CN117965032A - High-hardness polysiloxane scintillator and preparation method and application thereof - Google Patents
High-hardness polysiloxane scintillator and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polysiloxane scintillator for discriminating neutrons and gamma rays with high hardness and a preparation method and application thereof, and relates to the technical field of organic scintillator preparation. The polysiloxane scintillator consists of a scintillator matrix, a cross-linking agent, a main fluorescent dye and a secondary fluorescent dye, wherein the main fluorescent dye and the secondary fluorescent dye are doped in the matrix, the scintillator matrix is a polymethylphenylsiloxane-polymethylphenylmethylhydrogen siloxane copolymer, the cross-linking agent is 1, 3-divinyl, 1, 3-diphenyl, 1, 3-dimethyl siloxane, the main fluorescent dye is diphenyl oxazole (PPO), and the secondary fluorescent dye is 7-diethylamino-4-Methylcoumarin (MDAC). The obtained polysiloxane scintillator has the capability of discriminating neutrons and gamma rays, has good anti-radiation performance, improves the hardness, stability and optical transparency of the scintillator by introducing the cross-linking agent, and can be used for neutron detectors.
Description
Technical Field
The invention relates to a high-hardness polysiloxane scintillator for discriminating neutrons and gamma rays in radiation field energy, and a preparation method and application thereof, belonging to the preparation technology of organic scintillators.
Background
Neutron detection is becoming increasingly important in many areas, including nuclear waste reservoir monitoring, illegal fissile material transportation inspection at the border, specialized plants for nuclear physical research (e.g., radioactive ion beam production, neutron spallation sources, etc.), and other areas related to safety control. Traditional plastic scintillators have poor radiation resistance, limited heat resistance, and are difficult to use in certain complex environments. In the late 80 s of the 20 th century, the use of polysiloxanes as an alternative material to polystyrene has been proposed for the manufacture of plastic scintillators. This is because the Si-O bond has a higher strength than the C-C bond, so that the probability of damage to the polymer chain by the high-energy particles is significantly reduced. Even at high doses of radiation, no significant coloration of the polysiloxane scintillators was observed. However, the polysiloxane molecules are less strong due to their weaker interactions. As a plastic scintillator matrix, polysiloxanes have the major disadvantage of poor mechanical properties.
Pulse shape discrimination (Pulse shape Discrimination, PSD) techniques can identify particles that interact with the scintillator by analyzing the shape of the signal. The interaction process of the different particles results in differences in shape. The signal generated by the interaction of neutrons with the scintillator is caused by recoil protons, which excite molecules in the scintillator by elastic and inelastic scattering. The gamma rays, when interacting with the organic scintillator, produce compton electrons. The scattered recoil protons have a shorter range and higher line energy transport, producing a high concentration of triplet molecular states in the scintillator. In contrast, compton electrons have longer ranges than protons and produce a lower concentration of triplet states and a higher concentration of singlet states, so neutron and gamma ray discrimination can be achieved based on the PSD method. Separation performance of PSD techniques is typically evaluated by a quality discrimination factor (Figure of merit, foM), which is defined as: fom=Δ/(Δγ+Δn), where Δ is the distance between the peak centroids of each PSD parameter distribution, and Δγ and Δn are the full width at half maximum (FWHM) values of the gamma ray and neutron PSD parameter distributions, respectively. Thus, the higher the FOM value, the greater the distance between neutron and gamma ray PSD parameter distributions, indicating a more optimal PSD capability. The dye doped with the traditional polysiloxane scintillator can be separated out after being stored for a long time, which is unfavorable for discriminating neutrons and gamma rays
Therefore, the polysiloxane scintillator which can be stored for a long time and has the effective screening capability of neutrons and gamma rays and excellent mechanical hardness and optical transparency is one of the research hotspots.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polysiloxane scintillator with higher optical transmittance, good neutron and gamma ray discrimination performance and high mechanical hardness, and a preparation method and application thereof.
In order to achieve the above purpose, the specific technical scheme adopted by the invention is as follows:
The invention relates to a polysiloxane scintillator, which consists of a scintillator matrix, a main fluorescent dye, a secondary fluorescent dye and a cross-linking agent, wherein the main fluorescent dye, the secondary fluorescent dye and the cross-linking agent are co-doped in the matrix, the scintillator matrix A is vinyl end-capped polymethylphenylsiloxane, the matrix B is polymethylphenylmethylhydrosiloxane, the matrix A and the matrix B form a matrix polymethylphenylsiloxane-polymethylphenylmethylhydrosiloxane copolymer (PSS), the main fluorescent dye is diphenyl oxazole (PPO), the secondary fluorescent dye is 7-diethylamino-4-Methylcoumarin (MDAC), and the cross-linking agent is 1, 3-divinyl, 1, 3-diphenyl and 1, 3-dimethyl siloxane.
The polysiloxane scintillator prepared by the invention takes polymethylphenylsiloxane-polymethylphenylmethylhydrosiloxane copolymer (PSS) as a scintillator matrix, is doped with a main fluorescent dye PPO and a secondary fluorescent dye MDAC, and introduces a cross-linking agent 1, 3-divinyl, 1, 3-diphenyl and 1, 3-dimethyl siloxane to increase the hardness of the scintillator. As a result, the polysiloxane scintillator with the cross-linking agent is improved in hardness, the dissolution concentration and the storage time of the dye can be improved, and the obtained polysiloxane-based plastic scintillator has good neutron and gamma ray discrimination capability, and also has good irradiation resistance, mechanical strength and optical stability.
Preferably, the mass fraction of the primary fluorescent dye in the polysiloxane-based plastic scintillator is 4-6%, and the mass fraction of the secondary fluorescent dye in the polysiloxane scintillator is 0.02-0.10%. The mass fraction of the cross-linking agent in the polysiloxane scintillator is 5% -15%.
The inventor finds that when the mass fraction of the PPO of the main fluorescent dye is 5-6wt% and the mass fraction of the MDAC of the secondary fluorescent dye is 0.04-0.10wt%, and the mass fraction of the crosslinking agent 1, 3-divinyl, 1, 3-diphenyl and 1, 3-dimethyl siloxane is 10-15%, the prepared polysiloxane-based plastic scintillator has better optical transparency, and simultaneously has the best neutron and gamma ray discrimination capability and also has excellent mechanical hardness.
It can be seen that in the present invention, the mass of the fluorescent dye doped in the polysiloxane scintillator matrix is very small, firstly because the solubility of the polysiloxane substrate to the dye is far lower than that of the polymethylstyrene substrate, and more importantly, the inventor finds that the polysiloxane scintillator can realize effective discrimination between neutrons and gamma rays under the condition of low-concentration dye doping when the fluorescent dye of the present invention is selected.
Of course, in the invention, the addition amount of the main fluorescent dye PPO needs to be controlled effectively, when the main fluorescent dye is added too much, the self-absorption phenomenon of PPO will be more obvious, resulting in the reduction of the overall luminous efficiency of the scintillator, and when the threshold of PPO dissolution is approached, obvious dye precipitation will occur, so that the optical transparency of the polysiloxane scintillator is poor, and the mechanical performance of the polysiloxane scintillator is also reduced. When the PPO amount is too small, the density of the singles in the scintillator is insufficient, so that the probability of mutual collision between singles is reduced, and finally, the discrimination capability of neutrons and gamma rays in the scintillator is reduced.
Meanwhile, the addition amount of the secondary fluorescent dye MDAC needs to be effectively controlled. When the MDAC is excessively added, the strong dyeing capability of the MDAC leads the scintillator to obviously yellow, so that the optical transparency of the scintillator is reduced, the luminous efficiency of the scintillator is further reduced, the excessive MDAC cannot exist stably in the polysiloxane matrix, and dye precipitation easily occurs, so that the optical life of the scintillator is reduced. When MADAC is added in an excessively small amount, the elimination effect on the PPO self-absorption phenomenon is weakened, resulting in a decrease in the scintillator luminous efficiency.
The addition of the crosslinking agent 1, 3-divinyl, 1, 3-diphenyl and 1, 3-dimethyl siloxane needs to be effectively controlled, and too little crosslinking agent is added, so that the hardness of the polysiloxane scintillator is reduced, and the finished product is seriously too soft and cannot be completely solidified. When the addition amount is too large, the polysiloxane hardness is too high, and product breakage easily occurs at the time of high-temperature curing.
In a preferred embodiment, the polymethylphenylsiloxane-polymethylphenylmethylhydrosiloxane copolymer (PSS) is obtained by copolymerizing vinyl-terminated polymethylphenylsiloxane and hydrogen-terminated polymethylphenylmethylhydrosiloxane, and the mass ratio of the vinyl-terminated polymethylphenylsiloxane to the hydrogen-terminated polymethylphenylmethylhydrosiloxane is 7:3, 8:2, or 9:1, respectively.
The inventor finds that in the polymerization reaction process of the invention, the mass ratio of vinyl-terminated polymethylphenylsiloxane to hydrogen-terminated polymethylphenylmethylhydrogen siloxane is controlled in the proportion, and the transparency and the mechanical property of the polysiloxane scintillator finally obtained by adding the cross-linking agent with proper concentration are optimal. The dissolution rate of the primary and secondary fluorescent dyes in the matrix is slow and difficult to uniformly distribute, and in order to accelerate the dissolution of the dyes, the inventors used toluene as a cosolvent, dissolved the primary and secondary fluorescent dyes in toluene, and added the mixed solution after the dissolution to the matrix.
The invention also provides a preparation method of the polysiloxane scintillator, which comprises the following steps: uniformly mixing vinyl-terminated polymethylphenylsiloxane and hydrogen-terminated polymethylphenylmethylhydrosiloxane to obtain a precursor solution; dissolving the main fluorescent dye and the secondary fluorescent dye in toluene, uniformly mixing with the precursor, and adding a cross-linking agent together to obtain a mixed solution; and (3) vacuum pumping toluene in the mixed solution by using a vacuum pump, adding Karstedt catalyst, sealing, placing into an oil bath pot with an initial temperature of 45 ℃, immediately heating to 60 ℃ for 4 hours, heating to 80 ℃ for solidification for 36 hours, stopping heating after solidification, and naturally cooling to room temperature to obtain the plastic scintillator.
In the polymerization reaction process of the invention, the ratio of the addition amount of the vinyl-terminated polymethylphenylsiloxane to the addition amount of the hydrogen-terminated polymethylphenylmethylhydrosiloxane and the addition amount of the crosslinking agent have great influence on the hardness of the polymerization product.
Toluene was chosen as a cosolvent during the polymerization. Because toluene has good solubility on PPO and MDAC, after the toluene cosolvent is added, the time required for completely dispersing the dye in the mixed solution is greatly shortened, and the phenomenon of local deposition of the dye caused by different diffusion speeds of the dye in the mixed solution is effectively avoided. And the inventors found that toluene co-solvent had minimal impact on the polymerization process and product compared to ethanol and acetone. And a vacuum pump was used to pump toluene. Because the boiling point of toluene is about 110 ℃ and is easy to volatilize, the scintillator matrix material selected by the invention has the advantages of over 250 ℃ in boiling point, difficult volatilization, good thermal stability, simple process, less toluene residue, small temperature change and short time compared with the process of heating and evaporating toluene by adopting vacuum to extract toluene.
Further, the Karstedt catalyst contains 2% Pt. The initial temperature of the polymerization reaction was 45℃and the heating rate of the polymerization reaction was 10℃per hour, and the reaction time was 40 hours. Since the excessive polymerization initiation temperature may cause difficulty in eliminating bubbles in the mixed solution, it may affect the uniformity of the scintillator, and the excessive polymerization initiation temperature may cause an increase in the polymerization time and a decrease in the hardness of the scintillator after polymerization. Too fast temperature rise in the polymerization reaction process can lead to too fast polymerization reaction speed, bubbles appear in the polymerized scintillator, too slow temperature rise can lead to the decrease of the polymerization degree of the scintillator, the decrease of the hardness and the increase of the polymerization time.
The invention also provides application of the plastic scintillator, and the plastic scintillator is applied to a neutron detector.
The invention has the following beneficial effects:
1. The invention provides a polysiloxane scintillator, which comprises a scintillator matrix, and a main fluorescent dye, a secondary fluorescent dye and a cross-linking agent which are co-doped in the matrix. Wherein the scintillator matrix is polymethylphenylsiloxane-polymethylphenylmethylhydrosiloxane copolymer, and contains Si-O bond with bond energy of 460kJ/mol, which is far greater than C-H bond energy of 304kJ/mol in polystyrene and polymethylstyrene in the prior art, thus having stronger radiation resistance. At the same time, si-O bond is longer in bond length And the larger rotation angle gives the polysiloxane scintillator matrix more stable physical properties, and the polysiloxane scintillator can still work normally in the high temperature range of 250 ℃. In addition, the phenyl connected with the polysiloxane Si-O main chain also contains pi electrons, which plays a role in absorbing radiation and protecting the main chain, so that the radiation resistance of the polysiloxane material is further enhanced. The energy transfer process of the invention is expressed as follows: the scintillator matrix was used as the energy donor, PPO as the first energy acceptor (primary fluorescent dye), and MDAC as the second energy acceptor (wave-shifting agent). The introduction of the cross-linking agent also improves the defect of poor mechanical property of the rubber matrix and improves the hardness.
2. The invention provides a preparation method for discriminating polysiloxane scintillators by neutrons and gamma rays with high hardness energy, which adopts a polysiloxane matrix to greatly improve the radiation resistance, the radiation resistance and the use ability of the scintillator in severe environments; the vinyl-terminated polymethylphenylsiloxane and the hydrogen-terminated polymethylphenylmethylhydrosiloxane are utilized to carry out hydrosilylation under the action of Karstedt's catalyst, and simultaneously the crosslinking agent 1, 3-divinyl, 1, 3-diphenyl and 1, 3-dimethyl siloxane are added, so that the reaction speed is extremely high and the polymerization degree is good; the precursor mixed liquid of the polymerization reaction is liquid and can be conveniently processed into various sizes and shapes; the whole polymerization reaction process is insensitive to water and oxygen, does not need a vacuum environment, and can be carried out in an oil bath after sealing, thus having the characteristic of simple reaction conditions; the polysiloxane plastic scintillator detector produced by the polymerization reaction can realize effective discrimination of neutron-gamma under extremely low dye load (< 7wt%) and further reduce the production cost. The advantages enable the polysiloxane plastic scintillator to have considerable commercial application prospect.
3. In the preparation process, toluene cosolvent is used, and a filtering method for extracting the cosolvent in vacuum is used. Because dissolution and dispersion of the primary fluorescent dye in the scintillator matrix employed in the present invention is a very slow process, mainly because the scintillator matrix is very viscous, and the dispersion and dissolution of the primary fluorescent dye therein takes longer. In order to improve the neutron and gamma ray discrimination capability of the scintillator, the solubility of the main fluorescent dye PPO must be improved, and the inventor finds that when the amount of PPO is more than 6% of the total mass of the scintillator matrix, PPO is difficult to disperse and dissolve in the scintillator matrix, and local dye aggregation occurs, which has a great influence on the uniformity and optical transparency of the polysiloxane scintillator. The solubility of PPO and MDAC in toluene is very good, and only 0.3-0.5g of toluene is needed to completely dissolve the fluorescent dye, and then the dissolved solution is mixed and doped into the scintillator matrix, so that the fluorescent dye can be quickly and uniformly dispersed into the scintillator matrix.
4. The polysiloxane scintillator prepared by the method has the capability of discriminating neutrons and gamma rays, and simultaneously has the characteristics of good anti-radiation performance, high hardness, high mechanical strength, simple synthesis process and low cost, and can be applied to commercial mass production. The obtained polysiloxane scintillator can be widely applied to neutron detectors.
Drawings
FIG. 1 is an emission-fluorescence spectrum of preferred embodiment 1 of the present invention.
FIG. 2 is a neutrons-gamma pulse shape screening chart of preferred embodiment 1 of the present invention.
FIG. 3 is an ultraviolet-visible light transmittance spectrum of preferred embodiment 1 of the present invention.
FIG. 4 is an emission-fluorescence spectrum of comparative example 1 of the present invention.
Fig. 5 is an ultraviolet-visible transmittance spectrum of comparative example 1 of the present invention.
Detailed Description
The method of preparing the modified polysiloxane-based plastic scintillator of the present invention is further described below by way of specific examples.
Example 1
(1) According to the following steps: 3, mixing 2.1g of vinyl-terminated polymethylphenylsiloxane and 0.9g of hydrogen-terminated polymethylphenylmethylhydrosiloxane, and uniformly stirring to obtain a matrix; then 0.18g of PPO and 0.0012gMDAC g of PPO are dissolved in a small amount of toluene cosolvent according to mass percentage, mixed with 0.45g (the mass is 15% of the mass of the matrix) of cross-linking agent doped into the matrix, and ultrasonically oscillated for 2 minutes to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
And taking out the test tube after solidification, cooling to room temperature, and crushing the test tube to obtain the polymerized polysiloxane scintillator, wherein the obtained scintillator has good optical transparency, high hardness and neutron and gamma ray discrimination capability.
FIG. 1 is an emission-fluorescence spectrum of example 1, showing that under excitation by ultraviolet light having a wavelength of 270nm, the emission spectrum of the polysiloxane scintillator exhibits a peak at 420-470nm, which is a characteristic emission peak of MDAC; the spectra show that the addition of the primary and secondary fluorescent dyes red shifts the luminescence wavelength of the matrix to the blue band of around 450nm for better matching with the photomultiplier. The addition amount of MDAC in the polysiloxane scintillator is far lower than that of PPO, the characteristic emission peak of PPO is about 320nm, and the characteristic emission peak does not appear about 320nm in the figure, which indicates that energy conversion occurs between PPO and MDAC, the energy transfer effect is good, and in addition, the addition of MDAC improves the luminous capacity of the scintillator to a certain extent.
Fig. 2 is a spectrum of the neutron-gamma pulse shape discrimination of example 1, in which the distribution of neutron and gamma ray energy bands can be clearly seen, the pulse signal generated for neutrons at high Q tail/Qtotal, and the pulse signal generated for gamma rays at low Q tail/Qtotal.
FIG. 3 shows the UV-visible spectrum of the polysiloxane scintillators developed by the invention, wherein the sample is seen to have higher transmittance.
Example 2
(1) According to the following steps: 3, mixing 2.1g of vinyl-terminated polymethylphenylsiloxane and 0.9g of hydrogen-terminated polymethylphenylmethylhydrosiloxane, and uniformly stirring to obtain a matrix; then 0.18g of PPO and 0.0012gMAAC are dissolved in a small amount of toluene cosolvent according to mass percentage, mixed with 0.3g (the mass is 10% of the mass of the matrix) of cross-linking agent doped into the matrix, and ultrasonic treated for 2 minutes to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
And taking out the test tube after solidification, cooling to room temperature, and crushing the test tube to obtain the polymerized polysiloxane scintillator, wherein the hardness of the taken scintillator sample is not high and the scintillator sample is easy to damage, so that the method is not beneficial to actual production and application.
Example 3
(1) According to the following steps: 3, mixing 2.1g of vinyl-terminated polymethylphenylsiloxane and 0.9g of hydrogen-terminated polymethylphenylmethylhydrosiloxane, and uniformly stirring to obtain a matrix; and then 0.18g of PPO and 0.0012gMDAC g of cross-linking agent (the mass is 5% of the mass of the matrix) are dissolved in a small amount of toluene cosolvent according to the mass percentage, mixed with 0.15g of cross-linking agent doped into the matrix, and ultrasonically oscillated for 2min to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
And taking out the test tube after solidification, cooling to room temperature, and crushing the test tube to obtain the polymerized polysiloxane scintillator, wherein the hardness of the taken scintillator sample is seriously reduced and the sample is difficult to take out.
Example 4
(1) According to the following steps: 3, mixing 2.1g of vinyl-terminated polymethylphenylsiloxane and 0.9g of hydrogen-terminated polymethylphenylmethylhydrosiloxane, and uniformly stirring to obtain a matrix; and then 0.18g of PPO and 0.0012gMDAC of PPO are dissolved in a small amount of toluene cosolvent according to the mass percentage, mixed with 0.6g (the mass of the cross-linking agent is 20% of that of the matrix) of the cross-linking agent doped matrix, and ultrasonically oscillated for 2min to obtain a polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
And taking out the test tube after solidification, cooling to room temperature, and crushing the test tube to obtain the polymerized polysiloxane scintillator, wherein the hardness of the taken scintillator sample is too high, so that the sample is easy to crack.
Example 5
(1) According to 8: 2a mass ratio of 2.4g of vinyl-terminated polymethylphenylsiloxane and 0.6g of hydrogen-terminated polymethylphenylmethylhydrogen siloxane are mixed and stirred uniformly to prepare a matrix; and then 0.18g of PPO and 0.0012gMDAC of PPO are dissolved in a small amount of toluene cosolvent according to the mass percentage, mixed with 0.45g (the mass of the cross-linking agent is 15% of that of the matrix) of the cross-linking agent doped matrix, and ultrasonically oscillated for 2min to obtain a polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
And taking out the test tube after solidification, cooling to room temperature, and crushing the test tube to obtain the polymerized polysiloxane scintillator, wherein the hardness of the taken scintillator sample is found to be too high, and the sample is cracked.
Example 6
(1) According to 8: 2a mass ratio of 2.4g of vinyl-terminated polymethylphenylsiloxane and 0.6g of hydrogen-terminated polymethylphenylmethylhydrogen siloxane are mixed and stirred uniformly to prepare a matrix; and then 0.18g of PPO and 0.0012gMDAC of PPO are dissolved in a small amount of toluene cosolvent according to the mass percentage, mixed with 0.3g (the mass is 10% of the mass of the matrix) of cross-linking agent doped into the matrix, and ultrasonically oscillated for 2min to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
And taking out the test tube after solidification, cooling to room temperature, and crushing the test tube to obtain the polymerized polysiloxane scintillator.
Example 7
(1) According to 8: 2a mass ratio of 2.4g of vinyl-terminated polymethylphenylsiloxane and 0.6g of hydrogen-terminated polymethylphenylmethylhydrogen siloxane are mixed and stirred uniformly to prepare a matrix; and then 0.18g of PPO and 0.0012gMDAC g of cross-linking agent (the mass is 5% of the mass of the matrix) are dissolved in a small amount of toluene cosolvent according to the mass percentage, mixed with 0.15g of cross-linking agent doped into the matrix, and ultrasonically oscillated for 2min to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
After solidification, the test tube is taken out and cooled to room temperature, and then the test tube is broken up, so that the polymerized polysiloxane scintillator is obtained, and the scintillator is too soft and difficult to take out.
Example 8
(1) According to 9: 1a mass ratio of 2.7g of vinyl-terminated polymethylphenylsiloxane and 0.3g of hydrogen-terminated polymethylphenylmethylhydrogen siloxane were mixed and stirred uniformly to prepare a matrix; and then 0.18g of PPO and 0.0012gMADC of PPO are dissolved in a small amount of toluene cosolvent according to the mass percentage, mixed with 0.3g (the mass is 10% of the mass of the matrix) of cross-linking agent doped into the matrix, and ultrasonically oscillated for 2min to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
After solidification, the test tube is taken out and cooled to room temperature, and then the test tube is broken up to obtain the polymerized polysiloxane scintillator, which is too viscous to be taken out.
Example 9
(1) According to 9: 1a mass ratio of 2.7g of vinyl-terminated polymethylphenylsiloxane and 0.3g of hydrogen-terminated polymethylphenylmethylhydrogen siloxane were mixed and stirred uniformly to prepare a matrix; then 0.18g of PPO and 0.0012gMDAC g of cross-linking agent (the mass is 5% of the mass of the matrix) are dissolved in a small amount of toluene cosolvent according to the mass percentage, mixed with 0.15g of cross-linking agent doped into the matrix, and ultrasonic oscillation is carried out to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
And taking out the test tube after solidification, cooling to room temperature, and crushing the test tube to obtain the polymerized polysiloxane scintillator, wherein the scintillator has high optical transparency but severely reduced hardness.
Comparative example 1
(1) According to the following steps: 3, mixing 2.1g of vinyl-terminated polymethylphenylsiloxane and 0.9g of hydrogen-terminated polymethylphenylmethylhydrosiloxane, and uniformly stirring to obtain a matrix; then 0.18g of PPO and 0.0012gMDAC are dissolved in a small amount of toluene cosolvent to be mixed with the matrix according to mass percent, and the mixture is sonicated for 2 minutes to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
After completion of the solidification, the tube was taken out and cooled to room temperature, and then the tube was broken to obtain a polymerized polysiloxane scintillator, and it was found that the scintillator sample without the crosslinking agent was too soft to take out the whole sample.
Comparative example 2
(1) According to 8: 2a mass ratio of 2.4g of vinyl-terminated polymethylphenylsiloxane and 0.6g of hydrogen-terminated polymethylphenylmethylhydrogen siloxane are mixed and stirred uniformly to prepare a matrix; then 0.18g of PPO and 0.0012gMDAC are dissolved in a small amount of toluene cosolvent to be mixed with the matrix according to mass percent, and the mixture is sonicated for 2 minutes to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
After completion of the solidification, the tube was taken out and cooled to room temperature, and then the tube was broken to obtain a polymerized polysiloxane scintillator, and it was found that a scintillator sample without the crosslinking agent was too soft to take out the whole sample.
Comparative example 3
(1) According to 9: 1a mass ratio of 2.7g of vinyl-terminated polymethylphenylsiloxane and 0.3g of hydrogen-terminated polymethylphenylmethylhydrogen siloxane were mixed and stirred uniformly to prepare a matrix; then 0.18g of PPO and 0.0012gMDAC are dissolved in a small amount of toluene cosolvent to be mixed with the matrix according to mass percent, and the mixture is sonicated for 2 minutes to obtain polysiloxane mixed solution.
(2) The polysiloxane mixed solution was added to a flat bottom test tube, vacuum filtered multiple times, then 3 μl of Karstedt catalyst with Pt loading of 2% was added, and the catalyst was dispersed uniformly by gentle shaking, and finally the test tube was sealed with a waterproof tape.
(3) The sealed test tube is placed into an oil bath pot with the initial temperature of 45 ℃, the temperature is gradually increased to 60 ℃ at 10 ℃/h, the heat is preserved for 4 hours, and the test tube is solidified for 36 hours at 80 ℃.
After curing, the tube was cooled to room temperature and broken to give a polymerized polysiloxane scintillator, and the scintillator sample without the crosslinker was found to have good optical clarity and reduced hardness compared to the samples of examples 1 and 6.
Experimental example
The samples of examples 1,6,9 were subjected to hardness testing and compared with the hardness of the samples of comparative examples 1,2, 3. The specific detection method of the hardness comprises the following steps: the polysiloxane scintillator is positively placed on a measuring base of a digital display portable pointer Shore hardness tester, a measuring handle is manually pressed downwards, data on a display is recorded, the measurement is repeated for five times, an average value is taken as a final measuring result,
| Hardness (HA) | |
| Example 1 | 37 |
| Example 6 | 30 |
| Example 9 | 9 |
| Comparative example 1 | 6 |
| Comparative example 2 | 7 |
| Comparative example 3 | 13 |
Measurement results are shown in the table, the modified polysiloxane scintillators prepared by the method provided by the invention can obviously improve the physical hardness of the scintillators on the premise of not affecting the optical transparency by crossing the cross-linking agent with the matrix in a proper proportion.
Claims (10)
1. A polysiloxane scintillator for discriminating neutrons and gamma rays with high hardness is characterized in that: the polysiloxane scintillator consists of a scintillator matrix, a cross-linking agent, a primary fluorescent dye and a secondary fluorescent dye which are co-doped in the matrix, wherein the scintillator matrix is polymethylphenylsiloxane-polymethylphenylmethylhydrosiloxane copolymer (PSS), the primary fluorescent dye is diphenyl oxazole (PPO), and the secondary fluorescent dye is 7-diethylamino-4-Methylcoumarin (MDAC).
2. The polysiloxane scintillator of claim 1, wherein: when the mass fraction of the main fluorescent dye in the polysiloxane scintillator is 4-6wt% and the mass fraction of the secondary fluorescent dye in the polysiloxane scintillator is 0.04-0.10wt%, the mass fraction of the crosslinking agent 1, 3-divinyl, 1, 3-diphenyl and 1, 3-dimethyl siloxane in the polysiloxane scintillator is 10-15%.
3. The polysiloxane scintillator of claim 1, wherein: the polymethylphenylsiloxane-polymethylphenylmethylhydrosiloxane copolymer (PSS) is obtained by copolymerizing vinyl-terminated polymethylphenylsiloxane and hydrogen-terminated polymethylphenylmethylhydrosiloxane, and the mass ratio of the vinyl-terminated polymethylphenylsiloxane to the hydrogen-terminated polymethylphenylmethylhydrosiloxane is 7:3,8:2 and 9:1 respectively.
4. The polysiloxane scintillator of claim 1, wherein: the main fluorescent dye is PPO, and the secondary fluorescent dye is MDAC, so that the luminous wavelength of the matrix is red-shifted to the wavelength interval of the optimal operation of the photomultiplier.
5. The method for producing a polysiloxane scintillator according to any one of claims 1 to 4, wherein: the preparation method comprises the steps of mixing vinyl-terminated polymethylphenylsiloxane and hydrogen-terminated polymethylphenylmethylhydrogen siloxane to obtain a precursor solution, dissolving a primary fluorescent dye and a secondary fluorescent dye in toluene, adding the primary fluorescent dye and the secondary fluorescent dye and a crosslinking agent 1, 3-divinyl 1, 3-diphenyl 1, 3-dimethyl siloxane into the precursor solution, adding a Karstedt catalyst to obtain a mixed solution, and curing to obtain the polysiloxane scintillator.
6. The method for producing a polysiloxane scintillator according to claim 5, wherein: in the precursor solution, the mass ratio of vinyl-terminated polymethylphenylsiloxane to hydrogen-terminated polymethylphenylmethylhydrosiloxane is 7:3,8:2,9:1.
7. The method for producing a polysiloxane-based plastic scintillator according to claim 5, wherein: in the precursor solution, when the mass fraction of the main fluorescent dye is 4-6% and the mass fraction of the secondary fluorescent dye is 0.04-0.10wt%, the mass fraction of the crosslinking agent 1, 3-divinyl, 1, 3-diphenyl and 1, 3-dimethyl siloxane is 10-15%.
8. The method for producing a polysiloxane scintillator according to claim 5, wherein: in the Karstedt catalyst, the Pt loading is 2wt%, and 1 mu L of the Karstedt catalyst is added into each gram of precursor solution.
9. The method for producing a polysiloxane scintillator according to claim 5, wherein: the polymerization reaction temperature is as follows: the polymerization reaction time is 40h at 45-80 ℃.
10. The use of a high hardness energy neutron and gamma ray screening polysiloxane scintillator according to any one of claims 1-4, wherein: the polysiloxane scintillator is applied to a neutron detector.
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