CN103334143A - Microarc oxidation method for quickly preparing wear-proof zirconia and alumina mixed coating on surface of zirconium alloy - Google Patents
Microarc oxidation method for quickly preparing wear-proof zirconia and alumina mixed coating on surface of zirconium alloy Download PDFInfo
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Abstract
The invention relates to the field of electrochemistry, and discloses a microarc oxidation method for quickly preparing a wear-proof zirconia and alumina mixed coating on the surface of a zirconium alloy. The microarc oxidation method comprises the steps of taking the pretreated zirconium alloy as an anode and a steel plate as a cathode, controlling the temperature of an electrolytic solution to be 10-30 DEG C, setting microarc oxidation power supply parameters, turning on a power supply, treating for 2-12min, turning off the power supply, taking the zirconium alloy out, washing the surface of the zirconium alloy with deionized water, and obtaining the wear-proof zirconia and alumina mixed coating, wherein the electrolytic solution comprises 30-60g sodium aluminate, 1-10g strong base, and 1000ml of deionized water. According to the method, the film-forming speed is high, a film layer is uniform in structure and contains a large amount of alumina, the abrasive resistance of the film layer is much higher than that of a general microarc oxidation film, obtained in an electrolytic solution with low concentration of aluminate, phosphate and the like, of the zirconium alloy.
Description
Technical field
The present invention relates to electrochemical field, further refer to the zirconium alloy surface wear-resisting ZrO of preparation fast
2/ Al
2o
3the differential arc oxidation method of mixed coating.
Background technology
Zirconium alloy is a kind of valve metal, and with it, the outstanding well behaved solidity to corrosion of core, biocompatibility etc. are widely used in the high-tech technical field, because the thermal neutron absorption cross section of zirconium alloy is low, good anti-neutron irradiation ability are arranged, with UO
2good consistency is arranged, and corrosion-resistant good in the High Temperature High Pressure water and steam, and there are suitable intensity and ductility, enough characteristics such as hot strength.Therefore, generally be used as fuel sheath and the heap inner structure parts of nuclear power reactor.And zirconium alloy also has very important value in the body implanting material field.But the wear resisting property of zirconium alloy is lower than other nuclear industry such as stainless steel, nickelalloy material, and the working condition in the nuclear reactor that zirconium alloy is on active service is very severe, be subject to the impact of high-temperature high pressure water, strong neutron irradiation, electrochemistry, complicated mechanical stress and the fission gas of nuclear fuel etc., be faced with very serious corrosion and friction condition, so friction and the erosion resistance thereof of zirconium alloy proposed to very high requirement.This external biomedical sector, as replacement of total hip (total hip arthroplasty, THA), in total knee arthroplasty (Total Knee arthroplasty TKA), embedded material is subject to very high load (body weight), in the urgent need to improving the wear resistance of zirconium alloy.Differential arc oxidization technique can, at the oxide film of zirconium alloy Surface Creation different thickness, greatly improve wear-resisting, the corrosion resisting property of zirconium alloy.
Differential arc oxidization technique claims again plasma electrolysis oxidation (Plasma electrolytic oxidation), it is a kind of novel surface modification technology grown up from the conventional anodization basis, this technology comes from the discovery of the Spark Discharges of electrolytic process before more than 100 year, but its practical application is until just developed by the former Russian scholar last century 60 to the seventies, and the scientist of the states such as Germany, the U.S., China has also carried out early stage research thereafter.It is more that this technology applies to the research of aluminium, magnesium alloy, but research is less concerning zirconium alloy, and this technology is still the focus of international research at present.With other process for treating surface, compare, plasma electrolysis oxidation has following clear superiority:
(1) the plasma electrolysis oxidation technology can be used for the workpiece of various complicated shapes.
(2) the plasma electrolysis oxidation film is at the metallic surface growth in situ, and rete and matrix metal bonding force are good, difficult drop-off.
(3) thicknesses of layers is subject to processing time control, and maximum can reach 200-300 μ m.
(4) device is simple, and floor space is little.Technical process is simple, easy to operate.Pretreatment procedure is few, and processing efficiency is high, is applicable to automatic production.
(5) electrolytic solution can be reused, and environmental pollution is few, meets current environmental requirement.
In the nuclear industry field, the oxide film on Zirconium alloy material surface should not too thick (and not having this requirement in the application of other field), because zirconic thermal conductivity is low, will affect the heat conductivility of the can material of nuclear reactor, therefore be necessary to develop the thin rete of high-performance on zirconium alloy surface.
Zirconium white has three kinds of crystal formations: Emission in Cubic (c-ZrO
2), Tetragonal (t-ZrO
2) and monoclinic phase (m-ZrO
2).First two is high-temperature-phase, and monoclinic phase is the ambient-temp-stable phase.Tetragonal also can exist at normal temperature under certain conditions.Usually can there be a certain amount of Tetragonal and monoclinic phase in micro-arc oxidation films.Tetragonal changes and belongs to martensitic transformation to monoclinic phase, can produce volumetric expansion, therefore, tends to exist tiny crack in the rete that contains monoclinic phase, thereby affects the performance of micro-arc oxidation films.If can make Tetragonal settle out at normal temperatures, thereby the crackle that will reduce rete improves the wear resistance of rete.
At present, the investigator is many about the document of zirconium alloy differential arc oxidation both at home and abroad, but generally adopt silicate, phosphoric acid salt etc., is main, and the coating phase structure obtained is mainly the monoclinic phase zirconium white and a small amount of tetragonal phase zirconium oxide forms.Nearest research paper ([1] Y. Cheng according to us, F. Wu, J. Dong, X. Wu, Z. Xue, E. Matykina, P. Skeldon, G.E. Thompson, Comparison of plasma electrolytic oxidation of zirconium alloy in silicate-and aluminate-based electrolytes and wear properties of the resulting coatings, Electrochim. Acta 85 (2012) 25), it is main rete that sodium aluminate electrolytic solution is conducive to obtain Tetragonal.But, in research paper [1], the electrolytic solution of use is 6 gl
-1naAlO
2with 8 gl
-1na
4p
2o
710H
2the mixing solutions of O.The shortcoming of this electrolytic solution is that concentration of sodium aluminate is low, can not generate and contain a large amount of aluminum oxide (Al
2o
3) rete, due to Al content in rete low (atomic percentage conc be about 3-10 at%), and rete ectonexine difference is larger.In addition because electrolytic solution contains phosphoric acid salt (Na
4p
2o
710H
2o) composition, cause coating growth after certain thickness (30 microns), and mechanically peel occurs, and can not generate thicker rete, and require high occasion (as biological implantation material) in wear resistance, and certain thickness rete need to be arranged.
In addition, the performance of micro-arc oxidation films and the relation of electrical parameter are also very large, and the electric current system of high-frequency impulse is better than the electric current system of direct current or low frequency.Adopting sodium aluminate is that electrolytic solution carries out differential arc oxidation to study at present report less, the researchist of Xi'an Communications University once was equivalent to 16.4g/L to 28.7g/L at 0.2-0.35 M() sodium aluminate solution in pure zirconium is carried out to differential arc oxidation ([Y.Yan, Y. Han, D. Li, J.Huang, Q.Lian, Effect of NaAlO2 concentration on microstructure and corrosion resistance of Al
2o
3/ ZrO
2coatings formed on zirconium by micro-arc oxidation, Applied Surface Science 256 (2010) 6359], the electric current system adopted is the low frequency pulse current of 100 Hz, and in the micro-arc oxidation films obtained, the monoclinic phase zirconium white still occupies larger mark.And the conclusion that they draw is that concentration of sodium aluminate is brought up to 0.35M(28.7g/L) time oxide film degradation.
Finally, differential arc oxidation is the technology of a highly energy-consuming, reach certain thickness rete, and the time of conventional differential arc oxidation is not wait in 30 minutes to 1 hour.If film process is slower, a large amount of heat releases during the course, cause power loss, energy consumption large, therefore, fast filming has decisive meaning aspect the energy consumption efficiency that improves differential arc oxidation, if can fast filming, will reduce greatly the energy consumption of this technology, for promoting this technology, positive meaning is also arranged.
Summary of the invention
For the deficiency existed about research differential arc oxidation coating technology both at home and abroad at present, improved, it is electrolytic solution that at present domestic and international differential arc oxidation adopts phosphoric acid salt, silicate more, the mixed membranous layer that the rete obtained is monocline and Tetragonal, its wear resistance is poor, the rete obtained in sodium aluminate for above-mentioned lower concentration in addition (research paper [1]), still there are a series of shortcomings: as on the low side as containing of aluminum oxide in film, film layer structure is divided into ectonexine, the composition heterogeneity, treatment time, there was the mechanically peel phenomenon in long rete, can not form the thick problems such as rete.The present invention aims to provide a kind of differential arc oxidation method for preparing fast wear-resisting zirconia and aluminum oxide mixed coating, it is main electrolytic solution that the method is selected high-concentration sodium aluminate, under specific current parameters, stablized the Tetragonal in the zirconium alloy rete, form the alumina-zirconia mixed membranous layer of homogeneous, wear resisting property effectively improves.This invention has important using value in nuclear industry field and technical field of biological material.
For achieving the above object, the technical solution adopted in the present invention is:
The zirconium alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast, concrete steps are: with pretreated zirconium alloy, do anode, steel plate is done negative electrode, and controlling electrolyte temperature is 10 ℃-30 ℃, and the mao power source parameter is set, opening power, process 2 min-12min, powered-down, take out zirconium alloy, use the deionized water rinsing surface, both;
Consisting of of described electrolytic solution: sodium aluminate 30g-60g, highly basic 1 g-10g, deionized water 1000ml;
Described mao power source parameter is set to: positive current density is 5-30A/dm
2an interior steady state value, negative current density is 5-30 A/dm
2an interior steady state value; Frequency: 500Hz-5000Hz; Positive negative duty: 5%-30%.
Described electrolyte temperature is preferably 20 ℃-30 ℃.
Described highly basic is preferably sodium hydroxide or potassium hydroxide.
The setting of described mao power source parameter is preferably: positive current density is 10-15A/dm
2an interior steady state value, negative current density is 10-15 A/dm
2an interior steady state value; Frequency: 1000Hz-3000Hz; Positive negative duty: 20%-30%.
The time of described processing is preferably the occasion that 2min(requires film)-10min(requires the occasion of thick film).
The preprocessing process of described zirconium alloy is preferably: first uses abrasive paper for metallograph surface finish, then washes with water successively, and the alcohol ultrasonic cleaning, the deionization washing, then use the E-44 epoxy sealing, polish with abrasive paper for metallograph in the zirconium alloy surface that finally will participate in reaction.
Below the present invention will be further explained:
The principle of differential arc oxidation is the anodic oxidation under a kind of high-voltage in essence, belong to electrochemical field, but due to the voltage breakdown of the voltage used higher than metal oxide film surface, can when processing, in metallic surface, produce the plasma body spark, therefore, the process of differential arc oxidation relates to chemical reaction, electrochemical reaction and plasma reaction, its complicated mechanism.The quality of differential arc oxidation film layer and bath composition, metal itself and electrical parameter have very large relation.The electrical parameter of relevant differential arc oxidization technique can be that direct current can be also to exchange.Early stage differential arc oxidization technique mostly is direct current, and along with the development of power technology, interchange or the pulse power become main flow.Because the latter can be by regulating dutycycle, positive negative pulse stuffing ratio etc. provide better control to discharge process, avoid the harm of long-time spark discharge to rete.And electrolytic solution has more conclusive effect to the quality of differential arc oxidation film layer.Main innovation part of the present invention has following 2 points:
(1) by carry out differential arc oxidation in the aluminate solution of high density, greatly improved the speed of growth (2min just can generate the rete of 10 m left and right) of micro-arc oxidation films, reduced the energy consumption of differential arc oxidation process.
(2) aluminum oxide (atomic fraction of aluminium can reach 15-40 at%) of high rigidity is mixed in a large number in success in the oxide film of zirconium alloy, and the microtexture that has changed rete (forms the rete that forms homogeneous, avoided the inhomogeneous phenomenon of ectonexine in the lower concentration aluminate), thus the wear resisting property (the rete wear resistance is far above the rete obtained in the lower concentration aluminate) of rete promoted greatly.
The present invention introduces large quantity high performance alumina-ceramic phase in rete, has improved greatly the wear resistance of zirconium alloy, and the zirconium alloy film forming speed also is greatly improved, at high density (32 gl
-1) sodium aluminate solution in process the rete can obtain 10.3 microns left and right in 2 minutes, and, in phosphate solution, the rete that generates same thickness at least needs 30 minutes.This rete is than the rete of the same thickness obtained in phosphoric acid salt, and its wear resisting property has improved 16 times nearly.Process in high-concentration sodium aluminate and within 10 minutes, can obtain 65 microns left and right retes (and in document [1], the thicknesses of layers of processing 10min is 30 microns left and right), its wear resistance also has a very significant increase than the similar thickness zirconium alloy micro-arc oxidation films obtained in the sodium aluminate of lower concentration.
Method of the present invention can form the rete that forms homogeneous, and resulting zirconium alloy micro-arc oxidation films is comprised of tetragonal phase zirconium oxide, gama-alumina and non-crystalline state aluminum oxide.
The sodium aluminate solution that contains high density in electrolytic solution of the present invention, make the better alumina-ceramic of mechanical property (hardness of aluminum oxide is zirconic 2 to 3 times) mix micro-arc oxidation films, greatly improves the performance of micro-arc oxidation films.The micro-arc oxidation films of the high alumina content obtained in the present invention is compared with the micro-arc oxidation films of al suboxide content, and its film performance is relatively good a lot.
The detection of floating coat performance characteristic of the present invention need to be used following plant and instrument:
TT260 carries out layer thickness tester: Beijing Time Zhifeng Science Co., Ltd.Can be used to measure the thickness of rete.
Environmental scanning electron microscope and energy spectrometer: (SEM, QUANTA2000, FEI, USA): observe the coating microscopic appearance and carry out composition analysis.
X-ray diffractometer: (place of production Japan, model is Rigaku D/MAX 2500).Detect the composition of rete phase.
CETR UMT-3 frictiograph: adopt ball-fast formula rub(bing)test, detect the sample wear resistance.
Optical profilometer (Wyko NT 9100, VEECO Instruments Inc.): detect the polishing scratch degree of depth
Compared with prior art, advantage of the present invention is:
1. in the present invention, coating growth speed is fast, has adopted high concentration of aluminium hydrochlorate (32g/LNaAlO of the present invention
2) and lower concentration aluminate (8g/LNaAlO
2) and phosphoric acid salt electrolytic solution in carry out the differential arc oxidation processing, the results are shown in Figure 1.Can find out, adopt high-concentration sodium aluminate to improve greatly coating growth speed.Its speed of growth is considerably beyond phosphoric acid salt electrolyte membrane layer growth speed, in addition, and than coating growth thickness in lower concentration aluminate also fast 2 times of left and right.
2. in the present invention, film layer structure is uniform single layer structure, there is no large hole and crackle, and short sample surfaces for the treatment of time is smooth.Phase composite is tetragonal phase zirconium oxide, gama-alumina and non-crystalline state aluminum oxide.In rete, the atomic fraction of aluminium can reach 15-40 at%, far above the Al content in the rete obtained in the lower concentration aluminate solution (rete of research paper [1], its aluminium content is 3-10 at%) as described in the background art.
3. in the present invention, the rete wear resisting property is very strong, to reacting the sample of 65.4 micron thickness that 10 min generate, with research paper described in background technology [1], compare, in 10 N load, under the friction condition of 30 min, in paper [1], the polishing scratch degree of depth is about 20 m, and the polishing scratch degree of depth in the present invention is only 10 m left and right.And 10min rete of the present invention can be used the power friction 30min of 30N, frictional depth is only 20 m, and is worn through under the load of rete at 30N obtained in the lower concentration aluminate in research paper described in background technology [1].
4. its wear resistance of the film that is 10.3 microns left and right for thickness (making by reacting 2 min) is far above the rete of the similar thickness made in phosphoric acid salt electrolytic solution.
the accompanying drawing explanation
Fig. 1 is the differential arc oxidation layer-growth rate curve of zirconium alloy in high concentration of aluminium hydrochlorate electrolytic solution, lower concentration aluminate electrolytic solution and the aluminate electrolytic solution of the present invention's employing
.
Fig. 2 is that the back scattering scanning electron microscope image of 5000 times is amplified in the oxide film cross section that in the aluminate electrolytic solution prepared of the present invention, differential arc oxidation is processed 2min.
Fig. 3 is that the back scattering scanning electron microscope image of 18000 times is amplified in the oxide film cross section that in the aluminate electrolytic solution prepared of the present invention, differential arc oxidation is processed 2min.
Fig. 4 is that the back scattering scanning electron microscope image of 200 times is amplified in the oxide film cross section that in the aluminate electrolytic solution prepared of the present invention, differential arc oxidation is processed 10 min.
Fig. 5 is that the back scattering scanning electron microscope image of 2000 times is amplified in the oxide film cross section that in the aluminate electrolytic solution prepared of the present invention, differential arc oxidation is processed 10 min.
Fig. 6 adopts the same electrical parameter, at lower concentration aluminate electrolytic solution (8 g/L NaAlO
2+ 1 g/L KOH) process the oxide film cross section of 30 min in and amplify the back scattering scanning electron microscope image of 1000 times.
Fig. 7 adopts the same electrical parameter, processes the oxide film cross section of 20 min and amplify the back scattering scanning electron microscope image of 20000 times in phosphoric acid salt electrolytic solution.
Fig. 8 is the oxide film X ray diffracting spectrum that in the aluminate electrolytic solution prepared of the present invention, differential arc oxidation is processed 10 min.
Fig. 9 adopts the same electrical parameter, processes the oxide film X ray diffracting spectrum of 20 min in phosphoric acid salt electrolytic solution.
Figure 10 is the polishing scratch depth profile after metal to-metal contact 30 min under 30 N conditions: the oxide film of processing 30min, thickness 75.8 m in the high concentration of aluminium hydrochlorate that (a) prepared by the present invention in oxide film (b) the lower concentration aluminate of processing 10 min, thickness 65.4 m.
Figure 11 is the polishing scratch depth profile after metal to-metal contact 30 min under 10 N conditions: process 2 min oxide film (b) phosphatizing 20 min oxide films in the high concentration of aluminium hydrochlorate that (a) prepared by the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
embodiment 1:
1, the zirconium alloy surface prepares wear-resisting ZrO fast
2/ Al
2o
3the differential arc oxidation coating method comprises:
(1) preparation of zirconium alloy surface by micro-arc oxidation electrolytic solution;
The composition of described electrolytic solution is that every 1000 ml deionized waters contain:
NaAlO
2：32?g
KOH ：1?g
(2) setting of mao power source parameter: positive current 15 A/dm
2negative current 10 A/dm
2
Frequency: 1000Hz
Positive negative duty: 20%
(3) processing of zirconium alloy surface sample: specimen size 10 * 20mm, with E-44 type epoxy sealing, after sample solidifies, polished step by step with the abrasive paper for metallograph of 800-2000# in the zirconium alloy surface that participates in reaction, then washing from the beginning, the alcohol ultrasonic cleaning, deionized water is cleaned.
(4) the zirconium alloy surface prepares the processing step of wear-resisting differential arc oxidation fast: it is 20 ℃ that the electrolytic solution prepared is placed in to maintenance temperature under circulating water cooling system, the zirconium alloy that pre-treatment is good is done anode, and steel plate is done negative electrode, sets the mao power source parameter, opening power, start test, after reaching the scheduled time (2min-10min selects as required), powered-down, take out zirconium alloy, use the deionized water rinsing surface, both.
(5) simultaneously at lower concentration aluminate (8g/L NaAlO
2+ 1g/LKOH) (8g/L Na in neutralising phosphoric acid salt
3pO
4+ 1g/L KOH) adopt top method to make micro-arc oxidation films, carry out correlation detection, the performance of the micro-arc oxidation films made with the present invention compares.
2, coating growth speed:
Fig. 1 is high concentration of aluminium hydrochlorate (the 32g/L NaAlO that the present invention adopts
2), lower concentration aluminic acid (8g/L NaAlO
2) and phosphoric acid salt (8g/LNa
3pO
4) growth curve of micro-arc oxidation films in electrolytic solution.As seen from Figure 1, in the high concentration of aluminium hydrochlorate that the present invention adopts, the speed of growth of micro-arc oxidation films is the highest.
3, coating structure and composition analysis:
When using 32g/L sodium aluminate electrolytic solution, when reacting for 2min, film layer structure is one deck, the film layer structure densification.As Fig. 2 and Fig. 3.
When with the reaction of 32g/L sodium aluminate, being 10min, the aluminum oxide that coating is black and linen zirconium white mixolimnion (the aobvious black of the Al that back scattering Electronic Speculum Atom ordinal number is low, and the high zirconium of ordination number is white), there is no large crackle and hole, with matrix, be combined very tight.As Fig. 4 and Fig. 5.A in Fig. 5 point is carried out to the elemental composition analysis, and result is O 54.77, and Al 39.15, Zr 6.08 (at%), and its main component is aluminum oxide.
While adopting the electrolytic solution of lower concentration, as shown in Figure 6, rete is divided into external and internal compositions to film layer structure, and the composition that in Fig. 6, B is ordered is O 58.28, and Al 5.07, Zr 36.35 (at.%), and its main component is zirconium white.Before us, publish an article (Research Literature in background technology [1]) and the composition analysis result of Fig. 6 similar (because being all lower concentration aluminate electrolytic solution), therefore, the present invention has obviously changed the content of aluminum oxide in the coating, and its content is raise greatly.
When adopting the same electrical parameter, in phosphoric acid salt electrolytic solution, the oxide film coating of processing 20 min is two-layer inside and outside being divided into, with a large amount of crackles, as shown in Figure 7.
4, phase composite analysis:
In the present invention, in the film generated with the aluminate reaction, phase composite is tetragonal phase zirconium oxide and gamma-alumina, as Fig. 8.In the rete that adopts the same electrical parameter to prepare at phosphoric acid salt, phase composite is monoclinic phase zirconium white (m-ZrO
2) (Fig. 9).
5. wearability test:
The wear resistance of micro-arc oxidation films is with using CETR UMT-3 frictiograph, this method is to be 9.5mm with diameter, the Cr steel ball that hardness is 62HRC carries out reciprocating friction at film surface, stroke is 7.2 mm, the power that maneuvering load is 10N and 30N respectively, controlled frequency is 5Hz. and with contourgraph, the polishing scratch degree of depth and grinding defect morphology is analyzed.
(1) the rete wear resistance obtained in the present invention and lower concentration aluminate relatively
High-concentration sodium aluminate electrolytic solution (the 32g/LNaAlO that the present invention is used
2) react 10 min, the rete (Fig. 4, Fig. 5) that the thicknesses of layers obtained is ~ 65.4 μ m and the aluminate (8g/LNaAlO of lower concentration
2+ 1g/L KOH) rete (the thickness 75.8 μ m of reaction 30 min in, Fig. 6) carried out the dry wear test of 30 min under load 30 N, its result is as Figure 10, its polishing scratch degree of depth of rete obtained in the high concentration of aluminium hydrochlorate that the present invention adopts is approximately 20 μ m, and the polishing scratch degree of depth of the rete prepared in the lower concentration aluminate is worn through for ~ 114 μ m(retes).Equally, the rete in the Research Literature in background technology [1] also is worn through under 30 N.
(2) the rete wear resistance obtained in the present invention and phosphoric acid salt electrolytic solution relatively
Dense sodium aluminate electrolytic solution (the 32g/L NaAlO used in the present invention
2) react 2 min, rete (Fig. 2 that the thicknesses of layers obtained is ~ 10.3 μ m, Fig. 3) and in phosphoric acid salt, reaction 20min obtains ~ 10 μ m left and right retes (Fig. 7) have carried out the dry wear test of 30 min under load 10N, its result is as Figure 11, in the high concentration of aluminium hydrochlorate that the present invention adopts, the sample of reaction 2min its polishing scratch degree of depth after friction is approximately 3 μ m, and the polishing scratch degree of depth of the rete prepared in phosphoric acid salt electrolytic solution is worn through for ~ 40 μ m(retes).
The present invention adopts high concentration of aluminium hydrochlorate electrolytic solution to prepare fast wear-resisting ZrO
2/ Al
2o
3differential arc oxidation coating, coating growth speed is 2 times of left and right of coating growth speed in the lower concentration aluminate, compares the rete obtained in phosphoric acid salt, its speed of growth improves 10 times of left and right, thereby can greatly reduce the energy consumption of technique.And the wear resistance of rete obtains the raising of very big degree, make it there is larger use value aspect nuclear reactor and biologic applications thereof.
Comprehensively described, advantage of the present invention is that film forming speed is fast, and film layer structure is even, contains a large amount of aluminum oxide; The micro-arc oxidation films that the rete wear resistance obtains in the electrolytic solution such as lower concentration aluminate and phosphoric acid salt considerably beyond general zirconium alloy.
embodiment 2:all the other preparation and determination methods steps are with embodiment 1, and just electrolytic solution and parameter are different:
(1) preparation of zirconium alloy surface by micro-arc oxidation electrolytic solution;
The composition of described electrolytic solution is that every 1000ml deionized water contains:
NaAlO
2：45g
NaOH ：5g
(2) setting of mao power source parameter: positive current 15 A/dm
2negative current 15 A/dm
2
Frequency: 2500Hz
Positive negative duty: 10%
Effect is with embodiment 1, and film forming speed is fast, and film layer structure is even, contains a large amount of aluminum oxide; The micro-arc oxidation films that the rete wear resistance obtains in the electrolytic solution such as lower concentration aluminate and phosphoric acid salt considerably beyond general zirconium alloy.
embodiment 3:all the other preparation and determination methods steps are with embodiment 1, and just electrolytic solution and parameter are different:
(1) preparation of zirconium alloy surface by micro-arc oxidation electrolytic solution;
The composition of described electrolytic solution is that every 1000ml deionized water contains:
NaAlO
2：60?g
KOH ：10g
(2) setting of mao power source parameter: positive current 20A/dm
2negative current 10 A/dm
2
Frequency: 5000Hz
Positive negative duty: 30%
Effect is with embodiment 1, and film forming speed is fast, and film layer structure is even, contains a large amount of aluminum oxide; The micro-arc oxidation films that the rete wear resistance obtains in the electrolytic solution such as lower concentration aluminate and phosphoric acid salt considerably beyond general zirconium alloy.
Claims (6)
1. the zirconium alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast, it is characterized in that, concrete steps are: do anode with pretreated zirconium alloy, steel plate is done negative electrode, controlling electrolyte temperature is 10 ℃-30 ℃, the mao power source parameter is set, and opening power, process 2 min-12min, powered-down, take out zirconium alloy, use the deionized water rinsing surface, both;
Consisting of of described electrolytic solution: sodium aluminate 30g-60g, highly basic 1 g-10g, deionized water 1000ml;
Described mao power source parameter is set to: positive current density is 5 A/dm
2-30A/dm
2an interior steady state value, negative current density is 5 A/dm
2-30 A/dm
2an interior steady state value; Frequency: 500Hz-5000Hz; Positive negative duty: 5%-30%.
2. the zirconium alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast according to claim 1, it is characterized in that, described electrolyte temperature is 20 ℃-30 ℃.
3. prepare fast the method for wear-resisting zirconia and aluminum oxide differential arc oxidation coating according to the described zirconium alloy of claim 1 or 2 surface, it is characterized in that, described highly basic is sodium hydroxide or potassium hydroxide.
4. prepare fast the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating according to the described zirconium alloy of claim 1 or 2 surface, it is characterized in that, described mao power source parameter is set to: positive current density is 10 A/dm
2-15A/dm
2an interior steady state value, negative current density is 10 A/dm
2-15 A/dm
2an interior steady state value; Frequency: 1000Hz-3000Hz; Positive negative duty: 20%-30%.
5. prepare fast the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating according to the described zirconium alloy of claim 1 or 2 surface, it is characterized in that, the time of described processing is 2min-10min.
6. prepare fast the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating according to the described zirconium alloy of claim 1 or 2 surface, it is characterized in that, the preprocessing process of zirconium alloy is: first use abrasive paper for metallograph surface finish, then wash with water successively, the alcohol ultrasonic cleaning, the deionization washing, then use the E-44 epoxy sealing, polish with abrasive paper for metallograph in the zirconium alloy surface that finally will participate in reaction.
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|---|---|---|---|
| CN201310294857.4A CN103334143B (en) | 2013-07-15 | 2013-07-15 | A kind of Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast |
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|---|---|---|---|
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Cited By (6)
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| CN108018592A (en) * | 2017-10-10 | 2018-05-11 | 上海核工程研究设计院有限公司 | A kind of zircaloy differential arc oxidization surface method of modifying |
| CN113005498A (en) * | 2021-02-22 | 2021-06-22 | 佳木斯大学 | Self-lubricating zirconium-based amorphous alloy and preparation method and application thereof |
| CN113355715A (en) * | 2021-04-30 | 2021-09-07 | 上海交通大学 | Method for improving micro-arc oxidation film forming rate of zirconium alloy surface |
| CN113774459A (en) * | 2021-09-29 | 2021-12-10 | 上海交通大学 | Preparation method of compact high-corrosion-resistance micro-arc oxidation film layer on surface of zirconium alloy |
| CN113774458A (en) * | 2021-09-29 | 2021-12-10 | 上海交通大学 | Method for in-situ synthesis of layered double-metal hydroxide sealed micro-arc oxidation coating on surface of zirconium alloy |
| CN115096675A (en) * | 2022-06-07 | 2022-09-23 | 佛山科学技术学院 | Zirconium tube calibration sample for underwater eddy current detection and preparation method thereof |
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| CN106702459B (en) * | 2016-11-28 | 2018-07-27 | 燕山大学 | A method of preparing abradable porous zirconia ceramic layer in Zr alloy surface |
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| CN113774459A (en) * | 2021-09-29 | 2021-12-10 | 上海交通大学 | Preparation method of compact high-corrosion-resistance micro-arc oxidation film layer on surface of zirconium alloy |
| CN113774458A (en) * | 2021-09-29 | 2021-12-10 | 上海交通大学 | Method for in-situ synthesis of layered double-metal hydroxide sealed micro-arc oxidation coating on surface of zirconium alloy |
| CN115096675A (en) * | 2022-06-07 | 2022-09-23 | 佛山科学技术学院 | Zirconium tube calibration sample for underwater eddy current detection and preparation method thereof |
| CN115096675B (en) * | 2022-06-07 | 2023-08-11 | 佛山科学技术学院 | Zirconium tube calibration sample for underwater vortex detection and preparation method thereof |
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