WO2022021537A1 - 一种粉末渗锌剂、防腐蚀金属件以及渗锌方法 - Google Patents

一种粉末渗锌剂、防腐蚀金属件以及渗锌方法 Download PDF

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WO2022021537A1
WO2022021537A1 PCT/CN2020/113896 CN2020113896W WO2022021537A1 WO 2022021537 A1 WO2022021537 A1 WO 2022021537A1 CN 2020113896 W CN2020113896 W CN 2020113896W WO 2022021537 A1 WO2022021537 A1 WO 2022021537A1
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powder
magnesium
parts
zinc
agent
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PCT/CN2020/113896
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English (en)
French (fr)
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乐林江
沈伟
乐政
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盐城科奥机械有限公司
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Priority to US17/599,748 priority Critical patent/US20230146573A1/en
Publication of WO2022021537A1 publication Critical patent/WO2022021537A1/zh

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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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/09—Mixtures of metallic powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step

Definitions

  • the present application relates to the technical field of chemical heat treatment on the surface of metal materials, in particular to a powder zincizing agent, an anti-corrosion metal part and a zincizing method.
  • Sherardizing is a chemical heat treatment process in which zinc is infiltrated into the surface of a metal material.
  • Zinc treatment on the surface of metal materials can significantly improve its resistance to atmospheric corrosion.
  • powder galvanizing is widely used in the surface anti-corrosion treatment of metal parts because of its advantages of no hydrogen embrittlement, high bonding strength, and good corrosion resistance.
  • most of the global railway fasteners, high-strength fasteners, etc. use the powder zinc anti-corrosion treatment method for surface protection.
  • the infiltration layer is formed on the metal parts after powder infiltration is carried out on the metal parts with powder infiltration agent. It is an anisotropic close-packed hexagonal structure, and the lattice constants are represented by a and c.
  • the self-diffusion coefficient of zinc in the direction parallel to the c-axis is nearly 20 times that in the direction perpendicular to the c-axis. Due to the existence of anisotropy, the grain boundaries between zinc crystals during the growth process are weak grain boundary structures.
  • this weak grain boundary structure is transparent to corrosive substances such as chloride ions, and the corrosive substances can directly The grain boundary of zinc penetrates into the steel matrix, resulting in red rust spots on the surface of the seepage layer.
  • the salt spray resistance life of ordinary seepage layers is often only tens of hours, which is far from meeting the requirements of hundreds of hours or even thousands of hours of salt spray life in engineering.
  • the surface sealing and Dacromet are mostly organic or inorganic coatings. Under the conditions of sandstorm and erosion in the actual use environment, the sealing layer is easily worn away, and premature corrosion often occurs, causing premature failure of metal parts. .
  • the existing technology to improve the corrosion resistance of the zinc coating layer is mainly achieved by adding aluminum, nickel, rare earth and other methods, and these methods are still limited to improve the corrosion resistance of the zinc coating layer in practical applications.
  • the patent of "Metal Anticorrosion Process” discloses the composition and powder infiltration process of a zinc-nickel infiltration layer, in which the nickel powder content is 0.5wt%-1.4wt%, but when the powder infiltration treatment is carried out within 500 °C, it is difficult for nickel to penetrate. Therefore, it is difficult to form a high corrosion-resistant infiltrating layer, and its corrosion resistance is basically equivalent to that of traditional powder galvanizing, and it does not achieve the effect of improving the corrosion resistance of the infiltrating layer.
  • magnesium powder is seldom added to the powder zincizing agent. Even if the powdered zincizing agent contains magnesium powder, the amount of magnesium powder is very small, and it does not rely on magnesium powder to play its role. Primary action, often in combination with a variety of other ingredients.
  • the patent titled "a high-activity, fast-penetrating powder zincizing agent” discloses a high-activity, fast-penetrating powdered zincizing agent, in which aluminum and magnesium are added for the purpose of improving the activity of the infiltrating agent so as to achieve The purpose of fast infiltration has not achieved the effect of improving the corrosion resistance of the infiltration layer.
  • the magnesium powder added to the existing powder zincizing agent usually has a particle size below 10 ⁇ m, and the content of the magnesium powder in the metal powder is often less than 5%.
  • the purpose of adding magnesium powder to the existing powder zincizing agent is to clean the surface of metal parts through the high-temperature reaction of the magnesium powder, and the particle size and content of the magnesium powder are sufficient to achieve the purpose.
  • magnesium powder with a particle size of less than 10 ⁇ m can clean the surface, it is prone to explosion, has low safety, and will react to form gaseous compounds under high temperature conditions.
  • the content of magnesium powder in the metal powder is less than 5%, almost all of the magnesium powder reacts with the metal surface under high temperature conditions, so that it cannot or rarely enter the infiltration layer.
  • magnesium can be used in powder zincizing agent, whether it can play a positive role in powder zincizing agent, and whether the addition of magnesium can bring unexpected effect to powder zincizing agent is a difficult problem that has not been solved.
  • the embodiments of the present application provide a powder zincizing agent, an anti-corrosion metal part, and a zincizing method to solve the technical defects existing in the prior art.
  • the application provides a powder zincizing agent, which includes the following components in parts by mass: 20-100 parts of metal powder, 40-80 parts of dispersant, and 0.2-5 parts of decomposer, wherein the The metal powder includes 60-97 parts of zinc powder and 3-40 parts of magnesium powder.
  • the parts by mass of the metal powder are 40-80 parts, more preferably, the parts by mass of the metal powder are 50-70 parts, such as 55 parts, 60 parts, 65 parts, and the like.
  • the mass fraction of the zinc powder is preferably 70-90 parts, more preferably 75-85 parts, such as 77 parts, 80 parts, 83 parts, etc.
  • the mass fraction of the magnesium powder is preferably 5 parts -38 parts, more preferably 10-35 parts, such as 15 parts, 20 parts, 25 parts, 30 parts, etc.
  • magnesium alloy phase promotes the transformation of the weak grain boundary structure into a strong grain boundary structure that can effectively block corrosive substances such as chloride ions, thereby greatly improving the corrosion resistance of the infiltration layer.
  • the magnesium powder is pure magnesium powder or magnesium alloy powder.
  • the magnesium powder is preferably pure magnesium powder with a purity of more than 95% or magnesium alloy powder with a weight ratio of magnesium of not less than 40%.
  • the dispersant is ceramic powder, which can effectively prevent the metal powder from sticking
  • the decomposer is ammonia halide, which can decompose to provide ammonia and hydrogen halide gas, which can not only clean the surface of metal parts, but also activate other component, which contributes to the progress of sherardizing.
  • the ceramic powder includes at least one of aluminum oxide, silicon oxide, magnesium oxide, aluminum nitride, silicon nitride, and silicon carbide;
  • the decomposing agent is ammonia halide, and the ammonia halide includes ammonium chloride, At least one of ammonium fluoride, ammonium iodide, ammonium bromide, and ammonium hydrogen fluoride.
  • the powder zinc infiltration agent also includes 0.5-3 parts of an active agent capable of promoting the infiltration of magnesium into the infiltration layer.
  • the active agent is magnesium halide.
  • Magnesium halide can promote the interaction between magnesium and zinc, can promote the aggregation of magnesium at the zinc grain boundary, and further improve the corrosion resistance of the infiltration layer.
  • the magnesium halide includes at least one of magnesium chloride, magnesium fluoride, magnesium iodide, and magnesium bromide.
  • the particle size of the magnesium powder is 10 ⁇ m-500 ⁇ m
  • the particle size of the zinc powder is 1 ⁇ m-200 ⁇ m
  • the particle size of the dispersant is 5 ⁇ m-500 ⁇ m.
  • the powder zincizing agent further includes manganese dioxide, and the mass fraction of the manganese dioxide is not greater than the mass fraction of the decomposer.
  • Manganese dioxide can promote the diffusion of magnesium to the infiltration layer during the process of zinc infiltration, thereby promoting the reaction of more magnesium and zinc to form a highly corrosion-resistant zinc-magnesium alloy phase, and improving the corrosion resistance of the infiltration layer.
  • the present application also provides an anti-corrosion metal piece, the surface of the anti-corrosion metal piece is infiltrated with zinc and magnesium through the above-mentioned powder galvanizing agent to form an infiltration layer capable of preventing the metal piece from corroding.
  • the average content of magnesium in the infiltration layer is 0.5wt%-20wt%.
  • the content of magnesium in the infiltration layer is within this range, its corrosion resistance is the strongest. If the magnesium content is too low, the magnesium will mainly react with the oxygen in the oxygen-containing substances and cannot enter the infiltration layer. If the magnesium content is too high, it will lead to the formation of too many magnesium alloys. Since the magnesium alloy is not corrosion-resistant, it will lead to the infiltration layer. Corrosion resistance decreased.
  • the thickness of the infiltration layer is 5 ⁇ m-200 ⁇ m.
  • the present application also provides a method for sherardizing, comprising:
  • the S2 includes:
  • the airtight infiltration tank is vacuumed, or a protective atmosphere is introduced into the airtight infiltration tank to drive out the air in the airtight infiltration tank, and the valve of the airtight infiltration tank is closed.
  • the S3 includes:
  • the airtight infiltration tank is heated up, and the temperature is raised to 360°C-415°C or 320°C-480°C for 1-10 hours to complete the zinc penetration.
  • the powder infiltration agent provided by the present application includes metal powder, dispersant and decomposer, wherein the metal powder includes zinc powder and magnesium powder. Due to the anisotropy of zinc, the grain boundaries between zinc crystals are weak during the growth process. Grain boundary structure, this weak grain boundary structure is transparent to corrosive substances such as chloride ions, and corrosive substances can directly penetrate these weak grain boundary structures to corrode, while magnesium can gather at the weak grain boundary structure of zinc.
  • the high-temperature reaction forms MgZn 2 , Mg 2 Zn 11 and other zinc-magnesium alloy phases with high corrosion resistance, which promotes the transformation of the weak grain boundary structure into a strong grain boundary structure that can effectively block corrosive substances such as chloride ions, thereby greatly improving the permeability.
  • the corrosion resistance of the layer is highly improved.
  • the mass fraction of magnesium powder is 3-40 parts, so that the average content of magnesium in the infiltrating layer can be guaranteed to be between 0.5wt%-20wt%, so as to ensure the maximum Improve the corrosion resistance of the seepage layer.
  • the magnesium content in the infiltrated layer is greater than 20wt%, that is, when the mass fraction of magnesium powder is greater than 40 parts, the magnesium content in the infiltrated layer will be too high, resulting in the formation of more magnesium alloy phases, because the magnesium alloy itself is extremely intolerant. Corrosion, so the corrosion resistance of the infiltrated layer is significantly reduced.
  • the permeation layer containing 0.5wt%-20wt% magnesium can increase its resistance to neutral salt spray by dozens of times, and has extremely high engineering application value and application prospect.
  • the powder zinc infiltration agent provided by the present application may also include an active agent, and the active agent is preferably magnesium halide.
  • the magnesium halide can promote the interaction between magnesium and zinc, and can promote the aggregation of magnesium at the zinc grain boundary, and further to improve the corrosion resistance of the infiltrated layer.
  • the anti-corrosion metal piece provided by the present application, its surface is infiltrated with zinc and magnesium through the above-mentioned powder galvanizing agent to form an infiltration layer capable of preventing corrosion of the metal piece, and the interaction between magnesium and zinc to form MgZn 2 , Mg 2 Zn 11 and the like has high corrosion resistance
  • the zinc-magnesium alloy phase of the metal parts can build a solid protective barrier for the metal parts, block the corrosion of the metal parts by corrosive substances such as chloride ions, effectively improve the corrosion resistance of the metal parts, and prolong the service life of the metal parts.
  • the cost is low and it is easy to popularize. use.
  • the method for sherardizing provided by the present application can effectively avoid the reaction between magnesium and air in the powdered zincizing agent by driving the air in the hermetically sealed tank. At the same time, the air in the tank also creates suitable environmental conditions for the completion of metal parts infiltration. The temperature is raised to the preset temperature and then kept for 1-10 hours to complete the infiltration. The effect of infiltration is good and the quality of the infiltration layer is high.
  • the zinc-hardening method provided by the present application has the advantages of simple operation, convenient use, low cost, high economic benefit and wide application range.
  • Fig. 1 is the composition distribution diagram of the magnesium-containing galvanizing layer with an average magnesium content of 5wt% on the steel surface of an embodiment of the present application;
  • Fig. 2 is the X-ray diffraction (XRD) phase structure comparison diagram of three kinds of different magnesium content infiltration layers;
  • Fig. 3 is the surface state diagram of the salt spray corrosion of magnesium-containing galvanizing layer at different times in an embodiment of the present application
  • Fig. 4 is the sectional state diagram of the 0-hour salt spray corrosion of the magnesium-containing galvanizing layer according to an embodiment of the present application
  • Fig. 5 is the sectional state diagram of the salt spray corrosion of magnesium-containing galvanizing layer for 1000 hours according to an embodiment of the present application;
  • Fig. 6 is the cross-sectional state diagram of the salt spray corrosion of magnesium-containing galvanizing layer for 2000 hours according to an embodiment of the present application;
  • Fig. 7 is the cross-sectional state diagram of the salt spray corrosion of the magnesium-containing galvanizing layer for 4000 hours according to an embodiment of the present application;
  • FIG. 9 is a cross-sectional topography diagram of the seepage layer with an average magnesium content of 43% in an embodiment of the present application.
  • FIG. 10 is an enlarged view of the corrosion product on the surface of the ordinary sherardizing layer of an embodiment of the present application.
  • 11 is an enlarged view of the corrosion product on the surface of the magnesium-containing galvanized layer of the anti-corrosion metal piece according to an embodiment of the present application;
  • FIG. 12 is a comparison diagram of the salt spray test results of metal parts according to an embodiment of the present application.
  • This embodiment provides a powder infiltrating agent, which includes the following components in parts by mass: 20-100 parts of metal powder, 40-80 parts of dispersant, and 0.2-5 parts of decomposer, wherein, the The metal powder includes 60-97 parts of zinc powder and 3-40 parts of magnesium powder.
  • the atomic radius of zinc is 0.1332 nanometers
  • the atomic half-valence of magnesium is 0.1598 nanometers.
  • the difference between the atomic radii of the two is less than 15%.
  • magnesium and zinc are both close-packed hexagonal structures, so they can work together to form a permeation layer.
  • magnesium itself is not resistant to corrosion, it can occupy the position of part of zinc atoms in the crystal structure of zinc, especially at the grain boundary, a certain amount of magnesium can gather at the weak grain boundary of zinc and form through high temperature reaction MgZn 2 , Mg 2 Zn 11 and other zinc-magnesium alloy phases, MgZn 2 , Mg 2 Zn 11 and other alloy phases themselves are highly corrosion-resistant phases, and their formation at the grain boundary can promote the original weak grain boundary structure to become a strong grain boundary structure, In particular, these strong grain boundary structures are opaque to corrosive substances such as chloride ions, which can block these corrosive substances from the outside.
  • the mass fraction of magnesium powder in the powder zincizing agent is 3-40 parts, which can ensure that 0.5wt%-20wt% of magnesium can be dissolved in the infiltration layer, thereby promoting the formation of high corrosion-resistant MgZn 2 , Mg 2 Zn 11 and other high corrosion-resistant alloy phases, thus greatly improving the corrosion-resistant life of metal parts.
  • magnesium itself is very active, in general, magnesium will preferentially react with oxygen in oxygen-containing substances, such as oxygen in the air, oxygen in iron oxides, oxygen in zinc oxides, etc. Once the surface of magnesium forms a certain content of oxygen After the oxide, it is difficult for magnesium to diffuse into the metal body again.
  • Figure 1 is a composition distribution diagram of the magnesium-containing galvanizing layer with an average magnesium content of 5wt% on the steel surface. It can be seen from the figure that the average magnesium content is 19% at 0-4 ⁇ m, and the magnesium content at 4-8 ⁇ m is 19%.
  • the average content of magnesium is 4.2%, the average content of magnesium at 8-12 ⁇ m is 3.5%, and the average content of magnesium at 12-16 ⁇ m is 2%, that is, the magnesium content of the seepage layer gradually increases from the inside to the outside. This is because the diffusion of zinc to the surface of the iron and steel parts occurs first, forming a zinc-iron alloy layer with iron, and then the diffusion of magnesium into the zinc. Increase and increase, the salt spray resistance life of the seepage layer can reach 4000 hours.
  • Figure 2 is the X-ray diffraction (XRD) phase structure comparison diagram of three different magnesium content infiltration layers. It can be seen that no matter whether the magnesium content in the infiltration layer is 1wt%, 5wt% or 8wt%, it has MgZn 2. High corrosion resistance zinc-magnesium alloy phase such as Mg 2 Zn 11 .
  • Figure 4- Figure 7 are the cross-sectional state diagrams of steel parts for 0 hours, 100 hours, 2000 hours, and 4000 hours of salt spray respectively. It can be seen that the thickness of the seepage layer gradually decreases with the passage of time. In the case of 4000 hours of salt spray, the steel parts are corroded. It can be seen that adding an appropriate amount of magnesium to the powder galvanizing agent can greatly improve the neutral salt spray resistance life of the infiltrating layer.
  • magnesium content If the magnesium content is too low, it will mainly react with the oxygen in the oxygen-containing material and cannot enter the infiltration layer. Because magnesium cannot react directly with metals (such as iron), only the diffusion of zinc to the metal parts occurs in the initial stage of the reaction. When the concentration of zinc in the infiltration layer reaches a certain level, magnesium will diffuse into the zinc, thereby forming a magnesium-containing the zinc coating. Especially when the content of magnesium in the powder zincizing agent is less than 2wt%, since magnesium will not directly penetrate into the metal parts at the initial stage of the reaction, at this time, magnesium reacts with the oxide film on the surface of the metal parts and the oxide film on the zinc surface to improve the reaction activity.
  • metals such as iron
  • the magnesium content in the infiltration layer reaches the condition that magnesium can infiltrate, the magnesium content is too small, and it has been almost consumed by the initial reaction, and cannot provide enough active magnesium atoms, and then cannot penetrate into the infiltration layer. If the magnesium content is too high, more magnesium alloys will be formed. Since the magnesium alloys are not corrosion-resistant, the corrosion resistance of the infiltrated layer will decrease. Moreover, due to the extremely strong activity of magnesium, excessive magnesium content will easily cause explosions. low sex.
  • FIG. 8 is a surface view of the seepage layer with an average magnesium content of 32%
  • FIG. 9 is a cross-sectional topography view of the seepage layer with an average magnesium content of 32%.
  • the infiltration layer which is mainly a magnesium alloy structure.
  • the magnesium content is too high, the infiltration layer cracks, and the corrosive medium directly enters the matrix through the crack. Therefore, if the magnesium content is too high, the corrosion resistance of the infiltrated layer will decrease instead.
  • the magnesium powder can be pure magnesium powder with a purity of more than 95%, or magnesium alloy powder with a weight ratio of magnesium of not less than 40%, so as to provide enough magnesium atoms to infiltrate the infiltration layer.
  • the parts by mass of the metal powder can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, etc., preferably 40-80 parts, more preferably 50-70 parts
  • the mass parts of zinc powder in the metal powder can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, etc., preferably 70-90 parts, more preferably 75-85 parts
  • the particle size of the zinc powder is preferably 1 ⁇ m-200 ⁇ m, can be 1 ⁇ m, 10 ⁇ m , 30 ⁇ m, 50 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, etc.
  • the mass fraction of magnesium powder can be 3 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc., preferably 8-38 parts, more preferably 10-35 parts
  • the particle size of the magnesium powder is less than 10 ⁇ m, the magnesium powder is prone to explosion, and the safety is extremely low.
  • the particle size of magnesium powder is not arbitrarily limited, and its effect is most stable only when its particle size is in the range of 10 ⁇ m-500 ⁇ m.
  • the dispersant is preferably a ceramic powder
  • the ceramic powder includes at least one of aluminum oxide, silicon oxide, magnesium oxide, aluminum nitride, silicon nitride, and silicon carbide. Adding ceramic powder to the powder zincizing agent provided in this embodiment can effectively prevent the metal powder from sticking.
  • the particle size of the dispersant is preferably 5 ⁇ m-500 ⁇ m, specifically 5 ⁇ m, 10 ⁇ m, 50 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 250 ⁇ m, 300 ⁇ m, 350 ⁇ m, 400 ⁇ m, 450 ⁇ m, 500 ⁇ m, etc.
  • the number of copies can be 40 copies, 45 copies, 50 copies, 55 copies, 60 copies, 65 copies, 70 copies, 75 copies, 80 copies, etc., depending on the specific situation, which is not limited in this application.
  • the decomposing agent is preferably an ammonia halide
  • the ammonia halide includes at least one of ammonium chloride, ammonium fluoride, ammonium iodide, ammonium bromide, and ammonia hydrogen fluoride, preferably ammonium chloride.
  • ammonia halide can decompose to provide ammonia and hydrogen halide gas, one can clean the surface of metal parts, and then hydrogen halide can activate other components and promote the effect of zinc halide. conduct.
  • the mass parts of the decomposer can be 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.
  • the powder zincizing agent provided in this embodiment includes metal powder, dispersant and decomposer, wherein the metal powder includes zinc powder and magnesium powder, so that the infiltration of magnesium can be realized during the zincizing process, and zinc and magnesium can A highly corrosion-resistant zinc-magnesium alloy phase is formed, which can greatly improve the corrosion resistance of the infiltrated layer.
  • this embodiment provides a powder zincizing agent, which further includes 0.5-3 parts of an active agent that can promote the penetration of magnesium into the infiltration layer, such as 0.5 parts, 1 part, 1.5 parts, 2 copies, 2.5 copies, 3 copies, etc., which are not limited in this application.
  • the active agent is preferably magnesium halide
  • the magnesium halide includes at least one of magnesium chloride, magnesium fluoride, magnesium iodide, and magnesium bromide.
  • magnesium halide In the process of powder galvanizing, magnesium halide is always in solid state, which can fully contact and react with the surface of steel parts and the infiltration layer, which is helpful to realize the infiltration of magnesium more easily, and then adding magnesium halide as an activator can promote magnesium to quickly Effective infiltration into the infiltration layer can promote the interaction between magnesium and zinc, and can promote the aggregation of magnesium at the zinc grain boundary, thereby effectively improving the corrosion resistance of the infiltration layer.
  • ammonia halides such as ammonium chloride and ammonium fluoride also have the effect of activating and catalyzing penetration, their activating and catalyzing effect on magnesium is not strong.
  • ammonium chloride is decomposed by heat to generate ammonia and hydrogen chloride gas, and most of the active magnesium atoms generated by the reaction of magnesium and gaseous hydrogen chloride will not attach to the surface of the permeation layer and react with the permeation layer.
  • the powder zincizing agent provided in this embodiment includes metal powder, dispersant, decomposing agent and activator, wherein the metal powder includes zinc powder and magnesium powder, so that the infiltration of magnesium can be realized during the zincizing process. It can form a highly corrosion-resistant zinc-magnesium alloy phase with magnesium, which can greatly improve the corrosion resistance of the infiltration layer.
  • the addition of the activator can further promote the infiltration of magnesium powder into the infiltration layer, and further improve the performance of the powder zinc infiltration agent. .
  • the present embodiment provides a powder zincizing agent
  • the powder zincizing agent further includes manganese dioxide
  • the mass fraction of manganese dioxide is not greater than the mass fraction of the decomposer, specifically , the mass fraction of manganese dioxide can be 0-3 parts, such as 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 1 part, 1.5 part, 2 part, 2.5 part, 3 part
  • the number of copies, etc. may be determined according to the specific situation, which is not limited in this application.
  • manganese dioxide can be added to the powder zinc infiltration agent as a catalyst for the infiltration reaction of magnesium, which promotes the diffusion of magnesium into the infiltration layer by reacting with ammonia halide as a decomposer.
  • ammonia halide is decomposed at high temperature to obtain ammonia and hydrogen halide gas, and then hydrogen halide gas reacts with manganese dioxide to obtain gas such as manganese halide and chlorine gas.
  • Gases such as chlorine gas can provide a large number of active ions, and the reaction of active ions with magnesium can generate active anhydrous halogenated Magnesium gas, the final active anhydrous magnesium halide gas can exchange with zinc in the infiltration layer, and then the diffusion of magnesium into the infiltration layer occurs.
  • ammonium chloride begins to decompose to generate ammonia and hydrogen chloride.
  • the reaction between hydrogen chloride and manganese dioxide can generate manganese chloride and chlorine gas, and chlorine gas can provide a large amount of active chloride ions on the surface of the permeable layer.
  • the active chloride ion reacts with magnesium to generate active anhydrous magnesium chloride gas, and the active anhydrous magnesium chloride gas can replace the zinc in the infiltration layer, thereby promoting the diffusion of magnesium into the infiltration layer.
  • the solid magnesium halide can have a double catalytic effect with the gaseous magnesium halide, and promote the continuous infiltration of magnesium into the sherardizing layer, so that the sherardizing layer can be infiltrated. It contains enough magnesium and reacts with zinc to form a zinc-magnesium alloy phase with high corrosion resistance, which improves the corrosion resistance of the infiltrated layer.
  • This embodiment provides an anti-corrosion metal piece, the surface of the anti-corrosion metal piece is infiltrated with zinc and magnesium through the powder zinc infiltration agent described in any one of Embodiments 1-3 to form an infiltration layer capable of preventing the metal piece from corroding.
  • the average content of magnesium in the infiltration layer is between 0.5wt% and 20wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt% , 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, etc., to ensure that the corrosion resistance of the permeation layer can be improved to the greatest extent.
  • the magnesium content in the infiltration layer is less than 0.5wt%, that is, the mass fraction of magnesium is less than 3 parts, the magnesium mainly reacts with the oxygen in the oxygen-containing substances and cannot enter the infiltration layer.
  • the magnesium content in the infiltrated layer is greater than 12wt%, that is, when the mass fraction of magnesium is greater than 40 parts, the magnesium content in the infiltrated layer will be high, resulting in more magnesium alloy phases formed. It is extremely resistant to corrosion, so the corrosion resistance of the infiltrated layer is significantly reduced.
  • the permeation layer containing 0.5wt%-20wt% magnesium can increase its resistance to neutral salt spray by dozens of times, and has extremely high engineering application value and application prospect.
  • the thickness of the permeation layer is preferably 20-100 ⁇ m, which may specifically be 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, etc., depending on the specific situation, which is not limited in this application.
  • the content of magnesium in the seepage layer decreases with the increase of the depth of the seepage layer. In the shallower position in the seepage layer, the content of magnesium is more, and at the deeper position in the seepage layer, the content of magnesium is less.
  • the surface magnesium content of the infiltration layer may be greater than 20%, which is due to the excessive magnesium powder adhering to the surface of the infiltration layer.
  • the surface layer of the infiltration layer has a high magnesium content. However, this part only appears on the surface of the infiltration layer. As the corrosion progresses, the surface layer of the infiltration layer with high magnesium content will be corroded soon, and then the infiltration layer with a magnesium content of 0.5wt%-20wt% can prevent the metal parts from being corroded.
  • magnesium can gather at the weak grain boundary of zinc, and form zinc-magnesium alloy phases such as MgZn 2 and Mg 2 Zn 11 through high temperature reaction.
  • the alloy phases such as MgZn 2 and Mg 2 Zn 11 are highly resistant to
  • the etch phase, formed at the grain boundary can promote the original weak grain boundary structure to become a strong grain boundary structure, especially these strong grain boundary structures are opaque to corrosive substances such as chloride ions, which can block these corrosive substances from the outside. .
  • the corrosion products are transformed from the loose structure of ordinary powder herdizing to dense structure, which greatly improves the corrosion resistance of metal parts and greatly prolongs the time. service life of metal parts.
  • Figure 10 is an enlarged view of the corrosion product on the surface of the ordinary sherardizing layer
  • Figure 11 is an enlarged view of the corrosion product on the surface of the magnesium-containing zinc herdizing layer of the anti-corrosion metal part provided in this embodiment.
  • the quantity of the surface corrosion products of the sherardizing layer is far more than that of the surface corrosion products of the magnesium-containing sherardizing layer of the anti-corrosion metal piece provided in this embodiment.
  • the anti-corrosion metal piece provided in this embodiment has significantly improved anti-corrosion performance due to the fact that the zinc coating layer contains a certain amount of magnesium.
  • This embodiment provides a method for sherardizing, including steps S1 to S3.
  • the airtight seepage tank may be vacuumed, or a protective atmosphere may be introduced into the sealed seepage tank to drive out the air in the sealed seepage tank, and the valve of the sealed seepage tank may be closed.
  • the protective atmosphere is preferably an inert gas.
  • the closed infiltration tank can be heated for 1-10 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, when the temperature is raised to 360°C-415°C or 320°C-480°C Wait, you can complete the zinc penetration.
  • the preset temperature is preferably 360°C-415°C, such as 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 415°C, etc.
  • the preset temperature is preferably 320°C-480°C, such as 320°C, 340°C, 360°C, 380°C, 400°C, 420°C, 440°C, 460°C, 480°C, etc.
  • the method for sherardizing provided in this embodiment can effectively avoid the reaction between magnesium in the powder zincizing agent and the air by driving out the air in the hermetically sealed pot.
  • the air in the infiltration tank also creates suitable environmental conditions for completing the infiltration of metal parts.
  • the temperature is raised to the preset temperature and then kept for 1-10 hours to complete the infiltration.
  • the effect of infiltration is good and the quality of the infiltration layer is high.
  • the zinc-hardening method provided by the present application has the advantages of simple operation, convenient use, low cost, high economic benefit and wide application range.
  • the powder zincizing agent and the zincizing method provided in this application have brought significant improvements in many aspects of its application.
  • lightning protection, railway fasteners, and high-strength fasteners are taken as examples for specific explanations. .
  • the current anti-corrosion method used for lightning protection and connection is copper electroplating.
  • the cost of electroplating copper is very high.
  • copper is prone to corrosion, which can easily lead to premature corrosion of grounding parts and failure, and also cause heavy metal pollution to soil, water and other environments.
  • the corrosion resistance of pure electro-galvanizing, hot-dip galvanizing and powder galvanizing cannot meet the requirements of grounding standards.
  • the above-mentioned problems can be solved perfectly by using the powder zincizing agent and the zincizing method provided in the present application. Since magnesium powder is added to the powder zincizing agent, its corrosion resistance after zincizing is greatly improved, and the corrosion resistance and service life can meet the standard requirements without sealing and other treatments. Will not cause any pollution. At the same time, the total cost of the powder zincizing agent and the zincizing method provided in this application is less than 5,000 yuan/ton, which can greatly reduce the overall cost of the lightning protection and power connection industry.
  • railway fasteners are generally treated by powder sherardizing and sealing treatment, but in the high vibration service environment of the railway, the actual service life is far from the design requirements, and the actual use The service life often has not reached half of the design life, and the railway fasteners have been replaced as a whole.
  • the wind power bolts in the wind power industry are high-strength fasteners.
  • the current methods are mostly powder galvanizing plus sealing or Dacromet, and subsequent maintenance basically relies on brushing. paint. Once installed, wind power bolts are difficult to replace. Once they break and fail due to corrosion problems, they will cause great property losses and even casualties.
  • Magnesium is introduced into the infiltration layer, and corrosion-resistant alloy phases such as MgZn 2 and Mg 2 Zn 11 are formed during thermal diffusion.
  • corrosion-resistant alloy phases such as MgZn 2 and Mg 2 Zn 11 are formed during thermal diffusion.
  • the magnesium-zinc alloy phase promotes the production of dense and insoluble corrosion products; at the same time, the MgZn 2 and other alloys have a dense structure, which effectively reduces the corrosion rate.
  • a dense compound layer can be quickly formed on the damaged part to prevent the further occurrence of corrosion, so it has the function of self-healing and can be perfectly suitable for high-strength fasteners.
  • test example provides test groups 1-4.
  • the same metal parts were used in test groups 1-4.
  • the test group 1 carried out electrogalvanizing treatment on the metal parts
  • the test group 2 carried out hot-dip galvanizing treatment on the metal parts
  • the test group 3 carried out powder galvanizing and sealing treatment on the metal parts.
  • Test group 4 used the powder sherardizing agent described in Example 1 and the method described in Example 4 to carry out sherardizing treatment on metal parts. After the treatment was completed, the hardness, corrosion resistance life, hydrogen embrittlement, and salt resistance of each group of metal parts were tested. The properties of haze, thickness of infiltrated layer, wear resistance, sulfur dioxide resistance and other properties were tested, and the results are shown in Table 1.
  • Test group 1 Test group 2 Test group 3 Test group 4 Hardness(HV) 180-200 180-200 300-380 300-400 Corrosion resistance life ⁇ 1 year 5-10 years >20 years >50 years hydrogen embrittlement hydrogen embrittlement hydrogen embrittlement No hydrogen embrittlement No hydrogen embrittlement Salt spray resistance test ⁇ 100h >100h 300-1000h >1500h Layer thickness 5-30 ⁇ m 5-70 ⁇ m 20-120 ⁇ m 5-200 ⁇ m Tolerance Impact smaller larger smaller smaller smaller Abrasion resistance generally generally good good Anti-sulfur dioxide Difference Difference generally good Appearance uniformity better Difference good good good
  • the powder zincizing agent and the zincizing method provided by this application are used to carry out zincizing treatment on metal parts, which have strong hardness, long corrosion resistance life, no hydrogen embrittlement, and good resistance to salt spray and sulfur dioxide.
  • the powder galvanizing agent provided by the present application will not cause any pollution to the environment, and can be built and manufactured in urban areas, and has broad prospects.
  • the powder zincizing agent of this embodiment includes the following components: 35 parts of zinc powder with a particle size of 10 ⁇ m, 10 parts of magnesium powder with a particle size of 20 ⁇ m, 50 parts of alumina powder with a particle size of 50 ⁇ m, and 5 parts of ammonium chloride.
  • the components of the corresponding parts by weight were weighed together with No. 45 steel round bars (4000 parts by weight) and put into the rotary zinc-hardening furnace (rotating speed 15 rev/min), and when the temperature was raised to 300°C, the ammonium chloride Start to decompose, and a large amount of gas is discharged.
  • the temperature reaches 350 °C, close the valve of the infiltration tank of the zinc furnace to make it in a low-oxygen sealed state.
  • zinc and magnesium can form a highly corrosion-resistant zinc-magnesium alloy phase, which can greatly improve the corrosion resistance of the infiltrated layer.
  • the powder zincizing agent of this embodiment includes the following components: 32 parts of zinc powder with a particle size of 10 ⁇ m, 5 parts of AZ91 magnesium alloy powder with a particle size of 30 ⁇ m, 60 parts of alumina powder with a particle size of 50 ⁇ m, 2 parts of ammonium chloride, magnesium chloride 1 serving.
  • the components in the corresponding weight parts and the Q235 lightning protection grounding rod are respectively weighed and put into the rotary zincizing furnace. It is in a hypoxic sealed state. Heat preservation at 410°C for 6 hours to obtain a magnesium-containing galvanized layer with a thickness of 62 ⁇ m and a neutral salt spray resistance time of 1000 hours (after 1000 hours of neutral salt spray test, no red rust appeared on the surface of the sample).
  • the magnesium halide activator can promote the rapid and effective penetration of magnesium into the infiltration layer, thereby further improving the corrosion resistance of the infiltration layer.
  • the powder galvanizing agent of this embodiment includes the following components: 32 parts of zinc powder with a particle size of 5 ⁇ m, 15 parts of AZ31 magnesium alloy powder with a particle size of 20 ⁇ m, 50 parts of alumina powder with a particle size of 20 ⁇ m, 2 parts of ammonium chloride, magnesium chloride 1 serving.
  • the powder and the activator of the corresponding weight parts were weighed, and the Q235 lightning protection grounding rod (3000 parts by weight) was put into the rotary galvanizing furnace (rotation speed 20 rpm), and the vacuum was evacuated to the degree of vacuum. When it reaches less than 1000Pa, close the valve of the sherardizing tank to make it in a low-oxygen sealing state. Heat preservation at 410°C for 6 hours to obtain a magnesium-containing galvanizing layer with a thickness of 62 ⁇ m and a neutral salt spray resistance time of 1600 hours (after 1600 hours of neutral salt spray test, no red rust appeared on the surface of the sample).
  • the magnesium halide activator can promote the rapid and effective penetration of magnesium into the infiltration layer, thereby further improving the corrosion resistance of the infiltration layer.
  • the powder zincizing agent of this embodiment includes the following components: 38 parts of zinc powder with a particle size of 5 ⁇ m, 5 parts of self-made magnesium alloy powder with a particle size of 10 ⁇ m, 55 parts of alumina powder with a particle size of 20 ⁇ m, 1 part of ammonium chloride, magnesium chloride 1 serving.
  • the components of the self-made magnesium alloy powder are: magnesium 80%, aluminum 15%, and zinc 5% by weight.
  • the powder and the activator of the corresponding weight portion were respectively weighed, and together with the 60Si 2 Mn railway gasket (5000 parts by weight) were put into the rotary zincizing furnace (rotation speed 30 rpm), filled with argon gas
  • the argon gas is filled with the infiltration tank to drive away the air, the temperature starts to rise, and the argon gas is continuously introduced in the process of heating, heat preservation and cooling to ensure that the whole process is a protective atmosphere environment.
  • the magnesium halide activator can promote the rapid and effective penetration of magnesium into the infiltration layer, thereby further improving the corrosion resistance of the infiltration layer.
  • the powder galvanizing agent in this embodiment includes the following components: 44 parts of zinc powder with a particle size of 1 ⁇ m, 14 parts of AZ91 magnesium alloy powder with a particle size of 5 ⁇ m, 40 parts of silicon oxide powder with a particle size of 10 ⁇ m, and 2 parts of magnesium chloride.
  • the magnesium halide activator can promote the rapid and effective penetration of magnesium into the infiltration layer, thereby further improving the corrosion resistance of the infiltration layer.
  • test group and a control group are set, and the composition of the powder sherardizing agent in each group is shown in Table 2.
  • composition of powder galvanizing agent test group 40 parts of zinc powder + 8 parts of magnesium powder + 50 parts of alumina powder + 1 part of ammonium chloride + 1 part of magnesium fluoride control group 40 parts of zinc powder + 8 parts of aluminum powder + 50 parts of alumina powder + 1 part of ammonium chloride + 1 part of magnesium fluoride
  • the metal parts of the test group and the control group are in the initial state without any rust at 0h of the salt spray test, that is, when the test has just started.
  • the metal parts of the control group appear A large amount of white rust appeared on the metal parts of the test group, while only a small amount of white rust appeared on the metal parts of the test group.
  • the salt spray test was carried out for 200 hours, the metal parts of the control group appeared obvious red rust.
  • the control group test was ended, but the metal parts of the test group still remained on the metal parts. There was only a small amount of white rust.
  • the salt spray test was carried out for 1000 hours, there was only a small amount of white rust on the metal parts of the test group.
  • the salt spray test was carried out for 2000 hours, the white rust on the metal parts of the test group increased.
  • the time for red rust to appear on the metal parts of the control group is much shorter than the time for red rust to appear on the metal parts of the test group, and the test results of the control group are far worse than the test results of the test group, so zinc powder, aluminum powder, etc.
  • the zinc-aluminum infiltrating layer formed by the powder sherardizing agent of the composition is very limited in improving the corrosion resistance, and the powder sherardizing agent provided in this embodiment is used to carry out the zinc-infiltrating treatment on the metal parts. Significantly improve the corrosion resistance of its infiltration layer, significantly prolong the service life of metal parts.
  • test groups 1-4 are set up, and the composition of the powder sherardizing agent in each group is shown in Table 3.
  • the metal parts formed with infiltration layer have a lot of white rust after 100h of salt spray test, and obvious red rust at 200h; using test group 2 and test group 3 That is, after the metal parts are treated with the powder zincizing agent provided in this application, the metal parts forming the zinc-magnesium infiltrating layer have only a small amount of white rust in the salt spray test for 100h-3000h, and a large amount of rust appears after 3500h.
  • powder zincizing is a solid-solid reaction, and the layer is formed by solid-phase diffusion. Powder zincizing with a single element is easy to achieve, while multi-component co-seeding is the opposite.
  • a chemical compound with a high temperature diffusion temperature or an intermetallic compound with a small solid solubility is formed between the elements contained in the powder infiltrating agent, the activity of the infiltrating agent is significantly reduced.
  • binary infiltration agents as the concentration of one of the elements increases, the activity of the atoms of the other group decreases.
  • the ratio of the two infiltrating elements in the infiltrating agent is exactly in line with the composition ratio of the chemical compound, the infiltration layer cannot be formed by diffusion.
  • the amount of one of the infiltrating elements of the powder sherardizer is greater than that required to form the compound, only infiltration of that element will occur.
  • the mechanism is more complicated. Therefore, for powder galvanizing, the simplest components and the simplest catalysts are used to form a specific infiltration layer, which has engineering application value.
  • the powder powder zincizing agent provided by this group is simultaneously added with zinc powder, magnesium powder, aluminum powder and other metal powders.
  • zinc powder, magnesium powder and aluminum powder as an example, the activity of aluminum is strong. Because of zinc, magnesium reacts with aluminum first. Once magnesium reacts with aluminum, a stable magnesium-aluminum compound is formed. The stable magnesium-aluminum compound cannot penetrate into the infiltrating layer because it cannot provide the chemical driving force required for diffusion. . Therefore, when magnesium and aluminum are added to the powder infiltrating agent at the same time, in order for magnesium to penetrate into the infiltrating layer, the content of magnesium is usually higher than that of aluminum.
  • the content can be 7 wt %, etc., to provide a sufficient amount of active magnesium atoms to diffuse into the sherardizing layer. If there are other alloying elements in addition to magnesium and aluminum in the infiltrating agent, the content of magnesium often needs to be further increased to promote the diffusion of magnesium into the infiltrating layer.
  • magnesium in the infiltration layer mainly composed of zinc-aluminum alloy, a certain amount of magnesium is added to the powder infiltration agent, and magnesium can penetrate into the infiltration layer structure to a certain extent, but due to the existence of aluminum in the infiltration layer, Magnesium will also preferentially react with aluminum and form a magnesium-aluminum alloy phase structure in the infiltrated layer. Although the magnesium-aluminum alloy phase can play a role in refining the grains of the infiltrated layer, it cannot improve the corrosion resistance.
  • magnesium preferentially reacts with aluminum in the infiltration layer, magnesium can basically no longer react with zinc in the infiltration layer to form high corrosion-resistant zinc-magnesium alloy phases such as MgZn 2 and Mg 2 Zn 11 , which cannot improve the corrosion resistance of the infiltration layer. performance.

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Abstract

本申请提供一种粉末渗锌剂、防腐蚀金属件以及渗锌方法。其中，所述粉末渗锌剂包括以下质量份数的组分：金属粉末20-100份，分散剂40-80份，分解剂0.2-5份，其中，所述金属粉末包括锌粉60-97份和镁粉3-40份。本申请提供的粉末渗锌剂，可以在渗锌的过程中实现镁的渗入，锌与镁能够形成高耐腐蚀的锌镁合金相，从而能够大幅提高渗层的耐腐蚀性能。本申请提供的渗锌方法，操作简单，使用方便，成本低廉，经济效益高，适用范围广。

Description

一种粉末渗锌剂、防腐蚀金属件以及渗锌方法 技术领域
本申请涉及金属材料表面化学热处理技术领域，特别涉及一种粉末渗锌剂、防腐蚀金属件以及渗锌方法。
背景技术
渗锌是使金属材料表面渗入锌的化学热处理工艺。对金属材料表面进行渗锌处理，能够显著提高其抗大气腐蚀的能力。其中，粉末渗锌因其具有无氢脆、结合强度高、耐腐蚀好等一系列优点，而被广泛应用于金属件表面防腐处理中。目前，全球铁路扣件、高强度紧固件等大多都采用粉末渗锌防腐处理方法进行表面防护。
但是，现有的粉末渗锌技术仍存在着耐腐蚀性能不高的问题。采用粉末渗锌剂对金属件进行粉末渗锌后会在金属件上形成渗层，采用目前市面上的粉末渗锌剂渗锌形成的渗层主要为锌铁合金相和锌相，锌的晶体结构为各向异性的密排六方结构，点阵常数由a和c表示。渗锌过程中，锌的生长具有取向性，会优先沿着c轴方向生长，锌的自扩散系数在平行c轴方向是在垂直c轴方向的近20倍。而由于各向异性的存在，生长过程中锌晶体之间的晶界为弱晶界结构，腐蚀过程中，这种弱晶界结构对氯离子等腐蚀性物质是透明的，腐蚀性物质可以直接穿透锌的晶界进入钢铁基体，从而导致很快会在渗层表面出现红色锈斑，盐雾性能测试中，表面出现红锈的时间一般会被判定为耐盐雾腐蚀寿命。而普通渗层耐盐雾寿命往往只有几十小时，远远无法满足工程中盐雾寿命几百小时甚至上千小时的要求。这需要在粉末渗锌结束后进行表面封闭、涂敷达克罗等方法进行处理，以提前其整体耐腐蚀性能。然而表面封闭及达克罗等多为有机或无机涂料，在实际使用环境的风沙、冲蚀等条件下，封闭层又很容易被磨损掉，往往会发生过早腐蚀，引起金属件过早失效。
目前，现有技术提高渗锌层耐腐蚀性能主要靠添加铝、镍、稀土等方法来实现，而实际应用中这些方法对提高渗锌层耐腐蚀性能仍然有限，名称为“锌镍渗层黑色金属防腐工艺”的专利公开了一种锌镍渗层的组分及粉末渗工艺，其中镍粉含量0.5wt％—1.4wt％，但是在500℃以内进行粉末渗处理时，镍很难渗进去形成渗层，因此难以形成高耐腐蚀的渗层，其耐腐蚀性能与传统粉末渗锌基本相当，并没有达到提高渗层耐腐蚀性的效果。
镁的化学性质十分活泼，可以与O 2、N 2、H 2O等众多非金属物质反应，用 量十分难以把握。由于镁的化学性质特殊，在现有技术中很少会将镁粉加入至粉末渗锌剂中，即使粉末渗锌剂中含有镁粉成分，其用量也极少，也并不依靠镁粉发挥主要作用，通常需要与多种其他成分配合使用。比如名称为“一种高活性、快渗速的粉末渗锌剂”的专利公开了一种高活性、快渗速的粉末渗锌剂，其中铝和镁加入目的是为了提高渗剂活性从而达到快渗速的目的，也没有达到提高渗层耐腐蚀性的效果。此外，现有粉末渗锌剂中加入的镁粉通常粒径均在10μm以下，镁粉在金属粉末中的含量往往小于5％。现有的粉末渗锌剂中加入镁粉的目的大多为通过镁粉的高温反应对金属件表面进行清洁，上述镁粉的粒径和含量已经足以达到其目的。但是，粒径小于10μm的镁粉虽然能够起到清洁表面的作用，却易发生爆炸，安全性低，且在高温条件下还会反应形成气态化合物。此外，镁粉在金属粉末中的含量小于5％的情况下，其在高温条件下几乎全部与金属表面进行反应，而导致无法或极少进入到渗层中。
因此，镁是否能用于粉末渗锌剂、是否能在粉末渗锌剂中发挥积极作用、镁的加入是否能为粉末渗锌剂带来意想不到的效果是一直未被解决的难题。
发明内容
有鉴于此，本申请实施例提供了一种粉末渗锌剂、防腐蚀金属件以及渗锌方法，以解决现有技术中存在的技术缺陷。
本申请提供一种粉末渗锌剂，所述粉末渗锌剂包括以下质量份数的组分：金属粉末20-100份，分散剂40-80份，分解剂0.2-5份，其中，所述金属粉末包括锌粉60-97份和镁粉3-40份。
优选地，所述金属粉末的质量份数为40-80份，更为优选地，所述金属粉末的质量份数为50-70份，比如55份、60份、65份等。
在金属粉末中，所述锌粉的质量份数优选为70-90份，更优选为75-85份，比如77份、80份、83份等，所述镁粉的质量份数优选为5-38份，更优选为10-35份，比如15份、20份、25份、30份等。
其中，在粉末渗锌剂对金属件进行渗锌的过程中，一定量的镁能够聚集在锌的弱晶界处，通过高温反应形成MgZn 2、Mg 2Zn 11等具有高耐蚀性的锌镁合金相，促使弱晶界结构转变为对能够有效阻挡氯离子等腐蚀性物质的强晶界结构，从而能够大幅提高渗层的耐腐蚀性能。
进一步地，所述镁粉为纯镁粉或镁合金粉。所述镁粉优选为纯度大于95％的纯镁粉或镁的重量比不小于40％的镁合金粉。
进一步地，所述分散剂为陶瓷粉末，其可以有效防止金属粉末发生粘结，所述分解剂为卤化氨，其可以分解提供氨和卤化氢气体，不仅能够清洁金属件表面，还可以活化其他组分，有助于渗锌的进行。
进一步地，所述陶瓷粉末包括氧化铝、氧化硅、氧化镁、氮化铝、氮化硅、碳化硅中的至少一种；所述分解剂为卤化氨，所述卤化氨包括氯化铵、氟化铵、碘化铵、溴化铵、氟化氢氨中的至少一种。
进一步地，所述粉末渗锌剂还包括能够促进镁渗入渗层的活性剂0.5-3份。
进一步地，所述活性剂为卤化镁。卤化镁能够促进镁与锌之间的相互作用，能够促进镁在锌晶界处的聚集，进一步地提高渗层的耐腐蚀性能。
进一步地，所述卤化镁包括氯化镁、氟化镁、碘化镁、溴化镁中的至少一种。
进一步地，所述镁粉的粒径为10μm-500μm，所述锌粉的粒径为1μm-200μm，所述分散剂的粒径为5μm-500μm。
进一步地，所述粉末渗锌剂还包括二氧化锰，所述二氧化锰的质量份数不大于所述分解剂的质量份数。二氧化锰能够在渗锌的过程中促进镁向渗层的扩散，进而促进更多的镁与锌反应形成高耐蚀的锌镁合金相，提高渗层耐腐蚀性能。
本申请还提供一种防腐蚀金属件，所述防腐蚀金属件的表面通过如上所述的粉末渗锌剂渗入锌与镁形成能够防止金属件腐蚀的渗层。
进一步地，所述渗层中镁的平均含量为0.5wt％-20wt％。在渗层中镁的含量位于此范围内的情况下，其抗腐蚀性能最强。若镁含量过低，镁会主要与含氧物质中的氧反应进而无法进入渗层中，若镁含量过高，会导致形成的镁合金偏多，由于镁合金不耐腐蚀进而导致渗层的耐腐蚀性能反而下降。
进一步地，所述渗层的厚度为5μm-200μm。
本申请还提供一种渗锌方法，包括：
S1、对待渗锌的金属件进行除油除锈处理，并将处理后的金属件与如上所述的粉末渗锌剂共同置于密闭渗罐中；
S2、驱赶所述密闭渗罐中的空气，并关闭所述密闭渗罐的阀门；
S3、对所述密闭渗罐进行升温处理，升温至预设温度后保温1-10小时，完成渗锌。
进一步地，所述S2，包括：
对所述密闭渗罐进行抽真空处理，或向所述密闭渗罐中通入保护气氛驱赶所述密闭渗罐中的空气，并关闭所述密闭渗罐的阀门。
进一步地，所述S3，包括：
对所述密闭渗罐进行升温处理，升温至360℃-415℃或320℃-480℃的情况下保温1-10小时，完成渗锌。
本申请提供的粉末渗锌剂，包括金属粉末、分散剂和分解剂，其中，金属粉末包括锌粉和镁粉，由于锌存在各向异性，在生长过程中锌晶体之间的晶界为弱晶界结构，这种弱晶界结构对氯离子等腐蚀性物质是透明的，腐蚀性物质能够直接穿过这些弱晶界结构进行腐蚀，而镁能够聚集在锌的弱晶界结构处，通过高温反应形成MgZn 2、Mg 2Zn 11等具有高耐蚀性的锌镁合金相，促使弱晶界结构转变为对能够有效阻挡氯离子等腐蚀性物质的强晶界结构，从而能够大幅提高渗层的耐腐蚀性能。
在本申请提供的粉末渗锌剂中，镁粉的质量份数为3-40份，如此能够保证渗层中的镁的平均含量在0.5wt％-20wt％之间，以保证能够最大限度的提高渗层的耐腐蚀性能。经过大量实验证明，在渗层中的镁含量小于0.5wt％，即镁粉的质量份数小于3份的情况下，镁主要与含氧物质中的氧发生反应，无法进入渗层中，在渗层中的镁含量大于20wt％，即镁粉的质量份数大于40份的情况下，渗层中镁含量会偏高，导致形成的镁合金相偏多，由于镁合金自身是极不耐腐蚀的，故渗层的耐腐蚀性能反而明显下降。与普通渗层相比，含有0.5wt％—20wt％镁的渗层其耐中性盐雾寿命可以提高数十倍，具有极高的工程应用价值和应用前景。
此外，本申请提供的粉末渗锌剂中还可以包括活性剂，该活性剂优选为卤化镁，卤化镁能够促进镁与锌之间的相互作用，能够促进镁在锌晶界处的聚集，进一步地提高渗层的耐腐蚀性能。
本申请提供的防腐蚀金属件，其表面通过上述粉末渗锌剂渗入锌与镁形成能够防止金属件腐蚀的渗层，镁与锌相互作用形成MgZn 2、Mg 2Zn 11等具有高耐蚀性的锌镁合金相，为金属件构建起坚实的保护屏障，阻挡氯离子等腐蚀性物质对金属件的侵蚀，有效提高金属件的耐腐蚀性能，延长金属件的使用寿命，成本低，易于推广使用。
本申请提供的渗锌方法，通过驱赶所述密闭渗罐中的空气，可以有效避免 粉末渗锌剂中的镁与空气反应，通过对所述密闭渗罐进行升温处理，不仅可以进一步驱赶密闭渗罐中的空气，同时还创造了完成金属件渗锌的适宜环境条件，升温至预设温度后保温1-10小时，完成渗锌，渗锌效果好，渗层质量高。本申请提供的渗锌方法，操作简单，使用方便，成本低廉，经济效益高，适用范围广。
附图说明
图1是本申请一实施例的钢铁表面平均镁含量5wt％的含镁渗锌层成分分布图；
图2是三种不同镁含量渗层的X射线衍射(XRD)相结构对比图；
图3是本申请一实施例的含镁渗锌层盐雾腐蚀不同时间的表面状态图；
图4是本申请一实施例的含镁渗锌层盐雾腐蚀0小时断面状态图；
图5是本申请一实施例的含镁渗锌层盐雾腐蚀1000小时断面状态图；
图6是本申请一实施例的含镁渗锌层盐雾腐蚀2000小时断面状态图；
图7是本申请一实施例的含镁渗锌层盐雾腐蚀4000小时断面状态图；
图8是本申请一实施例的平均镁含量为43％的渗层表面图；
图9是本申请一实施例的平均镁含量为43％的渗层断面形貌图；
图10是本申请一实施例的普通渗锌层表面腐蚀产物放大图；
图11是本申请一实施例的防腐蚀金属件的含镁渗锌层表面腐蚀产物放大图；
图12是本申请一实施例的金属件盐雾试验结果对比图。
具体实施方式
下面结合附图对本申请的具体实施方式进行描述。
在本发明中，除非另有说明，否则本文中使用的科学和技术名词具有本领域技术人员所通常理解的含义。并且，本文中所用的试剂、材料和操作步骤均为相应领域内广泛使用的试剂、材料和常规步骤。
实施例1
本实施例提供一种粉末渗锌剂，所述粉末渗锌剂包括以下质量份数的组分：金属粉末20-100份，分散剂40-80份，分解剂0.2-5份，其中，所述金属粉末包括锌粉60-97份和镁粉3-40份。
一方面，锌的原子半径为0.1332纳米，镁的原子半价为0.1598纳米，二者 原子半径差值小于15％，同时镁与锌均为密排六方结构，所以二者可以共同作用形成渗层。虽然镁自身不耐腐蚀，但是其在锌的晶体结构中，能够占据部分锌原子的位置，特别是在晶界处，一定量的镁能够聚集在锌的弱晶界处，并通过高温反应形成MgZn 2、Mg 2Zn 11等锌镁合金相，MgZn 2、Mg 2Zn 11等合金相自身为高耐蚀相，在晶界处形成可以促使原来的弱晶界结构变为强晶界结构，特别是这些强晶界结构对氯离子等腐蚀性物质是不透明的，可以将这些腐蚀性物质阻挡在外面。同时，MgZn 2、Mg 2Zn 11等锌镁合金相在腐蚀过程中，腐蚀产物由普通粉末渗锌的疏松组织转变为致密组织，从而极大提高了金属件的耐腐蚀性能，极大延长了金属件的使用寿命。
另一方面，粉末渗锌剂中镁粉的质量份数为3-40份可以保证在渗层能溶入0.5wt％—20wt％的镁，进而促使形成高耐蚀的MgZn 2、Mg 2Zn 11等高耐蚀合金相，从而极大提高了金属件的耐腐蚀寿命。由于镁自身极为活泼，一般情况下镁总会优先与含氧物质中的氧反应，比如空气中的氧、铁氧化物中的氧、锌氧化物中的氧等，一旦镁表面形成一定含量的氧化物后，镁很难再扩散进入金属体内。
大量实验数据表明，与普通粉末渗锌剂形成的渗层相比，含有0.5wt％—20wt％镁的渗层其耐中性盐雾寿命可以提高数十倍，具有极高的工程应用价值和应用前景。
参见图1，图1为钢铁表面平均镁含量5wt％的含镁渗锌层成分分布图，从图中可以看出，在0-4μm处镁的平均含量为19％，在4-8μm处镁的平均含量为4.2％，在8-12μm处镁的平均含量为3.5％，在12-16μm处镁的平均含量为2％，即渗层从内向外镁含量逐渐增加。这是由于首先发生锌向钢铁件表面的扩散，与铁形成锌铁合金层，然后是镁向锌中的扩散，越向外，锌含量越高铁含量越少，对应的镁含量随着锌含量的增加而增加，该渗层耐盐雾寿命能够达到4000小时。
参见图2，图2为三种不同镁含量渗层的X射线衍射(XRD)相结构对比图，可以看出不论渗层中镁的含量为1wt％、5wt％还是8wt％，其均具有MgZn 2、Mg 2Zn 11等高耐蚀锌镁合金相。
我们对平均含镁5wt％的钢铁件渗层的盐雾寿命进行了分析，检测依据为GB/T10125—2012，结果参见图3，图3是盐雾100小时、2000小时和4000小时后的钢铁件表面状态图，可以看出，在盐雾100小时和2000小时的情况下，钢铁件表面均未出现红锈，在盐雾4000小时的情况下，钢铁件表面才出现红锈。
参见图4-图7，图4-图7分别是盐雾0小时、100小时、2000小时、4000小时钢铁件的断面状态图，可以看出，随着时间的推移，渗层的厚度逐渐减小，在盐雾4000小时的情况下，钢铁件出现腐蚀，可见在粉末渗锌剂中加入适量镁，可以极大的提高渗层的耐中性盐雾寿命。
若镁含量过低，其会主要与含氧物质中的氧反应进而无法进入渗层中。因为镁无法与金属(比如铁)直接反应，因此反应的初始阶段只会发生锌向金属件的扩散，当渗层中锌的浓度达到一定程度时镁才会向锌中扩散，从而形成含镁的渗锌层。尤其是当粉末渗锌剂中镁的含量小于2wt％时，由于反应初期镁不会直接渗入金属件中，此时镁通过与金属件表面氧化膜、锌表面氧化膜发生反应来提高反应活性。当渗层中锌含量达到镁能够渗入条件时，这时由于镁的含量太少，已经几乎被初期的反应消耗殆尽，无法提供足够多的活性镁原子，进而无法渗入到渗层中。若镁含量过高，会导致形成的镁合金偏多，由于镁合金不耐腐蚀进而导致渗层的耐腐蚀性能反而下降，并且，由于镁的活性极强，镁含量过高易引起爆炸，安全性低。
参见图8和图9，图8是平均镁含量为32％的渗层表面图，图9是平均镁含量为32％的渗层断面形貌图。从表面看，渗层表面生成了大量的疏松组织，其主要为镁合金组织。从断面看，镁含量过高，渗层发生了开裂现象，腐蚀性介质直接通过裂纹进入到基体。所以，若镁含量过高，渗层的耐腐蚀性能反而下降。
此外，镁粉可以为纯度大于95％的纯镁粉，也可以为镁的重量比不小于40％的镁合金粉，以提供足够的镁原子渗入渗层。
在本实施例中，金属粉末的质量份数可以为20份、25份、30份、35份、40份、45份、50份、55份、60份、65份、70份、75份、80份、85份、90份、95份、100份等，优选为40-80份，更优选为50-70份，在该金属粉末中锌粉的质量份数可以为60份、65份、70份、75份、80份、85份、90份、95份等，优选为70-90份，更优选为75-85份，锌粉的粒径优选为1μm-200μm，可以为1μm、10μm、30μm、50μm、100μm、150μm、200μm等，镁粉的质量份数可以为3份、5份、10份、15份、20份、25份、30份、35份、40份等，优选为8-38份，更优选为10-35份，镁粉的粒径优选为10μm-500μm，可以为1μm、10μm、30μm、50μm、100μm、150μm、200μm、250μm、300μm、350μm、400μm、450μm、500μm等，均可视具体情况而定，本申请对此不做限制。需要说明的是，若镁粉的粒径小于10μm，则镁粉极易发生爆炸，安 全性极低，若镁粉的粒径大于500μm，则其活性和渗速会快速下降，所以，本实施例对镁粉的粒径并不是随意限定的，只有在其粒径处于10μm-500μm的范围内，其效果发挥才是最为稳定的。
具体地，分散剂优选为陶瓷粉末，陶瓷粉末包括氧化铝、氧化硅、氧化镁、氮化铝、氮化硅、碳化硅中的至少一种。在本实施例提供的粉末渗锌剂中加入陶瓷粉末，可以有效防止金属粉末发生粘结。
在本实施例中，分散剂的粒径优选为5μm-500μm，具体可以为5μm、10μm、50μm、100μm、150μm、200μm、250μm、300μm、350μm、400μm、450μm、500μm等，分散剂的质量份数可以为40份、45份、50份、55份、60份、65份、70份、75份、80份等，可视具体情况而定，本申请对此不做限制。
具体地，分解剂优选为卤化氨，所述卤化氨包括氯化铵、氟化铵、碘化铵、溴化铵、氟化氢氨中的至少一种，优选为氯化铵。在粉末渗锌的温度条件下，卤化氨可以分解提供氨和卤化氢气体，一则能够起到清洁金属件表面的作用，再则卤化氢能够起到活化其他组分的作用，促进渗锌的进行。其中，分解剂的质量份数可以为0.2份、0.5份、1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份等。
总而言之，本实施例提供的粉末渗锌剂，包括金属粉末、分散剂和分解剂，其中，金属粉末包括锌粉和镁粉，如此可以在渗锌的过程中实现镁的渗入，锌与镁能够形成高耐腐蚀的锌镁合金相，从而能够大幅提高渗层的耐腐蚀性能。
实施例2
在实施例1的基础上，本实施例提供一种粉末渗锌剂，该粉末渗锌剂还包括能够促进镁渗入渗层的活性剂0.5-3份，比如0.5份、1份、1.5份、2份、2.5份、3份等，本申请对此不做限制。
具体地，活性剂优选为卤化镁，卤化镁包括氯化镁、氟化镁、碘化镁、溴化镁中的至少一种。
由于在粉末渗锌过程中，卤化镁始终为固态，可以充分的与钢铁件表面及渗层接触反应，有助于从而更易实现镁的渗入，进而加入卤化镁作为活化剂，能够促使镁能快速有效的渗入渗层中，能够促进镁与锌之间的相互作用，能够促进镁在锌晶界处的聚集，进而有效提高渗层的耐腐蚀性能。虽然氯化铵、氟化铵等卤化氨同样具有活化催渗的作用，但其对于镁的活化催渗作用并不强烈。 以氯化铵为例，氯化铵受热分解生成氨和氯化氢气体，镁与气态的氯化氢反应生成的活性镁原子大多数都不会附着在渗层表面与渗层反应。
总而言之，本实施例提供的粉末渗锌剂，包括金属粉末、分散剂、分解剂和活化剂，其中，金属粉末包括锌粉和镁粉，如此可以在渗锌的过程中实现镁的渗入，锌与镁能够形成高耐腐蚀的锌镁合金相，从而能够大幅提高渗层的耐腐蚀性能，活化剂的加入可以进一步促使镁粉向渗层的渗入，进而更进一步地提高粉末渗锌剂的性能。
实施例3
在实施例1或2的基础上，本实施例提供一种粉末渗锌剂，该粉末渗锌剂还包括二氧化锰，二氧化锰的质量份数不大于分解剂的质量份数，具体地，二氧化锰的质量份数可以为0-3份，比如0.01份、0.05份、0.1份、0.2份、0.3份、0.4份、0.5份、1份、1.5份、2份、2.5份、3份等，可视具体情况而定，本申请对此不做限制。
在实际应用中，二氧化锰加入至粉末渗锌剂中可以作为镁的渗入反应催化剂，其通过与作为分解剂的卤化氨反应来促进镁向渗层中的扩散。首先，卤化氨高温分解得到氨和卤化氢气体，然后卤化氢气体与二氧化锰反应得到卤化锰和氯气等气体，氯气等气体能够提供大量活性离子，活性离子与镁反应能够生成活性无水卤化镁气体，最终活性无水卤化镁气体可以与渗层中的锌发生交换，进而发生镁向渗锌层中的扩散。
以氯化铵为例，在350℃的条件下，氯化铵开始分解生成氨和氯化氢，氯化氢与二氧化锰反能够生成氯化锰和氯气，氯气能够在渗层表面提供大量的活性氯离子，活性氯离子与镁反应生成活性无水氯化镁气体，而活性无水氯化镁气体能够与渗层中的锌发生置换反应，进而促进镁向渗层中扩散。
特别是在粉末渗锌剂中还包括卤化镁活性剂的情况下，固态卤化镁能够与气态卤化镁产生双重催渗作用，推动镁源源不断地渗入渗锌层中，以使渗锌层中能够含有足量的镁，并与锌反应形成高耐蚀的锌镁合金相，提高渗层的耐腐蚀性能。
实施例4
本实施例提供一种防腐蚀金属件，该防腐蚀金属件的表面通过实施例1-3任意一项所述的粉末渗锌剂渗入锌与镁形成能够防止金属件腐蚀的渗层。
将表面清理过的金属件与粉末渗锌剂一同装入密封容器中，加热到锌的熔 点(419.4℃)以下，保温一定的时间，然后随炉冷却到室温，金属件的表面就形成了能够防止其腐蚀的渗层。
渗层中镁的平均含量在0.5wt％-20wt％之间，比如1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％等，以保证能够最大限度的提高渗层的耐腐蚀性能。经过大量实验证明，在渗层中的镁含量小于0.5wt％的情况下，即镁的质量份数小于3份的情况下，，镁主要与含氧物质中的氧发生反应，无法进入渗层中，在渗层中的镁含量大于12wt％的情况下，即镁的质量份数大于40份的情况下，渗层中镁含量会偏高，导致形成的镁合金相偏多，由于镁合金自身是极不耐腐蚀的，故渗层的耐腐蚀性能反而明显下降。与普通渗层相比，含有0.5wt％—20wt％镁的渗层其耐中性盐雾寿命可以提高数十倍，具有极高的工程应用价值和应用前景。
渗层的厚度优选为20-100μm，其具体可以为20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm、100μm等，可视具体情况而定，本申请对此不做限制。
其中，渗层中镁的含量随着渗层深度的增加而减少，在渗层中较浅的位置处，镁的含量较多，在渗层中较深的位置处，镁的含量较少。
此外，需要说明的是，渗层的表面镁含量可能会大于20％，这是由于渗层表面会粘附过量的镁粉而导致的渗层表层镁含量较高。但该部分仅仅出现在渗层表层，随着腐蚀的进行，高镁含量的渗层表层很快会被腐蚀，进而露出镁含量在0.5wt％-20wt％的能够防止金属件被腐蚀的渗层，在该渗层中，镁能够聚集在锌的弱晶界处，并通过高温反应形成MgZn 2、Mg 2Zn 11等锌镁合金相，MgZn 2、Mg 2Zn 11等合金相自身为高耐蚀相，在晶界处形成可以促使原来的弱晶界结构变为强晶界结构，特别是这些强晶界结构对氯离子等腐蚀性物质是不透明的，可以将这些腐蚀性物质阻挡在外面。同时，MgZn 2、Mg 2Zn 11等锌镁合金相在腐蚀过程中，腐蚀产物由普通粉末渗锌的疏松组织转变为致密组织，从而极大提高了金属件的耐腐蚀性能，极大延长了金属件的使用寿命。
参见图10和图11，图10是普通渗锌层表面腐蚀产物放大图，图11是本实施例提供的防腐蚀金属件的含镁渗锌层表面腐蚀产物放大图，可以明显看出，普通渗锌层的表面腐蚀产物数量远远多于本实施例提供的防腐蚀金属件的含镁渗锌层表面腐蚀产物。换而言之，本实施例提供的防腐蚀金属件，由于其渗锌层含有一定量的镁而使得其耐腐蚀性能得到了显著的提高。
实施例5
本实施例提供一种渗锌方法，包括步骤S1至步骤S3。
S1、对待渗锌的金属件进行除油除锈处理，并将处理后的金属件与实施例1或2所述的粉末渗锌剂共同置于密闭渗罐中。
S2、驱赶所述密闭渗罐中的空气，并关闭所述密闭渗罐的阀门。
在实际应用中，可以对所述密闭渗罐进行抽真空处理，或向所述密闭渗罐中通入保护气氛以驱赶所述密闭渗罐中的空气，并关闭所述密闭渗罐的阀门。其中，保护气氛优选为惰性气体。
S3、对所述密闭渗罐进行升温处理，升温至预设温度后保温1-10小时，完成渗锌。
在实际应用中，可以对所述密闭渗罐进行升温处理，升温至360℃-415℃或320℃-480℃的情况下保温1-10小时，比如2小时、4小时、6小时、8小时等，即可完成渗锌。其中，在粉末渗锌剂为静态粉末的情况下，预设温度优选为360℃-415℃，比如360℃、370℃、380℃、390℃、400℃、410℃、415℃等，在粉末渗锌剂为动态粉末的情况下，预设温度优选为320℃-480℃，比如320℃、340℃、360℃、380℃、400℃、420℃、440℃、460℃、480℃等。
本实施例提供的渗锌方法，通过驱赶所述密闭渗罐中的空气，可以有效避免粉末渗锌剂中的镁与空气反应，通过对所述密闭渗罐进行升温处理，不仅可以进一步驱赶密闭渗罐中的空气，同时还创造了完成金属件渗锌的适宜环境条件，升温至预设温度后保温1-10小时，完成渗锌，渗锌效果好，渗层质量高。本申请提供的渗锌方法，操作简单，使用方便，成本低廉，经济效益高，适用范围广。
实施例6
本申请提供的粉末渗锌剂及渗锌方法对于其能够应用的多个方面均带来了显著的改善，在此以防雷接电、铁路扣件、高强度紧固件为例进行具体说明。
其一，防雷接电方面，目前防雷接电采用的防腐方式普遍为电镀铜，一方面电镀铜成本很高，目前一吨接地件的电镀铜加工费两万多元，另一方面，在碱性土壤等环境中，铜容易发生腐蚀，易导致接地件的提前腐蚀而失效，同时还会对土壤、水源等环境造成重金属污染。目前单纯的电镀锌、热镀锌、粉末渗锌这些产品耐腐蚀性能达不到接地标准要求，要想达到耐腐蚀要求就必须要做封闭等处理，但一旦做了封闭等处理，接地件电导率明显下降，达不到防雷 接地的导电性要求。
采用本申请提供的粉末渗锌剂及渗锌方法，可以完美解决上述问题。由于粉末渗锌剂中加入了镁粉，极大的提高了其渗锌后的耐腐蚀性能，不需要封闭等处理耐腐蚀性能、使用寿命即可达到标准要求，并且锌和镁对生态环境也不会造成任何污染。同时，本申请提供的粉末渗锌剂及渗锌方法总共成本不到五千元/吨，能够极大降低防雷接电行业的整体成本。
其二，铁路扣件方面，目前铁路扣件普遍采用粉末渗锌加封闭处理的方法进行渗锌处理，但在铁路的高震动服役环境下，实际使用寿命远远达不到设计要求，实际使用寿命往往还没有达到设计寿命一半的时间，铁路扣件就已经整体更换了一遍。
采用本申请提供的粉末渗锌剂及渗锌方法，通过实现铁路扣件渗层中适量镁的渗入，能够大大提高其耐腐蚀性能，极大延长其使用寿命，完全可以满足地铁等特殊场景的高标准要求。
福建郭坑铁路工务设备有限公司于2019年10月对采用本申请所述粉末渗锌剂及渗锌方法的铁路电频进行了盐雾、二氧化硫腐蚀等试验，检测结果显示采用本申请所述粉末渗锌剂及渗锌方法进行渗锌处理后的铁路垫片在吹砂后盐雾的使用寿命大于2000小时和1000小时。而现有的粉末渗锌后续的封闭、达克罗等处理都是无机、有机涂料，在模拟风沙吹蚀条件下，通常会迅速被吹落直接露出渗锌层，普通渗锌层耐盐雾寿命往往只有几十小时。特别是针对地铁铁路高达100年以上设计寿命的要求，该技术具有极好的应用前景。
机械工业表面覆盖层产品质量监督检测中心(武汉材料保护研究所有限公司表面工程实验室)于2019年12月对采用本申请所述粉末渗锌剂及渗锌方法渗锌的地铁铁路垫片进行了中性盐雾试验(NSS试验)检测，检测结果显示通过本实施例所述的方法进行渗锌处理的地铁铁路垫片，经1500小时中性盐雾试验后，试样表面未出现红锈。
这足以说明本申请提供的粉末渗锌剂及渗锌方法完全能够实现铁路所用金属件高耐蚀的渗锌层制备，金属件在渗锌后其耐中性盐雾寿命可以达到1500小时以上，同时还可以省去后续封闭、达克罗等涂层处理，不仅简化了工艺，还极大提高了金属件的性能。
其三，高强度紧固件方面，以风电行业为例，风电行业中的风电螺栓为高强度紧固件，目前采用的方法多为粉末渗锌加封闭或者达克罗，后续维护基本 靠刷漆。风电螺栓一旦安装后很难更换，一旦因为腐蚀问题发生断裂失效，会造成极大的财产损失甚至人员伤亡。
采用本申请提供的粉末渗锌剂及渗锌方法则不会出现上述问题。在渗层中引入镁元素，热扩散过程中形成MgZn 2与Mg 2Zn 11等耐腐蚀的合金相。渗层在腐蚀过程中，镁锌合金相促使产生致密不易溶的腐蚀产物；同时，MgZn 2等合金组织自身结构致密，有效降低了腐蚀速率。当渗层表面被划伤后，在受损部位还能很快形成一层致密的化合物层，阻止腐蚀的进一步发生，从而具有自修复的功能，能够完美适用于高强度紧固件。
实施例7
本试验例提供试验组1-4。试验组1-4均使用相同的金属件，其中试验组1对金属件进行电镀锌处理，试验组2对金属件进行热浸锌处理，试验组3对金属件进行粉末渗锌和封闭处理，试验组4采用实施例1所述的粉末渗锌剂和实施例4所述的方法对金属件进行渗锌处理，处理完成后检测各组金属件的硬度、耐腐蚀寿命、氢脆性、抗盐雾性、渗层厚度、耐磨性、抗二氧化硫性等性能进行检测，结果如表1所示。
表1各组金属件使用性能对比表
使用性能 试验组1 试验组2 试验组3 试验组4
硬度(HV) 180-200 180-200 300-380 300-400
耐腐蚀寿命 ＜1年 5-10年 ＞20年 ＞50年
氢脆性 有氢脆 有氢脆 无氢脆 无氢脆
抗盐雾试验 ＜100h ＞100h 300-1000h ＞1500h
渗层厚度 5-30μm 5-70μm 20-120μm 5-200μm
公差影响 较小 较大 较小 较小
耐磨性 一般 一般 好 好
抗二氧化硫 差 差 一般 好
外观均匀性 较好 差 好 好
从以上数据中可以看出，采用本申请提供的粉末渗锌剂及渗锌方法对金属件进行渗锌处理，硬度强，耐腐蚀寿命长，无氢脆，抗盐雾和抗二氧化硫效果好，此外，本申请提供的粉末渗锌剂不会对环境造成任何污染，能够在市区进行建厂制造，前景广阔。
实施例8
本实施例的粉末渗锌剂包括以下组分：粒径10μm的锌粉35份、粒径20μm的镁粉10份、粒径50μm的氧化铝粉50份、氯化铵5份。
按照上述比例分别称取相应重量份的组分与45号钢圆钢(重量份为4000份)共同放入旋转渗锌炉中(转速15转/分钟)，升温至300℃时，氯化铵开始分解，有大量气体排出，温度至350℃时，关闭渗锌炉渗罐阀门，使其处于低氧密封状态。400℃保温6小时，得到含镁渗锌层，渗层厚度55μm，耐中性盐雾时间400小时(经400小时中性盐雾试验后，试样表面未出现红锈)。
由此可见，锌与镁能够形成高耐腐蚀的锌镁合金相，从而能够大幅提高渗层的耐腐蚀性能。
实施例9
本实施例的粉末渗锌剂包括以下组分：粒径10μm的锌粉32份、粒径30μm的AZ91镁合金粉5份、粒径50μm的氧化铝粉60份、氯化铵2份、氯化镁1份。
按照上述比例分别称取相应重量份的组分与Q235防雷接地杆(重量份为3000份)共同放入旋转渗锌炉中，抽真空至真空度达到1000Pa以内，关闭渗锌罐阀门，使其处于低氧密封状态。410℃保温6小时，得到含镁渗锌层，渗层厚度62μm，耐中性盐雾时间1000小时(经1000小时中性盐雾试验后，试样表面未出现红锈)。
由此可见，在粉末渗锌剂中既加入镁粉又加入卤化镁活性剂的情况下，卤化镁活性剂能够促使镁能快速有效的渗入渗层中，进而更进一步提高渗层的耐腐蚀性能。
实施例10
本实施例的粉末渗锌剂包括以下组分：粒径5μm的锌粉32份、粒径20μm的AZ31镁合金粉15份、粒径20μm的氧化铝粉50份、氯化铵2份、氯化镁1份。
按照上述比例分别称取相应重量份的粉体及活化剂，与Q235防雷接地杆(重量份为3000份)共同放入旋转渗锌炉中(转速20转/分钟)，抽真空至真空度达到1000Pa以内，关闭渗锌罐阀门，使其处于低氧密封状态。410℃保温6小时，得到含镁渗锌层，渗层厚度62μm，耐中性盐雾时间1600小时(经1600小时中性盐雾试验后，试样表面未出现红锈)。
由此可见，在粉末渗锌剂中既加入镁粉又加入卤化镁活性剂的情况下，卤化镁活性剂能够促使镁能快速有效的渗入渗层中，进而更进一步提高渗层的耐腐蚀性能。
实施例11
本实施例的粉末渗锌剂包括以下组分：粒径5μm的锌粉38份、粒径10μm的自制镁合金粉5份、粒径20μm的氧化铝粉55份、氯化铵1份、氯化镁1份。其中自制镁合金粉成分按重量百分比为：镁80％、铝15％、锌5％。
按照上述比例分别称取相应重量份的粉体及活化剂，与60Si 2Mn铁路垫片(重量份为5000份)共同放入旋转渗锌炉中(转速30转/分钟)，充入氩气，待氩气充满渗罐赶走空气后开始升温，升温、保温、降温过程中持续通入氩气，保证整个过程都是保护气氛环境。415℃保温8小时，得到含镁渗锌层，渗层厚度80μm，耐中性盐雾时间2000小时(经2000小时中性盐雾试验后，试样表面未出现红锈)。
由此可见，在粉末渗锌剂中既加入镁粉又加入卤化镁活性剂的情况下，卤化镁活性剂能够促使镁能快速有效的渗入渗层中，进而更进一步提高渗层的耐腐蚀性能。
实施例12
本实施例的粉末渗锌剂包括以下组分：粒径1μm的锌粉44份、粒径5μm的AZ91镁合金粉14份、粒径10μm的氧化硅粉40份、氯化镁2份。
按照上述比例分别称取相应重量份的粉体及活化剂，与40CrMo钢模具(重量份为1000份)共同放入静态渗锌炉中(转速0转/分钟，保证精密件产品之间不会发生碰撞变形)，抽真空至真空度达到100Pa以内，关闭渗锌罐阀门，使其处于真空状态。385℃保温8小时，保温过程中保证渗罐内真空度在100Pa以内，得到含镁渗锌层，渗层厚度40μm，耐中性盐雾时间1000小时(经1000小时中性盐雾试验后，试样表面未出现红锈)。
由此可见，在粉末渗锌剂中既加入镁粉又加入卤化镁活性剂的情况下，卤化镁活性剂能够促使镁能快速有效的渗入渗层中，进而更进一步提高渗层的耐腐蚀性能。
实施例13
本实施例设置试验组和对照组，各组的粉末渗锌剂组成成分如表2所示。
表2各组粉末渗锌剂组成成分示意表
组别 粉末渗锌剂组成成分
试验组 锌粉40份+镁粉8份+氧化铝粉50份+氯化铵1份+氟化镁1份
对照组 锌粉40份+铝粉8份+氧化铝粉50份+氯化铵1份+氟化镁1份
采用试验组和对照组的粉末渗锌剂以及实施例5所述的渗锌方法对金属件进行渗锌处理，并进行盐雾试验，结果如图12所示。
参见图12，其中在盐雾试验进行0h即试验刚刚开始时，试验组和对照组的金属件均处于无任何锈迹的初始状态，在盐雾试验进行100h时，对照组的金属件上出现大量白锈，而试验组的金属件上仅出现少量白锈，在盐雾试验进行200h时，对照组的金属件上出现明显红锈，至此结束对照组试验，而试验组的金属件上仍然仅存在少量白锈，在盐雾试验进行1000h时，试验组的金属件上还是仅存在少量白锈，在盐雾试验进行2000h时，试验组的金属件上白锈增多。
可见，在盐雾试验中，对照组金属件出现红锈的时间远小于试验组金属件出现红锈的时间，对照组的试验结果远不如试验组的试验结果，所以采用锌粉、铝粉等成分组成的粉末渗锌剂对金属件进行渗锌处理，形成的锌铝渗层对于耐腐蚀性能的提高十分有限，而采用本实施例提供的粉末渗锌剂对金属件进行渗锌处理，可以显著提高其渗层的耐腐蚀性能，显著延长金属件的使用寿命。
实施例14
本实施例设置试验组1-4，各组的粉末渗锌剂组成成分如表3所示。
表3各组粉末渗锌剂组成成分示意表
Figure PCTCN2020113896-appb-000001
分别采用试验组1-4的粉末渗锌剂以及实施例5所述的渗锌方法对金属件进行渗锌处理，并进行盐雾试验，结果如表4所示。
表4各组粉末渗锌剂盐雾试验结果对比表
Figure PCTCN2020113896-appb-000002
Figure PCTCN2020113896-appb-000003
可见，采用试验组1的粉末渗锌剂对金属件进行渗锌处理后，形成渗层的金属件在盐雾试验100h后出现大量白锈，200h出现明显红锈；采用试验组2和试验组3即本申请提供的粉末渗锌剂对金属件进行渗锌处理后，形成锌镁渗层的金属件在盐雾试验100h-3000h的情况下均仅出现少量白锈，在3500h后才出现大量白锈，可见其耐腐蚀性能有了显著的提高；采用试验组4的粉末渗锌剂对金属件进行渗锌处理后，形成渗层的金属件在盐雾试验100h后出现大量白锈，200h出现明显红锈，与试验组1无甚差异，可见如试验组4的在粉末渗锌剂中加入过多组分并未对其耐腐蚀性能有任何改善。
这是由于粉末渗锌属于固固反应，是通过固相扩散形成渗层的，单一元素的粉末渗锌易于实现，而多元共渗则相反。当粉末渗锌剂中所含各元素之间形成在高温扩散温度下温度的化学化合物或固溶度很小的金属间化合物时，渗剂的活性显著降低。在二元渗剂中，随着其中一组元浓度的增加，会减少另一组元原子的活性。而在渗剂中的两个渗入元素比例恰好符合化学化合物的成分比例的情况下，无法扩散形成渗层。如果粉末渗锌剂的其中一种渗入元素的量多于形成化合物所要求的量，则仅会产生该元素的渗入。对于三元以上多元合金共渗，则机理更为复杂。因此，对于粉末渗锌而言，采用最简单的组分和最简化的催化剂形成特定的渗层，才具有工程应用价值。
参见试验组4，该组提供的粉末粉末渗锌剂中同时添加了锌粉、镁粉、铝粉等多种金属粉末，以其中的锌粉、镁粉、铝粉为例，铝的活性强于锌，因此镁首先与铝发生反应，一旦镁与铝反应就会形成性能稳定的镁铝化合物，性能稳定的镁铝化合物无法渗入渗锌层中，因为其无法提供扩散所需的化学驱动力。因此，在粉末渗锌剂中同时添加镁和铝，要想镁能够渗入渗锌层中，镁的含量通常要高于铝的含量，比如若渗剂金属中铝的含量为5wt％，则镁的含量可以为 7wt％等，以提供足量的活性镁原子向渗锌层中扩散。若渗剂中除了镁、铝还有其它合金元素时，则镁的含量往往还需进一步提高以促使镁向渗锌层中的扩散。
此外，在以锌铝合金为主的渗层中，在粉末渗锌剂中添加一定量的镁，镁在一定程度上是可以渗入渗层组织中的，但由于渗锌层中铝的存在，镁同样会优先与铝反应，并在渗层中形成镁铝合金相组织，镁铝合金相虽然可以起到细化渗层组织晶粒的作用，但无法起到提高耐腐蚀性能的作用。由于镁优先与渗层中的铝反应，镁基本无法再与渗层中的锌反应形成高耐蚀的MgZn 2、Mg 2Zn 11等高耐蚀锌镁合金相，无法提高渗层的耐腐蚀性能。
在本文中，“上”、“下”、“前”、“后”、“左”、“右”等仅用于表示相关部分之间的相对位置关系，而非限定这些相关部分的绝对位置。
在本文中，“第一”、“第二”等仅用于彼此的区分，而非表示重要程度及顺序、以及互为存在的前提等。
在本文中，“相等”、“相同”等并非严格的数学和/或几何学意义上的限制，还包含本领域技术人员可以理解的且制造或使用等允许的误差。
除非另有说明，本文中的数值范围不仅包括其两个端点内的整个范围，也包括含于其中的若干子范围。
上面结合附图对本申请优选的具体实施方式和实施例作了详细说明，但是本申请并不限于上述实施方式和实施例，在本领域技术人员所具备的知识范围内，还可以在不脱离本申请构思的前提下做出各种变化。

Claims (10)

  1. 一种粉末渗锌剂，其特征在于，所述粉末渗锌剂包括以下质量份数的组分：金属粉末20-100份，分散剂40-80份，分解剂0.2-5份，其中，所述金属粉末包括锌粉60-97份和镁粉3-40份。
  2. 根据权利要求1所述的粉末渗锌剂，其特征在于，所述镁粉为纯镁粉或镁合金粉；
    优选地，所述镁粉为纯度大于95％的纯镁粉或镁的重量比不小于40％的镁合金粉。
  3. 根据权利要求1所述的粉末渗锌剂，其特征在于，所述分散剂为陶瓷粉末，所述分解剂为卤化氨。
    优选地，所述陶瓷粉末包括氧化铝、氧化硅、氧化镁、氮化铝、氮化硅、碳化硅中的至少一种；
    更为优选地，所述卤化氨包括氯化铵、氟化铵、碘化铵、溴化铵、氟化氢氨中的至少一种。
  4. 根据权利要求1所述的粉末渗锌剂，其特征在于，所述粉末渗锌剂还包括能够促进镁渗入渗层的活性剂0.5-3份；
    优选地，所述活性剂为卤化镁。
  5. 根据权利要求1所述的粉末渗锌剂，其特征在于，所述镁粉的粒径为10μm-500μm，所述锌粉的粒径为1μm-200μm，所述分散剂的粒径为5μm-500μm。
  6. 根据权利要求1所述的粉末渗锌剂，其特征在于，所述粉末渗锌剂还包括二氧化锰，所述二氧化锰的质量份数不大于所述分解剂的质量份数。
  7. 一种防腐蚀金属件，其特征在于，所述防腐蚀金属件的表面通过权利要求1-6任意一项所述的粉末渗锌剂渗入锌与镁形成能够防止金属件腐蚀的渗层。
  8. 根据权利要求7所述的防腐蚀金属件，其特征在于，所述渗层中镁的平均含量为0.5wt％-20wt％；
    优选地，所述渗层的厚度为5μm-200μm。
  9. 一种渗锌方法，其特征在于，包括：
    S1、对待渗锌的金属件进行除油除锈处理，并将处理后的金属件与权利要求1-6任意一项所述的粉末渗锌剂共同置于密闭渗罐中；
    S2、驱赶所述密闭渗罐中的空气，并关闭所述密闭渗罐的阀门；
    S3、对所述密闭渗罐进行升温处理，升温至预设温度后保温1-10小时，完成渗锌。
  10. 根据权利要求9所述的渗锌方法，其特征在于，在步骤S2中，对所述密闭渗罐进行抽真空处理，或向所述密闭渗罐中通入保护气氛驱赶所述密闭渗罐中的空气，并关闭所述密闭渗罐的阀门。
    在步骤S3中，对所述密闭渗罐进行升温处理，升温至360℃-415℃或320℃-480℃的情况下保温1-10小时，完成渗锌。
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