CN104213176A - Method for forming corrosion resistant electrochemical conversion film on surface of copper-nickel alloy - Google Patents
Method for forming corrosion resistant electrochemical conversion film on surface of copper-nickel alloy Download PDFInfo
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- CN104213176A CN104213176A CN201410448507.3A CN201410448507A CN104213176A CN 104213176 A CN104213176 A CN 104213176A CN 201410448507 A CN201410448507 A CN 201410448507A CN 104213176 A CN104213176 A CN 104213176A
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- cupronickel
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- copper
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- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 18
- 230000007797 corrosion Effects 0.000 title abstract description 27
- 239000000956 alloy Substances 0.000 title abstract description 17
- 229910045601 alloy Inorganic materials 0.000 title abstract description 16
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002161 passivation Methods 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 230000010287 polarization Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000003637 basic solution Substances 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 6
- 239000013527 degreasing agent Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 abstract description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 4
- 239000007832 Na2SO4 Substances 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention provides a method for forming a corrosion resistant electrochemical conversion film on a surface of a copper-nickel alloy. The electrochemical treatment is performed for the copper-nickel alloy after the surface pretreatment, and then the after-treatment is performed; and the electrochemical treatment is to perform the carrier passivation after the increasing potential cycle scanning under the conditions of 0.1-1.0 mol/L Na2SO4 and 0.05-0.5 mol/L NaHCO3 in each liter of water serving as electrolyte solution, the copper-nickel alloy to be treated serving as a working electrode, a platinum electrode serving as a counter electrode and an Ag/AgCl electrode serving as a reference electrode. The method can perform the electrochemical treatment to form a layer of corrosion resistant film so as to cut off the contact between a copper-nickel alloy matrix and a working environment corrosive medium before the alloy in on service. The conversion firm formed by the method has the characteristics of excellent corrosion resistance, greater thickness of the film layer, uniformity, compactness and excellent bonding with the matrix.
Description
Technical field
What the present invention relates to is a kind of metal surface treating method, specifically a kind of method forming anti-corrosion electrochemical conversion film on cupronickel surface.
Background technology
Ocean environment is a kind of corrosive environment of complexity.In this environment, seawater itself is a kind of stronger corrosive medium, ripple, wave, tide, stream produce low frequency toward combined stress and impact to hardware again simultaneously, add that marine microorganism, settled organism and their meta-bolites etc. all produce direct or indirect booster action to corrosion process.So require that material therefor also possesses corrosion resisting property special in ocean environment.
Cupronickel is all abnormal compared with the mechanical property of other copper alloys, physicals good, ductility is good, hardness is high, color and luster is attractive in appearance, corrosion-resistant, be rich in deep drawability, be widely used in shipbuilding field, studying its solidity to corrosion has very large realistic meaning.B10, B30 cupronickel is all the excellent copper alloy of the sea water corrosion resistant of generally acknowledging in the world, is used widely in oceanographic engineering.Most investigator thinks, the seawater scouring corrosion resistant excellent property of B10, B30 alloy, the temperature sensitivity of corrosion is lower, and possesses excellent antifouling property.
Cupronickel can form the surface protective rete of the rich iron of rich nickel in long period of soaking, can alleviate the corrosion of seawater to material matrix.Although the corrosion product rete that alloy surface is formed can prevent matrix to be corroded further, but alloy there occurs corrosion before alloy surface forms corrosion products film, particularly local corrosion may be there is under certain condition, the destruction of meeting accelerated material itself, thus greatly reduce the performance of material itself.So necessary when doing certain solidity to corrosion process to its surface before alloy is on active service.
At present at other field or other alloys, as stainless steel and Mg alloy surface process have similar technique also in the middle of research, but its concrete technological process is very different.The existing technique more close with magnesium alloy about stainless steel only uses the method for alternating voltage passivation, and choosing of concrete electrochemical parameter can be different because of the difference of material, so the electrochemical conversion technique of other materials is inapplicable to cupronickel.
The cupronickel that present stage is on active service in ocean environment, the performance of the main dependence material of its corrosion resisting property itself, the raising of its surface property need research.Therefore, the cupronickel surface electrochemistry conversion film treatment process developing a kind of suitability wide, easy to operate has very large realistic meaning to Chuan Hai field.
Summary of the invention
The object of the present invention is to provide a kind of method forming anti-corrosion electrochemical conversion film on cupronickel surface that can improve cupronickel corrosion resisting property.
The object of the present invention is achieved like this:
After carrying out electrochemical treatment through the cupronickel of surface preparation, carry out aftertreatment again, described electrochemical treatment is: with every premium on currency containing 0.1-1.0mol/L Na
2sO
4with 0.05-0.5mol/L NaHCO
3for electrolyte solution, using pending cupronickel be working electrode, platinum electrode as to electrode, Ag/AgCl electrode as reference electrode, first carry out increasing progressively potential duration scanning, then carry out alternating voltage passivation.
The present invention can also comprise:
1, the described method increasing progressively potential duration scanning is: give operating potential one low potential Ea, and with constant scan speed increase to noble potential Eb, multiple scanning is this potential region for several times, described low potential Ea, noble potential Eb is determined at the dynamic potential polarization curve of described electrolyte solution by the naked sample of described cupronickel, low potential Ea gets this cupronickel in this electrolyte solution, is greater than open circuit E (ocp) 10mV-70mV, noble potential Eb gets cupronickel and is less than from anodic polarization curves and breaks up current potential E (bup) 100mV-300mV, sweep velocity is between 20-60mV/min, multiplicity 2-4 time.
2, the method for described alternating voltage passivation is: utilize little amplitude square wave alternating electric field to process cupronickel surface, relating to parameter has subcarrier time t, alternating electric field cycle T, noble potential E
h, low potential E
l, wherein noble potential E
hget between 500mV-700mV, low potential E
lget between-150mV to 0, T=t
h+ t
l, f=1/T, k=t
h/ T, t are at 10-30min, T at 0.01-0.1s, and frequency f is at 10-30Hz, and dutycycle k is between 10%-80%.
3, the method for surface preparation comprises:
A. soak oil removing with degreaser, soak supersound process simultaneously, time 1-5h;
B. deionized water rinsing;
C. put into 60-80 DEG C of basic solution and soak 1-5min;
D. deionized water rinsing.
Due to its unique complicated corrosive environment of ocean environment, require the corrosion resistance nature that marine material surface is special.Utilize technology of the present invention can carry out electrochemical treatment before alloy is on active service, form one deck corrosion-resistant film, cut off the contact of cupronickel matrix and Working environment corrosive medium.It is good that the conversion film that this technology is formed has solidity to corrosion, and thicknesses of layers is comparatively large, and even compact, with matrix in conjunction with good feature.
Technique effect of the present invention mainly comprises:
(1) utilize this technology before alloy is on active service, electrochemical treatment can be carried out to it and form electrochemical conversion film, the material such as pipeline or hull can be made to be protected before its surface forms corrosion products film, reduce the corrosion in material military service early stage.
(2) compared with the corrosion products film of cupronickel long period of soaking Nature creating in the seawater, this electrochemical conversion film thicknesses of layers is larger, more effectively can resist the corrosion in mechanical erosion class.
(3) illustrate, common B10 cupronickel soaks 30 days in artificial seawater, and its surface can start to observe coming off of corrosion product; And occur that similar phenomenon at least soaks more than 90 days through the alloy surface of process of the present invention.
Accompanying drawing explanation
Fig. 1 carries out increasing progressively potential duration scanning externally-applied potential schematic diagram.
The naked sample of Fig. 2 B10 cupronickel is at Na
2sO
4add NaHCO
3dynamic potential polarization curve in solution.
Fig. 3 alternating voltage passivation externally-applied potential schematic diagram.
Specimen cross section high magnification SEM photo after the process of Fig. 4 B10 cupronickel electrochemical conversion film.
Fig. 5 B10 cupronickel sample is at Na
2sO
4add NaHCO
3in situ test alternating-current impedance spectrogram after each step electrochemical treatment in solution.
After Fig. 6 electrochemical treatment, B10 cupronickel sample soaks in situ test alternating-current impedance spectrogram in artificial seawater.
Embodiment
Illustrate below and the present invention is described in more detail.
Method of the present invention mainly comprises the following steps:
(1) cupronickel surface preparation;
(2) electrochemical treatment step by step;
(3) clean, dry.
Wherein the method steps of (1) cupronickel surface preparation process is as described below:
A. soak oil removing with degreaser, during immersion, container is put into together ultrasonic device supersound process simultaneously, time 1-5h;
B. deionized water rinsing;
C. put into 60-80 DEG C of basic solution and soak 1-5min;
D. deionized water rinsing;
Wherein said degreaser is selected from: dehydrated alcohol, acetone and other organic solvent; Described basic solution is: sodium carbonate and sodium hydroxide solution, and the proportioning of basic solution is containing sodium carbonate 10-20g, sodium hydroxide 15-30g in every premium on currency.
The electrolyte solution proportioning that this electrochemical conversion membrane technology uses is that every premium on currency is containing 0.1-1.0mol/L Na2SO4 and 0.05-0.5mol/L NaHCO3.
Wherein (2) step by step electrochemical treatment be the key point of this technology, electrochemical process selection standard three-electrode system in experimental study, pending sample is as working electrode, platinum electrode is as to electrode, Ag/AgCl electrode is as reference electrode, as claimed in claim 4, electrochemical process carries out a. and increases progressively potential duration scanning electrolyte solution in two steps; B. alternating voltage passivation.
A. increasing progressively potential duration scanning is give operating potential a certain low potential Ea, and with a certain constant scan speed increase to a certain noble potential Eb, multiple scanning changes potential region for several times, as shown in Figure 1.Wherein the selection of current potential Ea, Eb can with reference to the dynamic potential polarization curve of the naked sample of alloy at this electrolyte solution, as shown in Figure 2.Ea gets this alloy material and in this electrolyte solution, is greater than open circuit E (ocp) 10mV-70mV, Eb takes from cupronickel anodic polarization curves and be less than and break up current potential E (bup) 100mV-300mV.Sweep velocity between 20-60mV/min, multiplicity 2-4 time.
B. alternating voltage passivation utilizes little amplitude square wave alternating electric field to process cupronickel surface, and as shown in Figure 3, relating to parameter has subcarrier time t, alternating electric field cycle T, high low potential Eh, El, wherein noble potential E
hget between 500mV-700mV, E
lget between-150mV to 0, T=t
h+ t
l, f=1/T, k=t
h/ T, t are at 10-30min, T at 0.01-0.1s, and frequency f is at 10-30Hz, and dutycycle k is between 10%-80%.
Wherein (3) cleaning, the method steps of oven dry is as described below:
After taking-up, should be advisable with deionized water rinsing, hot blast drying, can not ultrasonic cleaning.
Do electrochemical treatment for B10 cupronickel to be below illustrated.
B10 tubing is cut into thick 1.5mm, diameter 13mm disc-shaped sample
The greasy dirt remained when soaking removing cutting sample with acetone, puts into ultrasonic device supersound process simultaneously, time 3h together by beaker during immersion;
Use 400#, 1000#, 2000# sand papering sample successively, then polishing, being convenient to the later stage does morphology observation;
Deionized water rinsing; Due to the step having sanding and polishing, the step of alkali cleaning can be saved;
Configuration electrochemical treatment ionogen: weigh 71g Na in the balance
2sO
4, 8.4g NaHCO
3add deionized water to liter, stir;
B10 sample powder coating and AB glue are coated with sample side and back side envelope, expose working face as electrode, conveniently do electrochemical treatment;
Select the Zahner electrochemical workstation of German global analytical and testing instrument company limited, adopt standard three-electrode system, pending B10 sample is as working electrode, and platinum electrode is as to electrode, and Ag/AgCl electrode is as reference electrode; By electrode as in above-mentioned electrolyte solution, select electrochemical workstation PVI module, carry out increasing progressively potential duration scanning, set the potential waveform as Fig. 1, if Ea=100mV, Eb=500mV, T=20min, loop cycle is 2; Then carry out alternating voltage passivation, set the potential waveform as Fig. 2, if El=-100mV, Eh=700mv, k=30%, T=0.02s, time length 10min.
After the B10 sample processed is taken out, with deionized water rinsing, hot blast drying;
SEM/EDX (scanning electron microscope and energy spectrum analysis) and XPS (XPS Analysis) is done to sample.
Sea water immersion experimental study example is done to the B10 cupronickel after electrochemical treatment film forming
B10 cupronickel is done the electrochemical treatment as above described in embodiment;
By process after sample be immersed in artificial seawater, long period of soaking and Real Time Observation film shape change;
Artificial seawater (GB/T 15748-1995) chemical composition is as shown in the table
Periodic monitoring electrode surface rete electrochemical impedance spectroscopy, adopt three-electrode system, to electrode platinum electrode, the saturated KCl standard electrode of reference electrode Ag/AgCl-, test soln is artificial seawater in situ test.
Claims (5)
1. form a method for anti-corrosion electrochemical conversion film on cupronickel surface, after carrying out electrochemical treatment through the cupronickel of surface preparation, carry out aftertreatment again, it is characterized in that: described electrochemical treatment is containing 0.1-1.0mol/L Na with every premium on currency
2sO
4with 0.05-0.5mol/L NaHCO
3for electrolyte solution, using pending cupronickel be working electrode, platinum electrode as to electrode, Ag/AgCl electrode as reference electrode, first carry out increasing progressively potential duration scanning, then carry out alternating voltage passivation.
2. the method forming anti-corrosion electrochemical conversion film on cupronickel surface according to claim 1, the method increasing progressively potential duration scanning described in it is characterized in that is: give operating potential one low potential Ea, and with constant scan speed increase to noble potential Eb, multiple scanning is this potential region for several times, described low potential Ea, noble potential Eb is determined at the dynamic potential polarization curve of described electrolyte solution by the naked sample of described cupronickel, low potential Ea gets this cupronickel in this electrolyte solution, is greater than open circuit E (ocp) 10mV-70mV, noble potential Eb gets cupronickel and is less than from anodic polarization curves and breaks up current potential E (bup) 100mV-300mV, sweep velocity is between 20-60mV/min, multiplicity 2-4 time.
3. the method forming anti-corrosion electrochemical conversion film on cupronickel surface according to claim 1 and 2, it is characterized in that the method for described alternating voltage passivation is: utilize little amplitude square wave alternating electric field to process cupronickel surface, relating to parameter has subcarrier time t, alternating electric field cycle T, noble potential E
h, low potential E
l, wherein noble potential E
hget between 500mV-700mV, low potential E
lget between-150mV to 0, T=t
h+ t
l, f=1/T, k=t
h/ T, t are at 10-30min, T at 0.01-0.1s, and frequency f is at 10-30Hz, and dutycycle k is between 10%-80%.
4. the method forming anti-corrosion electrochemical conversion film on cupronickel surface according to claim 1 and 2, is characterized in that the method for surface preparation comprises:
A. soak oil removing with degreaser, soak supersound process simultaneously, time 1-5h;
B. deionized water rinsing;
C. put into 60-80 DEG C of basic solution and soak 1-5min;
D. deionized water rinsing.
5. the method forming anti-corrosion electrochemical conversion film on cupronickel surface according to claim 3, is characterized in that the method for surface preparation comprises:
A. soak oil removing with degreaser, soak supersound process simultaneously, time 1-5h;
B. deionized water rinsing;
C. put into 60-80 DEG C of basic solution and soak 1-5min;
D. deionized water rinsing.
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|---|---|---|---|
| CN201410448507.3A CN104213176B (en) | 2014-09-04 | 2014-09-04 | Method for forming corrosion resistant electrochemical conversion film on surface of copper-nickel alloy |
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|---|---|---|---|
| CN201410448507.3A CN104213176B (en) | 2014-09-04 | 2014-09-04 | Method for forming corrosion resistant electrochemical conversion film on surface of copper-nickel alloy |
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| CN104213176B CN104213176B (en) | 2017-01-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483800A (en) * | 2015-12-09 | 2016-04-13 | 北京市医疗器械检验所 | Process for forming film on medical nickel titanium shape memory alloy in cyclic potentiodynamic manner |
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|---|---|---|---|---|
| CN101245484A (en) * | 2008-03-21 | 2008-08-20 | 哈尔滨工程大学 | Wave carrier process technique for improving corrosion resisting property of magnesium and magnesium alloy |
| CN101245483A (en) * | 2008-03-21 | 2008-08-20 | 哈尔滨工程大学 | Wave carrier passivating treatment method of diphasic stainless steel |
| CN103898497A (en) * | 2014-03-08 | 2014-07-02 | 哈尔滨工程大学 | Copper-nickel alloy cerate chemical conversion coating treatment method |
-
2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245484A (en) * | 2008-03-21 | 2008-08-20 | 哈尔滨工程大学 | Wave carrier process technique for improving corrosion resisting property of magnesium and magnesium alloy |
| CN101245483A (en) * | 2008-03-21 | 2008-08-20 | 哈尔滨工程大学 | Wave carrier passivating treatment method of diphasic stainless steel |
| CN103898497A (en) * | 2014-03-08 | 2014-07-02 | 哈尔滨工程大学 | Copper-nickel alloy cerate chemical conversion coating treatment method |
Non-Patent Citations (2)
| Title |
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| SHANSHAN CHEN ET AL: "Oxidation Resistance of Graphene-Coated Cu and Cu/Ni Alloy", 《ACS NANO》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483800A (en) * | 2015-12-09 | 2016-04-13 | 北京市医疗器械检验所 | Process for forming film on medical nickel titanium shape memory alloy in cyclic potentiodynamic manner |
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