CN105755455B - Magnesium alloy AZ31 hair blackening liquids and blackening method - Google Patents
Magnesium alloy AZ31 hair blackening liquids and blackening method Download PDFInfo
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- CN105755455B CN105755455B CN201610164844.9A CN201610164844A CN105755455B CN 105755455 B CN105755455 B CN 105755455B CN 201610164844 A CN201610164844 A CN 201610164844A CN 105755455 B CN105755455 B CN 105755455B
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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
A kind of magnesium alloy AZ31 hair blackening liquids and blackening method, including ammonium molybdate and acetic acid acetate buffer solution, in magnesium alloy AZ31 hair blackening liquids：The total concentration of a concentration of 5~100g/L of ammonium molybdate, acetate ion are 1~100g/L.Above-mentioned magnesium alloy AZ31 hair blackening liquids are used as using ammonium molybdate and are oxidized to film, and coordinate acetic acid acetate buffer solution for adjusting pH, allow molybdenum acid ion that a degree of redox reaction can occur with ammonium ion, play slow releasing function, thus in the preferable black of Surface Creation quality of magnesium alloy AZ31 or shiny black oxidation film, and blackening effect is fabulous.In addition, above-mentioned magnesium alloy AZ31 hair blackening liquids are free of chromium, it is smaller to human body and environmental hazard.
Description
Technical field
The present invention relates to technical field of metal material surface treatment, more particularly to a kind of magnesium alloy AZ31 hair blackening liquids and
Blackening method.
Background technology
In field of magnesium alloy, magnesium alloy AZ31 and Mg alloy AZ91 are as common two kinds of magnesium alloys.Wherein, magnesium alloy
AZ31 has higher intensity, plasticity, vibration resistance and heat absorption capacity, is widely used in the fields such as aerospace, automobile, electronics.
For demands such as the antiseptic property, product appearance, the electromagnetic wave absorptions that meet magnesium alloy device, it need to be often surface-treated into black,
For example, black or shiny black surface have stronger absorbing ability, therefore, the photo absorption performance of these nigrescence materials determines its table
Face has to form black or shiny black film layer.
Currently, the hair blackening liquid technology of Mg alloy AZ91 is more ripe, when it is used for Mg alloy AZ91, it can arrive and relatively manage really
The black film layer thought is still, more difficult on the surfaces magnesium alloy AZ31 when these existing hair blackening liquids are applied to magnesium alloy AZ31
Form the higher black film layer of quality.
For example, the patent documents such as Chinese patent CN 102747351 and Japan Patent JP 2003213446 disclose it is several
Kind magnesium alloy hair blackening liquid, but do not meet environmental protection containing serious pollution environment and the chromium being detrimental to health in such hair blackening liquid and want
It asks.For another example, two kinds of the patent literatures such as Japan Patent JP 2010084203 and Japan Patent JP 2003003274 are free of
The environmentally friendly hair blackening liquid of chromium, still, such blackening agent for surface is only applicable to Mg alloy AZ91, when it is used for magnesium alloy AZ31, just no
To the film layer of black.For another example, Chinese patent CN 101845628 disclose it is a kind of with molybdate, it is pyrophosphate coalescents, strong
Acidic activator hair blackening liquid as the main component, but the hair blackening liquid is also only applicable to Mg alloy AZ91, when it is used for magnesium alloy
When AZ31, obtained film layer is in yellow.
Invention content
Based on this, it is necessary to provide it is a kind of without chromium, it is smaller to human body and environmental hazard and suitable in magnesium
The magnesium alloy AZ31 hair blackening liquids and blackening method of the preferable black film layer of quality are formed on alloy AZ31.
A kind of magnesium alloy AZ31 hair blackening liquids, including ammonium molybdate and acetic acid-acetate buffer solution；
Wherein：The total concentration of a concentration of 5~100g/L of the ammonium molybdate, acetate ion are 1~100g/L.
The acetate includes at least one of sodium acetate, ammonium acetate and potassium acetate in one of the embodiments,.
The acetate is sodium acetate in one of the embodiments,.
A kind of blackening method of magnesium alloy AZ31, includes the following steps：
Ammonium molybdate, acetic acid, acetate and water are uniformly mixed, obtain magnesium alloy AZ31 hair blackening liquids, wherein the ammonium molybdate
A concentration of 5~100g/L, the total concentration of acetate ion is 1~100g/L；
After pretreatment, it will immerse into the magnesium alloy AZ31 hair blackening liquids, sent out wait the magnesium alloy AZ31 to black
Black operation；
It from the magnesium alloy AZ31 after blacking is taken out in the magnesium alloy AZ31 hair blackening liquids, is post-processed, is closed in the magnesium
Shiny black oxidation film is formed on golden AZ31.
In one of the embodiments, in the operation for being uniformly mixed ammonium molybdate, acetic acid, acetate and water, also wrap
Include following steps：The ratio for adjusting the acetic acid and the acetate makes the pH of the magnesium alloy AZ31 hair blackening liquids reach default
Range.
The pH preset ranges are 3.6~6 in one of the embodiments,.
The pretreatment specifically comprises the following steps in one of the embodiments,：
By magnesium alloy AZ31 to be blacked by oil removing, washing, activation, washing, table reconciliation water washing operations.
The post-processing specifically comprises the following steps in one of the embodiments,：
Magnesium alloy AZ31 after nigrescence is subjected to washing and drying process.
Magnesium alloy AZ31 is immersed to before the magnesium alloy AZ31 hair blackening liquids in one of the embodiments, further includes
Following steps：
The temperature of the magnesium alloy AZ31 hair blackening liquids is adjusted to 20~100 DEG C.
The nigrescence operation continues 2~30min in one of the embodiments,.
Above-mentioned magnesium alloy AZ31 hair blackening liquids are used as using ammonium molybdate and are oxidized to film, and coordinate acetic acid-acetate salt buffer
Solution is for adjusting pH so that with ammonium ion a degree of redox reaction can occur for molybdenum acid ion, play
Slow releasing function, thus in the preferable black of Surface Creation quality of magnesium alloy AZ31 or shiny black oxidation film, and blackening effect pole
It is good.In addition, above-mentioned magnesium alloy AZ31 hair blackening liquids are free of chromium, it is smaller to human body and environmental hazard.
Description of the drawings
Fig. 1 is the step flow chart of the magnesium alloy AZ31 blackening methods of an embodiment of the present invention.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings to the present invention
Specific implementation mode be described in detail.Many details are elaborated 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 of violating intension of the present invention, therefore the present invention is not limited by following public specific embodiment.
Magnesium alloy AZ31 hair blackening liquids in one embodiment, the magnesium alloy AZ31 hair blackening liquids include ammonium molybdate and acetic acid-
Acetate buffer solution, and in the magnesium alloy AZ31 hair blackening liquids：A concentration of 5~100g/L of the ammonium molybdate, acetic acid
The total concentration of radical ion is 1~100g/L.
When above-mentioned magnesium alloy AZ31 hair blackening liquids make buffer solution using acetic acid and acetate, e.g., using acetic acid and acetate
When making buffer solution the pH of the magnesium alloy AZ31 hair blackening liquids being adjusted to 3.6~6, under the oxidation of ammonium molybdate, magnesium closes
The surface of golden AZ31 generates magnesia (MgO) and aluminium oxide (Al by oxidation2O3), molybdenum acid ion is reduced into the oxide of molybdenum,
Such as Mo2O3And Mo2O5Combined deposition Deng, these oxide fine particles in Mg alloy surface, based on to light scattering effect, it is above-mentioned
The combination of oxide fine particle absorbs most incident lights, thus in the oxidation film of magnesium alloy AZ31 Surface Creation black, such as
Shiny black oxidation film.
For example, the main component of magnesium alloy AZ31 and Mg alloy AZ91 refers to table 1.
Table 1
| Model | Mg | Al | Zn | Mn | Si | Ca | Fe | Cu | Ni |
| AZ31 | Surplus | 2.5~3.5 | 0.6~1.4 | 0.2~1.0 | 0.08 | 0.04 | 0.003 | 0.01 | 0.001 |
| AZ91 | Surplus | 8.5~9.5 | 0.45~0.90 | 0.17~0.4 | <=0.05 | <=0.004 | <=0.025 | <=0.001 |
As it can be seen from table 1 Mg alloy AZ91 with respect to magnesium alloy AZ31 for, the aluminium element content of Mg alloy AZ91 compares magnesium
Wanting for alloy AZ31 is high, but the magnesium element content of Mg alloy AZ91 is lower than magnesium alloy AZ31.For example, when special using China
When hair blackening liquid disclosed in sharp CN101845628 respectively blacks to magnesium alloy AZ31 and Mg alloy AZ91, using pyrophosphoric acid
Salt makees coalescents, and highly acid substance makes pH be 1.5~3.5 as acidity regulator, under the oxidation of molybdate, magnesium alloy
The surface of AZ31 and Mg alloy AZ91 is aoxidized respectively, and the surface of the two generates phosphomolybdic acid magnesium, phosphomolybdic acid aluminium, aluminum phosphate, phosphorus
The deposits such as sour magnesium, since Mg alloy AZ91 is with respect to magnesium alloy AZ31, the aluminium element content of Mg alloy AZ91 is more, and magnesium elements contain
Amount is smaller, the ratio of the deposits such as the phosphomolybdic acid magnesium of the Surface Creation of Mg alloy AZ91, phosphomolybdic acid aluminium, aluminum phosphate, magnesium phosphate, with
The ratio of the deposits such as the phosphomolybdic acid magnesium of magnesium alloy AZ31 Surface Creations, phosphomolybdic acid aluminium, aluminum phosphate, magnesium phosphate differs, and magnesium closes
Scattering degree of the deposit of different proportion to light or the degree of absorption to light are different on the surfaces golden AZ91 and magnesium alloy AZ31,
On the one hand, the surface of Mg alloy AZ91 can form black or shiny black oxidation film, the i.e. preferable black film of quality；Another party
The surface in face, magnesium alloy AZ31 forms the oxidation film of yellow, i.e. the hair blackening liquid is not suitable for the blackening of magnesium alloy AZ31.
Above-mentioned magnesium alloy AZ31 hair blackening liquids use the reason of ammonium molybdate to be：On the one hand, under conditions of acidity, e.g.,
Under conditions of pH is 3.6~6, ammonium molybdate, which dissociates the molybdenum acid ion come, has stronger oxidisability, is dissociated based on ammonium molybdate
Ammonium ion out has certain reproducibility, and it is anti-that with ammonium ion a degree of redox can occur for molybdenum acid ion
It answers, so as to slow down the oxidation reaction generated between molybdenum acid ion and aluminium element and magnesium elements, and then can to aoxidize
Product magnesia (MgO) and aluminium oxide (Al2O3) be relatively slowly deposited on magnesium alloy AZ31 so that nigrescence film layer is finer and close
With it is secured.That is, ammonium ion can play the effect of furtherance film and sustained release, magnesia (MgO) and aluminium oxide are avoided
(Al2O3) generating rate it is too fast, so as to prevent from causing because deposition rate is too fast film layer it is loose, it is easy to fall off fall ash problem.
In other words, in the case of using such as sodium molybdate and potassium molybdate as oxidant, since sodium ion and potassium ion do not restore centainly
Property, it is easy because of magnesia (MgO) and aluminium oxide (Al2O3) generate and deposition rate it is too fast, cause film layer loose, it is easy to fall off fall ash
The problem of occur.On the other hand, molybdenum acid ion and ammonium ion reaction, can be such that the molybdic acid salt dopping of conversion film increases, from
And the performance of nigrescence film layer is improved, for example, the doping of magnesium molybdate and molybdic acid aluminium can improve the performance of nigrescence film layer, so as to
It is loose to avoid film layer, easy to fall off fall ash problem.
Above-mentioned magnesium alloy AZ31 hair blackening liquids use the reason of acetic acid-acetate buffer solution to be：Acetate ion is rising
To except cushioning effect, that is, plays the role of adjusting except pH, the ingredient for influencing nigrescence film layer color change, example will not be generated
Such as, with aluminium ion and magnesium ion complex reaction will not occur for acetate ion, generate the complex compound for influencing the discoloration of nigrescence film layer, this
Outside, acetate will not precipitate, and not interfere with the variation of nigrescence Film color.For another example, by taking phosphoric acid as an example, phosphoric acid meeting and aluminium ion
Phosphate is generated with magnesium ion, phosphatic deposition can influence the color of nigrescence film layer, i.e., can film layer be changed colour, e.g., cause
Film layer is turned to be yellow.For another example, by taking ascorbic acid and citric acid as an example, ascorbic acid and citric acid can generate network with aluminium ion and magnesium ion
Object is closed, complex reaction, which occurs, to get off deposited magnesia and alumina dissolution, and oxidation film layer is made to dissolve.
It is emphasized that using magnesium alloy AZ31 hair blackening liquids to the nigrescence of magnesium alloy AZ31 after, can be in magnesium alloy
The Surface Creation black or shiny black oxidation film of AZ31, and blackening effect is fabulous.
For example, above-mentioned magnesium alloy AZ31 hair blackening liquids are made of ammonium molybdate, acetate and acetate buffer solution, wherein ammonium molybdate is dense
Degree is 5~100g/L, preferably 10~40g/L；Acetate ion total concentration is 1~100g/L, preferably 10~60/L.Work as molybdenum
Sour ammonium concentration is less than 5g/L, and reaction speed is excessively slow, and the blackness of the film layer of formation is inadequate；And work as molybdic acid ammonium concentration and be more than 100g/L,
Reaction speed is too fast, and Corrosion Behaviors of Magnesium Alloys is serious, and the film layer of formation is uneven, and cost increases.When acetate total ion concentration is low
When 1g/L, solution buffer capacity is insufficient, and with the progress of reaction, pH value gradually rises, to make above-mentioned magnesium alloy AZ31 send out
Black liquor fails；When acetate total ion concentration is more than 100g/L, reaction speed is too fast, and Corrosion Behaviors of Magnesium Alloys is serious, gained film layer
It is uneven, and cost increases.
In one embodiment, the acetate includes at least one of sodium acetate, ammonium acetate and potassium acetate；Preferably,
The acetate is sodium acetate.
Above-mentioned magnesium alloy AZ31 hair blackening liquids are used as using ammonium molybdate and are oxidized to film, and coordinate acetic acid-acetate salt buffer
Solution is for adjusting pH so that with ammonium ion a degree of redox reaction can occur for molybdenum acid ion, play
Slow releasing function, thus in the preferable black of Surface Creation quality of magnesium alloy AZ31 or shiny black oxidation film, and blackening effect pole
It is good.In addition, above-mentioned magnesium alloy AZ31 hair blackening liquids are free of chromium, it is smaller to human body and environmental hazard.
Above-mentioned magnesium alloy AZ31 hair blackening liquids are nontoxic, environmentally friendly, Chrome-free, low cost, are suitable for the nigrescence of magnesium alloy AZ31.Pass through
Above-mentioned magnesium alloy AZ31 hair blackening liquids are uniformly glossy by the oxidation film layer obtained by nigrescence, blackness is high, strong adhesive force, is not easy to take off
It falls.
Referring to Fig. 1, the blackening method of the magnesium alloy AZ31 of an embodiment, includes the following steps：
S110：Ammonium molybdate, acetic acid, acetate and water are uniformly mixed, obtain magnesium alloy AZ31 hair blackening liquids, wherein described
The total concentration of a concentration of 5~100g/L of ammonium molybdate, acetate ion are 1~100g/L.
Further include as follows in the operation that ammonium molybdate, acetic acid, acetate and water are uniformly mixed in one embodiment
Step：The ratio for adjusting the acetic acid and the acetate makes the pH of the magnesium alloy AZ31 hair blackening liquids reach preset range；Again
Such as, the preset range is 3.6~6.
S120：It after pretreatment, will be immersed into the magnesium alloy AZ31 hair blackening liquids wait the magnesium alloy AZ31 to black, into
Row, which blacks, to be operated.
In one embodiment, the pretreatment specifically comprises the following steps：By magnesium alloy AZ31 to be blacked by oil removing,
Washing, activation, washing, table reconciliation water washing operations, subsequently nigrescence operation is carried out in this way, being more advantageous to magnesium alloy AZ31.For example,
Table tune is that surface modulation operation e.g. removes surface porosity substance.
In one embodiment, magnesium alloy AZ31 is immersed to before the magnesium alloy AZ31 hair blackening liquids, further includes walking as follows
Suddenly：The temperature of the magnesium alloy AZ31 hair blackening liquids is adjusted to 20~100 DEG C；For another example, the nigrescence operation continues 2~30min；
For another example, in this way, being more advantageous to the blackening effect for playing the magnesium alloy AZ31 hair blackening liquids.
S130：From the magnesium alloy AZ31 after blacking is taken out in the magnesium alloy AZ31 hair blackening liquids, post-processed, described
Shiny black oxidation film is formed on magnesium alloy AZ31.
In one embodiment, the post-processing specifically comprises the following steps：Magnesium alloy AZ31 after nigrescence is washed
And drying process, in this way, being more advantageous to form shiny black oxidation film.
Another example is that the blackening method of the magnesium alloy AZ31 of an embodiment includes the following steps：
S210：Oil removing：It will wait for that nigrescence magnesium alloy AZ31 is put into the degreaser that temperature is 50~60 DEG C, impregnate 3~10min
Afterwards, it takes out, is rinsed with water clean, wherein the degreaser is by 5~10g/L NaOH, 15~30g/L Na2CO3, 30~50g/L
Na3PO4, 10~15g/L sodium pyrophosphates, 1~3g/L OP-10 composition.
S220：Activation：After magnesium alloy AZ31 after oil removing is immersed 0.5~2min of activating solution that temperature is 50~60 DEG C,
It takes out, is rinsed with water clean.The activator is by 1~10g/L citric acids, 1~10g/L tartaric acid, 1~10g/L malic acid groups
At.
S230：Table tune：Magnesium alloy AZ31 after activation is immersed into table tune 1~10min of liquid that temperature is 50~70 DEG C, is taken
Go out, is rinsed with water clean.The table adjustment is made of 20~400g/L NaOH solutions.
S240：Black：The ammonium molybdate, acetic acid and sodium acetate measured is taken, with deionized water dissolving, and adjusts sour and vinegar
The ratio of sour sodium makes its pH keep in a certain range, obtaining magnesium alloy AZ31 hair blackening liquids.By the magnesium alloy AZ31 leachings after table tune
Enter in magnesium alloy AZ31 hair blackening liquids, keep magnesium alloy AZ31 hair blackening liquids in certain temperature range, after a period of time that blacks, by magnesium
Alloy AZ31 takes out, washes, is dry, and surface can obtain one layer of shiny black oxidation film, wherein the magnesium alloy AZ31's
In hair blackening liquid：The total concentration of a concentration of 5~100g/L of the ammonium molybdate, acetate ion are 1~100g/L.
In one embodiment, in the step S210, the pH of the magnesium alloy AZ31 hair blackening liquids is 3.6~6.0, preferably
It is 4.0~5.5, when pH is less than 3.6, reaction speed is too fast, and easily keeps the magnesia, aluminium oxide, molybdenum oxide on surface etc. molten
Solution, and cannot get the film layer of black；When pH is higher than 6.0, the oxidability of ammonium molybdate is insufficient, and magnesium alloy AZ31 is not easy to be aoxidized,
Also cannot black film layer.
In one embodiment, in the step S220, the temperature of the magnesium alloy AZ31 hair blackening liquids is 20~100 DEG C,
Preferably 50~70 DEG C；The nigrescence time is 2~30min, preferably 5~15min, and when temperature is too low, reaction speed is excessively slow, is blacked
Required time is long；When temperature is excessively high, reaction speed is very fast, shortens the time required to blacking.
Specific embodiment is as follows：
Embodiment 1
Step 1：Prepare magnesium alloy AZ31 hair blackening liquids：In following ratio dispensing：(NH4)2MoO4 6g、NaAc3.0g、H2O
300g is used in combination HAc that the pH of magnesium alloy AZ31 hair blackening liquids is adjusted to 5.0 to get magnesium alloy AZ31 hair blackening liquids.
Step 2：Prepare 1L degreasing fluids：Take 8g NaOH, 20g Na2CO3、40g Na3PO4, 12g sodium pyrophosphates, 3g OP-
10, add 1000g water dissolutions.
Step 3：Prepare 1L activating solutions：8g citric acids, 5g tartaric acid, 5g malic acid are taken, 1000g water dissolutions are added.
Step 4：Prepare 1L table tune liquid：80g NaOH are taken, with 1000g water dissolutions.
Step 5：Oil removing
By the magnesium alloy AZ31 of required nigrescence be put into temperature by 55 DEG C it is above-mentioned match degreasing fluid, impregnate 5min, take out, use
Tap water is rinsed well.
Step 6：Activation
By the magnesium alloy AZ31 after oil removing be put into temperature by 55 DEG C it is above-mentioned match activating solution, impregnate 1min, take out, use water
It rinses well.
Step 7：Table tune
Magnesium alloy AZ31 after activation is immersed into temperature and impregnates 4min in table tune liquid for 60 DEG C above-mentioned, takes out use
Tap water is rinsed well.
Step 8：Black
Magnesium alloy AZ31 after table tune is immersed in above-mentioned matched magnesium alloy AZ31 hair blackening liquids, magnesium alloy AZ31 is kept to black
Liquid temperature takes out after 70 DEG C, nigrescence 10min, washes, it is dry after, the surfaces magnesium alloy AZ31 can be obtained one layer of black even,
The film layer of firm adhesion.
Embodiment 2
Step 1：Prepare magnesium alloy AZ31 hair blackening liquids.In following ratio dispensing：(NH4)2MoO4 3g、NaAc0.5g、H2O
300g is used in combination HAc to adjust magnesium alloy AZ31 hair blackening liquid pH value to 4.0 to get magnesium alloy AZ31 hair blackening liquids.
Step 2：Prepare 1L degreasing fluids：Take 6g NaOH, 18g Na2CO3、35g Na3PO4, 14g sodium pyrophosphates, 1.5g
OP-10 adds 1000g water dissolutions.
Step 3：Prepare 1L activating solutions：6g citric acids, 4g tartaric acid, 7g malic acid are taken, 1000g water dissolutions are added.
Step 4：Prepare 1L table tune liquid：60g NaOH are taken, with 1000g water dissolutions.
Step 5：Oil removing
By the magnesium alloy AZ31 of required nigrescence be put into temperature by 50 DEG C it is above-mentioned match degreasing fluid, impregnate 7min, take out, use
Tap water is rinsed well.
Step 6：Activation
By the magnesium alloy AZ31 after oil removing be put into temperature by 60 DEG C it is above-mentioned match activating solution, impregnate 0.5min, take out, use
Water is rinsed well.
Step 7：Table tune
Magnesium alloy AZ31 after activation is immersed into temperature and impregnates 6min in table tune liquid for 50 DEG C above-mentioned, takes out use
Tap water is rinsed well.
Step 8：Black
Magnesium alloy AZ31 after table tune is immersed in above-mentioned matched magnesium alloy AZ31 hair blackening liquids, keeps hair blackening liquid temperature 50
DEG C, it takes out, wash after nigrescence 12min, after drying, the surfaces magnesium alloy AZ31 can be obtained one layer of black even, firm adhesion
Film layer.
Embodiment 3
Step 1：Prepare magnesium alloy AZ31 hair blackening liquids.In following ratio dispensing：(NH4)2MoO4 3g、NaAc0.5g、H2O
300g is used in combination HAc to adjust magnesium alloy AZ31 hair blackening liquid pH value to 4.0 to get magnesium alloy AZ31 hair blackening liquids.
Step 2：Prepare 1L degreasing fluids：Take 6g NaOH, 18g Na2CO3、35g Na3PO4, 14g sodium pyrophosphates, 1.5g
OP-10 adds 1000g water dissolutions.
Step 3：Prepare 1L activating solutions：6g citric acids, 4g tartaric acid, 7g malic acid are taken, 1000g water dissolutions are added.
Step 4：Prepare 1L table tune liquid：60g NaOH are taken, with 1000g water dissolutions.
Step 5：Oil removing
By the Mg alloy AZ91 of required nigrescence be put into temperature by 50 DEG C it is above-mentioned match degreasing fluid, impregnate 7min, take out, use
Tap water is rinsed well.
Step 6：Activation
By the Mg alloy AZ91 after oil removing be put into temperature by 60 DEG C it is above-mentioned match activating solution, impregnate 0.5min, take out, use
Water is rinsed well.
Step 7：Table tune
Mg alloy AZ91 after activation is soaked into temperature and impregnates 6min in table tune liquid by 50 DEG C above-mentioned, takes out and uses
Tap water is rinsed well.
Step 8：Black
Mg alloy AZ91 after table tune is immersed in above-mentioned matched magnesium alloy AZ31 hair blackening liquids, keeps hair blackening liquid temperature 50
DEG C, it takes out, wash after nigrescence 12min, after drying, Mg alloy AZ91 surface can be obtained one layer of black even, firm adhesion
Film layer.
It can be seen that nigrescence of the magnesium alloy AZ31 hair blackening liquids to magnesium alloy AZ31 and Mg alloy AZ91 from embodiment 1-3
Effect is all preferable.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of every technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Only several embodiments of the present invention are expressed for embodiment described above, the description thereof is more specific and detailed, but
It cannot be construed as a limitation to the scope of the present invention.It should be pointed out that for the ordinary skill people of this field
For member, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the present invention's
Protection domain.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (2)
1. a kind of blackening method of magnesium alloy AZ31, which is characterized in that include the following steps：
Ammonium molybdate, acetic acid, acetate and water are uniformly mixed, magnesium alloy AZ31 hair blackening liquids are obtained, wherein the ammonium molybdate it is dense
Degree is 10~40g/L, and the total concentration of acetate ion is 10~60g/L；The ratio for adjusting the acetic acid and the acetate, makes
The pH of the magnesium alloy AZ31 hair blackening liquids is 4~5；Wherein, the acetate include in sodium acetate, ammonium acetate and potassium acetate extremely
Few one kind；
After pretreatment, it will immerse into the magnesium alloy AZ31 hair blackening liquids wait the magnesium alloy AZ31 to black, carry out nigrescence behaviour
Make；Wherein, the pretreatment specifically comprises the following steps：By magnesium alloy AZ31 to be blacked by oil removing, washing, activation, water
It washes, table reconciliation water washing operations；Wherein, magnesium alloy AZ31 is immersed to before the magnesium alloy AZ31 hair blackening liquids, further includes as follows
Step：The temperature of the magnesium alloy AZ31 hair blackening liquids is adjusted to 20~100 DEG C；The nigrescence operation continues 2~30min；
From the magnesium alloy AZ31 after blacking is taken out in the magnesium alloy AZ31 hair blackening liquids, post-processed, in the magnesium alloy
Shiny black oxidation film is formed on AZ31.
2. the blackening method of magnesium alloy AZ31 according to claim 1, which is characterized in that it is described post-processing specifically include as
Lower step：
Magnesium alloy AZ31 after nigrescence is subjected to washing and drying process.
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| JP7432355B2 (en) * | 2019-12-20 | 2024-02-16 | 日本パーカライジング株式会社 | Base material with film |
| CN113151878B (en) * | 2021-02-01 | 2022-03-11 | 湖北叒成科技有限公司 | ZK61M magnesium alloy black formation liquid and formation process |
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| CN1673412A (en) * | 2005-04-12 | 2005-09-28 | 沈阳工业大学 | Magnesium and magnesium alloy chemical oxidation process |
| CN101845628A (en) * | 2009-03-25 | 2010-09-29 | 中国科学院金属研究所 | Method for preparing environment-friendly black film on magnesium alloy surface and film-forming liquid |
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| CN1673412A (en) * | 2005-04-12 | 2005-09-28 | 沈阳工业大学 | Magnesium and magnesium alloy chemical oxidation process |
| CN101845628A (en) * | 2009-03-25 | 2010-09-29 | 中国科学院金属研究所 | Method for preparing environment-friendly black film on magnesium alloy surface and film-forming liquid |
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| CN105755455A (en) | 2016-07-13 |
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