CN103334143B - A kind of Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast - Google Patents
A kind of Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast Download PDFInfo
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Abstract
The present invention relates to electrochemical field, disclose the differential arc oxidation method that a kind of Zr alloy surface prepares wear-resisting zirconia and aluminum oxide mixed coating fast, concrete steps are: do anode with pretreated zirconium alloy, steel plate does negative electrode, controlling electrolyte temperature is 10 DEG C-30 DEG C, mao power source parameter is set, opening power, process 2min-12min, powered-down, take out zirconium alloy, with deionized water rinsing surface, to obtain final product; Consisting of of described electrolytic solution: sodium aluminate 30g-60g, highly basic 1g-10g, deionized water 1000ml.Method film forming speed is fast, and film layer structure is even, containing a large amount of aluminum oxide; The micro-arc oxidation films that rete wear resistance obtains in the electrolytic solution such as lower concentration aluminate and phosphoric acid salt considerably beyond general zirconium alloy.
Description
Technical field
The present invention relates to electrochemical field, refer to that Zr alloy surface prepares wear-resisting ZrO fast further
2/ Al
2o
3the differential arc oxidation method of mixed coating.
Background technology
Zirconium alloy is a kind of valve metal, is widely used in high-tech technical field, because the thermal neutron absorption cross section of zirconium alloy is low, has good anti-neutron irradiation ability, with UO with the core solidity to corrosion of good performance, biocompatibility etc. that it is outstanding
2there is good consistency, and well corrosion-resistant in High Temperature High Pressure water and steam, and there is suitable intensity and the feature such as ductility, enough hot strengths.Therefore, fuel sheath and the heap inner structure parts of nuclear power reactor are commonly used as.And zirconium alloy also has very important value in body implanting material field.But the wear resisting property of zirconium alloy is lower than other nuclear industry materials such as stainless steel, nickelalloy, and zirconium alloy be on active service nuclear reactor in working condition very severe, by the impact of high-temperature high pressure water, strong neutron irradiation, electrochemistry, the mechanical stress of complexity and the fission gas of nuclear fuel etc., be faced with very serious corrosion and friction condition, so propose very high requirement to the friction of zirconium alloy and erosion resistance thereof.This external biomedical sector, as replacement of total hip (totalhiparthroplasty, THA), in total knee arthroplasty (TotalKneearthroplastyTKA), 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 generate the oxide film of different thickness at Zr alloy surface, greatly improve wear-resisting, the corrosion resisting property of zirconium alloy.
Differential arc oxidization technique is also known as plasma electrolysis oxidation (Plasmaelectrolyticoxidation), it is a kind of new surface modifications technology grown up from 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, the scientist of the state such as Germany, the U.S., China has also carried out early stage research thereafter.This Technology application is more in the research of Al alloys andMg alloys, but less concerning research zirconium alloy, and this technology is still the focus of international research at present.Compare with other process for treating surface, plasma electrolysis oxidation has following clear superiority:
(1) plasma electrolysis oxidation technology can be used for the workpiece of various complicated shape.
(2) plasma electrolysis oxidation film is at metallic surface growth in situ, rete and matrix metal bonding force good, difficult drop-off.
(3) thicknesses of layers is subject to processing time controling, maximumly reaches 200-300 μm.
(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 nuclear industry field, the oxide film on Zirconium alloy material surface should not too thick (and not having this to require in the application of other field), because zirconic thermal conductivity is low, the heat conductivility of the can material of nuclear reactor will be affected, be therefore necessary to develop the rete that the high-performance of Zr alloy surface is thin.
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 ambient-temp-stable phase.Tetragonal also can exist at normal temperature under certain conditions.Usually a certain amount of Tetragonal and monoclinic phase can be there is in micro-arc oxidation films.Tetragonal belongs to martensitic transformation to monoclinic phase transformation, can produce volumetric expansion, therefore, often there is tiny crack containing in the rete of monoclinic phase, thus affect the performance of micro-arc oxidation films.If Tetragonal can be made to settle out at normal temperatures, the crackle of rete will be reduced thus the wear resistance of raising rete.
At present, domestic and international investigator is many about the document of zirconium alloy differential arc oxidation, but generally adopts silicate, phosphoric acid salt etc. to be main, and the coating phase structure obtained is mainly monoclinic phase zirconium white and a small amount of tetragonal phase zirconium oxide composition.According to we nearest research paper ([1] Y.Cheng, F.Wu, J.Dong, X.Wu, Z.Xue, E.Matykina, P.Skeldon, G.E.Thompson, Comparisonofplasmaelectrolyticoxidationofzirconiumalloyi nsilicate-andaluminate-basedelectrolytesandwearpropertie softheresultingcoatings, Electrochim.Acta85 (2012) 25), it is main rete that sodium aluminate electrolytic solution is conducive to obtaining Tetragonal.But in research paper [1], the electrolytic solution of use is 6gl
-1naAlO
2and 8gl
-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 containing a large amount of aluminum oxide (Al
2o
3) rete, due to Al content in rete low (atomic percentage conc is about 3-10at%), and rete ectonexine difference is larger.In addition because electrolytic solution contains phosphoric acid salt (Na
4p
2o
710H
2, after causing coating growth to certain thickness (30 microns), there is mechanically peel, thicker rete can not be generated, and require high occasion (as biological implantation material) in wear resistance, need certain thickness rete in O) composition.
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.Adopt sodium aluminate be electrolytic solution carry out differential arc oxidation study at present report less, the researchist of Xi'an Communications University once carried out differential arc oxidation ([Y.Yan to pure zirconium in the sodium aluminate solution of 0.2-0.35M (being equivalent to 16.4g/L to 28.7g/L), Y.Han, D.Li, J.Huang, Q.Lian, EffectofNaAlO2concentrationonmicrostructureandcorrosionr esistanceofAl
2o
3/ ZrO
2coatingsformedonzirconiumbymicro-arcoxidation, AppliedSurfaceScience256 (2010) 6359], the electric current system adopted is the low frequency pulse current of 100Hz, and in the micro-arc oxidation films obtained, monoclinic phase zirconium white still occupies larger mark.And the conclusion that they draw is the degradation of concentration of sodium aluminate oxide film when bringing up to 0.35M (28.7g/L).
Finally, differential arc oxidation is the technology of a highly energy-consuming, reach certain thickness rete, time of conventional differential arc oxidation be 30 minutes to 1 hour not etc.If film process is slower, by a large amount of heat release during the course, cause power loss, energy consumption large, therefore, fast filming has decisive meaning in the energy consumption efficiency improving differential arc oxidation, if can fast filming, the energy consumption of this technology will be reduced greatly, also have positive meaning for this technology of popularization.
Summary of the invention
Improve for the domestic and international deficiency existed about research differential arc oxidation coating technology at present, domestic and international differential arc oxidation many employings phosphoric acid salt at present, silicate is electrolytic solution, the rete obtained is the mixed membranous layer of monocline and Tetragonal, its wear resistance is poor, in addition the rete (research paper [1]) obtained in the sodium aluminate for above-mentioned lower concentration, still there is a series of shortcoming: as in film, the content of aluminum oxide is on the low side, film layer structure is divided into ectonexine, composition heterogeneity, there is mechanically peel phenomenon in the treatment time rete of length, the problems such as thick rete can not be formed.The present invention aims to provide a kind of differential arc oxidation method preparing wear-resisting zirconia and aluminum oxide mixed coating fast, the method selects high-concentration sodium aluminate to be main electrolytic solution, under specific current parameters, stabilize the Tetragonal in zirconium alloy rete, form homogeneous alumina-zirconia mixed membranous layer, 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:
Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast, concrete steps are: do anode with pretreated zirconium alloy, steel plate does negative electrode, and controlling electrolyte temperature is 10 DEG C-30 DEG C, arranges mao power source parameter, opening power, process 2min-12min, powered-down, takes out zirconium alloy, with deionized water rinsing surface, to obtain final product;
Consisting of of described electrolytic solution: sodium aluminate 30g-60g, highly basic 1g-10g, deionized water 1000ml;
Described mao power source optimum configurations is: positive current density is 5-30A/dm
2an interior steady state value, negative current density is 5-30A/dm
2an interior steady state value; Frequency: 500Hz-5000Hz; Positive negative duty: 5%-30%.
Described electrolyte temperature is preferably 20 DEG C-30 DEG C.
Described highly basic is preferably sodium hydroxide or potassium hydroxide.
Described mao power source optimum configurations is preferably: positive current density is 10-15A/dm
2an interior steady state value, negative current density is 10-15A/dm
2an interior steady state value; Frequency: 1000Hz-3000Hz; Positive negative duty: 20%-30%.
The time of described process is preferably 2min (requiring the occasion of film)-10min (requiring the occasion of thick film).
The preprocessing process of described zirconium alloy is preferably: first use abrasive paper for metallograph surface finish, then wash with water successively, alcohol ultrasonic cleaning, and deionization is washed, then uses E-44 epoxy sealing, is finally polished by the Zr alloy surface abrasive paper for metallograph participating in reaction.
The present invention will be further explained below:
It the essence of differential arc oxidation is the anodic oxidation under a kind of high-voltage, belong to electrochemical field, but because the voltage used is higher than the voltage breakdown of metal oxide film surface, plasma spark can be produced in metallic surface when processing, 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.About the electrical parameter of differential arc oxidization technique, can be direct current also can be exchanges.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 provide better control by the ratio etc. of adjustment dutycycle, positive negative pulse stuffing to discharge process, avoid long-time spark discharge to the harm of rete.And the quality of electrolytic solution to differential arc oxidation film layer has more conclusive effect.Main innovation part of the present invention has following 2 points:
(1) by carrying out differential arc oxidation in the aluminate solution of high density, drastically increasing the speed of growth (2min just can generate the rete of about 10 μm) of micro-arc oxidation films, reducing the energy consumption of micro-arc oxidation process.
(2) aluminum oxide (atomic fraction of aluminium can reach 15-40at%) of high rigidity is mixed in success in a large number in the oxide film of zirconium alloy, and the microtexture changing rete (forms the rete that composition is homogeneous, avoid the phenomenon that in lower concentration aluminate, ectonexine is uneven), thus improve the wear resisting property (rete wear resistance is far above the rete obtained in lower concentration aluminate) of rete greatly.
The present invention introduces large quantity high performance alumina-ceramic phase in rete, greatly improve the wear resistance of zirconium alloy, and zirconium alloy film forming speed is also greatly improved, at high density (32gl
-1) sodium aluminate solution in process the rete of 10.3 microns within 2 minutes, can be obtained, and in phosphate solution, the rete generating same thickness at least needs 30 minutes.This rete is compared to the rete of the same thickness obtained in phosphoric acid salt, and its wear resisting property improves 16 times nearly.In high-concentration sodium aluminate, process can obtain 65 microns retes for 10 minutes (and in document [1], the thicknesses of layers of process 10min is 30 microns), 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 homogeneous rete of composition, and the zirconium alloy micro-arc oxidation films obtained is made up of tetragonal phase zirconium oxide, gama-alumina and amorphous alumina.
Sodium aluminate solution containing high density in electrolytic solution of the present invention, makes 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 low alumina content, and its film performance is relatively good a lot.
The detection of floating coat performance characteristic of the present invention needs to use following plant and instrument:
TT260 carries out layer thickness tester: Beijing Time Zhifeng Science Co., Ltd.Can be used to the thickness measuring rete.
Environmental scanning electron microscope and energy spectrometer: (SEM, QUANTA2000, FEI, USA): observe coating microscopic appearance and carry out composition analysis.
X-ray diffractometer: (place of production Japan, model is RigakuD/MAX2500).Detect the composition of rete phase.
CETRUMT-3 frictiograph: adopt ball-fast formula rub(bing)test, detect sample wear resistance.
Optical profilometer (WykoNT9100, VEECOInstrumentsInc.): detect Wear track depth compared with prior art, advantage of the present invention is:
1., in the present invention, coating growth speed is fast, have employed 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 differential arc oxidation process, the results are shown in Figure 1.Can find out, adopt high-concentration sodium aluminate to greatly improve coating growth speed.Its speed of growth considerably beyond phosphoric acid salt electrolyte membrane layer growth speed, in addition, than coating growth thickness in lower concentration aluminate also fast about 2 times.
2. in the present invention, film layer structure is uniform single layer structure, does not have large hole and crackle, and treatment time short sample surfaces is smooth.Phase composite is tetragonal phase zirconium oxide, gama-alumina and amorphous alumina.In rete, the atomic fraction of aluminium can reach 15-40at%, far above the Al content (rete of research paper [1] as described in the background art, its aluminium content is 3-10at%) in the rete obtained in lower concentration aluminate solution.
3. in the present invention, rete wear resisting property is very strong, to the sample of 65.4 micron thickness that reaction 10min generates, compared with research paper described in background technology [1], in 10N load, under the friction condition of 30min, in paper [1], Wear track depth is about 20 μm, and the Wear track depth in the present invention is only about 10 μm.Further, 10min rete of the present invention can with the power of 30N friction 30min, and frictional depth is only 20 μm, and the rete obtained in lower concentration aluminate in the introduction in described research paper [1] is worn through under the load of 30N.
4. be the rete of film (being obtained by reaction 2min) its wear resistance far above similar thickness obtained in phosphoric acid salt electrolytic solution of 10.3 microns for thickness.
Accompanying drawing explanation
Differential arc oxidation layer-growth rate curve in Fig. 1 high concentration of aluminium hydrochlorate electrolytic solution, lower concentration aluminate electrolytic solution and aluminate electrolytic solution that to be zirconium alloy adopt in the present invention.
Fig. 2 is the back scattering scanning electron microscope image that the oxide film cross section of differential arc oxidation process 2min in the aluminate electrolytic solution prepared of the present invention amplifies 5000 times.
Fig. 3 is the back scattering scanning electron microscope image that the oxide film cross section of differential arc oxidation process 2min in the aluminate electrolytic solution prepared of the present invention amplifies 18000 times.
Fig. 4 is the back scattering scanning electron microscope image that the oxide film cross section of differential arc oxidation process 10min in the aluminate electrolytic solution prepared of the present invention amplifies 200 times.
Fig. 5 is the back scattering scanning electron microscope image that the oxide film cross section of differential arc oxidation process 10min in the aluminate electrolytic solution prepared of the present invention amplifies 2000 times.
Fig. 6 adopts same electrical parameter, at lower concentration aluminate electrolytic solution (8g/LNaAlO
2+ 1g/LKOH) in the oxide film cross section of process 30min amplify the back scattering scanning electron microscope image of 1000 times.
Fig. 7 adopts same electrical parameter, and the back scattering scanning electron microscope image of 20000 times is amplified in the oxide film cross section processing 20min in phosphoric acid salt electrolytic solution.
Fig. 8 is the oxide film X ray diffracting spectrum of differential arc oxidation process 10min in the aluminate electrolytic solution prepared of the present invention.
Fig. 9 adopts same electrical parameter, processes the oxide film X ray diffracting spectrum of 20min in phosphoric acid salt electrolytic solution.
Figure 10 is the Wear track depth profile under 30N condition after metal to-metal contact 30min: process the oxide film processing 30min, thickness 75.8 μm in oxide film (b) the lower concentration aluminate of 10min, thickness 65.4 μm in high concentration of aluminium hydrochlorate prepared by (a) the present invention.
Figure 11 is the Wear track depth profile under 10N condition after metal to-metal contact 30min: process 2min oxide film (b) phosphatizing 20min oxide film in high concentration of aluminium hydrochlorate prepared by (a) the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1:
1, Zr alloy surface prepares wear-resisting ZrO fast
2/ Al
2o
3differential arc oxidation coating method, comprising:
(1) preparation of Zr alloy surface micro-arc oxidation electrolyte;
The composition of described electrolytic solution is, every 1000ml deionized water contains:
NaAlO
2：32g
KOH：1g
(2) setting of mao power source parameter: positive current 15A/dm
2negative current 10A/dm
2frequency: 1000Hz
Positive negative duty: 20%
(3) process of Zr alloy surface sample: specimen size 10 × 20mm, with E-44 type epoxy sealing, after sample solidification, the abrasive paper for metallograph of the Zr alloy surface 800-2000# participating in reaction is polished step by step, then wash from the beginning, alcohol ultrasonic cleaning, deionized water is cleaned.
(4) Zr alloy surface prepares the processing step of wear-resisting differential arc oxidation fast: keep temperature to be 20 DEG C under the electrolytic solution prepared is placed in circulating water cooling system, the zirconium alloy that pre-treatment is good does anode, and steel plate does negative electrode, sets mao power source parameter, opening power, start test, after reaching the scheduled time (2min-10min selects as required), powered-down, take out zirconium alloy, with deionized water rinsing surface, to obtain final product.
(5) simultaneously at lower concentration aluminate (8g/LNaAlO
2+ 1g/LKOH) (8g/LNa in neutralising phosphoric acid salt
3pO
4+ 1g/LKOH) adopt method above to obtain micro-arc oxidation films, carry out correlation detection, the performance of the micro-arc oxidation films obtained with the present invention compares.
2, coating growth speed:
Fig. 1 is the high concentration of aluminium hydrochlorate (32g/LNaAlO that the present invention adopts
2), lower concentration aluminic acid (8g/LNaAlO
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 adopts of the present invention, the speed of growth of micro-arc oxidation films is the highest.
3, coating structure and composition analysis:
When with 32g/L sodium aluminate electrolytic solution, when reacting for 2min, film layer structure is one deck, and film layer structure is fine and close.As Fig. 2 and Fig. 3.
When being 10min with the reaction of 32g/L sodium aluminate, coating is that (Al that back scattering Electronic Speculum Atom ordinal number is low shows black for the aluminum oxide of black and linen zirconium white mixolimnion, and the high zirconium of ordination number is white), there is no large crackle and hole, be combined closely with matrix.As Fig. 4 and Fig. 5.Carry out elemental composition analysis to the A point in Fig. 5, result is O54.77, Al39.15, Zr6.08 (at%), and its main component is aluminum oxide.
When 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 in Fig. 6, the composition of B point is O58.28, Al5.07, Zr36.35 (at.%), and its main component is zirconium white.Publish an article (Research Literature [1] in background technology) before us and the composition analysis result of Fig. 6 similar (because being all lower concentration aluminate electrolytic solution), therefore, the present invention obviously changes the content of aluminum oxide in coating, and its content is raised greatly.
When employing same electrical parameter, the oxide film coating processing 20min in phosphoric acid salt electrolytic solution is divided into inside and outside two-layer, with a large amount of crackle, as shown in Figure 7.
4, crystal species analysis:
In the present invention, when in the film generated with aluminate reaction, phase composite is tetragonal phase zirconium oxide and gamma-alumina, as Fig. 8.When in the rete adopting 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 CETRUMT-3 frictiograph, this method is 9.5mm with diameter, hardness is that the Cr steel ball of 62HRC carries out reciprocating friction at film surface, stroke is 7.2mm, maneuvering load is the power of 10N and 30N respectively, and controlled frequency is 5Hz. and analyzes Wear track depth and grinding defect morphology with contourgraph.
(1) the rete wear resistance obtained in the present invention and lower concentration aluminate compares
By the high-concentration sodium aluminate electrolytic solution (32g/LNaAlO that the present invention uses
2) reaction 10min, the thicknesses of layers obtained is the rete (Fig. 4, Fig. 5) of ~ 65.4 μm and the aluminate (8g/LNaAlO of lower concentration
2+ 1g/LKOH) the middle rete (thickness 75.8 μm reacting 30min, Fig. 6) under load 30N, carry out the dry wear test of 30min, its result is as Figure 10, its Wear track depth of rete obtained in the high concentration of aluminium hydrochlorate that the present invention adopts is approximately 20 μm, and the Wear track depth of the rete prepared in lower concentration aluminate is ~ 114 μm (rete is worn through).Equally, the rete in the Research Literature [1] in background technology is also worn through under 30N.
(2) the rete wear resistance obtained in the present invention and phosphoric acid salt electrolytic solution compares
At the dense sodium aluminate electrolytic solution (32g/LNaAlO that the present invention uses
2) reaction 2min, the thicknesses of layers obtained is rete (Fig. 2 of ~ 10.3 μm, Fig. 3) and react in phosphoric acid salt that 20min obtains ~ about 10 μm retes (Fig. 7) have carried out the dry wear test of 30min under load 10N, its result is as Figure 11, sample its Wear track depth after friction reacting 2min in the high concentration of aluminium hydrochlorate that the present invention adopts is approximately 3 μm, and the Wear track depth of the rete prepared in phosphoric acid salt electrolytic solution is ~ 40 μm (rete is worn through).
The present invention adopts high concentration of aluminium hydrochlorate electrolytic solution to prepare wear-resisting ZrO fast
2/ Al
2o
3differential arc oxidation coating, coating growth speed is about 2 times of coating growth speed in lower concentration aluminate, compares the rete obtained in phosphoric acid salt, and its speed of growth improves about 10 times, thus greatly can reduce the energy consumption of technique.And the wear resistance of rete obtains the raising of high degree, make it in nuclear reactor and biologic applications thereof, have larger use value.
Described in comprehensive, advantage of the present invention is that film forming speed is fast, and film layer structure is even, containing a large amount of aluminum oxide; The micro-arc oxidation films that 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, with embodiment 1, are that electrolytic solution and parameter are different:
(1) preparation of Zr alloy surface micro-arc oxidation electrolyte;
The composition of described electrolytic solution is, every 1000ml deionized water contains:
NaAlO
2：45g
NaOH：5g
(2) setting of mao power source parameter: positive current 15A/dm
2negative current 15A/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, containing a large amount of aluminum oxide; The micro-arc oxidation films that 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, with embodiment 1, are that electrolytic solution and parameter are different:
(1) preparation of Zr alloy surface micro-arc oxidation electrolyte;
The composition of described electrolytic solution is, every 1000ml deionized water contains:
NaAlO
2：60g
KOH：10g
(2) setting of mao power source parameter: positive current 20A/dm
2negative current 10A/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, containing a large amount of aluminum oxide; The micro-arc oxidation films that rete wear resistance obtains in the electrolytic solution such as lower concentration aluminate and phosphoric acid salt considerably beyond general zirconium alloy.
Claims (5)
1. Zr 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 does negative electrode, controlling electrolyte temperature is 10 DEG C-30 DEG C, mao power source parameter is set, opening power, process 2min-12min, powered-down, take out zirconium alloy, with deionized water rinsing surface, to obtain final product;
Consisting of of described electrolytic solution: sodium aluminate 30g-60g, highly basic 1g-10g, deionized water 1000ml; Described highly basic is sodium hydroxide or potassium hydroxide;
Described mao power source optimum configurations is: positive current density is 5A/dm
2-30A/dm
2an interior steady state value, negative current density is 5A/dm
2-30A/dm
2an interior steady state value; Frequency: 500Hz-5000Hz; Positive negative duty: 5%-30%.
2. Zr 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 DEG C-30 DEG C.
3. according to claim 1 or 2, Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast, it is characterized in that, described mao power source optimum configurations is: positive current density is 10A/dm
2-15A/dm
2an interior steady state value, negative current density is 10A/dm
2-15A/dm
2an interior steady state value; Frequency: 1000Hz-3000Hz; Positive negative duty: 20%-30%.
4. according to claim 1 or 2, Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast, it is characterized in that, the time of described process is 2min-10min.
5. according to claim 1 or 2, Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast, 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, alcohol ultrasonic cleaning, deionization is washed, then uses E-44 epoxy sealing, is finally polished by the Zr alloy surface abrasive paper for metallograph participating in reaction.
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