CN103357867A - Scaly multi-element aluminum-zinc-silicon alloy powder and preparation method thereof - Google Patents
Scaly multi-element aluminum-zinc-silicon alloy powder and preparation method thereof Download PDFInfo
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- CN103357867A CN103357867A CN2013103312710A CN201310331271A CN103357867A CN 103357867 A CN103357867 A CN 103357867A CN 2013103312710 A CN2013103312710 A CN 2013103312710A CN 201310331271 A CN201310331271 A CN 201310331271A CN 103357867 A CN103357867 A CN 103357867A
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Abstract
The invention relates to scaly multi-element aluminum-zinc-silicon alloy powder and a preparation method thereof. The slice thickness of the scaly multi-element aluminum-zinc-silicon alloy powder is 0.1-1 mum, and the average slice diameter of the scaly multi-element aluminum-zinc-silicon alloy powder is 5-35 mum; the specific constituent of a particle size is that the slice diameter which is smaller than 5 mum is smaller than or equal to 20 percent, the slice diameter which is 5-33 mum is more than or equal to 70 percent, and the slice diameter which is more than 33 mum is smaller than or equal to 10 percent; a diameter-to-thickness ratio of the average slice diameter to the slice thickness of the scaly multi-element aluminum-zinc-silicon alloy powder is 35-200. The scaly multi-element aluminum-zinc-silicon alloy powder and the preparation method thereof which are provided by the invention are particularly suitable for the fields of the production of Dacromet coating liquid, inorganic zinc-enriched painting, high-corrosion-resistance coating and the like.
Description
Technical field
The present invention relates to the polynary aluminium zinc of a kind of flakey silicon alloy powder and preparation method thereof.
Background technology
Dacromet Technology is born in later 1950s the earliest, it is a kind of metal coating treatment technology of similar electrogalvanizing, the scientist Mai Ke Martin of the U.S. has developed take the metal zinc metal sheet and has added simultaneously the high dispersive water soluble paint that aluminium flake, chromic acid, deionized water are made solvent as main, coating sticks on the metallic matrix, apply baking through the circulation of full cut-off road, form very thin coating.Dacromet/steel is successfully resisted the erosion of chlorion, and aseptic technic has entered new step, has reformed short defective of anticorrosion life-span of traditional handicraft.The Dacromet/steel outward appearance is uniform silver gray, contains 80% thin zinc metal sheet and aluminium flake in the coating, and all the other are chromate, have good performance, such as extremely strong corrosion resistance etc.; Be specially adapted to the high strength stressed member, as being used for the high-strength bolt of subway engineering; High-fire resistance; Heat resisting temperature can reach 300 ℃.In addition, also have the advantages such as high osmosis, high tack, high antifriction quality, high weather resistance, high resistance to chemicals product stability and non-environmental-pollution.In the various fields such as the automobile of industrially developed country, civil construction, electric power, chemical industry, ocean engineering, household electrical appliance, railway, highway, bridge, tunnel, war industry, obtained using very widely.The Dacroment masking liquid is of a great variety at present, but it is further perfect generally still to exist defective to need, and realization is dechromised and needed further to improve its performance etc. such as needs, and the performance of the flakey alloyed powder of especially comparatively common employing still can't satisfy technological requirement fully.
In addition, the manufacture method at domestic existing scaled metal powder end mainly contains Mechanical Method, Physical and chemical method etc. at present.Wherein Mechanical Method mainly contains ball-milling method and Ultrasonic Pulverization method, and wherein ball-milling method comparatively generally adopts in actual production.Ball-milling method is divided into again dry grinding and two kinds of processing technologys of wet-milling, and wherein wet grinding mainly is included in and adds the operation that solvent wet goods medium for example grinds in the process of metal powder grinding, again by sorting, filter drying, screening, redrying, the operations such as packing are achieved.Above-mentioned wet grinding drying process is complicated, and the cycle is long, and efficient is low, the easy oxidation of metal powder, and more seriously after drying metal powder is understood residual a part of medium, affects the scope of application and the quality of metal powder.And dry mill process needs long dispersed with stirring, increase energy consumption, and dry mill process the manufacturing Superfine Zn powder, the aluminium powder that obtain, its shape and performance all have again larger gap with the powder of Dacroment arts demand, thereby have limited the process of Non-chromium Zn-al Coating technology industrialization.
Therefore, provide a kind of improved flakey alloyed powder and preparation method thereof just to become the technical barrier that solution is badly in need of in this field.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of polynary Zn-Al alloy powder of high-quality flakey that can satisfy extraordinary coating process requirement, and provide that a kind of efficient is high, cost is low and be applicable to the preparation method of actual production.
The polynary Zn-Al alloy powder of flakey provided by the present invention, its components based on weight percentage is: Al:15%-69%; Si:0.2-3%; Mg:0.1-5%; The total amount of at least two kinds of rare earth elements: 0.02-0.9%; Total amount is no more than 1% impurity; Surplus is Zn, the sheet of the polynary Zn-Al alloy powder of wherein said flakey is thick to be 0.1～1 μ m, average sheet directly is 5～35 μ m, and specifically consisting of of granularity wherein: the sheet footpath less than 5 μ m account for≤20%, sheet footpath 5～33 μ m account for 〉=and 70%, sheet footpath is greater than 33 μ m≤10%, and the thick radius-thickness ratio of the average sheet footpath of the polynary Zn-Al alloy powder of described flakey and sheet is 35～200.
Preferably, the apparent density of the polynary Zn-Al alloy powder of wherein said flakey is 1.0～3.0gcm
-3
Preferably, the lid water area of the polynary Zn-Al alloy powder of wherein said flakey is 0.4～2.0m
2G
-1
Preferably, wherein said at least two kinds of rare earth elements mainly comprise lanthanum (La), cerium (Ce), praseodymium (Pr), in the neodymium (Nd) any two or more.
Preferably, wherein said at least two kinds of rare earth elements comprise lanthanum (La), cerium (Ce), praseodymium (Pr), in the neodymium (Nd) any two kinds, and this any two kinds content and account for the percentage of rare earth element total amount 〉=85%.
On the other hand, the present invention is the manufacture method of the polynary Zn-Al alloy powder of a kind of flakey that provides also, percentage by weight according to polynary each component of Zn-Al alloy powder of described flakey is got the raw materials ready, each component is made allumen by proportioning in smelting furnace, pour into the allumen rod by the deep-well forging type again, then, the allumen rod is put into the vacuum atomizing powder manufacturing apparatus be atomized into the spherical allumen powder of 200～500 purposes, again described spherical allumen powder is joined in the ball mill, add simultaneously grinding aid and ball-milling medium and carry out ball milling, and pass into again inert gas after vacuumizing first, pass in the ball mill interlayer cooling liquid take control mechanical milling process in temperature as 20-60 ℃, Ball-milling Time is 8～20 hours, keeping drum's speed of rotation is 30～100 rev/mins, thereby the described spherical polynary allumen sphere of powder is worn into the sheet alloy powder, prepare the polynary Zn-Al alloy powder of described flakey.
Preferably, wherein grinding aid is one or more mixing in zinc stearate, calcium stearate, molybdenum sulfide, polyvinyl alcohol, neopelex, the glyceryl alcohol.
Preferably, wherein grinding aid adds according to 1%～10% ratio of described spherical polynary zinc-aluminium powder weight.
Preferably, wherein ball-milling medium is Ceramic Balls or steel ball, and its particle diameter is the 1-15 millimeter.
Preferably, wherein ball-milling medium and described spherical polynary zinc-aluminium powder are (6～20) by weight: 1.
Average sheet footpath 5～35 μ m of the polynary Zn-Al alloy powder of flakey of the present invention, and specifically consisting of of granularity wherein: the sheet footpath less than 5 μ m account for≤20%, sheet footpath 5～33 μ m account for 〉=70%, the sheet footpath is greater than 33 μ m≤10%.The concrete composition of this granularity of the present invention has not only guaranteed the requirement in average sheet footpath, and so that the powder physical dimension is evenly distributed, and uniform size distribution is conducive to reduce the defectives such as hole in the coating, form the uniformly structure of " layer upon layer of ", thereby be conducive to suppress the infiltration of corrosive medium, thereby improve the antiseptic property of coating.
The sheet of the polynary Zn-Al alloy powder of flakey of the present invention is thick to be 0.1～1 μ m, average sheet directly is 5～35 μ m, average sheet footpath is 35～200 with the thick radius-thickness ratio of sheet, has improved greatly the radius-thickness ratio of the polynary allumen powder of flakey, and this is of great immediate significance.Because the raising of radius-thickness ratio, the use amount of per unit area allumen powder reduces production cost greatly in the time of can reducing on the one hand the coating coating; On the other hand, the raising of radius-thickness ratio can make the sheet allumen powder that is coated in workpiece spare surface more closely knit, when reduce applying owing to the sheet alloy powder the blocked up or space that causes in uneven thickness, sheet footpath, improve the antiseptic property after the coating coating.Therefore, the polynary Zn-Al alloy powder of described flakey is obtained important breakthrough with respect to prior art.
Further, the apparent density of the polynary Zn-Al alloy powder of flakey of the present invention is 1.0～3.0gcm
-3, this also is that the inventor has paid just finally acquisition of performing creative labour.Because it is a lot of to affect the factor of apparent density of powder, such as powder particle shape, size and size distribution etc.And these factors can have again significant difference because of the preparation method of powder and the difference of process conditions thereof.And the polynary Zn-Al alloy powder of flakey described in the present invention is to satisfy particle size less, under the higher precondition of sheet degree, further realized less apparent density by the improvement on the production technology, thereby improved the dispersiveness of the polynary allumen powder of flakey in coating, also further more satisfied the instructions for use of Dyclo paint.
Further, the present invention by the improvement on the production technology so that the lid water area of the polynary Zn-Al alloy powder of described flakey is 0.4～2.0m
2G
-1, illustrating that the polynary allumen powder of flakey of the present invention sheet degree is higher, spreadability is better, good dispersion in water.The lid water area of the polynary allumen powder of the flakey among the present invention has surpassed the lid water area of domestic simple zinc powder, even can reach the standard of external simple zinc powder product, has obtained very outstanding technique effect.
On the other hand, the preparation method of scaled metal powder provided by the present invention has compared with prior art replaced in the wet-milling with the defective of liquid as the grinding medium, grind by adding grinding aid and ball-milling medium, metal powder after drying can residual any medium, has guaranteed the scope of application and the quality of metal powder.
Further, the grinding aid and the ball-milling medium that wherein add have also guaranteed can not produce the cold welding phenomenon between the metal powder.
Further, in airtight ball mill, pass into inert gas, can avoid oxygen to enter, prevent the metal powder oxidation.
Further, the temperature of controlling metal powder by the method for regulating the cooling water inflow in the ball mill interlayer in mechanical milling process is between 20～60 ℃, and the rotating speed of regulating simultaneously ball mill carries out ball milling at 30-100 rev/min, can be with spherical metal powder ball milling slabbing metal powder.
In addition, by controlling different rotational speed of ball-mill, can also improve quality and the scope of application of metal powder, make prepared metal powder not only can be used for Dyclo paint, also can be used for other anticorrosive paints such as zinc rich paint.
Further, the sandwich of ball mill by setting up among the present invention, make cooling liquid for example water be to be passed into by the ball mill interlayer, rather than directly contact with powder.Compare with traditional wet-milling and long dry grind process, and adopt water-cool control ball milling temperature, not only still avoided the defective of wet-milling, also having overcome needs long-time dry deficiency, has improved greatly production efficiency.
In addition, the polynary allumen powder of flakey provided by the present invention adopts the dry type ball grinding method to obtain, and the medium that powder surface coats when having avoided wet grinding fully such as solvent naphtha are on the impact of follow-up coating property.
At last, allumen powder provided by the invention is because the passivation of aluminium, greatly slowed down the wear rate of zinc, for the powder or its mixed-powder of the domestic and international single zinc that does not have alloying of producing, aluminium, antiseptic property and the anticorrosion life-span of having improved greatly coating.
In sum, scaled metal powder provided by the invention end and preparation method thereof is particularly suitable for producing the Dacroment masking liquid, inorganic zinc rich paint, the fields such as heavy-duty anticorrosive coating.Moreover, adopt the preparation method who provides of the present invention to go for equally the production of other flake metal powders, for example: aluminium powder, copper powder, cu-zn alloy powder, silver powder etc.
Description of drawings
Fig. 1 horizontal ball mill sandwich figure
The specific embodiment
The polynary aluminium zinc of flakey of the present invention silicon alloy powder is comprised of elements such as Al, Si, Mg, Zn and rare earths, some preferred specific embodiments of each composition percentage by weight among the present invention have been listed in the table 1, but the content of each constituent of the present invention is not limited to listed concrete numerical value among the table 1-10, to those skilled in the art, can rationally summarize on the basis of the listed concrete numerical value of table 1 and derive fully.
Of particular note, the present invention is on the basis that a kind of polynary Zn-Al alloy powder of high-quality flakey that can satisfy extraordinary coating process requirement is provided, by the further improvement on the production technology, make the performance of described flakey aluminium zinc silicon alloy powder all be more than flakey alloy powder of the prior art far away, the interior microscopic that flakey aluminium zinc silicon alloy powder of the present invention is described is organized very large variation has also been occured, although these micro-variations can't with the structure of flakey aluminium zinc silicon alloy powder and/or composition etc. further restriction described, but by further describing of table 1 performance parameter, those skilled in the art can know clearly that it is to the restriction effect of playing of flakey aluminium zinc silicon alloy powder of the present invention.
But showing the performance parameters such as apparent density related among the 1-10 and lid water area but is not to solve the requisite technical characterictic of the present invention, and it only is the more excellent technical scheme that the present invention further obtains with respect to prior art.For the present invention, the content of core is the setting of the polynary Zn-Al alloy powder composition of flakey, especially the setting of the concrete composition of thick, the sheet of sheets of powder footpath, granularity and radius-thickness ratio and reach the goal of the invention that is suitable for producing the masking liquids such as Dacroment.And on this basis, the further improvement by production technology all is to make this technique effect more outstanding, and is more superior.Therefore, put down in writing simultaneously apparent density and these two performance parameters of lid water area in the following table 1 in specification, also just in order to introduce more in detail, easily technical scheme of the present invention, and described as the essential features that solves the technology of the present invention problem.
Similar therewith, table 1-10 further provides composition and the concrete content thereof of the concrete rare earth element that adopts of the present invention and is described as preferred embodiment, those skilled in the art should determine that the rare earth element and the content thereof that provide among the inevitable requirement employing table 1-10 not can solve its technical problem, and namely it is not described as necessary condition equally.
Each composition of table 1 (percentage by weight) and performance parameter thereof
Each composition of table 2 (percentage by weight) and performance parameter thereof
Each composition of table 3 (percentage by weight) and performance parameter thereof
Each composition of table 4 (percentage by weight) and performance parameter thereof
Each composition of table 5 (percentage by weight) and performance parameter thereof
Each composition of table 6 (percentage by weight) and performance parameter thereof
Each composition of table 7 (percentage by weight) and performance parameter thereof
Each composition of table 8 (percentage by weight) and performance parameter thereof
Each composition of table 9 (percentage by weight) and performance parameter thereof
Each composition of table 10 (percentage by weight) and performance parameter thereof
Below in conjunction with accompanying drawing 1, specify the present invention and prepare the polynary Zn-Al alloy powder embodiment of flakey, at first, get the raw materials ready on request, and each component is made allumen by proportioning in smelting furnace, pour into the allumen rod by the deep-well forging type again.Then, the allumen rod is put into the vacuum atomizing powder manufacturing apparatus be atomized into 200～500 purpose spherical powders, again spherical allumen powder is joined in the ball mill, add simultaneously grinding aid, ball-milling medium carries out ball milling, pass into again inert gas after vacuumizing first, pass into cooling liquid in the ball mill interlayer 1 take control ball milling temperature as 20-60 ℃, Ball-milling Time is 8～20 hours, keeping drum's speed of rotation is 30～100 rev/mins, the spherical polynary allumen sphere of powder is worn into the sheet alloy powder, prepare the polynary Zn-Al alloy powder of flakey.
The ball mill that the present invention adopts is to have set up a ball mill interlayer 1 on the basis of horizontal ball mill of prior art, thereby can in interlayer 1, pass into cooling liquid with control ball milling temperature, thereby realize that cooling liquid and powder separation do not contact to overcome the goal of the invention of wet-milling defective.
Preferably, ball-milling additive comprises zinc stearate, calcium stearate, molybdenum sulfide, polyvinyl alcohol, neopelex, glyceryl alcohol etc.Stearate, molybdenum sulfide consumption are the 1-10% of metal dust weight.
Preferably, adopting the ball-milling medium diameter is 1-15mm, preferably ceramic ball or steel ball etc., and the ratio of itself and raw material aluminium zinc silicon alloy powder is 6: 1 to 20: 1.
Preferably, the ball mill running speed is not less than 30r/min, and preferred range of choice is 30-100r/min.
Embodiment 1:
Get 300 order aluminium zinc silicon alloy powder raw material 10Kg, zinc stearate 0.4Kg, steel ball 200Kg drops in the ball mill, passes into nitrogen after vacuumizing, and connects cooling water, guarantees that temperature is between 30-40 ℃ in the mechanical milling process.With discharging behind the rotating speed ball milling 10h of 50r/min, with polishing in the input of the powder behind the ball milling polishing machine, make flaky aluminum zinc silicon alloy powder after the powder after the polishing is classified.
Embodiment 2:
Get 200 order aluminium zinc silicon alloy powder raw material 10Kg, polyvinyl alcohol 0.1Kg, calcium stearate 0.2Kg, steel ball 120Kg drops in the ball mill, passes into nitrogen after vacuumizing, and connects cooling water, guarantee that temperature is between 30-40 ℃ in the mechanical milling process, with the rotating speed ball milling 14h discharging of 100r/min, with polishing in the input of the powder behind the ball milling polishing machine, make flaky aluminum zinc silicon alloy powder after the powder after the polishing is classified.
Claims (10)
1. polynary Zn-Al alloy powder of flakey, its components based on weight percentage is: Al:15%-69%; Si:0.2-3%; Mg:0.1-5%; The total amount of at least two kinds of rare earth elements: 0.02-0.9%; Total amount is no more than 1% impurity; Surplus is Zn, the sheet of the polynary Zn-Al alloy powder of wherein said flakey is thick to be 0.1～1 μ m, average sheet directly is 5～35 μ m, and specifically consisting of of granularity wherein: the sheet footpath less than 5 μ m account for≤20%, sheet footpath 5～33 μ m account for 〉=and 70%, sheet footpath is greater than 33 μ m≤10%, and the thick radius-thickness ratio of the average sheet footpath of the polynary Zn-Al alloy powder of described flakey and sheet is 35～200.
2. the polynary Zn-Al alloy powder of flakey as claimed in claim 1, the apparent density of the polynary Zn-Al alloy powder of wherein said flakey is 1.0～3.0gcm
-3
3. the polynary Zn-Al alloy powder of flakey as claimed in claim 1, the lid water area of the polynary Zn-Al alloy powder of wherein said flakey is 0.4～2.0m
2G
-1
4. the polynary Zn-Al alloy powder of flakey as claimed in claim 1, wherein said at least two kinds of rare earth elements mainly comprise lanthanum (La), cerium (Ce), praseodymium (Pr), in the neodymium (Nd) any two or more.
5. the polynary Zn-Al alloy powder of flakey as claimed in claim 4, wherein said at least two kinds of rare earth elements comprise lanthanum (La), cerium (Ce), praseodymium (Pr), in the neodymium (Nd) any two kinds, and this any two kinds content and account for the percentage of rare earth element total amount 〉=85%.
6. method for preparing the polynary Zn-Al alloy powder of the described flakey of claim 1, percentage by weight according to polynary each component of Zn-Al alloy powder of the described flakey of claim 1 is got the raw materials ready, each component is made allumen by proportioning in smelting furnace, pour into the allumen rod by the deep-well forging type again, then, the allumen rod is put into the vacuum atomizing powder manufacturing apparatus be atomized into the spherical allumen powder of 200～500 purposes, again described spherical allumen powder is joined in the ball mill, add simultaneously grinding aid and ball-milling medium and carry out ball milling, and pass into again inert gas after vacuumizing first, pass in the ball mill interlayer cooling liquid take control mechanical milling process in temperature as 20-60 ℃, Ball-milling Time is 8～20 hours, keeping drum's speed of rotation is 30～100 rev/mins, thereby the described spherical polynary allumen sphere of powder is worn into the sheet alloy powder, prepare the polynary Zn-Al alloy powder of described flakey.
7. method as claimed in claim 6, wherein grinding aid is one or more mixing in zinc stearate, calcium stearate, molybdenum sulfide, polyvinyl alcohol, neopelex, the glyceryl alcohol.
8. method as claimed in claim 6, wherein grinding aid adds according to 1%～10% ratio of described spherical polynary zinc-aluminium powder weight.
9. method as claimed in claim 6, wherein ball-milling medium is Ceramic Balls or steel ball, its particle diameter is the 1-15 millimeter.
10. method as claimed in claim 6, wherein ball-milling medium and described spherical polynary zinc-aluminium powder are by weight being (6～20): 1.
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| CN107523209A (en) * | 2017-09-26 | 2017-12-29 | 河南青山环保科技有限公司 | A kind of water-based non-crystaline amorphous metal corrosion resistant coating and preparation method thereof |
| CN107523106A (en) * | 2017-09-26 | 2017-12-29 | 河南青山环保科技有限公司 | A kind of high mode waterborne zinc-rich high-temperature resistant anti-corrosive paint and preparation method thereof |
| CN109021773A (en) * | 2018-06-08 | 2018-12-18 | 江苏麟龙新材料股份有限公司 | A kind of flakey aluminium Zinc-based multi-element alloy water corrosion-resistant epoxy paint |
| CN109365828A (en) * | 2018-12-25 | 2019-02-22 | 江苏科创金属新材料有限公司 | A kind of ultra-fine powder producing method of flake zinc aluminium alloy |
| CN111167569A (en) * | 2019-12-31 | 2020-05-19 | 曲靖华益兴新材料有限公司 | Method and equipment for preparing easily-dispersible aluminum powder pigment by direct ball milling |
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