WO2012113242A1 - Low-zinc hot dip aluminum alloy coating material containing be and combination of agents, and preparation method thereof - Google Patents

Low-zinc hot dip aluminum alloy coating material containing be and combination of agents, and preparation method thereof Download PDF

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Publication number
WO2012113242A1
WO2012113242A1 PCT/CN2011/081741 CN2011081741W WO2012113242A1 WO 2012113242 A1 WO2012113242 A1 WO 2012113242A1 CN 2011081741 W CN2011081741 W CN 2011081741W WO 2012113242 A1 WO2012113242 A1 WO 2012113242A1
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alloy
combination
zinc
low
aluminum alloy
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PCT/CN2011/081741
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French (fr)
Chinese (zh)
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车云
门三泉
张中可
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贵州华科铝材料工程技术研究有限公司
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Publication of WO2012113242A1 publication Critical patent/WO2012113242A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent

Definitions

  • the invention relates to an aluminum alloy coating material and a preparation method thereof, in particular to a low-zinc hot-dip aluminum alloy coating material with Be and multi-combination metamorphism and a preparation method thereof. Background technique
  • Galfan is a coating material of 5% A1-Zn system developed in Belgium. It contains trace elements such as Fe, Si, Pb, Cd, Sn and rare earth.
  • the focus is to achieve the best combination of aluminum coating protection and zinc sacrificial cathodic protection, and to ensure As simple as possible hot dip plating technology and equipment, to achieve the anti-flaking, high strength, easy processing, easy welding, high temperature resistance, resistance to 5 acid and alkali corrosion of the coated steel plate, research and development and promotion of green steel
  • the hot dip plating process is a technical problem that needs to be solved in the two stages of production and application of coating materials to reduce pollution, reduce cost, increase efficiency and improve quality. Summary of the invention
  • the present invention is to solve the technical problem are: to provide a series of multi-factor can be formed on the aluminum-zinc mixed system perspective Modification quality becomes 0, and thus form the structure to achieve optimization aluminum-zinc alloy, so that the steel substrate and the coating material Produces good wettability, solid adhesion and matrix strengthening, which makes the plate easy to process, easy to weld, high temperature resistant, acid and alkali resistant, and can improve cycle efficiency and reuse value, in the production and application of coating materials.
  • the two links realize the reduction of pollution, cost reduction, efficiency improvement, quality improvement, and the provision of basic material support for the upgrading of the technology at the macroeconomic level, product replacement and industrial agglomeration, and the combination of low-zinc hot-dip aluminized alloy coating Materials and methods for their preparation.
  • a low-zinc hot-dip aluminum alloy coating material with Be and multi-combination metamorphism the alloy composition is Zn 30, Be: 10 - 4 ⁇ 0.05, alloy strengthening agent 10 - 4 ⁇ 6.0, solvent blunt ⁇ 1.0 agent 10-4, 10-4 precipitation hardening agent, and 0.5 grain refiner 10-4 ⁇ 1.0, ⁇ 1.0 10-4 rare earth additives, reaction buffer 0.001 ⁇ 2.0 matrix interface, and the remainder being non-A1 Trace impurities that are avoided.
  • ° Alloy strengtheners include Cu or Li, and alloys containing Cu or Li.
  • the solvent deactivator includes Co, Cr or Nb, and an alloy containing Co, Cr or Nb; each of these elements may be used singly or in combination.
  • the precipitation hardener includes Bi, In or Tl, and each element may be used singly or in combination.
  • the grain refiner includes C or Zr and a compound formed therebetween, and C or Zr forms a high hardness and high stability compound with a high melting point transition element: 5 .
  • the rare earth additive includes Pr or Nd as a rare earth element, and a mixed rare earth formed of one or more rare earth elements.
  • the matrix interfacial reaction buffer includes Fe and an alloy containing Fe.
  • a method for preparing a low-zinc hot-dip aluminum alloy coating material with Be and multi-combination as described above includes the following steps:
  • the alloy liquid is poured out of the furnace and filtered at the same time; the filtrate is gently poured into the casting ingot mold, and the melt is in the form of sequential crystallization.
  • the ingot mold is condensed from the bottom to the top to form a silver-white ingot type.
  • the smelting furnace refers to an industrial furnace which can smelt various aluminum alloys, zinc alloys or copper alloys, including a power frequency induction heating furnace, an intermediate frequency induction heating furnace, an electric resistance furnace, a gas heating furnace or a fuel heating furnace.
  • the main advantages of the present invention are: the use of Be and matrix interfacial reaction buffer, solvent passivator, grain refiner, high temperature enhancer, rare earth additive and precipitation hardener, etc.
  • the three-dimensional metamorphism of the zinc-aluminum alloy system takes the comprehensive performance of the coating material to a new level, optimizes the microstructure of the aluminum-zinc alloy, and produces good wettability, solid adhesion and matrix strengthening of the coating material and the steel matrix. It is easy to process, easy to weld, high temperature resistant, acid and alkali resistant corrosion, improve cycle efficiency and reuse value, and achieve both pollution reduction, cost reduction and efficiency in the production and application of coating materials.
  • Be is one of the alkali metal elements with the smallest atomic radius and is one of the smallest specific metal elements.
  • the specific gravity of Be is one-third smaller than that of A1. Its strength is similar to that of steel. Its heat transfer performance is three times that of steel. It is a good conductor in metal. Be has a small specific gravity and a high hardness. Its melting point is up to 2,400 degrees Celsius. Ten degrees, so it has high temperature anti-corrosion ability, bismuth oxides and halides have obvious covalency, Be can also form polymers and covalent compounds with obvious thermal stability, even in red heat, Be is in the air It is also very stable, covering the surface of the substrate to form a dense and stable surface oxide protective layer.
  • the protective substrate is not oxidized and has good thermal conductivity, which enhances the heat resistance of the substrate.
  • the element A is used for the solvent element A1 and
  • the atomic polarization reduction effect of Al+Zn effectively adjusts the atomic size and the close-range ordered structure in the microscopic state, makes the melt uniform in macroscopic structure, reduces the surface tension, and improves the affinity of the melt and the plated substrate. And to achieve improved adhesion between the coating and the substrate.
  • the addition of Be to the coated alloy can significantly reduce the crack tendency of the ingot, improve the strength of the material, and the appearance of the (steel) product after casting and immersion is more beautiful and bright; but when the total addition exceeds the saturated solubility of Be in the solvent, The crack tendency of the alloy increases and the mechanical properties decrease.
  • the plating solution of the invention has good wettability to the steel substrate when it is in contact with the steel substrate, and the sol Sol and the solvent A1 can react rapidly with the iron oxide on the steel-based surface to form an oxide having a small specific gravity, a stable property and a dense structure. Floating on the surface of the coating, it protects the inner layer, and at the same time reduces the amount of steel plating agent or does not use the plating agent, thereby saving costs and reducing environmental hazards.
  • the plating solution of the present invention can reduce the generation of bottom slag and scum during immersion plating.
  • Be's standard electrode potential (-1.70V) is almost exactly the same as A1, and the outer electronic structure 2s 2 is 2 valence electrons. Therefore, the addition of Be in A1 increases the free electron concentration of the matrix and increases the imbalance of the matrix electron cloud structure. Degree, enhances the liquid mobility of the matrix; Be has a smaller atomic radius than A1 and a density of 1.85. It easily diffuses, rises and enriches in the surface and grain boundaries in the A1 melt, due to the low equilibrium solubility in A1 (almost Zero), so the addition of a trace amount of Be can form an Al-Be supersaturated solid solution.
  • the concentration of Be enriched at the surface and the subgrain boundary When the concentration of Be enriched at the surface and the subgrain boundary reaches a certain concentration, it forms a higher melting point than the solid solution, has a higher dispersion, and has a uniform overall distribution.
  • the fine crystal nucleus guides the surrounding solid solution to crystallize in the peritectic or eutectic form; since the equilibrium of Be and the solid solution is close to the elemental form, the mechanism of crystal growth is a smooth interface in the microscopic state and a rough interface in the macroscopic state, thus forming The grain growth rate is slow, and the result is that the alloy grains are fine, the liquid fluidity is good, and the strength after solidification is high; meanwhile, the Be atoms enriched in the alloy surface are absorbed.
  • the volume ratio of BeO formed by oxidation of oxygen atoms is in the appropriate range (1.59).
  • the structure of the film is dense, stable, and corrosion-resistant. It can compensate for the low salt corrosion resistance of AlCu alloy, so that more alloys can be added. Cu, in order to give full play to the strengthening effect of Cu on the alloy.
  • the refinement effect of Be on the aluminum-based solid solution grains is also suitable for the refinement of the metal compound; in the supersaturated solid solution, Be is an element capable of refining the impurity Si in a near-simplex form.
  • Solvent passivation element Co, Cr or Nb which can enrich the surface of the solvent with acid, alkali, salt and high temperature atmospheric corrosion, combined with microscopic grid fixed protection and fluidity to automatically cover the damage surface and protect the surface.
  • the passivation film layer has better physical and chemical properties for the substrate covered by the plating layer; in order to prevent unwanted color from appearing after oxidation of a single passivation element, two or more mixed element passivating agents can be used.
  • ⁇ Rare earth element additive Pr or Nd has various auxiliary functions of atomic polarization, alloy strengthening, grain refinement, surface beautification, hydrogen removal and enhanced corrosion resistance, and can enhance Be, alloy strengthening agent, solvent passivating agent, crystal The role of the grain refiner and make up for its shortcomings.
  • Precipitation hardener Bi, In or T1 is also an ageing enhancer. They are metal elements with low melting point and low chemical activity. A small amount of these elements are added to maintain a near-monolithic state in the alloy system. At a still high temperature, they remain liquid, which gives the system a semi-solid characteristic at the macroscopic level, which provides an opportunity to accelerate the transformation of the strengthening elements in the alloy into the actual strengthening state (precipitation hardening or precipitation hardening) during the age strengthening process. Conditions; At the same time, it will give the alloy excellent processing properties and wear resistance; by controlling the type and amount of precipitation hardening elements, the surface pattern of the plated parts can also be obtained.
  • interfacial reaction buffer elements Fe and Si, and alloys containing Fe or Si can effectively suppress the strong chemical reaction between A1 and Fe matrix during immersion plating, reduce or eliminate the formation of "lenticular Fe 2 Al 5 ", strengthen The formation mechanism of "thin layered Fe 2 Al 5 " establishes a reaction mechanism of Fe - A1 - Zn uniform gradient, thereby improving the quality of the coating, reducing the thickness of the coating and saving materials.
  • the present invention utilizes the super-multiple alloying and microalloying reaction of Be and a six-type modifier with a low-zinc aluminum alloy, and has good wettability to the steel base, strong bonding force, high strength, and good elongation.
  • Aluminium alloy coating material for high-quality steel hot-dip plating with high temperature resistance, thin coating, high corrosion resistance, good workability and good weldability.
  • the role of some elements in the alloy is multiplicity: In addition to the multiple effects of rare earth elements, most of the elements of the invention reduce the surface tension of the Al-Zn melt and improve the iron-based The effects of wetting properties, Be, Li, Co, Cr, Nb, etc. have the effect of improving the strength and high temperature properties of the alloy. Fe and Si have the effect of improving the hardness and wear resistance of the alloy. Bi, In and T1 are also refined. The role of grains.
  • test results show that the most suitable hot dip coating process temperature of the present invention is 680 ⁇ 720 °C, and the bath liquidity is good in this temperature range, and the plating rate and the slag formation rate are low.
  • the hot-dip-plating front-end process that is, the hot-rolled steel strip
  • the hot-dip-plating front-end process has an oxidation control temperature higher than 850 ° C higher than the hot-dip galvanizing process, and the coiling temperature is controlled at 600.
  • the coiling temperature is controlled at 600.
  • it can suppress the thickness and passivation of the oxide film on the surface of the steel strip, and at the same time reduce the acid washing amount and the environmental pollution of the pickling waste liquid.
  • the sampling analysis in the smelting if process shows that the melt contains different phase phases that are difficult to determine: the fine structure morphology, which is mostly a high melting point metal compound having a complex: heterocyclic structure. According to the analysis, this is one of the main signs of fine grain and improved hardness. .
  • the sullen structure of the sample fracture shows that: the material crystallized ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Nie nuclear exists.
  • This apparatus has verified the fine crystallization of the heterogeneous nucleus in the present invention.
  • the results of the melt treatment show that the efficient melt net means: the strength and elongation of the test bar can be simultaneously improved.
  • the heat resistance test proves that after 24 hours of high temperature gas environment of 700° or more, the ffi immersion plating of the new material of the invention has the appearance of ⁇ 3 3 ⁇ 4 obviously change s
  • Salt zero test sample, coating thickness: 20:, during the experiment: between 28011, the surface of the enamel is not obviously corroded (black spots or black spots will appear on the galvanized sheet for 48h); the heat rate is 70%; Warm oxidation fe does not change color in 315 high temperature environment for more than 100h; heat resistance: Q, S degree 93 ⁇ 2 Environment ⁇ 168h: 3 ⁇ 43 ⁇ 4 candle, no obvious discoloration; plating bending: d a: distance from the edge of the sample There is no plating on the outside of 5mm; the surface of the coating is smooth and flat, and the crystal flower is even.
  • the obtained phase is up to hundreds of species, of which only the binary phase has more than 200. Bifurcation can eliminate the binary phase, which is only a part of more binary compounds that may actually exist.
  • the ⁇ is a molecular phase: the same compound often has many different crystal structures, although it is difficult to distinguish it with gold analysis. However, due to the different stability, it should also be regarded as different qualities.
  • Co, Cr, N are typical multi-part d-region transition elements in the periodic table, and they are characterized by the formation of various metalized silvers with Ak Zn solvent and Fe matrix elements, so that they are all sacrificial protective elements of the matrix.
  • the surface of the solid solution interacts with the oxidant, it can generate a plurality of different oxidation state compounds and water ions under different pH values, and both have a higher oxygen volume ratio (greater than L, The ability to passivate protection is far as simple as oxidized membranes;: Some of these compounds and hydrated ions are just 'sexual' ; in 3 ⁇ 4, they are: long-lasting: the existence of ⁇ , some are weakly fluid, Some have better fluidity, and when the surface of the enamel is smothered, the singularity and hydration ions will immediately make up and cover the wound, and the plating and the base will not be exposed for a long time. Suffering from excessive corrosion, this solves the j3 ⁇ 4 problem of poor protection of pure metalized
  • ⁇ cannot be explained by the multiple superposition method of the two-phase alloy phase diagram, nor can it be used in the existing 3 ⁇ 4J multi-alloy alloy.
  • the order of change of new elements into the alloy solution system is ionization, that is, first becoming a single ion, at which time there will be a change in the size of the elementary particles as an alloy solution: the element having a higher electronegativity than the solvent element has a reduced atomic radius. At the same time, it attracts the surrounding free electrons with a certain negative charge and becomes a quasi-negative ion, while the element with weaker electronegativity than the solvent element produces the opposite change, becoming a quasi-positive ion. When finally reaching equilibrium, there should be two types.
  • Solute ions negative ions smaller than the atomic radius of the elemental state and positive ions larger than the atomic radius of the elemental state;
  • the second step is to dissolve into the crystal lattice of the solvent matrix;
  • the third step is diffusion, occupying as wide a system space as possible, dissolving And the diffusion is always carried out at the same time;
  • the fourth step is to change within the lattice of the matrix to form a solid solution of substitution or gap;
  • fifth, the concentration of the solid solution is saturated;
  • sixth the solid solution lattice formed changes and becomes the matrix a compound that is not coherent;
  • seventh, the intermetallic compound formed is dissolved in the matrix, Forming a region-specific coherent structure involving matrix coherence in units of molecules and molecular groups;
  • eighth, the solid solution of the element and the solid solution of the metal compound are saturated together;
  • the element forms a complex structure with other solute elements or compounds (number of atoms Compounds with multiple, diverse spatial groups; tenth
  • the formation of the element solid solution and the formation of the compound are also carried out simultaneously, whether or not the compound is formed with the matrix, and the amount and stability of the formation, the electronegativity difference between the matrix and the new element, the atomic spacing, the number of valence electrons It depends on parameters such as the price of the electronic track structure.
  • the behavior and function of transition elements in alloys is extremely complex, unlike metallic and non-metallic elements with distinct chemical properties. Due to the misalignment of the outer and outer outer electron orbital levels, the ability of the transition element to lose electrons, the ability to provide covalent electrons, and the ability to adjust the number are very powerful, plus a smaller atomic radius. It is easy to chemically react with active metals, active non-metals, and even inactive elements at room temperature, producing compounds and complexes that are relatively stable, but vary with temperature and pH, and accompany various color changes.
  • the bond shape and bond energy structure are complex, easy to form, and easily disintegrated by external influences. Even atoms of the same type (same period or adjacent or similar elements of the same subgroup) can be easily changed.
  • the complex structures formed, even ions of different valences of the same element can easily change the complex structures that have been formed, such as Co, Cr, Nb and Fe.
  • Co, Cr, Nb and Fe are the same type of transition elements. They act as solute elements.
  • solvent elements Al, Zn react with the matrix Fe, they also participate in the reaction, acting as a buffer matrix and solvent. The effect of the intensity of the reaction effectively prevents the occurrence of the Zn-Al-Fe "cleavage effect" and forms a passivation sub-layer on the near-substrate surface to enhance the protection of the substrate.
  • the rare earth elements Pr and Nd When the rare earth elements Pr and Nd are alloyed with the transitional elements, they have three characteristics: 1 the element is insoluble or the solubility is very low, all are below 0.1% (mass percent), and 2 easily reacts with the transition elements to form various contents. Intermetallic compounds, whose characteristics correspond to the ratio of solute components and the temperature of the alloy system. For example, Pr and A1 can form 6 different compositions and different compositions from Pr 3 Al to Pr 3 Al u between 630 and 1240 ° C.
  • Nd and A1 can also be similar to Pr-A1 between 635 ⁇ 1235 °C, 3 intermetallic compounds in matrix (Al), (Zn), (Fe) Both have a certain solubility, and the solubility product of the components of the intermetallic compound in the alloy is relatively stable. These characteristics increase the complexity of the alloy structure and also enhance the resistance changeability of the alloy, so that the physicochemical properties of the alloy system remain relatively stable.
  • Si is an element with a small atomic radius in the alloy system. It is easily soluble in (Al), (Zn) and can form various compounds with Fe. Due to these characteristics, it is an element with strong diffusion ability in the system. Inhibiting Al-Fe reaction by "interstitial" and resisting Zn intervening in Al-Fe compounds, Si is used as the main inhibitor of Al-Fe violent reaction in Galvalume and Galfan coating alloys, and in the alloy system of the present invention, Si Can be combined with a variety of solvent passivation elements enriched near the reaction surface With the use of 3 ⁇ 4 ⁇ swordsman.
  • thermoelectric furnace is the best, not used: which kind of melting equipment, should make the body of the body uniform, ⁇ as much as possible to seal the flow lightly reduce the metal burning Damage and health hazard;
  • the alloy material of the present invention can be quenched and smelted with an aluminum alloy, a zinc alloy, a copper alloy industrial furnace for 3 ⁇ 4 ⁇ 4 with 3 ⁇ 4 production, and often with a furnace at &6, with good enthalpy.
  • a variety of alloy companies can be charged: tongs, ⁇ 3 ⁇ 4, ⁇ low.
  • Tests proved:, selected ingredients such as aluminum gold ⁇ ;, zinc alloy, copper alloy satisfying mixed waste A in the formulation of other elements to vehicle, only the river to use aluminum, zinc food gold, copper alloy or the like mixed waste swash Add a small amount of bismuth as a raw material oblique ingredient. . detailed description
  • the alloy liquid is poured out of the furnace and filtered at the same time; the filtrate is gently poured into the casting ingot mold, and the melt is in the form of sequential crystallization.
  • the ingot mold is condensed from the bottom to the top to form a silver-white ingot type.

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Abstract

A low-zinc hot dip aluminum alloy coating material containing Be and a combination of agents and a preparation method thereof. The alloy coating material comprises, by weight percent of the elements, Zn of less than 30, Be of 10-4 to 0.05, alloy strengthening agent of 10-4 to 6.0, solvent passivating agent of 10-4 to 1.0, precipitation hardening agent of 10-4 to 0.5, crystal grain size reducing agent of 10-4 to 1.0, rare earth additive of 10-4 to 1.0, and substrate-interface reaction buffer of 0.001 to 2.0, with the remainder being Al and inevitable trace impurities.

Description

Be与多组合变质的低锌热浸镀铝合金镀层材料及其制备方法  Low-zinc hot-dip aluminum alloy coating material with Be and multi-combination metamorphism and preparation method thereof
技术领域  Technical field
本发明涉及一种铝合金镀层材料及其制备方法，特别涉及一种 Be与多组合变质的低锌热 浸镀铝合金镀层材料及其制备方法。 背景技术  The invention relates to an aluminum alloy coating material and a preparation method thereof, in particular to a low-zinc hot-dip aluminum alloy coating material with Be and multi-combination metamorphism and a preparation method thereof. Background technique
目前， 全世界已经建成投产的镀锌机组有 400多条线， 遍布 60多个国家， 镀锌钢制品产 量接近 2亿吨， 其中大部分是镀锌钢板。 由于全世界每年热浸镀用锌消耗量达到锌金属总产 量的 70%以上， 造成锌资源短缺的形势越来越严峻。 2008年以来世界锌产量平均每年保持在 1200万吨左右， 热镀锌产业的消费量就达到 850万吨以上， 而镀锌钢铁制品的覆盖面还不到 全世界钢产量的 1/5。 随着经济社会的发展， 高端的镀层钢铁制品所占比例越来越大， 但即使 把全世界的锌都用来做镀层材料， 也远远不能满足钢铁热浸镀需要。 这种情况， 在中国显得 尤其突出。 也就是说， 开发可替代锌的钢铁热浸镀用新材料， 是世界和中国技术经济发展的 必然趋势和要求； 而最有希望作为代锌的材料， 是铝锌合金和铝合金。  At present, there are more than 400 lines of galvanizing units that have been built and put into operation in more than 60 countries. The output of galvanized steel products is close to 200 million tons, most of which are galvanized steel sheets. Since the annual zinc consumption for hot dip plating reaches more than 70% of the total zinc metal production in the world, the shortage of zinc resources is becoming more and more serious. Since 2008, the world's zinc production has remained at an average of 12 million tons per year, and the hot-dip galvanizing industry has consumed more than 8.5 million tons, while galvanized steel products have less than one-fifth of the world's steel production. With the development of economy and society, the proportion of high-end coated steel products is increasing, but even if the world's zinc is used as a coating material, it is far from meeting the needs of steel hot dip coating. This situation is particularly prominent in China. That is to say, the development of new materials for hot dip coating of steel, which is an alternative to zinc, is an inevitable trend and requirement for the development of the world's and China's technological economy; and the most promising material for zinc is aluminum-zinc alloy and aluminum alloy.
有关锌铝合金或铝锌合金为主体组分的新型高性能镀层材料专利， 主要集中在欧美和日 本等发达国家， 国内也有一些本行业的专利。 Galvalume 是美国专利， 成份为 55 Al-43.4 Zn-1.6 Si, 是目前得到实际产业化应用的高铝型锌合金镀层材料， 虽然它对钢 基的保护能力是纯锌镀层的 2〜7倍，又能大量节约锌资源，但由于浸镀温度高 (590〜600°C)、 镀液对钢基的浸润能力差、 易产生钢板针状漏镀、 镀层对划伤、 切口的阴极保护能力不足、 成型加工、 焊接以及涂装性能等方面与纯锌镀层存在差距等原因， 抵消了很多优势， 使之不 能很好地为市场接受。 Galfan是比利时研制的 5%A1-Zn体系的镀层材料， 含有 Fe、 Si、 Pb、 Cd、 Sn和稀土等微量元素， 它的熔点低于纯锌， 解决了 Galvalume镀液对钢基的浸润能力差 的问题， 依靠钢板的快速冷却产生细小的共晶组织， 因此镀层具有高于锌的耐蚀性和良好的 涂装性能、 加工成型性能和和可焊性， 但因 Pb、 Cd、 Sn等低熔点金属容易引起镀层的晶间 腐蚀 (造成颜色改变)、 对钢板冷却速度有着严格的限制、 镀层容易产生大面积的坑凹、 耐高 温氧化能力差等问题， 影响了 Galfan的市场应用， 加上它仍含有 90%以上的 Zn， 在节约锌 资源方面的意义不大， 不能解决热浸镀行业长期发展的问题。 近年来， 出现了 Zn-Al-Mg 及 其相关组成的多元体系合金镀层材料， 美国有 Zn-Al-Mg-Ti-B-Si、 Zn-Al-Mg-Si专利产品； 日 本有铝含量 5 %〜12%的热镀锌合金板、 Zn-Al-Mg-Si、 Zn-Al-Mg-Si-Mn-Cr和 Zn-Al-Mg专利 等等， 但这些新产品和专利的铝含量大多在 50%以下； 而且基本上没有可以实现低成本产业 化应用的新型镀层材料专利技术。 The patents on new high-performance coating materials with zinc-aluminum alloy or aluminum-zinc alloy as main components are mainly concentrated in developed countries such as Europe, America and Japan. There are also some patents in this industry in China. Galvalume is a US patent with a composition of 55 Al-43.4 Zn-1.6 Si. It is a high-aluminum zinc alloy coating material that is currently in practical industrial application. Although it has a protective ability of steel base of 2 to 7 times that of pure zinc coating, It can also save a lot of zinc resources, but due to the high immersion temperature (590~600 °C), the poor wetting ability of the plating solution to the steel base, the easy occurrence of needle-shaped leakage plating of the steel plate, the scratching of the plating layer, and the cathodic protection ability of the slit. The gap between the molding process, the welding and the coating performance and the pure zinc coating have offset many advantages, making it not acceptable for the market. Galfan is a coating material of 5% A1-Zn system developed in Belgium. It contains trace elements such as Fe, Si, Pb, Cd, Sn and rare earth. Its melting point is lower than that of pure zinc, which solves the infiltration ability of Galvalume plating solution on steel base. The problem of poorness relies on the rapid cooling of the steel sheet to produce a fine eutectic structure, so the coating has higher corrosion resistance than zinc and good coating properties, processing properties and weldability, but due to Pb, Cd, Sn, etc. Low-melting-point metals are prone to cause intergranular corrosion of the coating (causing color change), strict restrictions on the cooling rate of the steel sheet, easy to produce large-area pits and coatings, and poor high-temperature oxidation resistance, which affects the market application of Galfan. It still contains more than 90% Zn, which has little significance in saving zinc resources and cannot solve the long-term development of the hot dip coating industry. In recent years, Zn-Al-Mg and its related composition of multi-component alloy coating materials have appeared. The United States has patented products of Zn-Al-Mg-Ti-B-Si and Zn-Al-Mg-Si; Japan has aluminum content of 5 %~12% of hot-dip galvanized alloy sheets, Zn-Al-Mg-Si, Zn-Al-Mg-Si-Mn-Cr and Zn-Al-Mg patents, etc., but most of these new products and patented aluminum content Below 50%; and basically no low-cost industry can be realized Patented technology for new coating materials.
因此， 围绕添加多种合金元素来改善镀层的综合性能， 采用更多的 A1组分来代替 Zn， 重点是实现铝的包覆保护能力与锌的牺牲阴极保护能力的最佳结合， 并保证以尽可能简单的 热浸镀工艺技术装备， 实现镀层钢板的抗剥落、 高强度、 易加工、 易焊接、 耐更高温度、 耐 5 酸碱盐类腐蚀等优良性能于一体， 研发和推广绿色钢铁热浸镀工艺流程， 在镀层材料的生产 和应用两个环节同时实现减污、 降本、 增效、 提质， 是一个急需解决的技术难题。 发明内容 Therefore, around the addition of a variety of alloying elements to improve the overall performance of the coating, the use of more A1 components instead of Zn, the focus is to achieve the best combination of aluminum coating protection and zinc sacrificial cathodic protection, and to ensure As simple as possible hot dip plating technology and equipment, to achieve the anti-flaking, high strength, easy processing, easy welding, high temperature resistance, resistance to 5 acid and alkali corrosion of the coated steel plate, research and development and promotion of green steel The hot dip plating process is a technical problem that needs to be solved in the two stages of production and application of coating materials to reduce pollution, reduce cost, increase efficiency and improve quality. Summary of the invention
本发明要解决的技术问题是： 提供一种系列化的， 能对铝锌混合体系形成多因素立体变 0 质改性作用， 从而实现铝锌合金的组织结构形态优化， 使镀层材料与钢铁基体产生良好的润 湿性、 固态附着性和基体强化性， 实现镀层板易加工、 易焊接、 耐高温、 耐酸碱盐类腐蚀， 可提高循环效率和再利用价值， 在镀层材料的生产和应用两个环节同时实现减污、 降本、 增 效、 提质， 为实现宏观经济层面的技术升级、 产品换代和产业聚集提供基础材料支撑的 Be 与多组合变质的低锌热浸镀铝合金镀层材料及其制备方法。 The present invention is to solve the technical problem are: to provide a series of multi-factor can be formed on the aluminum-zinc mixed system perspective Modification quality becomes 0, and thus form the structure to achieve optimization aluminum-zinc alloy, so that the steel substrate and the coating material Produces good wettability, solid adhesion and matrix strengthening, which makes the plate easy to process, easy to weld, high temperature resistant, acid and alkali resistant, and can improve cycle efficiency and reuse value, in the production and application of coating materials. At the same time, the two links realize the reduction of pollution, cost reduction, efficiency improvement, quality improvement, and the provision of basic material support for the upgrading of the technology at the macroeconomic level, product replacement and industrial agglomeration, and the combination of low-zinc hot-dip aluminized alloy coating Materials and methods for their preparation.
5 本发明的技术方案： 5 Technical solution of the invention:
一种 Be与多组合变质的低锌热浸镀铝合金镀层材料，按元素重量百分比计，该合金成分 为 Zn 30， Be:10— 4〜0.05， 合金强化剂 10— 4〜6.0， 溶剂钝化剂 10— 4〜1.0， 沉淀硬化剂 10— 4〜 0.5， 晶粒细化剂 10-4〜1.0， 稀土添加剂 10-4〜1.0， 基体界面反应缓冲剂 0.001〜2.0， 其余为 A1和不可避免的微量杂质。 A low-zinc hot-dip aluminum alloy coating material with Be and multi-combination metamorphism, the alloy composition is Zn 30, Be: 10 - 4 ~ 0.05, alloy strengthening agent 10 - 4 ~ 6.0, solvent blunt ~1.0 agent 10-4, 10-4 precipitation hardening agent, and 0.5 grain refiner 10-4 ~1.0, ~1.0 10-4 rare earth additives, reaction buffer 0.001~2.0 matrix interface, and the remainder being non-A1 Trace impurities that are avoided.
：° 合金强化剂包括 Cu或 Li， 以及含有 Cu或 Li的合金。 : ° Alloy strengtheners include Cu or Li, and alloys containing Cu or Li.
溶剂钝化剂包括 Co、 Cr或 Nb， 以及含有 Co、 Cr或 Nb的合金； 每种元素每种可以单独 使用， 也可以混合使用。  The solvent deactivator includes Co, Cr or Nb, and an alloy containing Co, Cr or Nb; each of these elements may be used singly or in combination.
沉淀硬化剂包括 Bi、 In或 Tl， 每种元素可以单独使用， 也可以混合使用。  The precipitation hardener includes Bi, In or Tl, and each element may be used singly or in combination.
晶粒细化剂包括 C或 Zr和它们相互形成的化合物， 以及 C或 Zr与高熔点过渡元素形成 ：5 的高硬度高稳定性化合物。 The grain refiner includes C or Zr and a compound formed therebetween, and C or Zr forms a high hardness and high stability compound with a high melting point transition element: 5 .
稀土添加剂包括作为稀土元素的 Pr或 Nd， 及一种以上稀土元素形成的混合稀土。  The rare earth additive includes Pr or Nd as a rare earth element, and a mixed rare earth formed of one or more rare earth elements.
基体界面反应缓冲剂包括 Fe以及含有 Fe的合金。  The matrix interfacial reaction buffer includes Fe and an alloy containing Fe.
一种如上所述 Be 与多组合变质的低锌热浸镀铝合金镀层材料的制备方法， 包括如下步 骤：  A method for preparing a low-zinc hot-dip aluminum alloy coating material with Be and multi-combination as described above includes the following steps:
10 (1)在上述元素比例范围内， 选定一组元素比例， 再根据需要配制的合金总量， 推算出所 需的每种单质金属的质量， 或者合金的质量， 或者混合金属添加剂的质量， 编制合金生产配 料表， 并按配料表选足备料； 10 (1) Within the above element ratio range, select a set of element ratios, and then calculate the mass of each elemental metal required, or the quality of the alloy, or the quality of the mixed metal additive, according to the total amount of the alloy to be formulated. , preparation of alloy production Material list, and according to the ingredient list, select the preparation materials;
(2)先往熔炼炉中加入适量的铝锭或熔融铝液， 加热使之完全融化并在 700〜800°C下保 温；  (2) Firstly add an appropriate amount of aluminum ingot or molten aluminum liquid to the melting furnace, heat it to completely melt and keep it at 700~800 °C;
(3)再按配方比例加入基体界面反应缓冲剂、 Be、溶剂钝化剂、 晶粒细化剂、合金强化剂、 稀土添加剂和沉淀硬化剂， 最后再加入锌， 搅拌均匀； 现场取样分析， 根据分析结果和配方 范围， 调整添加量； 然后继续熔炼和搅拌， 再次取样分析， 直至各元素比例完全符合配方要 求。  (3) Add the matrix interface reaction buffer, Be, solvent passivator, grain refiner, alloy enhancer, rare earth additive and precipitation hardener according to the proportion of the formula, and finally add zinc and stir evenly; on-site sampling analysis, According to the analysis results and the scope of the formula, adjust the amount of addition; then continue to smelt and stir, sample again and analyze until the proportion of each element fully meets the formulation requirements.
(4)然后对上述合金熔体进行炉内精炼； 往合金熔体中加入精炼剂， 并搅拌均匀， 熔体精 炼在封闭环境中完成。  (4) The above alloy melt is then subjected to in-furnace refining; a refining agent is added to the alloy melt, and the mixture is uniformly stirred, and the melt refining is completed in a closed environment.
(5)精炼后除渣、 除气、 静置、 调温至 660〜720°C， 合金液倾倒出炉， 同时过滤； 滤液 平缓倾入铸造锭模中， 通过顺序式结晶方式， 使熔体在锭模中自下而上凝结， 形成银白色锭 型。  (5) After refining, slag removal, degassing, standing, and tempering to 660~720 °C, the alloy liquid is poured out of the furnace and filtered at the same time; the filtrate is gently poured into the casting ingot mold, and the melt is in the form of sequential crystallization. The ingot mold is condensed from the bottom to the top to form a silver-white ingot type.
在步骤 (2)中， 熔炼炉是指可以熔炼各种铝合金、 锌合金或铜合金的工业熔炉， 包括工频 感应加热炉、 中频感应加热炉、 电阻炉、 燃气加热炉或燃油加热炉。  In the step (2), the smelting furnace refers to an industrial furnace which can smelt various aluminum alloys, zinc alloys or copper alloys, including a power frequency induction heating furnace, an intermediate frequency induction heating furnace, an electric resistance furnace, a gas heating furnace or a fuel heating furnace.
本发明的优点：  Advantages of the invention:
与现有技术相比， 本发明的主要优点是： 运用 Be与基体界面反应缓冲剂、 溶剂钝化剂、 晶粒细化剂、 高温强化剂、 稀土添加剂和沉淀硬化剂等多元素组合对低锌铝合金体系的立体 变质作用， 把镀层材料的综合性能提升到一个新水平， 实现铝锌合金的组织结构形态优化， 使镀层材料与钢铁基体产生良好的润湿性、 固态附着性和基体强化性， 实现镀层板易加工、 易焊接、 耐高温、 耐酸碱盐类腐蚀， 提高了循环效率和再利用价值， 在镀层材料的生产和应 用两个环节同时实现减污、 降本、 增效、 提质， 为实现宏观经济层面的技术升级、 产品换代 和产业聚集提供基础材料支撑， 体现了在变温条件下以 "溶液模型"研究铝合金在多元溶质 的复杂组分结构中行为特征的最新技术方法， 其制备方法采用的均是冶金行业的常用设备， 不需特制， 可提高循环效率和再利用价值。  Compared with the prior art, the main advantages of the present invention are: the use of Be and matrix interfacial reaction buffer, solvent passivator, grain refiner, high temperature enhancer, rare earth additive and precipitation hardener, etc. The three-dimensional metamorphism of the zinc-aluminum alloy system takes the comprehensive performance of the coating material to a new level, optimizes the microstructure of the aluminum-zinc alloy, and produces good wettability, solid adhesion and matrix strengthening of the coating material and the steel matrix. It is easy to process, easy to weld, high temperature resistant, acid and alkali resistant corrosion, improve cycle efficiency and reuse value, and achieve both pollution reduction, cost reduction and efficiency in the production and application of coating materials. Providing basic material support for technological upgrading, product replacement and industrial agglomeration at the macroeconomic level, reflecting the latest development of the behavioral characteristics of aluminum alloys in the complex composition of multi-solutes with a "solution model" under variable temperature conditions. The technical method, the preparation method thereof are all commonly used equipments in the metallurgical industry, and no special system is required. High cycle efficiency and re-use value.
—— Be与六类变质剂的具体作用如下：  —— The specific effects of Be and six types of modifiers are as follows:
•Be是原子半径最小的碱金属元素之一， 同时也是比重最小的金属元素之一。 Be 的比 重比 A1小三分之一， 强度跟钢差不多， 传热性能是钢的三倍， 是金属中良好的导体； Be的 氧化物比重小， 硬度大， 熔点高达摄氏二千四百五十度， 因此具有高温防腐能力， 铍的氧化 物、 卤化物都具有明显的共价性， Be还能形成聚合物以及具有明显热稳定性的共价化合物， 即使在红热时， Be在空气中也很稳定，其覆盖在基体表面，形成致密稳定的表面氧化保护层， 保护基体不被氧化且导热性能良好， 强化了基体的耐热效果； 利用 Be元素对溶剂元素 A1和 Al+Zn 的原子极化变径作用， 在微观状态下有效调整原子尺寸和近程有序的结构， 使熔体在 宏观上结构均匀， 降低表面张力， 并改善熔体与镀件基体的亲和性， 达到改善镀层与基体附 着性。 • Be is one of the alkali metal elements with the smallest atomic radius and is one of the smallest specific metal elements. The specific gravity of Be is one-third smaller than that of A1. Its strength is similar to that of steel. Its heat transfer performance is three times that of steel. It is a good conductor in metal. Be has a small specific gravity and a high hardness. Its melting point is up to 2,400 degrees Celsius. Ten degrees, so it has high temperature anti-corrosion ability, bismuth oxides and halides have obvious covalency, Be can also form polymers and covalent compounds with obvious thermal stability, even in red heat, Be is in the air It is also very stable, covering the surface of the substrate to form a dense and stable surface oxide protective layer. The protective substrate is not oxidized and has good thermal conductivity, which enhances the heat resistance of the substrate. The element A is used for the solvent element A1 and The atomic polarization reduction effect of Al+Zn effectively adjusts the atomic size and the close-range ordered structure in the microscopic state, makes the melt uniform in macroscopic structure, reduces the surface tension, and improves the affinity of the melt and the plated substrate. And to achieve improved adhesion between the coating and the substrate.
本镀层合金中加入 Be可明显降低铸锭裂纹倾向，提高材料强度，并且铸造和浸镀后的 (钢 铁)制品外表更加美观、 亮丽； 但当总加入量超过 Be在溶剂中的饱和溶解度时， 合金的裂纹 倾向增大， 力学性能下降。  The addition of Be to the coated alloy can significantly reduce the crack tendency of the ingot, improve the strength of the material, and the appearance of the (steel) product after casting and immersion is more beautiful and bright; but when the total addition exceeds the saturated solubility of Be in the solvent, The crack tendency of the alloy increases and the mechanical properties decrease.
本发明镀液在与钢铁基板接触时， 对钢基体具有良好的润湿性， 溶质 Be和溶剂 A1能够 与钢基表面的氧化铁快速反应， 生成比重小、 性质稳定而结构致密的氧化物， 浮于镀层表面， 起到对内层的保护作用， 同时可减少钢板助镀剂的用量或不使用助镀剂， 从而节约成本及降 低对环境的危害。  The plating solution of the invention has good wettability to the steel substrate when it is in contact with the steel substrate, and the sol Sol and the solvent A1 can react rapidly with the iron oxide on the steel-based surface to form an oxide having a small specific gravity, a stable property and a dense structure. Floating on the surface of the coating, it protects the inner layer, and at the same time reduces the amount of steel plating agent or does not use the plating agent, thereby saving costs and reducing environmental hazards.
由于 Be有效地分解了 Fe-Al、 Fe-Zn形成的金属化合物， 本发明镀液在浸镀时能减少底 渣和浮渣产生。  Since Be effectively decomposes the metal compound formed by Fe-Al or Fe-Zn, the plating solution of the present invention can reduce the generation of bottom slag and scum during immersion plating.
Be的标准电极电位 (-1.70V)与 A1几乎完全一样， 外层电子结构 2s2即 2个价电子， 因此 A1中加入 Be会增加基体自由电子浓度， 同时增加了基体电子云结构的不平衡度， 增强基体 的液态流动性； Be的原子半径较 A1小， 密度 1.85， 在 A1熔体中容易扩散、 上升和富集在表 面和晶界， 由于在 A1中的平衡溶解度较小 (几乎为零)， 所以加入微量的 Be即能形成 Al-Be 过饱和固溶体， 当富集在表面和亚晶界的 Be达到一定浓度时， 形成比固溶体熔点高、弥散度 高、整体分布均匀度好的细小晶核， 引导周围固溶体以包晶或共晶形态结晶； 由于 Be与固溶 体平衡相接近单质形态， 结晶长大的机理是微观状态下的光滑界面而在宏观状态下的粗糙界 面， 因此形成的晶粒长大速度较缓慢， 其结果是使合金晶粒细小， 液态流动性好， 凝固后强 度高； 同时， 富集在合金表面的 Be原子在吸收氧原子氧化后形成的 BeO容积比处于合适的 范围 (1.59)， 膜层结构致密、 性质稳定、 耐腐蚀性好， 能弥补 AlCu合金抗盐蚀性低的缺陷， 从而可以使合金中加入更多的 Cu， 以充分发挥 Cu对合金的强化作用。 Be对铝基固溶体晶粒 的细化作用， 同样适用于对金属化合物的细化； 在过饱和固溶体中， Be是能以近单质形态对 杂质 Si进行细化的元素。 Be's standard electrode potential (-1.70V) is almost exactly the same as A1, and the outer electronic structure 2s 2 is 2 valence electrons. Therefore, the addition of Be in A1 increases the free electron concentration of the matrix and increases the imbalance of the matrix electron cloud structure. Degree, enhances the liquid mobility of the matrix; Be has a smaller atomic radius than A1 and a density of 1.85. It easily diffuses, rises and enriches in the surface and grain boundaries in the A1 melt, due to the low equilibrium solubility in A1 (almost Zero), so the addition of a trace amount of Be can form an Al-Be supersaturated solid solution. When the concentration of Be enriched at the surface and the subgrain boundary reaches a certain concentration, it forms a higher melting point than the solid solution, has a higher dispersion, and has a uniform overall distribution. The fine crystal nucleus guides the surrounding solid solution to crystallize in the peritectic or eutectic form; since the equilibrium of Be and the solid solution is close to the elemental form, the mechanism of crystal growth is a smooth interface in the microscopic state and a rough interface in the macroscopic state, thus forming The grain growth rate is slow, and the result is that the alloy grains are fine, the liquid fluidity is good, and the strength after solidification is high; meanwhile, the Be atoms enriched in the alloy surface are absorbed. The volume ratio of BeO formed by oxidation of oxygen atoms is in the appropriate range (1.59). The structure of the film is dense, stable, and corrosion-resistant. It can compensate for the low salt corrosion resistance of AlCu alloy, so that more alloys can be added. Cu, in order to give full play to the strengthening effect of Cu on the alloy. The refinement effect of Be on the aluminum-based solid solution grains is also suitable for the refinement of the metal compound; in the supersaturated solid solution, Be is an element capable of refining the impurity Si in a near-simplex form.
•利用合金强化元素 Cu或 Li的作用， 生成强化相， 最大程度地提高镀层的强度， 实际 强度可以超过钢基体， 达到更高的强度性能。  • Using the effect of the alloy strengthening element Cu or Li, a strengthening phase is formed to maximize the strength of the coating, and the actual strength can exceed the steel matrix to achieve higher strength properties.
•溶剂钝化元素 Co、 Cr或 Nb， 可在溶剂表面富集一层耐酸、 碱、 盐和高温环境大气腐 蚀、 兼有微观下网格固定保护和流动性自动覆盖损伤面而起保护功能的钝化膜层， 使镀层覆 盖下的基体具有更好的物理化学性能； 为防止单一钝化元素氧化后出现不需要的颜色， 可使 用两种和两种以上混合元素钝化剂。 •利用晶粒细化元素 C或 Zr和细化剂， 在高温时通过溶解、扩散和弥散， 成为纳米级乃 至更为细小的异类原子团簇和稳定的分子团簇， 在熔体冷却结晶时提供大量分布均匀的细小 "晶种"、 间隙相和间隙化合物， 高效细化基体的结晶粒度， 提高了镀层材料的强度、 韧性、 硬度、 耐磨性和高温性能， 进而提高镀件的加工性和可焊性。 • Solvent passivation element Co, Cr or Nb, which can enrich the surface of the solvent with acid, alkali, salt and high temperature atmospheric corrosion, combined with microscopic grid fixed protection and fluidity to automatically cover the damage surface and protect the surface. The passivation film layer has better physical and chemical properties for the substrate covered by the plating layer; in order to prevent unwanted color from appearing after oxidation of a single passivation element, two or more mixed element passivating agents can be used. • Using grain refinement elements C or Zr and refiner to dissolve, diffuse and disperse at high temperatures to become nanoscale or even finer heterogeneous clusters and stable molecular clusters, provided during melt cooling crystallization A large number of evenly distributed fine "seeds", gap phase and interstitial compounds, high-efficiency refinement of the crystal grain size of the substrate, improve the strength, toughness, hardness, wear resistance and high temperature properties of the coating material, thereby improving the processability of the plated parts and Solderability.
·稀土元素添加剂 Pr或 Nd具有原子极化、 合金强化、 晶粒细化、 表面美化、 除氢和增 强抗腐蚀性的多种辅助作用， 可增强 Be、 合金强化剂、 溶剂钝化剂、 晶粒细化剂的作用， 并 弥补其不足。  ·Rare earth element additive Pr or Nd has various auxiliary functions of atomic polarization, alloy strengthening, grain refinement, surface beautification, hydrogen removal and enhanced corrosion resistance, and can enhance Be, alloy strengthening agent, solvent passivating agent, crystal The role of the grain refiner and make up for its shortcomings.
•沉淀硬化剂 Bi、 In或 T1也是时效强化剂， 它们是熔点不高、 化学活性也不高的金属 元素， 加入少量的这类元素， 在合金体系中保持近单质状态， 在体系虽然凝固但温度仍较高 的状态下， 它们依然保持液态， 从而使体系在宏观上具备了半固态特征， 为时效强化过程中 加速合金中强化元素转化为实际的强化态 (沉淀硬化或析出硬化)提供了条件； 同时会赋予合 金优良的加工性能和耐磨性能； 通过控制沉淀硬化元素的种类和添加量， 还可以得到镀件表 面花纹。  • Precipitation hardener Bi, In or T1 is also an ageing enhancer. They are metal elements with low melting point and low chemical activity. A small amount of these elements are added to maintain a near-monolithic state in the alloy system. At a still high temperature, they remain liquid, which gives the system a semi-solid characteristic at the macroscopic level, which provides an opportunity to accelerate the transformation of the strengthening elements in the alloy into the actual strengthening state (precipitation hardening or precipitation hardening) during the age strengthening process. Conditions; At the same time, it will give the alloy excellent processing properties and wear resistance; by controlling the type and amount of precipitation hardening elements, the surface pattern of the plated parts can also be obtained.
•利用界面反应缓冲元素 Fe和 Si， 以及含有 Fe或 Si的合金， 可以有效抑制在浸镀时 A1与 Fe基体之间剧烈的化合反应， 减少或杜绝生成 "透镜状 Fe2Al5"， 强化 "薄层状 Fe2Al5" 的生成机制， 建立 Fe— A1— Zn均匀梯度的反应机制， 从而提高镀层质量、减薄镀层厚度， 节 省材料。 • Using the interfacial reaction buffer elements Fe and Si, and alloys containing Fe or Si, can effectively suppress the strong chemical reaction between A1 and Fe matrix during immersion plating, reduce or eliminate the formation of "lenticular Fe 2 Al 5 ", strengthen The formation mechanism of "thin layered Fe 2 Al 5 " establishes a reaction mechanism of Fe - A1 - Zn uniform gradient, thereby improving the quality of the coating, reducing the thickness of the coating and saving materials.
因此， 本发明利用 Be和六类变质剂与低锌铝合金进行的超多元合金化和微合金化反应， 获得了具有对钢基润湿性好、 结合力强、 强度高、 延伸性好、 耐高温、 镀层薄、 耐蚀性强、 加工性和可焊性好等集多种优点于一身的优质钢铁热浸镀用铝合金镀层材料。  Therefore, the present invention utilizes the super-multiple alloying and microalloying reaction of Be and a six-type modifier with a low-zinc aluminum alloy, and has good wettability to the steel base, strong bonding force, high strength, and good elongation. Aluminium alloy coating material for high-quality steel hot-dip plating with high temperature resistance, thin coating, high corrosion resistance, good workability and good weldability.
在 Be与六类变质剂中，某些元素在合金中的作用角色具有多重性： 除稀土元素具有多重 作用外， 本发明大部分元素都有降低 Al-Zn熔体表面张力、提高对铁基润湿性能的作用， Be、 Li、 Co、 Cr、 Nb等都有提高合金强度和高温性能的作用， Fe和 Si具有提高合金硬度和耐磨 性的作用， Bi、 In、 T1还具有细化晶粒的作用。  In Be and six types of modifiers, the role of some elements in the alloy is multiplicity: In addition to the multiple effects of rare earth elements, most of the elements of the invention reduce the surface tension of the Al-Zn melt and improve the iron-based The effects of wetting properties, Be, Li, Co, Cr, Nb, etc. have the effect of improving the strength and high temperature properties of the alloy. Fe and Si have the effect of improving the hardness and wear resistance of the alloy. Bi, In and T1 are also refined. The role of grains.
试验结果表明， 本发明最适宜采用的热浸镀工艺温度为 680〜720°C， 该温度范围内镀液 流动性好， 漏镀率、 成渣率低。  The test results show that the most suitable hot dip coating process temperature of the present invention is 680~720 °C, and the bath liquidity is good in this temperature range, and the plating rate and the slag formation rate are low.
在使用本发明热浸镀工艺的温度范围内， 会使热浸镀前端工序即热轧带钢的防氧化控温 比热镀锌时高达到 850°C以上， 而卷取温度则控制在 600°C左右， 从而可以抑制钢带表面氧化 膜长厚和钝化， 同时可降低酸洗量和酸洗废液对环境的污染。  In the temperature range of using the hot dip coating process of the present invention, the hot-dip-plating front-end process, that is, the hot-rolled steel strip, has an oxidation control temperature higher than 850 ° C higher than the hot-dip galvanizing process, and the coiling temperature is controlled at 600. Around °C, it can suppress the thickness and passivation of the oxide film on the surface of the steel strip, and at the same time reduce the acid washing amount and the environmental pollution of the pickling waste liquid.
在使用本发明热浸镀工艺的温度范围内， 在钢板浸镀后无须进行强制降温处理， 从而为 镀层材料自发的合金化钝化提供了合适的温度和尽可能长的时间条件。 浸镀后的钢:板 过追 ifc处理后:， 表面镀层具有窩强: it.韧髙硬度特征， 钪愈漲度可迗 00M a 上， 艇后伸长率可达: 3%以上.， 硬度 HBS 150以上 ¾： 经 析〈 Al-C 相具有最高的 强度增长效应。 In the temperature range in which the hot dip coating process of the present invention is used, it is not necessary to perform a forced cooling treatment after the immersion plating of the steel sheet, thereby providing a suitable temperature and a long time condition for the spontaneous alloying passivation of the plating material. Steel after immersion plating: after the board has been chased by ifc treatment: the surface coating has a nest strength: it. The toughness hardness characteristic, the recovery can be 迗 00M a, the elongation after the boat can reach: 3% or more. Hardness HBS 150 or more 3⁄4 : Analyzed <Al-C phase has the highest strength growth effect.
熔铸试验和电镜分析发现， C与 Zr、 Co, Cf Fe、 Nb形成:的化合物， 再与 Al组成中间 合金后， 具有良好的细化变质效果； M-稀土化合物具弃相 细化和变滅特怔。  The melting casting test and electron microscopy analysis found that C and Zr, Co, Cf Fe, Nb form a compound, and then form an intermediate alloy with Al, which has good refinement and deterioration effect; M-rare earth compound has abandoning phase refinement and extinction Special.
对凝固的 400〜 1000 斤重型锭进行超声波探伤检查， 等厚度各部位 強均勾 （¾:部¾ 裂纹。 Ultrasonic inspection of the solidified ingots of 4 00~1000 kg solidified, and the strength of each part of the thickness is thick (3⁄4: 3⁄4 crack).
对本发明镀层钢板进行 X射线荧光分析表明， 内部结抅均匀无缺陷。  X-ray fluorescence analysis of the coated steel sheet of the present invention showed that the internal crucible was uniform and defect free.
熔炼 if程中取样分析表明，. 熔体中包含难以确定的不同物相:的细小结构形态， 太多数是 高熔点的具有复:杂晶袼结构的金属化合物。 分析认为， 这是晶粒细：化、 硬度提高的主要标志 之一。 .  The sampling analysis in the smelting if process shows that the melt contains different phase phases that are difficult to determine: the fine structure morphology, which is mostly a high melting point metal compound having a complex: heterocyclic structure. According to the analysis, this is one of the main signs of fine grain and improved hardness. .
试样断口哀舞结构分 表明： 材料结晶弒種 产 ¾了太量昀 晶 应、 包聶反应、 共 ffi 反应和胀溶效应， 在韧窝和晶粒内外有大量的细 Φ球港异质聶核存在。 此輛聶体绪构验证了 异质晶核的在本发明中的细晶化作用。  The sullen structure of the sample fracture shows that: the material crystallized 弑 弑 了 了 了 了 太 太 太 太 太 太 应 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 包 包 包 包 包 包 包 包 包Nie nuclear exists. This apparatus has verified the fine crystallization of the heterogeneous nucleus in the present invention.
熔体处理的结果显示， 高效的熔体净 it手段:可以使试棒的強度和:延伸率同时提升.， 提升 的幅度： 强度提升可达到 lOOMpa'以上.， 延伸率提升可达 1Όΰ/。¾上.。 The results of the melt treatment show that the efficient melt net means: the strength and elongation of the test bar can be simultaneously improved. The extent of the increase: the strength can be increased above 100Mpa', and the elongation can be increased by up to 1Ό ΰ / . 3⁄4上.
耐热试验证明， 经过 24小时 700° 以上高温 气环境 ffi浸镀本发明镀层新材料的钢铢 制品外观巅色 ¾明显变化 s  The heat resistance test proves that after 24 hours of high temperature gas environment of 700° or more, the ffi immersion plating of the new material of the invention has the appearance of 巅 3 3⁄4 obviously change s
盐零试验样品， 镀层厚度 :20 :， 实验时:间 28011， 彖面无明显受腐蚀现象 (f 通镀锌板 48h即会出现黑点或黑斑)； 热 射率 70%； 抗高:温氧化 fe 在 315 高温环境 100h以上不发生变色； 耐渔热： Q , S度 93±2 环境卞经 168h:¾¾烛，无明显变色； 镀 层弯曲： d=a:时， 距离试样边部 5mm 外不出现镀层幾落; 镀层表面光滑平整， 晶花均匀。  Salt zero test sample, coating thickness: 20:, during the experiment: between 28011, the surface of the enamel is not obviously corroded (black spots or black spots will appear on the galvanized sheet for 48h); the heat rate is 70%; Warm oxidation fe does not change color in 315 high temperature environment for more than 100h; heat resistance: Q, S degree 93±2 Environment 卞 168h: 3⁄43⁄4 candle, no obvious discoloration; plating bending: d=a: distance from the edge of the sample There is no plating on the outside of 5mm; the surface of the coating is smooth and flat, and the crystal flower is even.
几种合金镀层钢板救 ft蚀性对 铽验 熟浸鴒钢弒为, 钢,；热浸载液为本发期新型热 浸镀铝合金 浸镀温度为 80^720 ¾, 浸獰时间,为 10s. 样 蜍稱4 冼一弱酸锓蚀 烘千 浸幾 空冷； 然 分耕在 :¾ 5%Ν¾ .盐水:中浸抱 26 :， &j Several kinds of alloy-coated steel plates are used to save ft-etching 铽 熟 熟 熟 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 新型 新型 新型 新型 新型 新型10s. Sample nickname 4 冼 a weak acid etched and immersed in a few air chills; then ploughed in: 3⁄4 5% Ν 3⁄4. Saline: immersed in 26 : , &j
35 °C ,相对.湿度 93〜94%， 含 SQ210ppm的酸雾中进行腐蚀试验， ¾量的竭 对比如下表 1 : 表 1 耐蚀性对'比结果 35 ° C, relative humidity 93 ~ 9 4 %, corrosion test with SQ 2 10ppm acid mist, 3⁄4 amount of exhaustion comparison as shown in Table 1: Table 1 Corrosion resistance versus 'ratio
Figure imgf000007_0001
Figure imgf000007_0001
替换页 （细则第 26条) 在.窒温下对几种材料进行了屈菔强度和抗拉强度的测定，. 结果如表 .2: Replacement page (Article 26) The flexural strength and tensile strength of several materials were measured at .窒. The results are shown in Table 2 .
表.2 材料强度对.比结果
Figure imgf000008_0001
研究镀层材料和钢基体结合层的物相组^和形貌特征， 得到的物相达数百种之多， 其中 仅二元物系的物相种类就有 200.多种， 而通过金賴分菥能够滅剁的二元物相, 仅仅是实际上 可能存在的更多二元化合物的一部分，囟为分子式相:同的化合物往往具有多种不同晶体结构， 虽然难以用金柺分析辨别' 但由于 有不一样的稳定 ¾， 也应该视为不同的翁质。 Table 2. Material strength versus ratio results
Figure imgf000008_0001
Studying the phase composition and morphology of the coating material and the steel matrix bonding layer, the obtained phase is up to hundreds of species, of which only the binary phase has more than 200. Bifurcation can eliminate the binary phase, which is only a part of more binary compounds that may actually exist. The 囟 is a molecular phase: the same compound often has many different crystal structures, although it is difficult to distinguish it with gold analysis. However, due to the different stability, it should also be regarded as different qualities.
当合金中某种元素食量相对较多时倒如:， * F i%wt), 会与其它獰质元素反 而生成更 加复杂的三元和三元以上的金属化合物， 例如 Al13Cr4Si4， Al7C Fe， Al13Si4((S|¾)4， 等等.。： 这些多元缉合而 的金属«合物也是不稳定的.， 在温 和酸碱度 化够， 佘自：动:分解， 释放出有錄原子， 以保持整个合金体系.的稳定， 而起到对镇层的钝化作用， 提高对基体的 保护能力。 When the amount of a certain element in the alloy is relatively large, it is as follows: , * F i% wt), which will form more complicated ternary and ternary metal compounds, such as Al 13 Cr 4 Si 4 , with other enamel elements. Al 7 C Fe, Al 13 Si 4 ((S| 3⁄4 ) 4 , etc..: These multi-component metal complexes are also unstable. In mild acidity and alkalinity, 佘自:动:分解, release of recorded atoms to maintain the stability of the entire alloy system, and play a role in the passivation of the town layer, improve the protection of the substrate.
Co、 Cr、 N 是周期表中典型的多份位 d区过渡元素， 从它钔能与 Ak Zn溶剂和 Fe基 体元素生成多种金属化合银的特点， 以 道它们都是基体的牺牲保护元素； 此外， 它们在 固溶体表面与氧化剂发生作用时， 在不同的 pH值条种下能够生成多种不同氧化态的化合物 和水食离子， 由亍都具有较高的氧 容积比 (大于 L , 其钝化保护的能力远 if于单纯的 氧化^膜;： 这些化合物和水合离子有些是刚'性;的， 在 ¾ 炸为： 久性:的捋格保 募存在， 有些是弱流动性的， 而有些具有较好的流动性， 当镞悴表面被划翁后， 具智滅动性:的化合 和水合离子会立即弥补、 覆盖创口， 俊镀层和基.体不至于因长时闳裸露而遭受过量腐蚀， 这 就解决了 纯的 铮合金包覆保护能力差的 j¾题。 Co, Cr, N are typical multi-part d-region transition elements in the periodic table, and they are characterized by the formation of various metalized silvers with Ak Zn solvent and Fe matrix elements, so that they are all sacrificial protective elements of the matrix. In addition, when the surface of the solid solution interacts with the oxidant, it can generate a plurality of different oxidation state compounds and water ions under different pH values, and both have a higher oxygen volume ratio (greater than L, The ability to passivate protection is far as simple as oxidized membranes;: Some of these compounds and hydrated ions are just 'sexual'; in 3⁄4, they are: long-lasting: the existence of 捋格保保, some are weakly fluid, Some have better fluidity, and when the surface of the enamel is smothered, the singularity and hydration ions will immediately make up and cover the wound, and the plating and the base will not be exposed for a long time. Suffering from excessive corrosion, this solves the j3⁄4 problem of poor protection of pure niobium alloy coating.
关于超多元合金化的变质机理， 目'前没有一种公 ¾的¾论解稞； .旣不能用二 ¾合金相图 的多重迭加法来说明， 也不能用已有 ¾J多元合金中各微量 ¾素对志元素作用.的一般么知常识 和经验进 解 #。 ■ ' 但有两种椟式可以对超多元合金的元素作用 理进狞定 分 :， 一禅是对原子结构层 面的解析， 一种是溶质在溶剂中溶解和析出溶液捧型理论方法的运用:， 二者的结合， 可以对 新墨镀层材料的优异性能 出具有很好符 性的 *¾鎖。 Regarding the metamorphic mechanism of super-multi-alloying, there is no such thing as a public solution. The 迭 cannot be explained by the multiple superposition method of the two-phase alloy phase diagram, nor can it be used in the existing 3⁄4J multi-alloy alloy. The general knowledge and experience of the 3⁄4 primes on the role of the elements. ■ 'But there are two types of 椟 type that can be used to determine the elemental action of super-alloys : one is the analysis of the atomic structure, and the other is the application of the solution method of the dissolution and precipitation of the solution of the solute in the solvent. :, the combination of the two, can have a very good *3⁄4 lock for the excellent performance of the new ink coating material.
在超多元合金体系:处 均匀稳定的液态状态时，：整 体絜 上是一种份电 由 包围的多核 "海洋"， 假定每一种微量元素都在主: 素的 "海^ 里均勾分布:，邵处于一种 理想钛态 这时候描¾整个体系特征的因素， 主.実应该包 乎 电子浓度、 ;平均电负性或 In the super-multi-alloy system: in a uniform and stable liquid state, the whole crucible is a multi-core "ocean" surrounded by electricity. It is assumed that each trace element is in the "sea" of the main: : Shao is a factor that titanium over the entire state system features described ¾ this time, the package should be almost Mika main electron concentration; or average electronegativity.
替换页 （细则第 26条) 平均电极电位、 密度、 温度、 体积、 压力， 以及体系自由能、 焓、 熵等热力学指标。 但从微 观角度看， 不同的原子对其周围自由电子的吸引作用是千差万别的， 因此各类元素的原子与 其单质状态下的原子结构和性质就产生了差异， 这些差异表现在合金的宏观性质上， 即造成 显著的性能变化。 Replacement page (Article 26) Average electrode potential, density, temperature, volume, pressure, and thermodynamics of system free energy, enthalpy, entropy, etc. However, from a microscopic point of view, the attraction of different atoms to their surrounding free electrons is very different. Therefore, the atoms of various elements differ from the atomic structure and properties of the elemental state. These differences are manifested in the macroscopic properties of the alloy. , which causes significant performance changes.
新元素进入合金溶液体系的变化顺序： 第一步是电离， 即首先变成单个的离子， 这时候 会有作为合金溶液基本粒子的尺寸变化： 电负性比溶剂元素强的元素本身原子半径縮小， 同 时吸引周围自由电子而带有一定的负电荷， 成为准负离子， 而电负性比溶剂元素弱的元素则 产生相反的变化， 成为准正离子， 最后达到平衡时， 应有两种类型的溶质离子： 比单质状态 原子半径小的负离子和比单质状态原子半径大的正离子； 第二步是溶解， 进入溶剂基体的晶 格； 第三步是扩散， 占据尽可能广阔的体系空间， 溶解和扩散总是同时进行； 第四步， 在基 体的晶格内变化， 形成置换的或间隙的固溶体； 第五， 固溶体浓度达到饱和； 第六， 形成的 固溶体晶格发生变化， 变成与基体不共格的化合物； 第七， 形成的金属间化合物又溶解于基 体之中， 形成以分子和分子团为单位参与基体共格的区域特异共格结构； 第八， 元素的固溶 体和金属化合物的固溶体一起达到饱和； 第九， 元素与其它溶质元素或化合物形成复杂结构 (原子数目多、 空间群多样化)的化合物大分子； 第十， 各种原子与分子的聚集和分解， 随温 度、压力和界面而发生的应变。 实际上， 元素固溶体的形成与化合物的形成也是同时进行的， 是否与基体生成化合物， 以及生成的量及其稳定性， 则视基体与新元素的电负性差值、 原子 间距、 价电子数及价电子轨道结构等参数而定。  The order of change of new elements into the alloy solution system: The first step is ionization, that is, first becoming a single ion, at which time there will be a change in the size of the elementary particles as an alloy solution: the element having a higher electronegativity than the solvent element has a reduced atomic radius. At the same time, it attracts the surrounding free electrons with a certain negative charge and becomes a quasi-negative ion, while the element with weaker electronegativity than the solvent element produces the opposite change, becoming a quasi-positive ion. When finally reaching equilibrium, there should be two types. Solute ions: negative ions smaller than the atomic radius of the elemental state and positive ions larger than the atomic radius of the elemental state; the second step is to dissolve into the crystal lattice of the solvent matrix; the third step is diffusion, occupying as wide a system space as possible, dissolving And the diffusion is always carried out at the same time; the fourth step is to change within the lattice of the matrix to form a solid solution of substitution or gap; fifth, the concentration of the solid solution is saturated; sixth, the solid solution lattice formed changes and becomes the matrix a compound that is not coherent; seventh, the intermetallic compound formed is dissolved in the matrix, Forming a region-specific coherent structure involving matrix coherence in units of molecules and molecular groups; eighth, the solid solution of the element and the solid solution of the metal compound are saturated together; ninth, the element forms a complex structure with other solute elements or compounds (number of atoms Compounds with multiple, diverse spatial groups; tenth, aggregation and decomposition of various atoms and molecules, strains that occur with temperature, pressure, and interface. In fact, the formation of the element solid solution and the formation of the compound are also carried out simultaneously, whether or not the compound is formed with the matrix, and the amount and stability of the formation, the electronegativity difference between the matrix and the new element, the atomic spacing, the number of valence electrons It depends on parameters such as the price of the electronic track structure.
过渡元素在合金中的表现及作用是极其复杂的， 它们不同于化学特性明显而确定的金属 和非金属元素。 由于最外层和次外层电子轨道能级的错位， 过渡元素得失电子的能力、 提供 共价电子的能力及其数目调整的能力都是很强大的， 加上较小的原子半径， 使之容易与活泼 的金属、 活泼的非金属乃至常温下不活泼的元素都能发生化学反应， 生成相对稳定、 但随温 度和酸碱度变化比较明显、 伴随各种颜色变化的化合物和配合物， 其分子内部的键形和键能 结构复杂， 既容易形成， 也容易受外界影响而解体， 即使是同类元素 (同一周期或同一副族的 相邻或相近的元素)的原子， 也能很容易地改变已经形成的复杂结构， 甚至同一种元素的不同 价位的离子， 也能很容易地改变已经形成的复杂结构， 如 Co、 Cr、 Nb与 Fe等都是如此。  The behavior and function of transition elements in alloys is extremely complex, unlike metallic and non-metallic elements with distinct chemical properties. Due to the misalignment of the outer and outer outer electron orbital levels, the ability of the transition element to lose electrons, the ability to provide covalent electrons, and the ability to adjust the number are very powerful, plus a smaller atomic radius. It is easy to chemically react with active metals, active non-metals, and even inactive elements at room temperature, producing compounds and complexes that are relatively stable, but vary with temperature and pH, and accompany various color changes. The bond shape and bond energy structure are complex, easy to form, and easily disintegrated by external influences. Even atoms of the same type (same period or adjacent or similar elements of the same subgroup) can be easily changed. The complex structures formed, even ions of different valences of the same element, can easily change the complex structures that have been formed, such as Co, Cr, Nb and Fe.
电极电位或电负性相差越大， 两种元素间越易形成稳定的 (熔点高)的化合物， 根据溶度 积原理， 其它含有一种或多种同样组分的不稳定的化合物将会溶解， 以释放出可以保持平衡 的溶质原子浓度， 而稳定的化合物则继续产生， 直至整个体系达到新的平衡， 这种重组运动 才会停止。 最终的总体趋势， 是每加入一种新元素或化合物， 体系的各组成部分都产生相关 的反应， 要么减少 (浓度降低)， 要么增多 (浓度升高)， 要么保持不变， 而给新元素或化合物留 出存在的空间， 达到平衡后每一种物质的化学势保持相等。 The greater the difference in electrode potential or electronegativity, the easier it is to form a stable (high melting point) compound. According to the solubility product principle, other unstable compounds containing one or more of the same components will dissolve. To release a concentration of solute atoms that can maintain equilibrium, and stable compounds continue to be produced until the entire system reaches a new equilibrium, and this reorganization movement will stop. The final general trend is that each time a new element or compound is added, the various components of the system react, either decreasing (reduced concentration), increasing (increased concentration), or remaining unchanged, giving new elements. Or compound stay Out of the existing space, the chemical potential of each substance remains equal after reaching equilibrium.
当体系中一种元素受到氧化而失去电子后， 体系中该元素浓度降低， 根据化学势平衡和 溶度积平衡原理， 体系中含有该元素的物质将自动分解以释放出适量的该元素， 弥补体系中 该元素浓度， 同时引起一系列连锁反应， 最终仍然要达到新的化学势平衡和溶度积平衡。 元 素种类越多， 连锁反应越复杂， 但最终达到新的化学势平衡和溶度积平衡的结果是不变的。 这就是体系抵抗腐蚀的 "多元方程式"控制机制； 这种机制， 同样适用于热浸镀时铁-铝-锌 合金化反应， 从而实现在厚度方向内部各层面间均匀梯度的 "多元方程式"控制机制。  When an element in the system is oxidized and loses electrons, the concentration of the element in the system decreases. According to the principle of chemical potential balance and solubility balance, the substance containing the element in the system will be automatically decomposed to release an appropriate amount of the element to make up The concentration of this element in the system causes a series of chain reactions, and finally a new chemical potential balance and solubility balance are still to be achieved. The more species, the more complex the chain reaction, but the result of the new chemical potential equilibrium and solubility product balance is unchanged. This is the "multiple equation" control mechanism of the system against corrosion; this mechanism is also applicable to the iron-aluminum-zinc alloying reaction during hot dip coating, so as to achieve the "multiple equation" control of the uniform gradient between the layers in the thickness direction. mechanism.
另一方面， Co、 Cr、 Nb与 Fe都是同类型的过渡元素， 它们作为溶质元素， 当溶剂元素 Al、 Zn与基体 Fe发生反应时， 它们也同时参与反应， 起到缓冲基体与溶剂主反应激烈程度 的作用， 有效阻止 Zn-Al-Fe "迸裂效应" 的发生， 并在近基体面也形成钝化亚层， 加强对基 体的保护能力。  On the other hand, Co, Cr, Nb and Fe are the same type of transition elements. They act as solute elements. When the solvent elements Al, Zn react with the matrix Fe, they also participate in the reaction, acting as a buffer matrix and solvent. The effect of the intensity of the reaction effectively prevents the occurrence of the Zn-Al-Fe "cleavage effect" and forms a passivation sub-layer on the near-substrate surface to enhance the protection of the substrate.
当合金中存在少量电位适中而熔点很低的元素时， 如 Bi、 In、 Tl， 这些元素在合金中的 性质基本上不受影响， 而以近单质形态存在， 在合金结晶时可以提供"间隙流体"或 "液膜" 的作用， 对在合金液中数量较多而固态溶解度差别大的元素和化合物， 这种 "间隙流体"或 "液膜"在退火再结晶和时效处理过程中的作用是极为重要的， 它能为固溶体溶质的溶入和 析出提供快速畅通渠道， 从而显著縮短淬火和时效时间， 提高热处理功效， 同时又不会造成 高温下的晶间腐蚀 (因为含量极少)； 同时如果这些低熔点元素具有一定的扩散能力， 则可以 "填坑式"进入合金中结晶领先相长大时形成的坑洼中 (高自由能区)， 从而抑制结晶长大， 产生变质作用。  When there are a small amount of elements with moderate potential and low melting point in the alloy, such as Bi, In, Tl, the properties of these elements in the alloy are basically unaffected, but exist in the near-simular form, which can provide "gap fluid" when the alloy crystallizes. The role of "or" liquid film", the role of such "gap fluid" or "liquid film" in annealing recrystallization and aging treatment for elements and compounds with a large amount in the alloy liquid and large difference in solid solubility. Extremely important, it provides a fast and clear channel for the dissolution and precipitation of solid solution solutes, significantly reducing quenching and aging time, improving heat treatment efficiency without causing intergranular corrosion at high temperatures (because of very little); If these low-melting-point elements have a certain diffusion ability, they can be "filled-in" into the potholes formed in the alloy when the crystallographic leading phase grows up (high free energy region), thereby inhibiting crystal growth and causing metamorphism.
稀土元素 Pr、 Nd在与过渡族元素发生合金化时， 有三个特点： ①单质不溶解或溶解度很 低， 都在 0.1% (质量百分比)以下，②容易与过渡元素反应形成多种不同含量的金属间化合物， 其特点与溶质组分比例和合金体系的温度相对应， 比如： Pr与 A1在 630〜1240°C之间能形成 从 Pr3Al到 Pr3Alu等 6种不同组成、不同结构、不同存在温度范围的化合物; Nd与 A1在 635〜 1235°C之间也能与 Pr— A1类似的化合物， ③形成的金属间化合物在基体 (Al)、 (Zn), (Fe)中都 有一定的溶解度， 金属间化合物的组分在合金中的溶度积相对稳定。 这些特点， 增加了合金 结构的复杂程度， 同时也增强了合金的抗性变能力， 使合金体系的物理化学性质保持相对稳 定。 When the rare earth elements Pr and Nd are alloyed with the transitional elements, they have three characteristics: 1 the element is insoluble or the solubility is very low, all are below 0.1% (mass percent), and 2 easily reacts with the transition elements to form various contents. Intermetallic compounds, whose characteristics correspond to the ratio of solute components and the temperature of the alloy system. For example, Pr and A1 can form 6 different compositions and different compositions from Pr 3 Al to Pr 3 Al u between 630 and 1240 ° C. Structure, different temperature range of compounds; Nd and A1 can also be similar to Pr-A1 between 635~ 1235 °C, 3 intermetallic compounds in matrix (Al), (Zn), (Fe) Both have a certain solubility, and the solubility product of the components of the intermetallic compound in the alloy is relatively stable. These characteristics increase the complexity of the alloy structure and also enhance the resistance changeability of the alloy, so that the physicochemical properties of the alloy system remain relatively stable.
Si是本合金体系中原子半径很小的元素， 它易溶解于 (Al)、 （Zn)而能与 Fe生成多种化合 物， 由于这些特点， 它是体系中扩散能力很强的元素， 也能以 "填隙"方式抑制 Al-Fe反应 并抵制 Zn介入 Al-Fe化合物中， 在 Galvalume和 Galfan镀层合金中用 Si作为 Al-Fe激烈反 应的主要抑制剂， 而在本发明合金体系中， Si能与富集在反应面附近的多种溶剂钝化元素共 同承担 ¾ί劍剂的祚用。 Si is an element with a small atomic radius in the alloy system. It is easily soluble in (Al), (Zn) and can form various compounds with Fe. Due to these characteristics, it is an element with strong diffusion ability in the system. Inhibiting Al-Fe reaction by "interstitial" and resisting Zn intervening in Al-Fe compounds, Si is used as the main inhibitor of Al-Fe violent reaction in Galvalume and Galfan coating alloys, and in the alloy system of the present invention, Si Can be combined with a variety of solvent passivation elements enriched near the reaction surface With the use of 3⁄4ί swordsman.
实验表明，. 在保证较好的餘气、 餘杂质效 时 可以采用：的瑢炼设备暴多种多样的， 包 括加热炉、 中频感应加热炉、 电阻炉:、 燃气加热炉、 燃油加热炉， 其中:以保护性焰炼 .0U工频 感 ^加:热电炉效 最好， 而不訾 用:哪一种熔炼设备， 都应该使獰体翁捽均匀， 弁尽可能密 封流輕 减 金属烧损和对健康危害； 本发明合金材枓可 儻滅与 §炼 #铝合金、 锌合 金、 铜合金的工业熔炉进行 ¾¾配¾产， 在 &6时 要经常 炉， 具有良好的桀眷 . 对于生 多种合金的企业可 ^充: 利箝设务、 提脔 ¾ 、 獰低 本。  Experiments show that: In order to ensure better residual gas and residual impurities, there are various types of smelting equipment, including heating furnace, medium frequency induction heating furnace, electric resistance furnace: gas heating furnace and fuel heating furnace. Among them: protective flame refining. 0U power frequency feeling ^ plus: thermoelectric furnace is the best, not used: which kind of melting equipment, should make the body of the body uniform, 弁 as much as possible to seal the flow lightly reduce the metal burning Damage and health hazard; The alloy material of the present invention can be quenched and smelted with an aluminum alloy, a zinc alloy, a copper alloy industrial furnace for 3⁄4⁄4 with 3⁄4 production, and often with a furnace at &6, with good enthalpy. A variety of alloy companies can be charged: tongs, 脔 3⁄4, 狞 low.
试验证明:， 如 选择配料的铝 ^金 ;、 锌合金， 铜合金等废杂 A中 有满足配方要辆的其 它元素, 河以只使用铝合金、 锌食金、 铜合金等的废杂斜加微量变虡剂作 原材斜配料。 . 具体实施方式 Tests proved:, selected ingredients such as aluminum gold ^;, zinc alloy, copper alloy satisfying mixed waste A in the formulation of other elements to vehicle, only the river to use aluminum, zinc food gold, copper alloy or the like mixed waste swash Add a small amount of bismuth as a raw material oblique ingredient. . detailed description
*发明 ：实雜例 ¾配方组合 :: *Invention: Really mixed 3⁄4 formula combination ::
配方 合表: ：.  Formulated table: :.
Figure imgf000011_0001
替换页 （细则第 26条) 实施例 1 : Be-Cu-Cr-Bi-C-Pr-Si组合
Figure imgf000011_0001
Replacement page (Article 26) Example 1: Be-Cu-Cr-Bi-C-Pr-Si combination
(1)按配方组合表选定一组元素， 按照重量百分比例为： 极化变质剂 Be:0.05， 合金强化剂 Cu:6.0， 溶剂钝化剂 Cr:0.8， 沉淀硬化剂 Bi:0.1， 晶粒细化剂 C:0.001， 稀土添加剂 Pr:0.01， 基体界面反应缓冲元素 Si:2.0， 第二溶剂元素 Zn:30， 余量为 A1; 配制的合金总量为 1000kg, 则推算出所需的每种物质的重量为： Be:5kg， Cu:60kg, Cr:8kg， Bi:lkg， C:0.01kg, Pr:0.1kg, Si:20kg, Zn:300kg， Al:605.89kg。  (1) Select a group of elements according to the formula combination table, according to the weight percentage: Polarization modifier Be: 0.05, alloy strengthener Cu: 6.0, solvent passivator Cr: 0.8, precipitation hardener Bi: 0.1, crystal Grain refiner C: 0.001, rare earth additive Pr: 0.01, matrix interfacial reaction buffer element Si: 2.0, second solvent element Zn: 30, balance A1; the total amount of alloy prepared is 1000 kg, then calculate the required The weight of each substance was: Be: 5 kg, Cu: 60 kg, Cr: 8 kg, Bi: lkg, C: 0.01 kg, Pr: 0.1 kg, Si: 20 kg, Zn: 300 kg, Al: 605.89 kg.
(2)先往熔炼炉中加入铝锭或熔融铝液， 加热使之完全融化并在 700〜800°C下保温； (2) first adding aluminum ingot or molten aluminum liquid to the melting furnace, heating it to completely melt and maintaining at 700~800 ° C;
(3)再按配方比例加入基体界面反应缓冲剂、 Be、溶剂钝化剂、 晶粒细化剂、合金强化剂、 稀土添加剂和沉淀硬化剂， 最后再加入锌， 搅拌均匀； 现场取样分析， 根据分析结果和配方 范围， 调整添加量； 然后继续熔炼和搅拌， 再次取样分析， 直至各元素比例完全符合配方要 求。 (3) Add the matrix interface reaction buffer, Be, solvent passivator, grain refiner, alloy enhancer, rare earth additive and precipitation hardener according to the proportion of the formula, and finally add zinc and stir evenly; on-site sampling analysis, According to the analysis results and the scope of the formula, adjust the amount of addition; then continue to smelt and stir, sample again and analyze until the proportion of each element fully meets the formulation requirements.
(4)然后对上述合金熔体进行炉内精炼； 往合金熔体中加入精炼剂， 并搅拌均匀， 熔体精 炼在封闭环境中完成。  (4) The above alloy melt is then subjected to in-furnace refining; a refining agent is added to the alloy melt, and the mixture is uniformly stirred, and the melt refining is completed in a closed environment.
(5)精炼后除渣、 除气、 静置、 调温至 660〜720°C， 合金液倾倒出炉， 同时过滤； 滤液 平缓倾入铸造锭模中， 通过顺序式结晶方式， 使熔体在锭模中自下而上凝结， 形成银白色锭 型。  (5) After refining, slag removal, degassing, standing, and tempering to 660~720 °C, the alloy liquid is poured out of the furnace and filtered at the same time; the filtrate is gently poured into the casting ingot mold, and the melt is in the form of sequential crystallization. The ingot mold is condensed from the bottom to the top to form a silver-white ingot type.
(6)热浸镀工艺条件确定及合金镀层板性能和质量的检测分析。  (6) Determination of hot dip plating process conditions and detection and analysis of alloy plating plate performance and quality.
实施例 2: Be-Li-Nb-Tl-Zr-Nd-Fe-Si组合  Example 2: Be-Li-Nb-Tl-Zr-Nd-Fe-Si combination
(1)按配方组合表选定一组元素， 按照重量百分比例为： Be: 10—4， 合金强化剂 Li: 10— 4， 溶剂钝化剂 Nb:10-4， 沉淀硬化剂 T1: ΙθΛ 晶粒细化剂 ΖπΙθΛ 稀土添加剂: Nd: ΙθΛ 基体界 面反应缓冲元素 Fe: 0.001、 Si:0.5，第二溶剂元素 Zn:l，余量为 A1;配制的合金总量为 1000kg, 则推算出所需的每种物质的重量为： 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。 (1) a formulated combination table selected group of elements, by percentage of weight Example: Be: 10- 4, an alloy enhancer Li: 10- 4, the solvent deactivators Nb: 10- 4, precipitation hardening agent T1: ΙθΛ Grain refiner ΖπΙθΛ Rare earth additive: Nd: ΙθΛ Matrix interface reaction buffer element Fe: 0.001, Si: 0.5, second solvent element Zn: l, balance A1; total amount of alloy prepared is 1000kg, then calculate The weight of each substance required is: Be: 0.001 kg, Li: 0.001 kg, Nb: 0.001 kg, Tl: 0.001 kg, Zr : 0.001 kg, Nd: 0.001 kg, Fe: 0.01 kg, Si: 5 kg, Zn : 10kg, Al: 984.984kg.
其余步骤同实施例 1。  The remaining steps are the same as in the first embodiment.
实施例 3:  Example 3:
(1)按配方组合表选定一组元素， 按照重量百分比例为： Be: 0.01， 合金强化剂 Cu:4.0、 Li:2.0， 溶剂钝化剂 Co:0.02、 Cr:0.8、 Nb:0.18， 沉淀硬化剂 Bi:0.1、 In:0.17、 Tl:0.1， 晶粒细化 剂 C:0.001、 Zr:0.28， 稀土添加剂 ΡπΟ.01、 Nd:0.2， 基体界面反应缓冲元素 Fe:1.0、 Si:1.0， 第 二溶剂元素 Ζι ΙΟ, 余量为 Al; 配制的合金总量为 1000kg, 则推算出所需的每种物质的重量 为 Be: 0.1kg, Cu: 40kg, Li: 20 kg, Co: 0.2kg, Cr: 8kg, Nb: 1.8kg, Bi: lkg, In: 1.7kg, Tl: lkg, C: 0.01kg, Zr ： 2.8kg, Pr: 0.1kg, Nd: 2kg, Fe: 10kg, Si: 10kg, Zn: 100kg, Al: 801.29kg (1) Select a group of elements according to the formula combination table, according to the weight percentage: Be: 0.01, alloy strengthening agent Cu : 4.0, Li: 2.0, solvent deactivator Co: 0.02, Cr: 0.8, Nb: 0.18, Precipitation hardener Bi: 0.1, In: 0.17, Tl: 0.1, grain refiner C: 0.001, Zr: 0.28, rare earth additive ΡπΟ.01, Nd: 0.2, matrix interfacial reaction buffer element Fe: 1.0, Si: 1.0 , the second solvent element Ζι ΙΟ, the balance is Al; the total amount of the alloy is 1000kg, then the weight of each substance required is calculated as Be: 0.1kg, Cu : 40kg, Li: 20 kg, Co: 0.2 Kg, Cr: 8kg, Nb: 1.8kg, Bi: lkg, In: 1.7kg, Tl: lkg, C: 0.01kg, Zr: 2.8kg, Pr: 0.1kg, Nd: 2kg, Fe: 10kg, Si: 10kg , Zn: 100kg, Al: 801.29kg
其余步骤同实施例 1。  The remaining steps are the same as in the first embodiment.
实施例 4: Be-Cu-Co-Nb-In-C-Pr-Si组合  Example 4: Be-Cu-Co-Nb-In-C-Pr-Si combination
(1)按配方组合表选定一组元素，按照重量百分比例为： Be: 0.0017，合金强化剂 Cu: 0.026， 溶剂钝化剂 Co:0.0032、 Nb:0.13, 沉淀硬化剂 In: 0.056， 晶粒细化剂 C:0.00019， 稀土添加剂 Pr: 0.0025, 基体界面反应缓冲元素 Si:0.68， 第二溶剂元素 Zn:19.5， 余量为 Al; 配制的合金 总量为 1000kg, 则推算出所需的每种物质的重量为： Be: 0.017kg, 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 0 其余步骤同实施例 1。 (1) Select a group of elements according to the formula combination table, according to the weight percentage: Be: 0.0017, alloy strengthener Cu: 0.026, solvent passivator Co: 0.0032, Nb: 0.13, precipitation hardener In: 0.056, crystal Grain refiner C: 0.00019, rare earth additive Pr: 0.0025, matrix interfacial reaction buffer element Si: 0.68, second solvent element Zn: 19.5, balance is Al; the total amount of alloy prepared is 1000kg, then calculate the required The weight of each substance is: Be: 0.017kg, 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 0 The remaining steps are the same as in Example 1.
实施例 5: Be-Li-Co-In-Bi-Zr-Nd-Fe组合  Example 5: Be-Li-Co-In-Bi-Zr-Nd-Fe combination
(1)按配方组合表选定一组元素，按照重量百分比例为： Be: 0.0072,合金强化剂 Li: 0.18， 溶剂钝化剂 Co:0.003， 沉淀硬化剂 In: 0.00053、 Bi:0.052, 晶粒细化剂 Zr:0.086， 稀土添加剂 Nd:0.063， 基体界面反应缓冲元素 Fe:1.0， 余量为 A1; 配制的合金总量为 1000kg, 则推算出 所需的每种物质的重量为： 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。 (1) Select a group of elements according to the formula combination table, as follows: Be: 0.0072, alloy strengthener Li: 0.18, solvent passivator Co: 0.003, precipitation hardener In: 0.00053, Bi: 0.052, crystal Grain refiner Zr: 0.086, rare earth additive Nd: 0.063, matrix interfacial reaction buffer element Fe: 1.0, balance A1; The total amount of alloy prepared is 1000kg, then the weight of each substance required is calculated as: 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.
其余步骤同实施例 1。  The remaining steps are the same as in the first embodiment.

Claims

权利要求书 Claim
1. 一种 Be与多组合变质的低锌热浸镀铝合金镀层材料， 其特征在于： 按元素重量百分 比计， 该合金成分为 Zn 30， Be:10-4〜0.05， 合金强化剂 10-4〜6.0， 溶剂钝化剂 10-4〜1.0， 沉淀硬化剂 10—4〜0.5， 晶粒细化剂 10—4〜1.0， 稀土添加剂 10—4〜1.0， 基体界面反应缓冲剂 0.001-2.0, 其余为 A1和不可避免的微量杂质。 1. A low-zinc hot-dip aluminum alloy plating material which is modified by Be and multi-combination, characterized in that: the alloy composition is Zn 30, Be: 10 - 4 ～ 0.05, alloy strengthening agent 10-% by weight of element 4 ~6.0, ~1.0 solvent deactivators 10-4, 10-4 ~ 0.5 precipitation hardening agents, grain refiners 10-4 ~1.0, ~1.0 10-4 rare earth additives, 0.001-2.0 matrix interfacial reaction buffer The rest are A1 and inevitable trace impurities.
2. 根据权利要求 1所述 Be与多组合变质的低锌热浸镀铝合金镀层材料， 其特征在于： 合金强化剂包括 Cu或 Li， 以及含有 Cu或 Li的合金。 2. The Be-and multi-combination modified low-zinc hot-dip aluminum alloy plating material according to claim 1, wherein the alloy strengthening agent comprises Cu or Li, and an alloy containing Cu or Li.
3. 根据权利要求 1所述 Be与多组合变质的低锌热浸镀铝合金镀层材料， 其特征在于： 溶剂钝化剂包括 Co、 Cr或 Nb， 以及含有 Co、 Cr或 Nb的合金；每种元素每种可以单独使用， 也可以混合使用。 3. The low-zinc hot-dip aluminum alloy plating material of Be and multi-combination according to claim 1, wherein: the solvent passivating agent comprises Co, Cr or Nb, and an alloy containing Co, Cr or Nb; Each of these elements may be used singly or in combination.
4. 根据权利要求 1所述 Be与多组合变质的低锌热浸镀铝合金镀层材料， 其特征在于： 沉淀硬化剂包括 Bi、 In或 Tl， 每种元素可以单独使用， 也可以混合使用。 4. The Be-and multi-combination modified low-zinc hot-dip aluminum alloy plating material according to claim 1, wherein the precipitation hardening agent comprises Bi, In or Tl, and each element may be used singly or in combination.
5. 根据权利要求 1所述 Be与多组合变质的低锌热浸镀铝合金镀层材料， 其特征在于： 晶粒细化剂包括 C或 Zr和它们相互形成的化合物， 以及 C或 Zr与高熔点过渡元素形成的高 硬度高稳定性化合物。 5. The low-zinc hot-dip aluminum alloy plating material of Be and multi-combination modified according to claim 1, wherein: the grain refiner comprises C or Zr and a compound formed therebetween, and C or Zr and high A high hardness and high stability compound formed by a melting point transition element.
6. 根据权利要求 1所述 Be与多组合变质的低锌热浸镀铝合金镀层材料， 其特征在于： 稀土添加剂包括作为稀土元素的 Pr或 Nd， 及一种以上稀土元素形成的混合稀土。 6. The Be-and multi-combination modified low-zinc hot-dip aluminum alloy plating material according to claim 1, wherein the rare earth additive comprises Pr or Nd as a rare earth element, and a mixed rare earth formed of one or more rare earth elements.
7. 根据权利要求 1所述 Be与多组合变质的低锌热浸镀铝合金镀层材料， 其特征在于： 基体界面反应缓冲剂包括 Fe或 Si， 以及含有 Fe或 Si的合金。 7. The Be-and multi-combination modified low-zinc hot-dip aluminum alloy plating material according to claim 1, wherein the matrix interfacial reaction buffer comprises Fe or Si, and an alloy containing Fe or Si.
8. 一种如权利要求 1〜7任意一项所述 Be与多组合变质的低锌热浸镀铝合金镀层材料的 制备方法， 其特征在于： 包括如下步骤： 8. A method for preparing a low-zinc hot-dip aluminum alloy coating material of a Be and a multi-combination modified according to any one of claims 1 to 7, characterized in that it comprises the following steps:
(1)在上述元素比例范围内， 选定一组元素比例， 再根据需要配制的合金总量， 推算出所 需的每种单质金属的质量， 或者合金的质量， 或者混合金属添加剂的质量， 编制合金生产配 料表， 并按配料表选足备料； (1) Within the above element ratio range, select a set of element ratios, and then calculate the mass of each elemental metal required, or the quality of the alloy, or the quality of the mixed metal additive, according to the total amount of the alloy to be formulated. Preparation of alloy production Material list, and according to the ingredient list, select the preparation materials;
(2)先往熔炼炉中加入适量的铝锭或熔融铝液， 加热使之完全融化并在 700〜800°C下保 温；  (2) Firstly add an appropriate amount of aluminum ingot or molten aluminum liquid to the melting furnace, heat it to completely melt and keep it at 700~800 °C;
(3)再按配方比例加入基体界面反应缓冲剂、 Be、溶剂钝化剂、 晶粒细化剂、合金强化剂、 稀土添加剂和沉淀硬化剂， 最后再加入锌， 搅拌均匀； 现场取样分析， 根据分析结果和配方 范围， 调整添加量； 然后继续熔炼和搅拌， 再次取样分析， 直至各元素比例完全符合配方要 求；  (3) Add the matrix interface reaction buffer, Be, solvent passivator, grain refiner, alloy enhancer, rare earth additive and precipitation hardener according to the proportion of the formula, and finally add zinc and stir evenly; on-site sampling analysis, According to the analysis results and the scope of the formula, adjust the amount of addition; then continue to smelt and stir, sample again and analyze until the proportion of each element fully meets the formulation requirements;
(4)然后对上述合金熔体进行炉内精炼； 往合金熔体中加入精炼剂， 并搅拌均匀， 熔体精 炼在封闭环境中完成；  (4) then in-furnace refining the above alloy melt; adding a refining agent to the alloy melt, stirring uniformly, and melt refining is completed in a closed environment;
(5)精炼后除渣、 除气、 静置、 调温至 660〜720°C， 合金液倾倒出炉， 同时过滤； 滤液平 缓倾入铸造锭模中， 通过顺序式结晶方式， 使熔体在锭模中自下而上凝结， 形成银白色锭型。  (5) After refining, slag removal, degassing, standing, and tempering to 660~720 °C, the alloy liquid is poured out of the furnace and filtered at the same time; the filtrate is gently poured into the casting ingot mold, and the melt is in the form of sequential crystallization. The ingot mold is condensed from the bottom to the top to form a silver-white ingot type.
9. 根据权利要求 8所述的 Be与多组合变质的低锌热浸镀铝合金镀层材料的制备方法， 其特征在于： 在步骤 (2)中， 熔炼炉是指可以熔炼各种铝合金、 锌合金或铜合金的工业熔炉， 包括工频感应加热炉、 中频感应加热炉、 电阻炉、 燃气加热炉或燃油加热炉。 9. The method for preparing a low-zinc hot-dip aluminum alloy plating material of Be and multi-combination modified according to claim 8, wherein: in the step (2), the melting furnace means that various aluminum alloys can be smelted, Industrial furnaces of zinc alloy or copper alloy, including power frequency induction heating furnaces, medium frequency induction heating furnaces, electric resistance furnaces, gas heating furnaces or fuel heating furnaces.
PCT/CN2011/081741 2011-02-25 2011-11-03 Low-zinc hot dip aluminum alloy coating material containing be and combination of agents, and preparation method thereof WO2012113242A1 (en)

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