CN103498073B - A kind of thermal dip plating of steel Zn-Al-Ti-B Alloy And Preparation Method - Google Patents
A kind of thermal dip plating of steel Zn-Al-Ti-B Alloy And Preparation Method Download PDFInfo
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Abstract
Patent of the present invention belongs to galvanizing technical field, refers in particular to a kind of thermal dip plating of steel Zn-Al-Ti-B Alloy And Preparation Method.It is characterized in that: the content of Al controls to control to control at 0.5 ~ 2wt.% at the content of 0.5 ~ 2wt.%, B at the content of 30wt.%, Ti, and all the other are Zn.The present invention is by the eutectic structure in titanium and boron refinement galvanized alloy, improve the corrosion resistance nature of galvanized alloy, simultaneously by reducing the aluminium content in galvanized alloy, reduce the formation volume of cadmia, and cadmia limited in zinc pond can be made to be converted into scum silica frost by end slag, thus reduction production cost, enhance productivity.Can be applied to some in the hot dip galvanizing process of corrosion resistance nature, component that appearance requirement is higher.
Description
Technical field
Patent of the present invention belongs to 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 one comparatively simply effective steel anti-corrosive method, because zinc aluminum alloy coating has taken into account the weather resistance of aluminium and the sacrificing cathode protectiveness of zinc, the performance of its coating is compared with 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, vessel fabrication, car and boat, electromechanics; For improving corrosion resistance and the galvanizing production quality of galvanizing production, alloying elements is often added among zinc pond, as aluminium, magnesium, titanium, boron, rare earth etc.; By consulting literatures shows, the research adding these elements in Galfan coating (containing 5wt.%Al) and Galvalume coating (containing 55wt.%Al) is more, but controls in the research of 30wt.% less to coating alloy aluminium content; At present, find the research work (patent CN102994929A and patent CN102392207B) of the people such as Tu Hao, aluminium content in galvanized alloy controls at 20 ~ 40wt.% by this patent, and what add is Si, Mg and rare earth element, but there are no the research report adding the alloying elements such as Ti and B in containing the galvanized alloy of 20 ~ 40wt.% aluminium.
At present, in existing hot dipping of zinc-aluminum alloy, Galvalume coating, due to its excellent corrosion resistance nature, is widely applied; But the problem that Galvalume alloy layer is blocked up, slag content is too much in molten bath badly influences quality product.Therefore, the slag problem in molten bath that solves is a very urgent problems on continuous zinc coating production line, research shows, in molten bath, oversaturated iron is the major cause that cadmia is formed, dissolving in of steel plate is the main source of iron in zinc pond, the solubleness of ferro element in zinc liquid increases with temperature and increases, immersion plating temperature is higher, diffusion between steel plate and zinc pond is faster, the dissolution rate of iron is also faster, therefore the iron of being dissolved in zinc pond by steel plate is reduced, just effectively can reduce the generation of end slag, in addition, when in zinc pond, aluminium content is more than 10%, reaction between steel plate and zinc liquid will be very violent, along with the raising of aluminium content in galvanizing flux, when particularly aluminium weight content is more than 20%, the dissolution rate of iron significantly improves rapidly, iron, thermopositive reaction between aluminium is more violent, visible, aluminium content high in molten bath is also the one of the main reasons that end slag is formed, the formation of cadmia can be reduced by the method effectively reducing aluminium content in zinc pond, and along with the reduction of aluminium content, zinc pond plating solution density increases, end slag can be made to 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; one deck can be formed stablize, and there is the TiO of stronger bonding force and protective value
2oxide film, it can make zinc coating be in passive state, even if also not easily destroyed by chlorion in ocean environment, and this oxide film has good self-healing property, and being corroded after destruction can self-healing fast; Wei Shicheng etc. also draw from electrochemical parameter, the Corrosion Resistance of Zinc Coating added after titanium can strengthen, Du Yan etc. are studied adding the galvanizing impact of Ti element on silicon containing steel in pure zinc bath, found that, along with in pure zinc bath, Ti content increases, inhibit ζ phase to grow, the interpolation of titanium has obvious thinning to thickness of coating, increases thinning effect also more obvious with titanium content.
Therefore, utilize titanium and boron to carry out the eutectic structure in refinement hot dipping of zinc-aluminum alloy and expand the range of application of zinc-aluminium titanium system galvanized alloy, having the galvanized alloy of independent intellectual property right to formation and meet production application better, is 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 reducing the content of cadmia in molten bath; By adding of titanium and boron, eutectic structure in refinement galvanized alloy, when production cost can not increase considerably, substantially increases the efficiency of continuous zinc coating production line, promote the corrosion resistance nature of hot dipping of zinc-aluminum alloy simultaneously, improve coating surface quality.Make Novel galvanizing Alloyapplication in some in the hot dip galvanizing process of erosion resistance, component that appearance requirement is higher.
Zn-Al-Ti-B alloy layer used for hot dip galvanizing, is characterized in that: the content of Al controls to control to control at 0.5 ~ 2wt.% at the content of 0.5 ~ 2wt.%, B at the content of 30wt.%, Ti, and all the other are Zn.
The preparation process of described zinc-aluminium Ti-B alloy is as follows:
(1) melt: Zn block good for proportioning, Al block are put into preheated crucible, be warming up to 720 DEG C and generate aluminium alloy, salt insulating covering agent is added on aluminium alloy surface, again Al-10Ti and the Al-16B master alloy press-in aluminium alloy wrapped with Aluminium Foil Package, melting, stirs and mixes, and is cooled to 550 DEG C, be incubated one hour, wait for and drag for Slag treatment;
(2) slag is dragged for: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, from molten bath, pull the slag in aluminium zinc liquid out;
(3) cast: be poured into by the zinc-aluminium Ti-B alloy solution without slag and water in mold, cooling at normal temperatures becomes column zinc-aluminium Ti-B alloy.
Described insulating covering agent is the mass percentage 30-50%CaCl through processed
2, 20-40%KCL and mass percentage 20%-30%NaCl mixed uniformly solid state powder, compared to the salt insulating covering agent of routine, it has better heat insulation effect.
Principle of the present invention derives from the Metamorphism treatment 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, when Al content remains on 30wt.% in the present invention, when adding the Ti of 0.5 ~ 2wt.% in molten bath, in galvanized alloy, eutectic structure is from large grained and dendritic crystal state refinement gradually, and the corrosion resistance nature of coating is significantly improved.
In the present invention, technique effect is at about 30wt.% by the content of control Al, can effectively reduce hot dip process temperature, make hot dip process temperature lower, reduce the iron level in zinc pond and the thermopositive reaction between iron and aluminium, thus continuously and effectively reduce the solubleness of iron in zinc pond, reduce the growing amount of cadmia in zinc pond, and make cadmia limited in zinc pond be converted into scum silica frost by end slag, namely there is the FeAl as cadmia main component making to produce in immersion processes
3the function of scum silica frost is become by end slag.Add a small amount of Ti element, be aided with adding of B element simultaneously, not only the refinement eutectic structure of galvanized alloy, more importantly defines intermetallic compound Al
3ti etc., thus the corrosion resistance nature improving coating alloy, and effectively reduce the thickness of coating.
Accompanying drawing explanation
Table 1 is the design nominal composition of 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 parts) and rich Zn interdendritic phase (part of shallow light tone) and Al
3ti mesophase spherule; Along with adding of Ti in alloy and B element, in alloy, eutectic structure particle is tiny gradually, thus affects the corrosion resistance nature of galvanized alloy;
Fig. 2 is Central China University of Science and Technology's electrochemical workstation matching used corrtest electro-chemical test software interface;
Fig. 3 is the Electrochemical corrosion rate of the zinc-aluminium Ti-B alloy of different-alloy number; Central China University of Science and Technology's galvanic corrosion workstation is used to record corrosion data, experimentally result, find that Ti's and B adds the corrosion resistance that can improve alloy layer, when Ti and the B content added all reaches 2wt.%, compared to the alloy layer adding separately 1.0wt.%Ti, electrochemical corrosion performance improves 3 ~ 4 times.
embodiment:
Thermal dip plating of steel aluminium zinc of the present invention is elementary composition by zinc, aluminium, titanium, boron four kinds, it is a kind of aluminium zinc used for hot dip galvanizing 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, often organizes 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, and surplus is Zn, sample gross weight 150g, wherein Al-10Ti master alloy 15g, Al block 31.5g, and all the other are Zn block.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) melt: put into preheated crucible by by proportioning load weighted Zn block, Al block, be warming up to 720 DEG C and generate aluminium alloy, salt insulating covering agent is added on aluminium alloy surface, again the Al-10Ti master alloy press-in aluminium alloy wrapped with Aluminium Foil Package, melting, stirs and mixes, and is cooled to 550 DEG C, be incubated one hour, wait for and drag for Slag treatment;
(2) slag is dragged for: treat that zinc-aluminium titanium alloy liquid all melts, and stir, from molten bath, pull the slag in aluminium zinc liquid out;
(3) cast: be poured into by the zinc-aluminium titanium alloy solution without slag and water in mold, cooling at normal temperatures becomes column zinc-aluminium titanium alloy.
Embodiment 2
A kind of aluminium zinc used for hot dip galvanizing, by weight percentage, component is 30%Al, 1.0%Ti, 0.5%B, and surplus is Zn, sample gross weight 150g, wherein Al-10Ti master alloy 15g, Al-16B master alloy 4.6875g, Al block 27.5625g, and surplus is Zn block.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) melt: put into preheated crucible by by proportioning load weighted Zn block, Al block, be warming up to 720 DEG C and generate aluminium alloy, salt insulating covering agent is added on aluminium alloy surface, again Al-10Ti and the Al-16B master alloy press-in aluminium alloy wrapped with Aluminium Foil Package, melting, stirs and mixes, and is cooled to 550 DEG C, be incubated one hour, wait for and drag for Slag treatment;
(2) slag is dragged for: treat that aluminium zinc liquid all melts, and stir, from molten bath, pull the slag in aluminium zinc liquid out;
(3) cast: be poured into by the zinc-aluminium Ti-B alloy solution without slag and water in mold, cooling at normal temperatures becomes column zinc-aluminium Ti-B alloy.
Embodiment 3
A kind of aluminium zinc used for hot dip galvanizing, by weight percentage, component is 30%Al, 1.0%Ti, 1.0%B, and surplus is Zn; Sample gross weight 150g, wherein Al-10Ti master alloy 15g, Al-16B master alloy 9.375g, Al block 23.625g, surplus is Zn block.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) melt: put into preheated crucible by by proportioning load weighted Zn block, Al block, be warming up to 720 DEG C and generate aluminium alloy, salt insulating covering agent is added on aluminium alloy surface, again Al-10Ti and the Al-16B master alloy press-in aluminium alloy wrapped with Aluminium Foil Package, melting, stirs and mixes, and is cooled to 550 DEG C, be incubated one hour, wait for and drag for Slag treatment;
(2) slag is dragged for: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, from molten bath, pull the slag in aluminium zinc liquid out;
(3) cast: be poured into by the zinc-aluminium Ti-B alloy solution without slag and water in mold, cooling at normal temperatures becomes column zinc-aluminium Ti-B alloy.
Embodiment 4
A kind of aluminium zinc used for hot dip galvanizing, by weight percentage, component is 30%Al, 2.0%Ti, 1.0%B, and surplus is Zn; Sample gross weight 150g, wherein Al-10Ti master alloy 30g, Al-16B master alloy 9.375g, Al block 10.125g, surplus is Zn block.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) melt: put into preheated crucible by by proportioning load weighted Zn block, Al block, be warming up to 720 DEG C and generate aluminium alloy, salt insulating covering agent is added on aluminium alloy surface, again Al-10Ti and the Al-16B master alloy press-in aluminium alloy wrapped with Aluminium Foil Package, melting, stirs and mixes, and is cooled to 550 DEG C, be incubated one hour, wait for and drag for Slag treatment;
(2) slag is dragged for: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, from molten bath, pull the slag in aluminium zinc liquid out;
(3) cast: be poured into by the zinc-aluminium Ti-B alloy solution without slag and water in mold, cooling at normal temperatures becomes column zinc-aluminium Ti-B alloy.
Embodiment 5
A kind of aluminium zinc used for hot dip galvanizing, by weight percentage, component is 30%Al, 2.0%Ti, 2.0%B, and surplus is Zn, sample gross weight 150g, wherein Al-10Ti master alloy 30g, Al-16B master alloy 18.75g, Al block 2.25g, and surplus is Zn block.
The preparation process of the zinc-aluminium Ti-B alloy of this embodiment is as follows:
(1) melt: put into preheated crucible by by proportioning load weighted Zn block, Al block, be warming up to 720 DEG C and generate aluminium alloy, salt insulating covering agent is added on aluminium alloy surface, again Al-10Ti and the Al-16B master alloy press-in aluminium alloy wrapped with Aluminium Foil Package, melting, stirs and mixes, and is cooled to 550 DEG C, be incubated one hour, wait for and drag for Slag treatment;
(2) slag is dragged for: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, from molten bath, pull the slag in aluminium zinc liquid out;
(3) cast: be poured into by the zinc-aluminium Ti-B alloy solution without slag and water in mold, cooling at normal temperatures becomes column zinc-aluminium Ti-B alloy.
Table 1
Claims (3)
1. a thermal dip plating of steel Zn-Al-Ti-B alloy, is characterized in that: the content of Al controls to control to control at 0.5 ~ 2wt.% at the content of 0.5 ~ 2wt.%, B at the content of 30wt.%, Ti, and all the other are Zn.
2. the preparation method of a kind of thermal dip plating of steel Zn-Al-Ti-B alloy as claimed in claim 1, is characterized in that preparation process is as follows:
(1) melt: Zn block good for proportioning, Al block are put into preheated crucible, be warming up to 720 DEG C and generate aluminium alloy, salt insulating covering agent is added on aluminium alloy surface, again Al-10Ti and the Al-16B master alloy press-in aluminium alloy wrapped with Aluminium Foil Package, melting, stirs and mixes, and is cooled to 550 DEG C, be incubated one hour, wait for and drag for Slag treatment;
(2) slag is dragged for: treat that zinc-aluminium Ti-B alloy liquid all melts, and stir, from molten bath, pull the slag in aluminium zinc liquid out;
(3) cast: be poured into by the zinc-aluminium Ti-B alloy solution without slag and water in mold, cooling at normal temperatures becomes column zinc-aluminium Ti-B alloy.
3. the preparation method of a kind of thermal dip plating of steel Zn-Al-Ti-B alloy as claimed in claim 2, is characterized in that: described insulating covering agent is mass percentage 30-50%CaCl
2, 20-40%KCl and mass percentage 20%-30%NaCl mixed uniformly salt insulating covering agent, compared to the salt insulating covering agent of routine, it has better heat insulation effect.
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Effective date of registration: 20191120 Address after: No.1 Renmin Road, Xiaoji Town, Jiangdu District, Yangzhou City, Jiangsu Province Patentee after: Jiangsu zhongchuantongda Technology Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Changzhou University Patentee before: Changzhou University |