CN102650026A - 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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- 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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- 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 hot dip aluminum plating alloy layer materials and preparation method thereof that make up 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 is near 200,000,000 tons, and wherein major part is a steel plate galvanized.Because the whole world annual used for hot dip galvanizing zinc consumption reaches more than 70% of zinc metal ultimate production, cause the situation of zinc resource shortage more and more severeer.Zinc output in the world's remains on about 1,200 ten thousand tons every year on average since 2008, 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 all be used for doing coating material to global zinc, also can not satisfy 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 used for hot dip galvanizing novel material of alternative zinc, is the inexorable trend and the requirement of the world and Chinese Technological Economy development; And be hopeful most as the material for zinc, be aluminium-zinc alloy and duraluminum.
Relevant aluminium zinc or aluminium-zinc alloy are the novel high-performance coating material patent of main body component, mainly concentrate on developed countries such as American-European and Japan, the more domestic patent that the industry are also arranged.Galvalume is a USP; Composition is 55%Al-43.4%Zn-1.6%Si; It is the high alumina type zn alloy coating material that obtains actual commercial application at present; Though it is 2～7 times of pure zinc coating to the protective capability of base steel, can practice thrift zinc resource in a large number again since immersion plating temperature high (590～600 ℃), plating bath poor to the wetting capacity of base steel, be prone to produce the plating leakage of steel plate needle-like, coating to scratch, there are reasons such as gap in aspect such as galvanic protection scarce capacity, forming process, welding and the coating performance of otch and pure zinc coating; Offset a lot of advantages, made it and to accept for market well.Galfan is the coating material of the 5%Al-Zn system of Belgium's development; Contain trace elements such as Fe, Si, Pb, Cd, Sn and rare earth; Its fusing point is lower than pure zinc, has solved the problem of Galvalume plating bath to the wetting capacity difference of base steel, relies on the quick cooling of steel plate to produce tiny eutectic structure; Therefore coating have the solidity to corrosion that is higher than zinc and good coating performance, machine-shaping property and and weldability; But because of low melting point metals such as Pb, Cd, Sn cause easily coating intergranular corrosion (causing color change), have strict restriction, coating to be easy to generate problems such as large-area hole is recessed, high temperature oxidation resisting ability to the steel plate speed of cooling, influenced the application market of Galfan, add that it still contains the Zn more than 90%; Having little significance aspect the saving zinc resource, can not solve the problem of hot dip process industry long-run development.In recent years, the multicomponent system alloy layer material of Zn-Al-Mg and relevant components thereof occurred, 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% or the like in Japan, but the aluminium content of these product innovations and patent is mostly below 50%; And there is not to realize the novel coating material patented technology of low-cost commercial application basically.
Therefore; Improve the over-all properties of coating around the multiple alloying element of interpolation; Adopt more Al component to replace Zn, emphasis is to realize the coating protective capability of aluminium and the best combination of the sacrificing cathode protective capability of zinc, and guarantees with as far as possible simple or immersion technical equipment; Premium propertiess such as the antistripping of realization Coated Steel, HS, easy processing, easy welding, anti-higher temperature, acid and alkali-resistance salt corrosion are in one; Research and development and promote green iron and steel or immersion flow process in the production of coating material with use two links and realize simultaneously subtracting dirt, falling basis, synergy, upgrading, are technical barriers of being badly in need of solution.
Summary of the invention
The technical problem that the present invention will solve 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 property; Realize that coated sheet is prone to processing, is prone to welding, high temperature resistant, acid and alkali-resistance salt corrosion; Can improve cycle efficiency and recycle value, in the production of coating material with use two links and realize subtracting dirt simultaneously, fall basis, synergy, upgrading, assembling for the technology upgrading, product renewal and the industry that realize the macroeconomy aspect provides rotten low zinc hot dip aluminum plating alloy layer materials of Be that base mateiral supports and many combinations and preparation method thereof.
Technical scheme of the present invention:
A kind of Be and the rotten low zinc hot dip aluminum plating alloy layer material of 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.
The 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 can use separately for every kind, also can mix use.
The precipitation hardening agent comprises Bi, In or Tl, and every kind of element can use separately, also can mix use.
Grain-refining agent comprises the compound that C or Zr and they form each other, and the high firmness high stability compound of C or Zr and the formation of HMP transition element.
Rare earth addition comprises as the Pr of REE or Nd, and the mishmetal of more than one REEs formation.
The alloy that the basal body interface reaction buffer comprises Fe and contains Fe.
A kind of Be as stated and the preparing methods that make up rotten low zinc hot dip aluminum plating alloy layer material comprise the steps: more
(1) in above-mentioned element ratio scope, a selected group element ratio, the alloy total amount of preparing as required again; Extrapolate the quality of every kind of required elemental metals, perhaps the quality of alloy, the perhaps quality of hybrid metal additive; Work out the alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
(2) in smelting furnace, add an amount of aluminium ingot or molten aluminum liquid earlier, heating makes it to melt fully and is incubated down at 700～800 ℃;
(3) press formula rate again and add basal body interface reaction buffer, Be, solvent passivator, grain-refining agent, alloy strengthening agent, rare earth addition and precipitation hardening agent, add zinc at last again, stir; On-site sampling is analyzed, according to analytical results and formula range, and the adjustment addition; Continue melting and stirring then, sampling analysis meets the prescription requirement fully until each element ratio once more.
(4) then above-mentioned alloy melt is carried out furnace refining; In alloy melt, add refining agent, and stir, the melt refining is accomplished in enclosed environment.
(5) slagging-off, degasification after the refining, leave standstill, temperature adjustment to 660～720 ℃, alloy liquid is toppled over and is come out of the stove, and filters simultaneously; Filtrate in the mild impouring casting ingot mould,, melt is condensed in ingot mould from bottom to top, form silvery white ingot shape through the sequential crystallization mode.
In step (2), smelting furnace is meant can the various duraluminums 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: the combination of multielements such as utilization Be and basal body interface reaction buffer, solvent passivator, grain-refining agent, High-Temperature Strengthening agent, rare earth addition and precipitation hardening agent is to the three-dimensional metamorphism of low aluminium zinc system; Rise to a new height to the over-all properties of coating material; 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 property, realize that coated sheet is prone to processing, is prone to welding, high temperature resistant, acid and alkali-resistance salt corrosion, has improved cycle efficiency and recycle value; In the production of coating material with use two links and realize subtracting dirt simultaneously, fall basis, synergy, upgrading; Assembling for the technology upgrading, product renewal and the industry that realize the macroeconomy aspect provides base mateiral to support, embodied under the alternating temperature condition with the complex component structure of " solution model " research duraluminum at polynary solute in the state-of-the-art technology method of behavioural characteristic, what its preparation method adopted all is common equipments of metallurgy industry; Do not need specially, can improve cycle efficiency and recycle value.
---the concrete effect of Be and six types of alterants is following:
Be is one of minimum alkali metal of atomic radius, also is simultaneously one of minimum metallic element of proportion.The proportion of Be is littler by 1/3rd than Al, and intensity is similar with steel, and heat transfer property is three times of steel, is conductor good in the metal; The oxide compound proportion of Be is little, and hardness is big, and fusing point is up to 2,450 degree Celsius; Therefore have the high-temperature anticorrosion ability, the oxide compound of beryllium, halogenide all have tangible covalency, the covalent compound that Be can also form polymkeric substance and have obvious thermostability; Even when red heat, Be is also very stable in air, and it covers matrix surface; Form the surface oxidation resist of form compact and stable, the protection matrix is not oxidized and heat conductivility is good, has strengthened the heat-resisting effect of matrix; Utilize of 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 on macroscopic view; Reduce surface tension, and improve the affinity of melt and plating piece matrix, reach and improve coating and matrix tack.
Add Be in this coating alloy and can obviously reduce ingot casting crackle tendency, improve the strength of materials, and (iron and steel) goods appearance after casting and the immersion plating is more attractive in appearance, beautiful; But when total add-on surpassed the saturation solubility of Be in solvent, the crackle tendency of alloy increased mechanical properties decrease.
Plating bath of the present invention is with the iron and steel substrate contacts time; Steel matrix is had good wettability, solute Be and solvent orange 2 A l can with the red stone rapid reaction of steel substrate surface, generate that proportion is little, stable in properties and the oxide compound of compact structure; Float on coating surface; Play provide protection, can reduce the consumption of steel plate plating assistant agent or not use plating assistant agent simultaneously, thereby practice thrift cost and reduce harm environment to internal layer.
Because Be has decomposed the metallic compound that Fe-Al, Fe-Zn form effectively, plating bath of the present invention when immersion plating, can reduce end slag and scum silica frost produces.
The standard potential of Be (1.70v) almost completely the same with Al, outer electronic structure 2s
2I.e. 2 valence electrons, so add Be among the Al and can increase the matrix free electronic concentration, increased the degree of unbalancedness of matrix electronic cloud structure simultaneously, strengthen the liquid fluidity of matrix; The atomic radius of Be is little than Al; Density 1.85 spreads easily, rises in the Al melt and is enriched in surface and crystal boundary, because the equilibrium solubility less (almost nil) in Al; Can form the Al-Be supersaturated solid solution so add the Be of trace; When the Be that is enriched in surface and subgrain boundary reaches finite concentration, form than sosoloid fusing point is high, dispersity is high, the tiny nucleus of overall distribution good evenness, sosoloid is with peritectoid or eutectic morphological crystal around the guiding; Because Be and sosoloid equilibrium phase are near the simple substance form; The mechanism of crystal growth is smooth interface and the rough interfaces under macrostate under the microstate, and the grain growth speed that therefore forms is slower, consequently makes alloy grain tiny; Liquid fluidity is good, solidifies back intensity height; Simultaneously; The Be atom that is enriched in alloy surface is in suitable scope (1.59) absorbing the BeO volumetric ratio that forms after the Sauerstoffatom oxidation; Film layer structure densification, stable in properties, good corrosion resistance; Can remedy the low defective of the anti-salt erosion property of AlCu alloy, add more Cu in the alloy thereby can make, to give full play to the strengthening effect of Cu to alloy.Be is equally applicable to the refinement to metallic compound to the refining effect of aluminium base sosoloid crystal grain; In supersaturated solid solution, Be is the element that can carry out refinement with nearly simple substance form 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 surpass 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 the fixing protection of grid under the microcosmic concurrently and mobilely cover damage surface automatically and play the passivation film of defencive function, make the matrix of coating under covering have better physical and chemical performance; For preventing unwanted color to occur after the oxidation of single passivation element, can use two kinds and two or more complex element passivator.
Utilize grain refining Elements C or Zr and fining agent; When high temperature through dissolving, diffusion and disperse; Become nano level and even more tiny foreign atom group bunch and stable molecular cluster, when the melt crystallisation by cooling, provide tiny " crystal seed " that be evenly distributed in a large number, gap mutually and interstitial compound, 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 the processibility and the weldability of plating piece.
REE additive Pr or Nd have that atomic polarization, alloy strengthening, grain refining, surface beautify, the multiple booster action of 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 also are the ageing strengthening agent; They are metallic elements that fusing point is not high, chemically reactive is not high yet, add a spot of this dvielement, in alloy system, keep nearly simple substance state; Though solidify but under the still higher state of temperature in system; They still keep liquid, thereby make system on macroscopic view, possess the semi-solid state characteristic, for strengthening element in the acceleration alloy in the ageing strengthening process is converted into actual reinforcement attitude (precipitation hardening or precipitation-hardening) condition are provided; Can give good processing characteristics of alloy and wear resisting property simultaneously; Kind and addition through control precipitation hardening element can also obtain the 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 the Fe matrix in the time of can effectively being suppressed at immersion plating reduces or stops generation " lensing Fe
2Al
5", strengthen " 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 present invention utilizes the ultra multi-element alloyed and microalloying reaction that Be and six types of alterants and low aluminium zinc carry out, obtained to have to the base steel wettability is good, bonding force is strong, intensity is high, good-extensibility, high temperature resistant, coating thin, solidity to corrosion strong, processibility and weldability are good etc. integrates the high-quality iron and steel used for hot dip galvanizing aluminum alloy coating material of multiple advantage.
In Be and six types of alterants; The effect role of some element in alloy has multiplicity: except that REE has multiple action; Most elements of the present invention all has reduction Al-Zn smelt surface tension, improves the effect to the iron-based wettability; Be, Li, Co, Cr, Nb etc. have the effect that improves alloy strength and high-temperature behavior, and 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 or immersion temperature that optimum of the present invention adopts is 680～720 ℃, plating bath good fluidity in this TR, and plating leakage rate, slagging rate are low.
In the TR of using or 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 ℃; Coiling temperature then is controlled at about 600 ℃; Thereby can suppress the long thick and passivation of steel strip surface sull, can reduce the pollution of pickling amount and spent pickle liquor simultaneously environment.
In the TR of using or immersion of the present invention, after steel plate immersion plating, need not carry out forced cooling and handle, thereby be that the spontaneous alloying passivation of coating material provides suitable temperature and long as far as possible time conditions.
After the annealed processing of steel plate after the immersion plating, overlay coating has high-strength and high ductility high firmness characteristic, and tensile strength can reach more than the 400Mpa, and elongation after fracture can reach more than 8%, more than the hardness HBS150; Through analyzing, 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, again with Al composition master alloy after, have good refinement modification effect; The Al-rare earth compound has identical refinement and stigma of degeneracy.
400～1000 kilograms of heavy ingots that solidify are carried out the UT inspection, and each position sound intensity of equal thickness is even, inner flawless.
Coated Steel of the present invention is carried out x-ray fluorescence analysis show, the even zero defect of internal structure.
Sampling analysis shows in the fusion process, comprises the small structure form of the not jljl phase that is difficult to confirm in the melt, and great majority are dystectic metallic compounds with complicated crystalline network.Think that this is one of item key of grain refining, hardness raising.
The fracture surface of sample microstructure analysis shows: produced a large amount of eutectic reactions, Peritectic Reaction, eutectoid reaction and precipitation effect in the material crystallisation process, outside dimple and intragranular, had the heterogeneous nucleus of a large amount of tiny spheries to exist.This kind crystalline structure has been verified the grain refining effect in the present invention of heterogeneous nucleus.
The result of melt treatment shows that the cleaning molten means can make the intensity of coupon and unit elongation promote simultaneously efficiently, the amplitude of lifting: strength enhancing can reach more than the 100Mpa, and unit elongation promotes and can reach more than 10%.
Oven test proves, through 24 hours high temperature atmosphere environment more than 700 ℃, do not have considerable change with the steel product appearance color of immersion plating coating novel material of the present invention.
Solidity to corrosion: the salt-fog test sample, thickness of coating 20 μ, experimental period >=280h, the surface nothing obviously receives corrosion phenomenon (common galvanized sheet 48h promptly stain or blackspot can occur); Heat reflectivity >=70%; High temperature oxidation resistance: variable color does not take place more than 315 ℃ of following hot environment 100h; Moisture-proof heat: 49 ℃, through the 168h non-corroding, do not have obvious variable color under humidity 93 ± 2% environment; Coating is crooked: during d=a, coating do not occur beyond the 5mm of portion of test coupon limit and come off; The coating surface smooth, crystalline substance is spent evenly.
The solidity to corrosion simultaneous test of several kinds of alloy layer steel plates: the hot dip process steel are Q
235Steel, the hot dipping plating bath is a novel hot-dip alloy plating of the present invention, the immersion plating temperature is 680～720 ℃, 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; In 35 ℃ of 5%NaCl salt solution, soak 260h respectively then, and, contain SO in 35 ℃ of temperature, relative humidity 93～94%
2Carry out corrosion test in the acid mist of 10ppm, the loss of weight contrasts like following table 1:
Table 1 solidity to corrosion comparing result
At room temperature different materials has been carried out the mensuration of ys and tensile strength, result such as table 2:
Table 2 strength of materials comparing result
The thing phase composite and the shape characteristic of research coating material and steel matrix key coat; The thing that obtains reach mutually hundreds of more than; Wherein only the thing phase kind of two-component system just has kind more than 200, and through the binary thing phase that metallurgical analysis can be distinguished, only is the part of the more polybinary compound that in fact possibly exist; Because the compound that molecular formula is identical often has multiple different crystal structure; Though be difficult to distinguish,, also should be regarded as different materials owing to have different stability with metallurgical analysis.
Certain constituent content (for example, greater than 1%wt) relatively more for a long time in alloy can generate complicated more ternary and the metallic compound more than the ternary, for example Al with other solute element reaction
13Cr
4Si
4, Al
7Cu
2Fe, Al
13Si
4(CrFe)
4, or the like.These polynary metallic compounds that combine also are unsettled, when temperature and potential of hydrogen change, can decompose automatically; Discharge effective atom; Keeping the stable of whole alloy system, thereby play passivation, improve protective capability matrix to coating.
Co, Cr, Nb are typical d district, multivalence position transition element in the periodictable, can generate the characteristics of multiple metallic compound with Al, Zn solvent and Fe matrix element from them, can know that they all are the sacrificing protection elements of matrix; In addition; When they are had an effect with oxygenant on the sosoloid surface; Under different pH value conditions, can generate the compound and the hydrated ion of multiple different oxidation state, owing to all have higher oxide compound volumetric ratio (greater than 1.5), the ability of its passivation protection is higher than simple pellumina far away; These compounds and hydrated ion are inflexible a bit; After formation, exist as nonvolatil grid protection layer, some is weak flowability, and some has good mobility; After the plating piece surface is scratched; Have mobile compound and hydrated ion and can remedy immediately, cover wound, coating and matrix are unlikely to because of the long-time exposed excessive corrosion that suffers, this has just solved the problem that simple aluminium-zinc alloy coats the protective capability difference.
About ultra multi-element alloyed metamorphic mechanism, there is not a kind of generally acknowledged theoretical explanation at present; Can not explain with the multiple Superposition Method of binary alloy phase diagram, can not make an explanation with the general common practise and the experience of each trace element in the existing multicomponent alloy to the principal element effect.
But there are two kinds of patterns to analyze qualitatively to the element interaction mechanism of ultra multicomponent alloy; A kind of is parsing to the atomic structure aspect; A kind of is solute dissolves and separate out the solution model theoretical method in solvent utilization; The combination of the two can be made the explanation with fine accordance to the excellent properties of novel coating material.
When ultra multicomponent alloy system is in uniform and stable liquid state; Whole system is actually the multinuclear heart " ocean " that a kind of valence electron (unbound electron) surrounds; Suppose all uniform distribution of each trace element in " seawater " lining of principal element; Promptly be in a kind of perfect condition; At this time describe the factor of whole architectural feature, mainly should comprise flat fare electron density, average electrical negativity or average electrical electrode potential, density, temperature, volume, pressure, and thermodynamics index such as system free energy, enthalpy, entropy.But see from microcosmic angle; Different atom pairss around it sucking action of unbound electron vary; Therefore atomic structure and the character under all kinds of atoms of elements and its simple substance state has just produced difference, on the macroscopic property of the present alloy of these difference tables, promptly causes significant performance change.
New element gets into the variation order of alloy solution system: the first step is ionization; Promptly at first become one ion; At this time have the dimensional change as the alloy solution ultimate particle: the atomic radius of the element that electronegativity is stronger than solvent element own dwindles, unbound electron around attracting simultaneously and have certain negative charge, and negative ion becomes to be as the criterion; The element of electronegativity a little less than than solvent element then produces opposite variation; The positive ion that becomes to be as the criterion when reaching balance at last, should have two types solute ions: than the little negative ion of simple substance state atomic radius with than the big positive ion of simple substance state atomic radius; Second step was dissolving, got into the lattice of solvent substrate; The 3rd step was diffusion, occupied wide as far as possible system space, and dissolving and diffusion are always carried out simultaneously; The 4th step changed in the lattice of matrix, formed the sosoloid in metathetical 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 the matrix, and forming with molecule and molecular grouping is the regional special coherence structure that unit participates in the matrix coherence; The 8th, the sosoloid of element and the sosoloid of metallic compound reach capacity together; 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 that takes place 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, and the amount and the stability thereof that generate, then look the parameter such as electronegativity difference, interatomic distance, valence electron number and valence orbit structure of matrix and new element and decide with matrix.
Performance and the effect of transition element in alloy is extremely complicated, and they are different from chemical property obvious and definite metal and non-metallic element.Because the dislocation of outermost layer and time out-shell electron orbital energy level; Transition element gets betatopic ability, the ability of shared electrons and the ability of number adjustment thereof are provided all is very powerful; Add less atomic radius, make it easily with active metal, active nonmetal and even normal temperature under inactive element chemical reaction can both take place, generates relatively stable but changes apparent in view, as to follow the shades of colour variation compound and title complex with temperature and potential of hydrogen; Its intramolecular key shape and bond energy complex structure; Both form easily, also receive ectocine easily and disintegrate, even the atom of same dvielement (with the adjacent or close element of one-period or same subgroup); Also can change the complex construction that has formed at an easy rate; Even, also can change the complex construction that has formed at an easy rate with a kind of ion of different prices of element, be not always the case like Co, Cr, Nb and Fe etc.
It is big more that electropotential or electronegativity differ; The compound of stable (fusing point is high) of easy more formation between two kinds of elements, according to solubility product principle, other unstable compounds that contains one or more same components will be dissolved; Can keep equilibrated solute atoms concentration to discharge; Stable compound then continues to produce, and reaches new balance until whole system, and this reorganization campaign just can stop.Final general trend; Be a kind of new element of every adding or compound, each integral part of system all produces relevant reaction, or reduces (concentration reduction); Increase (concentration rising); Remain unchanged, and the space of reserving existence for new element or compound, reach that the partial potential of each material keeps equating after the balance.
When a kind of element in the system receives oxidation and after losing electronics; This concentration of element reduces in the system; According to partial potential balance and solubility product equilibrium principle, the material that contains this element in the system will decompose to discharge this an amount of element automatically, remedy this concentration of element in the system; Cause a series of chain reactions simultaneously, finally still will reach new partial potential balance and solubility product balance.The element kind is many more, and chain reaction is more complicated, is constant but finally reach new partial potential balance and solubility product equilibrated result.System that Here it is opposing corrosive " equation with many unknowns formula " controlling mechanism; This mechanism, iron when being equally applicable to hot dip process-aluminum-zinc alloy reaction, thus be implemented in " equation with many unknowns formula " controlling mechanism of uniform gradient between inner each aspect of thickness direction.
On the other hand, Co, Cr, Nb and Fe are transition element of the same type, and they are as solute element; When solvent element al, Zn and matrix Fe react; They also participate in reaction simultaneously, play the effect of buffering matrix and solvent main reaction severity, effectively stop the generation of Zn-Al-Fe " effect of splitting "; And also form the passivation subgrade at nearly matrix face, strengthen protective capability to matrix.
When having moderate and the element that fusing point is very low of a small amount of current potential in the alloy; Like Bi, In, Tl; The character of these elements in alloy is unaffected basically, and exists with nearly simple substance form, and the effect of " interstitial fluid " or " liquid film " can be provided when the alloy crystallization; The solid solubility difference is big to quantity in alloy liquid is more element and compound; This " interstitial fluid " or " liquid film " effect in annealing recrystallization and ageing treatment process is very important, and it can be the dissolving in and separate out quick unimpeded channel is provided of sosoloid solute, and quenches and aging time thereby significantly shorten; Improve the thermal treatment effect, can not cause the intergranular corrosion (because content is few) under the high temperature simultaneously again; If these low melting point elements have certain diffusibility simultaneously, then can " fill out the hole formula " and get in the hollow that forms when crystallization is leading in the alloy grows up mutually (high free energy district), thereby suppress crystal growth, produce metamorphism.
REE Pr, Nd are with transition element generation alloying the time; Three characteristics are arranged: 1. simple substance do not dissolve or solubleness very low; All below 0.1% (mass percent); 2. easy and transition element reaction forms the intermetallic compound of multiple different content, and its characteristics are corresponding with the temperature of solute component ratio and alloy system, such as: Pr and Al can form from Pr between 630～1240 ℃
3Al is to Pr
3Al
11The compound that has TR Deng 6 kinds of different compositions, different structure, differences; Nd and Al between 635～1235 ℃ also can with Pr-Al similar compounds, the intermetallic compound that 3. forms all has certain solubleness in matrix (Al), (Zn), (Fe), the solubility product of the component of intermetallic compound in alloy is relatively stable.These characteristics 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 atomic radius in this alloy system; It is prone to be dissolved in (Al), (Zn) and can generates multiple compound with Fe; Because these characteristics; It is the very strong element of diffusibility in the system, also can suppress Al-Fe reaction and resist Zn and get involved in the Al-Fe compound with " calking " mode, in Galvalume and Galfan coating alloy with the main suppressor factor of Si as the Al-Fe intense reaction; And in alloy system of the present invention, Si can be enriched near the reaction surface multiple solvent passivation element and bear the effect of suppressor factor jointly.
Experiment shows that when guaranteeing degasification preferably, 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; It is best wherein to add the electrothermal stove effect with the line-frequency induction of protectiveness melting, and no matter adopt any melting equipment, melt is stirred; And seal flow process as far as possible, reduce metal loss and to Health hazard; Alloy material of the present invention can be easily carries out the segmentation allotment with the industrial smelting furnace of the various duraluminums of melting, zinc alloy, copper alloy and produces; When allotment, do not need frequent prepurging; Have favorable compatibility, can make full use of equipment, raise the efficiency, reduce cost for the enterprise that produces multiple alloy.
Evidence if contain other element that satisfied prescription requires in the useless assorted material such as the duraluminum of selection batching, zinc alloy, copper alloy, can only use the useless assorted of duraluminum, 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:
The formula combination table
Embodiment 1:Be-Cu-Cr-Bi-C-Pr-Si combination
(1) by the selected group element of formula combination table, is: polarization alterant Be:0.05, alloy strengthening agent Cu:6.0, solvent passivator Cr:0.8, precipitation hardening agent according to weight percent
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 then 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) in smelting furnace, add aluminium ingot or molten aluminum liquid earlier, heating makes it to melt fully and is incubated down at 700～800 ℃;
(3) press formula rate again and add basal body interface reaction buffer, Be, solvent passivator, grain-refining agent, alloy strengthening agent, rare earth addition and precipitation hardening agent, add zinc at last again, stir; On-site sampling is analyzed, according to analytical results and formula range, and the adjustment addition; Continue melting and stirring then, sampling analysis meets the prescription requirement fully until each element ratio once more.
(4) then above-mentioned alloy melt is carried out furnace refining; In alloy melt, add refining agent, and stir, the melt refining is accomplished in enclosed environment.
(5) slagging-off, degasification after the refining, leave standstill, temperature adjustment to 660～720 ℃, alloy liquid is toppled over and is come out of the stove, and filters simultaneously; Filtrate in the mild impouring casting ingot mould,, melt is condensed in ingot mould from bottom to top, form silvery white ingot shape through the sequential crystallization mode.
(6) the or immersion condition confirms to reach the check and analysis of alloy layer plate performance and quality.
Embodiment 2:Be-Li-Nb-Tl-Zr-Nd-Fe-Si combination
(1), according to weight percent is: Be:10 by the selected group element of formula combination table
-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 then 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), according to weight percent is: Be:0.01, alloy strengthening agent Cu:4.0, Li:2.0 by the selected group element of formula combination table; 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 then 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), according to weight percent is: Be:0.0017, alloy strengthening agent Cu:0.026 by the selected group element of formula combination table; 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 then 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), according to weight percent is: Be:0.0072, alloy strengthening agent Li:0.18 by the selected group element of formula combination table; 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 then 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 (9)
1. Be and the rotten low zinc hot dip aluminum plating alloy layer materials of many combinations, it 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.
2. according to said Be of claim 1 and the rotten low zinc hot dip aluminum plating alloy layer material of many combinations, it is characterized in that: the alloy strengthening agent comprises Cu or Li, and the alloy that contains Cu or Li.
3. according to said Be of claim 1 and the rotten low zinc hot dip aluminum plating alloy layer material of many combinations, it is characterized in that: solvent passivator comprises Co, Cr or Nb, and the alloy that contains Co, Cr or Nb; Every kind of element can use separately for every kind, also can mix use.
4. according to said Be of claim 1 and the rotten low zinc hot dip aluminum plating alloy layer material of many combinations, it is characterized in that: the precipitation hardening agent comprises Bi, In or Tl, and every kind of element can use separately, also can mix use.
5. according to said Be of claim 1 and the rotten low zinc hot dip aluminum plating alloy layer material of many combinations; It is characterized in that: grain-refining agent comprises the compound that C or Zr and they form each other, and the high firmness high stability compound of C or Zr and the formation of HMP transition element.
6. according to said Be of claim 1 and the rotten low zinc hot dip aluminum plating alloy layer material of many combinations, it is characterized in that: rare earth addition comprises as the Pr of REE or Nd, reaches the mishmetal that more than one REEs form.
7. according to said Be of claim 1 and the rotten low zinc hot dip aluminum plating alloy layer material of many combinations, it is characterized in that: the basal body interface reaction buffer comprises Fe or Si, and the alloy that contains Fe or Si.
8. the preparing methods like the rotten low zinc hot dip aluminum plating alloy layer material of any said Be of claim 1～7 and many combinations is characterized in that: comprise the steps:
(1) in above-mentioned element ratio scope, a selected group element ratio, the alloy total amount of preparing as required again; Extrapolate the quality of every kind of required elemental metals, perhaps the quality of alloy, the perhaps quality of hybrid metal additive; Work out the alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
(2) in smelting furnace, add an amount of aluminium ingot or molten aluminum liquid earlier, heating makes it to melt fully and is incubated down at 700～800 ℃;
(3) press formula rate again and add basal body interface reaction buffer, Be, solvent passivator, grain-refining agent, alloy strengthening agent, rare earth addition and precipitation hardening agent, add zinc at last again, stir; On-site sampling is analyzed, according to analytical results and formula range, and the adjustment addition; Continue melting and stirring then, sampling analysis meets the prescription requirement fully until each element ratio once more;
(4) then above-mentioned alloy melt is carried out furnace refining; In alloy melt, add refining agent, and stir, the melt refining is accomplished in enclosed environment;
(5) slagging-off, degasification after the refining, leave standstill, temperature adjustment to 660～720 ℃, alloy liquid is toppled over and is come out of the stove, and filters simultaneously; Filtrate in the mild impouring casting ingot mould,, melt is condensed in ingot mould from bottom to top, form silvery white ingot shape through the sequential crystallization mode.
9. Be according to claim 8 and the preparing methods that make up rotten low zinc hot dip aluminum plating alloy layer material more; It is characterized in that: in step (2); Smelting furnace is meant can the various duraluminums 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.
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| CN201110044893.6A CN102650026B (en) | 2011-02-25 | 2011-02-25 | Be and multi-combination degenerative low-zinc hot-dipped aluminum alloy coating material and preparation method thereof |
| 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978555A (en) * | 2012-11-22 | 2013-03-20 | 天长市飞龙金属制品有限公司 | Rare-earth salt plating assistant solvent |
| CN107955895A (en) * | 2017-11-21 | 2018-04-24 | 广西吉宽太阳能设备有限公司 | A kind of panel solar aluminum alloy coating containing Co and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
-
2011
- 2011-02-25 CN CN201110044893.6A patent/CN102650026B/en not_active Expired - Fee Related
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978555A (en) * | 2012-11-22 | 2013-03-20 | 天长市飞龙金属制品有限公司 | Rare-earth salt plating assistant solvent |
| CN102978555B (en) * | 2012-11-22 | 2015-08-12 | 天长市飞龙金属制品有限公司 | A kind of rare-earth salts helps plating solvent |
| CN107955895A (en) * | 2017-11-21 | 2018-04-24 | 广西吉宽太阳能设备有限公司 | A kind of panel solar aluminum alloy coating containing Co and preparation method thereof |
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