CN101545029B - Method for improving corrosion performance of bulk amorphous alloy through oxidizing annealing in air atmosphere - Google Patents
Method for improving corrosion performance of bulk amorphous alloy through oxidizing annealing in air atmosphere Download PDFInfo
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- CN101545029B CN101545029B CN2009100979764A CN200910097976A CN101545029B CN 101545029 B CN101545029 B CN 101545029B CN 2009100979764 A CN2009100979764 A CN 2009100979764A CN 200910097976 A CN200910097976 A CN 200910097976A CN 101545029 B CN101545029 B CN 101545029B
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- amorphous alloy
- bulk amorphous
- air atmosphere
- block amorphous
- alloy
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Abstract
The invention discloses a method for improving the corrosion performance of bulk amorphous alloy through oxidizing annealing in an air atmosphere. The method comprises the following steps: firstly, after polishing the surface of a bulk amorphous alloy, washing the surface of the bulk amorphous alloy with alcohol; secondly, placing the bulk amorphous alloy in a muffle furnace to heat the bulk amorphous alloy to between 286 and 336 DEG C at a speed of 10 DEG C/min; and thirdly, keeping the temperature constant for 5 to 10 hours to form a metallic oxide ceramic layer with high corrosion resistance on the surface of the bulk amorphous alloy. Compared with other common methods for improving the corrosion resistance of the bulk amorphous alloy, the technology has the advantages of greatly improving the corrosion resistance of the bulk amorphous alloy without influencing the glass forming ability of the alloy, along with simplicity, easy implementation and low cost. The process avoids changes in the original dimension and shape of a workpiece, ensures an excellent bonding force between a formed oxide layer and a substrate, and is applicable to the final processing of parts and products.
Description
Technical field
The present invention relates to the surface anticorrosion technology of amorphous alloy, relate in particular to the method that a kind of air atmosphere oxidizing annealing improves the block amorphous alloy corrosive nature.
Background technology
The eighties of last century the eighties, the Inoue study group of the Turnbull of the U.S. and northeastern Japan university has developed separately and has had good glass forming ability, critical size reaches several millimeters multicomponent alloy system, thereby has opened the flourish prelude of block amorphous alloy research.To having become one of most active subject of metallic substance research field as block amorphous alloy research.Since non-crystaline amorphous metal structurally singularity thereby make especially mechanical property of its physics, chemistry, magnetics with a series of excellences, as high strength, low modulus, high compression plasticity or the like.Non-crystaline amorphous metal has been used as sports equipment, high-performance spring and other miniature instruments etc. and has obtained application at present.
Recently, the Zr base noncrystal alloy that has the good mechanical performance and have a big glass forming ability is developed, and has represented extraordinary application prospect.But before using, its erosion resistance must be considered.The Zr base block amorphous alloy has good anti-corrosion in pure acid and soda ash solution, but erosion resistance is relatively poor in the aqueous solution of chloride ion-containing, and this has limited the development of Zr base noncrystal alloy in application facet to a certain extent.The method of traditional raising non-crystaline amorphous metal erosion resistance mainly contains microalloying method and surface-modification method such as ion implantation.But microalloying method usually can reduce glass forming ability, and the restriction of alloy element will be subjected to alloying rules such as thermodynamics balances each other, solid solubility, and the ion implantation cost is higher, is difficult to large-scale application.Therefore develop a kind of simple and easy to doly, neither reduce the method that glass forming ability can significantly improve block amorphous alloy erosion resistance in the aqueous solution again, be to the research of block amorphous alloy or use important meaning is all arranged.
Summary of the invention
At the deficiency that exists in the background technology, the purpose of this invention is to provide the method that a kind of air atmosphere oxidizing annealing improves the block amorphous alloy corrosive nature.Make the non-crystaline amorphous metal surface generate the anti-corrosion metal oxide ceramic layer of one deck by oxidizing annealing, greatly improve the corrosion resistance nature of non-crystaline amorphous metal in the aqueous solution.
The technical solution adopted for the present invention to solve the technical problems is as follows:
After the block amorphous alloy surface finish, use alcohol wash, put into retort furnace then and be warming up to 286～336 ℃, be incubated 5～10 hours then with 10 ℃/minute speed, block amorphous alloy is taken out, generate the surface oxide layer of strong corrosion resistant on the block amorphous alloy surface.
The block amorphous alloy composition that is adopted is Zr
64.13Cu
15.75Ni
10.12Al
10Or Zr
46Cu
37.6Ag
8.4Al
8
Used Zr
64.13Cu
15.75Ni
10.12Al
10The diameter of block amorphous alloy is the 1-5 millimeter; Used Zr
46Cu
37.6Ag
8.4Al
8The diameter of block amorphous alloy is the 1-20 millimeter.
The beneficial effect that the present invention has is:
1) improved the erosion resistance of block amorphous alloy in the aqueous solution especially chloride ion-containing aqueous solution greatly;
2) do not influence the glass forming ability of former alloy;
3) zone of oxidation and matrix bond closely do not have tangible separation surface;
4) annealing temperature is lower, helps saving cost;
5) adopt air atmosphere annealing, method is simple, and mechanical deformation does not generally take place processed parts, thereby very be suitable for the last processing of part and product.
Description of drawings
Fig. 1 is Zr
64.13Cu
15.75Ni
10.12Al
10Before the non-crystaline amorphous metal annealing, annealing back and the worn XRD figure of falling behind the surface oxide layer;
Fig. 2 is the resulting Zr that reaches before anneal after air atmosphere annealing
64.13Cu
15.75Ni
10.12Al
10Sample is at 0.5N NaCl and 1N H
2SO
4Corrosion polarization curve in the solution.
Fig. 3 is Zr
46Cu
37.6Ag
8.4Al
8Before the non-crystaline amorphous metal annealing, annealing back and the worn XRD figure of falling behind the surface oxide layer;
Fig. 4 is the resulting Zr that reaches before anneal after air atmosphere annealing
46Cu
37.6Ag
8.4Al
8Sample is at 0.5N NaCl and 1N H
2SO
4Corrosion polarization curve in the+0.01N NaCl solution.
Embodiment
Embodiment 1:
This embodiment adopts annealed method under the air atmosphere, makes Zr
64.13Cu
15.75Ni
10.12Al
10Non-crystaline amorphous metal surface generate one deck densification with ZrO
2And Al
2O
3Oxide ceramic layer for main component.
Step 1: with purity is 99.8% Zr, 99.9% Cu, and 99.8% Ni and 99.99% Al (being mass percent) press Zr
64.13Cu
15.75Ni
10.12Al
10Proportioning is arc melting in the argon atmospher of titanium absorption, obtains the alloy spindle that mixes.
Step 2: melting on the water cooled copper mould of spindle in the smelting furnace of argon shield of step 1 acquisition.Utilize pressure difference will obtain alloy liquid then and inject the water cooled copper mould of internal diameter, thereby make the block amorphous alloy that diameter is 3mm for 3mm.
Step 3: with of the diamond sand paper polishing of block amorphous alloy sample, be polished to minute surface then, use alcohol wash, in air, expose more than 24 hours with continuous order number.
Step 4: step 3 gained sample is put into retort furnace, be warming up to 320 ℃, be incubated after 5 to 10 hours and take out, at room temperature naturally cooling with 10 ℃/minute speed.
Step 5: characterize the structure that this block amorphous alloy is handled front and back with the x ray diffraction method, Fig. 1 is its x x ray diffration pattern x.
Step 6: characterize Zr with electrochemical method
64.13Cu
15.75Ni
10.12Al
10Block amorphous alloy anneal front and back are at NaCl and H
2SO
4Corrosion behavior in the solution, Fig. 2 (a) be preceding and annealing back Zr for annealing
64.13Cu
15.75Ni
10.12Al
10The electrokinetic potential polarization curve of alloy sample in 0.5N NaCl solution; Fig. 2 (b) reaches the Zr after the annealing for annealing is preceding
64.13Cu
15.75Ni
10.12Al
10Alloy sample is at 1N H
2SO
4Electrokinetic potential polarization curve in the solution.
Embodiment 2:
This embodiment adopts annealed method under the air atmosphere, makes Zr
46Cu
37.6Ag
8.4Al
8Non-crystaline amorphous metal surface generate one deck densification with ZrO
2Oxide ceramic layer for main component.
Step 1: with purity is 99.8% Zr, 99.9% Cu, and 99.9% Ag and 99.99% Al (being mass percent) press Zr
46Cu
37.6Ag
8.4Al
8Proportioning is arc melting in the argon atmospher of titanium absorption, obtains the alloy spindle that mixes.
Step 2: melting on the water cooled copper mould of spindle in the smelting furnace of argon shield of step 1 acquisition.Utilize pressure difference will obtain alloy liquid then and inject the water cooled copper mould of internal diameter, thereby make the block amorphous alloy that diameter is 5mm for 5mm.
Step 3: with of the diamond sand paper polishing of block amorphous alloy sample, be polished to minute surface then, use alcohol wash, in air, expose more than 24 hours with continuous order number.
Step 4: step 3 gained sample is put into retort furnace, be warming up to 286 or 336 ℃, be incubated after 5 hours and take out, at room temperature naturally cooling with 10 ℃/minute speed.
Step 5: characterize the structure that this block amorphous alloy is handled front and back with the x ray diffraction method, Fig. 3 is its x x ray diffration pattern x.
Step 6: characterize Zr with electrochemical method
46Cu
37.6Ag
8.4Al
8Block amorphous alloy anneal front and back are at NaCl and H
2SO
4Corrosion behavior in the+NaCl solution, Fig. 4 (a) be preceding and annealing back Zr for annealing
46Cu
37.6Ag
8.4Al
8The electrokinetic potential polarization curve of alloy sample in 0.5N NaCl solution; Fig. 4 (b) reaches the Zr after the annealing for annealing is preceding
46Cu
37.6Ag
8.4Al
8Alloy sample is at 1N H
2SO
4Electrokinetic potential polarization curve in the+0.01N NaCl solution.
Claims (2)
1. an air atmosphere oxidizing annealing improves the method for block amorphous alloy corrosive nature, it is characterized in that: after the block amorphous alloy surface finish, use alcohol wash, put into retort furnace then and be warming up to 286～336 ℃ with 10 ℃/minute speed, be incubated 5～10 hours then, block amorphous alloy is taken out, generate the surface oxide layer of strong corrosion resistant on the block amorphous alloy surface;
The block amorphous alloy composition that is adopted is Zr
64.13Cu
15.75Ni
10.12Al
10Or Zr
46Cu
37.6Ag
8.4Al
8
Adopt annealed method under the air atmosphere, make Zr
64.13Cu
15.75Ni
10.12Al
10Non-crystaline amorphous metal surface generate one deck densification with ZrO
2And Al
2O
3Oxide ceramic layer for main component;
Adopt annealed method under the air atmosphere, make Zr
46Cu
37.6Ag
8.4Al
8Non-crystaline amorphous metal surface generate one deck densification with ZrO
2Oxide ceramic layer for main component.
2. a kind of air atmosphere oxidizing annealing according to claim 1 improves the method for block amorphous alloy corrosive nature, it is characterized in that: used Zr
64.13Cu
15.75Ni
10.12Al
10The diameter of block amorphous alloy is the 1-5 millimeter; Used Zr
46Cu
37.6Ag
8.4Al
8The diameter of block amorphous alloy is the 1-20 millimeter.
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|---|---|---|---|
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| CN101545029B true CN101545029B (en) | 2011-01-05 |
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| CN108387423A (en) * | 2018-02-23 | 2018-08-10 | 深圳顺络电子股份有限公司 | A method of improving ltcc substrate salt fog reliability |
| CN111705204A (en) * | 2020-07-30 | 2020-09-25 | 常熟市市南模具有限责任公司 | Oxidation heat treatment process for glass mold |
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