offset by the substitution of one Al3+ by one Si4+ in the β-cage surrounding the vacancy. TD-DFT calculations were done using the Gaussian16 code along with the B3LYP functional on clusters extracted from the geometries optimised in PBC. The clusters were embedded in a sphere of pseudopotentials and an array of point charges. These point charges are used to simulate the Madelung potential of the crystal and were obtained through the Ewald package, using a 5 X 5 X 5 supercell. The fitting procedure led to an RMS error lower than 1 μV on the Ewald potential.
Results Preliminary tests with gamma, alpha and beta radiation The materials’ purity was first checked with X-ray powder diffraction and then their photochromic activity under UV and X-rays was confirmed as an initial proof of the samples being able to change colour under radiation treatment. Thereafter, preliminary tests were carried out for Na8Al6Si6O24(Cl,S)2 to see if there is any photochromic response when exposed to different gamma (Co-60, Cd-109, Ba-133, Cs-137 and Pb-210), alpha (Am-241 and depleted uranium) and beta (F-18) radiation sources. The beta source also gives two annihilation photons (511 keV) for each positron from F-18. It was evident that all of the studied sources induced a colouration in the sample, albeit weak in most cases. For the Am-241 source, colouring was tested with and without an Al shield between the source and the sample. Both resulted in the colouration of the sample with the colour being more intense without the shield. Since the shield blocks alpha but transmits gamma, this indicates that both gamma and alpha radiation induce colouring in hackmanite. The reflectance spectra indicate that the reflectance minimum is always centred at around 530 nm, i.e. at the same wavelength obtained previously with UV and X-ray irradiation. In addition to that symmetric wide band at 530 nm expected for the colour centre in hackmanite, some sources also induced narrower bands. These bands, observed at ca. 480 and 600 nm, were most prominent in the samples exposed to alpha-emitting nuclides, i.e. Am-241, depleted uranium and Pb-210. These additional bands will be discussed below. Further, preliminary tests with Co-60 were carried out to observe how the radiation dose affects the colour intensity and it was observed that increasing dose gives increasing colour intensity. The dose response will be discussed in detail below. Figure 1 illustrates reflectance spectra of a Na8Al6Si6O24(Br,S)2 sample exposed to different air kerma values from a 60Co source, the white reference being a non-exposed, white sample.
Comparison with X-ray induced photochromism For the comparison of photochromism induced by different radiation types, Na8Al6Si6O24(Cl,S)2, was again used as an example. Ignoring for the moment the additional reflectance peaks discussed in brief above, it can be said that the absorption spectrum of the colour centre is similar for UV, X-ray and gamma, alpha or beta induced photochromism, i.e. centred around the same wavelength. Also, to the naked eye, the additional peaks do not have any effect on the perceived colour. When taking into account only the centre of the reflectance signal (main peak, 480-580 nm), the optical bleaching spectrum of the gamma-induced colour is very similar to that of X-ray-induced colour. However, if only the red side of the reflectance signal (580-690 nm) is considered, the bleaching spectrum shifts by ca.100 nm to 450 nm. Furthermore, considering the blue side alone (440-480 nm), a broadening towards blue wavelengths can be observed. It was observed that gamma irradiation causes much more broadening of the reflectance band on the red than the blue side. Since the bleaching spectra are not the same for the main peak and the side peaks, it is reasonable to postulate that these peaks originate from different types of defects, as discussed above in the description. Next, fading of the colour under white light as a function of time was tested. When the colour intensity at the main peak wavelength (530 nm) is plotted in logarithmic scale, it can be observed that for UV-induced colour, the fading is single-component exponential, i.e. the curve looks linear. Similarly on the blue (450 nm) and red (650 nm) sides, the fading is single exponential. The lifetimes obtained with single exponential fitting are 16.4±0.1 (main peak), 13.5±0.2 (blue side) and 14.8±0.2 min (red side). Thus, the fading is very similar in all these three ranges. On the other hand, the fading curve of the main peak of the gamma-induced colour is clearly not linear when plotted with logarithmic intensity scale, i.e. it is multi-component exponential. With two-component fitting, 14.9±1.8 (30 % amplitude) and 187±67 min (70 %) as the lifetimes for the main peak are obtained. The former lifetime is similar to that of UV-induced colouring, and it can be assigned to the same colour centre. For the blue and red sides, single-component exponential fading with lifetimes 229±66 and 206±41 min, respectively, are observed. These two lifetimes are similar to the second component of the main peak’s fading indicating that the main peak’s fading is affected also by those of the sides.
It is clear that the main colour centre is similar to what is present in UV- and X-ray- induced photochromism, but with gamma and alpha irradiation there are additional absorbing species that affect the overall energetics of photochromism. The origin of the two additional reflectance signals will be discussed in more detail below. Origin of the additional absorption bands To test the dose response of the materials’ colour with gamma irradiation, a series of tests with different gamma doses were carried out. The dose response is discussed in more detail below. Again using Na8Al6Si6O24(Cl,S)2 as the example, it was clear that with increasing dose the width of the reflectance signal almost doubles. When a difference curve from the samples with the highest and lowest doses is calculated, it is evident that the gamma irradiation produces two extra peaks at ca. 450 and 630 nm. These wavelengths are also very similar to what was observed above for the materials irradiated with alpha radiation. Dose response and mechanism Since the energy of gamma and alpha radiation is usually even higher than that of X-rays, it was expected that gamma-induced photochromism would proceed with a similar mechanism as does X-ray induced photochromism, i.e. through the valence and conduction bands, rather than with a direct excitation of the disulphides. Then, absorbed gamma photons and alpha particles would create an electron-hole pair that induces a cascade of an increasing number of electrons and holes that lose their energy on the way towards the bottom of the conduction band (electrons) and top of the valence band (holes). Once the borders of the band gap are reached, the number of electron-hole pairs can be approximated to be Eexcitation photon/2Eband gap. Considering that approximation, there would usually be some ten to a hundred times more electron-hole pairs with gamma radiation than with X-rays. However, electron-hole pairs can be created only from absorbed photons. Thus, also the photoelectric absorption of hackmanite needs to be taken into account. To compare the dose response of hackmanites when excited with X-rays and gamma rays, experiments recording the colour intensity of the material with a commercial colour spectrometer after exposure to different doses of gamma and X radiation were carried out. The colour intensity was then normalised to account for the photoelectric absorption as well as the excitation energy. The results show that the colour yield obtained from
absorbed irradiation dose is rather similar between X-ray and gamma irradiation. The response is not exactly the same, but it is in the same order of magnitude. Based on the very similar colouring efficiency obtained with X-rays and gamma radiation, it can be assumed that the mechanism for colour creation is very similar with these two irradiation types, i.e. both involve the electron and hole cascades towards the band gap eventually leading to the formation of the colour centres. The one difference is that with gamma irradiation a part of the Na4VCl tetrahedra are converted to Na3VCl. Figure 2 illustrates a ratio of two different components in the reflectance spectra of Figure 1 and shows how it is dependent on the irradiation dose. Figure 3 illustrates reflectance spectra of a Na8Al6Si6O24(Cl,S)2 sample exposed to a 7- kGy air kerma value from a 60Co source, the same sample after bleaching and recolouring with 254 nm UV, and also a non-exposed sample coloured with 254 nm UV. The Figure clearly shows how the fact that the material has been exposed to gamma radiation has a different reflectance than the material un-exposed to gamma radiation. As shown above, hackmanite’s colour intensity increases with increasing gamma dose. Further five different compositions of hackmanite: Na8Al6Si6O24(Cl,S)2, (Li,Na) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Na,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Rb,Na) 8 Al 6 Si 6 O 24 (Cl,S) 2 and Na 8 Al 6 Si 6 O 24 (Br,S) 2 were tested. These compositions were chosen to investigate if changing the contents of the beta cage would affect the performance. Once the dose is high enough, a very intense colouring was obtained. The overall colour intensity vs. dose curves were rather similar for each of the studied materials and clearly the overall colour intensity can be calibrated to indicate the radiation dose. When considering the L*a*b* colour coordinates, each material loses lightness (L*value), becomes more red (a*) and more blue (b*) with increasing dose. Thus, also the L*a*b* coordinates can be used for the dose quantification. Based on these data, the Br material was noticed to be the most sensitive one to measure doses with each of these parameters, among the materials tested. This is probably because of the significant amount of the relatively heavy Br increasing the photoelectric absorption of the material in comparison with regular hackmanite. Rb is even heavier, but its solubility to the hackmanite matrix was rather low as shown by the X-ray powder diffraction data.
According to the results presented here, the hackmanites’ colour becomes visible to the naked eye at doses of 1000 Gy and higher when irradiating with gamma radiation from Co- 60. However, with the colorimetric spectrometer even lower doses are visible as suggested by the differences of each parameter (L*, a* and b*) between 200 and 1000 Gy. This dose range is clearly much too high than would be feasible for a dosimeter to be used to monitor people’s radiation exposure, since 100 Gy can result to instant death. Also in medical radiation therapy, the doses are only in the range of tens or hundreds of cGy to a few Gy. On the other hand, the hackmanites’ working range fits very well with that used in food irradiation. It typically employs doses from 1 to 50 kGy, but in many cases the highest allowed dose is less, e.g.150 Gy for potatoes and onions.
Claims
CLAIMS 1. A method for determining exposure of a used sensor material to nuclear radiation, the method comprising - exposing the used sensor material to ultraviolet or X-radiation to induce colouration, - subjecting the used sensor material to a measurement by a device configured to measure visible light to obtain a measured spectrum of reflected, transmitted, or detected light, - using at least one of - a comparison of a calculated ratio of intensity values of the used sensor material and a calculated ratio of intensity values of the sensor material un-exposed to nuclear radiation, wherein the ratios of intensity values are calculated from at least two different points of the measured spectra of reflected, transmitted, or detected light, - a comparison of a difference spectrum of reflected, transmitted or detected light to a baseline, wherein the difference spectrum is calculated as a difference between the measured spectrum of reflected, transmitted or detected light of the used sensor material and the measured spectrum of reflected, transmitted, or detected light of the sensor material un-exposed to nuclear radiation, - determining that the used sensor material has been exposed to nuclear radiation, if - the calculated ratio of intensity values of the used sensor material differs from the ratio of intensity values of the sensor material un-exposed to nuclear radiation, and/or - the difference spectrum differs from the baseline, wherein the sensor material comprises a material represented by formula (I) (M1’ 8-2a M2’ a )(M’’ 14-(4b/3) M’’’ b )O 24 (X 2-dc dX’ n c- ):M’’’’ (I) wherein - M1’ represents a monovalent monoatomic cation of an alkali metal selected from Group 1 of the IUPAC periodic table of the elements, or any combination of such cations; - M2’ represents a divalent monoatomic cation of an alkaline earth metal selected from Group 2 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC periodic table of the elements, or of a transition element selected from any of
Groups 3 – 12 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’’ represents a monoatomic cation of an element selected from Group 14 of the IUPAC periodic table of the elements, or any combination of such cations; - X represents an anion of an element selected from the halogens of Group 17 of the IUPAC periodic table of the elements, or any combination of such anions; - X’ represents an anion of one or more elements selected from the chalcogens of Group 16 of the IUPAC periodic table of the elements, or any combination of such anions; - M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements, or from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations, or wherein M’’’’ is absent; - a is a value of 0 – 4; - b is a value of 1 – 10; - c is a value of 1, 2, 3, or 4; - d is a value of above 0 – 2; and - n is a value of 1, 2, 3, or 4. 2. The method according to claim 1, wherein a is a value of 0.0002 – 4, typically 0.003 to 0.03. 3. The method according to claim 2, wherein a is a value of from 0.0002, 0.0003, 0.0005, 0.0007, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.01, 0.05, 0.1, 0.4, 0.7, 1, 1.5, 2, 2.5, 3, or 3.5 up to 0.0003, 0.0005, 0.0007, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.01, 0.05, 0.1, 0.4, 0.7, 1, 1.5, 2, 2.5, 3, 3.5, or 4. 4. The method according to any one of the preceding claims, further comprising, prior to exposing the used sensor material to ultraviolet or X-radiation, bleaching the used sensor material of colouration. 5. The method according to claim 4, wherein the bleaching is carried out with heat or white light. 6. The method according to any one of the preceding claims, further comprising determining the amount of radiation to which the used sensor material has been exposed, by comparing the calculated ratio of intensity values of a spectrum of reflected,
transmitted, or detected light of the used sensor material, to calculated ratio of intensity values of the sensor material exposed to known amounts of nuclear radiation. 7. The method according to any one of the preceding claims, wherein information for the sensor material un-exposed to nuclear radiation and optional information for the sensor material exposed to known amounts of nuclear radiation is contained in a database. 8. The method according to any one of the preceding claims, wherein the nuclear radiation is gamma radiation. 9. The method according to any one of the preceding claims, wherein M1’ does not represent the monoatomic cation of Na alone. 10. The method according to any one of the claims 1-8, wherein M1’ represents a combination of at least two monoatomic cations of different alkali metals selected from a group consisting of Li, Na, K, Rb, Cs, and Fr. 11. The method according to any one of the preceding claims, wherein M2’ represents a divalent monoatomic cation of an alkaline earth metal. 12. The method according to any one of the preceding claims, wherein M’’ represents a trivalent monoatomic cation of a metal selected from a group consisting of Al and Ga, or a combination of such cations. 13. The method of any one of claims 1-11, wherein M’’ represents a trivalent monoatomic cation of B. 14. The method of any one of the preceding claims, wherein M’’’ represents a monoatomic cation of an element selected from a group consisting of Si and Ge, or a combination of such cations. 15. The method of any one of the preceding claims, wherein X represents an anion of an element selected from a group consisting of F, Cl, Br, I, and At, or any combination of such anions. 16. The method of any one of the preceding claims, wherein X’ represents a monoatomic or a polyatomic anion of one or more elements selected from a group consisting of O, S, Se, and Te, or any combination of such anions.
17. The method of any one of the preceding claims, wherein M’’’’ represents a cation of an element selected from a group consisting of Yb, Er, Tb, and Eu, or any combination of such cations. 18. The method of any one of claims 1-16, wherein M’’’’ represents a cation of an element selected from a group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, W, and Zn, or any combination of such cations. 19. The method according to any one of the preceding claims, further comprising arranging the sensor material in a polymer matrix. 20. A dosimeter for gamma irradiation, comprising as sensor material material represented by formula (I) (M1’ 8-2a M2’ a )(M’’ 14-(4b/3) M’’’ b )O 24 (X 2-dc dX’ n c- ):M’’’’ (I) wherein - M1’ represents a monovalent monoatomic cation of an alkali metal selected from Group 1 of the IUPAC periodic table of the elements, or any combination of such cations; - M2’ represents a divalent monoatomic cation of an alkaline earth metal selected from Group 2 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’ represents a trivalent monoatomic cation of an element selected from Group 13 of the IUPAC periodic table of the elements, or of a transition element selected from any of Groups 3 – 12 of the IUPAC periodic table of the elements, or any combination of such cations; - M’’’ represents a monoatomic cation of an element selected from Group 14 of the IUPAC periodic table of the elements, or any combination of such cations; - X represents an anion of an element selected from the halogens of Group 17 of the IUPAC periodic table of the elements, or any combination of such anions; - X’ represents an anion of one or more elements selected from the chalcogens of Group 16 of the IUPAC periodic table of the elements, or any combination of such anions; - M’’’’ represents a dopant cation of an element selected from rare earth metals of the IUPAC periodic table of the elements, or from transition metals of the IUPAC periodic table of the elements, or of Ba, Sr, Tl, Pb, or Bi, or any combination of such cations, or wherein M’’’’ is absent; - a is a value of 0 – 4;
- b is a value of 1 – 10; - c is a value of 1, 2, 3, or 4; - d is a value of above 0 – 2; and - n is a value of 1, 2, 3, or 4.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017194825A1 (en) | 2016-05-09 | 2017-11-16 | Turun Yliopisto | Luminescent material |
| WO2019092308A1 (en) | 2017-11-07 | 2019-05-16 | Turun Yliopisto | Determining the amount of a predetermined type of radiation irradiated on a sensor material |
| WO2019092309A1 (en) | 2017-11-07 | 2019-05-16 | Turun Yliopisto | Indicating the intensity of a predetermined type of radiation |
| WO2022229509A1 (en) * | 2021-04-30 | 2022-11-03 | Turun Yliopisto | Uv-sensitive man-made cellulose textile fiber |
| WO2022269128A1 (en) * | 2021-06-23 | 2022-12-29 | Turun Yliopisto | A radiation sensing material |
| WO2023007058A1 (en) * | 2021-07-27 | 2023-02-02 | Turun Yliopisto | A method for determining an amount of radiation |
-
2023
- 2023-07-31 WO PCT/FI2023/050449 patent/WO2024028538A1/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017194825A1 (en) | 2016-05-09 | 2017-11-16 | Turun Yliopisto | Luminescent material |
| WO2017194834A1 (en) | 2016-05-09 | 2017-11-16 | Turun Yliopisto | Synthetic material for detecting ultraviolet radiation and/or x-radiation |
| WO2019092308A1 (en) | 2017-11-07 | 2019-05-16 | Turun Yliopisto | Determining the amount of a predetermined type of radiation irradiated on a sensor material |
| WO2019092309A1 (en) | 2017-11-07 | 2019-05-16 | Turun Yliopisto | Indicating the intensity of a predetermined type of radiation |
| EP3707533A1 (en) * | 2017-11-07 | 2020-09-16 | Turun Yliopisto | Determining the amount of a predetermined type of radiation irradiated on a sensor material |
| WO2022229509A1 (en) * | 2021-04-30 | 2022-11-03 | Turun Yliopisto | Uv-sensitive man-made cellulose textile fiber |
| WO2022269128A1 (en) * | 2021-06-23 | 2022-12-29 | Turun Yliopisto | A radiation sensing material |
| WO2023007058A1 (en) * | 2021-07-27 | 2023-02-02 | Turun Yliopisto | A method for determining an amount of radiation |
Non-Patent Citations (6)
| Title |
|---|
| AGAMAH CECILIA ET AL: "Hackmanite-The Natural Glow-in-the-Dark Material", CHEMISTRY OF MATERIALS, vol. 32, no. 20, 25 September 2020 (2020-09-25), US, pages 8895 - 8905, XP055936901, ISSN: 0897-4756, Retrieved from the Internet <URL:http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.0c02554> [retrieved on 20231004], DOI: 10.1021/acs.chemmater.0c02554 * |
| ARMSTRONG, J.A.WELLER, J.A.: "Structural Observation of Photochromism", CHEM. COMMUN., 2006, pages 1094 - 1096 |
| ISABELLA NORRBO ET AL: "Solar UV index and UV dose determination with photochromic hackmanites: from the assessment of the fundamental properties to the device - Materials Horizons (RSC Publishing) DOI:10.1039/C8MH00308D", 13 April 2018 (2018-04-13), XP055540063, Retrieved from the Internet <URL:https://pubs.rsc.org/en/content/articlehtml/2018/mh/c8mh00308d> [retrieved on 20190109] * |
| NORRBO ISABELLA ET AL: "Up-conversion luminescence - A new property in tenebrescent and persistent luminescent hackmanites", JOURNAL OF LUMINESCENCE, ELSEVIER BV NORTH-HOLLAND, NL, vol. 191, 22 February 2017 (2017-02-22), pages 28 - 34, XP085149888, ISSN: 0022-2313, DOI: 10.1016/J.JLUMIN.2017.02.046 * |
| NORRBO, 1.GLUCHOWSKI, P.PATURI, P.SINKKONEN, J.LASTUSAARI, M.: "Persistent Luminescence of Tenebrescent NagA1 Si 0 (C1,S) : Multifunctional Optical Markers", INORG. CHEM., vol. 54, 2015, pages 7717 - 7724, XP055540083, DOI: 10.1021/acs.inorgchem.5b00568 |
| VUORI SAMI ET AL: "Detection of X-Ray Doses with Color-Changing Hackmanites: Mechanism and Application", ADVANCED OPTICAL MATERIALS, vol. 9, no. 20, 19 July 2021 (2021-07-19), DE, pages 2100762 - 1, XP055965481, ISSN: 2195-1071, Retrieved from the Internet <URL:https://onlinelibrary.wiley.com/doi/full-xml/10.1002/adom.202100762> [retrieved on 20231004], DOI: 10.1002/adom.202100762 * |
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