CN101733406B - Method for preparing nano porous copper/ferroferric oxide composite material - Google Patents
Method for preparing nano porous copper/ferroferric oxide composite material Download PDFInfo
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- CN101733406B CN101733406B CN2009102299854A CN200910229985A CN101733406B CN 101733406 B CN101733406 B CN 101733406B CN 2009102299854 A CN2009102299854 A CN 2009102299854A CN 200910229985 A CN200910229985 A CN 200910229985A CN 101733406 B CN101733406 B CN 101733406B
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Abstract
The invention relates to a method for preparing nano porous copper/ferroferric oxide composite material by adopting the rapid solidifying method and the dealloying method, belonging to the field of the novel material. The method for preparing the nano porous copper/ferroferric oxide composite material comprises the following steps: firstly heating the pure metal of aluminum, copper and iron to melt; then preparing an alloy strip by using rapid solidification; finally dealloying the alloy strip in alkaline solution, removing the aluminium element therein, thereby preparing the nano porous copper/ferroferric oxide composite material. The method for preparing the nano porous copper/ferroferric oxide composite material is simple and is convenient to operate and is suitable for the large-scale industrial production. The substrate of the nano porous copper/ferroferric oxide composite material prepared with the method is porous bicontinuous nano porous copper inlaid with nano ferroferric oxide particles. The structure and magnetic properties of the nano porous copper/ferroferric oxide composite material can be adjusted according to the component of master alloy, at the same time the material has good electrical conductivity and can be widely applied to the sensing and the biomedical fields.
Description
Technical field
The invention belongs to field of new, relate in particular to a kind of preparation method of nano porous copper/ferroferric oxide composite material.
Background technology
The nano ferriferrous oxide granule synthetic method is a lot, mainly is divided into physics method, chemical method and materialization synthesis.Chemical method divides by the decentralized medium kind can be divided into vapor phase method, liquid phase method and solid phase method.Nano ferriferrous oxide has excellent magnetism, all has potential application prospect in many fields such as magnetic recording, sensor, suction ripple, target location, catalyst, electrochemistry.In actual applications, when nano material is applied to target location, catalyst, these fields of electrochemistry, usually all need these nano materials are loaded on the specific carrier material, as silica, diatomite, aluminium oxide, active carbon (AC), CNT carriers such as (CNTs), its objective is activity, efficient and the stability etc. that improve nano material.
Recently, the research of nano ferriferrous oxide is gradually to synthetic more complicated structural development, as hud typed tri-iron tetroxide and the nano composite material that contains tri-iron tetroxide.Utilize the method for above-mentioned synthesis of nano ferriferrous oxide particles to prepare copper/ferroferric oxide composite material and yet there are no report.M.Pardavi-Horvath (M.Pardavi-Horvath, and L.Takacs, applicating physical magazine, 1993,73,6958) utilize ball-milling method reaction cupric oxide powder and iron powder to prepare the copper/ferroferric oxide nano composite material, this method only is applicable to that the preparation powder body material can't obtain whole successional nano composite material.At present, the method that has a whole successional copper/ferroferric oxide nano composite material about preparation yet there are no report both at home and abroad.
Removal alloying method (dealloying) is meant optionally removes semiprecious metal (reactive metal) in the alloy, thereby obtains needed metal with nano-porous structure.The patent No. is 200610045500.2 Chinese patent, discloses a kind of nanometer porous metal catalyst and preparation method thereof.At present, the multiple nano porous metal that utilized the successful preparation of removal alloying method, but utilizing this method to prepare nano porous metal/metal oxide composite yet there are no relevant report.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, provide that a kind of cost is low, the preparation method of the simple nano porous copper/ferroferric oxide composite material of technology.The matrices of composite material of this method preparation is the nano porous copper of perforate, co-continuous, and is inlaid with ferroferric oxide nano granules, has good magnetic and electric conductivity concurrently.And this composite can keep whole continuity.
The present invention realizes in the following manner.
A kind of preparation method of novel nano porous copper/ferroferric oxide composite material adopts rapid solidification and takes off the method that alloying combines to prepare, and it is characterized in that may further comprise the steps:
(1) pure metallic aluminum, copper, iron are heated to molten state, foundry alloy liquid is fully mixed; Wherein, the atomic percent of aluminium, copper, iron content is an aluminium 50～80%, copper 10～50%, and all the other are iron;
(2) utilize inert gas that alloy liquid is blown out fast, make liquid metal rapid solidification on the high speed copper roller rotating of fusion, prepare alloy strip;
(3) in being the aqueous solution of 5～30% NaOH or potassium hydroxide, mass percent takes off Alloying Treatment; Corrosion process is washed till neutrality with nano porous copper/ferroferric oxide composite material after finishing in distilled water; At last, sample dries and preserves.
The preparation method of above-mentioned nano porous copper/ferroferric oxide composite material is characterized in that the inert gas in the step (2) is argon gas or nitrogen.Aluminium copper iron (the content of aluminium in the step (3), with atomic percent is 50～80%, the content of copper, with atomic percent is 10～50%, all the other are iron, total amount is 100%) with mass percent be 5～30% NaOH or potassium hydroxide solution room temperature reaction 0.5～3 hour, be heated to 65～95 ℃ then and continue reaction 1～2 hour again.The freezing rate of aluminium copper iron strip is 10 in the step (2)
2～10
6K/s.
Concrete operations are as follows: aforementioned fine aluminium, fine copper and pure iron metal are joined in the smelting furnace, be heated to molten condition, make its alloying through fully stirring.Blow out fast under 0.05～1MPa pressure with the liquid metal of inert gas with fusion, Quench on the high speed copper roller rotating makes alloy with 10
2～10
6K/s speed is solidified, and obtaining thickness is 10～200 microns, and width is 1～10 millimeter, and length is 0.5～10 centimetre of alloy strip.Wherein the content of aluminium is 50～80% (atomic percents), and the content of copper is 10～50% (atomic percents), and all the other are Fe.With above-mentioned alloy strip join mass percent be in 5～30% NaOH or the potassium hydroxide solution room temperature reaction 0.5～3 hour, be heated to 65～95 ℃ then and continue reaction 1～2 hour again.Filter out the strips of composite material in the solution then, be washed till the pH test paper with distilled water and be neutral, take out at last and place.
Method of the present invention has the following advantages: the magnetic property of the magnetic Nano porous copper/ferroferric oxide composite material of (1) this method preparation can obtain regulation and control by the control alloy ratio.(2) this composite has had good electric conductivity concurrently when having better magnetic property.(3) this method can be prepared composite and has ferroferric oxide nano granules and be embedded in special construction in the nano porous copper matrix.Matrices of composite material is a nano porous copper, and evenly inlays ferroferric oxide nano granules, has good magnetic and electric conductivity concurrently, can be widely used in fields such as sensing and biomedicine.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment one
(1) according to atomic percent 50% aluminium, 45% bronze medal, all the other are the proportioning of iron, and aluminium copper iron is put into smelting furnace.Alloy is heated to molten condition, makes its alloying through fully stirring.Blow out fast under 0.2MPa pressure with the liquid of argon gas fusion, Quench on the high speed copper roller rotating, obtaining thickness is 30～60 microns, and width is 2～5 millimeters, and length is 0.5～10 centimetre alloy thin band.The freezing rate of alloy thin band is 10 under this condition
3～10
4K/s
(2) be 30% sodium hydroxide solution reaction 0.5 hour down at 25 ℃ with mass percent, and then be heated to 95 ℃ of reactions 1 hour to not significantly the reaction bubble produce, stop to heat.
(3) reacted product is collected, washed repeatedly to chemical attack solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.This sample has typical co-continuous nano-porous structure, and has a spot of ferriferrous oxide particles to be distributed in nano porous copper matrix inside.Wherein, nano porous copper is of a size of 20～60nm, and tri-iron tetroxide is of a size of 200～400nm.
Embodiment two
(1) according to atomic percent 70% aluminium, 10% bronze medal, all the other are the proportioning of iron, and aluminium copper iron is put into smelting furnace.Alloy is heated to molten condition, makes its alloying through fully stirring.Blow out fast under 0.05MPa pressure with the liquid of nitrogen fusion, Quench on the high speed copper roller rotating, obtaining thickness is 30～50 microns, and width is 2～5 millimeters, and length is 0.5～10 centimetre alloy thin band.The freezing rate of alloy thin band is 10 under this condition
2～10
3K/s
(2) be 5% sodium hydroxide solution reaction 3 hours down at 25 ℃ with mass percent, and then be heated to 65 ℃ of reactions 2 hours to not significantly the reaction bubble produce, stop to heat.
(3) reacted product is collected, washed repeatedly to chemical attack solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.This sample has typical co-continuous nano-porous structure, and has a large amount of ferriferrous oxide particles to be distributed in nano porous copper matrix inside.Wherein, nano porous copper is of a size of 20～60nm, and tri-iron tetroxide is of a size of 200～400nm.
Embodiment three
(1) according to atomic percent 62.5% aluminium, 20% bronze medal, all the other are the proportioning of iron, and aluminium copper iron is put into smelting furnace.Alloy is heated to molten condition, makes its alloying through fully stirring.Blow out fast under 1MPa pressure with the liquid of argon gas with fusion, obtaining thickness is 30～40 microns, and width is 1～5 millimeter, and length is 0.5～10 centimetre alloy thin band.The freezing rate of alloy thin band is 10 under this condition
5～10
6K/s
(2) 25 ℃ down with mass percent 20% potassium hydroxide solution reaction 1 hour, and then be heated to 80 ℃ of reactions 1.5 hours to not significantly the reaction bubble produce, stop to heat.
(3) reacted product is collected, washed repeatedly to chemical attack solution clean fully (wide pH value test paper check flushing distilled water is neutral) with distilled water.Under 25 ℃, dry then and preserve.This sample has typical co-continuous nano-porous structure, and has more ferriferrous oxide particles to be distributed in nano porous copper matrix inside.Wherein, nano porous copper is of a size of 20～60nm, and tri-iron tetroxide is of a size of 200～400nm.
Embodiment four
Remove according to atomic percent 80% aluminium, 10% bronze medal, all the other carry out proportioning for iron, and gas pressure is 1MPa, and reaction solution is outside the potassium hydroxide solution, and other are operated with embodiment one.
Embodiment five
Remove according to atomic percent 60% aluminium, 30% bronze medal, all the other carry out proportioning for iron, and gas pressure is 0.5MPa, and reaction solution is outside the potassium hydroxide solution, and other are operated with embodiment two.
Embodiment five
Remove according to atomic percent 75% aluminium, 20% bronze medal, all the other carry out proportioning for iron, and reaction solution is that mass percent is that other are operated with embodiment two outside 10% the potassium hydroxide solution.
Claims (4)
1. the preparation method of a nano porous copper/ferroferric oxide composite material adopts rapid solidification and takes off the method that alloying combines to prepare nano porous copper/ferroferric oxide composite material, it is characterized in that may further comprise the steps:
(1) fine aluminium, copper, iron are heated to molten state, foundry alloy liquid is fully mixed; Wherein, the atomic percent of aluminium, copper, iron content is an aluminium 50～80%, copper 10～50%, and all the other are iron;
(2) utilize inert gas that alloy liquid is blown out fast, make liquid metal rapid solidification on the high speed copper roller rotating of fusion, prepare alloy strip;
(3) in being the aqueous solution of 5～30% NaOH or potassium hydroxide, mass percent takes off Alloying Treatment; Corrosion process is washed till neutrality with nano porous copper/ferroferric oxide composite material after finishing in distilled water; At last, sample dries and preserves.
2. the preparation method of nano porous copper/ferroferric oxide composite material according to claim 1 is characterized in that the inert gas in the step (2) is argon gas or nitrogen; Inert gas pressure is 0.05～1MPa; The freezing rate of aluminium copper iron strip is 10
2～10
6K/s.
3. the preparation method of nano porous copper/ferroferric oxide composite material according to claim 1, it is characterized in that taking off Alloying Treatment technology in the step (3) is: aluminium copper iron and mass percent are 5～30% NaOH or potassium hydroxide solution room temperature reaction 0.5～3 hour, are heated to 65～95 ℃ then and continue reaction 1～2 hour again.
4. the preparation method of nano porous copper/ferroferric oxide composite material according to claim 1, the nano porous copper/ferroferric oxide composite material that it is characterized in that preparation in the step (3) has ferroferric oxide nano granules and is embedded in special construction in the nano porous copper matrix.
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| CN102363217B (en) * | 2011-10-26 | 2013-04-17 | 济南大学 | Method for preparing nanometer porous copper powder |
| CN102974345B (en) * | 2012-11-13 | 2014-06-04 | 西安交通大学 | Preparation method of noble metal load cerium oxide nano-porous catalytic material |
| CN104437344B (en) * | 2014-10-13 | 2016-08-24 | 中南大学 | A kind of Copper-cladding Aluminum Bar composite magnetic nano material and preparation thereof and application |
| CN105904470A (en) * | 2016-06-20 | 2016-08-31 | 张苡铭 | Method for preparing transformable robot through composition of shape memory alloy and liquid metal |
| CN108467061A (en) * | 2018-05-31 | 2018-08-31 | 济南大学 | A kind of superfine zirconia nanosphere and preparation method thereof |
| WO2023201710A1 (en) * | 2022-04-22 | 2023-10-26 | 赵远云 | Preparation methods for noble metal nanoparticle doped nano metal oxide and noble metal nanoparticles, and uses |
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Non-Patent Citations (3)
| Title |
|---|
| Zhen Qi et a.Formation and Characterization of Monolithic Nanoporous Copper by Chemical Dealloying of Al-Cu Alloys.《J. Phys. Chem. C.》.2009,第113卷(第16期),第6694页左栏第18-21行，右栏experimental section. * |
| 谭秀兰等.去合金化制备纳米多孔金属材料的研究进展.《材料导报:综述篇》.2009,第23卷(第3期),68-71,76. * |
| 谭秀兰等.去合金化制备纳米多孔铜.《强激光与粒子束》.2009,第21卷(第1期),63-66. * |
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