CN102268625B - Method for hot dipping aluminum for steel structure - Google Patents
Method for hot dipping aluminum for steel structure Download PDFInfo
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- CN102268625B CN102268625B CN 201110221124 CN201110221124A CN102268625B CN 102268625 B CN102268625 B CN 102268625B CN 201110221124 CN201110221124 CN 201110221124 CN 201110221124 A CN201110221124 A CN 201110221124A CN 102268625 B CN102268625 B CN 102268625B
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Abstract
The invention relates to the technical field of metal surface coatings, in particular to a hot dipping method for a steel structure. A hot dipping alloy consists of the following components in percentage by mass: 75 to 85 percent of Al, 3 to 5 percent of Mg, 3 to 5 percent of Si, 0.01 to 0.02 percent of rare earth Y, 0.04 to 0.10 percent of Ni, 0.04 to 0.10 percent of Bi, 0.04 to 0.10 percent of V, and the balance of Zn and inevitable impurities; and in the hot dipping process, a pulsed electric field is applied to a weld pool, and the parameter ranges of the pulsed electric field are that: the pulse width is 80 to 100ms, the acting frequency is 1 to 2Hz and the peak density of pulse current introduced into the weld pool is 0.1 to 10A/cm<2>. By the synergism of the rare earth Y, Ni, Bi and V, the fluidity and wettability of aluminum are improved; the strength and corrosion resistance of a coating are improved by nano Si and Mg2Si phases separated under the action of the pulsed electric field; and the pulsed electric field also has effects of refining grains and improving the compactness of the coating. By the invention, the coating quality is improved, metal consumption is reduced, a process is simple, the conventional process and equipment are mature, the cost is low and the method is worth promoting.
Description
Technical field
The present invention relates to coating technology field, metallic surface, particularly a kind of hot dip coating method of steel construction piece.
Background technology
Corrosion is the important way of ferrous materials loss, and is annual because the ferrous materials that corrosion is lost reaches tens million of tons, and is the effective way that improves the corrosion resistance of metals energy, reduces metallic corrosion consumption at metallic surface hot dip process preservative coat at present; For the ferrous materials of different purposes, because the aspects such as environment for use, material structure and performance is different, the hot-dip plating metal coated material that adopts at present mainly comprises: Zn system, rare earth Zn system, Zn-Al system, Al system, rare earth Al system etc.; In recent years, hot dip aluminum plating has obvious advantage aspects such as cost, environmental protection and coating performance and life-spans, receives increasing concern.
In the alloy for hot-dip of high aluminium content, the Galvalume alloy adopts the 55%Al-1.6%Si-Zn alloy layer to be considered to the alloy that prior art interalloy Match of elemental composition is best, the coating over-all properties is the best, it has had both the erosion resistance of zinc coating and the multiple excellent properties such as high temperature resistance of aluminium coated, uses so obtained widely; Also there is the deficiency of the poor and poor fluidity of high-aluminium alloy wettability in existing hot dip aluminum plating, so the quality and performance of the homogeneity of coating and coating has much room for improvement; Chinese patent application number: 200910044817.8 and 200910134953.6 propose to adopt Mg
2Si improves the corrosion resistance nature of coating, and introduces respectively Ti, B and rare earth La or Ce crystal grain thinning; Chinese patent application numbers 200910262758.1 also proposes to utilize Mg
2Si, TiO
2, CeO
2Improve coating performance Deng particle, this shows, introducing enhanced granule in aluminium coat is to improve the effective way of coating performance; But really exist 2 significantly deficiencies in the prior art: the one,, prior art has only proposed to utilize enhanced granule to improve the scheme of coating performance, but be only the most critical of the quality of coating factor that affects for the size of formation Particle Phase in the hot dip process process coating and the impact that pattern reaches coating crystal grain, studies have shown that, for warm feeling coating, enhanced granule only is controlled at below the 30-40nm, just has significant raising coating etch resistant properties, the effect of the quality such as coating density, particularly for the hot dip aluminum plating of steel construction piece, the hot dip process time is long, size and formation condition to coated metal liquid precipitated phase and enhanced granule in the prior art are uncontrollable, therefore, enhanced granule is on the impact of coating performance also uncontrollable and Effective Raise; The 2nd,, introduce enhanced granule in melt or in the coating, the mobile variation of melt, therefore, to further optimize the composition of alloy for hot-dip, controlling on the one hand Particle Phase is to form in the process of setting in coating formation as far as possible, to pass through on the other hand to introduce surface tension and its flowability of raising that alloying element reduces alloy for hot-dip liquid, thus but the hot dip process performance of raising melt.
In sum, hot dip aluminum plating to steel construction piece, the particle of introducing Nano grade in coating is the feasible way that improves coating performance, is optimized but need to form alloy for hot-dip, and the control Particle Phase is separated out in process of setting, and by the outfield means particle and precipitated phase are controlled at nanoscale, simultaneously, introduce alloying element, reduce viscosity and the surface tension of melt, that improves metal can be hot-dip, thereby improve performance and the surface quality of coating.
Summary of the invention
The objective of the invention is: invent a kind of polynary aluminium alloy for hot dipping aluminum for steel structure, and melt is applied the hot dip coating method of pulsed electrical field in the hot dip process process, by optimizing the composition of multicomponent alloy, be the process of setting precipitate particle phase of coated metal in the coating forming process, and Particle Phase is controlled at the best scale that can improve material property by the pulsed electrical field that adds, solve separating out and the problem of growing up of precipitated phase and particle in the uncontrollable coating of prior art; Simultaneously, introduce in the hot dip aluminum plating multicomponent alloy of optimization and reduce melt viscosity and capillary element, but the hot dip process performance of raising aluminium alloy, thus performance and the surface quality of raising coating.
The scheme imagination that realizes the object of the invention is:
Introduce simultaneously Mg and Si in the hot dip aluminum plating of the present invention, hot dip aluminum plating the coating forming process be to separate out Mg in the process of setting
2The Si particle, the addition of Mg and Si is with control Mg
2The Si particle only forms and separates out in process of setting and is principle, and in the hot dip process process melt is applied pulsed electrical field, utilizes pulsed electrical field control Mg
2The size of Si particle.
Introduce simultaneously Ni in the hot dip aluminum plating of the present invention, Bi, V and Rare Earth Y, these elements act synergistically in suitable interpolation scope can effectively fall low-alloyed viscosity and surface tension, separates out Mg to remedy owing in the alloy graining process melt
2But the aluminium alloy hot dip process performance that the viscosity that the Si particle causes increases severely and wettability descends to be caused descends, thereby improves the hot dip process performance of aluminium alloy; In addition, owing to containing the introducing of multiple alloying element, particularly Mg and Si in the hot dip aluminum plating alloy of the present invention, the grain boundary precipitate of aluminium alloy is more, and Rare Earth Y has very strong purification grain boundary precipitate and the effect of crystal grain thinning, thereby improves the performance of coating.
Owing to introducing Mg among the present invention
2The Si particle is for making Mg
2The size of Si particle is controlled, must apply the outfield with control particle size at nanoscale, pulsed electrical field of the present invention, the electric transient discharge effect that produces in melt be the effective precipitate in the refinement process of setting not only, but also has significant Grain refinement; Introduce the effect that Y, Ni, Bi, V have crystal grain thinning among the present invention, but the hot dip aluminum plating for steel construction piece, because setting time is long, the crystal grain of the element refining aluminum alloy coating that single dependence adds is difficult to satisfy the requirement of high-performance coating, therefore must utilize the crystal grain of Electro-pulsing Field refinement coating.
As mentioned above, aspect the hot dip aluminum plating alloy, creativeness of the present invention is to introduce Mg and Si, separates out Mg in the coating forming process
2The Si particle, and by outfield control particle at nanoscale; Introduce Rare Earth Y, Ni, Bi and V synergy in the alloy, fall low-alloyed viscosity and surface tension, carry heavy alloyed hot-dip; In addition, owing to introducing Mg among the present invention
2The Si particle, and long to the steel construction piece hot dip process time, must introduce the Mg that outfield refinement process of setting is separated out
2S particle and to the further refinement of coating crystal grain reaches the purpose that improves the coating over-all properties.
Based on above-mentioned thinking and principle, realize that technical scheme of the present invention is:
Hot dip coating method under a kind of hot dipping aluminum for steel structure multicomponent alloy and the pulsed electrical field, it is characterized in that adopting a kind of to hot dipping aluminum for steel structure is the multicomponent alloy of major components by Al-Mg-Si-Zn, the consisting of of described hot dip aluminum plating multicomponent alloy (massfraction %): Al 75-85%, Mg 3-5%, Si 3-5%, Rare Earth Y 0.01-0.02%, Ni 0.04-0.10%, Bi 0.04-0.10%, V 0.04-0.10%, surplus is Zn and inevitable impurity; Adopt the hot dip coating method of hot dipping aluminum for steel structure multicomponent alloy of the present invention, difference with the prior art is in the hot dip process process molten bath to be applied pulsed electrical field, the parameter area of described pulsed electrical field: pulse width is 80-100 ms, the effect frequency is 1-2 Hz, and the pulse current peak density that passes into melt is: 0.1-10 A/cm
2
In addition, implementation hot dip coating method of the present invention is basic identical with the method for present hot dipping aluminum for steel structure, its difference is that the alloy for hot-dip Composition Control that adopts is different and apply pulsed electrical field in hot dip process process alloy molten bath, the equipment aspect, pulsed electrical field equipment can adopt plant-scale commercial equipment, the introducing of pulsed electrical field can adopt fixed electorde or traveling electrode to introduce flexibly in the molten bath, for preventing that Aluminum from polluting, the general Graphite Electrodes that adopts, electrode can be fixed on for the sidewall of the aluminum pot of hot dip process and the bottom of a pan, also can put into and hang under the prerequisite of extract operation not affecting steel construction piece, insert from top, molten bath; Therefore, the technique of implementing this invention is simple, flexible operation, and existing tooling is ripe, and cost is low, is worthy to be popularized.
The composition range of hot dipping aluminum for steel structure multicomponent alloy of the present invention is determined according to following principle:
(1) the Al content range is determined
The corrosion resistance of high-aluminium alloy improves with aluminium content, existing for the Galvalume alloy (55%Al-1.6%Si-Zn) that present hot dip aluminum plating extensively adopts mutually, the content of aluminium element among the present invention (massfraction %) is brought up to 75-85%, is conducive to improve the corrosion resistance of coating; But, Aluminum in Alloy content improves again, wettability to steel obviously descends, and occurs easily that plating leakage and uneven coating are even, discontinuous phenomenon, adopts among the present invention the content (massfraction %) of Aluminum in Alloy element is brought up to 75-85%, under the elements such as Mg, Si, Ni, Bi, Y synergy and pulsed electrical field oscillation action, the hot dip process of alloy is satisfactory for result, not only improved corrosion resistance, and coating is even, smooth, have extraordinary quality of coating.
(2) content range of Mg and Si is determined
The span of control of Mg and Si content is (massfraction %) 3-5% among the present invention, and Mg and Si can reduce fusing point and the viscosity of aluminium alloy, after addition is higher than this scope, can separate out the Mg of some amount in the melt
2Si can make the hot-dip remarkable decline of alloy, and therefore, Mg and Si content should be controlled under the hot dip process temperature, do not separate out Mg in the melt
2The Si particle is limit, and its span of control is 3-5%; Wherein the best relative proportion of Mg and Si (massfraction ratio) is controlled at the scope of Mg:Si=2:1-3:2; Because the scaling loss situation of Mg and Si is different, therefore, its content allows surplus to a certain degree.
(3) the Rare Earth Y content range determines
The effect of rare earth element y comprises: fall low-alloyed viscosity and surface tension, thereby carry heavy alloyed hot-dip; The cleaning molten effect particularly purifies the crystal boundary of coating; The effect of crystal grain thinning; The Rare Earth Y addition is in＜0.1% scope, have significant purification and thin brilliant effect, its addition increases again, can increase the quantity of slag in molten bath, among the present invention rare earth adding quantity is controlled at the 0.01-0.02% scope, under the booster action in other element synergy and outfield, obtain desirable hot dip process effect.
(4) Ni, Bi and V content range determines
The purpose of adding Ni, Bi and V element is to reduce viscosity and the surface tension of aluminium alloy melt, and simultaneously, these elements have the effect of crystal grain thinning, and during addition＜0.1%, these beneficial effects are obvious; But work as addition〉after 0.1%, not only can increase cost, can cause that also the precipitate between the coating crystal boundary increases, affect corrosion resistance, therefore, the addition of Ni, Bi and V element is more satisfactory at 0.04-0.10%.
(5) surplus Zn and inevitably impurity
All the other elements in the hot dip aluminum plating multicomponent alloy of the present invention are Zn and inevitable impurity, and the Zn amount increases the temperature that can reduce hot dip process, and therefore the scope of surplus Zn generally should be greater than 5% in the alloy for hot-dip of the present invention; Described impurity content should be less than 0.06%.
Adopting another key character of the present invention is in the hot dip process process molten bath to be applied pulsed electrical field, and the current parameters scope of described pulsed electrical field is determined according to following principle:
(1) about pulse width and effect frequency
To the action rule of alloy for hot-dip process of setting, the pulse width of pulsed electrical field determines at 80-100ms in conjunction with at present pulse electric field technology condition and pulsed electrical field, and the effect frequency of pulsed electrical field is 1-2Hz.
(2) about the peak strength of pulsed current
The pulse current peak density that passes into melt is: 0.1-10 A/cm
2, the visual fusion pond holds the aluminium amount and power supply capacity is determined.
Compared with prior art major advantage of the present invention is as follows:
(1), the present invention and existing hot dip aluminum plating or hot dip aluminum plating alloy phase ratio, have following prominent feature: fine corrosion resistance, in the salt air corrosion environment, corrosion resistance improves about 20% than the Galvalume alloy layer that adopts at present extensively; The immersion plating excellent property, smooth surface, smooth without defectives such as plating leakage, drosses, overcome that prior art adopts high-aluminium alloy coating because the surface imperfection such as the poor plating leakage that causes of hot dip process performance, uneven coating be even.
(2), the present invention adopts the multielement synergy to improve the hot dip process performance of high-aluminium alloy, be aided with under the effect of pulsed electrical field shock oscillation, changed the thermodynamics and kinetics that cenotype is separated out, control coating endoparticle is separated out in process of setting, and refinement precipitated phase particle size is below 30-40nm, overcome the grow up hot dip process performance that causes of opportunity of separating out of uncontrollable particle in the prior art and particle poor, the problems such as coating is rough, plating leakage.
(3), adopt the aluminium zinc hot dip process of low aluminium with prior art and adopt in the Galvalume alloy phase ratio of aluminium content, aluminium content increases, not only improved the corrosion resistance of coating, and reduced zinc content in the alloy, zinc is compared with aluminium, price is high and volatile and oxidation loss is large, so, improve aluminium content, reduce zinc content, can reduce the coating cost, compare by present aluminium, zinc price, save cost more than 20%; In addition, aluminium is in 690-750 ℃ of scope of hot dip process temperature, and aluminium volatilizees hardly, therefore, is conducive to the innoxious of execute-in-place environment.
(4), introduced Mg owing in the coating among the present invention
2The Si particle, therefore the hot dip process process must apply outfield control particle size within useful scope, the present invention adopts pulsed electrical field, utilize pulse to discharge and recharge technology, reach very high oscillation intensity in moment, this transient state electricoscillation not only effectively refinement the precipitated phase particle, to the effect of grain refining also highly significant, compare Mg with not applying the outfield
2Si Particle Phase size is by the above rank of 100nm, refine to below the 30-40nm, the average grain size of coating aluminium refine to Nano grade (50nm is following) by micron level (0.2-0.5 μ m), and these beneficial effects directly cause the raising of coating corrosion resistance, coating tightness and antistrip performance.
(5), adopt the present invention, can utilize the metallurgical equipment of existing maturation, do not need the new tooling of development research, facility investment is few, technique is simple, cost is low, is worthy to be popularized.
Embodiment
Be that checking adopts effect of the present invention, the steel construction piece of No. 20 steel matter carried out following a series of hot dip aluminum plating simultaneous test:
Series 1: adopt the present invention fully, namely adopt simultaneously hot dip aluminum plating multicomponent alloy of the present invention and adopt the method that in the hot dip process process, applies pulsed electrical field; (remarks: numbering 1-4 group in the table 1).
Series 2: only adopt hot dip aluminum plating multicomponent alloy of the present invention, the hot dip process process does not apply pulsed electrical field; (remarks: numbering 5-8 group in the table 1).
Series 3: existing hot dip aluminum plating alloy, adopt the Galvalume alloy; (remarks: numbering is the 9th group in the table 1).
Series 4: choose and adopt Mg in the prior art (Chinese patent application number 200910044817.8)
2The alloy that the Si particle improves coating performance carries out the hot dip process test; (remarks: numbering 10-11 group in the table 1, apply the effect of pulsed electrical field for comparative illustration, the alloy of prior art has also been carried out applying the test of pulsed electrical field).
By relatively coating performance is estimated in visual appearance, thickness of coating, coating hardness, the salt air corrosion zero-G test of coating; Evaluation result sees Table 2; Remarks: table 1 is consistent with numbering in the table 2.
Whether distinguish and apply the pulsed electrical field in the hot dip process process except the alloying constituent that adopts, the method and apparatus that the simultaneous test of carrying out adopts is identical, namely traditional hot-dipping aluminium-plating method need not too much explanation.
Table 1 hot dip process scheme (aluminium alloy composition and condition)
(annotate: * for not applying or not adding)
The hot dip aluminum plating testing program of his-and-hers watches 1, the method and apparatus that the simultaneous test of carrying out adopts is identical, it is traditional hot-dipping aluminium-plating method, its pre-treatment and aftertreatment all need not too much explanation, parameter in the hot dip process process is: 710 ℃ of hot dip process operation temperature of aluminum liquid, the time 7min that aluminizes, immersion plating mode: instrument lifting suspention; Pulling speed 10m/min. table 2 is hot dip process effect comparable situation.
The contrast effect of table 2 embodiment and prior art
The explanation of note table 2:
1) numbering in the table 2 is consistent with numbering in the table 1;
2) thickness of coating scope and mean value are measured definite maximum value and minimum value for getting 5 points in the table 2, determine average thickness values with the method for averaging;
3) coating apparent mass: the smooth finish aspect, any surface finish smoothly is best; Rough taking second place, rough have convex dot shape coarse the poorest; Have or not the plating leakage aspect, best without plating leakage, there is obvious plating leakage the poorest, be defined as defective; The hardness aspect, hardness is high, illustrates that coating is fine and close, and good corrosion resistance, micro-hardness measurement are got 5 mean values;
4) salt air corrosion experiment: etch in 5% the NaCl solution, 30 ± 2 ℃ of test temperatures are measured the time that plating piece keeps rustless state, h;
5) intensity and wear-resisting rank: carry out wear test with file under the same conditions, without unified standard, this case is divided into A, B, C, four grades of D with the result because of at present, and A is that intensity is the highest, and coating is without peeling off flawless; B is that intensity is taken second place, and coating has crackle, without peeling off; C is that intensity is low, and coating has crackle and peeling; D is worst, and intensity is low, and plating exfoliation is obvious.
Comparative test result is as can be known:
1) adopts the present invention, thickness of coating good uniformity (the thickness fluctuation scope is little), coating microhardness reaches more than the 9000MPa, coating grain-size and precipitate size Nano grade (＜40nm), the corrosion resistance of coating and intensity, peeling resistance are best; Particularly the effect of the 4th group of test is the most desirable, illustrates that the matching of alloying element is best, and the pulsed electrical field parameter effect that applies is the most desirable;
2) test-results of organizing (only adopting aluminium multicomponent alloy of the present invention) by contrast 1-4 group (adopting the present invention fully) and 5-8 as can be known, only adopt aluminium multicomponent alloy of the present invention to carry out hot dip aluminum plating, difference aspect thickness of coating is that the thickness of coating fluctuation range becomes large, the continuity that coating is described is bad, the apparent mass of coating is poor in addition, be embodied in two aspects of smooth finish and hardness, particularly, with adopt 1-4 of the present invention group fully and compare, grain-size, the precipitate size significant difference, cause coating hardness, corrosion resistance and intensity have very big difference, and this explanation adopts effect of the present invention remarkable fully;
3) adopt the Galvalume alloy phase ratio of the present invention's (1-4 group) and the optimal heat dip calorizing that adopts under the same conditions prior art to report, thickness of coating is attenuate slightly, this is the inevitable outcome that aluminium content raises, the Zn content causes, but surface quality, hardness, corrosion resistance and coating strength are all not as employing the present invention during the Galvalume alloy;
4) with in the prior art (Chinese patent application number 200910044817.8) adopt Mg
2The alloy that the Si particle improves coating performance carries out hot dip process, the present invention not only improved Aluminum in Alloy content, optimized the content of Mg, Si element, and introduce Y, Ni, Bi, V synergy improves the hot dip process performance, particularly apply pulsed electrical field in the hot dip process process, so quality of coating of the present invention is better than the coating of prior art at aspects such as thickness evenness, surface quality, microhardness and corrosion resistances comprehensively.
In addition, for existing hot dipping aluminum for steel structure technology, adopt the present invention, also have the tooling maturation, the advantage such as cost is low is worthy to be popularized.
Claims (1)
1. the method for a hot dipping aluminum for steel structure, it is characterized in that: adopt the hot dipped multi-element aluminium alloy to replace existing hot dip aluminum plating alloy steel construction piece is carried out hot dip process, simultaneously in the hot dip aluminum plating process, the alloy for hot-dip molten bath is applied pulsed electrical field, described hot dipped multi-element aluminium alloy consists of (massfraction %): Al 75-85%, Mg 3-5%, Si 3-5%, Rare Earth Y 0.01-0.02%, Ni 0.04-0.10%, Bi 0.04-0.10%, V 0.04-0.10%, surplus is Zn and inevitable impurity, the current parameters of described pulsed electrical field is: pulse width is 80-100 ms, and the effect frequency is 1-2 Hz, and the pulse current peak density that passes into melt is: 0.1-10 A/cm
2
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| KR101736737B1 (en) | 2013-03-28 | 2017-05-17 | 제이에프이 스틸 가부시키가이샤 | HOT-DIP Al-Zn ALLOY COATED STEEL SHEET AND METHOD FOR PRODUCING SAME |
| JP6042445B2 (en) * | 2013-04-18 | 2016-12-14 | 新日鐵住金株式会社 | Hot-pressed plated steel sheet, hot-pressing method of plated steel sheet, and automotive parts |
| WO2016002040A1 (en) * | 2014-07-03 | 2016-01-07 | 日新製鋼株式会社 | MOLTEN Al PLATED STEEL WIRE AS WELL AS STRANDED WIRE AND MANUFACTURING METHOD THEREFOR |
| CN108796417A (en) * | 2017-05-02 | 2018-11-13 | 贵州理工学院 | A kind of Aldip process continuously prepares the method and its device of corrosion-resistant I-steel |
| CN109943796A (en) * | 2019-03-21 | 2019-06-28 | 珠海弘德表面技术有限公司 | A kind of thermal spraying material and preparation method thereof of resistance to molten aluminum etch |
| CN111471948B (en) * | 2020-04-15 | 2020-10-23 | 湖南省美程陶瓷科技有限公司 | Metallization method of ceramic insulating ring for microwave magnetron |
| CN113046672A (en) * | 2021-03-11 | 2021-06-29 | 江苏中远稀土新材料有限公司 | Rare earth multi-element alloy coating for surface of metal support and hanger and hot galvanizing process thereof |
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| CN101082117A (en) * | 2006-05-30 | 2007-12-05 | 宝山钢铁股份有限公司 | Electromagnetic assistant dip coating method and device |
| CN101717905A (en) * | 2009-12-04 | 2010-06-02 | 江苏大学 | Method and device for preparing high-performance aluminum-base composite material under the action of pulsed magnetic field |
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| JPH06212382A (en) * | 1993-01-14 | 1994-08-02 | Nippon Steel Corp | Hot dip metal coating method for high tension steel sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101082117A (en) * | 2006-05-30 | 2007-12-05 | 宝山钢铁股份有限公司 | Electromagnetic assistant dip coating method and device |
| CN101717905A (en) * | 2009-12-04 | 2010-06-02 | 江苏大学 | Method and device for preparing high-performance aluminum-base composite material under the action of pulsed magnetic field |
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