CN117555011A - CT scintillating ceramic area array and CT detector - Google Patents
CT scintillating ceramic area array and CT detector Download PDFInfo
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Abstract
The invention belongs to the technical field of scintillation detectors, and particularly relates to a CT scintillation ceramic area array and a CT detector. The CT scintillating ceramic area array provided by the invention comprises a plurality of scintillating ceramic blocks and an encapsulation body which encapsulates the scintillating ceramic blocks; the scintillating ceramic blocks are vertically and horizontally arranged on a plane to form an area array, and the scintillating ceramic blocks emit visible light under the excitation of X rays; the encapsulation body coats the surface of the scintillating ceramic block and only exposes one side surface as a light-emitting surface; the encapsulation body is formed by solidifying pouring sealant, and the pouring sealant comprises epoxy resin, anhydride, a solidifying catalyst, a defoaming agent, a first filler and a second filler. The CT scintillating ceramic area array provided by the invention has excellent light output performance and durability, and the attenuation of light output is smaller under the condition of being subjected to large-dose irradiation, so that the stable intensity of image signals generated by long-time operation of CT equipment is ensured. On the basis of the CT scintillation ceramic area array, the invention further provides a CT detector.
Description
Technical Field
The invention belongs to the technical field of scintillation detectors, and particularly relates to a CT scintillation ceramic area array and a CT detector.
Background
The scintillator ceramic area array for medical CT is a core component of an X-ray computed tomography (X-CT) scanner, and the principle is that high-energy rays are converted into visible light, and the visible light is matched with a detector array and a photoelectric converter to obtain an image.
The scintillator itself can receive the irradiation damage of high energy ray in the use, and the epoxy resin reflection layer that is used for encapsulation also can receive the destruction under irradiation condition, and whole yellowing takes place, influences light reflection efficiency. Both the damage of the scintillator and the damage of the reflecting layer affect the light output of the scintillation area array, and thus the sensitivity of the CT. In practical use, the light output influence caused by irradiation damage of the reflecting layer is far greater than the light output influence caused by performance reduction of the scintillator. Therefore, for the scintillation ceramic area array for CT, on the premise of keeping high light output performance, the improvement of the radiation resistance of the reflecting layer to inhibit the rapid attenuation of light output along with the increase of irradiation dose is the key to improve the service life of medical CT and reduce the maintenance cost.
In addition, in order to obtain a higher resolution image, the size of individual scintillators and the spacing between scintillators tend to be reduced, and thus the thickness of the reflective layer is also severely limited. The internal temperature of the CT equipment is increased during operation, so that the stability of the shape and the size of the packaged reflecting layer under the actual use condition is also a limiting factor which must be faced when the scintillator ceramic area array is improved.
In summary, under the premise of being suitable for a heated working condition and limited thickness of the reflecting layer, the CT scintillation ceramic area array with strong light output and good durability is developed, so that the CT scintillation ceramic area array has obvious challenges and great practical significance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a CT scintillating ceramic area array and a CT detector.
The CT scintillating ceramic area array provided by the invention comprises a plurality of scintillating ceramic blocks and an encapsulation body which encapsulates the scintillating ceramic blocks; the scintillating ceramic blocks are vertically and horizontally arranged on a plane to form an area array, and the scintillating ceramic blocks emit visible light under the excitation of X rays; the encapsulation body coats the surface of the scintillating ceramic block and only exposes one side surface as a light-emitting surface; the encapsulation body is formed by solidifying pouring sealant, and the pouring sealant comprises the following components in mass:
30-40 parts of epoxy resin;
22-28 parts of anhydride;
0.05-0.15 parts by mass of a curing catalyst;
0.5-2.5 parts by mass of defoamer;
30-40 parts by mass of a first filler;
0.3-8.5 parts by mass of a second filler;
the epoxy resin is organic silicon modified alicyclic epoxy resin, and the first filler is titanium dioxide with the particle size within the range of 50-300 nm; the particle size of the second filler is within the range of 20-300 nm, and is selected from one or more of chromium trioxide, cerium dioxide, zirconium dioxide and hafnium dioxide.
Experiments show that the CT scintillating ceramic area array provided by the invention has strong light output and good durability, and still maintains about 90% of light output performance after high-energy irradiation with the dosage of 10 kGy. And the TG point of the main body of the organic silicon modified alicyclic epoxy resin and anhydride after curing is more than 70 ℃ and higher than the internal temperature of CT equipment in operation, so the organic silicon modified alicyclic epoxy resin is not easy to deform under the condition of using working conditions after packaging and curing, and has good dimensional stability. In addition, in the implementation process of the invention, the organic silicon modified alicyclic epoxy resin in the pouring sealant, the titanium pigment with the particle size in the range of 50-300 nm and the second filler (chromium oxide, cerium oxide, zirconium oxide and hafnium oxide) with the particle size in the range of 20-300 nm are cooperated with each other, so that the organic silicon modified alicyclic epoxy resin plays a vital role in improving the light output performance and durability of the GOS scintillator ceramic array.
Further, the anhydride in the pouring sealant is 4-methyl-1, 2-cyclohexanedicarboxylic anhydride.
Further, the curing catalyst in the pouring sealant is N, N-dimethylbenzylamine. The curing agent promotes ring opening, accelerates the reaction of anhydride and epoxy resin, and is a catalyst for conventional commercial epoxy resin.
Further, the defoaming agent in the pouring sealant is one or more of ethylene glycol, propylene glycol and amp-95.
Further, the particle size of the second filler used for the pouring sealant is preferably as follows: the grain size of the nano chromium oxide is 80-200nm, the grain size of the nano cerium oxide is 30-150nm, the grain size of the nano zirconium oxide is 50-180nm, and the grain size of the nano hafnium oxide is 50-120 nm.
Further, the particle size of the second filler used for the pouring sealant is more preferably as follows: in the second filler, the grain diameter of the nano chromium oxide is in the range of 50-100nm, the grain diameter of the nano cerium oxide is in the range of 30-50nm, the grain diameter of the nano zirconium oxide is in the range of 50-100nm, and the grain diameter of the nano hafnium oxide is in the range of 50-80 nm.
Further preferably, the second filler in the pouring sealant is selected from any two of chromium oxide, cerium oxide, zirconium oxide, hafnium oxide.
Further preferably, the thickness of the envelope at the interval between adjacent scintillating ceramic blocks is 0.08-0.12 mm, more preferably 0.10mm. Under the condition that the thickness of the encapsulation body is thinner, the CT scintillating ceramic area array provided by the invention shows excellent light output performance and durability in experiments, which shows that the encapsulation body has excellent blocking and reflecting performance and good stability under the high-energy irradiation condition.
Further preferably, the scintillating ceramic blocks are GOS scintillating ceramic, i.e., gadolinium oxysulfide scintillating ceramic.
On the basis of the CT scintillating ceramic surface array, the invention also provides a CT detector which comprises a photoelectric converter and a CT scintillating ceramic surface array, wherein the photoelectric converter is coupled with each light-emitting surface of the CT scintillating ceramic surface array. Under the irradiation of X-rays, visible light emitted by the scintillating ceramic blocks acts on the photoelectric converter through the light-emitting surface, and the photoelectric converter generates an electric signal under the action of the visible light for generating images subsequently.
Advantageous effects
The CT scintillating ceramic area array provided by the invention has excellent light output performance and durability, and the attenuation of light output is smaller under the condition of being subjected to large-dose irradiation, so that the stable intensity of image signals generated by long-time operation of CT equipment is ensured.
The TG temperature point of the encapsulation body of the CT scintillation ceramic area array provided by the invention is higher than 70 ℃, the temperature is higher than the internal temperature of the CT equipment in long-term use, the thermal deformation is small in long-term use, and the use condition of medical CT is satisfied.
Drawings
Fig. 1 is a schematic diagram of the overall structure of a CT scintillation ceramic area array.
Fig. 2 is a schematic diagram showing a partial structure of a CT scintillation ceramic area array.
Raw material compositions of the pouring sealants in examples 1 to 6 shown in fig. 3.
Fig. 4 shows the light output properties before and after irradiation of examples 1 to 6.
Fig. 5 shows the light output properties before and after irradiation of comparative examples 1 to 6.
FIG. 6 is a photograph of the sample of example 1 before and after irradiation.
FIG. 7 is a photograph of the sample of comparative example 1 before and after irradiation.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the problem and to explain the invention, without limiting it.
The CT scintillating ceramic area array provided by the invention is shown in figures 1 and 2, and comprises a plurality of scintillating ceramic blocks 1 and an encapsulation body 2 which encapsulates the scintillating ceramic blocks 1; the scintillating ceramic blocks 1 are vertically and horizontally arranged on a plane to form an area array, and the surface of the scintillating ceramic blocks 1 is coated by the encapsulation body 2, and only one side surface is exposed to be used as a light-emitting surface 11; the encapsulation body 2 is formed by solidifying pouring sealant. The scintillating ceramic block 1 emits visible light under the excitation of X rays, and the visible light emitted by the scintillating ceramic block 1 mainly emits through the light emitting surface 11 under the blocking effect of the encapsulation body 2 so as to facilitate the subsequent photoelectric conversion.
The CT scintillation ceramic area array provided by the invention can be further coupled with a photoelectric converter to prepare a CT detector. Specifically, a photoelectric converter is coupled to each light-emitting surface 11 of the CT scintillation ceramic planar array. Thus, under the irradiation of X-rays, visible light emitted by the scintillating ceramic blocks 1 acts on the photoelectric converter through the light emitting surface 11, the photoelectric converter generates an electric signal under the action of the visible light, and the generated electric signal is further processed by an image processing algorithm to obtain an image.
The preparation method of the CT scintillation ceramic area array mainly comprises the steps of slotting of a GOS ceramic plate substrate, cleaning of the GOS ceramic plate substrate, pouring of pouring sealant, curing and shaping of the pouring sealant.
The slotting of the GOS ceramic plate substrate is to form checkerboard grid slots which are transversely and longitudinally interwoven on the surface of the substrate; the GOS ceramic wafer substrate is cleaned by removing impurities such as attachments and the like on the surface of the substrate and in the grid grooves; pouring sealant is to pour the pouring sealant on the clean surface of the substrate and in the grid groove, and fully fill the pouring sealant; the curing of the pouring sealant is to cure the pouring sealant poured on the surface of the substrate and in the grid groove by heating; and the shaping is to polish and smooth the surface of the solidified pouring sealant and the surface of the uncoated base material, and remove the GOS ceramic chip base material residues at the edge.
The formulation of the pouring sealant is described below. The pouring sealant mainly comprises the following components in parts by mass:
30-40 parts of epoxy resin;
22-28 parts of anhydride;
0.05-0.15 parts by mass of a curing catalyst;
0.5-2.5 parts by mass of defoamer;
30-40 parts by mass of a first filler;
and 0.3-8.5 parts by mass of a second filler.
In the specific implementation process, the epoxy resin is organic silicon modified alicyclic epoxy resin, and is purchased from the Japan Xinyue company; the first filler is titanium dioxide with the particle size within 50-300 nm and is selected from R-104, R-706 and R-902+ titanium dioxide produced by Dupont company; the particle size of the second filler is within 20-300 nm, and is selected from one or more of chromium oxide, cerium oxide, zirconium oxide and hafnium oxide, wherein the specific use is nanometer chromium oxide (50-100 nm), nanometer cerium oxide (30-50 nm), nanometer zirconium oxide (50-100 nm) and nanometer hafnium oxide (50-80 nm).
In addition, in the specific implementation process, 4-methyl-1, 2-cyclohexanedicarboxylic anhydride is used as the anhydride; the curing catalyst is N, N-dimethylbenzylamine; the defoamer is one or more of ethylene glycol, propylene glycol and amp-95 (green chemical industry).
When the pouring sealant is prepared, epoxy resin, anhydride and a curing catalyst are firstly subjected to vacuum glue mixing according to the formula amount until uniform transparent liquid is formed, then a defoaming agent and a filler are added, and the pouring sealant is prepared through dispersion and defoaming treatment.
Example 1
The scintillator substrate used in this example was a GOS ceramic sheet, which was rectangular plate-like and had a thickness of about 2mm.
The GOS scintillator ceramic area array manufacturing method comprises the following steps:
step S1: and using the heated rosin as an adhesive to adhere the GOS ceramic wafer substrate to the glass substrate.
Step S2: cutting and grooving on the surface of the GOS ceramic chip substrate by using a precise dicing saw, wherein the grooving depth is 1.6mm. Slots are equally spaced in a direction parallel to the length. The width of the groove is 0.1mm, and the spacing is 0.9mm.
Step S3: the GOS ceramic wafer substrate and the glass substrate are integrally rotated by 90 degrees horizontally and grooved at equal intervals along the direction parallel to the width. The width of the groove is 0.1mm, and the spacing is 0.9mm.
Step S4: and (3) ultrasonically cleaning the surface of the grooved GOS ceramic wafer substrate by using absolute ethyl alcohol, and cleaning by using Plasma for later use.
Step S5: preparing an irradiation-resistant epoxy pouring sealant, adding 35 parts of modified epoxy resin, 25 parts of anhydride and 0.1 part of curing catalyst into a vacuum planetary glue mixer tank according to the formula amount of the embodiment 1 in fig. 3, and pouring the mixture into another container after vacuum glue mixing for about 3 minutes until the mixture is uniform transparent liquid.
Step S6: in another container, 2.4 parts of defoaming agent glycol, 35 parts of R-104 titanium pigment, 0.1 part of nano chromium oxide and 2.4 parts of nano cerium oxide are added according to the formula of the embodiment 1 in fig. 3, and after being dispersed for 5 minutes by using a high-speed dispersing machine 6000R/min, vacuum defoaming is carried out for 15 minutes, so that the irradiation-resistant epoxy pouring sealant is obtained.
Step S7: and (3) putting waterproof adhesive tapes around the ceramic wafer substrate and the glass substrate, slowly dripping the pouring sealant obtained in the step (S6) into the grooves on the surface of the GOS ceramic wafer substrate 1, fully filling the grooves, continuously dripping the pouring sealant, forming a covering adhesive layer with the thickness of 1mm on the surface, and then carrying out vacuum defoaming for 10 minutes.
Step S8: and (3) placing the sample obtained in the step (S7) into an oven, heating for 20 hours at 80 ℃, heating to 100 ℃, heating for 20 hours, fully solidifying the pouring sealant, naturally cooling, and taking out.
Step S9: tearing off the waterproof adhesive tape 3, fixing the glass substrate 2 on a grinding machine, and polishing the surface adhesive layer until the thickness of the adhesive layer is 0.3mm; heating to melt rosin, taking down the ceramic substrate with the reflecting layer, polishing the surface of one side without glue filling by a grinder, and exposing the flat crystal surface (namely the light-emitting surface 11 of the scintillating ceramic block 1) and the surface of the reflecting layer with the chess board grooves. And cutting off the surplus ceramic wafer base material by using a precise dicing saw to obtain the CT scintillation ceramic area array.
Examples 2 to 6
Examples 2-6 the steps for manufacturing the GOS scintillator ceramic arrays were the same as those of example 1, except that the corresponding radiation-resistant epoxy potting adhesive was manufactured according to the variation formulation in fig. 3.
Comparative examples 1 to 6
Comparative examples 1-6 the production of GOS scintillator ceramic arrays was identical to the procedure of example 1, except for the composition of the potting adhesive. Specifically, the following is described.
Comparative example 1 differs from example 1 only in that a silicone modified cycloaliphatic epoxy resin was not used, but an ordinary epoxy resin of the E44 bisphenol a type of epoxy resin of the same quality was used.
Comparative example 2 differs from example 1 only in that a silicone modified cycloaliphatic epoxy resin is not used, but an equivalent quality EPSI-6862 resin, which is a non-cycloaliphatic silicone modified hydrogenated bisphenol A resin, is used.
Comparative example 3 differs from example 1 only in that the same mass but different kinds of the first filler were used, and the first filler of comparative example 3 was titanium white powder R-960 having a particle diameter of about 350 nm.
Comparative example 4 differs from example 1 only in that the first filler was not added.
Comparative example 5 differs from example 1 only in that the same mass but different kinds of second filler were used, and the second filler of comparative example 5 was 0.1 part by mass of ceria having a particle diameter of 1 μm and 2.4 parts by mass of chromia having a particle diameter of 2 μm.
Comparative example 6 differs from example 1 only in that no second filler was added.
As described above, the different GOS scintillator ceramic area array samples prepared in examples 1 to 6 and comparative examples 1 to 6 were subjected to a high-energy irradiation test to simulate irradiation damage caused by irradiation with high-energy rays in the actual use process, and the light output values and the change rates before and after irradiation were detected, respectively.
The irradiation conditions were as follows:
radiation source type: 60 CO；
the source is strong: 12.8 ten thousand curies;
irradiation distance: 22cm;
irradiation time: 1h;
dose rate: 10000 Gy/h;
total dose: 10000 Gy.
FIGS. 4 and 5 show the initial light output, the light output after irradiation and the rate of change of the GOS scintillator ceramic area array samples prepared in examples 1 to 6 and comparative examples 1 to 6. The scintillator ceramic area array is used as a core component of an X-ray computed tomography (X-CT), and the intensity of light output has a critical influence on the sensitivity of CT. In addition, the rate of change of the light output after irradiation and before and after irradiation directly determines the service life and maintenance period of the CT.
As shown in FIG. 4, the GOS scintillator ceramic area array samples prepared in examples 1-6 all have excellent initial light output performance, and after 10kGy dose irradiation, the overall light output can still be kept about 90%, and the light output of the optimal sample is reduced by only 9.2%. The light output and the irradiation resistance are obviously superior to those of the existing scintillating ceramic surface for conventional medical CT, the requirements of the scintillator surface array for medical CT on sensitivity and service life can be fully met, and the cost is lower.
As shown in FIG. 5, comparative example 1 uses a general epoxy resin E44 bisphenol A type epoxy resin, and the prepared sample has a good initial light output, but the light output after high-energy irradiation is significantly reduced, and the change rate is-37.7%. Comparative example 2 used no silicone-modified cycloaliphatic epoxy resin, but instead used a silicone-modified non-cycloaliphatic epoxy resin, and the resulting sample also had good initial light output, but the light output after high-energy irradiation also showed a significant drop with a rate of change of-27.9%. Comparative example 3, in which the first filler was replaced and titanium white powder R-960 having a particle diameter of about 350nm was used, had a significant decrease in initial light output as compared with example 1, and the rate of change in light output was slightly increased in the case of the decrease in initial light output. Comparative example 4 differs from example 1 only in that the first filler was not added, in contrast, the initial light output was significantly reduced, and the rate of change of the light output was also increased to some extent. Comparative example 5 uses a second filler having a different particle diameter than that of example 1, the second filler being 0.1 part by mass of ceria having a particle diameter of 1 μm and 2.4 parts by mass of chromia having a particle diameter of 2 μm, the initial light output is significantly decreased, and the rate of change in light output is slightly increased. Comparative example 6 differs from example 1 only in that no second filler was added, resulting in a significant decrease in light output after high-energy irradiation. In summary, in the pouring sealant, the organic silicon modified alicyclic epoxy resin, the titanium pigment with the particle size within the range of 50-300 nm and the second filler (chromium oxide, cerium oxide, zirconium oxide and hafnium oxide) with the particle size within the range of 20-300 nm cooperate with each other, so that the pouring sealant plays a vital role in improving the light output performance and durability of the GOS scintillator ceramic surface array.
More intuitively, fig. 6 shows a photograph of a sample of example 1 before and after high-energy irradiation, wherein a region A1 shows a photograph before irradiation, and a region A2 shows a photograph after irradiation, and no difference is visible between the two. Fig. 7 shows the photographs of the samples of comparative example 1 before and after high energy irradiation, wherein the B1 region shows the photograph before irradiation, and the B2 region shows the photograph after irradiation, and the GOS scintillator ceramic surface array after irradiation shows significant yellowing compared with the photograph before irradiation.
The above embodiments are illustrative for the purpose of illustrating the technical concept and features of the present invention so that those skilled in the art can understand the content of the present invention and implement it accordingly, and thus do not limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The utility model provides a CT scintillation ceramic area array which characterized in that: comprises a plurality of scintillating ceramic blocks (1) and an encapsulation body (2) which encapsulates the scintillating ceramic blocks (1); the scintillating ceramic blocks (1) are vertically and horizontally arranged on a plane to form an area array, and the scintillating ceramic blocks (1) emit visible light under the excitation of X rays; the encapsulation body (2) coats the surface of the scintillating ceramic block (1) and only exposes one side surface as a light-emitting surface (11); the encapsulation body (2) is formed by solidifying pouring sealant, and the pouring sealant comprises the following components in mass:
30-40 parts of epoxy resin;
22-28 parts of anhydride;
0.05-0.15 parts by mass of a curing catalyst;
0.5-2.5 parts by mass of defoamer;
30-40 parts by mass of a first filler;
0.3-8.5 parts by mass of a second filler;
the epoxy resin is organic silicon modified alicyclic epoxy resin; the first filler is titanium dioxide with the particle size within the range of 50-300 nm; the particle size of the second filler is within the range of 20-300 nm, and the second filler is one or more selected from chromium oxide, cerium oxide, zirconium oxide and hafnium oxide.
2. The CT scintillation ceramic face array of claim 1, wherein: the anhydride is 4-methyl-1, 2-cyclohexanedicarboxylic anhydride.
3. The CT scintillation ceramic face array of claim 1, wherein: the curing catalyst is N, N-dimethylbenzylamine.
4. The CT scintillation ceramic face array of claim 1, wherein: the defoaming agent is one or more of ethylene glycol, propylene glycol and amp-95.
5. The CT scintillation ceramic face array of claim 1, wherein: in the second filler, the grain diameter of the nano chromium oxide is in the range of 80-200nm, the grain diameter of the nano cerium oxide is in the range of 30-150nm, the grain diameter of the nano zirconium oxide is in the range of 50-180nm, and the grain diameter of the nano hafnium oxide is in the range of 50-120 nm.
6. The CT scintillation ceramic face array of claim 1, wherein: in the second filler, the grain diameter of the nano chromium oxide is in the range of 50-100nm, the grain diameter of the nano cerium oxide is in the range of 30-50nm, the grain diameter of the nano zirconium oxide is in the range of 50-100nm, and the grain diameter of the nano hafnium oxide is in the range of 50-80 nm.
7. The CT scintillation ceramic face array of claim 6 wherein: the second filler is selected from any two of chromium oxide, cerium oxide, zirconium oxide and hafnium oxide.
8. The CT scintillation ceramic face array of claim 1, wherein: the thickness of the enveloping body (2) at intervals between the adjacent scintillating ceramic blocks (1) is 0.08-0.12 mm.
9. The CT scintillation ceramic face array of claim 1, wherein: the scintillating ceramic block (1) is GOS scintillating ceramic.
10. A CT detector, characterized by: comprising a photoelectric converter and a CT scintillating ceramic matrix according to any of claims 1 to 9, the photoelectric converter being coupled at each light exit face (11) of the CT scintillating ceramic matrix; under the irradiation of X rays, visible light emitted by the scintillating ceramic blocks (1) acts on the photoelectric converter through the light emitting surface (11), and the photoelectric converter generates an electric signal under the action of the visible light.
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