CN109192388B - Superconducting material for nuclear magnetic resonance human body imaging and preparation method thereof - Google Patents
Superconducting material for nuclear magnetic resonance human body imaging and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000005481 NMR spectroscopy Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 24
- 238000003384 imaging method Methods 0.000 title claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 113
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000010949 copper Substances 0.000 claims abstract description 55
- PZKRHHZKOQZHIO-UHFFFAOYSA-N [B].[B].[Mg] Chemical compound [B].[B].[Mg] PZKRHHZKOQZHIO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 36
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- 229910052788 barium Inorganic materials 0.000 claims abstract description 31
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 14
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005751 Copper oxide Substances 0.000 claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 10
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 21
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000002595 magnetic resonance imaging Methods 0.000 claims 2
- 239000013078 crystal Substances 0.000 abstract description 18
- 239000011258 core-shell material Substances 0.000 abstract description 8
- 239000000084 colloidal system Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 229910008051 Si-OH Inorganic materials 0.000 description 7
- 229910006358 Si—OH Inorganic materials 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical compound [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WKWVTNARZXNZQY-UHFFFAOYSA-N azanide;copper(1+) Chemical compound [Cu]N WKWVTNARZXNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
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Abstract
The invention discloses a method for forming a nuclear magnetic resonance human bodyThe image superconducting material comprises the following raw materials in parts by weight: 13.2-13.8 parts of modified graphite powder, 11.1-11.3 parts of yttrium oxide, 23.9-24.2 parts of copper oxide, 52.1-52.3 parts of barium nitrate, 22.4-22.7 parts of diethylenetriamine, 132.6-134.7 parts of propionic acid, 6.9-7.2 parts of carbon/titanium doped magnesium diboride, a proper amount of water and a proper amount of dilute nitric acid. The modified graphite powder and each colloid of the material prepared by the invention have the advantages that yttrium sol, copper sol and barium sol are distributed on a modified graphite powder framework through the chemical bond effect, and after calcination, organic components in the yttrium sol, the copper sol and the barium sol are decomposed and yttrium, copper and barium generate YBa on the modified graphite powder framework2Cu3OXSuperconducting crystal, and carbon/titanium doped magnesium diboride coated on YBa2Cu3OXA core-shell structure is formed inside the superconducting crystal, so that the prepared superconducting material is stable in structure and uniform in component distribution.
Description
Technical Field
The invention belongs to the field of superconducting material preparation, and relates to a superconducting material for nuclear magnetic resonance human body imaging and a preparation method thereof.
Background
The superconducting material is taken as the most important high-technology energy-saving environment-friendly material in the 21 st century and is widely applied to the fields of large-scale power transmission and distribution, super magnets, energy storage, transformers, magnetic levitation trains and the like, the main superconducting material in the market at present is a low-temperature superconducting material, the superconducting material must operate under the condition of liquid helium due to very low superconducting transition temperature, the cost of helium is high, the application range of the superconducting material is influenced, the copper oxide superconducting material which is widely applied at present cannot be used for a long time due to the phenomenon of super-interception capability degradation, so that the yttrium barium copper oxygen high-temperature superconducting material developed at present is widely applied due to the high-temperature superconductivity and the durability of the copper oxide superconducting material, but the supercritical current density of the yttrium barium copper oxygen superconducting material still cannot reach an ideal value, and the existing sol method is used most widely in the process of preparing the superconducting material, however, in the preparation process of the sol method, several colloids are mixed together and then calcined to prepare the superconducting material, but the uniformity of the mixing of the colloids affects the type and structure of the calcined product, so that the properties of the prepared superconducting material are unstable.
Disclosure of Invention
The invention aims to provide a superconducting material for nuclear magnetic resonance human body imaging and a preparation method thereof, wherein the surface of modified graphite powder in the superconducting material contains Si-OH, yttrium sol contains amino, and copper sol and barium sol both contain hydroxyl, and can be uniformly dispersed on a skeleton structure of the modified graphite powder through dehydration reaction at 70 ℃, and carbon/titanium doped magnesium diboride can be uniformly distributed in the skeleton gaps of the modified graphite powder due to smaller volume and higher dispersion performance, so that the carbon/titanium doped magnesium diboride is wrapped by the skeleton of the modified graphite powder, and the yttrium sol, the copper sol and the barium sol are all distributed on the skeleton of the modified graphite powder, and after calcination, organic components in the yttrium sol, the copper sol and the barium sol are decomposed to generate YBa on the skeleton of the modified graphite powder with yttrium, copper and barium2Cu3OXSuperconducting crystal, and carbon/titanium doped magnesium diboride coated on YBa2Cu3OXA core-shell structure is formed inside the superconducting crystal, so that the prepared superconducting material is stable in structure, and all components are uniformly distributed, so that the prepared superconducting material is stable in property, and the problem that the prepared superconducting material is unstable in property because a plurality of colloids are mixed together and then calcined in the existing preparation process of the superconducting material by using a sol method, but the type and structure of the calcined product are influenced by the uniform mixing degree of the colloids is solved.
The superconducting performance of the carbon/titanium doped magnesium diboride prepared by the invention is higher than YBa2Cu3OXSuperconducting crystals, so that when current enters the core-shell center, the current is rapidly dispersed, and YBa outside the core-shell2Cu3OXThe superconductive crystal is distributed uniformly, so that the current is uniformly and rapidly dispersed, and the central skeleton graphite powder also has higher conductivity, so that the critical current density of the material is increased to 3.81 multiplied by 104And the addition of graphite powder canThe high temperature resistance of the material can be improved, the critical transition temperature of the material can be further improved to 38.7K, and the problem that the critical current density and the critical transition temperature of the conventional superconducting material cannot reach the practical range and limit the use is solved.
The purpose of the invention can be realized by the following technical scheme:
a superconducting material for nuclear magnetic resonance human body imaging comprises the following raw materials in parts by weight:
13.2-13.8 parts of modified graphite powder, 11.1-11.3 parts of yttrium oxide, 23.9-24.2 parts of copper oxide, 52.1-52.3 parts of barium nitrate, 22.4-22.7 parts of diethylenetriamine, 132.6-134.7 parts of propionic acid, 6.9-7.2 parts of carbon/titanium doped magnesium diboride, a proper amount of water and a proper amount of dilute nitric acid;
wherein the dilute nitric acid is 55% nitric acid solution;
the specific preparation process of the modified graphite powder is as follows: weighing a certain amount of graphite, adding the graphite into an ethanol solution, performing ultrasonic dispersion for 10min at normal temperature, adding the dispersed graphite solution into a three-neck flask, heating to 90 ℃, adding sodium dodecyl benzene sulfonate and vinyl triethoxysilane into the three-neck flask, performing constant temperature reaction for 1h, filtering, washing and drying, and grinding the obtained product to obtain modified graphite powder; the method comprises the following steps of (1) fully mixing vinyl triethoxysilane in ethanol due to the interface action of sodium dodecyl benzene sulfonate, wherein the surface of graphite contains a small amount of hydroxyl, and simultaneously hydrolyzing the vinyl triethoxysilane in the ethanol to obtain Si-OH, wherein the Si-OH undergoes a dehydration condensation reaction to generate Si-OH oligosiloxane, the Si-OH in the oligosiloxane is combined with the hydroxyl on the surface of the graphite through a hydrogen bond action at a high temperature, so that the vinyl triethoxysilane is grafted on the surface of the graphite, and the reaction structural formula is as follows; adding 8mL of ethanol into each gram of graphite, adding 0.85-0.87g of sodium dodecyl benzene sulfonate, adding 1.32g of vinyl triethoxysilane, adding sodium dodecyl benzene sulfonate during the process of adding sodium dodecyl benzene sulfonate and vinyl triethoxysilane, stirring for reaction for 5min, and then adding vinyl triethoxysilane; the sodium dodecyl benzene sulfonate is used as a surfactant, the surface tension can be changed when the sodium dodecyl benzene sulfonate is added into ethanol, and when the sodium dodecyl benzene sulfonate is fully dispersed in the ethanol solution, the vinyltriethoxysilane is added, so that the vinyltriethoxysilane can be uniformly dispersed in the ethanol and can further react with graphite in the ethanol solution, the situation that the vinyltriethoxysilane is agglomerated due to the addition of the vinyltriethoxysilane together is prevented, and the graphite is not uniformly modified;
the specific preparation process of the carbon/titanium doped magnesium diboride is as follows:
adding magnesium diboride and nano titanium dioxide into acetic acid, uniformly mixing to obtain sol, adding the sol into a tubular furnace, and roasting to obtain carbon/titanium doped magnesium diboride, wherein carbon, carbon dioxide and water are generated in the decomposition process of the acetic acid, the carbon dioxide and the water are evaporated, the carbon is adsorbed on the surface of the magnesium diboride, and the prepared carbon doped magnesium diboride has higher dispersing capacity due to the higher dispersity of carbon atoms; adding 0.83g of nano titanium dioxide into each gram of magnesium diboride, adding 3mL of acetic acid, heating to 300 ℃ in the roasting process in a tubular furnace, roasting for 2h, then heating to 650 ℃ and roasting for 1h, then cooling to 200 ℃ and taking out, wherein the acetic acid can be fully decomposed to generate carbon by roasting at 300 ℃, and oxygen in the titanium dioxide is combined with the carbon through covalent bonds when the titanium dioxide is heated to 450 ℃ to form Ti-O-C bonds;
the specific preparation process of the superconducting material is as follows:
firstly, respectively dissolving a certain amount of yttrium oxide and copper oxide in dilute nitric acid to prepare a yttrium nitrate solution with the concentration of 1mol/L and a copper nitrate solution with the concentration of 3mol/L, and simultaneously adding barium nitrate into water to prepare a barium nitrate solution with the concentration of 2 mol/L;
secondly, adding the yttrium nitrate solution prepared in the first step into a reaction vessel, heating to 60 ℃, then dropwise adding diethylenetriamine into the yttrium nitrate solution while violently stirring, and reacting at constant temperature for 30min after complete dropwise addition to obtain yttrium sol;
thirdly, respectively adding the copper nitrate solution and the barium nitrate solution prepared in the first step into a reaction container, raising the temperature of the container to 50 ℃, respectively adding propionic acid into the copper nitrate solution and the barium nitrate solution, and reacting at constant temperature for 30min after the addition is completed to respectively obtain copper sol and barium sol;
fourthly, adding the self-made modified graphite powder into ethanol, after uniform ultrasonic dispersion, adding the yttrium sol prepared in the second step, the copper sol and the barium sol prepared in the third step, after uniform ultrasonic dispersion, adding the self-made carbon/titanium doped magnesium diboride, and performing ultrasonic dispersion for 30min to obtain a uniform colloidal solution;
fifthly, evaporating the colloidal solution prepared in the fourth step to be viscous at 70 ℃, and then putting the colloidal solution into a tubular furnace to be roasted for 5 hours at 950 ℃ to obtain a superconducting material; because the surface of the modified graphite powder contains Si-OH, the yttrium sol contains amino, and the copper sol and the barium sol both contain hydroxyl, the modified graphite powder can be uniformly dispersed on a skeleton structure of the modified graphite powder through dehydration reaction at 70 ℃, meanwhile, the carbon/titanium doped magnesium diboride can be uniformly distributed in gaps of a skeleton of the modified graphite powder due to small volume and high dispersion performance, so that the carbon/titanium doped magnesium diboride is wrapped by the skeleton of the modified graphite powder, and the yttrium sol, the copper sol and the barium sol are all distributed on the skeleton of the modified graphite powder, and after calcination, organic components in the yttrium sol, the copper sol and the barium sol are decomposed to generate YBa on the skeleton of the modified graphite powder with yttrium, copper and barium2Cu3OXSuperconducting crystal, and carbon/titanium doped magnesium diboride coated on YBa2Cu3OXThe superconducting performance of the carbon/titanium doped magnesium diboride is higher than that of YBa2Cu3OXSuperconducting crystals, so that when current enters the core-shell center, the current is rapidly dispersed, and YBa outside the core-shell2Cu3OXThe superconducting crystals are uniformly distributed, so that the current is uniformly and quickly dividedThe graphite powder of the central framework has higher conductive capability, so that the critical current density of the material is increased, the high-temperature resistance of the material can be improved by adding the graphite powder, and the critical transition temperature of the material is improved.
The invention has the beneficial effects that:
the surface of modified graphite powder in the material prepared by the invention contains Si-OH, yttrium sol contains amino, copper sol and barium sol both contain hydroxyl, the modified graphite powder can be uniformly dispersed on a skeleton structure of the modified graphite powder through dehydration reaction at 70 ℃, carbon/titanium doped magnesium diboride can be uniformly distributed in gaps of a skeleton of the modified graphite powder due to small volume and high dispersion performance, so that the carbon/titanium doped magnesium diboride is wrapped by the skeleton of the modified graphite powder, the yttrium sol, the copper sol and the barium sol are distributed on the skeleton of the modified graphite powder, and after calcination, organic components in the yttrium sol, the copper sol and the barium sol are decomposed to generate YBa on the skeleton of the modified graphite powder together with yttrium, copper and barium2Cu3OXSuperconducting crystal, and carbon/titanium doped magnesium diboride coated on YBa2Cu3OXA core-shell structure is formed inside the superconducting crystal, so that the prepared superconducting material is stable in structure, and all components are uniformly distributed, so that the prepared superconducting material is stable in property, and the problem that the prepared superconducting material is unstable in property because a plurality of colloids are mixed together and then calcined in the existing preparation process of the superconducting material by using a sol method, but the type and structure of the calcined product are influenced by the uniform mixing degree of the colloids is solved.
The superconducting performance of the carbon/titanium doped magnesium diboride prepared by the invention is higher than YBa2Cu3OXSuperconducting crystals, so that when current enters the core-shell center, the current is rapidly dispersed, and YBa outside the core-shell2Cu3OXThe superconductive crystal is distributed uniformly, so that the current is uniformly and rapidly dispersed, and the central skeleton graphite powder also has higher conductivity, so that the critical current density of the material is increased to 3.81 multiplied by 104And the addition of the graphite powder can improve the high temperature resistance of the material,and the critical transition temperature of the material is further improved to 38.7K, and the problem that the critical current density and the critical transition temperature of the conventional superconducting material cannot reach the practical range and the use is limited is solved.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic structural diagram of a modified graphene powder preparation process according to the present invention;
Detailed Description
Referring to fig. 1, the following examples are given for illustration in detail:
example 1:
the specific preparation process of the modified graphite powder is as follows: weighing 1kg of graphite, adding the graphite into 8L of ethanol solution, ultrasonically dispersing for 10min at normal temperature, adding the dispersed graphite solution into a three-neck flask, heating to 90 ℃, adding 0.85kg of sodium dodecyl benzene sulfonate into the three-neck flask, stirring for reacting for 5min, adding 1.32kg of vinyl triethoxysilane into the three-neck flask, reacting for 1h at constant temperature, filtering, washing and drying to obtain a product, and grinding to obtain modified graphite powder;
the specific preparation process of the carbon/titanium doped magnesium diboride is as follows:
adding 1kg of magnesium diboride and 0.83kg of nano titanium dioxide into 3L of acetic acid, uniformly mixing to obtain sol, adding the sol into a 300 ℃ tubular furnace, roasting for 2h, then heating to 650 ℃, roasting for 1h, then cooling to 200 ℃, and taking out to obtain the carbon/titanium doped magnesium diboride.
Example 2:
the specific preparation process of the modified graphite powder is as follows: weighing 1kg of graphite, adding the graphite into 8L of ethanol solution, ultrasonically dispersing for 10min at normal temperature, adding the dispersed graphite solution into a three-neck flask, heating to 90 ℃, adding 0.87kg of sodium dodecyl benzene sulfonate into the three-neck flask, stirring for reacting for 5min, adding 1.32kg of vinyl triethoxysilane into the three-neck flask, reacting for 1h at constant temperature, filtering, washing and drying to obtain a product, and grinding the product to obtain modified graphite powder;
the specific preparation process of the carbon-doped magnesium diboride is as follows:
adding 1kg of magnesium diboride into 3L of acetic acid, uniformly mixing to obtain sol, adding the sol into a 300 ℃ tubular furnace, roasting for 2h, then heating to 650 ℃, roasting for 1h, then cooling to 200 ℃, and taking out to obtain the carbon-doped magnesium diboride.
Example 3:
the specific preparation process of the superconducting material for nuclear magnetic resonance human body imaging comprises the following steps:
firstly, respectively dissolving 1.11kg of yttrium oxide and 2.39kg of copper oxide in 55% dilute nitric acid to prepare a yttrium nitrate solution with the concentration of 1mol/L and a copper nitrate solution with the concentration of 3mol/L, and simultaneously adding barium nitrate into water to prepare a barium nitrate solution with the concentration of 2 mol/L;
secondly, adding the yttrium nitrate solution prepared in the first step into a reaction vessel, heating to 60 ℃, then dropwise adding 2.24kg of diethylenetriamine into the yttrium nitrate solution while violently stirring, and reacting at constant temperature for 30min after complete dropwise addition to obtain yttrium sol;
thirdly, respectively adding the copper nitrate solution and the barium nitrate solution prepared in the first step into a reaction container, raising the temperature of the container to 50 ℃, then respectively adding 5.24kg of propionic acid and 8.02kg of propionic acid into the copper nitrate solution and the barium nitrate solution, and reacting at constant temperature for 30min after the addition is completed to respectively obtain copper sol and barium sol;
step four, adding 1.32kg of the modified graphite powder prepared in the embodiment 1 into ethanol, adding the yttrium sol prepared in the step two, the copper sol prepared in the step three and the barium sol after uniformly dispersing by ultrasound, adding 0.69kg of the carbon/titanium doped magnesium diboride prepared in the embodiment 1 after uniformly dispersing by ultrasound, and performing ultrasonic dispersion for 30min to obtain a uniform colloidal solution;
and fifthly, evaporating the colloidal solution prepared in the fourth step to be viscous at 70 ℃, and then putting the colloidal solution into a tubular furnace to be roasted for 5 hours at 950 ℃ to obtain the superconducting material.
Example 4:
the specific preparation process of the superconducting material for nuclear magnetic resonance human body imaging comprises the following steps:
firstly, respectively dissolving 1.13kg of yttrium oxide and 2.42kg of copper oxide in 55% dilute nitric acid to prepare a yttrium nitrate solution with the concentration of 1mol/L and a copper nitrate solution with the concentration of 3mol/L, and simultaneously adding barium nitrate into water to prepare a barium nitrate solution with the concentration of 2 mol/L;
secondly, adding the yttrium nitrate solution prepared in the first step into a reaction vessel, heating to 60 ℃, then dropwise adding 2.27kg of diethylenetriamine into the yttrium nitrate solution while stirring vigorously, and reacting at constant temperature for 30min after complete dropwise addition to obtain yttrium sol;
thirdly, respectively adding the copper nitrate solution and the barium nitrate solution prepared in the first step into a reaction container, raising the temperature of the container to 50 ℃, then respectively adding 5.83kg of propionic acid and 7.64kg of propionic acid into the copper nitrate solution and the barium nitrate solution, and reacting at constant temperature for 30min after the addition is completed to respectively obtain copper sol and barium sol;
step four, adding 1.38kg of the modified graphite powder prepared in the embodiment 2 into ethanol, adding the yttrium sol prepared in the step two, the copper sol prepared in the step three and the barium sol after uniformly dispersing by ultrasound, adding 0.72kg of the carbon-doped magnesium diboride prepared in the embodiment 2 after uniformly dispersing by ultrasound, and performing ultrasonic dispersion for 30min to obtain a uniform colloidal solution;
and fifthly, evaporating the colloidal solution prepared in the fourth step to be viscous at 70 ℃, and then putting the colloidal solution into a tubular furnace to be roasted for 5 hours at 950 ℃ to obtain the superconducting material.
Example 5:
the specific preparation process of the superconducting material for nuclear magnetic resonance human body imaging comprises the following steps:
firstly, respectively dissolving 1.11kg of yttrium oxide and 2.39kg of copper oxide in 55% dilute nitric acid to prepare a yttrium nitrate solution with the concentration of 1mol/L and a copper nitrate solution with the concentration of 3mol/L, and simultaneously adding barium nitrate into water to prepare a barium nitrate solution with the concentration of 2 mol/L;
secondly, adding the yttrium nitrate solution prepared in the first step into a reaction vessel, heating to 60 ℃, then dropwise adding 2.24kg of diethylenetriamine into the yttrium nitrate solution while violently stirring, and reacting at constant temperature for 30min after complete dropwise addition to obtain yttrium sol;
thirdly, respectively adding the copper nitrate solution and the barium nitrate solution prepared in the first step into a reaction container, raising the temperature of the container to 50 ℃, then respectively adding 5.24kg of propionic acid and 8.02kg of propionic acid into the copper nitrate solution and the barium nitrate solution, and reacting at constant temperature for 30min after the addition is completed to respectively obtain copper sol and barium sol;
fourthly, 0.69kg of carbon/titanium doped magnesium diboride prepared in the example 1 is added into the yttrium sol prepared in the second step, the copper sol prepared in the third step and the barium sol, and is subjected to ultrasonic dispersion for 30min to obtain a uniform colloidal solution;
and fifthly, evaporating the colloidal solution prepared in the fourth step to be viscous at 70 ℃, and then putting the colloidal solution into a tubular furnace to be roasted for 5 hours at 950 ℃ to obtain the superconducting material.
Example 6:
the specific preparation process of the superconducting material for nuclear magnetic resonance human body imaging comprises the following steps:
firstly, respectively dissolving 1.11kg of yttrium oxide and 2.39kg of copper oxide in 55% dilute nitric acid to prepare a yttrium nitrate solution with the concentration of 1mol/L and a copper nitrate solution with the concentration of 3mol/L, and simultaneously adding barium nitrate into water to prepare a barium nitrate solution with the concentration of 2 mol/L;
secondly, adding the yttrium nitrate solution prepared in the first step into a reaction vessel, heating to 60 ℃, then dropwise adding 2.24kg of diethylenetriamine into the yttrium nitrate solution while violently stirring, and reacting at constant temperature for 30min after complete dropwise addition to obtain yttrium sol;
thirdly, respectively adding the copper nitrate solution and the barium nitrate solution prepared in the first step into a reaction container, raising the temperature of the container to 50 ℃, then respectively adding 5.24kg of propionic acid and 8.02kg of propionic acid into the copper nitrate solution and the barium nitrate solution, and reacting at constant temperature for 30min after the addition is completed to respectively obtain copper sol and barium sol;
step four, uniformly mixing the yttrium sol prepared in the step two, the copper sol prepared in the step three and the barium sol to obtain mixed sol;
and fifthly, evaporating the mixed sol prepared in the fourth step to be viscous at 70 ℃, and then putting the mixed sol into a tubular furnace to be roasted for 5 hours at 950 ℃ to obtain the superconducting material.
Example 7:
the superconducting materials prepared in examples 3 to 6 were subjected to property measurement, and the specific measurement results are shown in Table 1:
TABLE 1 results of measuring properties of superconducting materials prepared in examples 3 to 6
As can be seen from table 1, since the surface of the modified graphite powder contains Si — OH, the yttrium sol contains amino groups, and the copper sol and the barium sol both contain hydroxyl groups, they can be uniformly dispersed on the framework structure of the modified graphite powder by dehydration reaction at 70 ℃, and the carbon/titanium doped magnesium diboride can be uniformly distributed in the gaps of the framework of the modified graphite powder due to its small volume and high dispersibility, so that the carbon/titanium doped magnesium diboride is wrapped by the framework of the modified graphite powder, and the yttrium sol, the copper sol and the barium sol are all distributed on the framework of the modified graphite powder, and after calcination, the organic components in the yttrium sol, the copper sol and the barium sol are decomposed and form YBa on the framework of the modified graphite powder with yttrium, copper and barium2Cu3OXSuperconducting crystal, and carbon/titanium doped magnesium diboride coated on YBa2Cu3OXThe superconducting performance of the carbon/titanium doped magnesium diboride is higher than that of YBa2Cu3OXSuperconducting crystals, so that when current enters the core-shell center, the current is rapidly dispersed, and YBa outside the core-shell2Cu3OXThe superconductive crystal is distributed uniformly, so that the current is uniformly and rapidly dispersed, and the central skeleton graphite powder also has higher conductivity, so that the critical current density of the material is increased to 3.81 multiplied by 104And the high temperature resistance of the material can be improved by adding the graphite powder, so that the critical transformation temperature of the material is improved to 38.7K.
Example 8:
the superconducting materials prepared in examples 3 to 6 were measured for their properties at 3 different positions, and the specific measurement results are shown in table 2:
TABLE 2 measurement results (A/cm) of critical current density Jc at different positions of superconducting material2)
| Example 3 | Example 4 | Example 5 | Example 6 | |
| Position one | 3.81×104 | 2.73×104 | 2.61×104 | 0.54×104 |
| Position two | 3.81×104 | 2.73×104 | 1.97×104 | 0.36×104 |
| Position three | 3.81×104 | 2.73×104 | 2.71×104 | 1.23×104 |
As can be seen from Table 2, when the yttrium sol, the copper sol and the barium sol are distributed on the modified graphite powder skeleton, after calcination, the organic components in the yttrium sol, the copper sol and the barium sol are decomposed to form YBa on the modified graphite powder skeleton with yttrium, copper and barium2Cu3OXSuperconducting crystal, and carbon/titanium doped magnesium diboride coated on YBa2Cu3OXA core-shell structure is formed in the superconducting crystal, the prepared superconducting material is uniformly dispersed, and when modified graphite is not added, the sol is uniformly dispersed, so that the prepared superconducting material is unstable in property.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. The superconducting material for nuclear magnetic resonance human body imaging is characterized by comprising the following raw materials in parts by weight:
13.2-13.8 parts of modified graphite powder, 11.1-11.3 parts of yttrium oxide, 23.9-24.2 parts of copper oxide, 52.1-52.3 parts of barium nitrate, 22.4-22.7 parts of diethylenetriamine, 132.6-134.7 parts of propionic acid, 6.9-7.2 parts of carbon/titanium doped magnesium diboride, a proper amount of water and a proper amount of dilute nitric acid;
the specific preparation process of the carbon/titanium doped magnesium diboride is as follows:
adding magnesium diboride and nano titanium dioxide into acetic acid, uniformly mixing to obtain sol, adding the sol into a tubular furnace, roasting for 2 hours by heating to 300 ℃, then roasting for 1 hour by heating to 650 ℃, then cooling to 200 ℃, and taking out to obtain carbon/titanium doped magnesium diboride;
the specific preparation process of the superconducting material is as follows:
firstly, respectively dissolving a certain amount of yttrium oxide and copper oxide in dilute nitric acid to prepare a yttrium nitrate solution with the concentration of 1mol/L and a copper nitrate solution with the concentration of 3mol/L, and simultaneously adding barium nitrate into water to prepare a barium nitrate solution with the concentration of 2 mol/L;
secondly, adding the yttrium nitrate solution prepared in the first step into a reaction vessel, heating to 60 ℃, then dropwise adding diethylenetriamine into the yttrium nitrate solution while violently stirring, and reacting at constant temperature for 30min after complete dropwise addition to obtain yttrium sol;
thirdly, respectively adding the copper nitrate solution and the barium nitrate solution prepared in the first step into a reaction container, raising the temperature of the container to 50 ℃, respectively adding propionic acid into the copper nitrate solution and the barium nitrate solution, and reacting at constant temperature for 30min after the addition is completed to respectively obtain copper sol and barium sol;
fourthly, adding the self-made modified graphite powder into ethanol, after uniform ultrasonic dispersion, adding the yttrium sol prepared in the second step, the copper sol and the barium sol prepared in the third step, after uniform ultrasonic dispersion, adding the self-made carbon/titanium doped magnesium diboride, and performing ultrasonic dispersion for 30min to obtain a uniform colloidal solution;
and fifthly, evaporating the colloidal solution prepared in the fourth step to be viscous at 70 ℃, and then putting the colloidal solution into a tubular furnace to be roasted for 5 hours at 950 ℃ to obtain the superconducting material.
2. A superconducting material for magnetic resonance imaging of the human body according to claim 1, wherein the dilute nitric acid is a 55% nitric acid solution.
3. The superconducting material for nuclear magnetic resonance human body imaging according to claim 1, wherein 0.83g of nano titanium dioxide and 3mL of acetic acid are added to each gram of magnesium diboride.
4. The superconducting material for magnetic resonance imaging of the human body according to claim 1, wherein the modified graphite powder is prepared by the following specific steps: weighing a certain amount of graphite, adding the graphite into an ethanol solution, performing ultrasonic dispersion for 10min at normal temperature, adding the dispersed graphite solution into a three-neck flask, heating to 90 ℃, adding sodium dodecyl benzene sulfonate and vinyl triethoxysilane into the three-neck flask, performing constant temperature reaction for 1h, filtering, washing and drying, and grinding the obtained product to obtain the modified graphite powder.
5. The superconducting material for nuclear magnetic resonance human body imaging according to claim 3, wherein 8mL of ethanol is added into each gram of graphite, 0.85-0.87g of sodium dodecyl benzene sulfonate is added, 1.32g of vinyl triethoxysilane is added, sodium dodecyl benzene sulfonate is added during the process of adding the sodium dodecyl benzene sulfonate and the vinyl triethoxysilane, and the vinyl triethoxysilane is added after stirring for 5 min.
6. A preparation method of a superconducting material for nuclear magnetic resonance human body imaging is characterized in that the specific preparation process of the superconducting material is as follows:
firstly, respectively dissolving a certain amount of yttrium oxide and copper oxide in dilute nitric acid to prepare a yttrium nitrate solution with the concentration of 1mol/L and a copper nitrate solution with the concentration of 3mol/L, and simultaneously adding barium nitrate into water to prepare a barium nitrate solution with the concentration of 2 mol/L;
secondly, adding the yttrium nitrate solution prepared in the first step into a reaction vessel, heating to 60 ℃, then dropwise adding diethylenetriamine into the yttrium nitrate solution while violently stirring, and reacting at constant temperature for 30min after complete dropwise addition to obtain yttrium sol;
thirdly, respectively adding the copper nitrate solution and the barium nitrate solution prepared in the first step into a reaction container, raising the temperature of the container to 50 ℃, respectively adding propionic acid into the copper nitrate solution and the barium nitrate solution, and reacting at constant temperature for 30min after the addition is completed to respectively obtain copper sol and barium sol;
fourthly, adding the self-made modified graphite powder into ethanol, after uniform ultrasonic dispersion, adding the yttrium sol prepared in the second step, the copper sol and the barium sol prepared in the third step, after uniform ultrasonic dispersion, adding the self-made carbon/titanium doped magnesium diboride, and performing ultrasonic dispersion for 30min to obtain a uniform colloidal solution;
and fifthly, evaporating the colloidal solution prepared in the fourth step to be viscous at 70 ℃, and then putting the colloidal solution into a tubular furnace to be roasted for 5 hours at 950 ℃ to obtain the superconducting material.
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