CN102650026B - Be and multi-combination degenerative low-zinc hot-dipped aluminum alloy coating material and preparation method thereof - Google Patents
Be and multi-combination degenerative low-zinc hot-dipped aluminum alloy coating material and preparation method thereof Download PDFInfo
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- CN102650026B CN102650026B CN201110044893.6A CN201110044893A CN102650026B CN 102650026 B CN102650026 B CN 102650026B CN 201110044893 A CN201110044893 A CN 201110044893A CN 102650026 B CN102650026 B CN 102650026B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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Abstract
The invention discloses a Be and multi-combination degenerative low-zinc hot-dipped aluminum alloy coating material and a preparation method thereof. The alloy comprises the following components in weight percentage: not greater than 30 percent of Zn, 10<-4>-0.05 percent of Be, 10<-4>-6.0 percent of alloy enhancer, 10<-4>-1.0 percent of solvent passivator, 10<-4>-0.5 percent of sediment hardening agent, 10<-4>-1.0 percent of grain refiner, 10<-4>-1.0 percent of rare earth addition, 0.001-2.0 percent of matrix interface reaction buffering agent and the balance Al and unavoidable trace impurities. The aluminum alloy coating material produced according to the technical scheme provided by the invention can be used for forming light and thin high-quality coatings on the surfaces of steel and iron alloy, wherein the light and thin high-quality coatings are attractive and are high in corrosion resistance, abrasion resistance, strength and ductility and good in matrix metallurgical bonding. The aluminum alloy coating material can be used for anti-corrosion coatings on the surfaces of steel and iron alloy products. Production equipment for the aluminum alloy coating material does not need to be specially made; the source of the raw material is rich; the starting cost is low; and the industrial waste can be conveniently and cyclically utilized.
Description
Technical field
The present invention relates to a kind of aluminum alloy coating material and preparation method thereof, particularly a kind of Be and the rotten low zinc aluminum alloy plating material for hot-dip platings and preparation method thereof that combine more.
Background technology
At present, the zinc-plated unit that the whole world has been constructed and put into operation has more than 400 line, spreads all over more than 60 country, and galvanized steel goods output approaches 200,000,000 tons, and wherein major part is steel plate galvanized.Because the annual zinc consumption used for hot dip galvanizing in the whole world reaches the more than 70% of zinc metal ultimate production, cause the situation of zinc resource shortage more and more severeer.Since 2008, zinc output in the world's remains on 1,200 ten thousand tons of left and right every year on average, and the consumption of pot galvanize industry just reaches more than 8,500,000 tons, and the coverage rate of zinc-plated iron-steel goods is less than 1/5 of whole world output of steel.Along with the development of economic society, high-end coated steel ferrous products proportion is increasing, even but global zinc is all used for doing coating material, also can not meet iron and steel hot dip process needs far away.This situation, seems especially outstanding in China.That is to say, develop the iron and steel novel material used for hot dip galvanizing of alternative zinc, is inexorable trend and the requirement of world and China Technological Economy development; And be hopeful most as the material for zinc, be aluminium-zinc alloy and aluminium alloy.
About aluminium zinc or aluminium-zinc alloy are the novel high-performance coating material patent of main body component, mainly concentrate on the developed countries such as American-European and Japan, the domestic patent that also has some industry.Galvalume is United States Patent (USP), composition is 55%Al-43.4%Zn-1.6%Si, it is the high alumina type zn alloy coating material that obtains at present actual commercial application, although it is 2～7 times of pure zinc coating to the protective capability of base steel, can save in a large number again zinc resource, but due to immersion plating temperature high (590～600 DEG C), plating solution is poor to the wetting capacity of base steel, easily produce the plating leakage of steel plate needle-like, coating is to scratching, the galvanic protection scarce capacity of otch, forming process, there is the reasons such as gap in the aspects such as welding and coating performance and pure zinc coating, a lot of advantages are offset, making it can not be well for market be accepted.Galfan is the coating material of the 5%Al-Zn system of Belgium's development, contain Fe, Si, Pb, Cd, the trace element such as Sn and rare earth, its fusing point is lower than pure zinc, solve the Galvalume plating solution problem poor to the wetting capacity of base steel, rely on the tiny eutectic structure of quick cooling generation of steel plate, therefore coating has higher than the solidity to corrosion of zinc and good coating performance, machine-shaping property and and weldability, but because of Pb, Cd, the low melting point metals such as Sn easily cause the intergranular corrosion (causing color change) of coating, steel plate speed of cooling is had to strict restriction, it is recessed that coating easily produces large-area hole, the problems such as high temperature oxidation resisting ability, affect the market application of Galfan, add that it still contains more than 90% Zn, having little significance aspect saving zinc resource, can not solve the problem of hot dip process industry long-run development.In recent years, occurred the multicomponent system alloy layer material of Zn-Al-Mg and relevant components thereof, there are Zn-Al-Mg-Ti-B-Si, Zn-Al-Mg-Si patented product in the U.S.; There are hot-dip galvanized alloy plate, Zn-Al-Mg-Si, Zn-Al-Mg-Si-Mn-Cr and Zn-Al-Mg patent of aluminium content 5%～12% etc. in Japan, but the aluminium content of these product innovations and patent is mostly below 50%; And there is no the novel coating material patented technology that can realize low cost commercial application.
Therefore, improve the over-all properties of coating around the multiple alloying element of interpolation, adopt more Al component to replace Zn, emphasis is the best combination that realizes the coated protective capability of aluminium and the sacrificing cathode protective capability of zinc, and ensure with simple as far as possible immersion technical equipment, realize the antistripping of Coated Steel, high strength, easily processing, easily welding, resistance to higher temperature, the premium propertiess such as acid and alkali-resistance salt corrosion are in one, research and develop and promote green iron and steel immersion flow process, realize simultaneously and subtract dirt in the production of coating material and two links of application, this falls, synergy, upgrading, be one and be badly in need of the technical barrier solving.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of seriation is provided, can form the rotten modifying function of multifactor solid to aluminium zinc mixed system, thereby realize the weave construction form optimization of aluminium-zinc alloy, make coating material and steel substrate produce good wettability, solid-state tack and matrix strengthening, realizing coated sheet easily processes, easily welding, high temperature resistant, acid and alkali-resistance salt corrosion, can improve cycle efficiency and recycle value, realize simultaneously and subtract dirt in the production of coating material and two links of application, this falls, synergy, upgrading, for realizing the technology upgrading of macroeconomy aspect, Be and the rotten low zinc aluminum alloy plating material for hot-dip platings and preparation method thereof that combine that product renewal and Industry Agglomeration provide base mateiral to support more.
Technical scheme of the present invention:
The low zinc aluminum alloy plating material for hot-dip plating that Be is rotten with many combinations, by element wt per-cent, this alloying constituent is Zn≤30, Be:10
-4～0.05, alloy strengthening agent 10
-4～6.0, solvent passivator 10
-4～1.0, precipitation hardening agent 10
-4～0.5, grain-refining agent 10
-4～1.0, rare earth addition 10
-4～1.0, basal body interface reaction buffer 0.001～2.0, all the other are Al and inevitable trace impurity.
Alloy strengthening agent comprises Cu or Li, and the alloy that contains Cu or Li.
Solvent passivator comprises Co, Cr or Nb, and the alloy that contains Co, Cr or Nb; Every kind of every kind of element can be used alone, but also also mix together.
Precipitation hardening agent comprises Bi, In or Tl, and every kind of element can be used alone, but also also mix together.
Grain-refining agent comprises the compound that C or Zr and they form mutually, and the high rigidity high stability compound of C or Zr and the formation of high-melting-point transition element.
Rare earth addition comprises as the Pr of rare earth element or Nd, and the mishmetal of more than one rare earth elements formation.
Basal body interface reaction buffer comprises Fe and contains the alloy of Fe.
Be described above and preparation methods that combine rotten low zinc aluminum alloy plating material for hot-dip plating, comprise the steps: more
(1) within the scope of above-mentioned element ratio, a selected group element ratio, the alloy total amount of preparing as required again, extrapolate the quality of every kind of required elemental metals, or the quality of alloy, or the quality of hybrid metal additive, establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
(2) first in smelting furnace, add appropriate aluminium ingot or molten aluminum liquid, heating makes it to melt completely and insulation at 700～800 DEG C;
(3) add basal body interface reaction buffer, Be, solvent passivator, grain-refining agent, alloy strengthening agent, rare earth addition and precipitation hardening agent by formula rate again, finally add again zinc, stir; On-site sampling is analyzed, and according to analytical results and formula range, adjusts addition; Then continue melting and stirring, sampling analysis again, until each element ratio meets formula requirement completely.
(4) then above-mentioned alloy melt is carried out to furnace refining; In alloy melt, add refining agent, and stir, melt refining completes in enclosed environment.
(5) slagging-off after refining, degasification, leave standstill, temperature adjustment to 660～720 DEG C, aluminium alloy is toppled over and is come out of the stove, and filters simultaneously; In the mild impouring casting of filtrate ingot mould, by sequential crystallization mode, melt is condensed in ingot mould from bottom to top, form silvery white ingot shape.
In step (2), smelting furnace refers to can the various aluminium alloys of melting, the industrial smelting furnace of zinc alloy or copper alloy, comprise mid freqency induction furnace, Medium Frequency Induction Heating Furnace, resistance furnace, gas-fired heater or fuel oil heating.
Advantage of the present invention:
Compared with prior art, major advantage of the present invention is: use Be and basal body interface reaction buffer, solvent passivator, grain-refining agent, High-Temperature Strengthening agent, the multielements such as rare earth addition and precipitation hardening agent combine the three-dimensional metamorphism to low aluminium zinc system, the over-all properties of coating material is risen to a new height, realize the weave construction form optimization of aluminium-zinc alloy, make coating material and steel substrate produce good wettability, solid-state tack and matrix strengthening, realize coated sheet and easily process, easily welding, high temperature resistant, acid and alkali-resistance salt corrosion, has improved cycle efficiency and recycle value, realizes simultaneously and subtracts dirt in the production of coating material and two links of application, this falls, synergy, upgrading, for realizing the technology upgrading of macroeconomy aspect, product renewal and Industry Agglomeration provide base mateiral to support, embody the state-of-the-art technology method with " solution model " research aluminium alloy behavioural characteristic in the complex component structure of polynary solute under temperature match curing conditions, what its preparation method adopted is all common equipments of metallurgy industry, do not need specially, can improve cycle efficiency and recycle value.
---the concrete effect of Be and six class alterants is as follows:
Be is one of alkali metal of atomic radius minimum, is also one of metallic element of proportion minimum simultaneously.The proportion of Be is less by 1/3rd than Al, and intensity is similar with steel, and heat transfer property is three times of steel, is conductor good in metal; The oxide compound proportion of Be is little, hardness is large, and fusing point, up to 2,450 degree Celsius, therefore has high-temperature anticorrosion ability, oxide compound, the halogenide of beryllium all have obvious covalency, Be can also form polymkeric substance and have the covalent compound of obvious thermostability, even in the time of red heat, Be is also very stable in air, it covers matrix surface, form form compact and stable surface oxidation protective layer, protection matrix is not oxidized and heat conductivility is good, has strengthened the heat-resisting effect of matrix; Utilize the atomic polarization reducing effect of Be element to solvent element al and Al+Zn, under microstate, effectively adjust the structure of atomic size and short-range order, make melt even structure in macroscopic view, reduce surface tension, and improve the affinity of melt and plating piece matrix, reach and improve coating and matrix tack.
In this coating alloy, add Be can obviously reduce ingot crack, improve the strength of materials, and (iron and steel) goods appearance after casting and immersion plating is more attractive in appearance, beautiful; But in the time that total add-on exceedes the saturation solubility of Be in solvent, the crackle tendency of alloy increases, mechanical properties decrease.
Plating solution of the present invention is when with iron and steel substrate contacts; steel matrix is had to good wettability; solute Be and solvent orange 2 A l can with the ferric oxide rapid reaction of steel substrate surface; generate little, the stable in properties of proportion and the oxide compound of compact structure; float on coating surface; play the provide protection to internal layer, can reduce the consumption of steel plate plating assistant agent or not use plating assistant agent simultaneously, thus the cost-saving and harm of reduction to environment.
Because Be has decomposed the metallic compound that Fe-Al, Fe-Zn form effectively, plating solution of the present invention in the time of immersion plating, can reduce end slag and scum silica frost produces.
The standard potential (1.70v) of Be is almost just the same with Al, outer electronic structure 2s
2i.e. 2 valence electrons, therefore add Be can increase matrix free electronic concentration in Al, increased the degree of unbalancedness of matrix electronic cloud structure simultaneously, strengthen the liquid fluidity of matrix; The atomic radius of Be is little compared with Al, density 1.85, in Al melt, easily spread, rise and be enriched in surface and crystal boundary, due to the equilibrium solubility in Al less (almost nil), so add micro-Be can form Al-Be supersaturated solid solution, in the time being enriched in surface and the Be of subgrain boundary and reaching finite concentration, forms higher than sosoloid fusing point, dispersity is high, the tiny nucleus of overall distribution good evenness, around guiding, sosoloid is with peritectoid or eutectic morphology crystallization; Because Be and sosoloid equilibrium phase approach simple substance form, the mechanism of crystal growth is the smooth interface under microstate and the rough interfaces under macrostate, and the grain growth slow speed therefore forming, consequently makes alloy grain tiny, liquid fluidity is good, solidifies rear intensity high; Simultaneously, the Be atom that is enriched in alloy surface is absorbing the BeO volumetric ratio forming after Sauerstoffatom oxidation in suitable scope (1.59), film layer structure densification, stable in properties, good corrosion resistance, can make up the low defect of AlCu Alloy Anti salt erosion property, thereby can make to add more Cu in alloy, to give full play to the strengthening effect of Cu alloy.The refining effect of Be to aluminium base sosoloid crystal grain, is equally applicable to the refinement to metallic compound; In supersaturated solid solution, Be is the element that can carry out with nearly simple substance form refinement to impurity Si.
Utilize the effect of alloy strengthening element Cu or Li, generate strengthening phase, farthest improve the intensity of coating, actual strength can exceed steel matrix, reaches higher strength property.
Solvent passivation Elements C o, Cr or Nb, can be in the acid-and base-resisting of solvent surface enrichment one deck, salt and hot environment atomospheric corrosion, have that the fixing protection of grid under microcosmic and mobility cover damage surface automatically concurrently and the passivation film that plays defencive function, make the matrix of coating under covering there is better physical and chemical performance; For preventing occurring unwanted color after single passivation element oxidation, can use two kinds and two or more complex element passivator.
Utilize grain refining Elements C or Zr and fining agent, in the time of high temperature by dissolving, diffusion and disperse, become nano level and even more tiny foreign atom cluster and stable molecular cluster, tiny " crystal seed ", gap phase and the interstitial compound that are evenly distributed are in a large number provided in the time of melt cooling crystallization, the grain size number of efficient refinement matrix, improve intensity, toughness, hardness, wear resistance and the high-temperature behavior of coating material, and then improved processibility and the weldability of plating piece.
Rare earth element additive Pr or Nd have the multiple booster action of atomic polarization, alloy strengthening, grain refining, surface-beautifying, dehydrogenation and enhancing erosion resistance, can strengthen the effect of Be, alloy strengthening agent, solvent passivator, grain-refining agent, and compensate its defect.
Precipitation hardening agent Bi, In or Tl are also ageing strengthening agent, they are that fusing point is not high, also not high metallic element of chemically reactive, add this small amount of dvielement, in alloy system, keep nearly simple substance state, although solidify but temperature still under higher state in system, they still keep liquid, thereby make system in macroscopic view, possess semi-solid state feature, be converted into actual strengthening state (precipitation hardening or precipitation-hardening) condition is provided for accelerating in alloy strengthening element in ageing strengthening process; Can give the good processing characteristics of alloy and wear resisting property simultaneously; By controlling kind and the addition of precipitation hardening element, can also obtain plating piece surface detail.
Utilize surface reaction buffering element of Fe and Si, and the alloy that contains Fe or Si, violent combination reaction between Al and Fe matrix can effectively be suppressed at immersion plating time, reduces or stops generation " lensing Fe
2al
5", strengthening " lamelliform Fe
2al
5" generting machanism, set up the reaction mechanism of Fe-Al-Zn uniform gradient, thereby improve quality of coating, attenuate thickness of coating, save material.
Therefore, the super multi-element alloyed and microalloying that the present invention utilizes Be and six class alterants to carry out with low aluminium zinc reacts, obtained have base steel wettability is good, bonding force is strong, intensity is high, good-extensibility, high temperature resistant, coating is thin, solidity to corrosion is strong, processibility and the weldability high-quality iron and steel aluminum alloy coating material used for hot dip galvanizing that integrates multiple advantage such as good.
In Be and six class alterants, the effect role of some element in alloy has multiplicity: except rare earth element has multiple action, most elements of the present invention has reduction Al-Zn smelt surface tension, improves the effect to iron-based wettability, Be, Li, Co, Cr, Nb etc. are improved the effect of alloy strength and high-temperature behavior, Fe and Si have the effect that improves alloy rigidity and wear resistance, and Bi, In, Tl also have the effect of crystal grain thinning.
Test-results shows, the immersion temperature that optimum of the present invention adopts is 680～720 DEG C, and in this temperature range, flow of the electrolyte is good, and plating leakage rate, slagging rate are low.
In the temperature range of use immersion of the present invention, can make hot dip process front end operation be the anti-oxidation temperature control of hot rolled strip during than pot galvanize up to more than 850 DEG C, coiling temperature is controlled at 600 DEG C of left and right, thereby can suppress the long thick and passivation of steel strip surface oxide film, can reduce pickling amount and the pollution of spent pickle liquor to environment simultaneously.
Using in the temperature range of immersion of the present invention, after steel plate immersion plating, need not carry out forced cooling processing, thereby provide suitable temperature and long as far as possible time conditions for the spontaneous alloying passivation of coating material.
After the annealed processing of steel plate after immersion plating, overlay coating has high-strength and high ductility high rigidity feature, and more than tensile strength can reach 400Mpa, elongation after fracture can reach more than 8%, more than hardness HBS150; By analysis, Al-Cu has the highest gain in strength effect mutually.
Founding test and electronic microscope photos are found, the compound that C and Zr, Co, Cr, Fe, Nb form, then form after master alloy with Al, there is good refinement modification effect; Al-rare earth compound has identical refinement and stigma of degeneracy.
Solidify 400～1000 kilograms of heavy ingots are carried out to UT (Ultrasonic Testing) inspection, and the each position of the equal thickness sound intensity is even, inner flawless.
Coated Steel of the present invention is carried out to x-ray fluorescence analysis and show, the even zero defect of internal structure.
In fusion process, sampling analysis shows, comprises the small structure form of the not jljl phase that is difficult to determine in melt, and great majority are dystectic metallic compounds with complicated crystalline network.Think, this is one of item key of grain refining, hardness raising.
Fracture surface of sample microstructure analysis shows: in material crystallisation process, produced a large amount of eutectic reactions, Peritectic Reaction, eutectoid reaction and precipitation effect, had a large amount of tiny spherical heterogeneous nucleus to exist inside and outside dimple and crystal grain.This kind of crystalline structure verified the grain refining effect in the present invention of heterogeneous nucleus.
The result demonstration of melt treatment, cleaning molten means can make the intensity of coupon and unit elongation promote simultaneously efficiently, the amplitude of lifting: more than strength enhancing can reach 100Mpa, unit elongation promotes and can reach more than 10%.
Oven test proves, through 24 hours more than 700 DEG C high temperature atmosphere environment, uses the steel product appearance color of immersion plating coating novel material of the present invention without considerable change.
Solidity to corrosion: salt spray test sample, thickness of coating 20 μ, experimental period >=280h, surface is without being obviously subject to corrosion phenomenon (common galvanized sheet 48h there will be stain or blackspot); Heat reflectivity >=70%; High temperature oxidation resistance: variable color more than hot environment 100h does not occur at 315 DEG C; Wet-heat resisting: 49 DEG C, under humidity 93 ± 2% environment through 168h non-corroding, without obviously variable color; Coating bending: when d=a, do not occur that coating comes off beyond the 5mm of portion of test coupon limit; Coating surface is smooth, and crystalline substance is spent evenly.
The solidity to corrosion simultaneous test of several alloy layer steel plates: hot dip process steel are Q
235steel, hot dipping plating solution is novel hot-dip alloy plating of the present invention, immersion plating temperature is 680～720 DEG C, the immersion plating time is 10s, sample through alkali cleaning oil removing → washing → weak acid corrode → wash → help plating → oven dry → immersion plating → air cooling; Then in 35 DEG C of 5%NaCl salt solution, soak 260h respectively, and in 35 DEG C of temperature, relative humidity 93～94%, containing SO
2in the acid mist of 10ppm, carry out corrosion test, the loss of weight contrasts as following table 1:
Table 1 solidity to corrosion comparing result
At room temperature different materials has been carried out the mensuration of yield strength and tensile strength, result is as table 2:
Table 2 strength of materials comparing result
Thing phase composite and the shape characteristic of research coating material and steel matrix key coat, the thing obtaining reach mutually hundreds of more than, wherein only the compound type of two-component system just has kind more than 200, and the binary thing phase that can distinguish by metallurgical analysis, it is only a part for the more polybinary compound that in fact may exist, because the compound that molecular formula is identical often has multiple different crystal structure, although be difficult to distinguish with metallurgical analysis, but owing to thering is different stability, also should be considered as different materials.
In the time that certain constituent content is relatively many in alloy, (for example, be greater than 1%wt), can react with other solute element and generate more complicated ternary and metallic compound more than ternary, for example Al
13cr
4si
4, Al
7cu
2fe, Al
13si
4(CrFe)
4, etc.These polynary metallic compounds that combine are also unsettled, in the time that temperature and potential of hydrogen change, and can automatic classifying; discharge effective atom; to keep the stable of whole alloy system, thereby play the passivation to coating, improve the protective capability to matrix.
Co, Cr, Nb are d district, typical multivalence position transition element in periodictable, can generate with Al, Zn solvent and Fe matrix element the feature of various metals compound from them, can know that they are all the sacrificing protection elements of matrix; In addition, when they are had an effect with oxygenant on sosoloid surface, under different pH value conditions, can generate compound and the hydrated ion of multiple different oxidation state, owing to all having higher oxide compound volumetric ratio (being greater than 1.5), the ability of its passivation protection is far away higher than simple pellumina; These compounds and hydrated ion are rigidity a bit; after formation, exist as permanent grid protection layer; some is weak mobility; and some has good mobility; after plating piece surface is scratched; compound and the hydrated ion with mobility can make up immediately, cover wound, and coating and matrix are unlikely to because of the long-time exposed excessive corrosion that suffers, and this has just solved the coated poor problem of protective capability of simple aluminium-zinc alloy.
About super multi-element alloyed metamorphic mechanism, there is no at present a kind of generally acknowledged theoretical explanation; Can not illustrate by the multiple Superposition Method of binary alloy phase diagram, can not make an explanation to general common practise and the experience of principal element effect with each trace element in existing multicomponent alloy.
But there are two kinds of patterns to analyze qualitatively the element interaction mechanism of super multicomponent alloy, a kind of is parsing to atomic structure aspect, a kind of is the utilization that solute dissolves and separate out solution model theoretical method in solvent, the combination of the two, can make the explanation with fine accordance to the excellent properties of novel coating material.
In super multicomponent alloy system during in uniform and stable liquid state, whole system is actually the multi-core " ocean " that a kind of valence electron (unbound electron) surrounds, suppose that each trace element is all " seawater " inner being uniformly distributed of principal element, in a kind of perfect condition, the factor of whole architectural feature is at this time described, mainly should comprise flat fare electron density, average electrical negativity or average electrical electrode potential, density, temperature, volume, pressure, and the Thermodynamic Criteria such as system free energy, enthalpy, entropy.But from microcosmic angle, different atom pairss its around the sucking action of unbound electron vary, therefore atomic structure and the character under the atom of each dvielement and its simple substance state has just produced difference, on the macroscopic property of the present alloy of these difference tables, causes significant performance variation.
New element enters the variation order of alloy solution system: the first step is ionization, first become single ion, at this time have the dimensional change as alloy solution ultimate particle: the own atomic radius of element that electronegativity is stronger than solvent element dwindles, attract around unbound electron and with certain negative charge simultaneously, negative ion becomes to be as the criterion, the element of electronegativity a little less than than solvent element produces contrary variation, positive ion becomes to be as the criterion, while finally reaching balance, should there is the solute ions of two types: than the little negative ion of simple substance state atomic radius with than the large positive ion of simple substance state atomic radius, second step is to dissolve, and enters the lattice of solvent substrate, the 3rd step is diffusion, occupies wide as far as possible system space, dissolves and spread always to carry out simultaneously, the 4th step changes in the lattice of matrix, forms sosoloid displacement or gap, the 5th, sosoloid concentration reaches capacity, the 6th, the solid solution lattice of formation changes, and becomes and the incoherent compound of matrix, the 7th, the intermetallic compound of formation is dissolved in again among matrix, forms the special coherent structural in region that participates in matrix coherence taking molecule and molecular grouping as unit, the 8th, the sosoloid of element reaches capacity together with the sosoloid of metallic compound, the 9th, the compound macromole of element and other solute element or compound formation complex construction (atom number is many, spacer is diversified), the tenth, the gathering of various atoms and molecule and decomposition, the strain occurring with temperature, pressure and interface.In fact, the formation of element solid solution body and the formation of compound are also carried out simultaneously, whether generate compound with matrix, and the amount and the stability thereof that generate, depending on parameters such as electronegativity difference, interatomic distance, valence electron number and the valence orbit structures of matrix and new element.
Performance and the effect of transition element in alloy is extremely complicated, and they are different from metal and the non-metallic element that chemical property is obvious and definite.Due to the dislocation of outermost layer and time out-shell electron orbital energy level, the ability of transition element receiving and losing electrons, it is all very powerful that the ability of shared electrons and the ability of number adjustment thereof are provided, add less atomic radius, make it easy and active metal, under active nonmetal and even normal temperature can there is chemical reaction in inactive element, generate relatively stable, but change obvious with temperature and potential of hydrogen, compound and the title complex of following shades of colour to change, its intramolecular key shape and bond energy complex structure, both easily formed, also be easily subject to ectocine and disintegrate, even the atom of same dvielement (the adjacent or close element of same period or same subgroup), also can change easily the complex construction having formed, the even ion of the different prices of same element, also can change easily the complex construction having formed, as Co, Cr, Nb and Fe etc. are not always the case.
Electropotential or electronegativity differ larger, between two kinds of elements, more easily form the compound of stable (fusing point is high), according to solubility product principle, other unsettled compound that contains one or more same components will dissolve, to discharge the solute atoms concentration that can keep balance, stable compound continues to produce, until whole system reaches new balance, this restructuring campaign just can stop.Final general trend, often to add a kind of new element or compound, each integral part of system all produces relevant reaction, reduce (concentration reduction), increase (concentration rising), remain unchanged, and the space of reserving existence to new element or compound, reach the partial potential of each material after balance and keep equating.
When a kind of element in system is oxidized and loses after electronics, in system, this concentration of element reduces, according to partial potential balance and solubility product equilibrium principle, the material that contains this element in system by automatic classifying to discharge this appropriate element, make up this concentration of element in system, cause a series of chain reactions simultaneously, finally still will reach new partial potential balance and solubility product balance.Element kind is more, and chain reaction is more complicated, but finally reaches new partial potential balance and the result of solubility product balance is constant.System that Here it is is supported erosion-resisting " equation with many unknowns formula " controlling mechanism; This mechanism, the reaction of iron while being equally applicable to hot dip process-aluminum-zinc alloyization, thereby " equation with many unknowns formula " controlling mechanism of realization uniform gradient between the inner each aspect of thickness direction.
On the other hand; Co, Cr, Nb and Fe are transition element of the same type; they are as solute element; in the time that solvent element al, Zn and matrix Fe react; they also participate in reaction simultaneously, play the effect of the fierce degree of buffering matrix and solvent main reaction, effectively stop the generation of Zn-Al-Fe " effect of splitting "; and also form passivation subgrade at nearly matrix face, strengthen the protective capability to matrix.
In the time there is the moderate and element that fusing point is very low of a small amount of current potential in alloy, as Bi, In, Tl, the character of these elements in alloy is substantially unaffected, and exist with nearly simple substance form, the effect of " interstitial fluid " or " liquid film " can be provided in the time of alloy crystallization, element and compound that to quantity in aluminium alloy is more, solid solubility difference is large, this " interstitial fluid " or " liquid film " effect in annealing recrystallization and ageing treatment process is very important, it can dissolving in and separating out quick unimpeded channel is provided for sosoloid solute, thereby significantly shorten and quench and aging time, improve thermal treatment effect, can not cause again the intergranular corrosion (because content is few) under high temperature simultaneously, if simultaneously these low melting point elements have certain diffusibility, can " fill out hole formula " and enter in alloy in the hollow forming when crystallization is leading grows up mutually (high free energy district), thereby suppress crystal growth, produce metamorphism.
Rare earth element Pr, Nd are when with transition element generation alloying, have three features: 1. simple substance do not dissolve or solubleness very low, all below 0.1% (mass percent), 2. easily react the intermetallic compound that forms multiple different content with transition element, its feature is corresponding with the temperature of solute component ratio and alloy system, such as: Pr and Al can form from Pr between 630～1240 DEG C
3al is to Pr
3al
11there is the compound of temperature range Deng 6 kinds of different compositions, different structure, differences; Nd and Al between 635～1235 DEG C also can with the similar compound of Pr-Al, 3. the intermetallic compound forming has certain solubleness in matrix (Al), (Zn), (Fe), and the solubility product of the component of intermetallic compound in alloy is relatively stable.These features, have increased the complexity of alloy structure, and the resistance that has also strengthened alloy simultaneously becomes ability, and the physicochemical property of alloy system are kept relative stability.
Si is the very little element of this alloy system Atom radius, it is soluble in (Al), (Zn) and can generate multiple compounds with Fe, due to these features, it is the very strong element of diffusibility in system, also can suppress Al-Fe in " calking " mode reacts and resists Zn and get involved in Al-Fe compound, in Galvalume and Galfan coating alloy, use the main inhibitor of Si as Al-Fe intense reaction, and in alloy system of the present invention, Si can with the effect that is enriched near multi-solvents passivation element shared inhibitor reaction surface.
Experiment shows, in the time ensureing good degasification, removal of impurity effect, the melting equipment that can adopt is diversified, comprise process furnace, Medium Frequency Induction Heating Furnace, resistance furnace, gas-fired heater, fuel oil heating, wherein add electrothermal stove effect with the line-frequency induction of protectiveness melting best, and no matter adopt any melting equipment, all should make Melt Stirring even, and seal as far as possible flow process, reduce metal loss and to Health hazard; Alloy material of the present invention can carry out segmentation allotment with the industrial smelting furnace of the various aluminium alloys of melting, zinc alloy, copper alloy easily and produce, in the time of allotment, do not need frequent prepurging, there is good compatibility, can make full use of equipment, raise the efficiency, reduce costs for the enterprise that produces multiple alloy.
Evidence, if contain other element that satisfied formula requires in the useless assorted material such as the aluminium alloy of selection batching, zinc alloy, copper alloy, can only be used the useless assorted of aluminium alloy, zinc alloy, copper alloy etc. to expect that adding micro-alterant prepares burden as starting material.
Embodiment
Embodiments of the invention and formula combination table:
Formula combination table
embodiment 1:Be-Cu-Cr-Bi-C-Pr-Si combination
(1) by the selected group element of formula combination table, according to weight percent be: polarization alterant Be:0.05, alloy strengthening agent Cu:6.0, solvent passivator Cr:0.8, precipitation hardening agent
bi: 0.1, grain-refining agent
c: 0.001, rare earth addition
pr: 0.01, basal body interface reaction buffering element Si:2.0, the second solvent element Zn:30, surplus is Al; The alloy total amount of preparation is 1000kg, and the weight of extrapolating every kind of required material is: Be:5kg, and Cu:60kg, Cr:8kg,
bi: 1kg,
c: 0.01kg,
pr: 0.1kg, Si:20kg, Zn:300kg, Al:605.89kg.
(2) first in smelting furnace, add aluminium ingot or molten aluminum liquid, heating makes it to melt completely and insulation at 700～800 DEG C;
(3) add basal body interface reaction buffer, Be, solvent passivator, grain-refining agent, alloy strengthening agent, rare earth addition and precipitation hardening agent by formula rate again, finally add again zinc, stir; On-site sampling is analyzed, and according to analytical results and formula range, adjusts addition; Then continue melting and stirring, sampling analysis again, until each element ratio meets formula requirement completely.
(4) then above-mentioned alloy melt is carried out to furnace refining; In alloy melt, add refining agent, and stir, melt refining completes in enclosed environment.
(5) slagging-off after refining, degasification, leave standstill, temperature adjustment to 660～720 DEG C, aluminium alloy is toppled over and is come out of the stove, and filters simultaneously; In the mild impouring casting of filtrate ingot mould, by sequential crystallization mode, melt is condensed in ingot mould from bottom to top, form silvery white ingot shape.
(6) immersion condition is determined and the detection analysis of Alloy Plating laminate Performance and quality.
embodiment 2:Be-Li-Nb-Tl-Zr-Nd-Fe-Si combination
(1), by the selected group element of formula combination table, according to weight percent be: Be:10
-4, alloy strengthening agent Li:10
-4, solvent passivator Nb:10
-4, precipitation hardening agent Tl:10
-4, grain-refining agent Zr:10
-4, rare earth addition: Nd:10
-4, basal body interface reaction buffering element Fe:0.001, Si:0.5, the second solvent element Zn:1, surplus is Al; The alloy total amount of preparation is 1000kg, and the weight of extrapolating every kind of required material is: Be:0.001kg, Li:0.001kg, Nb:0.001kg, Tl:0.001kg, Zr:0.001kg, Nd:0.001kg, Fe:0.01kg, Si:5kg, Zn:10kg, Al:984.984kg.
All the other steps are with embodiment 1.
embodiment 3:
(1) by the selected group element of formula combination table, according to weight percent be: Be:0.01, alloy strengthening agent Cu:4.0, Li:2.0, solvent passivator Co:0.02, Cr:0.8, Nb:0.18, precipitation hardening agent Bi:0.1, In:0.17, Tl:0.1, grain-refining agent C:0.001, Zr:0.28, rare earth addition Pr:0.01, Nd:0.2, basal body interface reaction buffering element Fe:1.0, Si:1.0, the second solvent element Zn:10, surplus is Al; The alloy total amount of preparation is 1000kg, and the weight of extrapolating every kind of required material is Be:0.1kg, Cu:40kg, Li:20 kg, Co:0.2kg, Cr:8kg, Nb:1.8kg, Bi:1kg, In:1.7kg, Tl:1kg, C:0.01kg, Zr: 2.8kg, Pr:0.1kg, Nd:2kg, Fe:10kg, Si:10kg, Zn:100kg, Al:801.29kg.
All the other steps are with embodiment 1.
embodiment 4:Be-Cu-Co-Nb-In-C-Pr-Si combination
(1) by the selected group element of formula combination table, according to weight percent be: Be:0.0017, alloy strengthening agent Cu:0.026, solvent passivator Co:0.0032, Nb:0.13, precipitation hardening agent In:0.056, grain-refining agent C:0.00019, rare earth addition Pr:0.0025, basal body interface reaction buffering element Si:0.68, the second solvent element Zn:19.5, surplus is Al; The alloy total amount of preparation is 1000kg, and the weight of extrapolating every kind of required material is: Be:0.017kg, and Cu:0.26kg, Co:0.032kg, Nb:1.3kg, In:0.56kg,
c: 0.0019kg, Pr:0.025kg, Si:6.8kg, Zn:195kg, Al:796.0041kg.
All the other steps are with embodiment 1.
embodiment 5:Be-Li-Co-In-Bi-Zr-Nd-Fe combination
(1) by the selected group element of formula combination table, according to weight percent be: Be:0.0072, alloy strengthening agent Li:0.18, solvent passivator Co:0.003, precipitation hardening agent In:0.00053, Bi:0.052, grain-refining agent Zr:0.086, rare earth addition Nd:0.063, basal body interface reaction buffering element Fe:1.0, surplus is Al; The alloy total amount of preparation is 1000kg, and the weight of extrapolating every kind of required material is: Be:0.072kg, Li:1.8kg, Co:0.03kg, In:0.0053kg, Bi:0.52kg, Zr:0.86kg, Nd:0.63kg, Fe:10kg, Al:986.0827kg.
All the other steps are with embodiment 1.
Claims (3)
1. a Be low zinc aluminum alloy plating material for hot-dip plating rotten with many combinations, is characterized in that: by element wt per-cent, this alloying constituent is Zn≤30, Be:10
-4～0.05, alloy strengthening agent 10
-4～6.0, solvent passivator 10
-4～1.0, precipitation hardening agent 10
-4～0.5, grain-refining agent 10
-4～1.0, rare earth addition 10
-4～1.0, basal body interface reaction buffer 0.001～2.0, all the other are Al and inevitable trace impurity; Alloy strengthening agent comprises Cu or Li, and the alloy that contains Cu or Li; Solvent passivator comprises Co, Cr or Nb, and the alloy that contains Co, Cr or Nb; Every kind of element uses separately or mixes and uses; Precipitation hardening agent comprises Bi, In or Tl, and every kind of element uses separately or mixes and uses; Grain-refining agent comprises the compound that C or Zr and they form mutually, and the high rigidity high stability compound of C or Zr and the formation of high-melting-point transition element; Rare earth addition comprises as the Pr of rare earth element or Nd, and the mishmetal of more than one rare earth elements formation; Basal body interface reaction buffer comprises Fe or Si, and the alloy that contains Fe or Si.
2. preparation methods for the low zinc aluminum alloy plating material for hot-dip plating that Be and many combinations are gone bad as claimed in claim 1, is characterized in that: comprise the steps:
(1) within the scope of above-mentioned element ratio, a selected group element ratio, the alloy total amount of preparing as required again, extrapolate the quality of every kind of required elemental metals, or the quality of alloy, or the quality of hybrid metal additive, establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
(2) first in smelting furnace, add appropriate aluminium ingot or molten aluminum liquid, heating makes it to melt completely and insulation at 700～800 DEG C;
(3) add basal body interface reaction buffer, Be, solvent passivator, grain-refining agent, alloy strengthening agent, rare earth addition and precipitation hardening agent by formula rate again, finally add again zinc, stir; On-site sampling is analyzed, and according to analytical results and formula range, adjusts addition; Then continue melting and stirring, sampling analysis again, until each element ratio meets formula requirement completely;
(4) then above-mentioned alloy melt is carried out to furnace refining; In alloy melt, add refining agent, and stir, melt refining completes in enclosed environment;
(5) slagging-off after refining, degasification, leave standstill, temperature adjustment to 660～720 DEG C, aluminium alloy is toppled over and is come out of the stove, and filters simultaneously; In the mild impouring casting of filtrate ingot mould, by sequential crystallization mode, melt is condensed in ingot mould from bottom to top, form silvery white ingot shape.
3. Be according to claim 2 and the preparation methods that combine rotten low zinc aluminum alloy plating material for hot-dip plating, is characterized in that: in step (2), smelting furnace refers to the industrial smelting furnace of the various aluminium alloys of melting, zinc alloy or copper alloy more.
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| PCT/CN2011/081741 WO2012113242A1 (en) | 2011-02-25 | 2011-11-03 | Low-zinc hot dip aluminum alloy coating material containing be and combination of agents, and preparation method thereof |
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| GB1387961A (en) * | 1972-07-12 | 1975-03-19 | Vaw Ver Aluminium Werke Ag | Age-hardenable aluminium alloy |
| CN101805857A (en) * | 2009-09-23 | 2010-08-18 | 贵州华科铝材料工程技术研究有限公司 | Be-RE high-strength heat-resisting aluminum alloy material and production method thereof |
| CN101935789A (en) * | 2009-11-19 | 2011-01-05 | 无锡麟龙铝业有限公司 | Hot-dipped cast aluminum alloy containing Al-Zn-Si-Mg-RE-Ti-Ni and manufacturing method thereof |
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| CN1161383A (en) * | 1996-12-10 | 1997-10-08 | 马鞍山市鼎泰金属制品公司 | Rare-earth, zinc and aluminium alloy coating material, and art for hot-dip plating |
| JPH10249580A (en) * | 1997-03-10 | 1998-09-22 | Furukawa Electric Co Ltd:The | Al alloy filler metal and manufacture of al alloy made heat exchanger |
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|---|---|---|---|---|
| GB1387961A (en) * | 1972-07-12 | 1975-03-19 | Vaw Ver Aluminium Werke Ag | Age-hardenable aluminium alloy |
| CN101805857A (en) * | 2009-09-23 | 2010-08-18 | 贵州华科铝材料工程技术研究有限公司 | Be-RE high-strength heat-resisting aluminum alloy material and production method thereof |
| CN101935789A (en) * | 2009-11-19 | 2011-01-05 | 无锡麟龙铝业有限公司 | Hot-dipped cast aluminum alloy containing Al-Zn-Si-Mg-RE-Ti-Ni and manufacturing method thereof |
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