CN1276840A - Method for producing hard protection coatings on articles made of aluminium alloy - Google Patents
Method for producing hard protection coatings on articles made of aluminium alloy Download PDFInfo
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- CN1276840A CN1276840A CN 97182480 CN97182480A CN1276840A CN 1276840 A CN1276840 A CN 1276840A CN 97182480 CN97182480 CN 97182480 CN 97182480 A CN97182480 A CN 97182480A CN 1276840 A CN1276840 A CN 1276840A
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Abstract
The present invention pertains to the field of electrolytic and plasmic oxidation of aluminium alloys. This invention more precisely relates to a method that comprises carrying out an anodic-cathodic oxidation in an alkaline electronlyte at a temperature of between 15 and 50 deg.c using an alternative current having a frequency ranging from 50 to 60 Hz. During the process initial stage and for a duration of between 5 and 90 seconds, the oxidation is carried out at a current density of between 160 and 180 A/dm2 after which the current density is lowered down to a range of between 3 and 30 A/dm2. The process is carried out according to a mode of spontaneous decrease in the power used and without any adjustment of said mode by an operator until a coating of a desired thickness is obtained. This method uses as an alkaline electrolyte an aqueous solution containing from 1 to 5 g/1 of an alkaline metal hydroxide, from 2 to 15 g/l of an alkaline metal silicate, from 2 to20 g/1 of an alkaline metal fyrophosphate and from 2 to 7 g/1 of peroxide compounds with a 30% H 2O2 conversion. This method is used for improving the protection propertise of oxide-ceramic coatings without additional power consumption and without temporary resources due to a better micro-hardness, a better density and a better adhesion force to the substrate.
Description
Technical field
The present invention relates to the method for articles made of aluminium alloy plating protection oxide covering.More precisely, be a kind of plasma electrolysis oxidation coating process of on the articles made of aluminium alloy surface, adopting.The present invention can be applicable to engineering, device fabrication and other industrial circle.
Since the physical and mechanical property of aluminium alloy and be used to make the technology of complex-shaped product, aluminium alloy (forged, casting) in making machine important and fast the use in the worn parts increase.Therefore, be badly in need of using protective coating in its surface, when it suffers wear particle and localized hyperthermia, resist the infringement of wearing and tearing and not being subjected to corrosive environment.A method of head it off is with the plasma electrolysis oxidation coating aluminium alloy to be plated ceramic oxide corundum coating.When having the product long-term operation of this coating, it is essential coating thickness, microhardness and be bonded to suprabasil intensity.When this method is applied to putting into practice, need have high yield and reliability, equipment should be simple, in the operation process to the environment toxicological harmless.
Prior art
Known aluminium oxide alloy method (DE, Al, 4209733) is to use the anode-cathode mode, and current density is 2-20A/dm
2, the positive pole terminal voltage amplitude is 300-750V, the cathode terminal voltage amplitude is 15-350V.Its pulse-repetition is that the 10-150 hertz does not wait, and the anode current impulse time length is the 10-15 millisecond, and the cathodic current pulse duration is 5 milliseconds.This method is used alkaline silicate or basic aluminate ionogen, can make the fine and close 50-250 μ of solid oxidation coat-thickness.
This method has following shortcoming: low yield, high energy consumption and need complex apparatus.In addition, use traditional alkaline silicate salt electrolyte, can not guarantee to produce on the articles made of aluminium alloy surface firm uniform coating.The life-time service ionogen can cause plating coating changes of properties, causes that thus the degeneration of coating quality and thickness reduce.Freeze thaw stability is uncontrollable in operation process within 30-90Ah/l.
The method that obtains low porosity on the aluminium alloy,, thickness good to substrate cohesiveness and be 100 μ or above solid-state ceramic oxide covering is known (US, A, 5616229).Formation at anode-cathode mode floating coat is carried out in several containing in the electrolytical coating bath of alkaline silicate in order.In these coating baths, first contains the 0.5g/l KOH aqueous solution; Second contains the 0.5g/lKOH aqueous solution and 4g/l tetrasilicic acid sodium; The 3rd contains the 0.5g/l KOH aqueous solution and 11g/l tetrasilicic acid sodium.The main drawback of this currently known methods is to use traditional unstable ionogen to follow with complex apparatus design and equipment layout.
Another known method (US, A, 5385662) can be plated to attrition resistant ceramic oxide covering on the aluminium alloy, and thickness is 50-150 μ, and with plasma chemical anodized coating method, used current density is at 5A/dm
2More than, electrolytical temperature reaches 15 ℃.The range of temperature that allows is very narrow to be had only ± and 2 ℃.This ionogen contains sodium phosphate aqueous solution and borate, also contains Neutral ammonium fluoride; Salt concn total in the solution is no more than 2M/l.Use this ionogen, can not form the coating (being no more than 7.5GPa) of high microhardness preset value on aluminium alloy, this is also shown by low terminal anode voltage (having only 250V).This ionogen also contains deleterious fluorochemical, handles the essential certain expense of this class fluorochemical.For obtaining the coating (up to 20GPa) of high rigidity, suggestion is added the sodium aluminate of 0.1M and the water glass of 0.1M (the pH value of this solution is 10-12) again with 100 times of aforesaid ionogen dilute with waters.Equally, the main drawback of this method is the electrolytical poor stability of water glass.The solubility of sodium aluminate in water is also low, and this just causes the in uneven thickness of oxide covering, and forms the settling that is difficult to remove on stainless steel coating bath wall.
Known (US, A, 5275713) disclosed method is, solid-state corrosion-resistant coating is applied on aluminium and the alloy product thereof, in the electrolyte solution that contains alkalimetal silicate, hydrogen peroxide and low amount of fluorinated hydrogen, alkali metal hydroxide and metal oxide (for example molybdenum oxide).The pH value of this solution is 11.2-11.8.Positive potential is sent to product by the direct current or the pulse power.First 1-60 is in second, and voltage is risen to 240-260V, just increases to 380-420V reposefully above (depending on needed coat-thickness) voltage after ensuing 1-20 minute.The introducing hydrogen peroxide is stored into the speed that helps the growth of raising oxide covering in the ionogen as the holder of oxygen, and the oxide covering of metal improves its hardness in the spark discharge zone by strengthening.
Yet the shortcoming of this method is to contain fluorochemical and heavy metallic salt in the ionogen.This heavy metallic salt also has bad influence to electrolytical wearing quality and stability, because heavy metal ion is a catalyzer, thereby quickens the decomposition of hydrogen peroxide in the solution widely.In first several seconds of present method, realized " voltage fluctuation ", thereby the cycle that makes pre-spark oxide covering, slightly some was shortened in addition because be under relatively low current density, finish (be no more than 15A/dm
2), therefore in fact to the not influence of performance of coating.This method is used to plate thin oxide film (near 30 μ), and this thin oxide film has good cohesiveness to substrate all the time.
Be with pulsed anode and/or anode-cathode mode electric current the solid-state ceramic oxide covering to be plated on the articles made of aluminium alloy extremely with industrial frequency with the plasma electrolysis oxidation coating similar in appearance to method of the present invention (RU, Cl, 2070622).The cleaning that use is made up of alkali metal hydroxide, silicate and alkali metal pyrophosphate, environmental protection aqueous electrolyte.P
2O
7 -4The silicate solutions of pyrophosphate ions stable colloid, and the spark in the oxide compound plasma chemical is synthetic dissociates in the approach and all plays the activatory effect in the lip-deep electrolytical negatively charged ion complexing electrochemistry polycondensation process of sparkless.These electrolytical characteristics are stability high (reaching 400Ah/l), and its capacity can be adjusted in use.The shortcoming of this currently known methods is the energy consumption height of the relatively low and commercial run of the formation speed of oxide covering.
Of the present invention open
Main purpose of the present invention is a quality of the cohesive strength and the microhardness of coating of substrate being improved ceramic oxide covering by improving.Another object of the present invention is the energy consumption that does not increase technology by strengthening the plasma chemical building-up reactions to improve the formation speed of oxide covering.A purpose again of technology of the present invention be utilize high stability and use in the adjustable ionogen of capacity guarantee that the quality of the oxide covering that obtained surpasses the relative very long time cycle.A further object of the invention is to utilize the simple and reliable equipment of minimum basic device and the cleaning of being made up of cheap, abundant composition, the cost that the environmental protection ionogen reduces oxide covering technology.
Described these purposes reach with the oxide covering that the anode-cathode mode is finished articles made of aluminium alloy with the alternating-current of 50-60 hertz in 15-50 ℃ alkaline electrolyte.In the starting stage of technology, with oxide covering with 160-180A/dm
2Current density carry out 5-90 second, current density is reduced to best 3-30A/dm then
2, therefore basic oxide covering technology of establishing continues to lower energy consumption till producing required coat-thickness in spontaneous mode.Alkaline electrolyte is that the alkali metal hydroxide of 1-5g/l, the alkalimetal silicate of 2-15g/l, the alkali metal pyrophosphate of 2-20g/l and the superoxide of 2-7g/l (are pressed H
2O
2-30%) the aqueous solution.
Spontaneous energy minimizing mode is exactly to set up initial polarizing current, does not have the online adjusting of current parameters subsequently, up to the end of oxide covering process.Because resistance raises with the growth of coating, for spark discharge continuously, need increase the potential difference between the electrode gradually.On just oxidized surface the spark discharge time reduce gradually but become stronger and " burning " longer.Therefore, in the process that reduces energy, voltage is level and smooth and spontaneously increase the level and smooth and spontaneously landing of current values.And few 30-40% when the energy loss-rate of oxide covering begins when technology finishes.
Known oxide covering method (DE, Al, 4209733; US, A, 5385662; RU, Cl, 2070622) main drawback be that to finish the needed time of spark discharge mode long, this has just increased the time length of whole coating forming procedure successively.Spark discharge finish special trouble, also very complicated technically for the oxide covering of silicon-aluminum containing alloy.
By improve electrolytic electrical parameter for example current density (surpass 30A/dm
2) the oxide covering time is not shortened, this is because coating quality degenerates and the energy consumption of sharp increase technology.Depend on initial current density from the anodic oxidation transition stage to the time in spark discharge stage.
Outside the aforesaid method (US, A, 5275713) that relates to, attempt to create the oxide covering method of high current density and also once used (SU, Al, 1398472) in the past.But, under all known situations, all used anonizing, in other words, promptly anodic polarization pulsed current or galvanic current are delivered to electrode.
Practice shows that the anodized coating method often delays the formation (boehmite Bayer body) of oxyhydroxide thing phase.
In anode spark discharge process, be not enough to continue to change the spark discharge of lip-deep newly developed area, cold-zone the intermittence between the pulse sometimes.Discharge occurs in the place that spark has just extinguished, and at this moment, do not discharge for a long time in this zone, the formation of the mutually poroid bottom of oxyhydroxide thing in the regular chemical oxide covering mode occurs.These local insulation strengths are very high, even may make the oxide covering process be tending towards gradually stopping, although increased anode voltage significantly.
The oxyhydroxide thing has the removing performance mutually, so dissociating of causing at the coating place of the applying of negative pulse (anode-cathode process) is nonpolar in itself.Anode discharge cathodic discharge subsequently begins at the hypertonicity place of zone of oxidation.Thereby with the alternating current aluminum alloy anode that polarizes, promptly form the fine and close oxide covering of uniform thickness thereon.
The technical project that proposes in this method is used well afoot, the starting stage that is included in technology is sent to the heteropole pulse on the electrode with high current density, be included in also that the current density with the best is sent to the heteropole pulse on the electrode in the mode of being set up, this is different from known the whole bag of tricks significantly.
Anode effect by the strong micro-arc discharge that takes place with the high current density value at the oxide covering initial stage obtains makes base metal and oxide film form intensive and mixes, and this has just strengthened the mutual diffusion of substrate and coating, therefore helps to improve its cohesive strength.Interface analysis between substrate and the coating demonstrates a fuzzy bond regions, and the formation of the spreading area of an expansion is described.In the short like this timed interval, nonproductive power consumption is minimum, and the variation of electrolyte temperature is very little in the coating bath.
Finish and set up the time that the spark discharge mode is spent, final just total oxide covering time, be reduced 10-25%.
The definite value of current density and oxide covering process persistent value have been tested and have been examined.The current density 160-180A/dm of starting stage
2Determine with the maximum oxide covering rate conditions of selected ionogen composition by aluminium.Time length starting stage of every kind of alloy all is special the selection, and still, the time increases to and can not cause any obvious variation of coating quality more than 90 seconds, but can cause higher power consumption.
In order to obtain uniform oxide covering, particularly on complex-shaped product surface, obtain uniform oxide covering, in the formation stage of oxide covering process, help the one after the other of anode-cathode process and cathodic process, in alternately, only cathode pulse is sent to product, therefore, there is the activation of increase on coated surface.In this case, power supply is equipped with and is used for mode round-robin unit, this element connects in turn or cut off anode-cathode or the negative electrode mode is used for adjusting its time length, and the time length of transmitting the anode-cathode pulse is 5-30 second, and the time length of transmission cathode pulse is 1-10 second.The current density of cathode pulse is the 5-25% of current density in the anode-cathode mode process in the negative electrode mode process.Anode-cathode and negative electrode mode alternately help to produce finer and close, hole even coating thickness still less by turns.
Diagram shows among Fig. 1-4 use the example and the time sequence thereof of the process current pulse shapes of various different electrolysis modes.
When Fig. 1 has illustrated by AC sine wave electric current acquisition polarization, the current shape in the anode-cathode mode.
Fig. 2 has illustrated when only obtaining polarization by anodic current, the current shape in the anode mode.
Fig. 3 has illustrated when only obtaining polarization by cathodic current, the current shape in the negative electrode mode.
Fig. 4 illustrated when by turns alternately (cycle in accordance with regulations) alternating current polarization and pure negative electrode asymmetric-when carrying out between the amplitude, the current shape in anode-cathode mode and the cathodic polarization, wherein:
Current amplitude in the A-anode-cathode cycle;
The current amplitude of (cathodic polarization) in the a-negative electrode mode
a＝0.05-0.25；
T
AcThe time that-anode-cathode the cycle continues, T
Ac=5-30 second;
T
cThe time that-cathode deposition period continues, T
c=1-10 second.
Attempt in ionogen, to have carried out studying (US, A, 5275713 by the numerical digit investigators as the source of Chemical bond oxygen with superoxide; US, A, 5069763; SU, Al, 1767094).Problem is the unstable of solution, because dissociating of superoxide improved widely under the influence of alkali, heat, light etc.
According to the present invention, superoxide adds in the known ionogen composition, makes new composition produce new features.The alkali metal pyrophosphate (bigger amount) and the alkalimetal silicate (less amount) that are present in the ionogen composition are good hydrogen peroxide-based oxidation stabilizer.
Although pyrophosphate salt has than other phosphoric acid salt Na for example solution
2HPO
4Higher pH value, H
2O
2Stabilising effect in ionogen is well beyond the effect that can show.After the ionogen of preparation keeps 10 days, H
2O
2Do not dissociate.This can be applied new ionogen composition in industrial production.
The peroxidation agent is introduced in alkaline pyrophosphate salt-silicate ionogen, the coating quality of electrolytic process and formation is all had good influence.
Hydrogen peroxide is the source of OH free radical and oxygen simultaneously.Oxygen moves to come out to having the H of dissociating from ionogen
2O
2Electrode surface diffusion causes on the coating product surface thermochemistry plasma reaction strong.The formation speed of zone of oxidation increases 10-25%.By improving the alumina content in its high temperature α phase phase component, microhardness of coating has also strengthened.
The singularity of oxide covering process is the increase associated that the unbound electron in the solution is caught by the peroxidation negatively charged ion in the new ionogen, and is certainly, also relevant with the rising that enters the positive ion energy in the solution owing to discharge.The result of this effect has more strengthened the polymerization of pyrophosphate salt and silicate.In the solution polycondensation chain begin cause that insulation layer fully forms on the electrode, thereby cause and understand increasing of ionization voltage, and cause the rising of coating microhardness successively.
At last, the oxide system of various inorganic polymers and aluminium forms the structure that interpenetrates and react to each other, and this structure has caused the elasticity of coating and the ability of shock resistance and resistance to shock loads.
In the electrolyte ingredient, the threshold value of each component concentration determines by experiment, and the component concentration value is lower than its threshold value explanation, and this oxide covering process is used high current density continuously, and thus obtained coating is uneven, and the hole of expansion is arranged at the edge of product.When improving the component concentration value and making it surpass threshold value, cause the thick coating, crisp and nonelastic of acquisition.
In these superoxide, utilizable is hydrogen peroxide and/or alkalimetal oxide (Na
2O
2, K
2O
2, Li
2O
2), or alkali-metal peroxide-solvated compounds (peroxidation phosphoric acid salt, peroxidation carbonate, peroxidation borate or the like).
The present invention illustrates with example given below and chart.Diameter is the D16 aluminium alloy (AlCu of 200mm
4Mg
2) disk, thickness is 20mm, is machined into predetermined size, must be through oxide covering (top coat 7.5dm
2).This disk is put into 600 liters energising coating bath, and this coating bath is one counter-electrode, and an anastomosing compressor makes air bubble by ionogen.Used ionogen is the solution that distilled water and 2g/l potassium hydroxide, 3g/l water glass, 4g/l trisodium phosphate and 3g/l hydrogen peroxide (30%) form.Alternately be sent to disk with 125kW power supply, positive pole and cathode voltage pulse (anode-cathode mode), and the frequency of coating bath is 50 hertz.In first process, oxide covering is with 160A/dm in ten second
2Current density carry out, then, current density is reduced to 10A/dm
2, oxide covering is proceeded and is not had any other interference, till coat-thickness reaches 130 μ.Current density during this end of processing is 6A/dm
2Electrolytical temperature remains between 35-45 ℃.After oxide covering finished, disk washed in warm water and 80 ℃ of dryings.
In the oxide covering process, the amplitude of the current/voltage assembly of mean current in the circuit and anode and negative electrode is monitored.Its immediate current and magnitude of voltage give record with oscilloscope.Agglutinating intensity is measured (calculating with the power of taking apart the ratio with the coating damage area) with the skill of handling needles between oxide covering and the metal.The measurement of microhardness is to carry out (arithmetical av with 10 measuring results on the different oxide covering degree of depth is as the criterion) on the taper microsection.
Show various electrolysis modes in the table and at AlCu
4Mg
2On the alloy product with the contrast of the coating characteristic that known method and method of the present invention obtained.
As can be seen from the table, method of the present invention has following technology and advantage economically: accelerated 1.1-1.25 and doubly formed the wear-resistant coating that can contrast thickness, and need not increase power consumption.Simultaneously, microhardness of coating has on average increased 15%, to the cohesive strength of the substrate 15-20% that raise.
Therefore, method of the present invention makes the stable ceramic oxide coating on the aluminium alloy that is obtained have excellent protection and physical/mechanical properties.Coating has high microhardness and to base metal agglutinating high strength, this has just thoroughly got rid of the stripping layer delamination when using.
Used in the methods of the invention electrolytical characteristics are, except stability with do not have the environmental pollution, and also not chloride, fluorine, ammonia or heavy metallic salt.
Method of the present invention can be carried out with simple and reliable processing unit, uses the industrial frequency alternating-current, has minimum running cost.
Industrial applicibility
Method of the present invention is applicable to the piston that is operated in the internal combustion engine in the abrasion and corrosion environment And cylinder body, pump and compressor part, hydraulic pressure and pneumatic part of appliance, bearing, prevention and control Adopt wear-resistant coating on the articles made of aluminium alloy such as valve, radiator, heat exchanger.
Table
| Composition of electrolyte, electrolysis mode, coating and oxide covering process characteristic | Known method (DE 4209733) | Known method (RU 2070622) | Method of the present invention |
| 1. composition of electrolyte: potassium hydroxide g/l sodium metasilicate g/l sodium pyrophosphate g/l hydrogen peroxide (30%) ml/l distilled water l | 2 9 - - ＜1 | 1 2 3 - ＜1 | 2 3 4 3 ＜1 |
| 2. form the mode of coating: cathode voltage amplitude V current density (anode and the negative electrode) A/dm when the anode voltage amplitude V process when process finishes finishes2-initial period-generation phase electrolyte temperature ℃ oxide covering time minute | 690 300 - 6 30 180 | 720 350 - 8 40 150 | 780 320 160 106 40 135 |
| 3. coating characteristic: oxide covering thickness μ microhardness Gpa is to the adhesion strength Mpa of substrate | 100 16.0 297 | 130 16.4 309 | 130 18.6 358 |
| 4. process characteristic: unit can need kWhdm-2/ μ freeze thaw stability Ah/l | 0.090 30-90 | 0.085 180-400 | 0.080 150-300 |
Claims (4)
1. on articles made of aluminium alloy, obtain the method for supercoat; when this method comprises 15-50 ℃, in alkaline electrolyte, carry out the anode-cathode oxide covering, it is characterized in that with 50-60 hz AC electricity; in the starting stage of process, oxide covering is with current density 160-180A/dm
2Carry out 5-90 second, current density reduces to 3-30A/dm then
2, continue this process in the mode that reduces required electric energy gradually, till obtaining needed coat-thickness.
2. according to the method for claim 1, wherein hocket and carry out in the mode that reduces the required electric energy of oxide covering gradually with anode-cathode or negative electrode mode, the time length of anode-cathode pulse output is 5-30 second, and the time length of cathode pulse output is 1-10 second, wherein, the current density with the cathode pulse of negative electrode mode is with the anode of anode-cathode mode and the 5-25% of pulse cathode current density.
3. according to the method for claim 1 or 2, wherein ionogen is that alkali metal hydroxide 1-5g/l, alkalimetal silicate 2-15g/l, alkali metal pyrophosphate 2-20g/l and peroxidase 12-7g/l (press H
2O
2-30%) the aqueous solution.
4. according to the method for claim 3, wherein superoxide is hydrogen peroxide and/or alkali metal peroxide or alkali-metal peroxide solvate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182480 CN1276840A (en) | 1997-12-17 | 1997-12-17 | Method for producing hard protection coatings on articles made of aluminium alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182480 CN1276840A (en) | 1997-12-17 | 1997-12-17 | Method for producing hard protection coatings on articles made of aluminium alloy |
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| CN1276840A true CN1276840A (en) | 2000-12-13 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316068C (en) * | 2004-03-11 | 2007-05-16 | 上海交通大学 | Preparation process for anode oxidation thick film of aluminium copper alloy |
| CN100450769C (en) * | 2003-03-25 | 2009-01-14 | 奥利梅克斯集团公司 | Composite article comprising a ceramic coating |
| CN1769526B (en) * | 2005-12-02 | 2010-08-25 | 中国科学院物理研究所 | Method and device for internal wall ceramic treatment of steel and iron pipe casting |
| CN101605929B (en) * | 2006-09-27 | 2011-11-09 | Zypro株式会社 | Ceramic coated metal material and production method thereof |
| CN102497892A (en) * | 2009-06-02 | 2012-06-13 | Aap生物材料有限公司 | Osteosynthesis with nano-silver |
| CN101040066B (en) * | 2004-07-23 | 2012-09-26 | 坎梅陶尔股份有限公司 | Method for producing a hard coating with high corrosion resistance on articles made of anodizable metals or alloys |
-
1997
- 1997-12-17 CN CN 97182480 patent/CN1276840A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450769C (en) * | 2003-03-25 | 2009-01-14 | 奥利梅克斯集团公司 | Composite article comprising a ceramic coating |
| CN1316068C (en) * | 2004-03-11 | 2007-05-16 | 上海交通大学 | Preparation process for anode oxidation thick film of aluminium copper alloy |
| CN101040066B (en) * | 2004-07-23 | 2012-09-26 | 坎梅陶尔股份有限公司 | Method for producing a hard coating with high corrosion resistance on articles made of anodizable metals or alloys |
| CN1769526B (en) * | 2005-12-02 | 2010-08-25 | 中国科学院物理研究所 | Method and device for internal wall ceramic treatment of steel and iron pipe casting |
| CN101605929B (en) * | 2006-09-27 | 2011-11-09 | Zypro株式会社 | Ceramic coated metal material and production method thereof |
| CN102497892A (en) * | 2009-06-02 | 2012-06-13 | Aap生物材料有限公司 | Osteosynthesis with nano-silver |
| US8652645B2 (en) | 2009-06-02 | 2014-02-18 | Aap Biomaterials Gmbh | Osteosynthesis with nano-silver |
| CN102497892B (en) * | 2009-06-02 | 2015-11-25 | Aap培植股份公司 | The bone adopting nanometer silver to carry out engages |
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