CN103215584A - Surface treatment method of rear-earth magnesium alloy casting product - Google Patents
Surface treatment method of rear-earth magnesium alloy casting product Download PDFInfo
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Abstract
The invention relates to a surface treatment method of a rear-earth magnesium alloy casting product. The surface treatment method sequentially comprises the following steps of: immersing the rear-earth magnesium alloy casting product in 0.02mol/L-0.12mol/L of cerium sulfate aqueous solution in an ultrasonic precipitating-crystallizing device after carrying out oil-removing and impurity-removing pre-treatment onto the rear-earth magnesium alloy casting product; adding a magnesium hydroxide solution to regulate the pH value to 8-11; adding hydrogen peroxide to generate cerium hydroxide, wherein the mass percentage concentration of the hydrogen peroxide is 5%-20%, and the weight ratio of the using amount of the hydrogen peroxide to the cerium hydroxide aqueous solution is (1-5):100; generating a precipitated and crystallized compact tetravalent cerium protective film on the surface of the rear-earth magnesium alloy casting product by the cerium hydroxide under the ultrasonic action; and getting out the rear-earth magnesium alloy casting product from the precipitating-crystallizing device, and drying at 120 DEG C to 240 DEG C after water-washing to obtain the rear-earth magnesium alloy casting product coated with cerium dioxide on the surface. The surface treatment method of the rear-earth magnesium alloy casting product can be used for forming a compact tetravalent cerium protective film on the surface of the rear-earth magnesium alloy casting product; moreover, the process is simple and reliable.
Description
Technical field
The present invention relates to a kind of surface treatment method of magnesium-rare earth foundry goods goods, belong to rare earth magnesium alloy material manufacturing technology field.
Background technology
Magnesium alloy becomes the preferred material of equipment manufacture lightweight development with numerous advantages such as light weight, structure properties are excellent and be easy to reclaim, the particularly extensive application of automobile component, telecommunication products makes the development of this brand-new material present very optimistic prospect to the demand that light, thin, short, little direction develops.Along with the breakthrough of magnesium alloy utilisation technology, the consumption of global magnesium alloy will increase fast with annual 20% amplitude.
From the eighties of last century later stage eighties so far, along with the application of magnesium alloy in the Aeronautics and Astronautics field, rare earth element is applied to Mg Alloy Research and comes into one's own again, magnesium-rare earth can overcome the shortcoming that traditional magnesium alloy materials exists, and satisfies modern industry and realizes that lightweight, energy-saving and environmental protection, safe, comfortable, Sustainable development etc. are to material institute requirement.Rare earth is being brought into play more and more important effect as main alloying element or micro alloying element in the magnesium alloy research field.
Because the chemical property of magnesium is very active, standard potential is very negative, easily oxidation in air, and the heat that oxidizing reaction is emitted can not in time be scattered and disappeared and can be burnt, cause the erosion resistance and the anti-oxidant incendivity of magnesium alloy very poor, in corrosive medium, be easy to take place serious corrosion.The PBR of the oxide M gO of magnesium (Pilling～Bedworth Ration; an important criterion of the oxide film integrity that forms; being defined as oxide compound and the volume ratio that forms the metal that this oxide compound consumes) value is 0. 81; surface film in MAGNESIUM METAL or magnesium alloy formation is loose porous; poor to the matrix protective capability, be difficult to satisfy the condition of using at corrosive environment.Therefore, up to now, the application of magnesium alloy materials is still very limited, and the corrosion and protection problem of magnesium alloy more and more is subject to people's attention.In order to realize the large-scale industrial application of magnesium alloy, must research and develop magnesium alloy surface treatment, magnesium alloy component is effectively protected.
The forms of corrosion of magnesium alloy has two kinds of situations usually: the one, and the corrosion in general environment claims " general corrosion " or " environmental corrosion ", also claims " chemical corrosion ", the 2nd, " galvanic corrosion " that produces under the galvanic cell environment.In corrosive medium, the magnesium matrix that chemically reactive is very high is easy to form corrosion cell with alloying element and impurity element, brings out galvanic corrosion.In addition, loose, the porous of the spontaneous corrosion product of magnesium alloy, protective capability is poor, causes the corrosion reaction of magnesium alloy can sustainable development.Mainly concentrate on aspect following three at the research-and-development activity that solves corrosion resistance of magnesium alloy and anti-oxidant incendivity problem:
(1) alloying process: adopt pure magnesium alloy chemical technology to improve erosion resistance and anti-oxidant combustionproperty.Alloying improves erosion resistance and the anti-oxidant incendivity and the flame retardant resistance basic thought of magnesium alloy, in magnesium alloy, add an amount of suboxide current potential and the big alloying element of PBR value, change the oxide film structure on alloy liquid surface, the complex oxide film that loose originally magnesium oxide films is changed into a kind of densification can improve performance.Representational solution is to add the performance that the metallic elements such as rare earth element with erosion resistance and anti-oxidant incendivity and flame retardant resistance can significantly improve magnesium alloy in magnesium alloy.But, adopt alloying process to improve the erosion resistance of magnesium alloy and the method for anti-oxidant incendivity and flame retardant resistance, still exist magnesium alloy that the shortcoming of galvanic corrosion easily takes place.By alloying with adopt high-purity magnesium alloy can improve the erosion resistance and the anti-oxidant combustionproperty of magnesium alloy, very limited to the effect of galvanic corrosion, because magnesium all is anode with respect to nearly all other metal.And by alloying with adopt high purity alloys to improve corrodibility and flame retardant resistance, influenced applying of magnesium alloy because the complicacy of technology has increased production cost.Therefore, the etching problem that how to solve Mg alloy castings has just become the key issue of a decision magnesium alloy application prospect.
(2) reasonably design and galvanic protection: in order to solve the galvanic corrosion problem of Mg alloy castings; reduce or avoid galvanic corrosion in employing reasonable method such as Mg alloy castings design, syndeton and assembling modes, adopt the method for galvanic protection to improve simultaneously.Galvanic protection is a kind ofly to be used for preventing that metal is in dielectric medium (media such as seawater, fresh water and soil) corrosive electro-chemical protection technology; the ultimate principle of this technology is that protected metallic surface is applied certain galvanic current; make it produce cathodic polarization; when the current potential of metal was defeated by a certain potential value, the corrosive anodic dissolution processes will be effectively suppressed.According to the mode difference that cathodic current is provided, galvanic protection is divided into two kinds of sacrificial anode protection and impressed current methods again, 1. sacrificial anode protection: the metal that a kind of current potential is more negative (as magnesium, aluminium, zinc etc.) electrically connects with protected metallic structures, continuous dissolving consumption by electronegative metals or alloy, provide protective current to protected object, make metallic structures obtain protection; 2. impressed current method: the external communication electricity is transformed into low-voltage DC, protective current is passed to protected metallic structures, thereby corrosion is inhibited by supplementary anode.No matter be sacrificial anode protection or impressed current method, its effective and reasonable design is used can obtain the excellent protection effect.
(3) surface treatment or coating process technology: adopt surface treatment or effective coating process technology on magnesium alloy, to apply protective coating.Magnesium alloy is carried out surface modification and surface treatment, apply certain coating thereon, improve the surface property of magnesium alloy, as wear resisting property, decorate properties, especially erosion resistance and anti-oxidant combustionproperty, being the important research field that magnesium alloy is used, also is one of the easiest popularization magnesium alloy key technologies for application.R﹠D work is carried out in following three aspects that mainly contain of magnesium alloy surface treatment: 1. phosphate conversion coating: the independent protective of prepared phosphate coating and be lower than chromate conversion coatings slightly as the performance of paint substrate; 2. anodized coating: mainly contained spark anodized coating and sparkless anodized coating, coatings prepared is uniform and smooth; 3. metallic coating: mainly adopt the composite deposite technology, coating can reach the above hardness of hour film substrate bond strength in salt spray corrosion test.But,,, can quicken the corrosion of matrix on the contrary if coating has perforation because the electropotential of coated metal is far longer than magnesium.And such complex process, cost are higher, and only are suitable for the processing of simple shape part.
Therefore, research and development are handled compound formation that precipitation obtains at Mg alloy surface and are had in the chemical treatment method of Protective Film of Magnesium Alloy and technology particularly important and have application and popularization value widely.
Summary of the invention
The objective of the invention is to, overcome problems of the prior art, a kind of surface treatment method of magnesium-rare earth foundry goods goods is provided, can be at the ceric protective membrane of magnesium-rare earth foundry goods product surface densification, and simple and reliable process.
For solving above technical problem, the surface treatment method of a kind of magnesium-rare earth foundry goods goods of the present invention, in turn include the following steps: the pre-treatment of ⑴ magnesium-rare earth foundry goods product surface: will carry out oil removing and mechanical removal of impurities processing after magnesium-rare earth foundry goods goods process mechanical workout, the thermal treatment, adopt the magnesium hydroxide alkaline aqueous solution of pH8～11 to remove the grease of magnesium-rare earth cast(ing) surface then, again the magnesium-rare earth foundry goods is immersed in 1～5min in the aqueous sulfuric acid of pH1～5; ⑵ prepare surface treatment liquid: the cerous sulfate powder dissolution is obtained the cerous sulfate aqueous solution that the cerous sulfate volumetric molar concentration is 0.02mol/L～0.12mol/L in water; ⑶ the finishing of magnesium-rare earth foundry goods goods: the cerous sulfate aqueous solution of step ⑵ is injected the ultrasound precipitation crystallizer, the magnesium-rare earth foundry goods goods that again step ⑴ obtained place the cerous sulfate aqueous solution of described ultrasound precipitation crystallizer, and the quality of the described cerous sulfate aqueous solution is 5～20 times of described magnesium-rare earth foundry goods quality of item; In the cerous sulfate aqueous solution, add magnesium hydroxide aqueous solution then the pH value is transferred to 8～11, then hydrogen peroxide generation ceric hydroxide is added in the back in the cerous sulfate aqueous solution, the mass percentage concentration of described hydrogen peroxide is 5%～20%, and the mass ratio of the hydrogen peroxide usage quantity and the described cerous sulfate aqueous solution is (1～5): 100; The temperature of the cerous sulfate aqueous solution described in the above process is controlled at 20 ℃～60 ℃, and the ultrasonic frequency of described ultrasound precipitation crystallizer is 19kHz～40kHz, and ultrasonication intensity is 2.0 W/cm2～5.0W/cm2, and the operating time is 10min～120min; Described ceric hydroxide produces the ceric protective membrane of precipitated crystal densification at magnesium-rare earth foundry goods product surface under ultrasonication; ⑷ the aftertreatment of magnesium-rare earth foundry goods goods: the magnesium-rare earth foundry goods goods that step ⑶ is obtained take out from described ultrasound precipitation crystallizer, it is dry under 120 ℃～240 ℃ to wash the back, obtains the magnesium-rare earth foundry goods goods that the surface is coated with cerium dioxide.
With respect to prior art; the present invention has obtained following beneficial effect: the present invention drops into magnesium hydroxide successively with magnesium-rare earth foundry goods goods and regulates the pH value in the cerous sulfate aqueous solution; add hydrogen peroxide then and produce the ceric hydroxide precipitated crystal; use pH regulation and control-hydrogen peroxide oxidation-precipitated crystal film forming protection coupling technique and carry out finishing, through further obtaining the magnesium-rare earth finished product that finishing is handled after washing, the drying treatment on the surface of magnesium alloy product.Utilize cerous sulfate that precipitin reaction takes place under alkaline condition and generate cerous hydroxide; cerous hydroxide is insoluble in water; the valency of cerium is upgraded to+4 valencys under hydrogen peroxide oxidation, is insoluble in water more, obtains the film forming protection of precipitated crystal surface through supersound process, drying process.The solution of the present invention also has following advantage:
⑴ make full use of the MAGNESIUM METAL magnesium hydroxide that the generates characteristics for alkalescence that react in the aqueous solution, when the magnesium-rare earth goods place the aqueous solution of cerous sulfate, near magnesium-rare earth goods and cerous sulfate aqueous solution interface, generate one deck basic solution, rare earth cerium metal ion generates the cerous hydroxide precipitation under alkaline condition, obtain littler ceric hydroxide of solubility product or cerium dioxide hydrate after the cerous hydroxide precipitation is oxidized, crystallization is to the surface of magnesium-rare earth goods.
⑵ make full use of the characteristic of the protective membrane stable in properties that the precipitated crystal of ceric hydroxide generates; become cerium dioxide after the ceric hydroxide dehydration; cerium dioxide is white or white-yellowish solid; be insoluble in water; it under normal temperature, the normal pressure the most stable compound of cerium; be insoluble to general bronsted lowry acids and bases bronsted lowry, the very little sedimentation equilibrium constant of its hydrate solubility product is solubility product Ksp=4 * 10
-51, the pH in the time of can precipitating fully is between 0.7～1.0, and the ion of other trivalent lanthanon will be just can be settled out in 6～8 o'clock at pH.
⑶ make full use of cerous hydroxide oxidizing reaction generation ceric hydroxide take place easily, and solubility product Ksp=4 * 10 of the ceric hydroxide that generates
-51, solubility product Ksp=1.5 * 10 of cerous hydroxide
-20, the Ksp=1.8 of magnesium hydroxide * 10
-11(25 ℃), magnesium hydroxide are alkalescence, are heated to 350 ℃ and lose water generation magnesium oxide, and reaction can get magnesium hydroxide to magnesium oxide with water, and the solubleness of ceric hydroxide is more much smaller than the magnesium hydroxide.
⑷ make full use of ultrasonic technique and strengthen mass transfer process; improve the precipitated crystal process of ceric hydroxide simultaneously at the magnesium-rare earth product surface; further improve the bonding force of formation speed and the protective membrane and the magnesium alloy product of protective membrane, make the protective membrane densification of generation.The cavitation effect, mechanical effect and the heat effect that produce when utilizing ultrasonic wave to propagate in medium are improved the Surface Renewal of liquid-solid interface, liquid-solid material transfer under certain condition, speed in the raising process and efficient greatly.Ultrasonic wave is a kind of mechanical wave in the elastic medium, and ultrasonication is the process of utilizing ultrasonic vibrational energy to change structure, state, the function of material or quickening these changes.Ultrasonic applications has demonstrated many-sided superiority in sepn process.Ultrasonic isolating strengthening effect is derived from ultrasonic cavitation, ultrasound-enhancedly be meant that the small complex in the liquid phase is activated under the high intense ultrasonic wave effect of low frequency, it shows as the vibration of complex, growth, a series of dynamic processes such as contraction and collapse, around cavitation bubble, produce High Temperature High Pressure in the utmost point short period of time of cavitation bubble collapse, and produce with the microjet that intensive shockwave and speed are exceedingly fast, ultrasonic cavitation produces various additive effects in microenvironment, as the turbulence effect, the perturbation effect, interfacial effect and cavity effect etc., wherein turbulence effect can make the frictional belt attenuate, increases rate of mass transfer; The perturbation effect has been strengthened the micropore diffusion; It is long-pending that interfacial effect has increased mass transfer surfaces.Therefore, ultrasonic cavitation can be strengthened the rate of mass transfer and the efficient of sepn process on the whole.
⑸ make full use of the surface treatment method of pH regulator-chemical oxidation-precipitated crystal film forming-surface adsorption coupling technique, at Mg (OH)
2Precipitation crystallizes into ceric protective membrane under the ambient condition, and by regulating the feed composition and the content control surface treatment condition of surface treatment liquid, component and the Adjustable structure that obtains surface film saves, may command.Cerous hydroxide and magnesium hydroxide all have flame-retardant nature, because they have the effect of dilution and isolated combustionmaterial surface air (oxygen), it then is high temperature resistant material that magnesium hydroxide decomposes the activated magnesia solid that generates, and is attached to the combustiblematerials surface and further stops burning to be carried out.
⑹ the rare-earth conversion coatings thickness of this method preparation evenly, surface compact is good, good with matrix bond, has excellent erosion resistance and anti-oxidant combustionproperty, can solve the problem of magnesium alloy heavy corrosion in cooling fluid.And the treatment solution composition of preparation conversion film is simple, does not contain hexavalent chromium compound used in the traditional chemical conversion process, is the rare-earth conversion coatings of chromium-free environment-friendly.
Since its special shape of magnesium-rare earth goods and environmental restraint the application of process for treating surface such as differential arc oxidation, gaseous phase deposition, laser treatment, spray treatment, the chemical conversion membrane processing method can overcome above technical deficiency.Yet existing magnesium alloy conversion film technology is compared with the present invention and all had certain defective, and is serious as environmental pollution, the composite membrane rete is not fine and close, formula solution complicated component etc.
⑻ the present invention has overcome problems such as the easy cast properties that exists of magnesium-rare earth foundry goods goods is poor, the production cycle long, the pollution heavy, efficient is low, rare earth magnesium alloy material erosion resistance and anti-oxidant combustionproperty have been improved, to promoting China's lightweight structural material industrial upgrading and improving supporting with it advanced manufacturing technology level, satisfy lightweight requirements such as Aeronautics and Astronautics, weaponry and vehicle, machinery, electronics and have important reality and strategic importance, have clear and definite vast market prospect.
As preferred version of the present invention, described ultrasound precipitation crystallizer comprises precipitated crystal container and ultrasonic generator, and described precipitated crystal container is still formula, slot type or tube container.
As preferred version of the present invention, described ultrasonic generator is the combination of any or they in probe type ultrasonic wave producer, vibrator type ultrasonic generator or the vibration plate formula ultrasonic generator.
Embodiment
Embodiment one
The surface treatment method of a kind of magnesium-rare earth foundry goods goods of the present invention in turn includes the following steps:
⑴ magnesium-rare earth foundry goods product surface pre-treatment: will carry out oil removing and mechanical removal of impurities processing after magnesium-rare earth foundry goods goods process mechanical workout, the thermal treatment, adopting the pH value then is the grease that 8 magnesium hydroxide alkaline aqueous solution is removed the magnesium-rare earth cast(ing) surface, the magnesium-rare earth foundry goods is immersed in the pH value again and is 1min in 1 the aqueous sulfuric acid.
⑵ prepare surface treatment liquid: the cerous sulfate powder dissolution is obtained the cerous sulfate aqueous solution that the cerous sulfate volumetric molar concentration is 0.02mol/L in water.
⑶ the finishing of magnesium-rare earth foundry goods goods: the cerous sulfate aqueous solution of step ⑵ is injected the ultrasound precipitation crystallizer, and the ultrasound precipitation crystallizer comprises precipitated crystal container and ultrasonic generator, and the precipitated crystal container is a still formula container.Ultrasonic generator is the probe type ultrasonic wave producer.The magnesium-rare earth foundry goods goods that again step ⑴ obtained place the cerous sulfate aqueous solution of ultrasound precipitation crystallizer, and the quality of the cerous sulfate aqueous solution is 5 times of magnesium-rare earth foundry goods quality of item; In the cerous sulfate aqueous solution, add magnesium hydroxide aqueous solution then the pH value is transferred to 8, then hydrogen peroxide generation ceric hydroxide is added in the back in the cerous sulfate aqueous solution, the mass percentage concentration of hydrogen peroxide is 5%, and the mass ratio of the hydrogen peroxide usage quantity and the cerous sulfate aqueous solution is 1:100; The temperature of the cerous sulfate aqueous solution is controlled at 20 ℃ in the above process, and the ultrasonic frequency of ultrasound precipitation crystallizer is 19kHz, and ultrasonication intensity is 2.0 W/cm2, and the operating time is 10min; Ceric hydroxide produces the ceric protective membrane of precipitated crystal densification at magnesium-rare earth foundry goods product surface under ultrasonication.
⑷ the aftertreatment of magnesium-rare earth foundry goods goods: the magnesium-rare earth foundry goods goods that step ⑶ is obtained take out from the ultrasound precipitation crystallizer, and it is dry under 120 ℃ to wash the back, obtains the magnesium-rare earth foundry goods goods that the surface is coated with cerium dioxide.
Embodiment two
The surface treatment method of a kind of magnesium-rare earth foundry goods goods of the present invention in turn includes the following steps:
⑴ magnesium-rare earth foundry goods product surface pre-treatment: will carry out oil removing and mechanical removal of impurities processing after magnesium-rare earth foundry goods goods process mechanical workout, the thermal treatment, adopting the pH value then is the grease that 10 magnesium hydroxide alkaline aqueous solution is removed the magnesium-rare earth cast(ing) surface, the magnesium-rare earth foundry goods is immersed in p H value again and is 3min in 3 the aqueous sulfuric acid.
⑵ prepare surface treatment liquid: the cerous sulfate powder dissolution is obtained the cerous sulfate aqueous solution that the cerous sulfate volumetric molar concentration is 0.08mol/L in water.
⑶ the finishing of magnesium-rare earth foundry goods goods: the cerous sulfate aqueous solution of step ⑵ is injected the ultrasound precipitation crystallizer, and the ultrasound precipitation crystallizer comprises precipitated crystal container and ultrasonic generator, and the precipitated crystal container is the slot type container.Ultrasonic generator is the vibrator type ultrasonic generator.The magnesium-rare earth foundry goods goods that again step ⑴ obtained place the cerous sulfate aqueous solution of ultrasound precipitation crystallizer, and the quality of the cerous sulfate aqueous solution is 12 times of magnesium-rare earth foundry goods quality of item; In the cerous sulfate aqueous solution, add magnesium hydroxide aqueous solution then the pH value is transferred to 10, then hydrogen peroxide generation ceric hydroxide is added in the back in the cerous sulfate aqueous solution, the mass percentage concentration of hydrogen peroxide is 13%, and the mass ratio of the hydrogen peroxide usage quantity and the cerous sulfate aqueous solution is 3:100; The temperature of the cerous sulfate aqueous solution is controlled at 40 ℃ in the above process, and the ultrasonic frequency of ultrasound precipitation crystallizer is 30kHz, and ultrasonication intensity is 3.5W/cm2, and the operating time is 60min; Ceric hydroxide produces the ceric protective membrane of precipitated crystal densification at magnesium-rare earth foundry goods product surface under ultrasonication.
⑷ the aftertreatment of magnesium-rare earth foundry goods goods: the magnesium-rare earth foundry goods goods that step ⑶ is obtained take out from the ultrasound precipitation crystallizer, and it is dry under 180 ℃ to wash the back, obtains the magnesium-rare earth foundry goods goods that the surface is coated with cerium dioxide.
Embodiment three
The surface treatment method of a kind of magnesium-rare earth foundry goods goods of the present invention in turn includes the following steps:
⑴ magnesium-rare earth foundry goods product surface pre-treatment: will carry out oil removing and mechanical removal of impurities processing after magnesium-rare earth foundry goods goods process mechanical workout, the thermal treatment, adopting the pH value then is the grease that 11 magnesium hydroxide alkaline aqueous solution is removed the magnesium-rare earth cast(ing) surface, the magnesium-rare earth foundry goods is immersed in the pH value again and is 5min in 5 the aqueous sulfuric acid.
⑵ prepare surface treatment liquid: the cerous sulfate powder dissolution is obtained the cerous sulfate aqueous solution that the cerous sulfate volumetric molar concentration is 0.12mol/L in water.
⑶ the finishing of magnesium-rare earth foundry goods goods: the cerous sulfate aqueous solution of step ⑵ is injected the ultrasound precipitation crystallizer, and the ultrasound precipitation crystallizer comprises precipitated crystal container and ultrasonic generator, and the precipitated crystal container is a tube container.Ultrasonic generator is a vibration plate formula ultrasonic generator.The magnesium-rare earth foundry goods goods that again step ⑴ obtained place the cerous sulfate aqueous solution of ultrasound precipitation crystallizer, and the quality of the cerous sulfate aqueous solution is 20 times of magnesium-rare earth foundry goods quality of item; In the cerous sulfate aqueous solution, add magnesium hydroxide aqueous solution then the pH value is transferred to 11, then hydrogen peroxide generation ceric hydroxide is added in the back in the cerous sulfate aqueous solution, the mass percentage concentration of hydrogen peroxide is 20%, and the mass ratio of the hydrogen peroxide usage quantity and the cerous sulfate aqueous solution is 5:100; The temperature of the cerous sulfate aqueous solution is controlled at 60 ℃ in the above process, and the ultrasonic frequency of ultrasound precipitation crystallizer is 40kHz, and ultrasonication intensity is 5.0W/cm2, and the operating time is 120min; Ceric hydroxide produces the ceric protective membrane of precipitated crystal densification at magnesium-rare earth foundry goods product surface under ultrasonication.
⑷ the aftertreatment of magnesium-rare earth foundry goods goods: the magnesium-rare earth foundry goods goods that step ⑶ is obtained take out from the ultrasound precipitation crystallizer, and it is dry under 240 ℃ to wash the back, obtains the magnesium-rare earth foundry goods goods that the surface is coated with cerium dioxide.
The above only is the present invention's preferable possible embodiments, and is non-so limit to scope of patent protection of the present invention.In addition to the implementation, the present invention can also have other embodiments, can be any two kinds of combinations in probe type ultrasonic producer, vibrator type ultrasonic generator or the vibration plate formula ultrasonic generator as ultrasonic generator.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop in the protection domain of requirement of the present invention.
Claims (3)
1. the surface treatment method of magnesium-rare earth foundry goods goods, it is characterized in that, in turn include the following steps: the pre-treatment of ⑴ magnesium-rare earth foundry goods product surface: will carry out oil removing and mechanical removal of impurities processing after magnesium-rare earth foundry goods goods process mechanical workout, the thermal treatment, adopt the magnesium hydroxide alkaline aqueous solution of pH8～11 to remove the grease of magnesium-rare earth cast(ing) surface then, again the magnesium-rare earth foundry goods is immersed in 1～5min in the aqueous sulfuric acid of pH1～5; ⑵ prepare surface treatment liquid: the cerous sulfate powder dissolution is obtained the cerous sulfate aqueous solution that the cerous sulfate volumetric molar concentration is 0.02mol/L～0.12mol/L in water; ⑶ the finishing of magnesium-rare earth foundry goods goods: the cerous sulfate aqueous solution of step ⑵ is injected the ultrasound precipitation crystallizer, the magnesium-rare earth foundry goods goods that again step ⑴ obtained place the cerous sulfate aqueous solution of described ultrasound precipitation crystallizer, and the quality of the described cerous sulfate aqueous solution is 5～20 times of described magnesium-rare earth foundry goods quality of item; In the cerous sulfate aqueous solution, add magnesium hydroxide aqueous solution then the pH value is transferred to 8～11, then hydrogen peroxide generation ceric hydroxide is added in the back in the cerous sulfate aqueous solution, the mass percentage concentration of described hydrogen peroxide is 5%～20%, and the mass ratio of the hydrogen peroxide usage quantity and the described cerous sulfate aqueous solution is (1～5): 100; The temperature of the cerous sulfate aqueous solution described in the above process is controlled at 20 ℃～60 ℃, and the ultrasonic frequency of described ultrasound precipitation crystallizer is 19kHz～40kHz, and ultrasonication intensity is 2.0 W/cm2～5.0W/cm2, and the operating time is 10min～120min; Described ceric hydroxide produces the ceric protective membrane of precipitated crystal densification at magnesium-rare earth foundry goods product surface under ultrasonication; ⑷ the aftertreatment of magnesium-rare earth foundry goods goods: the magnesium-rare earth foundry goods goods that step ⑶ is obtained take out from described ultrasound precipitation crystallizer, it is dry under 120 ℃～240 ℃ to wash the back, obtains the magnesium-rare earth foundry goods goods that the surface is coated with cerium dioxide.
2. the surface treatment method of magnesium-rare earth foundry goods goods according to claim 1 is characterized in that: described ultrasound precipitation crystallizer comprises precipitated crystal container and ultrasonic generator, and described precipitated crystal container is still formula, slot type or tube container.
3. the surface treatment method of magnesium-rare earth foundry goods goods according to claim 2 is characterized in that: described ultrasonic generator is the combination of any or they in probe type ultrasonic wave producer, vibrator type ultrasonic generator or the vibration plate formula ultrasonic generator.
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| CN108584997B (en) * | 2018-07-11 | 2021-04-27 | 营口松辽镁业有限公司 | Preparation method of magnesium oxide powder for fireproof cable |
| CN110670054A (en) * | 2019-10-11 | 2020-01-10 | 青海民族大学 | Magnesium alloy surface cerate conversion repair film and preparation method thereof |
| CN110670054B (en) * | 2019-10-11 | 2021-06-29 | 青海民族大学 | Magnesium alloy surface cerate conversion repair film and preparation method thereof |
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