CN104451317A - Hafnium-base mixed metal material and iodination preparation method thereof - Google Patents
Hafnium-base mixed metal material and iodination preparation method thereof Download PDFInfo
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- CN104451317A CN104451317A CN201310432324.8A CN201310432324A CN104451317A CN 104451317 A CN104451317 A CN 104451317A CN 201310432324 A CN201310432324 A CN 201310432324A CN 104451317 A CN104451317 A CN 104451317A
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- 239000007769 metal material Substances 0.000 title claims abstract description 73
- 238000006192 iodination reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000026045 iodination Effects 0.000 title abstract 2
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 126
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229910052751 metal Inorganic materials 0.000 claims abstract description 110
- 239000002184 metal Substances 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 35
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 31
- 239000011630 iodine Substances 0.000 claims description 30
- 229910052740 iodine Inorganic materials 0.000 claims description 30
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 21
- 238000010894 electron beam technology Methods 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 19
- 239000010936 titanium Substances 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- VSTCOQVDTHKMFV-UHFFFAOYSA-N [Ti].[Hf] Chemical compound [Ti].[Hf] VSTCOQVDTHKMFV-UHFFFAOYSA-N 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 description 6
- URXDOZXTRQGRIP-UHFFFAOYSA-N [Hf].[Zr].[Ti] Chemical compound [Hf].[Zr].[Ti] URXDOZXTRQGRIP-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 238000007499 fusion processing Methods 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- HGWOBERUERISLJ-UHFFFAOYSA-N hafnium iron Chemical compound [Fe].[Fe].[Hf] HGWOBERUERISLJ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YCJQNNVSZNFWAH-UHFFFAOYSA-J hafnium(4+);tetraiodide Chemical compound I[Hf](I)(I)I YCJQNNVSZNFWAH-UHFFFAOYSA-J 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention relates to a hafnium-base mixed metal material and an iodination preparation method thereof, and belongs to the field of synthesis and preparation of mixed metal materials. The hafnium-base mixed metal material is composed of a matrix metal hafnium and other metal compositions, and the other metal compositions comprise one or two or more of Zr, Ti, Al, B, Ba, Be, Ca, Ce, Co, Cs, Dy, Er, Fe, Gd, Ho, La, Mg, Mn, Mo, Nb, Ni, Pr, Sc, Sm, Sr, Ta, V, W, Y and Yb. The hafnium-base mixed metal material with the purity up to 99.95 wt% can be prepared through an iodination reaction, and continuous batch production can be realized, and the advantages of uniform product compositions, high production efficiency, relatively low production cost and the like are provided.
Description
Technical field
The present invention relates to a kind of hafnium based mixed-metal materials and iodate preparation method thereof, belong to mixed-metal materials synthesis preparation field.
Background technology
Hafnium based mixed-metal materials has a good application prospect in a lot of fields, as sputtering target material and numerous hybrid metal goods or alloy etc.The traditional preparation methods of its blank adds alloying element in the melting pool of base metal, or made in melting after required ratio mixing preparation in advance by various fusing starting material.Due to the difference of each metallic element fusing point, in above-mentioned fusion process, whole base material is difficult to melt simultaneously, thus causes the ununiformity of batch components, affects its final utilization performance.Be tending towards even for making batch components, repeatedly melt back must be carried out to blank, and fusion process easily produces shrinkage cavity, the defects such as shrinkage porosite, the loss of base material can be caused, and due to the different melting points of Addition ofelements, in fusion process, inevitably cause certain scaling loss, be difficult to the homogeneity ensureing final batch components.Simultaneously because hafnium inevitably makes the rising of gas content especially oxygen level in fusion process, the finished product gas content repeatedly after melting, can be caused to increase.Therefore, melt back makes final purity, and composition is all difficult to control.Therefore, traditional smelting preparation method production efficiency is lower, and improve all even constituent content accuracy of hafnium sill product composition, be a difficult problem prepared by hafnium sill always.In view of this, the present invention spy proposes a kind of method that hafnium based mixed-metal materials is prepared in iodate.The advantage of the mixed-metal materials that this method obtains is that oxygen level is low, and purity is high, and the method production efficiency is high, is suitable for batch production.
Summary of the invention
The present invention is directed to current traditional melting method, to prepare in hafnium based mixed-metal materials process production efficiency low, and cannot ensure that product composition is not enough uniformly, provides a kind of method that hafnium base mixing material is prepared in hafnium based mixed-metal materials and iodate.
Hafnium based mixed-metal materials of the present invention is made up of matrix metal hafnium and other metallic element following, and other metallic element is only limitted to Zr, Ti, Al, B, Ba, Be, Ca, Ce, Co, Cs, Dy, Er, Fe, Gd, Ho, La, Mg, Mn, Mo, Nb, Ni, Pr, Sc, Sm, one or more in Sr, Ta, V, W, Y and Yb.
Wherein, the matrix of described hafnium based mixed-metal materials is metal hafnium, namely hafnium element in the material content be more than or equal to 50wt.%, or hafnium element in the material content be less than 50wt.%, but be greater than the content of any one other metallic elements except hafnium.
In the present invention, " hafnium base " material is restricted in mixed-metal materials, and hafnium is principal element.In following two kinds of situations, hafnium is all the principal element in material.One is that hafnium content is all larger than the content of other element any of material, and namely hafnium content is more than or equal to 50wt.%.Although two is that hafnium content is less than 50wt.%, the content of other any elements of the residue in material is all less than hafnium constituent content.Such as, suppose that wherein hafnium only accounts for 30wt.% in this mixed-metal materials, but the content that there is not other element any except hafnium element is more than or equal to 30wt.%, then hafnium element is also the principal element of this material.
In above-mentioned hafnium based mixed-metal materials, the total content of other metallic element except hafnium is at least 0.01wt.%, is preferably greater than and equals 0.05wt.%, and the total content being more preferably other metallic element except hafnium is more than or equal to 0.1wt.%.The purity of hafnium based mixed-metal materials of the present invention is more than or equal to 99.95wt.%.
On the other hand, present invention also offers a kind of method that hafnium based mixed-metal materials is prepared in iodate.By by the mixture of hafnium and other metal of at least one by iodate building-up reactions to make hybrid metal goods.Specifically, using the mixture of one or more in the group comprising matrix metal hafnium and other metal above-mentioned composition as raw material, drop into iodination reaction device, above-mentioned each element reacts with iodine at a lower temperature and generates volatile iodide, the volatility iodide generated are passed on female silk of comparatively high temps, decompose and generate hafnium based mixed-metal materials, obtain hafnium base hybrid metal blank through further electron beam melting.Hafnium is the principal element of this blank, and the purity that this mixing blank has is at least 99.95wt.%.
A method for hafnium based mixed-metal materials is prepared in iodate, comprises the following steps:
(1) take matrix metal hafnium by composition proportion and be only limitted to Zr, Al, B, Ba, Be, Ca, Ce, Co, Cs, Dy, Er, Fe, Gd, Ho, La, Mg, Mn, Mo, Nb, Ni, Pr, Sc, Sm, Sr, Ta, Ti, other metal of one or more compositions in V, W, Y and Yb, mix, wherein each metallic element purity is 99.9w%;
(2) mixed-metal feedstock is put into iodate device, be evacuated to 1 × 10
-2pa ~ 1 × 10
-3pa, start to carry out iodination reaction, metal hafnium and other metallic element react with iodine steam at a lower temperature respectively and generate volatile iodide, and the volatility iodide generated are passed on female silk of comparatively high temps, decompose and generate hafnium based mixed-metal materials.
Further, also can comprise the following steps (3), above-mentioned obtained hafnium based mixed-metal materials is carried out electron beam melting, obtained hafnium base hybrid metal blank.
In step (1), the matrix of described hafnium based mixed-metal materials is metal hafnium, namely hafnium element in the material content be more than or equal to 50wt.%, or hafnium element in the material content be less than 50wt.%, but be greater than the content of any one other metallic elements except hafnium.
The total content of other metallic element except hafnium is at least 0.01wt.%, is preferably greater than and equals 0.05wt.%, is more preferably and is more than or equal to 0.1wt.%.
The granularity of selected metal (matrix metal hafnium, Al, B, Ba, Be, Ca, Ce, Co, Cs, Dy, Er, Fe, Gd, Ho, La, Mg, Mn, Mo, Nb, Ni, Pr, Sc, Sm, Sr, Ta, Ti, V, W, Ya or Yb) is between 1mm ~ 18mm.
In step (2), the condition of iodination reaction: lesser temps refers between 200 ~ 800 DEG C, the amount adding iodine in iodate device be iodine by the mass ratio of iodate metal: metal=1:(50 ~ 150) left and right, comparatively high temps refers between 1100 ~ 1600 DEG C, the whole iodination reaction time is different according to the difference of institute's alloyage, about 10 ~ 60 hours.
According to aforesaid method, the matrix of described hafnium based mixed-metal materials is metal hafnium, and the purity of gained hafnium based mixed-metal materials is more than or equal to 99.95wt.%.In hybrid metal blank obtained by the present invention, the total content of non-hafnium metal is between 0.001wt.% ~ 50wt.% scope.
Beneficial effect of the present invention: the method being prepared hafnium based mixed-metal materials by iodate provided by the invention, the hafnium based mixed-metal materials that purity reaches 99.95wt.% can be obtained, and the continuous batchization that effectively can realize hafnium based mixed-metal materials is produced, products obtained therefrom uniform composition.It is high that the inventive method has production efficiency, and product composition is even, the advantages such as production cost is lower.
Accompanying drawing explanation
Fig. 1 is the schema of the inventive method.
Fig. 2 is the iodate synthesis that the present invention includes, and decomposes the equipment simplified schematic diagram of deposition process.
Embodiment
As shown in Figure 1, prepare the schema of the method for hafnium based mixed-metal materials for iodate of the present invention, comprise joining and get raw material, raw material mixes, shove charge, heats degassed, adds iodine, and iodate is synthesized, obtain hafnium based mixed-metal materials, through electron beam melting, finally obtain hafnium base hybrid metal blank.
Concrete implementation step comprises:
(1) take other metal of one or more compositions in matrix metal hafnium and Zr, Ti, Al, B, Ba, Be, Ca, Ce, Co, Cs, Dy, Er, Fe, Gd, Ho, La, Mg, Mn, Mo, Nb, Ni, Pr, Sc, Sm, Sr, Ta, V, W, Y and Yb by composition proportion, mix.Wherein each metallic element purity is 99.9wt.%;
(2) taken mixed-metal feedstock is put into iodate device, be evacuated to 1 × 10
-2pa ~ 1 × 10
-3pa, start to carry out iodination reaction, metal hafnium and other metallic element react with iodine steam and generate volatile iodide between 200 ~ 800 DEG C, the volatility iodide generated are passed on female silk of 1100 ~ 1600 DEG C, decompose and generate hafnium based mixed-metal materials, after reaction terminates, obtain hafnium base hybrid metal goods;
(3) above-mentioned obtained hafnium based mixed-metal materials is obtained hafnium base hybrid metal blank through high temperature electron beam melting in electron beam furnace.
The hafnium based mixed-metal materials that the present invention relates to, the metallic element mixture in its iodate raw material comprises hafnium, and it can be exist, as metal hafnium with atomic form; Also can be exist, as tetraiodide hafnium with molecular form.The hafnium base hybrid metal blank that the present invention relates to can be hafnium sill (i.e. hafnium element in the material content be more than or equal to 50 percent), also can be hafnium Base Metal mixture (namely hafnium element in the material content be less than 50 percent, but be greater than the content of any one other metallic elements except hafnium).The total content of other metal is more than or equal to preferred 0.05wt.%, more preferably greater than equaling 0.1wt.%.
The iodate raw material that the present invention relates to is after course of iodization, and the Product Definition obtained is for being mixed-metal materials.This material is after electron beam melting, and the Product Definition obtained is hybrid metal blank.Metallic element in this blank is identical with the metallic element kind in mixed-metal feedstock, and content is different.This is that the final component therefore forming blank is different with the component element stoichiometric number of mixed-metal feedstock because in course of iodization, thermodynamics and kinetics is different on the impact of each metallic element.In hybrid metal blank obtained by the present invention, the total content of non-hafnium metal is between 0.001wt.% ~ 50wt.% scope.
Below in conjunction with Fig. 2, the iodination reaction process related in Fig. 1 is described further.
As shown in Figure 2, be iodate equipment schematic diagram, iodination reaction apparatus mainly comprises the parts such as resistance furnace 1, retort 2, molybdenum net 4, iodine adding device device 7, female silk 5 and heating electrode 6.Mixed-metal feedstock 3 is loaded between molybdenum net 4 and retort 2 inwall, and female silk 5 upper end is welded with heating electrode 6, and lower end extends to bottom retort 2.Solid-state iodine is added by iodine adding device device 7 and has in the retort 2 of certain temperature, each metallic element in the iodine steam generated and raw material reacts and generates volatile iodide, these volatility iodide are passed on the female silk 5 of alive high temperature, decompose and generate metal and iodine steam, the metal formation of deposits hafnium based mixed-metal materials on female silk 5 generated, iodine steam returns to raw material district to be continued to participate in iodination reaction.
Below for matrix metal hafnium, illustrate the behavior of hafnium in course of iodization.The chemical reaction occurred in process is as follows:
Hf（s）+2I
2（g）→HfI
4（g） （1）
HfI
4（g）→Hf（s）+2I
2（g） （2）
First, hafnium and iodine react (1) in the raw material district that temperature is lower, generate volatile hafnium iodide (HfI
4), subsequently, these volatile hafnium iodide are passed near the female silk 5 of alive high temperature, and be adsorbed on female silk 5 surface of high temperature, decomposition reaction (2) occurs, and the metal hafnium of generation is deposited on female silk 5 surface, and iodine steam returns to raw material district to be continued to participate in iodination reaction (1).In like manner, in course of iodization, also there is the iodination reaction similar with above-mentioned reaction (1) (2) in other metal in mixed-metal feedstock.Therefore, in iodination reaction process, each metallic element in mixed-metal feedstock by synchronous migration on the female silk 5 of high temperature, the uniform mixed-metal materials of final forming component.
The transformation efficiency of above-mentioned iodination reaction process Raw depends on following factor: the temperature head between (1) raw material and female silk 5; (2) concentration of iodine; (3) reaction kinetics that the metal comprised in raw material and iodine form iodide and the metal iodide formed by feed metal decompose with the reaction kinetics forming metallic element.Therefore, contained by the hybrid metal goods formed after iodination reaction and mixed-metal feedstock, component is identical, and content is different.This is owing to synthesizing in iodate, and in decomposition reaction process Raw, the reaction kinetics difference of each metallic element causes.
Embodiment 1
A method for hafnium titanium mixed-metal materials is prepared in iodate, comprises the following steps:
(1) matrix metal hafnium and the 0.01wt.% titanium of 99.9wt.% is taken, altogether 30kg.The granularity of hafnium and titanium, all at about 3 ~ 5mm, mixes; Hafnium, titanium purity are 99.9wt.%;
(2) mixed-metal feedstock 3 is put into iodate device, be loaded between molybdenum net 4 and retort 2 inwall, be evacuated to 1 × 10
-3pa, start to carry out iodination reaction, being added by iodine adding device device 7 by solid-state for 300g iodine has in the retort 2 of certain temperature, each metallic element Hf and Ti in the iodine steam generated and raw material reacts and generates volatile iodide at about 500 DEG C temperature, the volatility iodide generated are passed on female silk 5 of alive about 1300 DEG C temperature, decompose and generate metal and iodine steam, the metal formation of deposits hafnium titanium mixed-metal materials on female silk 5 generated, iodine steam returns to raw material district to be continued to participate in iodination reaction.Reaction process about 20 hours, the purity of gained hafnium titanium mixed-metal materials is 99.95w%, and in material, the composition of hafnium and titanium and the composition of raw material have certain proportionlity, and in gained hafnium titanium mixed-metal materials, the mass ratio of hafnium and titanium is roughly 3:1.
(3) above-mentioned obtained hafnium titanium mixed-metal materials is obtained hafnium titanium hybrid metal blank through high temperature electron beam melting in electron beam furnace.
Embodiment 2
A method for hafnium zirconium mixed-metal materials is prepared in iodate, comprises the following steps:
(1) take matrix metal hafnium and the 10wt.% zirconium of 90wt.%, altogether 20kg, the granularity of hafnium and zirconium, all at about 2 ~ 5mm, mixes; Each metallic element purity is 99.9wt.%;
(2) mixed-metal feedstock is put into iodate device, be evacuated to 5 × 10
-3pa, start to carry out iodination reaction, the iodine adding amount in iodate device reacts with iodine steam at 200g, Hf and Zr and generates volatile iodide at 400 DEG C of temperature, the volatility iodide generated are passed on female silk of about 1250 DEG C temperature, decompose and generate hafnium zirconium mixed-metal materials; Reaction process about 20 hours, the purity of gained hafnium zirconium mixed-metal materials is 99.95w%, and in material, the composition of hafnium and zirconium and the composition of raw material have certain proportionlity, and in gained hafnium zirconium mixed-metal materials, the mass ratio of hafnium and zirconium is roughly 2:1.
(3) above-mentioned obtained hafnium zirconium mixed-metal materials is obtained hafnium zirconium hybrid metal blank through electron beam melting in electron beam furnace.
Embodiment 3
A method for hafnium zirconium titanium mixed-metal materials is prepared in iodate, comprises the following steps:
(1) take the matrix metal of 70wt.%, 20wt.% zirconium and 10wt.% titanium, altogether 15kg, the granularity of hafnium, zirconium and titanium, all at about 1 ~ 6mm, mixes; Each metallic element purity is 99.9%;
(2) mixed-metal feedstock is put into iodate device, be evacuated to 1 × 10
-3pa, start to carry out iodination reaction, iodine adding amount in iodate device is at 300g, Hf, Zr and titanium react with iodine steam and generate volatile iodide at about 500 DEG C temperature, the volatility iodide generated are passed on female silk of about 1300 DEG C temperature, decompose and generate hafnium zirconium titanium mixed-metal materials; Reaction process about 30 hours, the purity of gained hafnium zirconium titanium mixed-metal materials is 99.95w%, in material, the composition of hafnium, zirconium, titanium and the composition of raw material have certain proportionlity, and in gained hafnium zirconium titanium mixed-metal materials, the mass ratio of hafnium, zirconium, titanium is roughly 7:2:1.
(3) above-mentioned obtained hafnium based mixed-metal materials is obtained hafnium zirconium titanium hybrid metal blank through electron beam melting in electron beam furnace.
Embodiment 4
A method for hafnium titanium mixed-metal materials is prepared in iodate, comprises the following steps:
(1) matrix metal hafnium and the 0.1wt.% iron of 99.9wt.% is taken, altogether 40kg.The granularity of hafnium and iron, all at about 3 ~ 10mm, mixes; Hafnium, iron purity are 99.9wt.%;
(2) mixed-metal feedstock 3 is put into iodate device, be loaded between molybdenum net 4 and retort 2 inwall, be evacuated to 1 × 10
-3pa, start to carry out iodination reaction, being added by iodine adding device device 7 by solid-state for 300g iodine has in the retort 2 of certain temperature, each metallic element Hf in the iodine steam generated and raw material and iron react and generate volatile iodide at about 500 DEG C temperature, the volatility iodide generated are passed on female silk 5 of alive about 1000 DEG C temperature, decompose and generate metal and iodine steam, the metal formation of deposits hafnium iron mixed-metal materials on female silk 5 generated, iodine steam returns to raw material district to be continued to participate in iodination reaction.Reaction process about 15 hours, the purity of gained hafnium iron mixed-metal materials is 99.95w%, and in material, the composition of hafnium and iron and the composition of raw material have certain proportionlity, and in gained hafnium titanium mixed-metal materials, the mass ratio of hafnium, titanium is roughly 3:1.
(3) above-mentioned obtained hafnium titanium mixed-metal materials is obtained hafnium iron hybrid metal blank through high temperature electron beam melting in electron beam furnace.
Prepared the method for hafnium based mixed-metal materials by iodate provided by the invention, the hafnium based mixed-metal materials that purity reaches 99.95wt.% can be obtained, and the continuous batchization that effectively can realize hafnium based mixed-metal materials is produced, products obtained therefrom uniform composition.It is high that the inventive method has production efficiency, and product composition is even, the advantages such as production cost is lower.
Claims (9)
1. a hafnium based mixed-metal materials, is characterized in that: be made up of matrix metal hafnium and other metallic element, other described metallic element is Zr, Ti, Al, B, Ba, Be, Ca, Ce, Co, Cs, Dy, Er, Fe, Gd, Ho, La, Mg, Mn, Mo, Nb, Ni, Pr, Sc, Sm, one or more in Sr, Ta, V, W, Y and Yb.
2. hafnium based mixed-metal materials according to claim 1, is characterized in that: the content >=50wt.% of described metal hafnium, or the content of described metal hafnium is less than 50wt.%, and is greater than the content of any one other metallic elements except hafnium.
3. hafnium based mixed-metal materials according to claim 1, is characterized in that: the total content >=0.01wt.% of other described metallic element.
4. hafnium based mixed-metal materials according to claim 1, is characterized in that: the total content >=0.05wt.% of other described metallic element.
5. hafnium based mixed-metal materials according to claim 1, is characterized in that: the total content >=0.1wt.% of other described metallic element.
6. the iodate preparation method of the hafnium based mixed-metal materials according to any one of claim 1-5, comprises the following steps:
(1) take matrix metal hafnium and other metallic element by composition proportion, mix, wherein each metallic element purity is 99.9wt.%;
(2) mixed-metal feedstock is put into iodate device, be evacuated to 1 × 10
-2pa ~ 1 × 10
-3pa, carries out iodination reaction, and metal hafnium and other metallic element react with iodine steam at a lower temperature and generate volatile iodide, and the volatility iodide generated are passed on female silk of comparatively high temps, decomposes and generates hafnium based mixed-metal materials.
7. the iodate preparation method of hafnium based mixed-metal materials according to claim 6, is characterized in that: also comprise step (3): the hafnium based mixed-metal materials obtained is carried out electron beam melting again, obtained hafnium base hybrid metal blank.
8. the iodate preparation method of hafnium based mixed-metal materials according to claim 6, is characterized in that: the granularity of metal hafnium and other metallic element is 1mm ~ 18mm.
9. the iodate preparation method of hafnium based mixed-metal materials according to claim 6, it is characterized in that: during iodination reaction, metal hafnium and other metallic element react with iodine steam and generate volatile iodide between 200 ~ 800 DEG C, the volatility iodide generated are passed on female silk of 1100 ~ 1600 DEG C, decompose and generate hafnium based mixed-metal materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506427A (en) * | 2015-12-10 | 2016-04-20 | 西北有色金属研究院 | Tantalum alloy surface modified composite Hf-Ta coating layer and preparation method thereof |
| CN108203765A (en) * | 2016-12-19 | 2018-06-26 | 南京佑天金属科技有限公司 | A kind of control method for production crystallization hafnium |
| CN112725641A (en) * | 2019-10-15 | 2021-04-30 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of high-purity metal vanadium |
| CN116040673A (en) * | 2023-03-31 | 2023-05-02 | 研峰科技(北京)有限公司 | A kind of synthetic method of samarium diiodide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949357A (en) * | 1958-01-16 | 1960-08-16 | Chicago Dev Corp | High purity titanium-manganese alloy |
| US5372659A (en) * | 1992-05-12 | 1994-12-13 | Cezus-Compagnie Europeenne Du Zirconium | Alloys of refractory metals suitable for transformation into homogeneous and pure ingots |
| CN1535326A (en) * | 2000-10-24 | 2004-10-06 | ����Τ�����ʹ�˾ | Method and sputtering target for forming titanium-based and zirconium-based mixed metal materials |
| CN102528066A (en) * | 2010-12-16 | 2012-07-04 | 北京有色金属研究总院 | Superfine high-purity hafnium powder as well as preparation method and application thereof |
| CN202925073U (en) * | 2012-11-12 | 2013-05-08 | 北京有色金属研究总院 | Iodination-purification reaction unit for rare metals |
| CN103846440A (en) * | 2012-12-07 | 2014-06-11 | 北京有色金属研究总院 | Preparation method of metal hafnium raw material for iodization |
-
2013
- 2013-09-22 CN CN201310432324.8A patent/CN104451317A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949357A (en) * | 1958-01-16 | 1960-08-16 | Chicago Dev Corp | High purity titanium-manganese alloy |
| US5372659A (en) * | 1992-05-12 | 1994-12-13 | Cezus-Compagnie Europeenne Du Zirconium | Alloys of refractory metals suitable for transformation into homogeneous and pure ingots |
| CN1535326A (en) * | 2000-10-24 | 2004-10-06 | ����Τ�����ʹ�˾ | Method and sputtering target for forming titanium-based and zirconium-based mixed metal materials |
| CN102528066A (en) * | 2010-12-16 | 2012-07-04 | 北京有色金属研究总院 | Superfine high-purity hafnium powder as well as preparation method and application thereof |
| CN202925073U (en) * | 2012-11-12 | 2013-05-08 | 北京有色金属研究总院 | Iodination-purification reaction unit for rare metals |
| CN103846440A (en) * | 2012-12-07 | 2014-06-11 | 北京有色金属研究总院 | Preparation method of metal hafnium raw material for iodization |
Non-Patent Citations (1)
| Title |
|---|
| 吴享南等: "碘化法生产可锻性铪晶棒", 《稀有金属》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506427A (en) * | 2015-12-10 | 2016-04-20 | 西北有色金属研究院 | Tantalum alloy surface modified composite Hf-Ta coating layer and preparation method thereof |
| CN108203765A (en) * | 2016-12-19 | 2018-06-26 | 南京佑天金属科技有限公司 | A kind of control method for production crystallization hafnium |
| CN112725641A (en) * | 2019-10-15 | 2021-04-30 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of high-purity metal vanadium |
| CN116040673A (en) * | 2023-03-31 | 2023-05-02 | 研峰科技(北京)有限公司 | A kind of synthetic method of samarium diiodide |
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