CN103498073A - Zn-Al-Ti-B alloy for steel hot dipping and preparation method thereof - Google Patents
Zn-Al-Ti-B alloy for steel hot dipping and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of hot-dip galvanizing and in particular relates to a Zn-Al-Ti-B alloy for steel hot dipping and a preparation method thereof. The Zn-Al-Ti-B alloy is characterized in that the content of Al is controlled to be 30wt.%, the content of Ti is controlled to be 0.5-2wt.%, the content of B is controlled to be 0.5-2wt.%, and the balance is Zn. The Zn-Al-Ti-B alloy and the preparation method have the technical effects that the eutectic structure in galvanizing alloy is refined via the elements including Ti and B, thus improving the corrosion resistance of the galvanizing alloy; meanwhile, the forming quantity of Zn slag is reduced by reducing the content of Al in the galvanizing alloy, and the limited Zn slag in a Zn pool can be converted to dross from bottom slag, thus reducing the production cost and improving the production efficiency; the Zn-Al-Ti-B alloy can be applied to the hot-dip galvanizing processes of some parts with relatively high requirements for corrosion resistance and appearance quality.
Description
Technical field
Patent of the present invention belongs to the galvanizing technical field, refers in particular to a kind of thermal dip plating of steel Zn-Al-Ti-B Alloy And Preparation Method.
Background technology
Hot dipping of zinc-aluminum alloy is a kind of comparatively simply and effectively steel anti-corrosive method, because zinc aluminum alloy coating has been taken into account the weather resistance of aluminium and the sacrificing cathode protectiveness of zinc, the performance of its coating is than the superior performance of the coating of single-element, Corrosion Protection exceeds several times than pure zinc coating especially, has been widely used in the fields such as household electrical appliances, building, container manufacture, car and boat, electromechanics; For improving corrosion resistance and the galvanizing production quality of galvanizing production, alloying elements often is added among the zinc pond, as aluminium, magnesium, titanium, boron, rare earth etc.; By consulting literatures shows, in Galfan coating (containing 5wt.%Al) and Galvalume coating (containing 55wt.%Al), adds the research of these elements more, but it is less that coating alloy aluminum content is controlled to the research of 30wt.%; At present, found the people's such as Tu Hao research work (patent CN 102994929 A and patent CN 102392207 B), this patent is controlled at 20 ~ 40wt.% by the aluminium content in galvanized alloy, and what add is Si, Mg and rare earth element, but there are no the research that adds the alloying elements such as Ti and B, report in containing the galvanized alloy of 20 ~ 40wt.% aluminium.
At present, in existing hot dipping of zinc-aluminum alloy, Galvalume coating, due to its good corrosion resistance nature, is widely applied; But the Galvalume alloy layer is blocked up, the too much problem of slag content badly influences quality product in molten bath.Therefore, solving slag problem in molten bath is a very urgent problem on the continuous zinc coating production line, research shows, in molten bath, oversaturated iron is the major cause that cadmia forms, dissolving in of steel plate is the main source of iron in the zinc pond, the solubleness of ferro element in zinc liquid is to increase with temperature, the immersion plating temperature is higher, diffusion between steel plate and zinc pond is faster, the dissolution rate of iron is also just faster, therefore reduce the iron amount of being dissolved in the zinc pond by steel plate, just can effectively reduce the generation of end slag, in addition, when in the zinc pond, aluminium content surpasses 10%, reacting between steel plate and zinc liquid will be very violent, raising along with aluminium content in galvanizing flux, when particularly the aluminium weight content surpasses 20%, the dissolution rate of iron significantly improves rapidly, iron, thermopositive reaction between aluminium is more violent, visible, in molten bath, high aluminium content is also the one of the main reasons that end slag forms, can reduce the formation of cadmia by the method for aluminium content in effective reduction zinc pond, and the reduction along with aluminium content, zinc pond plating solution density increases, can make end slag be converted into scum silica frost.
Titanium is a kind of refractory metal element; Chang Zuowei strengthening element or alterant add in other metal or alloy; titanium has high fusing point and excellent corrosion resistance; be widely used in the fields such as space flight, military project, nuclear reaction, nuclear power; when the dip galvanized of titaniferous is exposed in air or water; can form one deck stable, and the TiO with stronger bonding force and protective value
2oxide film, it can make zinc coating in passive state, even also be difficult for being destroyed by chlorion in ocean environment, and this oxide film has good self-healing property, is corroded after destruction self-healing fast; Wei Shicheng etc. also draw from electrochemical parameter, Corrosion Resistance of Zinc Coating after the interpolation titanium can strengthen, on interpolation Ti element in pure zinc is bathed, the galvanizing impact on silicon containing steel is studied Du Yan etc., found that, along with Ti content in pure zinc bath increases, suppressed ζ and grown mutually, the interpolation of titanium has obvious thinning to thickness of coating, increases the attenuate effect with titanium content also more obvious.
Therefore, utilizing titanium and boron to come eutectic structure and expansion zinc-aluminium titanium in the refinement hot dipping of zinc-aluminum alloy is the range of application of galvanized alloy, formation is had the galvanized alloy of independent intellectual property right and meets better production application, and be very necessary.
Summary of the invention
The object of the invention is to develop a kind of Novel galvanizing alloy, by reducing the content of Al element, effectively reduce the content of cadmia in molten bath; By adding of titanium and boron, eutectic structure in the refinement galvanized alloy, in the situation that production cost can not increase considerably, improved the efficiency of continuous zinc coating production line greatly, promote the corrosion resistance nature of hot dipping of zinc-aluminum alloy simultaneously, improve coating surface quality.Make the Novel galvanizing Alloyapplication in some in the hot dip galvanizing process to erosion resistance, component that appearance requirement is higher.
Used for hot dip galvanizing Zn-Al-Ti-B alloy layer is characterized in that: the content of Al is controlled at 30wt.%, and the content of Ti is controlled at 0.5 ~ 2wt.%, and the content of B is controlled at 0.5 ~ 2wt.%, and all the other are Zn.
The preparation process of described zinc-aluminium Ti-B alloy is as follows:
(1) fusing: Zn piece, Al piece that proportioning is good are put into preheated crucible, be warming up to 720 ℃ and generate aluminium alloy, add the salt insulating covering agent on the aluminium alloy surface, again the Al-10Ti wrapped with Aluminium Foil Package and Al-16B master alloy are pressed into to aluminium alloy, melting, stir and mix, and is cooled to 550 ℃, be incubated one hour, wait for that dragging for slag processes;
(2) drag for slag: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, pull the slag in aluminium zinc liquid out from molten bath;
(3) casting: will be poured into and water in mold without the zinc-aluminium Ti-B alloy solution of slag, at normal temperatures the cooling column zinc-aluminium Ti-B alloy that becomes.
Described insulating covering agent is the quality percentage composition 30-50%CaCl through processed
2, 20-40%KCL and quality percentage composition 20%-30%NaCl mixed uniformly solid state powder, than conventional salt insulating covering agent, it has better heat insulation effect.
Principle of the present invention derives from the rotten processing in cast Zn-Al alloy, wherein Ti and B element are except refinement hot dipping of zinc-aluminum alloy eutectic structure, also form the intermetallic compound of some amount, improve the corrosion resistance nature of galvanized alloy, work as Al content in the present invention and remain on 30wt.%, while adding the Ti of 0.5 ~ 2wt.% in molten bath, in galvanized alloy, eutectic structure, from macrobead shape and dendritic crystal state refinement gradually, and obviously improves the corrosion resistance nature of coating.
In the present invention, technique effect is controlled the content of Al in the 30wt.% left and right for passing through, can effectively reduce the hot dip process temperature, make the hot dip process temperature lower, iron level in the zinc pond and the thermopositive reaction between iron and aluminium have been reduced, thereby continuously and effectively reduce the solubleness of iron in the zinc pond, reduce the growing amount of cadmia in the zinc pond, and make cadmia limited in the zinc pond be converted into scum silica frost by end slag, have and make the FeAl as the cadmia main component produced in the immersion plating process
3become the function of scum silica frost by end slag.Add a small amount of Ti element, be aided with adding of B element simultaneously, not only refinement the eutectic structure of galvanized alloy, more main is to have formed intermetallic compound Al
3ti etc., thus the corrosion resistance nature of coating alloy improved, and effectively reduce the thickness of coating.
The accompanying drawing explanation
The design nominal composition that table 1 is each alloy;
fig. 1 is the scanning electronic microscope BSE picture that embodiment 1-5 adds the alloy of different content Ti and B element; As can be seen from the figure, alloy structure is mainly rich Al dendrite phase (grey color part) and rich Zn interdendritic phase (part of shallow light tone) and Al
3phase in the middle of Ti; Along with adding of Ti in alloy and B element, in alloy, the eutectic structure particle is tiny gradually, thereby affects the corrosion resistance nature of galvanized alloy;
Fig. 2 is the matching used corrtest electro-chemical test of Central China University of Science and Technology's electrochemical workstation software interface;
The Electrochemical corrosion rate of the zinc-aluminium Ti-B alloy that Fig. 3 is different-alloy number; Use Central China University of Science and Technology's galvanic corrosion workstation to record corrosion data, according to experimental result, find the corrosion resistance that can improve alloy layer that adds of Ti and B, when the Ti added and B content all reach 2wt.%, than the alloy layer that adds separately 1.0wt.%Ti, electrochemical corrosion performance improves 3 ~ 4 times.
embodiment:
Thermal dip plating of steel of the present invention is elementary composition by zinc, aluminium, titanium, four kinds of boron with aluminium zinc, it is a kind of used for hot dip galvanizing aluminium zinc of high corrosion resistance, wherein, by weight percentage, the aluminium contained is 30%, and titanium is 0.5 ~ 2.0%, and boron is 0.5 ~ 2.0%, surplus is zinc, every group of embodiment samples weighing 150 grams.
Embodiment 1
A kind of thermal dip plating of steel aluminium zinc, by weight percentage, component is 30%Al, 0.0%B, 1.0%Ti, surplus is Zn, sample gross weight 150g, Al-10Ti master alloy 15g wherein, Al piece 31.5g, all the other are the Zn piece.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) fusing: will put into preheated crucible by the load weighted Zn piece of proportioning, Al piece, be warming up to 720 ℃ and generate aluminium alloy, add the salt insulating covering agent on the aluminium alloy surface, again the Al-10Ti master alloy wrapped with Aluminium Foil Package is pressed into to aluminium alloy, melting, stir and mix, and is cooled to 550 ℃, be incubated one hour, wait for that dragging for slag processes;
(2) drag for slag: treat that zinc-aluminium titanium alloy liquid all melts, and stir, pull the slag in aluminium zinc liquid out from molten bath;
(3) casting: will be poured into and water in mold without the zinc-aluminium titanium alloy solution of slag, at normal temperatures the cooling column zinc-aluminium titanium alloy that becomes.
A kind of used for hot dip galvanizing aluminium zinc, by weight percentage, component is 30%Al, 1.0%Ti, 0.5%B, surplus is Zn, sample gross weight 150g, Al-10Ti master alloy 15g wherein, Al-16B master alloy 4.6875g, Al piece 27.5625g, surplus is the Zn piece.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) fusing: will put into preheated crucible by the load weighted Zn piece of proportioning, Al piece, be warming up to 720 ℃ and generate aluminium alloy, add the salt insulating covering agent on the aluminium alloy surface, again the Al-10Ti wrapped with Aluminium Foil Package and Al-16B master alloy are pressed into to aluminium alloy, melting, stir and mix, and is cooled to 550 ℃, be incubated one hour, wait for that dragging for slag processes;
(2) drag for slag: treat that aluminium zinc liquid all melts, and stir, pull the slag in aluminium zinc liquid out from molten bath;
(3) casting: will be poured into and water in mold without the zinc-aluminium Ti-B alloy solution of slag, at normal temperatures the cooling column zinc-aluminium Ti-B alloy that becomes.
A kind of used for hot dip galvanizing aluminium zinc, by weight percentage, component is 30%Al, 1.0%Ti, 1.0%B, surplus is Zn; Sample gross weight 150g, Al-10Ti master alloy 15g wherein, Al-16B master alloy 9.375g, Al piece 23.625g, surplus is the Zn piece.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) fusing: will put into preheated crucible by the load weighted Zn piece of proportioning, Al piece, be warming up to 720 ℃ and generate aluminium alloy, add the salt insulating covering agent on the aluminium alloy surface, again the Al-10Ti wrapped with Aluminium Foil Package and Al-16B master alloy are pressed into to aluminium alloy, melting, stir and mix, and is cooled to 550 ℃, be incubated one hour, wait for that dragging for slag processes;
(2) drag for slag: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, pull the slag in aluminium zinc liquid out from molten bath;
(3) casting: will be poured into and water in mold without the zinc-aluminium Ti-B alloy solution of slag, at normal temperatures the cooling column zinc-aluminium Ti-B alloy that becomes.
Embodiment 4
A kind of used for hot dip galvanizing aluminium zinc, by weight percentage, component is 30%Al, 2.0%Ti, 1.0%B, surplus is Zn; Sample gross weight 150g, Al-10Ti master alloy 30g wherein, Al-16B master alloy 9.375g, Al piece 10.125g, surplus is the Zn piece.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) fusing: will put into preheated crucible by the load weighted Zn piece of proportioning, Al piece, be warming up to 720 ℃ and generate aluminium alloy, add the salt insulating covering agent on the aluminium alloy surface, again the Al-10Ti wrapped with Aluminium Foil Package and Al-16B master alloy are pressed into to aluminium alloy, melting, stir and mix, and is cooled to 550 ℃, be incubated one hour, wait for that dragging for slag processes;
(2) drag for slag: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, pull the slag in aluminium zinc liquid out from molten bath;
(3) casting: will be poured into and water in mold without the zinc-aluminium Ti-B alloy solution of slag, at normal temperatures the cooling column zinc-aluminium Ti-B alloy that becomes.
A kind of used for hot dip galvanizing aluminium zinc, by weight percentage, component is 30%Al, 2.0%Ti, 2.0%B, surplus is Zn, sample gross weight 150g, Al-10Ti master alloy 30g wherein, Al-16B master alloy 18.75g, Al piece 2.25g, surplus is the Zn piece.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) fusing: will put into preheated crucible by the load weighted Zn piece of proportioning, Al piece, be warming up to 720 ℃ and generate aluminium alloy, add the salt insulating covering agent on the aluminium alloy surface, again the Al-10Ti wrapped with Aluminium Foil Package and Al-16B master alloy are pressed into to aluminium alloy, melting, stir and mix, and is cooled to 550 ℃, be incubated one hour, wait for that dragging for slag processes;
(2) drag for slag: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, pull the slag in aluminium zinc liquid out from molten bath;
(3) casting: will be poured into and water in mold without the zinc-aluminium Ti-B alloy solution of slag, at normal temperatures the cooling column zinc-aluminium Ti-B alloy that becomes.
Table 1
Claims (3)
1. a thermal dip plating of steel Zn-Al-Ti-B alloy, it is characterized in that: the content of Al is controlled at 30wt.%, and the content of Ti is controlled at 0.5 ~ 2wt.%, and the content of B is controlled at 0.5 ~ 2wt.%, and all the other are Zn.
2. the preparation method of Zn-Al-Ti-B alloy for a kind of thermal dip plating of steel as claimed in claim 1 is characterized in that preparation process is as follows:
(1) fusing: Zn piece, Al piece that proportioning is good are put into preheated crucible, be warming up to 720 ℃ and generate aluminium alloy, add the salt insulating covering agent on the aluminium alloy surface, again the Al-10Ti wrapped with Aluminium Foil Package and Al-16B master alloy are pressed into to aluminium alloy, melting, stir and mix, and is cooled to 550 ℃, be incubated one hour, wait for that dragging for slag processes;
(2) drag for slag: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, pull the slag in aluminium zinc liquid out from molten bath;
(3) casting: will be poured into and water in mold without the zinc-aluminium Ti-B alloy solution of slag, at normal temperatures the cooling column zinc-aluminium Ti-B alloy that becomes.
3. the preparation method of Zn-Al-Ti-B alloy for a kind of thermal dip plating of steel as claimed in claim 2, it is characterized in that: described insulating covering agent is quality percentage composition 30-50%CaCl
2, 20-40%KCL and quality percentage composition 20%-30%NaCl mixed uniformly salt insulating covering agent, than conventional salt insulating covering agent, it has better heat insulation effect.
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| CN105132723A (en) * | 2015-09-09 | 2015-12-09 | 上海大学 | Preparation method of zinc titanium alloy for hot dipping |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101984130A (en) * | 2010-10-12 | 2011-03-09 | 中国电力科学研究院 | High corrosion-resistant hot-dip alloy coating of fastening pieces and preparation method thereof |
| JP2011144429A (en) * | 2010-01-15 | 2011-07-28 | Nippon Steel Corp | Highly corrosion-resistant hot-dip galvanized steel sheet |
| CN102994928A (en) * | 2012-12-21 | 2013-03-27 | 常州大学 | Steel hot-dip galvanized base alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011144429A (en) * | 2010-01-15 | 2011-07-28 | Nippon Steel Corp | Highly corrosion-resistant hot-dip galvanized steel sheet |
| CN101984130A (en) * | 2010-10-12 | 2011-03-09 | 中国电力科学研究院 | High corrosion-resistant hot-dip alloy coating of fastening pieces and preparation method thereof |
| CN102994928A (en) * | 2012-12-21 | 2013-03-27 | 常州大学 | Steel hot-dip galvanized base alloy and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132723A (en) * | 2015-09-09 | 2015-12-09 | 上海大学 | Preparation method of zinc titanium alloy for hot dipping |
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