CN115725906A - Zinc-aluminum-magnesium-plated non-magnetization annealing electromagnetic pure iron steel plate for high-voltage direct-current relay and manufacturing method thereof - Google Patents
Zinc-aluminum-magnesium-plated non-magnetization annealing electromagnetic pure iron steel plate for high-voltage direct-current relay and manufacturing method thereof Download PDFInfo
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Abstract
Zinc-aluminum-magnesium-plated magnetization-free annealing electromagnetic pure material for high-voltage direct-current relayThe non-magnetized annealed electromagnetic pure iron comprises an electromagnetic pure iron substrate and a zinc-aluminum-magnesium alloy coating on the surface of the electromagnetic pure iron substrate, and the obtained non-magnetized annealed electromagnetic pure iron has better magnetic performance and excellent corrosion resistance by adjusting the components of the coating and controlling the coating amount of the coating, wherein the average coercive force is 50-100A/m, and the magnetic induction intensity B is 5000 Greater than 1.71T, magnetic permeability mu m The alloy is more than 8mH/m, can be directly processed into large-size parts represented by high-voltage direct-current relay yoke iron, saves the conventional part magnetizing annealing and Ni electroplating post-treatment process, shortens the manufacturing process, improves the production efficiency, reduces the environmental protection investment, reduces the part cost, has corrosion resistance on a bare substrate at a notch after being processed into the parts, and solves the problem of poor deep plating capability in the electroplated parts after the parts are prepared by adopting the traditional electromagnetic pure iron.
Description
Technical Field
The invention relates to the technical field of electromagnetic pure iron, in particular to a zinc-aluminum-magnesium plated non-magnetized annealed electromagnetic pure iron steel plate for a high-voltage direct-current relay and a manufacturing method thereof.
Background
The main circuit voltage of the new energy automobile is generally larger than 200V, and the current is also larger, so that the new energy automobile needs to specially develop a high-voltage direct-current relay besides a low-voltage relay needed by a traditional automobile. The high-voltage direct-current relay is different from a conventional low-voltage relay, in order to fully utilize the magnetic energy generated by an electromagnetic coil, a design that a circumferential magnetic field attracts a contact arc to leave a contact area is adopted in the structure of the high-voltage direct-current relay, a relay yoke is usually designed into a deep-drawing cylindrical or zigzag structure, and the volume of parts is obviously increased compared with that of the conventional low-voltage relay. The part not only requires the material to have good magnetic conductivity and small residual magnetism, but also requires the part to have certain corrosion resistance in the use environment.
Generally, magnetic conductive materials are made of electromagnetic pure iron with different grades specified in the national standard GB/T6983-2008, but the pure iron materials have poor corrosion resistance, and parts need to be subjected to nickel plating and chromium plating treatment to obtain a plating layer with good corrosion resistance. The GJB 360A standard stipulates that the 5% salt spray test adopted for 48h should not have cracking, sheet dropping, coating peeling or matrix metal uncovering phenomena which are caused by corrosion and can have harmful influence on the application or performance of the relay. Besides, part of users also put forward 96h, 192h and even 400h salt spray resistant time requirements without red rust according to product application occasions.
Based on the above requirements, in the conventional technology, the yoke iron in the high-voltage direct-current relay is manufactured by the following process: adopting an annealed cold-rolled electromagnetic pure iron base material, and shearing and stamping the base material to form a part; then carrying out magnetization annealing treatment on the part to eliminate cold machining lattice distortion, thereby fully exerting the magnetic property of the raw material; in order to avoid corrosion failure of the iron part in the using process, the part subjected to magnetization annealing is subjected to corrosion prevention post-treatment such as acid washing, ni electroplating and the like, and then the subsequent assembly link can be performed. The part processing process flow of the technology is long, and the following problems exist:
the first problem is that the efficiency of magnetizing annealing heat treatment and batch electroplating of parts is greatly reduced due to the large size of the high-voltage direct-current relay, and the improvement of the production efficiency is not facilitated.
To solve the problem, chinese patent CN106555034A discloses a "continuous annealing method for a low coercive force cold-rolled electromagnetic pure iron plate, and chinese patent CN108118250B discloses" a bending cracking resistant magnetization-free annealed electromagnetic pure iron and a manufacturing method thereof ", which respectively disclose two methods for obtaining magnetization-free annealed electromagnetic pure iron through composition control and continuous annealing process combination, but parts prepared by using the electromagnetic pure iron still need to be subjected to post-treatment such as electroplating, which is not favorable for improving production efficiency.
Chinese patent CN107794458A discloses "magnetization-free electromagnetic pure iron with high bending resistance and manufacturing method thereof", and also discloses a method for obtaining magnetization-free annealed electromagnetic pure iron through combination of component control and cover annealing process. For the high-voltage direct-current relay, the problems that the magnetizing annealing process is long in period, the requirement on annealing equipment is high, and the yield is limited by the charging amount are solved, but the problem that the corrosion resistance of the electromagnetic pure iron is poor is not solved, and post-treatment processes such as electroplating and the like are still needed after parts are made.
The second problem is that the deep plating capability inside the parts represented by deep-drawing cylindrical yoke iron is poor, it is always difficult to obtain uniform plating layers at positions such as deep recesses, blind holes and the like of the workpiece, the plated Ni layer is thin and even has no plating layer, and the internal corrosion-resistant effect is difficult to ensure.
Chinese patent CN1283849C discloses "a nickel-plated steel sheet for an alkaline manganese battery positive electrode can and an alkaline manganese battery positive electrode can" which solve the problem that it is difficult to obtain stable battery characteristics due to non-uniform cracking of a plating layer caused by fluctuation of press working conditions, which is caused by cracks generated in the plating layer during press working of a conventional nickel-plated steel sheet, by forming a nickel-based diffusion plating layer on a surface to be an inner surface of the can and by forming a large number of ultra-fine pinholes on the surface.
The method forms a pre-plated nickel diffusion coating on the surface of a steel plate, and then the pre-plated nickel diffusion coating is processed into an alkaline manganese battery anode tank body, so that the traditional method of plating Ni after being processed into the tank body is replaced, and the problem of poor deep plating capability in the battery shell is solved.
With the optimization of the new energy automobile product structure, the processing and production processes of parts are simplified, and the production of products with higher cost performance and market competitiveness is the requirement of the relay industry.
Disclosure of Invention
The invention aims to provide a zinc-aluminum-magnesium plated magnetization-free annealed electromagnetic pure iron steel plate for a high-voltage direct-current relay and a manufacturing method thereof, and the magnetization-free annealed electromagnetic pure iron steel plate with a zinc-aluminum-magnesium alloy coating is obtained, so that the magnetization-free annealed electromagnetic pure iron steel plate has good magnetic performance and corrosion resistance, a bare matrix at a notch of a part after processing also has corrosion resistance, and the magnetization-free annealed electromagnetic pure iron steel plate can be directly processed into a large-size part represented by a high-voltage direct-current relay yoke, so that the post-treatment processes of magnetization annealing, coating and the like after the conventional electromagnetic pure iron is prepared into the part are omitted, and the problem of poor deep plating capacity inside the part caused by electroplating after the conventional electromagnetic pure iron is prepared into the part is solved, the manufacturing process is shortened, the production efficiency is improved, the environmental protection investment is reduced, and the part cost is reduced. Meanwhile, the average coercive force of the electromagnetic pure iron steel plate is 50-100A/m, and the magnetic induction intensity B is 5000 1.71T and magnetic permeability mu m More than 8mH/m; in the neutral salt spray test of ASTM B117-73, the red embroidery resistance time of planes, cuts and drawing processing parts exceeds 1000h.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a non-magnetized annealed electromagnetic pure iron steel plate plated with zinc-aluminum-magnesium for a high-voltage direct-current relay comprises an electromagnetic pure iron substrate and a zinc-aluminum-magnesium alloy plating layer on the surface of the electromagnetic pure iron substrate; wherein the content of the first and second substances,
the electromagnetic pure iron substrate comprises the following chemical components in percentage by mass: c is less than or equal to 0.005%, si is less than or equal to 0.01%, mn:0.1 to 0.5 percent of Fe and other inevitable impurities, less than or equal to 0.015 percent of P, less than or equal to 0.01 percent of S, less than or equal to 0.005 percent of Al or less than or equal to 0.1 to 1.5 percent of Al, less than or equal to 0.005 percent of N, less than or equal to 0.015 percent of O, less than or equal to 0.007 percent of B or less than or equal to 0.1 percent of Cr, more than or equal to 10 percent of Mn/S, and the balance of Fe and other inevitable impurities; the coating amount of the zinc-aluminum-magnesium alloy coating is more than or equal to 30/30g/m 2 (ii) a Wherein:
the zinc-aluminum-magnesium alloy coating comprises the following chemical components in percentage by mass: al: 3.0-15.0%, mg:0.5 to 4%, ti:0 to 0.1%, B:0 to 0.05%, si:0 to 2.0%, fe:0 to 2.0 percent, and the balance of Zn and other inevitable impurities.
The zinc ratio index I of the magnetization-free annealed electromagnetic pure iron steel plate is as follows: 100-150 g/mm; the zinc ratio index I = total weight of zinc-aluminum-magnesium alloy plating layer/thickness of steel sheet.
The average coercive force of the magnetization-free annealed electromagnetic pure iron steel plate is 50-100A/m, and the magnetic induction intensity B 5000 1.71T and magnetic permeability mu m ＞8mH/m。
When the magnetization-free annealed electromagnetic pure iron steel plate is subjected to a neutral salt spray test of ASTM B117-73, the red embroidery resistance time of planes, notches and drawn parts exceeds 1000h.
In the component design of the electromagnetic pure iron substrate, the following components are adopted:
c: carbon is a harmful element in the electromagnetic pure iron, and the magnetic aging of the electromagnetic pure iron is iron nitride (Fe) which is a compound of N and C elements which are supersaturated and solid-dissolved at normal temperature 16 N 4 ) And the form of epsilon iron carbide. C. N is interstitial atom, and C and N in molten steel at high temperature haveThe higher solid solubility gradually reduces with the cooling of molten steel, so that the precipitated C and N cannot form supersaturated solid solution in alpha-Fe. When the electromagnetic pure iron material works for a long time, particularly because of temperature rise, redundant C and N atoms are in the form of finely dispersed epsilon carbide and acicular iron nitride (Fe) 16 N 4 ) Separating out particles. And the tiny C and N inclusions are nonmagnetic phases, and only can increase the internal stress of the material, pin magnetic domain movement is harmful to magnetism, so that the coercive force of the material is increased, the magnetic permeability is reduced and the magnetic induction intensity is reduced. Therefore, the mass percentage of carbon in steel should be reduced as much as possible in the substrate of the invention, and the content of C is controlled to be less than or equal to 0.005 percent.
Si: silicon exists in alpha-Fe in the form of solid solution, the saturation magnetic induction intensity is reduced due to the increase of the content of the silicon, and pure iron is generally only used in direct current occasions, so the silicon is not generally used as an addition element of electromagnetic pure iron, and the mass percentage of the silicon in the electromagnetic pure iron needs to be controlled. In the invention, the content of Si is controlled to be less than or equal to 0.01 percent.
Mn: manganese in the steel forms MnS with sulfur, and the hot brittleness phenomenon caused by FeS with low melting point formed along the grain boundary can be prevented. Therefore, the Mn/S ratio in the substrate composition is more than or equal to 10 (namely the mass percentage ratio of Mn to S is more than or equal to 10), so that the hot rolling plasticity is improved, and MnS is coarsened; in addition, the improvement of the Mn content can also play a certain strengthening role on the pure iron while having little influence on the magnetic performance of the electromagnetic pure iron, and meet the requirements of different strength levels, so the Mn content is controlled to be 0.10-0.50 percent in the invention.
P: phosphorus is used to reduce the gamma phase region and promote grain growth. Segregation of phosphorus along grain boundaries can increase the (110) component and decrease the (111) component, and therefore, also has an effect of increasing magnetic induction. In addition, phosphorus can improve the hardness; however, when the phosphorus content is more than 0.015% by mass, particularly when the carbon content is very low, cold workability deteriorates and cold brittleness of the product increases. Therefore, the P content is controlled to be less than or equal to 0.015 percent in the invention.
S: sulfur is an element extremely harmful to pure ferromagnetism, and Mn and S form MnS, so that the hot brittleness phenomenon caused by FeS with a low melting point formed along a grain boundary can be prevented, and therefore, mn/S is controlled to be more than or equal to 10 to improve hot rolling plasticity and coarsen the MnS in the technical scheme. Therefore, the S content is controlled to be less than or equal to 0.01 percent in the invention.
Al: aluminum is an important component of electromagnetic pure iron and has an important influence on the magnetic performance of products. The aluminum element significantly affects the existence form of the inclusion in the electromagnetic pure iron, and two extreme measures are generally taken for controlling the aluminum. This is because Al is most likely to form fine AlN in the range of 0.005 to 0.014%, thereby preventing ferrite grains from growing and increasing the orientation detrimental to magnetic properties, and when Al is less than or equal to 0.005%, the magnetically advantageous orientation component increases and the grains are coarser; when the aluminum content is more than 0.15%, coarse AlN can be formed, the grain growth resistance is reduced, the magnetic anisotropy is reduced, and simultaneously, the deoxidation is promoted and the inclusion quantity is reduced. Therefore, the Al content is controlled to be less than or equal to 0.005 percent or between 0.1 and 1.5 percent.
N: nitrogen is a harmful element in electromagnetic pure iron, and the magnetic aging of the electromagnetic pure iron is iron nitride (Fe) which is a compound of N and C elements which are supersaturated and solid-dissolved at normal temperature 16 N 4 ) And epsilon iron carbide. Therefore, the nitrogen content is controlled to be less than or equal to 0.005% in the present invention.
O: oxygen is a harmful element in electromagnetic pure iron, forming SiO 2 、Al 2 O 3 And oxides such as MnO and the like are doped to reduce magnetism, and fine oxides prevent crystal grains from growing, so that magnetization is strongly influenced, and coercive force is increased. In addition, oxygen can also accelerate the diffusion rate of nitrogen in alpha-Fe, and indirectly accelerate the occurrence of magnetic aging. Therefore, the oxygen content is controlled to be less than or equal to 0.015 percent in the invention.
B: boron preferentially forms BN with nitrogen in the gamma phase, prevents AlN precipitation during hot rolling, and reduces the harm of fine AlN. In addition, B can reduce the (111) phase strength, coarsen the crystal grains, and improve the magnetic properties. When the amount of B added is too high, the production cost is increased, the crystal grains become fine, and the mechanical properties are deteriorated. Therefore, the content of B is controlled to be less than or equal to 0.007 percent in the invention.
Cr: the addition of chromium causes the reduction of the magnetic performance of the steel sheet, but earlier researches found that the influence of the addition of a small amount of Cr on ferrite lattices is limited, and the addition of Cr does not cause magnetismThe strength and the hardness of the steel are improved while the performance is greatly changed, so that the processing performance of the electromagnetic pure iron is improved. However, in consideration of excessive addition of Cr, on one hand, the coercive force of the electromagnetic pure iron is improved, and on the other hand, feCr which is not easy to remove by acid washing is formed on the surface of the material in the heat treatment process 2 O 4 And in turn, surface properties. Based on the above, the content of C is controlled to be less than or equal to 0.1 percent in the invention.
In the chemical composition design of the zinc-aluminum-magnesium alloy plating layer, the chemical composition of the zinc-aluminum-magnesium alloy plating layer is as follows:
al: al in the coating can obviously improve the corrosion resistance of the steel plate, the corrosion resistance can be better improved by the Al content of more than 3.0 percent generally, when the Al content is more than 15.0 percent, the brittle Fe-Al compound is obviously increased on a molten plating solution and a basic interface, the bonding property of the coating and a substrate is deteriorated, and in order to ensure the good adhesion of the coating and the substrate, the Al content in the coating is controlled to be 3.0 to 15.0 percent, preferably 4.0 to 11.0 percent.
Mg: mg in the coating can uniformly generate corrosion products with certain fluidity on the surface of the coating, and the existence of the corrosion products enables the cut of the steel plate to have a self-healing mechanism. In order to fully exert the effect of Mg, the Mg content is ensured to be more than 0.5 percent. When the Mg content is more than 4.0%, large blocks of brittle MgZn are easy to appear in the coating 2 The phase itself is easy to crack, and the formability of the plating layer is seriously influenced. In order to obtain a high-quality plating layer having both corrosion resistance and formability, the content of Mg in the plating layer of the present invention is controlled to be 0.5 to 4.0%, preferably 2.0 to 3.0%.
Ti & B: when the plating solution contains Ti and B, the plating layer structure can be further refined, and the two elements can independently exist in the plating solution or can exist in a composite way. When the Ti and B contents are too large, ti-Al, al-B and Ti-B precipitates are formed in the coating layer, and fine particles are formed in the coating layer, resulting in appearance defects of the coated steel sheet. Therefore, the content of Ti in the coating is controlled to be 0-0.1%, and the content of B is controlled to be 0-0.05%.
Si: as explained in the function of the Al content in the plating solution, when the Al content is higher (in practical research, when the Al content is more than 8.0 percent), the brittle Fe-Al compound at the interface of the plating solution and the substrate is obviously increased, and the growth of the Fe-Al compound can be effectively inhibited by adding a small amount of Si in the plating solution, thereby being beneficial to improving the nucleation of the plating layer and the steel plate. In addition, the addition of a small amount of Si can also suppress blackening of the Zn-Al-Mg-based plating layer. However, too high Si content is not favorable for Fe-Al reaction on the substrate and also causes a large amount of dross in the zinc pot. Therefore, the content of Si in the coating is controlled to be 0-2.0%.
Fe: fe inevitably dissolves in the hot dip coating bath from the steel sheet as the raw material and the sink roll, and Fe is controlled not to exceed 2.0% in the coating layer of the present invention in order to ensure the corrosion resistance of the Zn-Al-Mg based coating layer.
According to the invention, the zinc-aluminum-magnesium plating solution is adopted during hot dip plating, and components such as Al, si and the like in the plating layer are controlled, so that a brittle Fe-Al intermetallic compound is prevented from being generated on the electromagnetic pure iron substrate, and the bonding property of the plating layer and a substrate is increased; in addition, by controlling the leveling elongation, crystal defects are introduced into the pure iron base material, the magnetic domain resistance is increased, and the good adhesion of the coating on the electromagnetic pure iron base body is ensured.
The corrosion resistance of the hot-dip galvanized zinc-aluminum-magnesium magnetization-free annealed electromagnetic pure iron is mainly ensured by depending on a zinc-aluminum-magnesium plating layer on the surface of a base material. Controlling the plating amount of the electromagnetic pure iron surface coating to be more than or equal to 30/30g/m 2 Meanwhile, the zinc ratio index I (the total weight of the zinc-aluminum-magnesium alloy coating/the thickness of the steel plate) is between 100 and 150g/mm, so that the product can obtain better magnetic property and excellent corrosion resistance at the same time, and the obtained non-magnetized annealed electromagnetic pure iron containing zinc-aluminum-magnesium has corrosion resistance at the notch after being prepared into a part.
In terms of plane corrosion resistance, the sacrificial anode protection effect of zinc is exerted, and on the other hand, the participation of aluminum and magnesium leads to unstable and easily decomposed loose Zn formed on the surface of a steel plate 4 CO 3 (OH) 6 ·H 2 O corrosion product is replaced by Zn containing aluminum and magnesium and having extremely high adhesion to the surface of the plating layer 4 CO 3 (OH) 6 ·H 2 O、Zn 5 (OH) 8 Cl 2 ·H 2 O a compact corrosion product which isolates the coating from the external corrosive environment,thereby slowing down the corrosion process of the plating.
With regard to notch corrosion resistance, aluminum and magnesium are involved, the micro-crack part processed by the notch and the plating layer has self-healing capacity, and with the corrosion of the plating layer near the notch, corrosion products are dissolved into a water film attached to the surface layer of the bare metal and continuously migrate to dip and dye the bare notch to form a coating consisting of Zn (OH) 2 、Zn 5 (OH) 8 Cl 2 ·H 2 O and Mg (OH) 2 And the corrosion product gradually covers the exposed notch metal and separates the external corrosion medium from the exposed metal matrix, so that the exposed notch is prevented from being further corroded, and the notch also has corrosion resistance.
The invention relates to a method for manufacturing a zinc-aluminum-magnesium plated non-magnetized annealed electromagnetic pure iron steel plate for a high-voltage direct-current relay, which comprises the following steps of:
1) Smelting
Smelting according to the chemical components of the electromagnetic pure iron substrate;
2) Hot rolling and acid washing;
3) Cold rolling;
4) Annealing;
5) Hot dip coating
After annealing, the electromagnetic pure iron substrate is immersed into a zinc pot for hot dip coating treatment, and is cooled to room temperature after being discharged from the zinc pot and blown by an air knife; the plating amount of the zinc-aluminum-magnesium alloy plating layer after hot dip plating is more than or equal to 30/30g/m 2 ；
The zinc-aluminum-magnesium alloy coating comprises the following chemical components in percentage by mass: al:3.0 to 15.0%, mg:0.05 to 4 percent, ti:0 to 0.1%, B:0 to 0.05%, si:0 to 2.0%, fe:0 to 2.0 percent, and the balance of Zn and other inevitable impurities;
6) Flat press down
The leveling elongation is 0-0.8%.
Preferably, in the step 2), the heating temperature is 1100-1250 ℃; the finishing temperature is 800-900 ℃; the coiling temperature is 550-720 ℃.
Preferably, in the step 3), the cold rolling reduction is 25 to 70%.
Preferably, in the step 4), the annealing temperature is 750-850 ℃, and the annealing soaking time is 100-150 s.
Preferably, in the step 5), the temperature of the plating solution in the zinc pot is 420-510 ℃, and the temperature of the plating solution before the substrate enters the plating solution is +/-10 ℃.
Preferably, in step 5), the blowing medium used in the air knife is nitrogen.
The hot rolling step comprises slab heating, finish rolling and coiling, and low-temperature finish rolling and low-temperature coiling are selected. Wherein the heating temperature of the control plate blank is 1100-1250 ℃, the finishing temperature is 800-900 ℃, and the coiling temperature is 550-720 ℃. The heating temperature of the plate blank is controlled to be 1100-1250 ℃, because when the hot rolling plate blank is prepared by adopting a continuous casting mode, the plate blank needs to be reheated, but the heating temperature is too high, the plate blank is over-burnt, the surface oxide scale is seriously thickened, and the defects of surface warping and the like are generated; in addition, solid solutions such as MnS and the like are precipitated and increased by high-temperature heating, so that the resistance of subsequent grain growth is increased, and the magnetic movement is influenced; and the heating temperature is lower than 1100 ℃, the deformation resistance of the plate is overlarge.
In addition, for the components of the electromagnetic pure iron substrate, the longer the retention time at high temperature is, the more beneficial to obtaining coarse grains, but the higher the finishing temperature of hot rolling is, the more mixed crystals are easily generated by two-phase region rolling, and the lower the finishing temperature is, the higher the deformation resistance of the plate is caused. Because the strength of a pure iron material is relatively low, the coiling temperature is generally set to be lower than 720 ℃, flat coils are easy to cause due to high-temperature coiling, and the inhomogeneity of microscopic structures of materials at the head, the middle and the tail of a hot-rolled coil is increased, so that the bending performance of a steel plate and the stability of coercive force are influenced. In the hot rolling process, the heating temperature of the control plate blank is 1100-1250 ℃, the finishing rolling temperature is 800-900 ℃, and the coiling temperature is 550-720 ℃.
In the cold rolling step, the cold rolling reduction of the cold-rolled sheet strip is controlled to be 25-70%. Although a lower cold rolling reduction may possibly achieve better magnetic properties by inducing grain boundary migration by inducing strain to the hot-rolled sheet to promote the growth of annealed grains, the cold rolling reduction of the present invention is controlled to be between 25 and 70% because the reduction is too small and the grains are mixed due to uneven deformation.
Continuous annealing is adopted for recrystallization annealing, soaking time is ensured to be 100-150 s at the temperature of 750-850 ℃, annealing treatment is carried out on the steel plate base material, and the annealing medium is H 2 +N 2 A non-oxidizing atmosphere. Because the rolling process causes a large amount of lattice distortion in ferrite crystal, the magnetic domain moving resistance is large, high-temperature annealing provides enough thermodynamic driving force for recrystallization to eliminate the cold-rolled lattice distortion, if the annealing temperature is too low or the annealing time is too short, the crystal grains grow insufficiently, and the electromagnetic pure iron plate strip keeps a certain rolling hard structure, so that the cold processing performance of the product is poor. In conclusion, the temperature of the soaking section is controlled to be 750-850 ℃, and the soaking time is ensured to be 100-150 s.
The difference of the zinc-aluminum-magnesium plating layer components can cause the difference of the actual solidifying points, so the actual plating liquid temperature can change along with the change of the plating layer components, the setting principle of the plating liquid temperature is 40-50 ℃ higher than the solidifying point of the plating layer, and the plating liquid temperature is set between 420-510 ℃ according to the change of the plating layer components. In order to control the temperature fluctuation in the zinc pot, the temperature of the substrate after recrystallization annealing is adjusted within +/-10 ℃ compared with the temperature fluctuation of the plating solution.
After the surface of the steel plate is dipped in the plating solution and comes out of a zinc pot, the plating amount is adjusted by air knife blowing, and the steel plate is subjected to a conventional post-plating cooling treatment process, wherein a blowing medium adopted to avoid the oxidation of the plating layer is nitrogen. The plating amount can be adjusted according to different requirements of the corrosive environment, and the plating amount is controlled to be more than or equal to 30/30g/m 2 The zinc ratio index I (the total weight of the zinc-aluminum-magnesium alloy plating layer/the thickness of the steel plate) is between 100 and 150g/mm, because the zinc-aluminum-magnesium alloy plating layer does not have magnetic permeability, and the plating amount is too thick, the magnetic performance of the magnetization-free annealing electromagnetic pure iron substrate plated with the zinc-aluminum-magnesium alloy plating layer is integrally reduced; the influence of thin plating on the plane corrosion resistance is the second, in the thick base plate material with the thickness of more than 1.5mm, the part notch is wide, and the notch is not covered by enough plating corrosion products, so the requirement of the corrosion resistance at the part notch is difficult to meet. Therefore, the reasonable plating amount needs to be controlled according to the thickness of the substrate, so that the product combination of the non-magnetized annealed pure iron substrate and the zinc-aluminum-magnesium plating layer has high strengthCorrosion resistance and enough magnetic performance.
The flattening elongation after plating is controlled to be 0-0.8%, because crystal defects are introduced into the pure iron base material under flattening pressure, the magnetic domain resistance is increased, the roller opening is prevented from being flattened optimally from the viewpoint of keeping the optimal magnetic performance, but the proper flattening pressure is also the key for ensuring the surface quality of the product, so that the flattening elongation is controlled to be 0-0.8%.
The hot-dip galvanized aluminum-magnesium magnetization-free annealed electromagnetic pure iron obtained by the invention has the average coercive force of 50-100A/m and the magnetic induction intensity B 5000 Greater than 1.71T, magnetic permeability mu m The thickness is more than 8mH/m, and the alloy can be directly processed and used without magnetizing annealing; in addition, the parts processed by the electromagnetic pure iron do not need conventional Ni electroplating post treatment, the parts such as notches and the like have self-healing capability, and the corrosion resistance requirements of different use environments can be met by adjusting the plating amount within the range specified by the invention. The product design also solves the problem that the deep plating capability inside the part is poor due to electroplating after the pure iron part of the traditional high-voltage direct-current relay is formed, shortens the manufacturing process and improves the production efficiency.
The invention has the beneficial effects that:
1. the non-magnetized annealed electromagnetic pure iron with the zinc-aluminum-magnesium alloy coating is obtained, has good magnetism and corrosion resistance, and can be directly processed into large-size parts represented by high-voltage direct-current relay yoke iron; the traditional iron parts are all processed by processing electromagnetic pure iron into parts, and then the parts are subjected to magnetization annealing treatment, acid washing, electroplating and other anticorrosion post-treatments. Compared with the traditional method for preparing the parts by using the electromagnetic pure iron steel plate containing the zinc-aluminum-magnesium alloy coating, the method for processing the parts by using the electromagnetic pure iron steel plate can save post-treatment processes such as part magnetizing annealing, ni electroplating and the like, shorten the manufacturing flow, improve the production efficiency, reduce the environmental protection investment and reduce the part cost.
2. The surface of the electromagnetic pure iron substrate is plated with the zinc-aluminum-magnesium alloy plating layer, the content of elements such as Zn, al, mg and the like in the zinc-aluminum-magnesium alloy plating layer is controlled, the plating amount of the plating layer is controlled according to the thickness of the substrate, the plating layer can be well attached to the electromagnetic pure iron substrate, and the obtained electromagnetic pure iron containing the zinc-aluminum-magnesium alloy plating layer has high corrosion resistance and magnetic performance. Further, since aluminum and magnesium are involved, the notch of the electromagnetic pure iron containing the zinc-aluminum-magnesium alloy plating layer has high corrosion resistance even after the electromagnetic pure iron is processed into a part.
In the prior art, the corrosion prevention of iron parts is realized by plating Ni on the surface of the part, pre-plating a Ni layer on the surface of a pure iron steel plate and then punching the part, so that the problem of uneven plating on the deep concave part of a workpiece is solved on the surface, but in fact, ni belongs to a cathode plating layer relative to Fe, the corrosion protection mechanism of the steel plate is physical isolation, fine cracks can occur on the pre-plated Ni layer in the drawing deformation of part forming, and the corrosion of the pure iron steel plate can be preferentially carried out under the action of an Fe-Ni micro battery; in addition, the Ni coating has no notch protection capability, most of pure iron parts are 1.5-3.0 mm, and the problem of corrosion of bare steel plates at the notches of the parts cannot be solved by pre-plating the Ni layer on the surfaces of the pure iron steel plates.
3. The non-magnetized annealed electromagnetic pure iron with the surface plated with the zinc-aluminum-magnesium alloy plating layer is adopted to process a high-voltage direct-current relay yoke as a representative large-size part, and the problem of poor deep plating capability inside the part caused by electroplating after the part is prepared by adopting the traditional electromagnetic pure iron is solved.
Drawings
FIG. 1 is a sectional electron micrograph of an electromagnetic pure iron steel sheet according to example 1 of the present invention.
FIG. 2 is an electron micrograph of a surface of an electromagnetic pure iron steel sheet according to example 1 of the present invention.
FIG. 3 is a B-H test curve of an electromagnetic pure iron steel plate according to example 1 of the present invention.
Fig. 4 is a shape photograph of the flat sample of the electromagnetic pure iron steel plate of example 1 of the present invention after a neutral Salt Spray Test (SST) for 1700 h.
Fig. 5 is a topographic photograph of the flat sample of the electromagnetic pure iron steel plate of example 1 of the present invention, which is subjected to a neutral Salt Spray Test (SST) for 3500 h.
FIG. 6 is a photograph of the notch sample of the electromagnetic pure iron steel plate of example 1 of the present invention after a neutral Salt Spray Test (SST) for 1700 h.
FIG. 7 is a photograph of the notch sample of the electromagnetic pure iron steel plate of example 1 of the present invention after a neutral Salt Spray Test (SST) 3300 h.
FIG. 8 is a photograph of the 0T-180 DEG bent sample of the electromagnetic pure iron steel plate according to example 1 of the present invention after a neutral Salt Spray Test (SST) for 1700 h.
FIG. 9 is a photograph showing the 0T-180 DEG bent sample of the electromagnetic pure iron steel plate according to example 1 of the present invention after a neutral Salt Spray Test (SST) 3300 h.
Detailed Description
The invention is further illustrated by the following examples and figures.
The components of the electromagnetic pure iron substrates of the examples and the comparative examples are shown in Table 1, and the balance is Fe and other inevitable impurities; the compositions of the coatings of the examples of the invention are shown in Table 2; the manufacturing processes of examples and comparative examples are shown in table 3; the properties of the electromagnetically pure iron of the examples and comparative examples are shown in Table 4.
As can be seen from FIGS. 1 and 2, the electromagnetic pure iron plating layer obtained in example 1 of the present invention exhibited Zn-rich phase, al-rich phase, and MgZn 2 Typical ternary alloy coating structure of phase, eutectic phase.
According to the test curve in FIG. 3 and the photographs of the neutral salt spray test in FIGS. 4, 5, 6, 7, 8 and 9, and in combination with Table 3, it can be seen that the average coercivity of the non-magnetized annealed electromagnetic pure iron steel plate obtained by the present invention is 50-100A/m, and the magnetic induction intensity B is 5000 Greater than 1.71T, magnetic permeability mu m More than 8mH/m; at the same time, the corrosion resistance is excellent, and in a neutral salt spray test which satisfies 5% NaCl and meets the standard ASTM B117-73, the red embroidery resistance time of the plane, the notch and the drawing part exceeds 1000h.
The magnetization-free annealed electromagnetic pure iron steel plate obtained by the invention can be directly processed into large-size parts represented by high-voltage direct-current relay yokes, so that the conventional part magnetization annealing and coating post-treatment processes are omitted, the manufacturing flow is shortened, the production efficiency is improved, the environmental protection investment is reduced, the part cost is reduced, and the problem of poor deep plating capability in parts electroplated after the parts are prepared by using the traditional electromagnetic pure iron is solved.
In comparative example 1, when the substrate composition is out of the range of the composition of the magnetization-free annealed electromagnetic pure iron substrate, the properties of the prepared electromagnetic pure iron steel plate are shown in table 4, the magnetic property is insufficient, the coercive force is obviously increased to 117.6A/m, the magnetic induction intensity is 1.638T, and the maximum magnetic permeability is 7.31mH/m.
In comparative example 2, when the flattening elongation adopted in the flattening reduction process is 1.2% and is greater than the maximum flattening elongation required by the invention by 0.8%, the properties of the prepared electromagnetic pure iron cold-rolled strip are shown in table 4, the magnetic properties are insufficient, the coercive force is obviously increased to 112.3A/m, the magnetic induction intensity is 1.667T, and the maximum magnetic permeability is 6.92mH/m.
Comparative example 3 is to reduce the plating amount to 30/30g/m based on example 8 2 Since the thickness of the plate is 1.0mm and the zinc ratio index I is 60, the control range of 100-150 is exceeded, although the magnetic performance can meet the requirement, the corrosion resistance of the plating layer is sharply reduced, in a salt spray test, the time of the notch red rust resistance is only 500h, and the notch protection capability is sharply reduced.
Comparative example 4 is based on the substrate composition and heat treatment process of example 4, further increasing the thickness of the zinc-aluminum-magnesium coating to 150/150g/m 2 The zinc ratio index I is 250, exceeds the control range of 100-150, is influenced by the thickening of the plating layer, and the corrosion resistance is further improved; but under the influence of poor magnetic permeability of the zinc-aluminum-magnesium plating layer, the coercive force is obviously improved to 103.1A/m, the magnetic induction intensity is 1.677T, and the maximum magnetic permeability is 8.21mH/m.
Therefore, the pure electromagnetic iron sheets obtained in comparative examples 1 to 4 cannot satisfy the requirements of the present invention in terms of corrosion resistance and magnetic properties at the same time, and in order to obtain pure electromagnetic iron that can be directly processed into large-sized parts represented by high-voltage direct-current relay yokes, it is also important to control the requirements for the flat elongation, the plating amount, and the zinc ratio index I (total weight of zinc-aluminum-magnesium alloy plating layer/thickness of steel sheet), in addition to the requirements for controlling the substrate composition and the plating layer composition of pure electromagnetic iron within a reasonable range.
TABLE 2
| Serial number | Al | Mg | Ti | B | Si | Fe |
| Example 1 | 5.9 | 2.5 | 0.05 | ＜0.001 | ＜0.001 | 0.22 |
| Example 2 | 11.3 | 2.0 | 0.02 | 0.01 | 0.27 | 0.41 |
| Example 3 | 3.5 | 1.5 | ＜0.001 | 0.02 | 0.10 | 0.58 |
| Example 4 | 8.1 | 0.5 | 0.07 | 0.04 | 1.05 | 0.37 |
| Example 5 | 6.5 | 0.8 | 0.1 | ＜0.001 | 0.55 | 1.37 |
| Example 6 | 9.2 | 1.5 | 0.03 | 0.03 | 1.31 | 0.81 |
| Example 7 | 12.5 | 3.2 | 0.08 | 0.05 | 1.52 | 1.05 |
| Example 8 | 14.8 | 3.9 | 0.01 | 0.01 | 1.98 | 1.89 |
| Comparative example 1 | 5.9 | 2.5 | ＜0.001 | ＜0.001 | ＜0.001 | 1.6 |
| Comparative example 2 | 8.1 | 1.6 | 0.08 | 0.02 | 0.6 | 1.8 |
| Comparative example 3 | 14.8 | 3.9 | 0.01 | 0.01 | 1.98 | 1.89 |
| Comparative example 4 | 8.1 | 0.5 | 0.07 | 0.04 | 1.05 | 0.37 |
Claims (12)
1. The non-magnetization annealing electromagnetic pure iron steel plate for plating the zinc-aluminum-magnesium for the high-voltage direct-current relay is characterized in that the hot-dip zinc-aluminum-magnesium non-magnetization annealing electromagnetic pure iron comprises an electromagnetic pure iron substrate and a zinc-aluminum-magnesium alloy plating layer on at least one surface of the electromagnetic pure iron substrate; the coating amount of the zinc-aluminum-magnesium alloy coating is more than or equal to 30/30g/m 2 (ii) a Wherein the content of the first and second substances,
the electromagnetic pure iron substrate comprises the following chemical components in percentage by mass: c is less than or equal to 0.005%, si is more than 0 and less than or equal to 0.01%, mn:0.1 to 0.5 percent of Fe and other inevitable impurities, less than or equal to 0.015 percent of P, less than or equal to 0.01 percent of S, less than or equal to 0.005 percent of Al or less than or equal to 0.1 to 1.5 percent of Al, less than or equal to 0.005 percent of N, less than or equal to 0.015 percent of O, less than or equal to 0.007 percent of B or less than or equal to 0.1 percent of Cr, more than or equal to 10 percent of Mn/S, and the balance of Fe and other inevitable impurities;
the zinc-aluminum-magnesium alloy coating comprises the following chemical components in percentage by mass: al: 3.0-15.0%, mg:0.5 to 4%, ti:0 to 0.1%, B:0 to 0.05%, si:0 to 2.0%, fe:0 to 2.0 percent, and the balance of Zn and other inevitable impurities.
2. The non-magnetized annealed electromagnetic pure iron steel sheet plated with zinc-aluminum-magnesium for a high-voltage direct-current relay according to claim 1, wherein the Al content in the coating composition of the zinc-aluminum-magnesium alloy is 4.0 to 11.0%.
3. The non-magnetized annealed electromagnetic pure iron steel sheet plated with zinc-aluminum-magnesium for a high-voltage direct-current relay according to claim 1 or 2, wherein the Mg content in the coating composition of the zinc-aluminum-magnesium alloy is 2.0 to 3.0%.
4. The non-magnetization annealed electromagnetic pure iron steel plate coated with zinc-aluminum-magnesium for high-voltage direct current relays as claimed in any one of claims 1 to 3, wherein the zinc ratio index I: 100-150 g/mm, and the zinc ratio index I = the total weight of the zinc-aluminum-magnesium alloy plating layer/the thickness of the steel plate.
5. The non-magnetization annealed zinc-aluminum-magnesium-plated electromagnetic pure iron steel plate for the high-voltage direct-current relay according to any one of claims 1 to 4, wherein the average coercive force of the non-magnetization annealed electromagnetic pure iron steel plate is 50 to 100A/m, and the magnetic induction intensity B is B 5000 Greater than 1.71T, magnetic permeability mu m ＞8mH/m。
6. The non-magnetized and annealed zinc-aluminum-magnesium plated electromagnetic pure iron steel plate for the high-voltage direct-current relay according to any one of claims 1 to 5, wherein the non-magnetized and annealed electromagnetic pure iron steel plate is subjected to a neutral salt spray test of ASTM B117-73, and the red embroidery resistance time of planes, notches and drawn parts exceeds 1000h.
7. The method for manufacturing the zinc-aluminum-magnesium-plated non-magnetized annealed electromagnetic pure iron steel plate for the high-voltage direct-current relay according to any one of claims 1 to 6, characterized by comprising the steps of:
1) Smelting
Smelting according to the components of the electromagnetic pure iron substrate;
2) Hot rolling and acid washing;
3) Cold rolling;
4) Annealing;
5) Hot dip coating
After annealing, the electromagnetic pure iron substrate is immersed into a zinc pot for hot dip coating treatment, and is cooled to room temperature after being discharged from the zinc pot and blown by an air knife; the plating amount of the zinc-aluminum-magnesium alloy plating layer after hot dip plating is more than or equal to 30/30g/m 2 ；
The zinc-aluminum-magnesium alloy coating comprises the following chemical components in percentage by mass: al:3.0 to 15.0%, mg:0.05 to 4%, ti:0 to 0.1%, B:0 to 0.05%, si:0 to 2.0%, fe:0 to 2.0 percent, and the balance of Zn and other inevitable impurities;
6) Flat press down
The leveling elongation is 0-0.8%.
8. The method for manufacturing the non-magnetized annealed electromagnetic pure iron steel plate plated with zinc-aluminum-magnesium for the high-voltage direct-current relay according to claim 7, wherein in the step 2), the heating temperature is 1100-1250 ℃, the finishing temperature is 800-900 ℃, and the coiling temperature is 550-720 ℃.
9. The method for manufacturing a zinc-aluminum-magnesium-plated non-magnetized annealed electromagnetic pure iron steel sheet for a high-voltage direct current relay according to claim 7, wherein the cold rolling reduction in step 3) is 25 to 70%.
10. The method for manufacturing the non-magnetized annealed electromagnetic pure iron steel plate plated with zinc, aluminum and magnesium for the high-voltage direct-current relay according to claim 7, wherein in the step 4), the annealing temperature is 750 to 850 ℃, and the annealing soaking time is 100 to 150s.
11. The method according to claim 7, wherein in step 5), the temperature of the plating solution in the zinc pot is 420-510 ℃, and the temperature of the electromagnetic pure iron substrate before entering the plating solution is ± 10 ℃ of the temperature of the plating solution.
12. The method for manufacturing a zinc-aluminum-magnesium-plated non-magnetized annealed electromagnetic pure iron steel plate for a high-voltage direct-current relay according to claim 7 or 11, wherein in the step 5), a blowing medium used in the air knife is nitrogen.
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| CN102851629A (en) * | 2011-06-28 | 2013-01-02 | 鞍钢股份有限公司 | Aluminum-silicon plated steel plate for hot-press molding and its fabrication method |
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| CN110114500A (en) * | 2016-12-23 | 2019-08-09 | Posco公司 | Excellent hot-forming with coated steel sheet, hot-forming component and their manufacturing method of impact characteristics |
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| CN108546887A (en) * | 2018-05-31 | 2018-09-18 | 马鞍山钢铁股份有限公司 | A kind of hot-dip aluminizing silicon steel plate and its production method with excellent processing forming |
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