CN102899710A - Silver electrochemical polishing solution, preparation method and use method thereof - Google Patents
Silver electrochemical polishing solution, preparation method and use method thereof Download PDFInfo
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- CN102899710A CN102899710A CN2012104112350A CN201210411235A CN102899710A CN 102899710 A CN102899710 A CN 102899710A CN 2012104112350 A CN2012104112350 A CN 2012104112350A CN 201210411235 A CN201210411235 A CN 201210411235A CN 102899710 A CN102899710 A CN 102899710A
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Abstract
The invention relates to a silver electrochemical polishing solution, a preparation method and a use method thereof. In the present silver electrochemical polishing technology, the surface smoothness of a silver sample is not high, a thin area of a silver transmission sample observed under a transmission electron microscope is small, the obtained definition of microstructure is low, the contrast is inferior and a corrosive pitting phenomenon even exists. The preparation method provided by the invention comprises the following steps: adding concentrated sulfuric acid into glacial acetic acid, and then adding perchloric acid and oxalic acid, keeping the temperature at 0-15 DEG C, thereby obtaining a solution A; adding thiourea into carbinol, thereby obtaining a solution B, and then keeping temperature at 0 DEG C+/-5 DEG C; and uniformly mixing the solution A with the solution B, and adjusting pH value to 0-2 by using the concentrated sulfuric acid, thereby obtaining a colorless transparent electrochemical polishing solution. A big thin area of the transmission sample treated by using the silver electrochemical polishing solution can be observed under the transmission electron microscope and the calibrating rate of an EBSD (Electron Back-Scattered Diffraction) sample under the transmission electron microscope is as high as above 85%.
Description
Technical field
The present invention relates to the electropolishing technical field, be specifically related to a kind of electrolytic polishing liquid and preparation method thereof and using method of silver.
Background technology
Along with electron microscope technique and the development that is orientated to the collection technology, more and more higher to silver-colored specimen surface specification of quality.A large amount of reference show, the electrolytic polishing process of traditional silver remains in deficiency, is mainly reflected in following four aspects: the first, contain the prussiate of severe toxicity in the electrolytic solution, and be unfavorable for people's healthy and environmental protection; The second, silver-colored specimen surface is the cycle variation phenomenon that black epithelium moment becomes white in the electropolishing process, is unfavorable for controlling the polishing of silver-colored specimen surface; The 3rd, silver-colored specimen surface planeness is not high enough behind the electropolishing, even trickle cut can occur, is difficult to obtain the silver-colored sample of high-quality surface; The 4th, electrolytic solution can not be reused, so that production cost increases substantially.Can't satisfy the electropolishing process of special dimension silver.
Summary of the invention
The electrolytic polishing liquid and preparation method thereof and the using method that the purpose of this invention is to provide a kind of silver, the thin district microtexture sharpness little, that obtain that high, the not silver-colored transmission sample of silver-colored specimen surface smooth finish that prior art exists observes under transmission electron microscope is not high, contrast is bad even also have point corrosion to overcome; The demarcation rate of EBSD sample under scanning electron microscope of silver is not high yet simultaneously, can't satisfy the problem to the requirement of microtexture and textile analysis.
The problem that exists for overcoming prior art, technical scheme of the present invention is:
A kind of preparation method of electrolytic polishing liquid of silver, its special character is:
Realized by following steps:
Step 1: in the glacial acetic acid under the 95-98% vitriol oil adding 140ml zero degrees celsius of 30-50ml, then add the perchloric acid of 10-15ml and the oxalic acid of 6-10g, and keep its temperature at 0-15 ℃, obtain solution A;
Step 2: the thiocarbamide of 50-70g is added in the methyl alcohol of 300ml, obtain solution B, temperature remains 0 ℃ ± 5 ℃;
Step 3: solution A is evenly mixed at 0-10 ℃ with solution B, by the 95-98% vitriol oil its pH value is adjusted to 0-2, obtain water white electrolytic polishing liquid.
The electrolytic polishing liquid of the silver that makes with aforesaid method.
The using method of the electrolytic polishing liquid of above-mentioned silver, its special character is:
Realized by following steps:
Adopt this electrolytic polishing liquid 80-100ml, voltage is 5-30V, room temperature, anode miles of relative movement negative electrode stainless steel thin slice 1-2cm, polishing time 2-5min.
The using method of the electrolytic polishing liquid of above-mentioned silver, its special character is:
The purging method of its sample is: put into rapidly methyl alcohol and dip in and wash, with the deionized water rinsing that flows, put into dehydrated alcohol and dip in and wash and dry up rapidly.
The using method of the electrolytic polishing liquid of above-mentioned silver, its special character is:
Realized by following steps:
Adopt this electrolytic polishing liquid 150ml-200ml, voltage is 10-25v, and temperature is 0-10 ℃, polishing time 150s.
The using method of the electrolytic polishing liquid of above-mentioned silver, its special character is:
The purging method of its sample is: use first the washed with methanol sample, then dip in ethanol and wash and dry up.
The present invention has the following advantages:
1, the present invention can prepare surface no-pollution, highly polished silver-colored part fast and effectively, can effectively guarantee the Stability and veracity of the electrolytic polishing process of silver.
2, the present invention helps the purification of silver in the industrial acid thiocarbamide.
3, the silver-colored part that polishes not only can satisfy the Surface Modification Effect, and can be used in the Analysis on Microstructure of silver-colored sample, for example the transmission sample of silver and the preparation of EBSD sample.
4, the present invention can also be used for special dimension, such as transmission electron microscope sample and Electron Back-Scattered Diffraction (Electron Backscatter Diffraction is called for short EBSD) sample preparation.Transmission coupons by the method preparation has larger thin district lower observation of TEM (Transmission Electron Microscopy), Effective Raise silver-colored microtexture characterize ability.Simultaneously, for the EBSD sample of preparation, its demarcation rate can reach more than 85%.
Description of drawings
Fig. 1 is the transmission electron microscope sample photo of the silver of employing this patent acquisition;
The silver-colored transmission sample photo of Fig. 2 for adopting early stage sour sulfur urea solution to obtain;
Fig. 3 is the transmission microstructure picture of the silver-colored sample of employing this patent acquisition;
Fig. 4 is the transmission microstructure picture of the silver-colored sample of the early stage sour sulfur urea solution acquisition of employing;
Fig. 5 is the EBSD sample photo of the silver of employing this patent acquisition;
The silver-colored EBSD sample photo of Fig. 6 for adopting early stage sour sulfur urea solution to obtain;
Fig. 7 organizes photo for the EBSD that adopts this patent to obtain silver-colored sample;
Fig. 8 organizes photo for the silver-colored sample EBSD that adopts early stage sour sulfur urea solution to obtain.
Embodiment
The present invention will be described in detail below in conjunction with embodiment.
Below be preparation method's the embodiment of the electrolytic polishing liquid of a kind of silver involved in the present invention:
Embodiment 1:
Step 1: in the glacial acetic acid under 95% vitriol oil adding 140ml zero degrees celsius of 30ml, then add the perchloric acid of 10ml and the oxalic acid of 6g, and keep its temperature at 0 ℃, obtain solution A;
Step 2: the thiocarbamide of 50g is added in the methyl alcohol of 300ml, obtain solution B, temperature remains-5 ℃;
Step 3: solution A is evenly mixed at 0 ℃ with solution B, by 95% vitriol oil its pH value is adjusted to 0, obtain water white electrolytic polishing liquid.
Embodiment 2:
Step 1: in the glacial acetic acid under 98% vitriol oil adding 140ml zero degrees celsius of 40ml, then add the perchloric acid of 12ml and the oxalic acid of 8g, and keep its temperature at 8 ℃, obtain solution A;
Step 2: the thiocarbamide of 60g is added in the methyl alcohol of 300ml, obtain solution B, temperature remains 0 ℃;
Step 3: solution A is evenly mixed at 5 ℃ with solution B, by 98% vitriol oil its pH value is adjusted to 1, obtain water white electrolytic polishing liquid.
Embodiment 3:
Step 1: in the glacial acetic acid under 95% vitriol oil adding 140ml zero degrees celsius of 50ml, then add the perchloric acid of 15ml and the oxalic acid of 10g, and keep its temperature at 15 ℃, obtain solution A;
Step 2: the thiocarbamide of 70g is added in the methyl alcohol of 300ml, obtain solution B, temperature remains 5 ℃;
Step 3: solution A is evenly mixed at 10 ℃ with solution B, by 98% vitriol oil its pH value is adjusted to 2, obtain water white electrolytic polishing liquid.
The using method of the electrolytic polishing liquid of silver involved in the present invention has two kinds:
(1) conventional electrolysis finishing method:
Adopt this electrolytic polishing liquid 80-100ml, voltage is 5-30V, room temperature, anode miles of relative movement negative electrode stainless steel thin slice 1-2cm, polishing time 2-5min; The purging method of its sample is: put into rapidly methyl alcohol and dip in and wash, with the deionized water rinsing that flows, put into dehydrated alcohol and dip in and wash and dry up rapidly.
Embodiment 1:
Adopt this electrolytic polishing liquid 80ml, voltage is 5V, room temperature, anode miles of relative movement negative electrode stainless steel thin slice 1cm, polishing time 2min; The purging method of its sample is: put into rapidly methyl alcohol and dip in and wash, with the deionized water rinsing that flows, put into dehydrated alcohol and dip in and wash and dry up rapidly.
Embodiment 2:
Adopt this electrolytic polishing liquid 90ml, voltage is 15V, room temperature, anode miles of relative movement negative electrode stainless steel thin slice 1cm, polishing time 3min; The purging method of its sample is: put into rapidly methyl alcohol and dip in and wash, with the deionized water rinsing that flows, put into dehydrated alcohol and dip in and wash and dry up rapidly.
Embodiment 3:
Adopt this electrolytic polishing liquid 100ml, voltage is 30V, room temperature, anode miles of relative movement negative electrode stainless steel thin slice 2cm, polishing time 5min; The purging method of its sample is: put into rapidly methyl alcohol and dip in and wash, with the deionized water rinsing that flows, put into dehydrated alcohol and dip in and wash and dry up rapidly.
(2) twin-jet electropolishing finishing method:
Adopt this electrolytic polishing liquid 150ml-200ml, voltage is 10-25v, and temperature is 0-10 ℃, polishing time 150s; The purging method of its sample is: use first the washed with methanol sample, then dip in ethanol and wash and dry up.
Embodiment 1:
Adopt this electrolytic polishing liquid 150ml, voltage is 10v, and temperature is 0 ℃, polishing time 150s; The purging method of its sample is: use first the washed with methanol sample, then dip in ethanol and wash and dry up.
Embodiment 2:
Adopt this electrolytic polishing liquid 175ml, voltage is 18v, and temperature is 5 ℃, polishing time 150s; The purging method of its sample is: use first the washed with methanol sample, then dip in ethanol and wash and dry up.
Embodiment 3:
Adopt this electrolytic polishing liquid 200ml, voltage is 25v, and temperature is 10 ℃, polishing time 150s; The purging method of its sample is: use first the washed with methanol sample, then dip in ethanol and wash and dry up.
The results of comparison of accompanying drawing is described as follows:
(1) the transmission sample of silver preparation
By once complete twin-jet electropolishing polishing experiments, can obtain the transmission sample of silver as shown in Figure 1, its surface no-pollution, highly polished can be observed larger thin district under transmission electron microscope.And can obtain 5000 times the microtexture photo as shown in Figure 3.By can obviously finding out twin that contrast is higher and the feature organization of high density dislocation wall among the figure, Effective Raise the ability that characterizes of silver-colored microtexture;
When the electrolytic polishing liquid of preparation silver, should follow two principles: temperature must be strict controlled in 0-10 ℃; PH must be strict controlled in 0-2.
(2) the EBSD sample of silver preparation
By once complete conventional electrolysis polishing experiments, can obtain the EBSD sample of silver as shown in Figure 2, its surface no-pollution, highly polished.And under scanning electron microscope, can obtain the demarcation rate and organize photo up to 85% EBSD, as shown in Figure 4.By equi-axed crystal and the twin feature organization that can find out obviously among the figure that contrast is higher.Effective Raise silver-colored deformed microstructure and the sign ability of texture.
Voltage must remain on 5-30V in the electropolishing process, and overtension can cause electrolyte temperature sharply to rise, and may set off an explosion.
It is cited that content of the present invention is not limited to embodiment, and the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention is claim of the present invention and contains.
Claims (6)
1. the preparation method of the electrolytic polishing liquid of a silver is characterized in that:
Realized by following steps:
Step 1: in the glacial acetic acid under the 95-98% vitriol oil adding 140ml zero degrees celsius of 30-50ml, then add the perchloric acid of 10-15ml and the oxalic acid of 6-10g, and keep its temperature at 0-15 ℃, obtain solution A;
Step 2: the thiocarbamide of 50-70g is added in the methyl alcohol of 300ml, obtain solution B, temperature remains 0 ℃ ± 5 ℃;
Step 3: solution A is evenly mixed at 0-10 ℃ with solution B, by the 95-98% vitriol oil its pH value is adjusted to 0-2, obtain water white electrolytic polishing liquid.
2. the electrolytic polishing liquid of the silver that makes of the method for claim 1.
3. the using method of the electrolytic polishing liquid of a silver as claimed in claim 2 is characterized in that:
Realized by following steps:
Adopt this electrolytic polishing liquid 80-100ml, voltage is 5-30V, room temperature, anode miles of relative movement negative electrode stainless steel thin slice 1-2cm, polishing time 2-5min.
4. the using method of the electrolytic polishing liquid of silver according to claim 3 is characterized in that:
The purging method of its sample is: put into rapidly methyl alcohol and dip in and wash, with the deionized water rinsing that flows, put into dehydrated alcohol and dip in and wash and dry up rapidly.
5. the using method of the electrolytic polishing liquid of a silver as claimed in claim 2 is characterized in that:
Realized by following steps:
Adopt this electrolytic polishing liquid 150ml-200ml, voltage is 10-25v, and temperature is 0-10 ℃, polishing time 150s.
6. the using method of the electrolytic polishing liquid of silver according to claim 5 is characterized in that:
The purging method of its sample is: use first the washed with methanol sample, then dip in ethanol and wash and dry up.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210411235.0A CN102899710B (en) | 2012-10-25 | 2012-10-25 | Silver electrochemical polishing solution, preparation method and use method thereof |
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| CN201210411235.0A CN102899710B (en) | 2012-10-25 | 2012-10-25 | Silver electrochemical polishing solution, preparation method and use method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103603027A (en) * | 2013-11-07 | 2014-02-26 | 昆明理工大学 | Electrochemical polishing method of palladium and alloy thereof |
| CN104862712A (en) * | 2015-05-11 | 2015-08-26 | 张恒 | Precious metal surface treatment method and precious metal surface treatment fluid |
| CN105334152A (en) * | 2015-10-28 | 2016-02-17 | 九江学院 | Physical method for evaluating pitting corrosion resistance of material |
| CN109778295A (en) * | 2017-11-15 | 2019-05-21 | 日本表面化学株式会社 | Electrolytic polishing liquid and the manufacturing method for processing metal |
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| CN1186127A (en) * | 1996-12-27 | 1998-07-01 | 株式会社亚南半导体技术 | Electrolytic silver stripping agent in lead frame manufacturing process |
| CN1411039A (en) * | 2001-10-03 | 2003-04-16 | 株式会社东芝 | Electrolysis polishing method |
| CN102127801A (en) * | 2011-01-20 | 2011-07-20 | 大连理工大学 | Electrolyte for electrochemical mechanical polishing of copper interconnecting layer and preparation method thereof |
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- 2012-10-25 CN CN201210411235.0A patent/CN102899710B/en not_active Expired - Fee Related
Patent Citations (3)
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| CN1186127A (en) * | 1996-12-27 | 1998-07-01 | 株式会社亚南半导体技术 | Electrolytic silver stripping agent in lead frame manufacturing process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103603027A (en) * | 2013-11-07 | 2014-02-26 | 昆明理工大学 | Electrochemical polishing method of palladium and alloy thereof |
| CN103603027B (en) * | 2013-11-07 | 2017-01-04 | 昆明理工大学 | A kind of palladium and the electrochemical polishing method of alloy thereof |
| CN104862712A (en) * | 2015-05-11 | 2015-08-26 | 张恒 | Precious metal surface treatment method and precious metal surface treatment fluid |
| CN105334152A (en) * | 2015-10-28 | 2016-02-17 | 九江学院 | Physical method for evaluating pitting corrosion resistance of material |
| CN109778295A (en) * | 2017-11-15 | 2019-05-21 | 日本表面化学株式会社 | Electrolytic polishing liquid and the manufacturing method for processing metal |
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| CN102899710B (en) | 2014-12-24 |
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