CN1819069A - Diamagnetic superconductive materials with CuHz-H+P chlorine oxide and production thereof - Google Patents
Diamagnetic superconductive materials with CuHz-H+P chlorine oxide and production thereof Download PDFInfo
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- CN1819069A CN1819069A CN200510136689.1A CN200510136689A CN1819069A CN 1819069 A CN1819069 A CN 1819069A CN 200510136689 A CN200510136689 A CN 200510136689A CN 1819069 A CN1819069 A CN 1819069A
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- 239000000463 material Substances 0.000 title claims abstract description 151
- 230000005292 diamagnetic effect Effects 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910001902 chlorine oxide Inorganic materials 0.000 title 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 title 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 83
- 239000003153 chemical reaction reagent Substances 0.000 claims description 62
- 239000000460 chlorine Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 26
- 239000011780 sodium chloride Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 239000002887 superconductor Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 9
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 abstract description 33
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 abstract description 2
- 229910001626 barium chloride Inorganic materials 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 63
- 239000010949 copper Substances 0.000 description 48
- 238000002474 experimental method Methods 0.000 description 46
- 230000005291 magnetic effect Effects 0.000 description 43
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000011701 zinc Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000011575 calcium Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 18
- 239000001103 potassium chloride Substances 0.000 description 18
- 235000011164 potassium chloride Nutrition 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 8
- 230000002950 deficient Effects 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- -1 BaCl 2 Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910000878 H alloy Inorganic materials 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000003537 Ficus benghalensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- CNEWPRQQHICZBP-UHFFFAOYSA-N [O].[Cu].[Ba].[La] Chemical compound [O].[Cu].[Ba].[La] CNEWPRQQHICZBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- XPPWAISRWKKERW-UHFFFAOYSA-N copper palladium Chemical compound [Cu].[Pd] XPPWAISRWKKERW-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
- H10N60/855—Ceramic superconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The composition of the super conductance material comprises Cu, K( or Na), Ba, Cl, O or OH and its composition. The super conductance material is made by evenly triturating CuH2, KCl( or NaCL),BaCl2, metal oxide, metal compound comprising OH, or other metal chlorides, and compressing them to isolate air, and heating them in high temperature. The super conductance material shows the ceiling temperature appearing at entirely antimagnetic and the possible super conductance critical temperature Tc is at 509k, 529k and 573k respectively.
Description
One, technical field
Critical temperature T
cThe superconductive material that is higher than normal temperature
Two, background technology
1, the existing technology status of superconductive material: the critical temperature T that improves superconductor
c, development high-critical temperature T
cSuperconductive material, be one of core topic of superconductor research always." possible high T in the barium lanthanum copper oxygen system up to nineteen sixty-eight A.Muller and J.G.Bednorz
cSuperconductivity " epoch-making invention, just make superconductor T
cBreak through the ultralow temperature barrier, reached 35K.According to literature search: 1. up at present, superconductor T
cTidemark still remain on 164K.This T
cThe value material is an oxide material for Hg-Ba-Ca-Cu-O copper, is developed in 1994 by [U.S.] Zhu Jingwu.2001.03[America and Japan] scientist invented MgB again
2Material, T
cBe 39K.Calendar year 2001 has report to inject (material is not quite clear) T with organic superconductor with the hole
cBring up to 117K.2001.03[beautiful] Bell Laboratory produces the well-regulated P3HT organic film of structure, and field-effect transistors occurs superconductivity toward the film iunjected charge at the 2.35K film.2000.12[beautiful] scientist is pure C
60The T of material
cBring up to 52K.And normal temperature T
cSuperconductive material still fails to break through so far.2. the copper system oxide superconductors will be made the long lead wire rod that is suitable on the engineering owing to the fragility defective of its ceramic-like, and is technical still very difficult so far.
2, superconduction mechanism theory background: since the century, famous superconduction mechanism theory is no less than 13 kinds so far, but the high-temperature superconductor mechanism problem is still the unsolved riddle that theoretical circles are generally acknowledged at present.On the basis of using for reference forefathers' research, I finish " the δ field of force and superconduct one superconductivity mechanism are newly discussed " paper in 2000.09 writings, this article 2001.02.03 does issue first by " global Chinese original works net under the banyan ", and 2003.08 finish contracting of this article again changes original text " the δ field of force and superconductivity " (this original text is waited to contribute).Paper has proposed new physical model and has satisfied two necessary and sufficient conditions of superconductivity.This provides useful theory to help for own to superconductor ground experimental exploring.According to the understanding of paper to superconduction mechanism, the exploration of normal temperature superconductor should be placed hope on metal ion type compound-material, and copper system oxide superconductors issue in 1986 and that carry out development was thus furtherd investigate its T through nearly 17 years (by 2003)
cValue can not increase again.Tentatively test based on this thinking and I, determine I am transferred to metal-metal chloride material to the exploration emphasis of normal temperature superconductor.Before and after year June in July, 2004 to 2005, done a large amount of experiments.
3, so far, with the immediate existing superconductor of the technology of the present invention feature, be cobalt/cobalt oxide " sticking water " material (Japanese material research institute, 2003.03.08 www.xinhuanet.com report, my 2005.03 retrievals).Cobalt/cobalt oxide does not possess superconductivity under the drying regime, in the time of negative 268 ℃ the cobalt/cobalt oxide layer is injected hydrone, and its magnetic susceptibility and resistance sharply descend, and make it to become superconducting material.Cobalt oxidation " sticking water " material has obviously used the polarization covalent bond H of hydrone
+Ion, the H that this technical characterictic and the present invention use
+ PIon characteristic is similar.The present invention is different with it to be characterised in that, the present invention has used Zn (OH) Cl or Sn (OH) Cl or Ba (OH)
2Or Ca (OH)
2In H
+ PThe valence electron of ion and simple substance Cu (or alloy CuH
zValence electron), and metal chloride and metal oxide, thus obtain complete diamagnetic state under the 573K, its T
cValue is far above the T of cobalt/cobalt oxide " sticking water " material
cValue (5K, negative 268 ℃).Another important difference is that the present invention does not belong to pure superconductive compound materials, but simple substance (or hydrogen alloy) superconductive compound materials that never occurs up to now.From H
+ PMeaning on say that cobalt/cobalt oxide " sticking water " material provides experiment support for validity of the present invention.
Three, summary of the invention
The objective of the invention is to, a kind of CuH is provided
z-H
+ PMetal oxygen chlorine is diamagnetic possible superconductive material fully, and this material is the complete diamagnetic possible superconductor that critical temperature is higher than normal temperature, and the neccessary composition of this material is: Cu, K (or Na), Ba, Cl, O or OH and combination thereof.To solve problems of the prior art.Be applied to superconductive power transmission and magnetic suspension.Another object of the present invention is to provide this preparation methods.Done a large amount of experiments for this reason.
The invention belongs to the invention of a total multinomial material of inventive concept, a total inventive concept is: CuH
z-H
+ PMetal oxygen chlorine is diamagnetic possible superconductive material fully, and this material is the complete diamagnetic possible superconductor that critical temperature is higher than normal temperature, and the neccessary composition that this material contains is Cu, K (or Na), Ba, Cl, O or OH and combination thereof.Here so-called necessity is indispensable.(2A) in the multinomial material, (2B) material, when z=0, its constituent promptly is these neccessary compositions, other material then all contains these neccessary compositions.The statement of the 3rd page footing section content is stated in the effect of neccessary composition and their combination as follows to contribution of the present invention.So far also there is not to find the superconductor material of similar composition with it.
A kind of CuH
z-H
+ PMetal oxygen chlorine is diamagnetic possible superconductive material fully, and the above-mentioned neccessary composition of this material comes naturally: CuH
z, KCl (or NaCl), BaCl
2, SnCl
2(or ZnCl
2), SnO (or ZnO), Sn (OH) Cl (or Zn (OH) Cl) reagent and combination thereof.
A kind of CuH
z-H
+ PMetal oxygen chlorine is diamagnetic possible superconductive material fully, and the above-mentioned neccessary composition of this material comes naturally: CuH
z, KCl (or NaCl), BaCl
2, BaO (or CaO), Ba (OH)
2(or Ca (OH)
2) reagent and combination thereof.
(0), by mole metering, and component and proportioning are:
CuH
z: KCl (or NaCl): BaCl
2: 0.4SnCl
2: 0.25 (1.2-x) SnO: 0.25 (1.2+x) Sn (OH) Cl wherein 0.25 (1.2-x) and 0.25 (1.2+x) from embodiment 4 or 5, according to said components and proportioning, can make composition by (0A) or (0B) material shown in the chemical formula: KBaSnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(0A) or NaBaSnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(0B)
(1), by mole metering, and component and proportioning are:
CuH
z: KCl (or NaCl): BaCl
2: 0.4ZnCl
2: 0.25 (1.2-x) ZnO: 0.25 (1.2+x) Zn (OH) Cl wherein 0.25 (1.2-x) and 0.25 (1.2+x) from embodiment 1,2 or 3, according to said components and proportioning, can make composition by (1A) or (1B) material shown in the chemical formula: KBaZnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(1A) or NaBaZnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(1B)
(2), by mole metering, and component and proportioning are:
2CuH
z: KCl (or NaCl): 1.5BaCl
2: 0.25 (1+y) BaO: 0.25 (1-y) Ba (OH)
20.25 (1+y) wherein and 0.25 (1-y) be from embodiment 6 or 7, according to said components and proportioning, can make composition by (2A) or (2B) material shown in the chemical formula: KBa
2Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(2A) or NaBa
2Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(2B)
(3), by mole metering, and component and proportioning are:
2CuH
z: KCl (or NaCl): 1.5BaCl
2: 0.25 (1+y) CaO: 0.25 (1-y) Ca (OH)
20.25 (1+y) wherein and 0.25 (1-y) be from embodiment 8,9 or 10, according to said components and proportioning, can make composition by (3A) or (3B) material shown in the chemical formula: KBa
1.5Ca
0.5Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(3A) or NaBa
1.5Ca
0.5Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(3B)
Wherein: 0≤x≤0.4,0≤y≤0.32,0≤z≤0.7; CuH
zBeing copper hydrogen alloy, is elemental copper during z=0; Sn (OH) Cl or Zn (OH) Cl are alkali formula stannous chloride or basic zinc chloride.
Through magnetic measurement: above-mentioned material shows complete ceiling temperature and possible superconduction critical temperature T when diamagnetic
c, (0) material is 509K, and (1), (3) material are 573K, and (2) material is 529K, is 0.4～0.7 o'clock at z, and (0), (1), (2), (3) material show that complete lower limit temperature when diamagnetic might reach 0K.Embodiment is seen in resistance measurement respectively.
Preparation technology: the preparation of above-mentioned material, respectively according to separately component and proportioning, take by weighing each component reagent of appropriate amount, the levigation mixing, the airtight secluding air of compacting, (0), under (1) 550 ℃～650 ℃, (2), under (3) 650 ℃～700 ℃, heated 4～5 hours, and be cooled to room temperature under the airtight secluding air state, sealing is preserved.
All there is Cu (or H)-H in above-mentioned material
+ PThe uneven relation of valence state.The H of band portion positive charge
+ PCome the O-H polarization covalent bond of the metallic compound of self-contained OH, and H
+ PThe communization ionization (ionization of H key) that produces when forming the H key with adjacent O, Cl in the material space structure, electronics and hole super stream is respectively from Cu (or CuH
z) and H
+ P, and the two the uneven relation of valence state, metal oxide wherein and metal chloride provide oxygen, chlorine anion and dislocation, layered metal cation respectively, the microcosmic correlation of Cu wherein and metal cation (as K, Ba cation) just makes ceiling temperature and possible superconduction critical temperature that this material is diamagnetic fully can be higher than normal temperature.
Above-mentioned material is red block that institutional framework is tight, hardness is bigger, (0), (1) material has thermoplasticity, and all has a cold brittleness, all has machinability, can be processed into the long line electric conducting material that uses on the engineering, might solve and realize the inaccessiable normal temperature of prior art or be higher than the superconductive power transmission and the magnetic levitation technology problem of normal temperature.
Improvement project: in order to improve CuH
zThe easy pyrolytic of composition, available Cu
0.45Pd
0.55H
z(0≤z≤0.7) replaces the CuH in the above-mentioned use reagent component
zComponent is carried out material preparation, through preparation, Cu
0.45Pd
0.55H
zIn material, decompose and be diffused as Cu, CuH
zOr PdH
zComposition, Pd composition wherein has the good adsorption performance to H.Cu
0.45Pd
0.55H
zBeing copper palladium hydrogen alloy, is the copper palldium alloy during z=0, referring to " superconductivity physical basis " P
15, work such as Guan Weiyan, Science Press, 1981.
The present invention prepares the magnetic measurement method and the resistance measurement method of material
[magnetic measurement] instrument: the needle that suspends, mercurial thermometer (measuring range-4 ℃～300 ℃).Method of measurement: material prepares through high temperature, when stopping to heat, will prepare material immediately near the static needle that suspends under hot state, carries out magnetic measurement.Magnetic measurement is got rid of and has been negated the environmental factor of influence measurement and possible galvanic current effect factor.
[resistance measurement] is limited to measuring equipment, and zero resistance is measured, and does not do.Measure under room temperature, normal state with ohmmeter commonly used * 1R shelves, the pointer nulling of measurement result can not be as the zero resistance data.
The present invention is defined as " diamagnetic possible superconductive material fully ", based on: " superconductor has zero resistance and these two simultaneous fundamental characteristics of perfect diamganetism.In fact strict, perfect diamganetism is the characteristic of the more intrinsic of superconductor.Because, for the difference of zero resistance and very little resistance, be to be difficult to definition on amount, so when differentiating whether certain material is superconductor, except the resistance that uses the resistance measurement sample, more be to use the magnetic measurement method to come the perfect diamganetism of measuring samples.Two kinds of methods are used simultaneously, can make conclusion more accurate.Up to now, also do not find other any material except superconductor and have perfect diamganetism ".Perfect diamganetism is the exclusive fundamental characteristics of superconductor (Meisser effect).The perfect diamganetism that the present invention obtains according to repeatedly magnetic measurement, its invention material should be a superconductor material, but exists zero resistance to measure disappearance (being measured device-restrictive), therefore, is defined as " diamagnetic possible superconductive material fully " the present invention is careful.
The superconductivity mechanism of material of the present invention: slightly.With reference to " the δ field of force and superconductivity " paper.
Four, embodiment
The present invention is described by the following examples further, following examples, embodiment 1,2 or 3 explanations (1A) and (1B) invention, embodiment 4 or 5 explanations (0A) and (0B) invention, embodiment 6 or 7 explanations (2A) and (2B) invention, embodiment 8,9 or 10 explanations (3A) and (3B) invention, embodiment 11 and the whole invention materials of Comparative Examples 1 to 5 explanation the present invention.By magnetic measurement, the perfect diamganetism and the possible superconductivity of preparation material is described, on the use instrument of magnetic measurement and resistance measurement and method of measurement were seen, measurement result was seen following table 1; By choosing different embodiment, further specify component and proportioning, proportioning is all in molar ratio; CuH among the embodiment
zComponent is self-control reagent, and the z of this self-control reagent is 0≤z≤0.1; Preparation among the embodiment is inconsistent with the heating time in " summary of the invention " heating time, and reason sees that the 11st page in specification " illustrates two: the airtight condition of preparation experiment and heating time ".
Embodiment 1
Component:
Cu powder (200 orders are analyzed pure), BaCl
22H
2O (chemical pure), KCl (analyzing pure) or NaCl, ZnCl
2(analyze pure, contain a small amount of hygroscopic moisture)
Material preparation
Four kinds of reagent 1: 1: 1 in molar ratio: 1 takes by weighing each reagent of appropriate amount, ZnCl
2Heat 10 minutes (550 ℃), BaCl
22H
2O heats 5 minutes (550 ℃), removes ZnCl
2Hygroscopic moisture and BaCl
22H
2The crystallization water of O, after, four kinds of reagent difference levigation mixings, tubulature, the mouth of pipe is jumped a queue, and under 550 ℃～650 ℃, heats 15～20 minutes preparation.HCl gas and H are arranged in the preparation process
2O separates out, at disposable discharge HCl and H
2Behind the O, in whole heating process, should compress mouth of pipe stopper.
The preparation material character detects
[magnetic measurement] makes material can make former static needle arrange, and maximum is scolded width of cloth 1.0cm, and 12 minutes repulsion time, the back needle phenomenon of being ostracised disappears.Temperature when this perfect diamganetism occurring arrives the room temperature interval 300 ℃ (having experiment to reach about 400 ℃).Under [resistance measurement] room temperature, the non-complete diamagnetic state situation, measure * 1R shelves pointer nulling (these data can not be done zero resistance and use) with ohmmeter commonly used.
Description of test
From then on the present invention tests to obtain the perfect diamganetism effect.This experiment had once been done repeatedly,, thought that this material might be a superconductive material by the perfect diamganetism (Meisser effect) that magnetic measurement obtains.But: do not do zero resistance and measure: still can not determine the necessary composition that makes material; Perfect diamganetism phenomenon instability.Especially neccessary composition is the problem of puzzling by it for a long time, various empirical factors and kinds of experiments scheme have been considered for this reason, carried out repeatedly experiment, wherein test as follows further, 1. change experiment and magnetic measurement environment, get rid of external force factor or the possible galvanic current effect factor of material itself that needle is arranged; 2. be basic scheme with this component of testing and proportioning, give up wherein KCl or BaCl respectively
2Reagent experimentizes, make material then needle do not have rejection; 3. the ZnCl in the experiment
2Use anhydrous assay pure (Xinxiang chemical reagent factory) respectively or contain the ZnCl that a small amount of hygroscopic moisture (uncovered placement moisture absorption) or different manufacturers contain a small amount of hygroscopic moisture with producer
2, other reagent component and proportioning are constant, and technology is constant, experimental result, the pure ZnCl of all employing anhydrous assay
2, making material does not then have perfect diamganetism, contains a small amount of hygroscopic moisture and must have under the situation that an amount of ZnO composition exists and adopt, and makes material and occurs perfect diamganetism again.By to a series of experiment and ZnCl
2Produce experimental observation and the experimental analysis of ZnO and Zn (OH) Cl during hydrolysis, determine that the necessary component when perfect diamganetism appears in this Experiment Preparation material is: Cu, KCl, BaCl
2, ZnCl
2, ZnO, Zn (OH) Cl.Thereby just determined the composition problem of this Experiment Preparation material.And understood fully thus by the effect and the correlation of the chemical composition shown in these components in the preparation material.This is other preparation experiment of the present invention, has established the understanding basis.After this, use CuH again
z(self-control) replaced C u powder is done this experiment again, and needle repels effect obviously to be strengthened, and maximum scolds the width of cloth to increase to 1.5cm.
Embodiment 2
Component and proportioning
CuH
z: 0.7NaCl: BaCl
2: 0.4ZnCl
2: 0.3ZnO: [0.3Zn (OH) Cl+0.3NaCl] [0.3Zn (OH) Cl+0.3NaCl] wherein takes from following [Zn (OH) ClNaCl] reagent of producing.
The preparation method
By component and proportioning, take by weighing each component reagent of appropriate amount, levigation, the high temperature resistant test tube of packing into, mixing, the mouth of pipe is jumped a queue, and under 550 ℃～650 ℃, heats 20 minutes.Produce in the process whole, should compress mouth of pipe stopper.When stopping to heat,,, carry out magnetic measurement near needle with being about to prepare material under hot state.
The magnetic measurement and the resistance measurement of preparation material the results are shown in Table 1.
Producing of [Zn (OH) ClNaCl] reagent
Under anhydrous condition, took by weighing an amount of anhydrous ZnCl in 1: 1 in molar ratio
2And anhydrous Na OH, levigation, the injector for medical purpose of packing into, the airtight secluding air of compacting, 300 ℃～350 ℃ were heated 45 minutes down, were cooled to room temperature, made mentioned reagent.Under anhydrous condition, levigation seals standby.Reaction equation is:
。Produce explanation: (1), be to guarantee to produce the airtight secluding air condition of compacting in the process with the purpose of injector for medical purpose.(2), above-mentioned reaction has accessory substance and produces, as Zn (OH)
2Deng, but, do not make the H that might generate in the process of producing as long as guarantee airtight condition
2O and HCl gas are overflowed, and can eliminate accessory substance.(3), above-mentioned product Zn (OH) Cl+NaCl, have following reversible reaction:
Na[ZnOCl wherein] be the chlorine sodium zincate, composition is ZnONaCl.By above-mentioned reversible reaction, guaranteeing airtight condition, when no HCl overflows, can guarantee evenly disperseing mutually of product Zn (OH) Cl and NaCl.(4), above-mentioned producing, ZnCl
2Amount Ying Wei measures greater than NaOH.
Embodiment 3
Component and proportioning
CuH
z: 0.6KCl: BaCl
2: 0.4ZnCl
2: 0.2ZnO: [0.4Zn (OH) Cl+0.4NaCl] [0.4Zn (OH) Cl+0.4NaCl] reagent wherein, take from [Zn (OH) ClNaCl] reagent of producing among the embodiment 2.
The magnetic measurement of preparation method and preparation material
Preparation method and magnetic measurement method are with embodiment 2, and be respectively heating time wherein:
1., heating 30 minutes, have small amount of H Cl gas to overflow once in the heating process, compress pipe close immediately again.When stopping to heat, carry out magnetic measurement with being about to prepare material near needle, measurement result sees Table 1.Diamagnetic fully ceiling temperature is detected to be 300 ℃, might reach 350 ℃～400 ℃ (showing as the upper limit that obviously can be higher than the thermometer measure scope when measuring, this data for reference).
2., for the second time heated 40 minutes, extrusion has volume HCl gas to emit, and stops heating, carries out magnetic measurement, no perfect diamganetism with being about to prepare material near needle.Resistance measurement sees Table 1.
Embodiment 4
Component and proportioning: CuH
z: 0.7NaCl: BaCl
2: 0.4SnCl
2: 0.3SnO: [0.3Sn (OH) Cl+0.3NaCl], SnCl wherein
2, SnO, Sn (OH) Cl is respectively stannous chloride, stannous oxide, alkali formula stannous chloride, [0.3Sn (OH) Cl+0.3NaCl] wherein is taken from [Sn (OH) ClNaCl] reagent, the preparation method of its reagent is same as the preparation method of [Zn (OH) ClNaCl] among the embodiment 2, only wherein ZnCl
2Use SnCl
2Replace.
Preparation method and method of measurement are same as embodiment 2.
The magnetic measurement and the resistance measurement of preparation material the results are shown in Table 1.
Embodiment 5
Component and proportioning: CuH
z: 0.6KCl: BaCl
2: 0.4SnCl
2: 0.2SnO: [0.4Sn (OH) Cl+0.4NaCl], [0.4Sn (OH) Cl+0.4NaCl] wherein are taken from [Sn (OH) ClNaCl] reagent of producing among the embodiment 4.
Preparation method and method of measurement are same as embodiment 3.
The magnetic measurement and the resistance measurement of preparation material the results are shown in Table 1.
Embodiment 6
Component: CuH
zPowder (self-control z is about 0.1), BaCl
22H
2O (chemical pure), KOH (analyzing pure) or NaOH
Proportioning: 2: 2: 1
Material preparation and character detect
Three kinds of reagent took by weighing each reagent of appropriate amount, levigation mixing, tubulature in 2: 2: 1 in molar ratio, the mouth of pipe is jumped a queue, and puts into the glass that is filled with water, and keeps 80 ℃～82 ℃ of water in the cup temperature, water-bath heating 5 minutes, reagent is anhydrous in the pipe separates out (observation inboard wall of test tube), and test tube is taken out in the blackening of reagent small part, immediately near needle, do magnetic measurement, can make former static needle arrange 0.6cm, 3 minutes repulsion time.After, continuation water-bath in 80 ℃～82 ℃ water was heated 10～15 minutes, and reagent black increases the weight of in the pipe, and reagent has elutriation to go out, and takes out, and does magnetic measurement, and needle does not have the phenomenon of being ostracised.
Test tube is directly put on the alcolhol burner lamp flame again and heated, have repeatedly that the volume elutriation goes out, and in time remove the water of separating out on the long-pending wall in vitro, when substantially anhydrous separating out, from fire, under hot state, do magnetic measurement immediately, needle does not have the phenomenon of being ostracised.Continue to put 7 minutes (about 650 ℃ of temperature) of heating on the lamp flame, the interior reagent of pipe no longer includes elutriation and goes out, reagent black disappears, volume-diminished, caking is the copper red look, from fire, do magnetic measurement immediately, near behind the needle 2 minutes, when temperature is 256 ℃, needle begins to be arranged 0.6～0.8cm, 6 minutes repulsion time.
Red caking sample under normal temperature, no complete diamagnetic state, is done resistance measurement with ohmmeter commonly used, * 1R shelves pointer nulling (non-zero resistance) in the take-off pipe.
The preparation experiment explanation
1. by paired observation, reagent is always separated out the water yield obviously more than the BaCl of equivalent in the experimentation
22H
2O always separates out the water yield when separately water is decrystallized in heating, shows in experimentation, as KOH and BaCl
2React and generate KCl and Ba (OH)
2After, during heat, part Ba (OH)
2Also participate in elutriation and gone out, generated the BaO composition.2. according to chemical reaction and experimental observation, determine that the composition of this preparation material is by CuH
z, KCl, BaCl
2, BaO, Ba (OH)
2Shown chemical composition is formed.3. replace the KOH in the above-mentioned experiment to do this experiment with NaOH, the perfect diamganetism effect that the two experiment obtains is basic identical.4. with the Cu powder replace this experiment in CuH
zDo this experiment, then experiment does not have perfect diamganetism all the time and shows, its reason is, in strong alkali environment, have water (to be mainly BaCl again simultaneously
22H
2The crystallization water of O) and under the oxygen situation about existing, during heating, Cu is very easily oxidized to be caused.After the oxidation, Cu then loses H
+ PSuction-operated, see below " illustrate one, perfect diamganetism defective and improvement project ".
Embodiment 7
Component and proportioning: 2CuH
z: NaCl: 1.5BaCl
2: 0.25BaO: 0.25Ba (OH)
2, Ba wherein (OH)
2By an amount of BaCl
2Obtain with the appropriate amount of NaOH reaction, it is the intact production recently of sealing that BaO requires.
The preparation method
By component and proportioning, take by weighing each component reagent of appropriate amount, levigation, the high temperature resistant test tube of packing into, mixing, the mouth of pipe is jumped a queue, and under 650 ℃～700 ℃, heats 30～40 minutes, produces in the process whole, should compress mouth of pipe stopper.When stopping to heat, under hot state,, carry out magnetic measurement immediately near needle.
The magnetic measurement and the resistance measurement of preparation material the results are shown in Table 1.
The CuH in embodiment 7 components and the proportioning
zReplace with the Cu powder, be prepared experiment, the perfect diamganetism effect of preparation material is substantially the same manner as Example 7.Explanation thus, embodiment 6 uses Cu powder replaced C uH again
zThe Cu that occurs during preparation is oxidized, is because KOH and water (BaCl
2 2H
2The crystallization water of O) existence causes, and CuH also is described simultaneously
zIn H the effect that is not corroded of protection Cu is arranged.
Embodiment 8
Component: CuH
zPowder (self-control z is about 0.1), BaCl
22H
2O (chemical pure), KCl (analyzing pure) or NaCl, Ca (OH)
2Contain CaO
Material preparation
[Ca (OH)
2Contain CaO] the producing of reagent, Ca (OH)
2It is interior under about 600 ℃ that stove fire is put in tubulature, heated 15～20 minutes, by portion C a (OH)
2Dehydration makes.Four kinds of reagent were by 4: 3: 2: 1 takes by weighing each reagent of appropriate amount, BaCl
22H
2O heated 5 minutes down at 550 ℃, removed its crystallization water fully, after, four kinds of reagent difference levigation mixings, tubulature, the mouth of pipe adds plug, 650 ℃～700 ℃ heating down, when being heated to 4 minutes, reagent volume is dwindled gradually in the pipe, caking, there is low amounts of water to separate out, continue heating 20～25 minutes, it is tight to make institutional framework, the red block material that hardness is bigger.
The preparation material character detects
Magnetic measurement makes material former static needle is arranged, and maximum is scolded width of cloth 1.0cm, and 20 minutes repulsion time, the temperature when this perfect diamganetism occurring arrives the room temperature interval 300 ℃ (＞300 ℃ reach about 400 ℃).Resistance measurement, with embodiment 7, making the material lower surface has a small amount of thin fusion cooling layer, R → ∞ herein.Put domestic refrigerator and be chilled to-18 ℃～-24 ℃ making material, do magnetic measurement again, no perfect diamganetism.
Description of test
1. repeated experiments, the perfect diamganetism effect that obtains is the same.2. change the reagent proportioning, as change into 2: 1: 1: 1, experimentize, from experiment effect, above-mentioned experiment proportioning best results.3. replace KCl with NaCl or with Cu powder replaced C uH
z, be prepared experiment, make material and all can obtain perfect diamganetism down at 300 ℃.
Embodiment 9
Component and proportioning: 2CuH
z: NaCl: 1.5BaCl
2: 0.25CaO: 0.25Ca (OH)
2
The preparation method: with embodiment 7, heating time wherein: 1., 30 minutes, do magnetic measurement; Heat again extending to 45 minutes heating time, H is arranged
2O separates out, and the magnetic measurement needle scolds the width of cloth to reduce; 2., extend to 1 hour heating time, magnetic measurement, the preparation material does not have perfect diamganetism.Reason: the airtight secluding air condition because of not guaranteeing in the preparation process to prepare causes Ca (OH)
2Dehydration loses that active ingredient causes.
The magnetic measurement and the resistance measurement of preparation material
Be respectively above-mentioned heating time the magnetic measurement results of 30 minutes or 1 hour and resistivity measurements see Table in 1 1. or 2..
Embodiment 10
Component and proportioning: 2CuH
z: KCl: 1.5BaCl
2: 0.33BaO: 0.17Ca (OH)
2
Preparation method: with embodiment 9
The magnetic measurement and the resistance measurement of preparation material the results are shown in Table 1.
Embodiment 11
The CuH in embodiment 9 components and the proportioning
zWith the replacement of Cu powder, Ca (OH)
2With anhydrous Ba (OH)
2Replace, make the perfect diamganetism effect of material, substantially the same manner as Example 9.
Above embodiment material is put domestic refrigerator, is cooled to-18 ℃～-24 ℃, carries out magnetic measurement, does not all have perfect diamganetism.
Comparative Examples 1
Cast out the 0.7NaCl in embodiment 2 components and the proportioning, preparation method and magnetic measurement method are same as embodiment 2, and the preparation material does not have perfect diamganetism, and resistance measurement sees Table 1.
Comparative Examples 2
With the 0.7NaCl in 0.7LiCl replacement embodiment 2 components and the proportioning, preparation method and magnetic measurement method are same as embodiment 2, and the preparation material does not have perfect diamganetism, and the Cu part is oxidized, and resistance measurement sees Table 1.
Comparative Examples 3
[the 0.5La of the CaO in embodiment 9 components and the proportioning
2O
3] replace, making material does not have perfect diamganetism, makes material and is Powdered, resistance R → ∞.The purpose of this experiment is the effect of checking lanthana rare earth composition.
Comparative Examples 4
Component: Cu powder (200 orders are analyzed pure) or CuH
z(z is about 0.1), BaCl
22H
2O (chemical pure), KCl (analyzing pure)
The magnetic measurement and the resistance measurement of preparation method and preparation material
Three kinds of reagent took by weighing BaCl by 2: 2: 1
22H
2O heated 5 minutes in advance, removed its crystallization water, after, three kinds of reagent levigation mixings, tubulature, the mouth of pipe adds plug, and under 650 ℃～700 ℃, heating is after heating 4 minutes, reagent volume is dwindled in managing, and caking continues heating 7 minutes, makes the red bulk material that institutional framework is tight, hardness is bigger.Magnetic measurement, making material does not have perfect diamganetism.Resistance measurement is with embodiment 7.
Comparative Examples 5
Cast out the KCl reagent in Comparative Examples 4 components, keep BaCl
2, two kinds of reagent of Cu powder and two set of dispense are than constant, technology is constant, heating-up temperature is constant, heat 10 to 20 minutes, makes material and is pale powder shape (also Cu pruinescence partial oxidation does not lump), no perfect diamganetism, resistance R → ∞.
Analyze, 1. relatively Comparative Examples 4 or 5 two experiments make the surface structure of material, and analysis draws, and the KCl composition forms the solid condensed state and plays an important role making material.2. Comparative Examples 4 makes material does not have perfect diamganetism, and embodiment 6 to 11 makes material and then has perfect diamganetism, and contrast its component and constitute, obviously, BaO, Ba (OH)
2Or CaO, Ca (OH)
2Composition is indispensable neccessary composition to making the perfect diamganetism of material.3. according to component and the proportioning of embodiment 1 to 11, with reference to the space structure of existing copper system oxide superconductors, analyze, material of the present invention has common coordination, the layering space structure.
1, preparation experiment explanation
Illustrate one, perfect diamganetism defective and improvement project
Above embodiment is the preparation experiment of doing for enforcement the present invention, the complete diamagnetic and possible superconduct problem under preparation experiment has solved 300 ℃, and the method for preparing this material is provided.From the listed data of table 1, there are two defectives in above preparation experiment: the 1. diamagnetic fully time is not lasting; 2. there is lower limit temperature (room temperature) in perfect diamganetism.According to experiment and experimental analysis, cause the reason of these two defectives to be: self-control reagent CuH
zH contain quantity not sufficient (≤0.1), resolve into Cu and H under the high temperature; Preparation technology fails to guarantee the process conditions of absolute airtight, secluding air heating and cooling, causes that the H loss of active ingredient causes.These are confirmed by a large amount of experiments.In this case, prepare Cu (or H)-H that material all exists
+ PThe uneven relation of valence state (seeing Instructions Page 3) then mainly shows as Cu-H
+ PThe uneven relation of valence state.When temperature is lower than lower limit temperature, H
+ PHot convergence or title H with Cu
+ PBe adsorbed in the short time can fade away (reference: 1. Cu takes off the temperature conditions Experiment of Organic Chemistry of H effect, 2. repeats heating, and the preparation material recovers perfect diamganetism again) with the total heat-transmission of Cu, this will cause Cu-H
+ PThe uneven system of valence state is destroyed.After the destruction, H
+ PThen become independently positive center with respect to Cu, and lose hole conductivity, also interrelated with no longer having the motion of electronics and hole, make material lose superconductivity, perfect diamganetism also disappears thereupon simultaneously.Analyze thus, the preparation material exists above-mentioned defective to be inevitable, and its basic reason is CuH
zThe H loss of reagent causes.Improvement project: 1. improve airtight technology, guarantee CuH
zDecomposition reaction reversible; 2. increase CuH
zIn z reach 0.4～0.7.Thereby realize H-H
+ PThe uneven relation of valence state (this concerns that temperature influence is not irrelevant with the time yet) can be eliminated two above-mentioned defectives.In order further to improve the thermal stability of institute's containing metal Hization thing in the preparation material, available Cu
0.45Pd
0.55H
zReplaced C uH
z, carrying out material preparation, Pd wherein (palladium) has good adsorption to H.
Illustrate two, the airtight condition and the heating time of preparation experiment
Because reagent C uH
z, Zn (OH) Cl and Sn (OH) Cl poor heat stability, high temperature (400 ℃) easily decomposes, and has reversible reaction (under the airtight situation):
Reagent Ba (OH)
2And Ca (OH)
2, begin to decompose mistake H in the time of 550 ℃
2O (under independent, the uncovered heating state), and have reversible reaction (under the airtight situation):
Therefore, the airtight condition in the time of must guaranteeing preparation.Guaranteeing to prolong heating time under the airtight condition, then can make the diffusion of composition and internal organizational structure more even, thereby obtain better perfect diamganetism effect.Preparation with reference to existing copper system oxide superconductors, and the main component of material of the present invention is a chloride and according to above preparation experiment, the preparation of material of the present invention is guaranteeing that should be extended for 4～5 hours heating time under definitely airtight, the secluding air condition.Because condition restriction, the preparation experiment of embodiment is difficult to guarantee above-mentioned process conditions, prolong heating time, then owing to decomposition reaction occurs, extrusion or pipe explosion lose active ingredient in the experimentation, detected perfect diamganetism is disappeared, so be 20～45 minutes the heating time of embodiment of the invention experiment, because experiment is short heating time, the diffusion of inner composition (especially Cu) is inhomogeneous.
Illustrate one, the airtight condition of explanation two described improvement projects and technology, can and easily solve with regard to prior art, therefore,, can make the superconductive power transmission material that is higher than normal temperature that uses on the engineering according to the above method that provides.
Another significance of the present invention is that it will provide important experimental basis for illustrating the superconduction mechanism problem.
2, the use reagent of preparation experiment
(1), self-control reagent
CuH
zProduce: produce by certain technology with copper powder (analyzing pure 200 orders), sodium metal, water.Concrete grammar is: got the sodium metal of copper powder and chopping in 1: 1 in molar ratio, tubulature, mixing, splash into water by per 1～3 minute 2～3 speed, after dripping at every turn, the mouth of pipe adds plug immediately, compress, drip at end copper, the sodium local temperature at place of pipe can reach about 400 ℃ (instantaneous rubescent, this temperature is to generate CuH
zReference temperature), drip until the pipe in the sodium metal total overall reaction finish.This process should be noted in the suitable discharge piping not hydrogen and the steam with the copper reaction, to prevent pipe explosion.After, with invisible spectro reactant impouring wide mouth cup together, wash with water to neutrality, be settled out CuH
z, low temperature drying (150 ℃) makes duskiness and is bolarious CuH
zWhether the check preparation is CuH
z, adopt the method for lighting.CuH
zThe also available copper powder of producing mix the altogether method of thermal cracking with organic sodium salt, can make CuH simultaneously in this way
zReach the soda (NaOH) that experiment needs.The reaction equation of above-mentioned first kind of preparation method is:
The CuH that adopts said method to make
zH content few, z is about 0.1.
ZnO or Zn (OH) Cl produces: because the ZnO that adopts during material preparation of the present invention must be a new system, and therefore must self-control.Concrete preparation method: 1., with the ZnCl that contains a small amount of hygroscopic moisture
2Through hydrolysis, and control and remove unnecessary HCl heating time, can make ZnO and Zn (OH) Cl simultaneously.Reaction equation is:
ZnCl wherein
2It is the chloride of very easily hygroscopic moisture and facile hydrolysis.The shortcoming of this preparation method is the content of ZnO and Zn (OH) Cl wayward (the present invention obtains the perfect diamganetism effect of testing thus, sees embodiment 1).2., producing of Zn (OH) Cl: do not need to produce separately.Preparation method is seen producing of [Zn (OH) ClNaCl] reagent among the embodiment 2.The method can be controlled the content of Zn (OH) Cl preferably.3., producing of ZnO: at the ZnCl of new preparation
2In the aqueous solution, gradation adds the NaOH that lacks than amount of calculation, generates Zn (OH)
2White precipitate, again with sediment through washing, low-temperature heat is decomposed and to be made ZnO.Seal standby, reaction equation:
1., the producing of SnO SnO and Sn (OH) Cl produces:: got stannous chloride SnCl in 1: 1.8 in molar ratio
2And NaOH, the NaOH gradation is added the new SnCl for preparing
2The aqueous solution stirs, and generates Sn (OH)
2Precipitation is washed to neutrality to sediment, and the unnecessary SnCl of flush away
2, water-soluble accessory substance Na
2SnO
2And product NaCl, low-temperature heat is decomposed, and makes stannous oxide SnO, seals standby.Reaction equation is:
2., producing of alkali formula stannous chloride Sn (OH) Cl: do not need to produce separately.Preparation method is seen producing of [Sn (OH) ClNaCl] reagent among the embodiment 4.The method can be controlled the content of Sn (OH) Cl preferably.
Ba (OH)
2Produce: with an amount of BaCl
2Hot altogether with appropriate amount of NaOH, can make the required Ba (OH) of invention material preparation experiment simultaneously
2And NaCl.NaCl must not separate.Reaction equation:
CaO or Ca (OH)
2Produce: because preparation material of the present invention required CaO and Ca (OH)
2Must be new system, therefore must self-control.Concrete preparation method is: 1. get the industrial oxidation calcium of the top grade that newly dispatches from the factory, add excessive water, stir repeatedly, with the precipitation method impurity is sunken to the bottom, the upper water of inclining liquid is got the calcium hydroxide pastel that is deposited in impure layer top, add water again, repeat said process four times.The flask of packing into, sealing post precipitation, the upper water of inclining liquid.2. pore is reserved in sealing, dries down, can make the Ca (OH) of new system for 200 ℃
2Take out the Ca (OH) of a part of new system
2, seal standby.3. pore is reserved in remainder sealing, put under 600 ℃～650 ℃ in the stove fire, heated 2 hours, can make the CaO of new system, seal standby.Reaction equation and process are:
Water washing and precipitating is removed impurity,
(2), the use reagent of preparation experiment
Copper powder (Cu), 200 orders, analyze pure, Tianjin good fortune chemical reagent in morning factory; CuH
z, self-control; Sodium metal (Na), chemical pure, reagent Co., Ltd is learned in triumphant Tonghua, Tianjin; Potassium chloride (KCl), analyze pure, Xi'an chemical reagent factory; Sodium chloride (NaCl) is with NaOH and hydrochloric acid self-control (use amount is less); NaOH (NaOH), chemical pure, outsourcing; Barium chloride (BaCl
22H
2O), chemical pure, Henan Jiaozuo City chemical industry three factories; Zinc chloride (ZnCl
2), 1. analyze purely, 2. chemical reagent factory in Xinxiang City's analyzes purely, contains a small amount of hygroscopic moisture, Tianjin Ke Miou Science and Technology Ltd.; Ca (OH)
2, CaO, common, self-control; Stannous chloride (SnCl
2), analyze pure, outsourcing; Main agents that other relevant experiment relates to: hydrochloric acid (HCl), analyzes pure, northern absolute sincerity chemical plant, Lip river, Luoyang City; Lithium hydroxide (LiOH), analyze pure, Tianjin chemical reagent three factories; LiCl, self-control, (being used for the influence of experimental verification ionic radius); Lanthana (La
2O
3), 99.95%, Shanghai chemical reagent station packing; LaCl
3, self-control (La
2O
3And LaCl
3Influence in order to experimental verification rare earth composition).
Table 1
| Embodiment | The magnetic measurement of preparation material | The resistance measurement (normal state) (ohmmeter * 1R shelves) of preparation material | ||||||
| () minute needle begins to be ostracised | Temperature when needle begins to be ostracised (℃) | Needle end maximum is scolded the width of cloth (cm) | The time that needle is ostracised (branch) | Material shows diamagnetic temperature range fully | ||||
| (1 A) or (1 B) | Embodiment 1 | 300 | 1.0 | 12 | 300 ℃～room temperature | Nulling | ||
| Embodiment 2 | (1) | 300 | 1.0 | 10 | 300 ℃～room temperature | Nulling | ||
| Embodiment 3 | ① | (0) | 300 | 1.5 | 12 | 300 ℃～room temperature | Nulling | |
| ② | × | × | × | × | No perfect diamganetism | |||
| (0 A) or, (0 B) | Embodiment 4 | (1.5) | 229 | 1.2 | 8 | 229 ℃～room temperature | Nulling | |
| Embodiment 5 | ① | (1.5) | 236 | 1.5 | 10 | 236 ℃～room temperature | Nulling | |
| ② | × | × | × | × | No perfect diamganetism | |||
| (2A) or (2B) | Embodiment 6 | ① | 80 | 0.6 | 3 | Nulling | ||
| ② | (2) | 256 | 0.8 | 6 | 256℃～45℃ | |||
| Embodiment 7 | (2) | 250 | 1.0 | 16 | 250 ℃～room temperature | Nulling | ||
| (3 A) or (3B) | Embodiment 8 | 300 | 1.0 | 20 | 300 ℃～room temperature | Nulling | ||
| Embodiment 9 | ① | (0) | 300 | 1.2 | 20 | 300 ℃～room temperature | Nulling | |
| ② | × | × | × | × | No perfect diamganetism | |||
| Embodiment 10 | ① | (2) | 247 | 0.8 | 10 | 247 ℃～room temperature | Nulling | |
| ② | × | × | × | × | No perfect diamganetism | |||
| Embodiment 11 | ① | (0) | 300 | 1.0 | 20 | 300 ℃～room temperature | Nulling | |
| ② | × | × | × | × | No perfect diamganetism | |||
| Comparative Examples 1 | No perfect diamganetism | R＞500 Europe | ||||||
| Comparative Examples 2 | No perfect diamganetism | R→∞ | ||||||
| Comparative Examples 3 | No perfect diamganetism | R→∞ | ||||||
| Comparative Examples 4 | No perfect diamganetism | Nulling | ||||||
| Comparative Examples 5 | No perfect diamganetism | R→∞ | ||||||
" () minute needle begins to be ostracised " refers in the table: stop heating, beginning to be ostracised near () minute needle behind the needle under the hot state with being about to material.
Claims (11)
1, a kind of CuH
z-H
+ PMetal oxygen chlorine is diamagnetic possible superconductive material fully, it is characterized in that this material is the complete diamagnetic possible superconductor that critical temperature is higher than normal temperature, and the neccessary composition that this material contains is: Cu, K (or Na), Ba, Cl, O or OH and combination thereof.
2, according to the described superconductive material of claim 1, neccessary composition wherein comes naturally: CuH
z(or to be selected from be Cu
0.45Pd
0.55H
z), KCl (or be selected from be NaCl), BaCl
2, SnCl
2(or to be selected from be ZnCl
2), SnO (or be selected from be ZnO), Sn (OH) Cl (or be selected from be Zn (OH) Cl) reagent and combination thereof.
3, according to the described superconductive material of claim 1, neccessary composition wherein comes naturally: CuH
z(or to be selected from be Cu
0.45Pd
0.55H
z), KCl (or be selected from be NaCl), BaCl
2, BaO (or be selected from be CaO), Ba (OH)
2(or to be selected from be Ca (OH)
2) reagent and combination thereof.
4, a kind of method for preparing the described superconductive material of claim 1 is characterized in that, by mole metering, and component and proportioning are:
CuH
z: KCl (or NaCl): BaCl
2: 0.4SnCl
2: 0.25 (1.2-x) SnO: 0.25 (1.2+x) Sn (OH) Cl takes by weighing each component reagent of appropriate amount, levigation mixing, the airtight secluding air of compacting, under 550 ℃～650 ℃, heated 4～5 hours, be cooled to room temperature under the airtight secluding air state, sealing is preserved, can make composition by:
KBaSnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(0A) or NaBaSnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(OB)
Complete diamagnetic possible superconductive material shown in the chemical formula, wherein, 0≤x≤0.4,0≤z≤0.7.
5, according to the described preparation method of claim 4, (0A) that wherein makes or (OB) material show complete ceiling temperature and possible superconduction critical temperature T when diamagnetic
cBe 509K, z is 0.4～0.7 o'clock, shows that complete lower limit temperature when diamagnetic might reach 0K.
6, a kind of method for preparing the described superconductive material of claim 1 is characterized in that, by mole metering, and component and proportioning are:
CuH
z: KCl (or NaCl): BaCl
2: 0.4ZnCl
2: 0.25 (1.2-x) ZnO: 0.25 (1.2+x) Zn (OH) Cl
Take by weighing each component reagent of appropriate amount, the levigation mixing, the airtight secluding air of compacting under 550 ℃～650 ℃, heated 4～5 hours, was cooled to room temperature under the airtight secluding air state, sealing is preserved, can make composition by:
KBaZnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(1A) or NaBaZnCuH
0.3+0.25x+zO
0.6Cl
4.1+0.25x(1B)
Complete diamagnetic possible superconductive material shown in the chemical formula, wherein, 0≤x≤0.4,0≤z≤0.7.
7, according to the described preparation method of claim 6, (1A) that wherein makes or (1B) material show complete ceiling temperature and possible superconduction critical temperature T when diamagnetic
cBe 573K, z is 0.4～0.7 o'clock, shows that complete lower limit temperature when diamagnetic might reach 0K.
8, a kind of method for preparing the described superconductive material of claim 1 is characterized in that, by mole metering, and component and proportioning are:
2CuH
z: KCl (or NaCl): 1.5BaCl
2: 0.25 (1+y) BaO: 0.25 (1-y) Ba (OH)
2
Take by weighing each component reagent of appropriate amount, the levigation mixing, the airtight secluding air of compacting under 650C～700 ℃, heated 4～5 hours, was cooled to room temperature under the airtight secluding air state, sealing is preserved, can make composition by:
KBa2Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(2A) or NaBa2Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(2B)
Complete diamagnetic possible superconductive material shown in the chemical formula, wherein, 0≤y≤0.32,0≤z≤0.7.
9, according to the described preparation method of claim 8, (2A) that wherein makes or (2B) material show complete ceiling temperature and possible superconduction critical temperature T when diamagnetic
cBe 529K, z is 0.4～0.7 o'clock, shows that complete lower limit temperature when diamagnetic might reach 0K.
10, a kind of method for preparing the described superconductive material of claim 1 is characterized in that, by mole metering, and component and proportioning are:
2CuH
z: KCl (or NaCl): 1.5BaCl
2: 0.25 (1+y) CaO: 0.25 (1-y) Ca (OH)
2
Take by weighing each component reagent of appropriate amount, the levigation mixing, the airtight secluding air of compacting under 650 ℃～700 ℃, heated 4～5 hours, was cooled to room temperature under the airtight secluding air state, sealing is preserved, can make composition by:
KBa
1.5Ca
0.5Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(3A) or NaBa
1.5Ca
0.5Cu
2H
0.5 (1-y)+2zO
0.75-0.25yCl
4(3B)
Complete diamagnetic possible superconductive material shown in the chemical formula, wherein, 0≤y≤0.32,0≤z≤0.7.
11, according to the described preparation method of claim 10, (3A) that wherein makes or (3B) material show complete ceiling temperature and possible superconduction critical temperature T when diamagnetic
cBe 573K, z is 0.4～0.7 o'clock, shows that complete lower limit temperature when diamagnetic might reach 0K.
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| PCT/CN2006/002060 WO2007019795A1 (en) | 2005-08-16 | 2006-08-14 | Superconducting material and preparing method thereof |
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|---|---|---|---|---|
| CN1044003A (en) * | 1987-03-27 | 1990-07-18 | 中国科学院物理所 | Superconductor and preparation method thereof |
| JPS63242920A (en) * | 1987-03-30 | 1988-10-07 | Komatsu Ltd | Superconductor |
| JPS6414150A (en) * | 1987-07-07 | 1989-01-18 | Fujikura Ltd | Production of superconductor |
| JPS6463216A (en) * | 1987-09-03 | 1989-03-09 | Fujikura Ltd | Oxide superconductor |
| US4994432A (en) * | 1988-01-15 | 1991-02-19 | University Of Arkansas | High temperature superconductor system and processes for making same |
| KR0125876B1 (en) * | 1988-02-25 | 1997-12-18 | 나까하라 쯔네오 | Method for preparing superconducting thin film |
| FR2660799A1 (en) * | 1990-04-09 | 1991-10-11 | Rhone Poulenc Chimie | Superconducting composition based on lanthanum, copper, oxygen, a halogen and, possibly, an alkaline earth and its preparation |
| CN1021672C (en) * | 1990-06-29 | 1993-07-21 | 厦门大学 | Preparation for oxide superconductive material |
| JPH04124032A (en) * | 1990-09-17 | 1992-04-24 | Hitachi Ltd | Superconductor and its synthesis |
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| CN100389471C (en) | 2008-05-21 |
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