CN103343253B - A kind of method preparing nano porous copper - Google Patents

A kind of method preparing nano porous copper Download PDF

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CN103343253B
CN103343253B CN201310276223.6A CN201310276223A CN103343253B CN 103343253 B CN103343253 B CN 103343253B CN 201310276223 A CN201310276223 A CN 201310276223A CN 103343253 B CN103343253 B CN 103343253B
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alloy
atomic percent
nano porous
cast ingot
copper
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CN103343253A (en
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秦春玲
赵维民
王志峰
刘丽
肖同娜
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Hebei University of Technology
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Abstract

A kind of method preparing nano porous copper of the present invention, include the manufacture of the metal of nano level hole, step is: according to subject alloy Cu atomic percent is 50.00%-Zr atomic percent is 42.50% ~ 50.00%(-Al) atomic percent is surplusin each Elements Atom percentage ratio at.% calculate the quality of desired raw material, take copper sheet, zirconium grain and aluminium block, be mixed to get mother alloy raw material, then this mother alloy raw material is placed in vacuum arc fumace melting, obtained Cu-Zr (-Al) alloy cast ingot, then melting-get rid of carrying equipment is adopted to prepare Cu-Zr(-Al) AMORPHOUS ALLOY RIBBONS, then a step removal alloying obtains nano porous metal copper bar band, being kept at vacuum tightness after being cleaned is 1 × 10 -1in the vacuum chamber of MPa, to avoid it oxidized, for subsequent use, overcome prior art complicated process of preparation, cost is high, is unfavorable for the shortcoming of industrial large-scale production.

Description

A kind of method preparing nano porous copper
Technical field
Technical scheme of the present invention includes the manufacture of the metal of nano level hole, specifically a kind of method preparing nano porous copper.
Background technology
In recent years, porous material is extensively paid close attention to by people because of the application performance of its excellence.The wherein physics of the uniqueness that shows due to its nano level aperture of nano porous metal material, chemistry and mechanical property, as the electromagnetic performance of uniqueness, optical property, higher chemical activity and the mechanical behavior etc. of change with aperture size change, make it in catalysis, sensing, to excite and there is huge application prospect in the field such as Chu Qing.The method being used for preparing nano porous metal material at present mainly contains template, sedimentation, powder metallurgic method, de-alloyage etc., and wherein de-alloyage is because obtained material aperture is little, enjoy people to favor to nanoporous size and morphology controllable, advantage simple to operate and with low cost.The precursor material utilizing de-alloyage to prepare nano porous metal use is divided into crystalline material and amorphous material two kinds, amorphous material is selected to do de-alloy precursor, avoid universals that the crystalline material such as lattice defect, segregation has prepare effect impact on nano porous metal, be conducive to the block nanometer porous metal structure preparing even structure.
CN102766893A disclosed " a kind of can graphically a kind of method preparing nano porous copper ", by carrying out de-alloy in an acidic solution to sputtering, galvanic deposit Cu-Zn alloy layer on the glass sheet, has prepared nano porous copper.But adopt and prepare complexity in this way, preparation cycle index is more, is not suitable for scale operation." a kind of method preparing nano porous copper " that CN102943198A discloses, at room temperature adopts the hydrofluoric acid of lower concentration to carry out freely taking off alloy to amorphous ribbon, thus obtained nano porous copper.The chemical composition of its non-crystaline amorphous metal is Cu:50% ~ 55%, Hf:40% ~ 45%, and all the other are Al.But because Hf element is expensive, add experimental cost, be unfavorable for industrialization.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of method preparing nano porous copper, with Cu-Zr (-Al) amorphous alloy material for starting materials, at room temperature, carry out freely taking off Alloying Treatment with low concentration hydrofluoric acid solution, prepare nano porous copper fast, overcome prior art complicated process of preparation, preparation cycle index is more, cost is high, is unfavorable for industrialization and is not suitable for the shortcoming of scale operation.
The present invention solves this technical problem adopted technical scheme: a kind of method preparing nano porous copper, and step is:
The first step, preparation Cu-Zr (-Al) alloy cast ingot
According to subject alloy Cu atomic percent is 50.00%-Zr atomic percent is 42.50% ~ 50.00%(-Al) atomic percent is surplusin each Elements Atom percentage ratio at.% calculate the quality of desired raw material, take the copper sheet that mass percent purity is 99.99%, mass percent purity be 99.99% zirconium grain and mass percent purity be the aluminium block of 99.99%, and the copper sheet that will take, zirconium grain and aluminium block are mixed to get mother alloy raw material, then this mother alloy raw material is placed in vacuum arc fumace, add 7g pure zirconium to be independently positioned in vacuum arc fumace as oxygen scavenging material and not with the mother alloy contact raw put into, under argon shield, melting electric current is slowly elevated to 110A from 30A, repeat melting 4 times, each 40 seconds, guarantee alloy structure homogeneity, furnace cooling, obtained Cu-Zr (-Al) alloy cast ingot, wherein the atomic percent of copper is 50.00%, the atomic percent of zirconium is 42.50% ~ 50.00%, the atomic percent of aluminium is its surplus or zero,
Second step, preparation AMORPHOUS ALLOY RIBBONS
Cu-Zr (-Al) alloy cast ingot obtained for the first step is removed superficial oxidation skin, and adopts melting-get rid of carrying equipment to prepare Cu-Zr(-Al) AMORPHOUS ALLOY RIBBONS, getting rid of SNNP is: 9.0 × 10 -4~ 8.0 × 10 -4under Pa vacuum tightness, be heated to 900 ~ 1100 DEG C, make the Cu-Zr(-Al of scale removal) alloy cast ingot melting, then the alloy of melting is blown cast and become AMORPHOUS ALLOY RIBBONS, blowing the required pressure of casting is 0.8 ~ 1.0MPa, and blowing the required copper wheel rotating speed of casting is 40 ~ 50m/s, is 60 ~ 300cm by blowing the length of the obtained AMORPHOUS ALLOY RIBBONS of casting, wide is 1.5 ~ 2mm, and thickness is 20 ~ 40 μm;
3rd step, a step removal alloying
The AMORPHOUS ALLOY RIBBONS obtained from second step intercepts the long sample of 30 ~ 40mm, be placed in 0.5M hydrofluoric acid corrosive fluid under room temperature and carry out removal alloying process 300 ~ 600s, thus the obtained nano porous metal copper bar band with the nano-porous structure of level changed with removal alloying time 300 ~ 600s;
4th step, the aftertreatment of nano porous metal copper bar band and protection
The nano porous metal copper bar band that 3rd step is obtained first adopts washed with de-ionized water, then cleans with dehydrated alcohol, and then clean nano porous metal copper bar band being kept at vacuum tightness is 1 × 10 -1in the vacuum chamber of MPa, to avoid it oxidized, for subsequent use.
A kind of above-mentioned method preparing nano porous copper, described subject alloy is Cu atomic percent is 50.00%-Zr atomic percent is 42.50% ~ 50.00%(-Al atomic percent is 0% ~ 7.5%).
A kind of above-mentioned method preparing nano porous copper, described subject alloy is Cu atomic percent is 50.00%-Zr atomic percent is 50.00%.
A kind of above-mentioned method preparing nano porous copper, described subject alloy is Cu atomic percent is 50.00%-Zr atomic percent is 45.00%-Al former sub-per-cent is 5%.
A kind of above-mentioned method preparing nano porous copper, described subject alloy is Cu atomic percent is 50.00%-Zr atomic percent is 42.50%-Al former sub-per-cent is 7.5%.
A kind of above-mentioned method preparing nano porous copper, it is known that involved raw-material source, equipment and operating procedure are those skilled in the art.
The invention has the beneficial effects as follows: compared with prior art, the outstanding advantages of the inventive method is:
(1) the inventive method adopts arc melting to prepare Cu-Zr (-Al) alloy pig, recycles single roller and gets rid of band machine, by the liquid metal of melting rapid solidification on the copper roller of high speed rotating, prepare Cu-Zr (-Al) amorphous thin ribbon; At room temperature, select the acid solution of lower concentration to carry out freely taking off alloying corrosion to Cu-Zr (-Al) amorphous alloy ribbon, therefore can prepare nano porous copper at short notice.
(2) the inventive method is that precursor employing freely takes off alloy prior with non-crystaline amorphous metal, has evenly and continuous print nano-porous structure compared with nano porous copper prepared by prepared nanoporous copper product and other de-alloy prioies.
(3) the inventive method greatly reduces the complicacy of equipment, and Preparation equipment cost is lower, has saved production cost, and has substantially reduced the process time, with short production cycle, suitability for scale production.In addition, the inventive method alloy used does not contain expensive noble metal component, alloying element relative moderate used.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the microstructure stereoscan photograph of nano porous copper obtained in embodiment 1.
Fig. 2 is the energy spectrum analysis figure in the stereoscan photograph of the nano porous copper obtained in embodiment 1.
Fig. 3 is the microstructure stereoscan photograph of nano porous copper obtained in embodiment 2.
Fig. 4 is the energy spectrum analysis figure in the stereoscan photograph of the nano porous copper obtained in embodiment 2.
Fig. 5 is the microstructure stereoscan photograph of nano porous copper obtained in embodiment 3.
Fig. 6 is the energy spectrum analysis figure in the stereoscan photograph of the nano porous copper obtained in embodiment 3.
Embodiment
Embodiment 1
The first step, preparation Cu-Zr alloy cast ingot
According to subject alloy Cu atomic percent is 50.00%-Zr atomic percent is 50.00%in each Elements Atom percentage ratio at.% calculate the quality of desired raw material, take the copper sheet 3.079g that mass percent purity is 99.99%, mass percent purity is the zirconium grain 4.421g of 99.99%, and the copper sheet taken and zirconium grain are mixed to get mother alloy raw material, then this mother alloy raw material is placed in vacuum arc fumace, add 7g pure zirconium to be independently positioned in vacuum arc fumace as oxygen scavenging material and not with the mother alloy contact raw put into, under argon shield, melting electric current is slowly elevated to 110A from 30A, repeat melting 4 times, each 40 seconds, guarantee alloy structure homogeneity, furnace cooling, obtained Cu-Zr alloy cast ingot, wherein the atomic percent of copper is 50.00%, the atomic percent of zirconium is 50.00%,
Second step, preparation AMORPHOUS ALLOY RIBBONS
Cu-Zr alloy cast ingot obtained for the first step is removed superficial oxidation skin, and adopts melting-get rid of carrying equipment to prepare Cu-Zr AMORPHOUS ALLOY RIBBONS, getting rid of SNNP is: 9.0 × 10 -4under Pa vacuum tightness, be heated to 900 DEG C, make the Cu-Zr alloy cast ingot melting of scale removal, then the alloy of melting is blown cast and become AMORPHOUS ALLOY RIBBONS, blowing the required pressure of casting is 0.8MPa, and blowing the required copper wheel rotating speed of casting is 40m/s, is 60cm by blowing the length of the obtained Cu-Zr AMORPHOUS ALLOY RIBBONS of casting, wide is 2mm, and thickness is 40 μm;
3rd step, a step removal alloying
The Cu-Zr AMORPHOUS ALLOY RIBBONS obtained from second step intercepts the long sample of 30mm, be placed in 0.5M hydrofluoric acid corrosive fluid under room temperature and carry out removal alloying process 300s, thus the obtained nano porous metal copper bar band with the nano-porous structure of level changed with removal alloying time 300s;
4th step, the aftertreatment of nano porous metal copper bar band and protection
The nano porous metal copper bar band that 3rd step is obtained first adopts washed with de-ionized water, then cleans with dehydrated alcohol, and then clean nano porous metal copper bar band being kept at vacuum tightness is 1 × 10 -1in the vacuum chamber of MPa, to avoid it oxidized, for subsequent use.
The microstructure stereoscan photograph display of the nano porous copper of Fig. 1, the tissue of nano porous copper obtained in the present embodiment is uniform nanoporous steel structure, and the pore size of nano-porous structure is 25 ~ 30nm, ligament width 15 ~ 25nm.Freely take off alloy when carrying out 300s, nano-porous structure is formed, because etching time is shorter, pore size and ligament size all less, pore structure is even.
Energy spectrum analysis figure in the stereoscan photograph of the nano porous copper of Fig. 2 shows, and the nano-porous structure of nano porous copper obtained in the present embodiment carries out energy spectrum analysis, and show that Zr is removed by selective corrosion, vesicular structure is made up of Cu.Embodiment 2
The first step, preparation Cu-Zr-Al alloy cast ingot
According to subject alloy Cu atomic percent is 50.00%-Zr atomic percent is 45.00%-Al atomic percent is 5.00%in each Elements Atom percentage ratio at.% calculate the quality of desired raw material, take the copper sheet 3.213g that mass percent purity is 99.99%, mass percent purity is the zirconium 4.151g of 99.99%, mass percent purity is the aluminium block 0.136g of 99.99%, and the copper sheet that will take, zirconium grain and aluminium block are mixed to get mother alloy raw material, then this mother alloy raw material is placed in vacuum arc fumace, add 7g pure zirconium to be independently positioned in vacuum arc fumace as oxygen scavenging material and not with the mother alloy contact raw put into, under argon shield, melting electric current is slowly elevated to 110A from 30A, repeat melting 4 times, each 40 seconds, guarantee alloy structure homogeneity, furnace cooling, obtained Cu-Zr-Al alloy cast ingot, wherein the atomic percent of copper is 50.00%, the atomic percent of zirconium is 45.00%, the atomic percent of aluminium is 5.00%,
Second step, preparation Cu-Zr-Al AMORPHOUS ALLOY RIBBONS
Cu-Zr-Al alloy cast ingot obtained for the first step is removed superficial oxidation skin, and adopts melting-get rid of carrying equipment to prepare Cu-Zr-Al AMORPHOUS ALLOY RIBBONS, getting rid of SNNP is: 8.5 × 10 -4under Pa vacuum tightness, be heated to 1000 DEG C, make the Cu-Zr-Al alloy cast ingot melting of scale removal, then the alloy of melting is blown cast and become AMORPHOUS ALLOY RIBBONS, blowing the required pressure of casting is 0.9MPa, and blowing the required copper wheel rotating speed of casting is 40m/s, is 180cm by blowing the length of the obtained AMORPHOUS ALLOY RIBBONS of casting, wide is 1.8mm, and thickness is 30 μm;
3rd step, a step removal alloying
The Cu-Zr-Al AMORPHOUS ALLOY RIBBONS obtained from second step intercepts the long sample of 35mm, be placed in 0.5M hydrofluoric acid corrosive fluid under room temperature and carry out removal alloying process 450s, thus the obtained nano porous metal copper bar band with the nano-porous structure of level changed with removal alloying time 450s;
4th step, the aftertreatment of nano porous metal copper bar band and protection
The nano porous metal copper bar band that 3rd step is obtained first adopts washed with de-ionized water, then cleans with dehydrated alcohol, and then clean nano porous metal copper bar band being kept at vacuum tightness is 1 × 10 -1in the vacuum chamber of MPa, to avoid it oxidized, for subsequent use.
The microstructure stereoscan photograph display of the nano porous copper of Fig. 3, the tissue of nano porous copper obtained in the present embodiment is uniform nanoporous steel structure, and the pore size of nano-porous structure is 30 ~ 60nm, ligament width 35 ~ 80nm.Freely take off alloy and carried out 450s, along with the increase freely taking off alloying time, hole and ligament size increase all to some extent.
Energy spectrum analysis figure in the stereoscan photograph of the nano porous copper of Fig. 4 shows, and the nano-porous structure of nano porous copper obtained in the present embodiment carries out energy spectrum analysis, and show that Zr and Al is removed by selective corrosion all, vesicular structure is made up of Cu.
Embodiment 3
The first step, preparation Cu-Zr-Al alloy cast ingot
According to subject alloy Cu atomic percent is 50.00%-Zr atomic percent is 42.50%-Al atomic percent is 7.50%in each Elements Atom percentage ratio at.% calculate the quality of desired raw material, take the copper sheet 3.284g that mass percent purity is 99.99%, mass percent purity is the zirconium 4.007g of 99.99%, mass percent purity is the aluminium block 0.209g of 99.99%, and the copper sheet that will take, zirconium grain and aluminium block are mixed to get mother alloy raw material, then this mother alloy raw material is placed in vacuum arc fumace, add 7g pure zirconium to be independently positioned in vacuum arc fumace as oxygen scavenging material and not with the mother alloy contact raw put into, under argon shield, melting electric current is slowly elevated to 110A from 30A, repeat melting 4 times, each 40 seconds, guarantee alloy structure homogeneity, furnace cooling, obtained Cu-Zr-Al alloy cast ingot, wherein the atomic percent of copper is 50.00%, the atomic percent of zirconium is 42.50%, the atomic percent of aluminium is 7.50%,
Second step, preparation Cu-Zr-Al AMORPHOUS ALLOY RIBBONS
Cu-Zr-Al alloy cast ingot obtained for the first step is removed superficial oxidation skin, and adopts melting-get rid of carrying equipment to prepare Cu-Zr-Al AMORPHOUS ALLOY RIBBONS, getting rid of SNNP is: 8.5 × 10 -4under Pa vacuum tightness, be heated to 1000 DEG C, make the Cu-Zr-Al alloy cast ingot melting of scale removal, then the alloy of melting is blown cast and become AMORPHOUS ALLOY RIBBONS, blowing the required pressure of casting is 0.9MPa, and blowing the required copper wheel rotating speed of casting is 50m/s, is 300cm by blowing the length of the obtained AMORPHOUS ALLOY RIBBONS of casting, wide is 1.5mm, and thickness is 20 μm;
3rd step, a step removal alloying
The AMORPHOUS ALLOY RIBBONS obtained from second step intercepts the long sample of 40mm, be placed in 0.5M hydrofluoric acid corrosive fluid under room temperature and carry out removal alloying process 600s, thus the obtained nano porous metal copper bar band with the nano-porous structure of level changed with removal alloying time 600s;
4th step, the aftertreatment of nano porous metal copper bar band and protection
The nano porous metal copper bar band that 3rd step is obtained first adopts washed with de-ionized water, then cleans with dehydrated alcohol, and then clean nano porous metal copper bar band being kept at vacuum tightness is 1 × 10 -1in the vacuum chamber of MPa, to avoid it oxidized, for subsequent use.
The microstructure stereoscan photograph display of the nano porous copper of Fig. 5, the tissue of nano porous copper obtained in the present embodiment is uniform nanoporous steel structure, and the pore size of nano-porous structure is 40 ~ 85nm, ligament width 35 ~ 50nm.When freely taking off alloy and proceeding to 600s, obviously see, because etching time is longer, hole dimension becomes large, and tough belt distance is elongated.
Energy spectrum analysis figure in the stereoscan photograph of the nano porous copper of Fig. 6 shows, and the nano-porous structure of nano porous copper obtained in the present embodiment carries out energy spectrum analysis, and show that Zr and Al is removed by selective corrosion all, vesicular structure is made up of Cu.
It is known that raw-material source involved in above-described embodiment, equipment and operating procedure are those skilled in the art.

Claims (1)

1. prepare a method for nano porous copper, it is characterized in that step is:
The first step, preparation Cu-Zr alloy cast ingot or Cu-Zr-Al alloy cast ingot
According to subject alloy Cu atomic percent is 50.00%-Zr atomic percent is 50.00%, Cu atomic percent is 50.00%-Zr atomic percent is 45.00%-Al atomic percent is 5.00%or Cu atomic percent is 50.00%-Zr atomic percent is 42.50%-Al atomic percent is 7.50%in each Elements Atom percentage ratio at.% calculate the quality of desired raw material, take the copper sheet that mass percent purity is 99.99%, mass percent purity be 99.99% zirconium grain and mass percent purity be the aluminium block of 99.99%, and the copper sheet taken and zirconium grain are mixed or copper sheet, zirconium grain and aluminium block are mixed to get mother alloy raw material, then this mother alloy raw material is placed in vacuum arc fumace, add 7g pure zirconium to be independently positioned in vacuum arc fumace as oxygen scavenging material and not with the mother alloy contact raw put into, under argon shield, melting electric current is slowly elevated to 110A from 30A, repeat melting 4 times, each 40 seconds, guarantee alloy structure homogeneity, furnace cooling, obtained Cu atom hundred proportion by subtraction is 50.00%-Zr atomic percent is 50.00%, Cu atomic percent is 50.00%-Zr atomic percent is 45.00%-Al atomic percent is 5.00%alloy cast ingot or Cu atomic percent is 50.00%-Zr atomic percent is 42.50%-Al atomic percent is 7.50%alloy cast ingot,
Second step, preparation AMORPHOUS ALLOY RIBBONS
Cu-Zr alloy cast ingot obtained for the first step or Cu-Zr-Al alloy cast ingot are removed superficial oxidation skin, and adopts melting-get rid of carrying equipment to prepare Cu-Zr or Cu-Zr-Al AMORPHOUS ALLOY RIBBONS, getting rid of SNNP is: 9.0 × 10 -4~ 8.0 × 10 -4under Pa vacuum tightness, be heated to 900 ~ 1100 DEG C, make Cu-Zr alloy cast ingot or the melting of Cu-Zr-Al alloy cast ingot of scale removal, then the alloy of melting is blown cast and become AMORPHOUS ALLOY RIBBONS, blowing the required pressure of casting is 0.8 ~ 1.0MPa, and blowing the required copper wheel rotating speed of casting is 40 ~ 50m/s, is 60 ~ 300cm by blowing the length of the obtained AMORPHOUS ALLOY RIBBONS of casting, wide is 1.5 ~ 2mm, and thickness is 20 ~ 40 μm;
3rd step, a step removal alloying
The AMORPHOUS ALLOY RIBBONS obtained from second step intercepts the long sample of 30 ~ 40mm, be placed in 0.5M hydrofluoric acid corrosive fluid under room temperature and carry out removal alloying process 300 ~ 600s, thus the obtained nano porous metal copper bar band with the nano-porous structure of level changed with removal alloying time 300 ~ 600s;
4th step, the aftertreatment of nano porous metal copper bar band and protection
The nano porous metal copper bar band that 3rd step is obtained first adopts washed with de-ionized water, then cleans with dehydrated alcohol, and then clean nano porous metal copper bar band being kept at vacuum tightness is 1 × 10 -1in the vacuum chamber of MPa, to avoid it oxidized, for subsequent use.
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