CN109457242A - Chrome-free tanning agent and its preparation method and application - Google Patents
Chrome-free tanning agent and its preparation method and application Download PDFInfo
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- CN109457242A CN109457242A CN201811558903.6A CN201811558903A CN109457242A CN 109457242 A CN109457242 A CN 109457242A CN 201811558903 A CN201811558903 A CN 201811558903A CN 109457242 A CN109457242 A CN 109457242A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
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Abstract
The present invention relates to a kind of chrome-free tanning agents and its preparation method and application.The pH of the chrome-free tanning agent is 1~4.5, and the chrome-free tanning agent includes: aqueous solvent and aluminum soluble salt, wherein by mass percentage, the mass concentration of the aluminum soluble salt is 0.05%~2%.Passivator of the invention can form passivation film on the surface of manganese metal, and the passivation film binding force is good, antiseptic property is excellent.The present invention also proposes a kind of preparation method of chrome-free tanning agent described above, it include: according to mass percent meter, 0.05~2% aluminium salt is added in aqueous solvent and stirring and dissolving obtains solution, the pH of solution is then adjusted to 1~4.5, obtains the chrome-free tanning agent.The invention also includes application of the chrome-free tanning agent of the preparation method preparation of chrome-free tanning agent described above or power chrome-free tanning agent described above in passive metal manganese.
Description
Technical field
The present invention relates to manganese metal anticorrosion fields, and in particular to a kind of chrome-free tanning agent and its preparation method and application.
Background technique
Manganese metal is as a kind of important metallic element, industrially using extensive, demand is big, to the hair of national economy
Exhibition has very important strategic importance, it has application in the various industries such as smelting iron and steel, construction industry, machinery and transport.Work
It is mainly electrolysis method that the method for manganese metal is produced in industry, but since the chemical potential of manganese metal is low, is just electrolysed the metal come out
Manganese surface is again very coarse, bigger with air contact area, therefore is easily oxidized and causes the corruption of manganese metal in air
Erosion, reduces the purity and mechanical performance of manganese metal.In order to ensure the commodity value and service performance of manganese metal, newly will be electrolysed out
Manganese metal to be passivated processing be a very important link.Passivation Treatment can form one layer of passivation on manganese metal surface
Film improves its corrosion resistance to ensure the storage and transport of manganese metal.Typical concentrations are come in industry for 3% potassium bichromate solution
Processing is passivated to manganese metal, not only simple process and low cost, tank liquor is stablized, and gained passivating film color is uniform, knot
Good with joint efforts, corrosion resistance is high, has good self-repairing capability.But Cr VI is severe toxicity and carcinogen, the passivation technology
A large amount of chromate waste water and waste liquid can be generated in the process, have serious harm to environment and human health.Due to environmental issue, mesh
Therefore the use that limitation chromating technique has all been give stricted orders by preceding many countries develops the passivator of novel environment friendly to replace chromium
Hydrochlorate has a very important significance the benign development of electrolytic manganese industry.
Currently, scientific worker is also in positive exploitation Novel electrolytic manganese chrome-free tanning agent.For example, patent
CN103805979A discloses one kind with phosphate, and cosolvent, corrosion inhibiter, brightener is the manganese metal chromium-free deactivation of principal component
Liquid has certain effect to the passivation of manganese metal.However, passivating solution can generate largely containing phosphor passivation due to the use of phosphoric acid
Waste liquid has certain harm to water body, while also be easy to causeing phosphorus content in metal manganese product exceeded.Patent CN103834941A
Disclose it is a kind of with molybdate for main passivator, triethanolamine and 1-hydroxy ethylidene-1,1-diphosphonic acid are the electrolytic manganese passivating liquid of complexing agent.
The corrosion resistance of the passivating solution treated manganese metal is close with the product after potassium bichromate passivation, but molybdate price ratio
It is more expensive, it is excessively high to will lead to cost after use, therefore do not utilize industrial application.Patent CN107034456A discloses one kind with silicon
Hydrochlorate is the metal Mn passivating liquid that film forming agent, hydrogen peroxide or potassium permanganate are oxidant.It does not need to wash after technique passivation,
It is dried at 60 DEG C half an hour, the product surface after passivating solution passivation is bright and has preferable corrosion resistance, but produces
Silicone content increases in product, can reduce the quality of Electrolytic Manganese Product to a certain degree.In conclusion existing manganese metal Chrome-free is blunt
Change technology, more or less exist phosphorus pollution, passivating solution is unstable, product quality is bad, does not have the drawbacks such as self-repairability, therefore,
It is badly in need of exploitation novel environment friendly, the chrome-free tanning agent product haveing excellent performance.
Summary of the invention
The object of the present invention is to provide a kind of chromium-free deactivations of the good manganese metal of good passivation effect, environmental protection, stability
Agent, to propose a kind of chrome-free tanning agent and its preparation method and application.
A kind of chrome-free tanning agent, which is characterized in that the pH of the chrome-free tanning agent is 1~4.5, the chrome-free tanning agent packet
It includes: aqueous solvent and aluminum soluble salt, wherein by mass percentage, the mass concentration of the aluminum soluble salt is 0.05%~
2%.
It further, further include hydrogen peroxide, the concentration of the hydrogen peroxide is 1~15ml/L.
Preferably, the aluminum soluble salt includes aluminum nitrate, aluminum sulfate, aluminium chloride, aluminium polychloride and polyaluminium sulfate
One of or it is a variety of.
It further, further include reinforcing agent, the mass ratio of the reinforcing agent and the aluminium salt is 0.01~0.5:1.
Preferably, the reinforcing agent includes soluble one or both of cerium salt and soluble molybdenum hydrochlorate.
Preferably, the soluble cerium salt includes one of cerous nitrate, cerous sulfate, cerium chloride and ceric sulfate or more
Kind.
Preferably, the soluble molybdenum hydrochlorate includes one in sodium molybdate, potassium molybdate, zinc molybdate, calcium molybdate and ammonium molybdate
Kind is a variety of.
The present invention also proposes a kind of preparation method of chrome-free tanning agent described above, comprising: according to mass percent meter,
0.05~2% aluminium salt is added in aqueous solvent and stirring and dissolving obtains solution, the pH of solution is then adjusted to 1~4.5, is obtained
To the chrome-free tanning agent.
The invention also includes the preparation method systems of chrome-free tanning agent described above or power chrome-free tanning agent described above
Application of the standby chrome-free tanning agent in passive metal manganese.
Further, the application includes: and manganese metal is immersed in the chrome-free tanning agent to be passivated 30 seconds~5 minutes.
The beneficial effect of the present invention compared with the prior art includes: chrome-free tanning agent, and the pH of the chrome-free tanning agent is 1~
4.5, the chrome-free tanning agent includes: aqueous solvent and aluminum soluble salt, wherein by mass percentage, the aluminum soluble salt
Mass concentration be 0.05%~2%.Contain H in acid passivation agent+, active manganese metal and hydrogen ion act on the surface of manganese
Generate suitable Mn2+Ion, due to H+Partial spent cause the pH on manganese metal surface to increase, lead to the Al in passivator3+Fastly
The Mn with manganese metal surface of speed2+Crystallization forms houghite passivation film, and the passivation film binding force is good, antiseptic property is excellent
It is good.Since passivator proposed by the invention is without containing the carcinogenic or toxic substance such as Cr VI, have the characteristics that it is environmental-friendly,
And compare with other metal inorganic salts, aluminium salt is cheap and easily-available, advantageously reduces cost, therefore before having good industrial application
Scape.
In addition, passivator adds a small amount of H in the present invention2O2It can promote needed for manganese metal surface in application process
Mn2+Generation.
In the present invention, used reinforcing agent is the one or two of soluble cerium salt and soluble molybdenum hydrochlorate, and purpose exists
In further promotion Al3+With Mn2+Form houghite passivation film.Wherein, soluble cerium salt, it is different based on atomic radius,
It can be with Al under acid condition3+、Mn2+Houghite passivation film is cooperatively formed together, and passivation film is more fine and close, be passivated
Performance more Optimality；In addition, passivator in application process, adds a small amount of H in the present invention2O2, in soluble cerium salt
Ce3+It in acid condition can be by H2O2Partial oxidation is Ce4+, when film layer is destroyed, the Ce that is stored in inoranic membrane4+Component can be with
It is acted on exposed fresh manganese metal, realizes the self-regeneration of passivation film；In addition, used soluble molybdenum salt,
In the solution mainly with MoO4 2-Anionic state preservation, work as Al3+、Mn2+、Ce3+Plasma is formed on electrolytic manganese metal surface
When houghite film layer, it is based on hydrotalcite compound plate layer electropositive feature, MoO4 2-Convenient for being intercalation between neatly slabstone layer,
Molybdenum salt precipitating is formed under conditions of manganese surface p H is relatively high, can further promote the compactness and assivation property of passivation film
Energy.
Detailed description of the invention
The features and advantages of the present invention will be more clearly understood by referring to the accompanying drawings, and attached drawing is schematically without that should manage
Solution is carries out any restrictions to the present invention, in the accompanying drawings:
Fig. 1 is the Tafel curve of the manganese metal after the manganese metal not being passivated and the prepared passivation of embodiment 5.Wherein: No. 1
Curve is the Tafel curve for the manganese metal not being passivated；No. 2 curves are that the Tafel of the manganese metal after the prepared passivation of embodiment 5 is bent
Line.
Fig. 2 is the scanning electron microscope (SEM) photograph for the manganese metal not being passivated.
Fig. 3 is the surface electron microscope of the manganese metal after the prepared passivation of embodiment 5.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
Electrolytic Manganese Product is prepared in diaphram tank with electrolysis method first: using stainless steel for cathode plate, and lead silver four closes
Golden plate is anode plate.Electrolytic condition: ammonium sulfate 120g/L, manganese sulfate 76.9g/L, the catholyte of selenium dioxide 0.05g/L, cathode
Liquid pH is about 6.8~7.0, current density 350A/m2, 38 DEG C of electrolysis temperature, electrolysis time 1.5h, electrolytic manganese production is prepared
Product, prepared electrolysis manganese product is for subsequent Inactivation experiment and is passivated a layer performance evaluation.
The preparation of passivator: by 3g aluminum nitrate, 5mLH2O2(30%) it is added in 1L water and is stirred dissolution, is then added
Solution is adjusted to pH=3.5 by sulfuric acid, and the chrome-free tanning agent (mass concentration of aluminum nitrate for electrolytic manganese metal surface treatment is made
About 0.3%).
The pH of the chrome-free tanning agent is 1~4.5, and the chrome-free tanning agent includes: 1L water, 3g aluminum nitrate and 5mLH2O2
(30%), wherein by mass percentage, the mass concentration of the aluminum nitrate is about 0.3%.
The passivation of electrolysis manganese product and performance detection: the chrome-free tanning agent of configuration is placed in deactivation slot, has been rinsed with clear water
At the cathode plate surface of electrolysis, then cathode plate is put into deactivation slot, chrome-free tanning agent is made to submerge cathode plate surface, passivation 1
It is taken out after minute and uses distilled water flushing, drying, the metal manganese product after being passivated.Electricity is carried out to the metal manganese product being passivated
Chemical property test, the results showed that, corrosion current is 2.020 × 10-9A/cm2。
Embodiment 2:
The preparation of Electrolytic Manganese Product is the same as embodiment 1.
The preparation of passivator: 3g aluminum nitrate being added in 1L water and is stirred dissolution, and sulfuric acid is then added by solution tune
To pH=3.5, the chrome-free tanning agent for electrolytic manganese metal surface treatment is made (mass concentration of aluminum nitrate is about 0.3%).
The pH of the chrome-free tanning agent is 3.5, and the chrome-free tanning agent includes 3g aluminum nitrate and 1L water；Wherein, by quality
Percentages, the mass concentration of the aluminum nitrate are about 0.3%.
The passivation of electrolysis manganese product and performance detection: the chrome-free tanning agent of configuration is placed in deactivation slot, has been rinsed with clear water
At the cathode plate surface of electrolysis, then cathode plate is put into deactivation slot, chrome-free tanning agent is made to submerge cathode plate surface, passivation 1
It is taken out after minute and uses distilled water flushing, drying, the metal manganese product after being passivated.Electricity is carried out to the metal manganese product being passivated
Chemical property test, the results showed that, corrosion current is 9.521 × 10-9A/cm2。
Embodiment 3:
The preparation of Electrolytic Manganese Product is the same as embodiment 1.
The preparation of passivator: by 3g aluminum nitrate, 0.3g cerous nitrate, 5mLH2O2(30%) be added in 1L water be stirred it is molten
Solution is then added sulfuric acid for solution and is adjusted to pH=3.5, the chrome-free tanning agent for electrolytic manganese metal surface treatment is made.
The pH of the chrome-free tanning agent is 3.5, and the chrome-free tanning agent includes 3g aluminum nitrate, 0.3g cerous nitrate, 5mLH2O2
(30%) and 1L water；Wherein, by mass percentage, the mass concentration of the aluminum nitrate is about 0.3%, the matter of the cerous nitrate
Measuring concentration is about 0.03%.
The passivation of electrolysis manganese product and performance detection: chrome-free tanning agent is placed in deactivation slot, is rinsed with clear water and is completed electrolysis
Cathode plate surface, then cathode plate is put into deactivation slot, make chrome-free tanning agent submerge cathode plate surface, passivation 1 minute after
It takes out and uses distilled water flushing, drying, the metal manganese product after being passivated.Electrochemistry is carried out to the metal manganese product being passivated
It can test, the results showed that, corrosion current is 8.024 × 10-10A/cm2。
Embodiment 4:
The preparation of Electrolytic Manganese Product is the same as embodiment 1.
The preparation of passivator: by 3g aluminum nitrate, 0.3g sodium molybdate, 5mLH2O2(30%) be added in 1L water be stirred it is molten
Solution, is then adjusted to pH=3.5 for solution, and the chrome-free tanning agent for electrolytic manganese metal surface treatment is made.
The pH of the chrome-free tanning agent is 3.5, and the chrome-free tanning agent includes 3g aluminum nitrate, 0.3g sodium molybdate, 5mLH2O2
(30%) and 1L water；Wherein, by mass percentage, the mass concentration of the aluminum nitrate is about 0.3%, the matter of the cerous nitrate
Measuring concentration is about 0.03%.
The passivation of electrolysis manganese product and performance detection: chrome-free tanning agent is placed in deactivation slot, is rinsed with clear water and is completed electrolysis
Cathode plate surface, then cathode plate is put into deactivation slot, make chrome-free tanning agent submerge cathode plate surface, passivation 1 minute after
It takes out and uses distilled water flushing, drying, the metal manganese product after being passivated.Electrochemistry is carried out to the metal manganese product being passivated
It can test, the results showed that, corrosion current is 1.542 × 10-10A/cm2。
Embodiment 5:
The preparation of Electrolytic Manganese Product is the same as embodiment 1.
The preparation of passivator: by 3g aluminum nitrate, 0.3g cerous nitrate, 0.2g sodium molybdate, 5mL H2O2(30%) it is added to 1L water
In be stirred dissolution, sulfuric acid is then added, solution is adjusted to pH=3.5, the Chrome-free for electrolytic manganese metal surface treatment is made
Passivator (mass concentration is about 0.35%).
The pH of the chrome-free tanning agent is 3.5, and the chrome-free tanning agent includes 3g aluminum nitrate, 0.3g cerous nitrate, 0.2g molybdenum
Sour sodium, 5mLH2O2(30%) and 1L water；Wherein, by mass percentage, the mass concentration of the aluminum nitrate is about 0.3%, institute
The mass concentration for stating cerous nitrate is about 0.03%.
The passivation of electrolysis manganese product and performance detection: the chrome-free tanning agent of preparation is placed in deactivation slot, has been rinsed with clear water
At the cathode plate surface of electrolysis, then cathode plate is put into deactivation slot, chrome-free tanning agent is made to submerge cathode plate surface, passivation 1
It is taken out after minute and uses distilled water flushing, drying, the metal manganese product after being passivated.To the manganese metal that is not passivated and it has been passivated
Manganese metal carries out electrochemical property test, and polarization curve result is as shown in Fig. 1 and table 1.
The non-passive metal manganese product of table 1 and passive metal manganese product Tafel Dependence Results
| Sample | Corrosion potential (V) | Corrosion current (A/cm2) |
| It is not passivated Mn | -1.446 | 3.434×10-4 |
| Mn after passivation | -1.346 | 6.458×10-11 |
By attached drawing 1 and 1 Electrochemical results of table it is found that metal manganese product is passivated after, product corrosion potential is obvious
It shuffles, corrosion potential size has shuffled 0.10V, and corresponding corrosion current reduces six orders of magnitude or more, significantly mentions
The resistance to corrosion of Electrolytic Manganese Product is risen.
Sample passivation front and back Electronic Speculum result is as shown in Fig. 2 and 3, and Fig. 2 is that just non-passive metal manganese product has been completed in electrolysis
Electron microscopic picture, Fig. 3 are the electron microscopic picture of metal manganese product after passivation.As shown in Figure 2, the metal manganese product that just electrolysis comes out, cone
Face is smooth；Manganese metal product surface after being passivated as seen from Figure 3 is obviously covered by one layer of passivation film.
Embodiment 6:
The preparation of electrolytic manganese metal is the same as embodiment 1.
The preparation of passivating solution: by 3g aluminum sulfate, 0.5g cerous nitrate, 10mLH2O2(30%) it is added in 1L water and is stirred
Dissolution is then added sulfuric acid for solution and is adjusted to pH=2, the chromium-free passivation liquid for electrolytic manganese metal surface treatment is made.
The pH of the chrome-free tanning agent is 2, and the chrome-free tanning agent includes 3g aluminum sulfate, 0.5g cerous nitrate, 10mLH2O2
(30%) and 1L water；Wherein, by mass percentage, the mass concentration of the aluminum nitrate is about 0.3%, the matter of the cerous nitrate
Measuring concentration is about 0.05%.
The passivation of electrolysis manganese product and performance detection: chromium-free passivation liquid is placed in deactivation slot, is rinsed with clear water and is completed electrolysis
Cathode plate surface, be then placed in deactivation slot, make chromium-free passivation liquid submerge cathode plate surface, passivation 1 minute after take out with steam
Distilled water is rinsed, drying, the metal manganese product after being passivated.Electrochemical property test is carried out to the manganese metal being passivated, as a result
Show that corrosion potential is -1.383V, corrosion current is 1.802 × 10-10A/cm2, passivation effect is good.
Embodiment 7:
The preparation of electrolytic manganese metal is the same as embodiment 1.
The preparation of passivating solution: by 3g aluminium chloride, 0.5g ammonium molybdate, 8mLH2O2(30%) be added in 1L water be stirred it is molten
Solution, is then adjusted to pH=2 for solution, and the chromium-free passivation liquid for electrolytic manganese metal surface treatment is made.
The pH of the chrome-free tanning agent is 2, and the chrome-free tanning agent includes 3g aluminium chloride, 0.5g ammonium molybdate, 8mLH2O2
(30%) and 1L water；Wherein, by mass percentage, the mass concentration of the aluminum nitrate is about 0.3%, the matter of the cerous nitrate
Measuring concentration is about 0.05%.
The passivation of electrolysis manganese product and performance detection: chromium-free passivation liquid is placed in deactivation slot, is rinsed with clear water and is completed electrolysis
Cathode plate surface, be then placed in deactivation slot, make chromium-free passivation liquid submerge cathode plate surface, passivation 1 minute after take out with steam
Distilled water is rinsed, drying, the metal manganese product after being passivated.Electrochemical property test is carried out to the manganese metal being passivated, as a result
Show that corrosion potential is -1.219V, corrosion current is 1.965 × 10-10A/cm2, passivation effect is good.
Individually use aluminum soluble salt for electrolytic manganese passivating agent it can be seen from Examples 1 to 7, in acid condition, just
It can be by the corrosion current of electrolytic manganese metal by 3.434 × 10-4It is reduced to 9.521 × 10-9A/cm2(embodiment 2), self-corrosion
Electric current reduce 4 orders of magnitude more than, illustrate aluminium salt in acid condition with manganese surface Mn2+It is very excellent to be formed by passivating film
It is good.Pass through H2O2, soluble cerium salt, the components such as soluble molybdenum salt are added in passivator then can further promote its assivation property
Can, corrosion current can further be reduced to 6.458 × 10-11(reducing 6 orders of magnitude or more), performance is very excellent.
Compared with prior art, other beneficial effects of the invention further include:
Main component in chromium-free passivation liquid of the invention is aluminum soluble salt, and compared to chromate, the present invention is passivated
There is no the use of Cr VI in journey, greatly reduces the pollution to environment and the injury to human health.
Compared to phosphate and silicate, phosphorus or the exceeded feelings of silicone content will not occur for the product after present invention passivation
Condition improves the use value of manganese metal；In particular, the elements such as aluminium used in the present invention are also manganese metal subsequent applications process
In Hubeiwan；For example, nitrogen agent determine in aluminium or deoxidation when being used as steel-making containing aluminon, refinement crystal grain, inhibit mild steel when
Effect improves toughness of the steel in low temperature, is especially reduction of the brittle transition temperature of steel；Improve the antioxygenic property of steel.
The present invention is using the acid system of pH=1~4.5, and under acid condition, Al element is with Al3+Form exists.Vivaciously
Manganese metal and H+And H2O2It acts on surface and generates suitable Mn2+, Mn2+The local raised environment of pH on manganese metal surface
Under, it is easy to and Al3+、Ce3+Equal trivalent metal ions are assembled into the hydrotalcite protective film of class densification, film layer and manganese metal surface without
Seam combines, and reaches ideal passivation effect.
(4) reinforcing agent used in chromium-free passivation liquid of the invention is soluble cerium salt or soluble molybdenum hydrochlorate, cerium salt and
Molybdate can further promote the compactness of passivation film, improve blunt on the basis of aluminium salt forms houghite passivating film
Change effect.
(5) chromium-free passivation liquid of the invention passes through the synergistic effect of two kinds of components of aluminium salt and reinforcing agent, so that passivating solution has
There are good passivation effect and good stability, and the feature of environmental protection is good, at low cost.It is produced after passivation compared to manganese metal before being passivated
The corrosion potential of product shuffles 0.10V or more, and corresponding corrosion current reduces six orders of magnitude or more.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Each technical characteristic of embodiment described above can carry out arbitrarily
Combination, for simplicity of description, it is not all possible to each technical characteristic in above-described embodiment combination be all described, so
And as long as there is no contradiction in the combination of these technical features, it all should be considered as described in this specification.
Claims (10)
1. a kind of chrome-free tanning agent, which is characterized in that the pH of the chrome-free tanning agent is 1~4.5, the chrome-free tanning agent packet
It includes: aqueous solvent and aluminum soluble salt, wherein by mass percentage, the mass concentration of the aluminum soluble salt is 0.05%~
2%.
2. chrome-free tanning agent according to claim 1, which is characterized in that it further include hydrogen peroxide, the concentration of the hydrogen peroxide
For 1~15ml/L.
3. chrome-free tanning agent according to claim 1, which is characterized in that the aluminum soluble salt includes aluminum nitrate, sulfuric acid
One of aluminium, aluminium chloride, aluminium polychloride and polyaluminium sulfate are a variety of.
4. chrome-free tanning agent according to claim 1 or 2, which is characterized in that it further include reinforcing agent, the reinforcing agent and institute
The mass ratio for stating aluminium salt is 0.01~0.5:1.
5. chrome-free tanning agent according to claim 4, which is characterized in that the reinforcing agent includes soluble cerium salt and solvable
One or both of property molybdate.
6. chrome-free tanning agent according to claim 5, which is characterized in that the solubility cerium salt includes cerous nitrate, sulfuric acid
One of cerium, cerium chloride and ceric sulfate are a variety of.
7. chrome-free tanning agent according to claim 5, which is characterized in that the soluble molybdenum hydrochlorate includes sodium molybdate, molybdenum
One of sour potassium, zinc molybdate, calcium molybdate and ammonium molybdate are a variety of.
8. a kind of preparation method of the described in any item chrome-free tanning agents of claim 1~7 characterized by comprising according to matter
Percentages are measured, 0.05~2% aluminium salt is added in aqueous solvent and stirring and dissolving obtains solution, then by the pH tune of solution
To 1~4.5, the chrome-free tanning agent is obtained.
9. the preparation method of the described in any item chrome-free tanning agents of claim 1~7 or chrome-free tanning agent according to any one of claims 8
Application of the chrome-free tanning agent of preparation in passive metal manganese.
10. application according to claim 9, which is characterized in that the application includes: that manganese metal is immersed in the Chrome-free
It is passivated 30 seconds~5 minutes in passivator.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110952082A (en) * | 2019-12-25 | 2020-04-03 | 廊坊师范学院 | Preparation method of hot-dip galvanized chromium-free passivation film |
| CN112962090A (en) * | 2021-02-03 | 2021-06-15 | 合肥华清方兴表面技术有限公司 | Zinc-aluminum-magnesium alloy self-repairing chromium-free passivator and preparation method and application thereof |
| CN113969401A (en) * | 2020-07-24 | 2022-01-25 | 中南大学 | Active metal chromium-free passivation method |
| CN115323365A (en) * | 2021-05-10 | 2022-11-11 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110952082A (en) * | 2019-12-25 | 2020-04-03 | 廊坊师范学院 | Preparation method of hot-dip galvanized chromium-free passivation film |
| CN110952082B (en) * | 2019-12-25 | 2022-01-04 | 廊坊师范学院 | Preparation method of hot-dip galvanized chromium-free passivation film |
| CN113969401A (en) * | 2020-07-24 | 2022-01-25 | 中南大学 | Active metal chromium-free passivation method |
| CN112962090A (en) * | 2021-02-03 | 2021-06-15 | 合肥华清方兴表面技术有限公司 | Zinc-aluminum-magnesium alloy self-repairing chromium-free passivator and preparation method and application thereof |
| CN115323365A (en) * | 2021-05-10 | 2022-11-11 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
| CN115323365B (en) * | 2021-05-10 | 2023-10-13 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
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