CN107675106A - A kind of ni-based amorphous alloy of surface pigmentable decoration - Google Patents
A kind of ni-based amorphous alloy of surface pigmentable decoration Download PDFInfo
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- CN107675106A CN107675106A CN201710847730.9A CN201710847730A CN107675106A CN 107675106 A CN107675106 A CN 107675106A CN 201710847730 A CN201710847730 A CN 201710847730A CN 107675106 A CN107675106 A CN 107675106A
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- amorphous alloy
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- pigmentable
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Abstract
The invention discloses a kind of ni-based amorphous alloy of surface pigmentable decoration.The amorphous alloy material composition expression formula is：NiaNbbZrcTidSne, wherein a, b, c, d, e is atomic percent, and a+b+c+d+e=100；58≤a≤62,12≤b≤16,13≤c≤17,8≤d≤12,1≤e≤5, by the non-crystaline amorphous metal less than its glass transformation temperature TgDifferent temperatures carry out waiting Warm annealing, be incubated different time, form the gorgeous oxide-film of one layer of color on its surface, and possess good wear and corrosion behavior.The ni-based amorphous alloy decoration technology of the present invention is simple, and production cost is low；The ni-based amorphous alloy shows golden yellow, royalblue, blue-green, purple respectively in different soaking times, beautiful in colour and have wear-corrosion resistance concurrently, has good application prospect.
Description
Technical field
The present invention relates to a kind of ni-based amorphous alloy of surface pigmentable decoration, belongs to the decorative appearance of non-crystaline amorphous metal product
Technical field.
Background technology
Non-crystaline amorphous metal is as the new material for having glass and metallic character concurrently, in machinery, electronics, medicine equipment, national defence, boat
The fields such as empty space flight have broad application prospects.Ni-based amorphous alloy is the amorphous alloy material for being applied to industry earliest.One
People have been enjoyed to pay close attention to due to its high intensity, elastic and excellent magnetic and high corrosion resistance since straight.
At present, non-crystaline amorphous metal is coloured and the research as ornament materials is less.Song says sea et al. and aluminium and aluminium is closed
Gold carries out electrolytic coloring and obtains the aluminium section bar of the colors such as titanium color, champagne.Li Qing have studied the coloring process of stainless steel, pass through
High heat colouring, electrolytic coloring, dipping coloring the methods of obtain colored stainless steel.Because technique is simple, cost is relatively low for heat-tinting
And attention.Therefore, heat-tinting is carried out to ni-based amorphous alloy, can have both retained the excellent performance of non-crystaline amorphous metal, and might be used also
To meet the needs of decorative appearance with relatively low cost.But also there is oxide-film color not in the heat-tinting of part non-crystaline amorphous metal
Uniformly, the shortcomings that color is whard to control.At this stage, during heat-tinting is carried out to Ni-Nb-Zr-Ti, oxygen made from discovery
Change film color is uneven, and color is difficult to control.
The content of the invention
It is an object of the invention to provide a kind of ni-based amorphous alloy of surface pigmentable decoration, described ni-based amorphous alloy
Rendering color is accurately controlled, beautiful in colour, wearability and corrosion resistance are good；Simultaneously trailing also have technique it is simple,
The characteristics of cost is low.
Realizing the technical scheme of the object of the invention is：A kind of ni-based amorphous alloy of surface pigmentable decoration, it is described Ni-based
The atomic expression of non-crystaline amorphous metal is：NiaNbbZrcTidSne, wherein a, b, c, d, e is atomic percent, and a+b+c+d+e=
100；58≤a≤62,12≤b≤16,13≤c≤17,8≤d≤12,1≤e≤5, then heat-tinting is carried out to the non-crystaline amorphous metal
The ni-based amorphous alloy of described surface pigmentable decoration is made.
Further, 2≤e≤4.
The preparation method of the ni-based amorphous alloy of above-mentioned surface pigmentable decoration, is prepared using amorphous alloy, then to this
Non-crystaline amorphous metal carries out heat-tinting, comprises the following steps that：
Step 1, the melting of foundry alloy：By pure metal Ni, Nb, Zr, Ti, Sn raw material according to Ni-Nb-Zr-Ti-Sn=a:
b:c:d:E carries out dispensing, is placed in vacuum arc melting furnace, high-purity Ar gas is passed through after vacuumizing, using electric arc melting and electromagnetism
Stir melt back foundry alloy at least more than 5 times, ensure the uniformity of foundry alloy；
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, the foundry alloy obtained by step 1 is cast
After ingot fusing on injection to the cooling copper roller of high speed rotation, completely amorphous ni-based amorphous alloy strip is obtained；
Step 3, heat-tinting：By the amorphous alloy ribbon described in step 2 in 300~500 DEG C of inferior Warm annealing 5min~
2h, different oxidizing temperatures and oxidization time are controlled, the different ni-based amorphous alloy of oxide-film color can be obtained.
Further, in step 1, vacuum arc melting furnace vacuum is 2*10-3Pa~5*10-3Pa。
Further, in step 2, the roller speed of cooling copper roller is 15m/s~20m/s.
Compared with prior art, ni-based amorphous alloy of the invention has the following advantages that：
(1) present invention adds Sn elements, and atomic ratio shared by controlling Sn elements in Ni-Nb-Zr-Ti, overcomes original
The problem of non-crystaline amorphous metal oxide-film irregular colour is even, and rendering color is difficult to control, so as to obtain the non-crystaline amorphous metal of surface aesthetic.
(2) ni-based amorphous alloy of the invention can be by controlling oxidizing temperature and oxidization time accurately to control rendering color.
(3) ni-based amorphous alloy oxide-film of the invention is beautiful in colour, rich in color.Show golden yellow, royalblue, indigo plant
Green and purple, have the advantages of surface aesthetic.
(4) ni-based amorphous alloy coloring film of the invention has good wearability, is able to take load 500g rubber
The friction of more than 200 times.
(5) ni-based amorphous alloy coloring film of the invention has good corrosion resistance, rotten in 6mol/L HCL solution
20min is lost, specimen surface does not fade and without weightlessness.
(6) trailing of the invention has that technique is simple, lower-cost advantage, has good application prospect.
Embodiment
The present invention is further illustrated below by embodiment.
Comparative example 1：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti raw material according to
Ni60Nb15Zr15Ti10Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum arc melting after alcohol ultrasonic cleansing
In stove, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is female using electric arc melting and electromagnetic agitation melt back
Alloy at least more than 5 times, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 350 DEG C of the medium Warm annealing of resistance furnace
10min、20min、40min.The oxide-film irregular colour of acquisition is even, and rendering color is difficult to control.
Comparative example 2：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti raw material according to
Ni60Nb15Zr15Ti10Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum arc melting after alcohol ultrasonic cleansing
In stove, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is female using electric arc melting and electromagnetic agitation melt back
Alloy at least more than 5 times, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 400 DEG C of the medium Warm annealing of resistance furnace
10min、20min、40min.The oxide-film irregular colour of acquisition is even, and rendering color is difficult to control.
Comparative example 3：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti raw material according to
Ni60Nb15Zr15Ti10Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum arc melting after alcohol ultrasonic cleansing
In stove, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is female using electric arc melting and electromagnetic agitation melt back
Alloy at least more than 5 times, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 450 DEG C of the medium Warm annealing of resistance furnace
10min、20min、40min.The oxide-film irregular colour of acquisition is even, and rendering color is difficult to control.
Comparative example 4：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti, Sn raw material according to
Ni56.4Nb14.1Zr14.1Ti9.4Sn6Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum after alcohol ultrasonic cleansing
In arc-melting furnace, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is anti-using electric arc melting and electromagnetic agitation
Master alloy melting at least more than 5 times again, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is that the ni-based amorphous alloy of acquisition is partially-crystallized on 17m/s cooling copper roller after ingot fusing.
Embodiment 1：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti, Sn raw material according to
Ni58.8Nb14.7Zr14.7Ti9.8Sn2Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum after alcohol ultrasonic cleansing
In arc-melting furnace, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is anti-using electric arc melting and electromagnetic agitation
Master alloy melting at least more than 5 times again, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 350 DEG C of the medium Warm annealing of resistance furnace
20min、40min、80min.Respectively obtain the ni-based amorphous alloy of golden yellow, purple, royalblue.
The ni-based amorphous alloy of the present invention not only has the advantages of attractive in appearance, also with good wearability, is able to take to bear
The friction of lotus 500g rubber more than 200 times.Meanwhile there is good corrosion resistance, corrode in 6mol/L HCL solution
20min, specimen surface do not fade and without weightlessnesses.
Embodiment 2：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti, Sn raw material according to
Ni58.8Nb14.7Zr14.7Ti9.8Sn2Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum after alcohol ultrasonic cleansing
In arc-melting furnace, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is anti-using electric arc melting and electromagnetic agitation
Master alloy melting at least more than 5 times again, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 400 DEG C of the medium Warm annealing of resistance furnace
10min、20min、40min、2h.Respectively obtain golden yellow, royalblue, blue-green, the ni-based amorphous alloy of purple.
The ni-based amorphous alloy of the present invention not only has the advantages of attractive in appearance, also with good wearability, is able to take to bear
The friction of lotus 500g rubber more than 200 times.Meanwhile there is good corrosion resistance, corrode in 6mol/L HCL solution
20min, specimen surface do not fade and without weightlessnesses.
Embodiment 3：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti, Sn raw material according to
Ni58.8Nb14.7Zr14.7Ti9.8Sn2Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum after alcohol ultrasonic cleansing
In arc-melting furnace, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is anti-using electric arc melting and electromagnetic agitation
Master alloy melting at least more than 5 times again, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
After ingot fusing on injection to cooling copper roller of the roller speed not less than 20m/s, completely amorphous ni-based amorphous alloy strip is obtained.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 450 DEG C of the medium Warm annealing of resistance furnace
10min、20min、40min、1h.Respectively obtain golden yellow, royalblue, blue-green, the ni-based amorphous alloy of purple.
The ni-based amorphous alloy of the present invention not only has the advantages of attractive in appearance, also with good wearability, is able to take to bear
The friction of lotus 500g rubber more than 200 times.Meanwhile there is good corrosion resistance, corrode in 6mol/L HCL solution
20min, specimen surface do not fade and without weightlessnesses.
Embodiment 4：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti, Sn raw material according to
Ni57.6Nb14.4Zr14.4Ti9.6Sn4Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum after alcohol ultrasonic cleansing
In arc-melting furnace, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is anti-using electric arc melting and electromagnetic agitation
Master alloy melting at least more than 5 times again, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 350 DEG C of the medium Warm annealing of resistance furnace
20min、40min、80min.Respectively obtain the ni-based amorphous alloy of golden yellow, purple, royalblue..
The ni-based amorphous alloy of the present invention not only has the advantages of attractive in appearance, also with good wearability, is able to take to bear
The friction of lotus 500g rubber more than 200 times.Meanwhile there is good corrosion resistance, corrode in 6mol/L HCL solution
20min, specimen surface do not fade and without weightlessnesses.
Embodiment 5：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti, Sn raw material according to
Ni57.6Nb14.4Zr14.4Ti9.6Sn4Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum after alcohol ultrasonic cleansing
In arc-melting furnace, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is anti-using electric arc melting and electromagnetic agitation
Master alloy melting at least more than 5 times again, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 400 DEG C of the medium Warm annealing of resistance furnace
10min、20min、40min、2h.Respectively obtain golden yellow, royalblue, blue-green, the ni-based amorphous alloy of purple.
The ni-based amorphous alloy of the present invention not only has the advantages of attractive in appearance, also with good wearability, is able to take to bear
The friction of lotus 500g rubber more than 200 times.Meanwhile there is good corrosion resistance, corrode in 6mol/L HCL solution
20min, specimen surface do not fade and without weightlessnesses.
Embodiment 6：
Step 1, the preparation of foundry alloy：By purity be 99.99% Ni, Nb, Zr, Ti, Sn raw material according to
Ni57.6Nb14.4Zr14.4Ti9.6Sn4Atomic ratio, be converted into weight than carry out dispensing.With being placed in vacuum after alcohol ultrasonic cleansing
In arc-melting furnace, 2*10 is evacuated to-3Pa~5*10-3High-purity Ar gas is passed through after Pa, it is anti-using electric arc melting and electromagnetic agitation
Master alloy melting at least more than 5 times again, ensure the uniformity of foundry alloy.
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, foundry alloy made from step 1 is cast
Injection to roller speed is on 17m/s cooling copper roller after ingot fusing, obtains completely amorphous ni-based amorphous alloy strip.
Step 3, heat-tinting：Amorphous alloy ribbon described in step 2 is put into 450 DEG C of the medium Warm annealing of resistance furnace
10min、20min、40min、1h.Respectively obtain golden yellow, royalblue, blue-green, the ni-based amorphous alloy of purple.
The ni-based amorphous alloy of the present invention not only has the advantages of attractive in appearance, also with good wearability, is able to take to bear
The friction of lotus 500g rubber more than 200 times.Meanwhile there is good corrosion resistance, corrode in 6mol/L HCL solution
20min, specimen surface do not fade and without weightlessnesses.
Found from above comparative example and embodiment：
(1) ni-based amorphous alloy of Sn elements is not added with, controls different oxidizing temperatures and oxidization time can not obtain
Color is uniform, the oxide-film of surface aesthetic.
(2) ni-based amorphous alloy of Sn elements is added, and when Sn constituent contents be 2~4at%, can pass through and control oxidation warm
Degree and oxidization time accurately control rendering color, and simultaneous oxidation film also has good wearability and corrosion resistance.
(3) when Sn constituent contents are more than 6at%, completely amorphous ni-based amorphous alloy can not be prepared.
The ni-based amorphous alloy of the embodiment of the present invention of table 1 is in different temperatures and the heat-tinting result of different annealing times.
Claims (5)
1. the ni-based amorphous alloy of surface pigmentable decoration, it is characterised in that the atomic expression of the ni-based amorphous alloy is：
NiaNbbZrcTidSne, wherein a, b, c, d, e is atomic percent, and a+b+c+d+e=100；58≤a≤62,12≤b≤16,
13≤c≤17,8≤d≤12,1≤e≤5, then the surface pigmentable decoration that heat-tinting is made described is carried out to the non-crystaline amorphous metal
Ni-based amorphous alloy.
2. the ni-based amorphous alloy of pigmentable decoration in surface as claimed in claim 1, it is characterised in that 2≤e≤4.
3. the preparation method of the ni-based amorphous alloy of pigmentable decoration in surface as claimed in claim 1 or 2, is quenched using the rotation of single roller
Prepared by method, then carry out heat-tinting to the non-crystaline amorphous metal, comprises the following steps that：
Step 1, the melting of foundry alloy：By pure metal Ni, Nb, Zr, Ti, Sn raw material according to Ni-Nb-Zr-Ti-Sn=a:b:c:
d:E carries out dispensing, is placed in vacuum arc melting furnace, high-purity Ar gas is passed through after vacuumizing, using electric arc melting and electromagnetic agitation
Melt back foundry alloy at least more than 5 times, ensure the uniformity of foundry alloy；
Step 2, melt spinning method：Using amorphous alloy, under Ar gas atmosphere protections, the mother alloy ingot obtained by step 1 is melted
After change on injection to the cooling copper roller of high speed rotation, completely amorphous ni-based amorphous alloy strip is obtained；
Step 3, heat-tinting：By the amorphous alloy ribbon described in step 2 in 300 ~ 500 DEG C of inferior Warm annealing 5min ~ 2h, control
Different oxidizing temperatures and oxidization time, the different ni-based amorphous alloy of oxide-film color can be obtained.
4. preparation method as claimed in claim 3, it is characterised in that in step 1, vacuum arc melting furnace vacuum is 2*10-3Pa~5*10-3Pa。
5. preparation method as claimed in claim 3, it is characterised in that in step 2, the roller speed of cooling copper roller is 15m/s ~ 20m/
s。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109822067A (en) * | 2019-04-08 | 2019-05-31 | 东北大学 | A kind of method that Ni-based non-crystalline thin-band is continuously prepared |
| CN109913673A (en) * | 2019-03-13 | 2019-06-21 | 湘潭大学 | The high-entropy alloy and preparation method thereof of resistance to aluminum melting corrosion |
| CN111074229A (en) * | 2018-10-19 | 2020-04-28 | 清华大学 | Method for regulating and controlling color of hard coating, hard coating and preparation method thereof |
| CN111321358A (en) * | 2020-04-17 | 2020-06-23 | 中国科学院物理研究所 | Amorphous alloy with spontaneous color change on surface, and preparation method and application thereof |
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| CN104745974A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Amorphous alloy product and preparation method thereof |
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| CN1354274A (en) * | 2000-11-22 | 2002-06-19 | 中国科学院金属研究所 | Nickel base amorphous alloy |
| CN106834803A (en) * | 2010-06-14 | 2017-06-13 | 科卢斯博知识产权有限公司 | Stanniferous non-crystaline amorphous metal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111074229A (en) * | 2018-10-19 | 2020-04-28 | 清华大学 | Method for regulating and controlling color of hard coating, hard coating and preparation method thereof |
| CN111074229B (en) * | 2018-10-19 | 2021-05-14 | 清华大学 | Method for regulating and controlling color of hard coating, hard coating and preparation method thereof |
| CN109913673A (en) * | 2019-03-13 | 2019-06-21 | 湘潭大学 | The high-entropy alloy and preparation method thereof of resistance to aluminum melting corrosion |
| CN109822067A (en) * | 2019-04-08 | 2019-05-31 | 东北大学 | A kind of method that Ni-based non-crystalline thin-band is continuously prepared |
| CN111321358A (en) * | 2020-04-17 | 2020-06-23 | 中国科学院物理研究所 | Amorphous alloy with spontaneous color change on surface, and preparation method and application thereof |
| CN111321358B (en) * | 2020-04-17 | 2022-02-18 | 中国科学院物理研究所 | Amorphous alloy with spontaneous color change on surface, and preparation method and application thereof |
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