WO2017201749A1 - 铁基纳米晶合金超薄宽带及其制造方法 - Google Patents

铁基纳米晶合金超薄宽带及其制造方法 Download PDF

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Publication number
WO2017201749A1
WO2017201749A1 PCT/CN2016/083738 CN2016083738W WO2017201749A1 WO 2017201749 A1 WO2017201749 A1 WO 2017201749A1 CN 2016083738 W CN2016083738 W CN 2016083738W WO 2017201749 A1 WO2017201749 A1 WO 2017201749A1
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nozzle
nozzle body
molten steel
ultra
iron
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PCT/CN2016/083738
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English (en)
French (fr)
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李宗臻
周少雄
张广强
董帮少
高慧
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安泰科技股份有限公司
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Priority to PCT/CN2016/083738 priority Critical patent/WO2017201749A1/zh
Priority to CN201680003709.4A priority patent/CN107710352B/zh
Publication of WO2017201749A1 publication Critical patent/WO2017201749A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals

Definitions

  • the invention belongs to the field of magnetic functional materials, and particularly relates to an ultra-thin broadband of iron-based nanocrystalline alloy and a preparation method thereof, in particular to a nanocrystalline ultra-thin broadband with a bandwidth of 50-200 mm, and a saturation magnetic flux density greater than 1.7T, and
  • the iron loss is less than 0.30 W/kg at a frequency of 50 Hz and a maximum magnetic flux density of 1.5 T.
  • the iron-based nanocrystalline soft magnetic material is a new type of soft magnetic material composed of an amorphous matrix and nano-sized ⁇ -Fe(Si) grains distributed on the substrate, and the grain size is smaller than the exchange coupling length, effectively The magnetocrystalline anisotropy is reduced.
  • the magnetostriction of the nanocrystalline alloy can be adjusted to be close to zero, and its performance combines the high saturation magnetic induction strength of the conventional crystalline soft magnetic material and the low coercive force and high magnetic permeability of the amorphous soft magnetic material. And many advantages such as low loss.
  • Nanocrystalline soft magnetic alloys have a wide range of applications and are used in almost all areas of power electronics.
  • Japanese Patent JP1156451A discloses a nanocrystalline alloy of high saturation magnetic induction with the expression FeCoCuSiBM', wherein M' represents one or more elements of Nb, W, Ta, Zr, Hf, Ti, and is controlled by The heat treatment system keeps the volume fraction of the crystal phase above 50%, so that the saturation magnetic induction of the alloy is 1.4T and above. This is actually to control the heat treatment method, to obtain more ⁇ -Fe grain precipitation, and to increase the saturation magnetic induction intensity of the alloy with the high B s of ⁇ -Fe itself. However, the potential for this approach is limited, and its highest B s is only 1.58T.
  • Chinese patent CN101834046 discloses an expression of Fe x Si y B z P a Cu b nanocrystalline alloy, which has a saturation magnetic induction strength of 1.9 T and excellent soft magnetic properties.
  • the amorphous forming ability of the component is very poor, and a high-density nanocrystal nucleus is produced in the preparation process.
  • the subsequent crystallization heat treatment must adopt rapid annealing to obtain a nano-biphase structure with excellent performance, and the annealing time cannot exceed 5 min, otherwise the soft magnetic property is obtained.
  • the deterioration is sharp, so the annealing process of the component is difficult to control and it is difficult to industrially produce.
  • Chinese patent CN1450570 discloses a nanocrystalline soft magnetic alloy ultra-thin ribbon and a preparation method thereof: the chemical composition and ultra-thin ribbon production process of an iron-based nanocrystalline soft magnetic alloy are provided.
  • the chemical composition of the alloy includes Fe, Zr, Nb, Si, Al, Cu.
  • the production process is to first obtain the mother alloy by induction melting, then spray the amorphous ribbon in a plane flow casting (linear velocity 40-70 m/s) in an Ar atmosphere, and finally heat-treat the magnetic field at 400-600 ° C for 30-60 minutes under vacuum conditions.
  • the best soft magnetic properties of the obtained alloy strips were: saturation magnetic induction of 1.7 T and coercive force of 9.6 A/m. Although the saturation magnetic induction intensity of the composition reaches 1.7T, it is necessary to spray the belt under a protective atmosphere, and it is difficult to achieve large-scale industrial production.
  • the commercial mainstream amorphous and nanocrystalline alloy ribbon manufacturing technology is a planar flow casting method.
  • the typical manufacturing process is: melting a metal component of a specific composition, and then flowing the molten steel through a nozzle slit having a width of 1 mm or less to a nozzle.
  • the molten steel spreads on the outer circumferential surface of the cooling roller to form a stable melting pool.
  • the melt at the bottom of the melting pool contacts the roll surface and rapidly cools at a rate of 10 6 ° C/sec.
  • a continuous strip of metal having a thickness of about 0.03 mm.
  • the bandwidth of the amorphous ribbon prepared by the planar flow casting method is determined by the nozzle slit length, and the strip thickness is mainly determined by three factors: nozzle nozzle slit width, melt bath stability and chill roll surface quality.
  • the size of the nozzle slit determines the flow rate of the mother alloy molten steel. Therefore, the uniformity of the width of the nozzle slit in the lateral direction (ie, the length of the nozzle slit) is one of the keys to the uniformity of the transverse width of the amorphous broadband.
  • the lateral disturbance of the molten steel in the inner layer of the molten pool and the instability of the molten pool increase the roughness of the free surface of the strip and the depth of the scratch, thereby indirectly affecting the thickness of the strip.
  • the surface roughness of the chill roll will be directly reflected on the surface of the strip, which will also affect the flatness of the strip, which indirectly affects the thickness of the strip.
  • US Patent No. US19970864892 provides a nozzle structure for broadband manufacturing of amorphous alloys.
  • a broadband width of amorphous alloy having a maximum width of 200 mm and a uniform lateral thickness can be obtained.
  • Chinese invention patent ZL99808439.5 discloses a method for manufacturing a 170 mm wide amorphous strip, which can be manufactured by controlling the surface roughness of the cooling roll to 0.005 mm or less and controlling the surface roughness of the nozzle slit to 0.005 mm or less.
  • amorphous broadband has been commercialized.
  • the iron-based amorphous alloy strip products (1K101) produced by Antai Technology Co., Ltd. have three width specifications of 142mm, 170mm and 213mm, which are used for transformer cores of different sizes.
  • the prior art can produce iron-based amorphous alloy strips having a width of not more than 213 mm, but commercially available nanocrystalline strips (1k107) are generally less than 50 mm wide. This is because the amorphous alloy contains about 20% of Si and B metal elements, and the alloy melt has a large amorphous forming ability and good fluidity, and the nanocrystalline alloy melt has a very large amount of Nb elements.
  • the nanocrystalline broadband is designed and manufactured by using the amorphous alloy strip of the existing specification, and the pressure of the spray belt can be greatly increased to increase the temperature of the spray belt to increase the fluidity of the melt. Excessive pressure will cause the nozzle to deform or even crack the nozzle. If the temperature of the spray belt is too high, it will lead to too much impurities in the molten metal, and also increase the risk of steel leakage, which is not technically feasible. Due to the energy-saving benefits of nanocrystalline alloy distribution transformers and their excellent high-frequency performance, it is highly desirable to use nanocrystalline alloys as core materials in large transformers, reactors, and motors. Therefore, it is necessary to use a nanocrystalline alloy strip with a larger bandwidth and a higher saturation magnetic induction strength to manufacture the nanocrystalline alloy, especially for the ultra-thin broadband of iron-based nanocrystalline alloy having a width of 50 mm or more. .
  • the object of the present invention is to provide an ultra-thin broadband of an iron-based nanocrystalline alloy and a manufacturing method thereof, wherein the nanocrystalline alloy has a wide width of 50 to 200 mm and a saturation magnetic induction strength of more than 1.7. T, the strip has a high surface flatness, good toughness after annealing, and low frequency loss.
  • the present invention provides the following technical solutions:
  • the atomic percentage content x of the component Fe ranges from 82 ⁇ x ⁇ 83.
  • the atomic percentage a of the component Si ranges from 1 ⁇ a ⁇ 6 (for example, 1.2, 2, 3, 4, 5) 5.8).
  • the atomic percentage b of the component B ranges from 2 ⁇ b ⁇ 7 (such as 2.1, 3, 4, 5, 6). 6.8).
  • the atomic percentage content c of the component P ranges from 2 ⁇ c ⁇ 5 (such as 2.1, 2.5, 3, 4, 4.5). ).
  • the atomic percentage content d of the component Nb ranges from 0.5 ⁇ d ⁇ 0.75 (for example, 0.55, 0.6, 0.65, 0.7, 0.74). ).
  • the atomic percentage e of the component Cu ranges from 0.5 ⁇ e ⁇ 0.75 (for example, 0.55, 0.6, 0.65, 0.7, 0.74). ).
  • the atomic percentage f of the component M ranges from 0.01 ⁇ f ⁇ 0.05 (for example, 0.015, 0.02, 0.025, 0.03, 0.035). , 0.04, 0.045).
  • the ultra-thin broadband of the iron-based nanocrystalline alloy has a width of 50 to 200 mm, a thickness of 0.001 to 0.02 mm, and a lateral (ie, ultra-thin broadband width direction) thickness deviation. Less than ⁇ 0.0015mm, the lamination coefficient is greater than 0.80, the saturation magnetic flux density is greater than 1.7T, and the iron loss is less than 0.30W/kg at a frequency of 50 Hz and a maximum magnetic flux density of 1.5T.
  • the atomic % of the Si element is required to satisfy: 0.5 ⁇ a ⁇ 10, and a preferred range is 1 ⁇ a ⁇ 6.
  • Si element is a common element constituting an amorphous alloy. The addition of Si element can not only improve the thermal stability and Curie temperature of the alloy, but also improve the amorphous forming ability of the alloy, and also improve the metal elements such as B and P.
  • the solubility in the alloy expands the composition range of the alloy; when the atomic % content of the Si element is less than 0.5, the effect of promoting the formation of the amorphous alloy by the Si element is difficult to fully exert, and when the atomic content of the Si element is greater than 10 , the content of ferromagnetic elements is lowered, and a soft magnetic alloy having high saturation magnetic induction strength cannot be obtained.
  • the atomic % of the B element is required to satisfy 0.5 ⁇ b ⁇ 12, and the preferred range is 5 ⁇ b ⁇ 8.
  • the B atom% is less than 0.5, the B element content is too low, and it is difficult to form a precursor of the nanocrystalline alloy, that is, an amorphous alloy.
  • the B atom% is greater than 12, the ferromagnetic element content in the alloy is lowered to lower the saturation magnetic induction strength of the alloy.
  • the atomic % of the P element is required to satisfy: 0.5 ⁇ c ⁇ 8, and a preferred range is 2 ⁇ c ⁇ 5.
  • P element is a common element constituting an amorphous alloy.
  • the proper addition of P element, P and other elements in the system have a large negative mixing heat, and the addition of P is beneficial to improve the stability of the supercooled liquid region. Properties can not only improve the amorphous forming ability of the alloy, but also improve the thermal stability of the alloy and expand the heat treatment temperature range of the amorphous alloy.
  • the atomic % of Nb is required to satisfy 0.1 ⁇ d ⁇ 1, and the preferred range is 0.5 ⁇ d ⁇ 0.75.
  • Nb is a large atomic element, and it is also an effective element for suppressing the growth of a-Fe nanocrystals, refining crystal grains, and improving the soft magnetic properties of nanocrystals. Since the Nb elements are all non-ferromagnetic elements, when the content exceeds 1 atom%, the content of ferromagnetic elements in the alloy is lowered, thereby lowering the saturation magnetic induction. When the content of the Nb element is less than 0.1 atom%, the effect of improving the amorphous forming ability, refining crystal grains, and improving the soft magnetic properties of the Nb element is difficult to exert.
  • the iron-based nanocrystalline alloy of the present invention since Cu is insoluble in Fe, it is first uniformly precipitated from the amorphous matrix during heat treatment, and promotes ⁇ -Fe nucleation, which is a general element for preparing a nanocrystalline alloy.
  • the atomic % of the Cu element is to satisfy: 0.1 ⁇ e ⁇ 3, and a preferred range is 0.5 ⁇ e ⁇ 0.75.
  • the Cu atom% is more than 3, the amorphous forming ability of the alloy is deteriorated and it is difficult to prepare.
  • Cu acts as a nano-alloy to promote the ⁇ -Fe nucleation during annealing.
  • the component M is one or a combination of two of the surface active elements Al or Sn, and the addition of the trace amount of surface active elements Al and Sn greatly reduces the surface of the melt. Tension maintains melt stability through the interaction of melt and surface tension.
  • a method for manufacturing an ultra-thin broadband of the above iron-based nanocrystalline alloy, which adopts a planar flow casting process, comprising the following steps:
  • Step one preparing a raw material according to the composition expression of the ultra-thin broadband of the alloy, and then melting and heat-treating the raw material by induction melting under a protective gas atmosphere to form a uniform molten steel;
  • Step two pouring the molten steel into the tundish and performing the molten steel purification treatment
  • Step 3 pouring the molten steel in the tundish into the nozzle package, and then flowing the molten steel from the nozzle of the nozzle disposed on the bottom surface of the nozzle package to the surface of the cooling roller rotating under the nozzle, and rapidly cooling Become an ultra-thin broadband of iron-based amorphous alloy;
  • step four the ultra-thin broadband of the iron-based amorphous alloy is heat-treated to obtain an ultra-thin broadband of the iron-based nanocrystalline alloy.
  • the heat treatment time is 5-120 min (such as 6 min, 20 min, 30 min, 50 min, 80 min, 90 min, 110 min), the heat treatment The temperature is 400-600 ° C (such as 410 ° C, 450 ° C, 500 ° C, 520 ° C, 550 ° C, 580 ° C, 595 ° C).
  • the ultra-thin broadband of the iron-based amorphous alloy obtained after cooling is immediately taken up by the coiler into a broadband roll.
  • the iron-based nanocrystalline alloy of the present invention adopts a process-improved planar flow casting method and a conventional isothermal annealing treatment method.
  • the basic process includes batching and master alloy smelting, molten steel sedation and purification treatment, and amorphous alloy broadband high speed. Continuous casting, alloy broadband online coiling, isothermal annealing treatment, the process flow is shown in Figure 1.
  • pure iron, boron iron, ferrosilicon, ferroniobium, ferrophosphorus, copper ingot, aluminum ingot, and tin ingot can be used as raw materials for the melting of the mother alloy, in an induction furnace or other manner.
  • the raw material is melted in the smelting furnace 1 and subjected to heat treatment to form a molten steel having a uniform composition.
  • the molten steel is poured into the tundish 2.
  • the tundish not only buffers the production rhythm, but also makes the molten steel get calm for a certain period of time.
  • the inclusions in the molten steel can be fully floated and the quality of the mother alloy molten steel can be improved.
  • the sedated and purified mother alloy molten steel is poured into the nozzle package 3, and the bottom of the nozzle package 3 is provided with a nozzle 7, which includes a slit nozzle 71 and a bath housing portion 78 located below the nozzle slit to make the steel The liquid flows out and is protected.
  • the temperature of the overheat treatment is not lower than 1500 ° C (such as 1500 ° C, 1550 ° C, 1600 ° C, 1660 ° C, 1700 ° C),
  • the heat treatment time is not less than 10 minutes (such as 11min, 13min, 15min, 18min, 20min, 30min, 50min or 60min).
  • the temperature of the molten steel is 1250-1300 ° C (such as 1250 ° C, 1280 ° C, 1290 ° C, 1290 ° C, 1300 ° C, 1350).
  • the purifying treatment is to add a purifying agent to the molten steel and slag multiple times to remove inclusions in the molten steel.
  • the silica and the rare earth are used as the purifying agent main body, and the calcium oxide and the silicon-manganese alloy are used as the purifying agent for the stabilizer, and the molten steel is purified after the molten steel reaches the calming temperature in the tundish.
  • Impurities such as oxides, nitrides, sulfides, etc., which are less dense during the purification process, are not melted in the molten steel and are adsorbed by the homogeneous purifying agent. Floating up and polymerizing on the surface of molten steel.
  • the slag layer covers the surface of the molten steel, isolating the atmosphere and the molten steel, avoids direct contact between the molten steel and O and N, and reduces the burning loss of the elements Si and B.
  • the content of silicon oxide is 20-35 wt%; the calcium oxide can not only deoxidize, but also remove S in the molten steel, the content of calcium oxide is 7-20 wt%; the silico-manganese alloy is mainly used for deoxidation
  • the presence of Mn can effectively remove the impurity element S, since S is almost an impurity element which must be contained in the source of boron iron, silicon and iron, and easily causes brittleness of the amorphous ribbon, and the presence of Mn can be compared with S.
  • the MnS low-melting compound is formed in the molten steel and floats up to enter the slag layer, thereby achieving the effect of desulfurization.
  • the content of the silicon-manganese alloy (such as silicon-manganese alloy 6517) is 10-20 wt%; the balance is rare earth; finally, the molten steel O, S The N content is controlled to be less than 10 ppm.
  • the nozzle is a molten pool in-line nozzle, and includes:
  • a nozzle body formed with a molten steel receiving portion for receiving and buffering molten steel from the nozzle package;
  • a nozzle slit disposed on a lower bottom surface of the nozzle body for ejecting molten steel in the nozzle body;
  • the molten pool protection body is disposed below the nozzle body and connected to the nozzle body, and is formed with a melting pot accommodating portion for protecting the molten pool formed by the molten steel after the nozzle is spouted.
  • the nozzle body in the molten-hole in-line nozzle, includes a first nozzle body sidewall, a second nozzle body sidewall, and a third nozzle body sidewall, a fourth nozzle body sidewall, the first nozzle body sidewall, the second nozzle body sidewall, the third nozzle body sidewall, and the fourth nozzle body sidewall are sequentially connected to form a closed nozzle body peripheral wall, the nozzle body peripheral wall And the molten steel receiving portion that is open on the upper bottom surface of the nozzle body; the first nozzle body side wall and the third nozzle body side wall are parallel to a longitudinal direction of the nozzle slit.
  • the width of the mouth slit is 0.05 to 0.3 mm (for example, 0.06 mm, 0.08 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3). Mm), more preferably, the lateral deviation of the mouth slit (ie, along the length of the mouth slit) is less than ⁇ 0.025 mm (eg, 0.002 mm, 0.005 mm, 0.008 mm, 0.01 mm, 0.015 mm, 0.018 mm, 0.02 mm) , 0.024mm).
  • the molten pool protection body includes:
  • a front lip extending vertically downward from a lower end surface of the side wall of the first nozzle body
  • the front lip, the first side lip, the rear lip, and the second side lip are sequentially connected to form the molten pool receiving portion having a lower bottom surface.
  • the shape of the molten pool containing portion is the same as or close to the shape of the molten pool formed by the molten steel after the nozzle is spouted.
  • the inner wall of the rear lip is inclined from top to bottom and the wall thickness of the rear lip gradually decreases from top to bottom. More preferably, the inner wall of the rear lip is a linear inclined arrangement or an arcuate inclined arrangement.
  • the shape of the lower end surface of the front lip is the same as the shape of the corresponding cooling roll surface;
  • the shape of the lower end surface of the rear lip is the same as the shape of the corresponding cooling roll surface;
  • the shape of the lower end surface of the first lip is the same as the shape of the corresponding cooling roll surface;
  • the shape of the lower end surface of the second side lip is the same as the shape of the corresponding cooling roll surface.
  • the height of the front lip is not lower than the height of the rear lip; preferably, the height of the front lip is higher than the height of the rear lip.
  • the vertical distance between the lower end surface of the front lip and the surface of the cooling roller is not less than 0.05 mm (for example, 0.06 mm, 0.08 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm); the vertical distance between the lower end surface of the rear lip and the surface of the cooling roller is not less than 0.1 mm (for example, 0.11 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm) More preferably, the vertical distance between the lower end surface of the rear lip and the surface of the chill roll is 0.1-0.3 mm.
  • the vertical distance between the mouth slit and the cooling roll surface is 0.25 mm.
  • the nozzle is taped by a post-spraying method.
  • the temperature at which the molten steel flows out from the nozzle is 1300 to 1350 ° C (for example, 1310 ° C, 1320 ° C, 1330 ° C or 1340 ° C), high temperature spray belt is conducive to unpacking and increase the fluidity of the melt.
  • the lateral direction of the cooling roll (ie, the width direction of the cooling roll) is less than 0.015 m; the surface roughness Ra of the cooling roll is always It is less than 0.0005 mm; preferably, the linear velocity of the outer surface of the cooling roll is 25 to 35 m/sec.
  • a nozzle is a melt tank in-line nozzle, comprising:
  • a nozzle body formed with a molten steel receiving portion for receiving and buffering molten steel from the nozzle package;
  • a nozzle slit disposed on a lower bottom surface of the nozzle body for ejecting molten steel in the nozzle body;
  • the molten pool protection body is disposed below the nozzle body and connected to the nozzle body, and is formed with a melting pot accommodating portion for protecting the molten pool formed by the molten steel after the nozzle is spouted.
  • the nozzle is a molten pool in-line nozzle.
  • the nozzle body includes a first nozzle body sidewall, a second nozzle body sidewall, a third nozzle body sidewall, and a fourth nozzle body sidewall.
  • the first nozzle body sidewall, the second nozzle body sidewall, the third nozzle body sidewall, and the fourth nozzle body sidewall are sequentially connected to form a closed nozzle body peripheral wall, the nozzle body peripheral wall and the nozzle body
  • the lower bottom surface encloses the molten steel containing portion having an upper bottom surface; the first nozzle body side wall and the third nozzle body side wall are parallel to a longitudinal direction of the nozzle slit.
  • the nozzle is a molten pool in-line nozzle.
  • the mouth slit has a width of 0.05 to 0.3 mm (for example, 0.06 mm, 0.08 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3). Mm), more preferably, the lateral deviation of the mouth slit (ie, along the length of the mouth slit) is less than ⁇ 0.025 mm (eg, 0.002 mm, 0.005 mm, 0.008 mm, 0.01 mm, 0.015 mm, 0.018 mm, 0.02 mm) , 0.024mm).
  • the nozzle is a molten-tank in-line nozzle.
  • the molten pool protection body includes:
  • a front lip extending vertically downward from a lower end surface of the side wall of the first nozzle body
  • the front lip, the first side lip, the rear lip, and the second side lip are sequentially connected to form the molten pool receiving portion having a lower bottom surface.
  • the nozzle is a molten pool in-line nozzle.
  • the shape of the bath receiving portion is the same as or close to the shape of the molten pool formed by the molten steel after the nozzle is spouted.
  • the nozzle is a molten pool in-line nozzle.
  • the inner wall of the rear lip is inclined from top to bottom and the wall thickness of the rear lip gradually decreases from top to bottom. More preferably, the inner wall of the rear lip is a linear inclined arrangement or an arcuate inclined arrangement.
  • the nozzle is a molten pool in-line nozzle.
  • the shape of the lower end surface of the front lip is the same as the shape of the corresponding cooling roller surface; the shape of the lower end surface of the rear lip and the corresponding cooling roller Face
  • the nozzle is a molten pool in-line nozzle.
  • the height of the front lip is not lower than the height of the rear lip; preferably, the height of the front lip is higher than that of the rear lip. height.
  • the nozzle is a molten pool in-line nozzle.
  • the vertical distance between the lower end surface of the front lip and the surface of the cooling roller is not less than 0.05 mm (for example, 0.06 mm, 0.08 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm); the vertical distance between the lower end surface of the rear lip and the surface of the cooling roller is not less than 0.1 mm (for example, 0.11 mm, 0.15 mm, 0.2 mm) 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm); more preferably, the vertical end surface of the rear lip has a vertical distance from the cooling roller of 0.1 to 0.3 mm.
  • the nozzle is a molten pool in-line nozzle.
  • the nozzle slit has a vertical distance from the cooling roller surface of 0.25 mm.
  • the nozzle is a molten pool in-line nozzle.
  • the thickness of the front lip is not less than the thickness of the side wall of the first nozzle body.
  • the nozzle is a molten pool in-line nozzle.
  • the thickness of the upper end of the rear lip is not less than the thickness of the side wall of the third nozzle body.
  • the molten pool is in a dynamic equilibrium state, and the melt from the nozzle package into the melt pool and the amorphous ribbon extracted from the bottom of the molten pool are dynamically balanced, and the stable production of the amorphous ribbon can be continued.
  • the planar flow casting process of the present invention can be completed in an atmospheric atmosphere without a special atmosphere.
  • the nozzle slit length directly determines the bandwidth, and the lateral dimension uniformity of the nozzle slit also determines the amorphous broadband lateral thickness uniformity.
  • the lateral disturbance of the molten steel in the inner layer of the molten pool and the instability of the molten pool will increase the roughness of the free surface of the strip and the depth of the scratch, thereby indirectly affecting the thickness of the strip.
  • the surface roughness of the copper roller will be directly reflected on the surface of the strip, which will also affect the flatness of the strip and indirectly affect the thickness of the strip.
  • the uniformity and cleanliness of the melt directly affect the fluidity of the melt and the ease and stability of the spray belt process.
  • the method of the invention adjusts the state of the melt, the size of the nozzle, the stability of the melt pool, and the state of the cooling roll surface on the basis of the conventional planar flow casting method, and the specific implementation scheme is as follows:
  • the nanocrystalline alloy melt has a liquid-liquid structure phase change in a high temperature superheating zone, and the liquid phase transition temperature of the alloy melt liquid of different compositions is between 1350-1450. Therefore, in order to obtain a highly uniform alloy melt, the melting temperature in the melting furnace must be superheated at 1500 degrees or more to sufficiently dissolve the insoluble crystal nuclei and macromolecular clusters in the melt.
  • Control of nozzle nozzle Control the range of nozzle width W of the nozzle: 0.05 mm ⁇ D ⁇ 0.3 mm. If the mouth is larger than 0.3 mm, it is difficult to obtain a thin strip with a thickness of less than 20 ⁇ m; when the mouth is less than 0.05 mm, the molten metal is difficult to flow out of the nozzle due to the surface tension, and a small amount of inclusion particles in the molten steel accumulate at the nozzle. The amorphous alloy is produced in a wide band of strips. Therefore, an important condition for obtaining a thin strip of 1-20 micrometers thick is that the slit width of the nozzle should not be too wide and must be limited to less than 0.3 mm.
  • the nozzle slit of the nozzle When the nozzle slit of the nozzle is relatively wide, increasing the rotation speed of the cooling roller can appropriately reduce the belt thickness, but excessively increasing the rotation speed of the cooling roller increases the roughness of the surface of the strip and the depth of the surface scratch.
  • the mouth when the mouth is sewn between 0.3 and 1.2 mm, only the amorphous ribbon can be made to have a thickness of 20 to 60 ⁇ m. That is to say, the mouth slit is too wide, no matter how to adjust the speed of the cooling roller or reduce the nozzle spacing, the strip thickness cannot be effectively reduced.
  • the invention adopts a built-in nozzle of the melting pool, and the molten pool is located inside the nozzle, which greatly reduces the impact of the airflow caused by the movement of the cooling roller on the molten pool; in addition, the invention is rationally designed
  • the composition greatly reduces the viscosity of the nanocrystalline alloy, increases the fluidity and filling ability of the alloy melt, especially the addition of trace surface active elements Al and Sn, which greatly reduces the surface tension of the melt, through the melt and the surface. The tension interaction maintains the stability of the melt.
  • the present invention adopts the post-spray method to carry out the spray belt, which greatly increases the cooling stroke of the strip on the cooling roller, reduces the stripping temperature of the strip, and adopts the melt pool in-line nozzle, and the melting pool is located In the nozzle bath housing, the distance between the rear lip of the nozzle and the lower end surface of the molten pool is small, and the scraping and correcting action is formed on the free surface of the molten pool, thereby reducing the lateral disturbance of the laminar molten steel of the amorphous alloy strip, thereby reducing The surface stress of the strip improves the surface quality of the amorphous strip and the stability of the finished product.
  • Control of the rotation speed of the cooling roller When the nozzle unit flow rate is constant, increasing the roller speed can increase the elongation rate, but the thickness of the strip is limited to decrease, and the surface of the strip is too large to make the surface rough. The degree is increased, and even the network structure and holes appear, and the quality is seriously degraded. Therefore, the cooling roller speed is generally not too large, and the linear speed is less than 35 m / sec.
  • Control of the flatness and roughness of the surface of the chill roll if there is lateral or longitudinal undulation on the surface of the chill roll, It will significantly affect the thickness of the amorphous alloy broadband in the transverse or longitudinal direction, which indirectly affects the thickness of the strip.
  • the invention finds through experiments that in order to make the lamination coefficient of the broadband of the amorphous alloy reach 80% or more, it is necessary to ensure that the lateral flatness deviation of the surface of the cooling roller is less than 0.015 mm, and the high-flatness cooling roller surface can be turned by a commercially available high-precision precision. The device is implemented.
  • the surface quality of the roll surface is gradually deteriorated due to the continuous erosion of the molten steel surface and thermal shock, and pit defects occur.
  • the present invention breaks through the limitations of the original nanocrystalline soft magnetic alloy ribbon on the alloy composition and develops a new alloy system.
  • the invention designs an ultra-thin broadband of Fe-based nanocrystalline soft magnetic alloy which has high saturation magnetization and strong amorphous forming ability through component design.
  • the large reduction of the Nb element and the large addition of the P element increase the amorphous forming ability while reducing the viscosity of the molten steel, increasing the fluidity and filling ability of the molten alloy, and greatly reducing the production cost of the material.
  • the invention adds a trace amount of surface active element to the alloy, can greatly reduce the surface tension of the melt at the time of spraying without lowering the viscosity of the melt, and adjusts the melting pool by coordinating the interaction of the surface tension and viscosity of the melt. Shape and size to improve the stability of the melting pool to achieve the requirements of stable spray belt.
  • the invention uses at least one component of Al and Sn in an atomic ratio of 0.001-0.05% based on the existing alloy composition thereof, and greatly reduces the surface of the alloy melt without destroying the soft magnetic properties of the alloy.
  • the tension reduces the difficulty of opening the nanocrystalline alloy ribbon, and increases the stability of the melting pool, thereby improving the flatness of the free surface of the strip, greatly improving the process of strip production and product quality stability.
  • the invention adopts the three-package method to make a belt, adopts high-temperature melting in a smelting furnace (the maximum temperature of melting is more than 1500 ° C), low temperature sedation of the tundish (below 1300 ° C), and the nozzle packs a higher temperature spray belt (higher than 1300 ° C).
  • High-temperature melting of the melting furnace can maximize the uniformity of the molten steel and reduce endogenous inclusions.
  • the low temperature sedation of the tundish can remove the inclusions that continue to precipitate due to the temperature drop.
  • the high temperature spray nozzle of the nozzle avoids the regeneration of the regenerated inclusions, reduces the viscosity of the melt, and increases the fluidity of the molten steel.
  • the three-package method at each stage of the steel liquid temperature control system can be independently adjusted according to the requirements, which can ensure the maximum removal of the inclusions generated by the molten steel in the production process in each process of production, and improve the cleanliness of the molten steel. Cost of production.
  • the invention adopts a melting tank in-line nozzle, the front lip of the nozzle is closely attached to the roller surface, and the melting pool is located in the nozzle bath housing portion, which reduces the influence of the airflow on the surface of the cooling roller on the melting pool, and improves the stability of the melting pool.
  • the existing nozzle melting pools are exposed to the air, and are rapidly cooled by the airflow of the surface of the rotating cooling roller, and the cooling temperature is relatively serious, and the nozzle must be exposed so as to form a necessary shape of the molten pool close to the cooling roller, and the exposed nozzle is exposed.
  • the plane cools quickly at the surface of the rapidly rotating chill roll.
  • the prior art cannot guarantee an amorphous ribbon having a bright surface and a thickness of 1 to 20 ⁇ m and a high filling factor.
  • the present invention controls the mouth slit width of the nozzle, emphasizing the range of the mouth slit width W: 0.05 mm ⁇ D ⁇ 0.30 mm. If the mouth slit is larger than 0.30 mm, a thin strip having a thickness of less than 20 ⁇ m cannot be obtained, and a thick strip having a thickness of more than 20 ⁇ m is usually obtained. Even if a strip having a thickness of about 20 ⁇ m is obtained, the surface roughness thereof is large, and the surface of the strip is not smooth. The value of use is not great. Therefore, an important condition for obtaining an ultrathin tape of 1-20 micrometers thick is that the slit width of the nozzle should not be too wide and must be limited to less than 0.30 mm.
  • the present invention uses an in-line automatic take-up mechanism to collect the strip, so that the strip obtained in the above step can be wound into a disc in a state of being always tensioned, and the strip does not wrinkle, and a device for automatically winding the core can be used subsequently.
  • the core winding is performed, and the shearing can be smoothly performed in the subsequent longitudinal and transverse shearing of the strip without breaking, while ensuring a high filling factor of the core. This is also an important condition for manufacturing high quality iron cores.
  • the online automatic coiling cannot be used, but is directly peeled off to the ground and collected. In the case of peeling, falling to the ground, strip movement and collection, many wrinkles and damages are generated, thereby reducing the quality and magnetic properties of the processed core.
  • the amorphous ultra-thin broadband of the present invention is heat-treated in a conventional heat treatment furnace to obtain an ultra-thin nanocrystalline broadband excellent in soft magnetic properties, the heat treatment time is 5-120 min, and the heat treatment temperature is 400-600. °C, the heat treatment temperature range is wide, and the soft magnetic properties of the heat treatment for a long time are not deteriorated. Further, the heat treatment of the present invention can be carried out under an air atmosphere, and is particularly suitable for industrial production.
  • the above 1-8 can work together to produce a uniform nanocrystalline ultra-thin broadband with high quality, high surface finish and thickness of 1-20 microns.
  • the production and annealing process of the invention is simple, low cost and easy to implement. Industrialized, the products produced have excellent soft magnetic properties, high filling factor, and are applied to electricity. Electronics, information, communications and other fields.
  • the ultra-thin broadband bandwidth prepared by the method of the invention is 50-200 mm, the thickness is 0.001-0.02 mm, the lateral thickness deviation of the strip is less than ⁇ 0.0015 mm, the lamination coefficient is greater than 0.80, the saturation magnetic flux density is greater than 1.7T, and the frequency is 50 Hz.
  • the iron loss is less than 0.30 W/kg at a maximum magnetic flux density of 1.5 T.
  • FIG. 1 is a schematic view showing the process principle of an iron-based nanocrystal ultra-thin broadband manufacturing method according to the present invention
  • Figure 2 is a side cross-sectional view of a conventional conventional nozzle
  • Figure 3 is a side cross-sectional view of the melt pool in-line nozzle of the present invention.
  • Figure 4 is a bottom view of the molten pool in-line nozzle of the present invention.
  • the reference numerals are as follows: 1, smelting furnace; 2, tundish; 3, nozzle package; 4, cooling roller; 5, coiler; 6, strip roll; 7, nozzle, 71, 71 ', mouth seam 72, the back lip; 73, the front lip; 74, the first side lip; 75, the second side lip; 76, the inner side of the back lip; 77, the molten steel receiving portion; 78, the melting pot housing portion; 79', a nozzle body side wall; 79", a second nozzle body side wall; 8, molten steel; 9, a thin strip; 10, a cooling roll.
  • the invention provides a nozzle which is a molten pool in-line nozzle 7, comprising: a nozzle body for receiving and buffering molten steel from the nozzle package 3; a nozzle slit 71 disposed on the lower bottom surface of the nozzle body and for protecting The molten pool protector of the molten pool formed by the molten steel 8 after the nozzle slit 71 is ejected.
  • a nozzle body for receiving and buffering molten steel from the nozzle package 3
  • a nozzle slit 71 disposed on the lower bottom surface of the nozzle body and for protecting The molten pool protector of the molten pool formed by the molten steel 8 after the nozzle slit 71 is ejected.
  • the nozzle body is formed with a molten steel containing portion 77 for receiving and buffering the molten steel from the nozzle pack 3.
  • the upper end surface of the nozzle body is fixed to the molten steel outlet of the nozzle pack 3.
  • the nozzle body includes a first nozzle body side wall 79', a second nozzle body side wall (not shown), a third nozzle body side wall 79", a fourth nozzle body side wall (not shown), and a first nozzle body side
  • the wall 79', the second nozzle body side wall, the third nozzle body side wall 79" and the fourth nozzle body side wall are sequentially connected to form a closed nozzle body peripheral wall, and the nozzle body peripheral wall and the lower surface of the nozzle body are enclosed
  • the molten steel containing portion 77 having the upper bottom surface; the first nozzle body side wall 79' and the third nozzle body side wall 79" are parallel to the length L direction of the nozzle slit 71.
  • the second nozzle body side wall and the fourth nozzle body side wall It is perpendicular to the length L direction of the mouth slit 71.
  • the nozzle slit 71 is disposed on the lower bottom surface of the nozzle body for ejecting the molten steel 8 in the nozzle body; the width W of the nozzle slit is 0.05 to 0.3 mm, and more preferably, the transverse direction of the nozzle slit (ie, the edge)
  • the length deviation of the length of the mouth slit L direction is less than ⁇ 0.025 mm (for example, 0.002 mm, 0.005 mm, 0.008 mm, 0.01 mm, 0.015 mm, 0.018 mm, 0.02 mm, 0.024 mm).
  • the molten pool protecting body is disposed below the nozzle body and connected to the nozzle body, and is formed with a melting pot accommodating portion 78 for protecting the molten pool formed after the molten steel is sprayed out of the nozzle slit 71.
  • the molten pool protection body includes a front lip 73, a rear lip 72, a first side lip 74, and a second side lip 75. The front lip 73, the first side lip 74, the rear lip 72 and the second side lip 75 are sequentially connected to form a lower bottom surface. An open bath receiving portion 78.
  • the front lip 73 is formed to extend vertically downward from the lower end surface of the side wall 79' of the first nozzle body; the rear lip 72 is formed to extend vertically downward from the lower end surface of the side wall 79" of the third nozzle body;
  • the side lip 74 is formed to extend vertically downward from the lower end surface of the second nozzle body sidewall; the second side lip 75 is formed to extend vertically downward from the lower end surface of the fourth nozzle body sidewall;
  • the front lip 73 rear lip 72 It is parallel to the length L direction of the mouth slit 71.
  • the first side lip 74 and the third side lip 75 are perpendicular to the length L direction of the mouth slit 71.
  • the melt housing portion 78 protects the molten steel and reduces the airflow of the surface of the cooling roll.
  • the influence on the melting pool improves the stability of the melting pool and prevents it from cooling rapidly.
  • the existing nozzle structure is shown in Fig. 2, which only includes the nozzle body and the nozzle slit 71', and the molten pool protecting body below the nozzle body
  • the melting pool is exposed to the air, and is rapidly cooled by the airflow of the surface of the rotating cooling roller.
  • the cooling temperature is relatively serious, and the nozzle must be exposed so as to form a necessary molten pool shape with the cooling roller, and the exposed plane of the nozzle is fast.
  • the nozzle of the invention has the molten pool protection body, which can well solve the technical problems existing in the existing nozzle.
  • the front lip 73 and the rear lip 72 are relative to the direction of movement of the cooling roller. After the cooling roller is turned on, the lowest point of the cooling roller is rotated to the vicinity of the nozzle, and the front lip 73 is passed first. Passed through the nozzle rear lip 74.
  • the shape of the melting pot accommodating portion 78 is close to or the same as the shape of the molten pool formed after the molten steel discharge nozzle 71.
  • the inner wall of the rear lip 72 is inclined from top to bottom and the wall thickness of the rear lip 72 gradually decreases from top to bottom. More preferably, the inner wall of the rear lip 72 is a linear inclined setting or an arcuate inclined setting.
  • the shape of the lower end surface of the front lip 73 is the same as the shape of the surface of the corresponding cooling roller 10; the shape of the lower end surface of the rear lip 72 is the same as the surface shape of the corresponding cooling roller 10; the shape and correspondence of the lower end surface of the first side lip 74
  • the surface shape of the cooling roll 10 is the same; the shape of the lower end surface of the second side lip 75 is the same as the surface shape of the corresponding cooling roll 10. That is to say, the lower end surface of the molten pool protection body is parallel to the cooling roller surface, and the front lip mainly blocks the gas driven by the roller surface from being entangled into the molten pool when the cooling roller rotates at a high speed, so the thickness of the front lip 73 is not less than the first nozzle.
  • the thickness of the body side wall 79' may be, and preferably both are the same thickness.
  • the rear lip 72 mainly functions to correct the scraping of the free surface of the molten pool and the lateral disturbance of the laminar molten steel, so that the corresponding shape of the rear lip 72 should be similar to the free end of the rear end of the molten pool, preferably the rear lip 72.
  • the inner wall is inclined from top to bottom and the wall thickness of the rear lip 72 gradually decreases from top to bottom; more preferably, the inner wall of the rear lip 72 is a linear inclined setting or an arc-shaped inclined setting; further, rear The thickness of the upper end of the lip 72 is not less than the thickness of the side wall 79" of the third nozzle body.
  • the lateral disturbance is corrected to form a thin strip 9 having a uniform thickness and a low surface roughness.
  • the height of the front lip 73 (ie, the distance from the lower surface of the nozzle body to the lower lip surface of the front lip) is not lower than the height of the rear lip (the distance from the lower surface of the nozzle body to the lower end surface of the rear lip); preferably, the front lip The height is higher than the height of the rear lip.
  • the vertical distance between the lower end surface of the front lip 73 and the surface of the cooling roller 10 is not less than 0.05 mm (for example, 0.06 mm, 0.08 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm), before The lip is too close to the roller surface to easily scratch the roller; the vertical distance between the lower end surface of the rear lip 72 and the surface of the cooling roller 10 is not less than 0.1 mm (for example, 0.11 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm); more preferably, the vertical distance between the lower end surface of the rear lip 72 and the surface of the cooling roll 10 is 0.1 to 0.3 mm.
  • the rear lip If the rear lip is too low, it is easy to directly contact the solidified strip, and the scratch is formed on the free surface of the strip. If the rear lip is too high, for example, the same distance from the roll nozzle, the rear lip of the nozzle does not scratch the free surface of the molten pool. Pressing and correcting the lateral disturbance of the laminar molten steel.
  • the lower end faces of the first side lip 74 and the second side lip 75 are not less than 0.05 mm from the surface directly below the cooling roll 10.
  • the vertical distance between the nozzle slit 71 and the cooling roller surface is 0.25 mm.
  • the chemical composition range of the iron-based amorphous alloy according to the present invention six different iron-based amorphous alloy components are selected, respectively, and the serial number is 1-6, and the nanocrystalline alloy broadband is produced by the planar flow casting process, and the main process parameters are as follows:
  • the raw materials are prepared under argon protection.
  • the induction furnace or other type of smelting furnace 1 melts and heat-treats the raw materials to form a uniform molten steel. Melting temperature The degree is 1400 ° C, the melting time is 30 min, the steel is hydrated and then heat treated at 1550 ° C, and the superheat time is 20 min to obtain a uniform molten steel.
  • the smelted molten steel was then poured into a tundish at a temperature of 1280 °C. After the molten steel temperature reaches the set temperature, silica and rare earth are used as the purifying agent main body, and the calcium oxide and the silicomanganese alloy are used as the purifying agent for the stabilizer, and the molten steel is purified.
  • the content of each component is 20 wt%.
  • the sedation time is 30 min.
  • the O, S and N contents in the molten steel are monitored in real time. After several times of sedation, the contents of O, S and N are controlled to be less than 10 ppm.
  • the nozzle is the molten pool in-line nozzle of the invention
  • the mouth slit length L is 51-201 mm
  • the mouth slit width W is 0.2-0.3 mm
  • the mouth slit transverse direction (along the mouth slit length direction) has a width deviation of not more than ⁇ 0.02mm
  • the vertical distance between the lower end surface of the nozzle front lip and the cooling roller directly below it is 0.05mm
  • the vertical distance between the lower end surface of the nozzle rear lip and the cooling roller directly below it is 0.15mm
  • the nozzle is perpendicular to the cooling roller directly below it.
  • the distance is 0.25mm; the linear speed of the cooling roller is 25m/s, the temperature of the spray belt is 1303-1350°C, the viscosity of the spray belt is 10.0-13.2mPa ⁇ S, the surface tension of the spray belt is 0.6-1.75N/m, and the surface of the cooling roller is rough.
  • the degree Ra is 0.00030-0.00050 mm, and the flatness of the surface of the cooling roll (ie, the width direction of the roll or the length direction of the slit) is 0.003-0.018 mm.
  • the online automatic take-up mechanism then collects the ultra-thin amorphous broadband to obtain a strip roll.
  • the ultra-thin amorphous broadband was placed in a conventional heat treatment furnace and treated at 560 ° C for 30 minutes.
  • the microstructure was characterized by X-ray diffractometry (XRD) and projection electron microscopy, and the magnetic properties of the alloy strip of the present invention were tested using conventional magnetic testing equipment.
  • the iron-based nanocrystalline alloy produced by the process of the embodiment has a wide-band thickness of 0.01 to 0.02 mm, a lateral deviation of the broadband thickness of not more than ⁇ 0.0015 mm, a lamination coefficient of more than 0.80, and a saturation magnetic flux density of more than 1.7 T.
  • the iron loss at a frequency of 50 Hz and a maximum magnetic flux density of 1.3 T is less than 0.20 W/kg.
  • the prepared alloy composition is Fe 82.5 Si 4 B 8 P 4 Nb 0.7 Cu 0.75 Al 0.02 Sn 0.03 .
  • the whole glass rod has a smooth surface and metallic luster.
  • XRD has only one broad taro peak, which is typical non- The crystal structure, when the thickness of the strip reaches 0.05 mm, still maintains a typical amorphous state, indicating that the system has a strong amorphous forming ability, and an amorphous strip having a uniform quenched structure can be prepared.
  • the Fe 82.5 Si 4 B 8 P 4 Nb 0.7 Cu 0.75 Al 0.02 Sn 0.03 amorphous ribbon is annealed at 560 ° C for 30 minutes and then isothermally annealed to form a typical nano-biphase composite structure with a large diameter of about 17 nm.
  • the ⁇ -Fe nanoparticles are uniformly distributed on the amorphous matrix.
  • the addition of the trace surface active elements Al and Sn of the invention can greatly reduce the surface tension of the melt at the time of spraying without lowering the viscosity of the melt, and adjust the shape of the molten pool by coordinating the interaction of the surface tension and viscosity of the melt.
  • the size is used to improve the stability of the melting pool, thereby improving the flatness of the free surface of the strip, and reducing the difficulty of opening the package, greatly improving the process of strip production and the stability of product quality.
  • the chemical composition range of the iron-based amorphous alloy according to the present invention six different iron-based amorphous alloy components are respectively selected, and the serial numbers are 7-12 (wherein the alloys of the numbers 7 and 11 are comparative examples), and the plane is used.
  • the raw materials are prepared under argon protection.
  • the induction furnace or other type of smelting furnace 1 melts and heat-treats the raw materials to form a uniform molten steel.
  • the melting temperature is 1400 ° C
  • the melting time is 30 min
  • the steel is hydrated and then heat treated at 1550 ° C
  • the superheat time is 20 min to obtain a uniform molten steel.
  • the smelted molten steel was then poured into a tundish at a temperature of 1280 °C. After the temperature of the molten steel reaches the set temperature, silicon oxide and rare earth are added as the main body of the purifying agent, and the calcium oxide and the silicon-manganese alloy are used as the purifying agent for the stabilizer, and the molten steel is purified, and the content of each component is 20 wt% of silicon oxide, 15 wt%. % calcium oxide, 15wt% silicon manganese alloy, the balance is rare earth.
  • the sedation time is 30min.
  • the O, S and N contents in the molten steel are monitored in real time. After several times of sedation, the O, S and N contents are controlled to below 10ppm.
  • the nozzle is the molten pool in-line nozzle of the invention
  • the mouth slit length is 151 mm
  • the mouth slit width is 0.02 mm
  • the mouth slit lateral width deviation is not more than ⁇ 0.02 mm
  • the nozzle front lip lower end surface is directly below
  • the vertical distance of the cooling roller is 0.05mm, the vertical distance between the lower end surface of the nozzle rear lip and the cooling roller directly below it is 0.15mm, the vertical distance between the nozzle and the cooling roller directly below it is 0.25mm
  • the linear speed of the cooling roller is 25m/ s
  • the temperature of the spray belt is 1300 ° C
  • the viscosity of the spray belt is 10.0-13.2 mPa ⁇ S
  • the online automatic take-up mechanism then collects the ultra-thin amorphous broadband to obtain a strip roll.
  • the ultra-thin amorphous broadband was placed in a conventional heat treatment furnace and treated at 560 ° C for 30 minutes.
  • the microstructure was characterized by X-ray diffractometry (XRD) and projection electron microscopy, and the magnetic properties of the alloy strip of the present invention were tested using conventional magnetic testing equipment.
  • the system has strong amorphous forming ability, and can prepare amorphous strips with uniform quenched structure; after isothermal annealing, a typical nano-dual phase composite structure can be formed. A large amount of ⁇ -Fe nanoparticles are uniformly distributed on the amorphous matrix.
  • the invention adopts the melt tank in-line nozzle spray belt, which greatly improves the stability of the molten pool, improves the surface quality of the free surface of the strip, and adopts the ultra-narrow nozzle to control the flow rate of the molten steel passing through the nozzle per unit time, and adopts high
  • the precision on-line grinding device improves the surface quality of the strip surface of the strip, and the three parameters are coordinated to further improve the quality of the ultra-thin broadband.
  • the chemical composition range of the iron-based amorphous alloy according to the present invention six different iron-based amorphous alloy components are respectively selected, the serial number is 13-18, and the nanocrystalline alloy broadband is manufactured by the planar flow casting process, and the main process parameters are as follows:
  • the raw materials are prepared under argon protection.
  • the induction furnace or other type of smelting furnace 1 melts and heat-treats the raw materials to form a uniform molten steel.
  • the melting temperature is 1400 ° C
  • the melting time is 30 min
  • the steel is hydrated and then heat treated at 1550 ° C
  • the superheat time is 20 min to obtain a uniform molten steel.
  • the smelted molten steel was then poured into a tundish at a temperature of 1280 °C.
  • the temperature of the molten steel reaches After setting the temperature, silica and rare earth are used as the purifying agent main body, and calcium oxide and silicon manganese alloy are used as the purifying agent for the stabilizer, and the molten steel is purified, and the content of each component is 20 wt% of silicon oxide and 15 wt% of calcium oxide. 15wt% silicon-manganese alloy, the balance is rare earth.
  • the sedation time is 30min.
  • the O, S and N contents in the molten steel are monitored in real time. After several times of sedation, the O, S and N contents are controlled to below 10ppm.
  • the nozzle is the molten pool in-line nozzle of the invention
  • the mouth slit length is 150 mm
  • the mouth slit width is 0.05-0.2 mm
  • the mouth slit lateral width deviation is not more than ⁇ 0.02 mm
  • the nozzle front lip lower end surface is positive
  • the vertical distance of the lower cooling roller is 0.05mm, the vertical distance between the lower end surface of the nozzle rear lip and the cooling roller directly below it is 0.15mm, the vertical distance between the nozzle and the cooling roller directly below it is 0.25mm
  • the linear speed of the cooling roller is 25m/s
  • spray belt temperature is 1320 °C
  • spray belt viscosity is 10.0mPa.S
  • spray belt surface tension is 0.6-1
  • the online automatic take-up mechanism then collects the ultra-thin amorphous broadband to obtain a strip roll.
  • the ultra-thin amorphous broadband was placed in a conventional heat treatment furnace and treated at 560 ° C for 30 minutes.
  • microstructure was characterized by X-ray diffractometry (XRD) and projection electron microscopy, and the invention was tested using conventional magnetic testing equipment.
  • the spray belt equipment and process have a great influence on the preparation of ultra-thin broadband. This is manifested in the following two aspects: 1. In terms of loss, the strip loss decreases rapidly with the strip thickness. 2. In terms of belt thickness, the width of the nozzle nozzle directly determines the thickness of the strip. 3. In terms of surface quality, the use of the in-line nozzle of the melt pool greatly reduces the roughness of the surface tension of the strip, thereby effectively increasing the lamination factor and indirectly reducing the strip thickness.
  • the amorphous strips prepared by plane flow casting are mainly determined by three factors: nozzle nozzle width dimension, melt bath stability and chill roll surface quality.
  • the size of the nozzle slit determines the flow rate of the mother alloy molten steel. Therefore, the uniformity of the lateral width of the nozzle slit is one of the keys to the uniformity of the transverse width of the amorphous broadband.
  • the lateral disturbance of the molten steel in the inner layer of the molten pool and the instability of the molten pool increase the roughness of the free surface of the strip and the depth of the scratch, thereby indirectly affecting the thickness of the strip.
  • the surface roughness of the chill roll will be directly reflected on the surface of the strip, which will also affect the flatness of the strip, which indirectly affects the thickness of the strip. Therefore, in this embodiment, eight comparative tests (commercial amorphous alloy Fe 78 Si 9 B 13 , commercial nanocrystalline alloy Fe 73.5 Cu 1 Nb 3 Si 13.5 B 9 , and the present invention Fe 82.5 Si 4 B 8 P are provided. 4 Nb 0.7 Cu 0.75 Al 0.02 Sn 0.03 ), the serial number is 19-26, except for some process parameters, see Table 3, and other processes are shown in Example 1. Focus on the shape and structure of the nozzle, the width of the nozzle joint, and the roughness of the roll surface on the quality and performance of the strip. The comprehensive embodiment can be seen that: 1.
  • the size of the nozzle slit directly determines the molten steel flowing through the nozzle per unit time, so the ultra-narrow slit is the premise for preparing the ultra-thin belt; 2.
  • the surface tension of the melt must be small to smoothly open the package; 3.
  • the alloy composition has strong amorphous forming ability to prepare the broadband; 4.
  • the molten pool in-line nozzle can effectively reduce the lateral disturbance and melting of the inner molten steel in the molten pool. The instability of the pool will increase the roughness of the free surface of the strip and the depth of the scratch, effectively improving the quality of the free surface of the strip. 5.
  • the high-precision online grinding device is used to improve the surface quality of the strip surface of the strip, thereby improving the quality of the strip surface of the strip.
  • the invention breaks through the limitation of the original nanocrystalline soft magnetic alloy ribbon on the alloy composition, and develops a nanocrystalline alloy system with strong amorphous forming ability, through the addition of trace surface active elements Al and Sn, The surface tension of the melt is greatly reduced, and the difficulty of opening the bag when spraying is greatly reduced.
  • the in-line grinding of the melt nozzle and the roller surface the surface quality of the strip was improved, and the ultra-thin nanocrystalline broadband was successfully prepared.
  • the invention adopts an improved planar flow casting method, and is of great significance for the industrial production of amorphous and nanocrystalline broadband. See Table 5 for the results.

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Abstract

一种铁基纳米晶合金超薄宽带及其制造方法，该超薄宽带的表达式为：Fe xSi aB bP cNb dCu eM f，其中M为Sn、Al中的至少一种，x、a、b、c、d、e和f为相应元素的原子百分比，0.5≤a≤10，0.5≤b≤12，0.5≤c≤8，0.1≤d≤3，0.1≤e≤1，0.001≤f≤0.05且x+a+b+c+d+e+f＝100。该方法采用了改进的平面流铸造法制带，制备的超薄宽带带宽为50～200mm，厚度为0.001～0.02mm，带材横向厚度偏差小于±0.0015mm，叠片系数大于0.80，饱和磁通密度大于1.7T，在频率为50Hz、最大磁通密度为1.5T条件下铁损小于0.30W/kg。

Description

铁基纳米晶合金超薄宽带及其制造方法 技术领域
本发明属于磁性功能材料领域，具体涉及一种铁基纳米晶合金超薄宽带及其制备方法，尤其涉及一种带宽为50～200mm的纳米晶超薄宽带，饱和磁通密度大于1.7T，且在频率为50Hz、最大磁通密度为1.5T条件下铁损小于0.30W/kg。
背景技术
铁基纳米晶软磁材料是一类新型软磁材料，它由非晶基体及分布在基体上纳米级尺寸的α-Fe(Si)晶粒组成，且晶粒尺寸小于交换耦合长度，有效地减小了磁晶各向异性。通过优化合金成分，也可以调节纳米晶合金磁致伸缩趋近于零，其性能兼备了传统晶态软磁材料的高饱和磁感应强度和非晶软磁材料的低矫顽力、高磁导率和低损耗等多项优点。纳米晶软磁合金的应用领域很广，几乎所有的电力电子领域都有应用。
近年来，能源与环境问题日益严重，电力电子技术的快速发展对电器设备能效、稳定性方面提出了更高的要求，使纳米晶软磁合金的应用领域不断拓展，需求量迅速增加。特别是在高效电机及电抗器方面，对纳米晶带材的饱和磁感强度及带材宽带提出了更高的要求。但市售的纳米晶合金(Finemet)的饱和磁感应强度仅为1.24T，而商业化硅钢片饱和磁感强度约在2T，铁基纳米晶合金饱和磁感应强度相对较低，且带宽一般小于50mm，难以满足小型化、高能效的发展需求。
日本专利JP1156451A公布了一种表达式为FeCoCuSiBM’的高饱和磁感应强度的纳米晶合金，其中，M’代表Nb、W、Ta、Zr、Hf、Ti中的一种或多种元素，并通过控制热处理制度，保持结晶相的体积分数在50％以上，使得合金的饱和磁感应强度在1.4T及以上。这实际上是控制热处理方式，更多地获得α-Fe晶粒析出，以α-Fe本身的高Bs来提高合金的饱和磁感应强度。但这种方法提升的潜力有限，其例举的最高Bs仅在1.58T。
中国专利CN101834046公开了一种表达式为FexSiyBzPaCub纳米晶合金，其饱和磁感应强度可达1.9T，软磁性能优异。但是该成分非晶形成能力很差，在制备过 程中即产生高密度纳米晶核，后续晶化热处理必须采用快速退火才能得到性能优异的纳米双相结构，退火时间不能超过5min，否则软磁性能急剧恶化，因此该成分退火工艺难于控制，难以工业化生产。
中国专利CN1450570公开一种纳米晶软磁合金超薄带及其制备方法：提供了一种铁基纳米晶软磁合金的化学成分和超薄带生产工艺。合金化学成分包括Fe、Zr、Nb、Si、Al、Cu，具体含量(质量百分比)为：Si＝0.1-0.2％、Zr＝6-8％、Nb＝4-6％、Al＝0.1-1％、B＝1-2％、Cu＝1-1.5％,其余为Fe。生产工艺为先感应熔炼制备母合金，然后Ar气氛中平面流铸造(线速度40-70m/s)喷射非晶带，最后于真空条件下400-600℃磁场热处理30-60分钟。所得到的合金条带的最佳软磁性能为：饱和磁感应强度1.7T，矫顽力9.6A/m。该成分虽然饱和磁感强度达到了1.7T，但是需要在保护气氛下喷带，难于实现大规模工业化生产。
商业化非晶、纳米晶合金主流制带技术是平面流铸造法，典型的制造工艺为：将特定成分的金属原材料熔化，再使钢液通过一条宽度为1mm以下的喷嘴狭缝流到一只高速旋转的、具有良好导热性的金属冷却辊上，钢液在冷却辊外圆周表面铺展成稳定的熔潭，熔潭底部熔体与辊面接触后以106℃/sec的速率迅速冷却形成厚度约为0.03mm左右的连续金属薄带。平面流铸造法制备的非晶带材带宽由喷嘴嘴缝长度决定，而带厚主要由喷嘴嘴缝宽度尺寸、熔潭稳定性及冷却辊表面质量三个因素决定。非晶合金带材制造时，喷嘴缝的尺寸决定了母合金钢液的流量，因此，喷嘴缝的横向(即嘴缝长度方向)宽度均匀性是非晶宽带横向厚度均匀性的关键之一。熔潭内层流钢液的横向扰动及熔潭不稳定性会增大带材自由面的粗糙度和划痕的深度，从而间接影响带材的厚度。冷却辊表面粗糙度会直接反映到带材的贴辊面，也会影响带材的平整度，从而间接地影响带材的厚度。
美国发明专利US19970864892提供了一种用于非晶合金宽带制造的喷嘴结构，通过专门的喷嘴外形设计，可以获得最大宽度为200mm的、横向厚度均匀的非晶合金宽带。中国发明专利ZL99808439.5公开了一种制造170mm宽非晶带材的方法，其通过将冷却辊表面粗糙度控制在0.005mm以下、并将喷嘴缝表面粗糙度控制在0.005mm以下，可以制造宽度170mm、叠片系数90％左右的铁基非晶宽带。然而，如果制造更宽的非晶合金宽带，由于喷嘴处的温度梯度很大，过长的喷嘴很容易发生变形，从而影响非晶合金宽带的横向厚度一致性，严重降低非晶宽带的叠片系数，严重时热应力甚至会使喷嘴开裂，而不能满足制造宽度在220mm以 上高质量铁基非晶合金宽带的要求。
目前，非晶宽带已经实现了商业化生产，例如安泰科技股份有限公司生产的铁基非晶合金带材产品(1K101)共有142mm、170mm、213mm三种宽度规格，用于不同尺寸的变压器铁芯。现有技术可以生产宽度不大于213mm的铁基非晶合金带材，但市售纳米晶带材(1k107)宽度一般小于50mm。这是由于非晶合金含有20％左右的Si、B类金属元素，其合金熔体具有较大的非晶形成能力和良好的流动性，而纳米晶合金熔体因为含有大量的Nb元素具有很高的粘度，因而流动性很差，制带困难，利用现有规格的非晶合金带材设计制造纳米晶宽带，只能大幅度增加喷带压力提高喷带温度来增加熔体的流动性，过大压力将导致喷嘴变形甚至使喷嘴开裂，而喷带温度过高会导致金属液中的杂质过多，同时也增加漏钢的危险，在技术上不可行。由于纳米晶合金配电变压器的节能效益、及其优异的高频性能，迫切希望能够在大型变压器、电抗器、电机中使用纳米晶合金作为铁芯材料。因此，需要使用带宽更大、饱和磁感应强度更高的纳米晶合金带材进行制造以发挥纳米晶合金的优势，特别是对宽度在50mm以上的铁基纳米晶合金超薄宽带提出了很大需求。
发明内容
针对现有技术中存在的缺陷和不足，本发明的目的在于提供一种铁基纳米晶合金超薄宽带及其制造方法，该纳米晶合金宽带的宽度为50～200mm，饱和磁感强度大于1.7T，带材表面平整度高，退火后韧性好，高频损耗低。
为了达到上述目的，本发明提供了如下技术方案：
一种铁基纳米晶合金超薄宽带，所述合金超薄宽带的组分表达式为FexSiaBbPcNbdCueMf，其中所述表达式中M为Sn和/或Al；所述表达式中x、a、b、c、d、e和f分别表示各对应组分的原子百分比含量且满足以下条件：0.5≤a≤10，0.5≤b≤12，0.5≤c≤8，0.1≤d≤1，0.1≤e≤3，0.001≤f≤0.05且x+a+b+c+d+e+f＝100。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述组分Fe的原子百分比含量x的取值范围为82≤x≤83。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述组分Si的原子百分比含量a的取值范围为1≤a≤6(比如1.2、2、3、4、5、5.8)。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述组分B的原子百分比含量b的取值范围为2≤b≤7(比如2.1、3、4、5、6、6.8)。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述组分P的原子百分比含量c的取值范围为2≤c≤5(比如2.1、2.5、3、4、4.5)。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述组分Nb的原子百分比含量d的取值范围为0.5≤d≤0.75(比如0.55、0.6、0.65、0.7、0.74)。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述组分Cu的原子百分比含量e的取值范围为0.5≤e≤0.75(比如0.55、0.6、0.65、0.7、0.74)。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述组分M的原子百分比含量f的取值范围为0.01≤f≤0.05(比如0.015、0.02、0.025、0.03、0.035、0.04、0.045)。
在上述铁基纳米晶合金超薄宽带中，作为一种优选实施方式，所述超薄宽带的宽度为50～200mm，厚度为0.001～0.02mm，横向(即超薄宽带的宽度方向)厚度偏差小于±0.0015mm，叠片系数大于0.80，饱和磁通密度大于1.7T，且在频率为50Hz、最大磁通密度为1.5T条件下铁损小于0.30W/kg。
下面对上述铁基纳米晶软磁合金的成分设计原理进行说明：
在本发明的铁基纳米晶合金中，Si元素的原子％要满足：0.5≤a≤10，优选的范围是1≤a≤6。Si元素是构成非晶态合金的常用元素，Si元素的适量添加，不仅能提高合金的热稳定性和居里温度，提高合金的非晶形成能力，而且还能提高B和P等类金属元素在合金中的溶解度，扩大合金的成分范围；当Si元素原子％含量少于0.5时，Si元素的促进形成非晶态合金的作用很难充分发挥出来，而当Si元素原子％含量大于10时，则会降低铁磁性元素的含量，无法获得高饱和磁感应强度的软磁合金。
在本发明的铁基纳米晶合金中，B元素的原子％要满足0.5≤b≤12，优选的范围是5≤b≤8。当B原子％小于0.5时，B元素含量太低，则不易形成纳米晶合金的前驱体，即非晶态合金。而当B原子％大于12时，则会降低合金中铁磁性元素含量而降低合金的饱和磁感应强度。
在本发明的铁基纳米晶合金中，P元素的原子％要满足：0.5≤c≤8，优选的范围是2≤c≤5。P元素是构成非晶态合金的常用元素，P元素的适量添加，P和体系里的其他元素都有较大的负的混合热，P的添加有利于提高过冷液相区的稳定 性，不仅可以提高合金的非晶形成能力，而且能提高合金的热稳定性和扩大非晶合金的热处理温区范围。当P元素原子％含量少于0.5时，P元素的促进形成非晶态合金的作用难以发挥出来，而当P元素原子％含量大于8时，则会降低铁磁性元素的含量，无法获得高饱和磁感应强度的软磁合金。
在本发明的铁基纳米晶合金中，Nb的原子％要满足0.1≤d≤1，优选的范围为0.5≤d≤0.75。Nb为大原子元素，同时也是抑制a-Fe纳米晶粒长大、细化晶粒、提升纳米晶软磁性能的有效元素。由于Nb元素均为非铁磁性元素，含量超过1原子％时，会降低合金中铁磁性元素含量，从而降低饱和磁感应强度。而Nb元素含量少于0.1原子％时，Nb元素的提高非晶形成能力、细化晶粒、改善软磁性能的作用难以发挥出来。
在本发明的铁基纳米晶合金中，Cu元素因其不溶于Fe，在热处理时，首先从非晶基体中均匀析出，促进α-Fe形核，是制备纳米晶合金的通用元素。Cu元素的原子％要满足：0.1≤e≤3，优选的范围是0.5≤e≤0.75。当Cu原子％大于3时，合金的非晶形成能力变差，难以制备。而当Cu原子％小于0.1时，Cu在退火时作为促进α-Fe形核，形成纳米晶合金的作用难以发挥出来。
在本发明的铁基纳米晶合金中，所述组分M是表面活性元素Al或者Sn的一种或者两种的任意组合，微量表面活性元素Al和Sn的加入，大大降低了熔体的表面张力，通过熔体及表面张力的相互作用维持了熔体的稳定性。
在上述铁基纳米晶软磁合金中，可能还含有少量不可避免的杂质元素，但是所有杂质元素的总重量百分比要小于0.5％。
一种上述铁基纳米晶合金超薄宽带的制造方法，其采用平面流铸造工艺，包括如下步骤：
步骤一，按照所述合金超薄宽带的组分表达式准备原料，然后在保护气体气氛下采用感应熔炼将所述原料熔化并进行过热处理，以形成成分均匀的钢液；
步骤二，将所述钢液浇入中间包镇静并进行钢液净化处理；
步骤三，将所述中间包中的钢液浇入喷嘴包中，然后所述钢液从设置于喷嘴包底面的喷嘴的嘴缝流至位于所述喷嘴下方旋转的冷却辊表面，并迅速冷却成为铁基非晶合金超薄宽带；
步骤四，将所述铁基非晶合金超薄宽带进行热处理，从而得到铁基纳米晶合金超薄宽带。
在上述制造方法中，作为一种优选实施方式，在所述步骤四中，所述热处理的时间为5-120min(比如6min、20min、30min、50min、80min、90min、110min)，所述热处理的温度为400-600℃(比如410℃、450℃、500℃、520℃、550℃、580℃、595℃)。
在上述制造方法中，作为一种优选实施方式，在所述步骤三中，冷却后得到的所述铁基非晶合金超薄宽带随即被卷取机同步卷取成宽带卷。
具体地，本发明的铁基纳米晶合金宽带采用工艺改进的平面流铸造法及传统的等温退火处理方法，基本工艺流程包括配料及母合金熔炼、钢液镇静及净化处理、非晶合金宽带高速连铸、合金宽带在线卷取、等温退火处理，工艺流程如图1所示。
对于本发明的铁基纳米晶合金宽带，可以采用纯铁、硼铁、硅铁、铌铁、磷铁、铜锭、铝锭、锡锭作为母合金熔炼的原材料，在感应炉或其它方式的冶炼炉1中将原材料熔化并进行过热处理以形成成分均匀的钢液。然后，将钢液浇入中间包2中。中间包既起到对生产节奏的缓冲作用，又使得钢液得到一定时间的镇静，配合现有技术的其它冶金手段可以使得钢液中的夹杂物充分上浮，改善母合金钢液质量。镇静并净化后的母合金钢液被浇入喷嘴包3中，喷嘴包3的底部设有喷嘴7，喷嘴7包括狭长的嘴缝71以及位于嘴缝下方的熔潭容纳部78，以使钢液流出并得到保护。在喷嘴缝的下方有一只高速旋转的铜合金冷却辊4，钢液流到冷却辊表面后立即铺展成为均匀的薄膜并迅速冷却成为非晶合金带材，带材随即通卷取机5同步卷取成带材卷6，再经热处理后得到本发明的铁基纳米晶合金宽带。
在上述制造方法中，作为一种优选实施方式，在所述步骤一中，所述过热处理的温度不低于1500℃(比如1500℃、1550℃、1600℃、1660℃、1700℃)，过热处理的时间不少于10min(比如11min、13min、15min、18min、20min、30min、50min或60min)。
在上述制造方法中，作为一种优选实施方式，在所述步骤二中，所述钢液镇静的温度为1250-1300℃(比如1250℃、1280℃、1290℃、1290℃、1300℃、1350℃)，所述净化处理是向所述钢液中加入净化剂并多次打渣以去除钢液中的夹杂物。优选地选用以氧化硅和稀土作为净化剂主体，同时以氧化钙和硅锰合金作为稳定剂的净化剂，在中间包内钢水达到镇静温度后进行钢液净化。净化过程中密度较小的氧化物、氮化物、硫化物等杂质不熔于钢水，被同质的净化剂所吸附，不断地 上浮、聚合在钢水表层。渣层覆盖在钢水表面，隔离大气和钢水，避免了钢水与O、N的直接接触，降低了元素Si和B的烧损。更优选地，在所述净化剂中，氧化硅含量为20-35wt％；氧化钙不仅能脱氧，而且能去除钢水中的S，氧化钙含量为7-20wt％；硅锰合金主要用于脱氧另外，Mn的存在可以有效地去除杂质元素S，由于S几乎是硼铁、硅和铁源中必含的杂质元素，且易导致非晶带材的发脆，而Mn的存在可以和S在钢水中形成MnS低熔点化合物而上浮，进入渣层，从而达到脱硫的效果，硅锰合金(比如硅锰合金6517)的含量为10-20wt％；余量为稀土；最终将钢水中O、S、N含量均控制在10ppm以下。
在上述制造方法中，作为一种优选实施方式，在所述步骤三中，所述喷嘴为熔潭内嵌式喷嘴，包括：
喷嘴本体，形成有钢液容纳部，用于接收并缓冲来自所述喷嘴包的钢液；
嘴缝，设置于所述喷嘴本体的下底面上，用于将所述喷嘴本体内的钢液喷出；以及
熔潭保护体：设置于所述喷嘴本体的下方并与所述喷嘴本体连接，形成有熔潭容纳部，用于保护所述钢液喷出所述嘴缝后形成的熔潭。
上述制造方法中，作为一种优选实施方式，在所述熔潭内嵌式喷嘴中，所述喷嘴本体包括第一喷嘴本体侧壁、第二喷嘴本体侧壁、第三喷嘴本体侧壁、第四喷嘴本体侧壁，所述第一喷嘴本体侧壁、第二喷嘴本体侧壁、第三喷嘴本体侧壁以及第四喷嘴本体侧壁依次连接以形成封闭的喷嘴本体周壁，所述喷嘴本体周壁和所述喷嘴本体下底面围成上底面开口的所述钢液容纳部；所述第一喷嘴本体侧壁和所述第三喷嘴本体侧壁与所述嘴缝的长度方向平行。
在所述熔潭内嵌式喷嘴中，作为一种优选实施方式，所述嘴缝的宽度为0.05～0.3mm(比如0.06mm、0.08mm、0.1mm、0.15mm、0.2mm、0.25mm、0.3mm)，更优选地，所述嘴缝的横向(即沿嘴缝的长度方向)宽度偏差小于±0.025mm(比如0.002mm、0.005mm、0.008mm、0.01mm、0.015mm、0.018mm、0.02mm、0.024mm)。
上述制造方法中，作为一种优选实施方式，在所述熔潭内嵌式喷嘴中，所述熔潭保护体包括：
前唇，自所述第一喷嘴本体侧壁下端面垂直向下延伸；
后唇，自所述第三喷嘴本体侧壁下端面垂直向下延伸；
第一侧唇，自所述第二喷嘴本体侧壁下端面垂直向下延伸；
第二侧唇，自所述第四喷嘴本体侧壁下端面垂直向下延伸；
所述前唇、所述第一侧唇、所述后唇以及所述第二侧唇依次连接以形成下底面开口的所述熔潭容纳部。
上述制造方法中，作为一种优选实施方式，所述熔潭容纳部的形状与钢液喷出所述嘴缝后形成的熔潭形状相同或接近。
上述制造方法中，作为一种优选实施方式，所述后唇的内壁自上到下是倾斜设置的且所述后唇的壁厚自上到下逐渐减小。更优选地，所述后唇的内壁为直线型倾斜设置或弧线型倾斜设置。
上述制造方法中，作为一种优选实施方式，所述前唇的下端面的形状与对应的冷却辊面形状相同；所述后唇的下端面的形状与对应的冷却辊面形状相同；所述第一侧唇的下端面的形状与对应的冷却辊面形状相同；所述第二侧唇的下端面的形状与对应的冷却辊面形状相同。
上述制造方法中，作为一种优选实施方式，所述前唇的高度不低于所述后唇的高度；优选地，所述前唇的高度高于所述后唇的高度。
上述制造方法中，作为一种优选实施方式，所述前唇的下端面与所述冷却辊表面的垂直距离不低于0.05mm(比如0.06mm、0.08mm、0.1mm、0.15mm、0.2mm、0.25mm、0.3mm、0.35mm、0.4mm)；所述后唇的下端面与所述冷却辊表面的垂直距离不低于0.1mm(比如0.11mm、0.15mm、0.2mm、0.25mm、0.3mm、0.35mm、0.4mm)；更优选地，所述后唇的下端面与所述冷却辊表面的垂直距离为0.1-0.3mm。
上述制造方法中，作为一种优选实施方式，所述嘴缝与所述冷却辊面的垂直距离为0.25mm。
在上述制造方法中，作为一种优选实施方式，在所述步骤三中，所述喷嘴制带时采用后喷法进行制带。
在上述制造方法中，作为一种优选实施方式，在所述步骤三中，所述喷嘴制带时，所述钢液自所述喷嘴流出的温度(即喷带温度)为1300～1350℃(比如1310℃、1320℃、1330℃或1340℃)，高温喷带有利于开包及增大熔体的流动性。
在上述制造方法中，作为一种优选实施方式，在所述步骤三中，所述冷却辊的横向(即冷却辊的宽度方向)平整度小于0.015m；所述冷却辊的表面粗糙度Ra始终小于0.0005mm；优选地，所述冷却辊外表面的线速度为25～35m/sec。
一种喷嘴为熔潭内嵌式喷嘴，包括：
喷嘴本体，形成有钢液容纳部，用于接收并缓冲来自所述喷嘴包的钢液；
嘴缝，设置于所述喷嘴本体的下底面上，用于将所述喷嘴本体内的钢液喷出；以及
熔潭保护体：设置于所述喷嘴本体的下方并与所述喷嘴本体连接，形成有熔潭容纳部，用于保护所述钢液喷出所述嘴缝后形成的熔潭。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述喷嘴本体包括第一喷嘴本体侧壁、第二喷嘴本体侧壁、第三喷嘴本体侧壁、第四喷嘴本体侧壁，所述第一喷嘴本体侧壁、第二喷嘴本体侧壁、第三喷嘴本体侧壁以及第四喷嘴本体侧壁依次连接以形成封闭的喷嘴本体周壁，所述喷嘴本体周壁和所述喷嘴本体下底面围成上底面开口的所述钢液容纳部；所述第一喷嘴本体侧壁和所述第三喷嘴本体侧壁与所述嘴缝的长度方向平行。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述嘴缝的宽度为0.05～0.3mm(比如0.06mm、0.08mm、0.1mm、0.15mm、0.2mm、0.25mm、0.3mm)，更优选地，所述嘴缝的横向(即沿嘴缝的长度方向)宽度偏差小于±0.025mm(比如0.002mm、0.005mm、0.008mm、0.01mm、0.015mm、0.018mm、0.02mm、0.024mm)。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，在所述熔潭内嵌式喷嘴中，所述熔潭保护体包括：
前唇，自所述第一喷嘴本体侧壁下端面垂直向下延伸；
后唇，自所述第三喷嘴本体侧壁下端面垂直向下延伸；
第一侧唇，自所述第二喷嘴本体侧壁下端面垂直向下延伸；
第二侧唇，自所述第四喷嘴本体侧壁下端面垂直向下延伸；
所述前唇、所述第一侧唇、所述后唇以及所述第二侧唇依次连接以形成下底面开口的所述熔潭容纳部。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述熔潭容纳部的形状与钢液喷出所述嘴缝后形成的熔潭形状相同或接近。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述后唇的内壁自上到下是倾斜设置的且所述后唇的壁厚自上到下逐渐减小。更优选地，所述后唇的内壁为直线型倾斜设置或弧线型倾斜设置。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述前唇的下端面的形状与对应的冷却辊面形状相同；所述后唇的下端面的形状与对应的冷却辊面 形状相同；所述第一侧唇的下端面的形状与对应的冷却辊面形状相同；所述第二侧唇的下端面的形状与对应的冷却辊面形状相同。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述前唇的高度不低于所述后唇的高度；优选地，所述前唇的高度高于所述后唇的高度。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述前唇的下端面与所述冷却辊表面的垂直距离不低于0.05mm(比如0.06mm、0.08mm、0.1mm、0.15mm、0.2mm、0.25mm、0.3mm、0.35mm、0.4mm)；所述后唇的下端面与所述冷却辊表面的垂直距离不低于0.1mm(比如0.11mm、0.15mm、0.2mm、0.25mm、0.3mm、0.35mm、0.4mm)；更优选地，所述后唇的下端面表面与所述冷却辊的垂直距离为0.1-0.3mm。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述嘴缝与所述冷却辊面的垂直距离为0.25mm。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述前唇的厚度不小于所述第一喷嘴本体侧壁的厚度。
上述喷嘴为熔潭内嵌式喷嘴中，作为一种优选实施方式，所述后唇上端部的厚度不小于所述第三喷嘴本体侧壁的厚度。
平面流铸造法制备非晶带材时熔潭处于动态平衡状态，从喷嘴包进入熔潭的熔体和从熔潭底部抽取的非晶带材达到动态平衡，非晶带材的稳定生产才能持续。本发明的平面流铸造过程无需特殊气氛，在大气气氛下即可完成。喷嘴嘴缝长度直接决定了带宽，而喷嘴缝的横向尺寸均匀性也决定了非晶宽带横向厚度均匀性。同时，熔潭内层流钢液的横向扰动及熔潭不稳定性会增大带材自由面的粗糙度和划痕的深度，从而间接影响带材的厚度。铜辊表面粗糙度会直接反映到带材的贴辊面，也会影响带材的平整度，也会间接的影响带材的厚度。而熔体的均匀性、洁净度直接影响熔体的流动性及喷带工艺的难易程度及稳定性。为了获得纳米晶超薄宽带，本发明方法在传统平面流铸造方法的基础上，对熔体状态、喷嘴尺寸、熔潭稳定性、冷却辊面状态均进行了调控，具体实施方案如下：
1)熔体即钢液均一性的控制：合金熔体存在结构遗传性，合金熔体的不均匀性会导致最终产品性能的不稳定。该纳米晶合金熔体在高温过热区存在液液结构相变，不同成分的合金熔体液液相变温度在1350-1450之间。因此，为了获得高度均一的合金熔体，在熔炼炉中的熔炼温度必须在1500度以上过热，使熔体内的难溶晶核、大分子团簇充分溶解。
2)喷嘴嘴缝的控制：控制喷嘴的嘴缝宽度W的范围：0.05毫米≤D≤0.3毫米。嘴缝大于0.3毫米，很难得到厚度小于20微米的薄带；嘴逢小于0.05毫米，由于表面张力的作用使金属液很难流出喷嘴，并且钢液中微量的夹杂物颗粒在喷嘴处积聚，使得非晶合金宽带产生分条。因此得到1-20微米厚的薄带的一个重要条件是喷嘴的缝隙宽度不能太宽，必须限制在小于0.3毫米。当喷嘴的嘴缝比较宽时，提高冷却辊的转速可以适当减薄带厚，但是过于提高冷却辊的转速会增大带材表面的粗糙度和表面划痕的深度。一般嘴缝在0.3-1.2毫米之间时，仅可以制得的非晶带材的厚度在20-60微米。也就是说嘴缝过宽，无论如何调整冷却辊的转速还是减小辊嘴间距，都不能有效减薄带厚。
3)喷嘴形状和结构的控制：本发明使用的熔潭内嵌型喷嘴，喷嘴前唇下端面几乎紧贴辊面，而喷嘴后唇的高度略高于前唇的高度即后唇下端面与辊面的距离大于前唇下端面与辊面的距离，这种设计极大的减少气流对熔潭的冲击，增加熔潭稳定性。另外，本发明要求喷嘴缝的横向宽度偏差小于±0.025mm。通过实验发现，如果喷嘴缝的横向宽度偏差大于±0.025mm，会对钢液流量均匀性有一定影响，导致宽带厚度均匀性略差，所生产宽带的叠片系数略差。
4)熔潭的形状及稳定性控制：首先本发明采用熔潭内嵌式喷嘴，熔潭位于喷嘴内部，大大降低了冷却辊运动引起的气流对熔潭的冲击；另外，本发明通过合理设计成分，大幅降低了纳米晶合金的粘度，增加了合金熔体的流动性及充型能力，特别是微量表面活性元素Al和Sn的加入，大大降低了熔体的表面张力，通过熔体及表面张力的相互作用维持了熔体的稳定性。
5)喷带方式的控制，本发明采用后喷法进行喷带，大大增加了带材在冷却辊上的冷却行程，降低了带材剥离温度，同时采用熔潭内嵌式喷嘴，熔潭位于喷嘴熔潭容纳部内，喷嘴后唇与熔潭下端面距离很小，对熔潭自由面形成刮压和修正作用，减小了非晶合金带材对层流钢液的横向扰动，从而减小了带材的表面应力，提高了非晶带材的表面质量品质及成品性能的稳定性。
6)冷却辊转速的控制：在喷嘴单位流量一定的情况下，加大辊速则可以加大其拉伸率，但是带材厚度下降有限，而带材表面的拉痕太大，使表面粗糙度加大，甚至出现网状结构和孔洞，质量严重下降。所以，冷却辊子转速一般不能太大，线速度要小于35米/秒。
7)冷却辊表面的平整度及粗糙度的控制：如果冷却辊表面存在横向或纵向起伏， 将显著影响非晶合金宽带的厚度在横向或纵向的一致性，进而间接的影响带材的厚度。本发明通过实验发现，要使非晶合金宽带的叠片系数达到80％以上，必须保证冷却辊表面的横向平整度偏差小于0.015mm，高平整度的冷却辊面可以通过市售的高精度车削装置来实现。而在非晶合金带材的连铸过程中，由于冷却辊表面不断承受钢液的侵蚀和热冲击，辊面质量会逐渐恶化，出现坑状缺陷。为了及时消除辊面缺陷，还需采用市售的在线高效的辊面修复装置对辊面不断地被清洁和修复。
8)超薄宽带收取方式的控制：由于非晶合金带材的连铸速度高达约20m/sec，所制造的合金带材必须与带材的连铸过程同步卷取，否则带材将迅速堆积，不但使后期卷取的效率低下，而且使带材形成大量皱褶，从而容易断裂和降低叠片系数。采用自动卷取装置，不但实现合金带材的同步卷取，实现非晶合金带材的大批量连续化生产。
与现有技术相比，本发明的有益效果在于：
1)本发明突破了原有纳米晶软磁合金带在合金成分上的限制，开发出了新的合金系。本发明通过成分设计，制备出兼备高饱和磁化强度、强非晶形成能力的Fe基纳米晶软磁合金超薄宽带。Nb元素的大幅降低及P元素的大量添加，提高了非晶形成能力的同时减少了钢水的粘度，增加了熔融合金的流动性及充型能力，并很大程度上降低了材料的生产成本。
2)本发明将微量表面活性元素添加到合金中，可以大幅度降低喷带时熔体的表面张力而不降低熔体的粘度，通过协调熔体表面张力及粘度的相互作用来调整熔潭的形状和尺寸来提高熔潭稳定性，达到稳定喷带的要求。本发明使用在其现有合金成分的基础上添加原子比为0.001-0.05％的Al和Sn中至少一种组分，在不破坏合金软磁性能的前提下，大大降低了合金熔体的表面张力，降低了纳米晶合金制带开包时的难度，同时增加了熔潭的稳定性，从而改善了带材自由面的平整度，极大提高了带材生产的工艺及产品质量稳定。
3)本发明通过三包法制带，采用冶炼炉中高温熔炼(熔炼最高温度大于1500℃)，中间包低温镇静(低于1300℃)，喷嘴包较高温度喷带(高于1300℃)。熔炼炉高温熔炼可以最大程度地提高钢液的均匀性，减少内生夹杂。中间包低温镇静可以最大限度的去除因温度降低而继续析出的夹杂物，喷嘴包较高温度喷带避免了再生夹杂物的新出，同时降低了熔体的粘度，增加了钢液的流动性，有利 于降低开包难度及因夹杂物堵塞产生的断带现象。三包法每个阶段钢液控温制度可根据要求独立调节，可以保证在生产的每个流程中最大限度的去除钢液在生产流程中产生的夹杂物，提高钢液洁净度的同时降低了生产成本。
4)本发明采用熔潭内嵌式喷嘴，喷嘴前唇紧贴辊面，且熔潭位于喷嘴熔潭容纳部内，减少了冷却辊子表层的气流对熔潭的影响，提高了熔潭的稳定性。现有的喷嘴熔潭均暴露在空气中，受转动的冷却辊子表层的气流的影响急速冷却，降温比较严重，加之喷嘴必须外露，以便与冷却辊接近形成必要的熔潭形状，喷嘴的外露的平面在快速转动的冷却辊的表面处降温很快。若要保持喷嘴的温度，需要不断流过喷嘴的金属液对喷嘴有加热作用，甚至采用复杂的火焰幕熔潭保护技术使喷嘴失去的热量与金属液对喷嘴的热量补充相平衡，技术难度高，效果差。因此现有技术不能保证喷出表面光亮、厚度为1-20微米、填充系数高的非晶带材。
5)本发明控制喷嘴的嘴缝宽度，强调嘴缝宽度W的范围：0.05毫米≤D≤0.30毫米。嘴缝大于0.30毫米不能得到厚度小于20微米的薄带，通常得到厚度大于20微米的厚带，即使得到20微米左右的带材，其表面的粗糙度会很大，带材的表面不光滑，使用价值不大。因此得到1-20微米厚的超薄带的一个重要条件是喷嘴的缝隙宽度不能太宽，必须限制在小于0.30毫米。
6)本发明使用在线自动卷取机构进行收取带材，使上述步骤获得的带材能够在始终张紧的状态下卷取成盘，薄带不产生皱折，后续可以使用自动绕铁心的设备进行铁心卷绕，并可以在随后的带材纵向和横向剪切过程中顺利剪切，而不发生断裂，同时保证铁心的填充系数很高。这也是制造高品质铁心的一个重要条件。而现有技术中，由于得不到优质薄带，就无法使用在线自动卷取，而是直接剥离到地面，再进行收集。而在剥离、打落到地面、带材移动和收集中将产生许多皱折和损伤，从而降低所加工成的铁心的品质和磁性能。
7)本发明所述非晶超薄宽带在传统热处理炉内进行热处理，即可获得软磁性能优异的超薄纳米晶宽带，所述热处理时间为5-120min，所述热处理温度为400-600℃，热处理温区宽，且长时间热处理软磁性能不会恶化，此外，本发明热处理可在大气气氛下进行，特别适合工业化生产。
8)上述1-8条共同作用，可以更好地生产高质量、表面光洁度高、厚度为1-20微米的均匀的纳米晶超薄宽带，本发明生产与退火工艺简单、成本低、易于实现工业化，所制得产品具有优异软磁性能，具有高的填充系数，应用于电力、 电子、信息、通讯等领域。
本发明方法制备的超薄宽带带宽为50～200mm，厚度为0.001～0.02mm，带材横向厚度偏差小于±0.0015mm，叠片系数大于0.80，饱和磁通密度大于1.7T，在频率为50Hz、最大磁通密度为1.5T条件下铁损小于0.30W/kg。
附图说明
图1为本发明的铁基纳米晶超薄宽带制造方法的工艺原理示意图；
图2为现有的传统喷嘴侧面剖视图；
图3为本发明的熔潭内嵌式喷嘴侧面剖视图；
图4为本发明的熔潭内嵌式喷嘴仰视图；
图5为本发明实施例Fe82.5Si4B8P4Nb0.7Cu0.75Al0.02Sn0.03合金不同厚度全非晶条带淬态XRD图片。
图6为本发明例Fe82.5Si4B8P4Nb0.7Cu0.75Al0.02Sn0.03合金全非晶条带经560℃退火30分钟的TEM图片；
其中，附图标记如下：1、冶炼炉；2、中间包；3、喷嘴包；4、冷却辊；5、卷取机；6、带材卷；7、喷嘴，71，71’、嘴缝；72、后唇；73、前唇；74、第一侧唇；75、第二侧唇；76、后唇内侧面；77、钢液容纳部；78、熔潭容纳部；79’、第一喷嘴本体侧壁；79”、第二喷嘴本体侧壁；8、钢液；9、薄带；10、冷却辊。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。
本发明提供了一种喷嘴为熔潭内嵌式喷嘴7，包括：用于接收并缓冲来自喷嘴包3的钢液的喷嘴本体；设置于喷嘴本体的下底面上的嘴缝71以及用于保护钢液8喷出嘴缝71后形成的熔潭的熔潭保护体。下面对上述部件一一进行介绍。
喷嘴本体，形成有钢液容纳部77，用于接收并缓冲来自喷嘴包3的钢液。喷嘴本体的上端面固定于喷嘴包3的钢液出口处。
喷嘴本体包括第一喷嘴本体侧壁79’、第二喷嘴本体侧壁(未示出)、第三喷嘴本体侧壁79”、第四喷嘴本体侧壁(未示出)，第一喷嘴本体侧壁79’、第二喷嘴本体侧壁、第三喷嘴本体侧壁79”以及第四喷嘴本体侧壁依次连接以形成封闭的喷嘴本体周壁，所述喷嘴本体周壁和所述喷嘴本体下底面围成上底面开口的钢液容纳部77；第一喷嘴本体侧壁79’和第三喷嘴本体侧壁79”与嘴缝71的长度L方向平行。第二喷嘴本体侧壁和第四喷嘴本体侧壁与嘴缝71的长度L方向垂直。
嘴缝71，设置于喷嘴本体的下底面上，用于将喷嘴本体内的钢液8喷出；嘴缝的宽度W为0.05～0.3mm，更优选地，所述嘴缝的横向(即沿嘴缝的长度L方向)宽度偏差小于±0.025mm(比如0.002mm、0.005mm、0.008mm、0.01mm、0.015mm、0.018mm、0.02mm、0.024mm)。
熔潭保护体：设置于喷嘴本体的下方并与喷嘴本体连接，形成有熔潭容纳部78，用于保护钢液喷出嘴缝71后形成的熔潭。熔潭保护体包括前唇73、后唇72、第一侧唇74、第二侧唇75，前唇73、第一侧唇74、后唇72以及第二侧唇75依次连接以形成下底面开口的熔潭容纳部78。其中：前唇73，自第一喷嘴本体侧壁79’下端面垂直向下延伸而形成的；后唇72，自第三喷嘴本体侧壁79”下端面垂直向下延伸而形成的；第一侧唇74，自第二喷嘴本体侧壁下端面垂直向下延伸而形成的；第二侧唇75，自第四喷嘴本体侧壁下端面垂直向下延伸而形成的；前唇73后唇72与嘴缝71的长度L方向平行。第一侧唇74和第三侧唇75与嘴缝71的长度L方向垂直。熔潭容纳部78对钢液形成保护作用，减少了冷却辊表层的气流对熔潭的影响，提高了熔潭的稳定性，防止其快速降温。现有的喷嘴结构如图2所示，其仅包括喷嘴本体和嘴缝71’，无喷嘴本体下方的熔潭保护体，熔潭均暴露在空气中，受转动的冷却辊子表层的气流的影响急速冷却，降温比较严重，加之喷嘴必须外露，以便与冷却辊接近形成必要的熔潭形状，喷嘴的外露的平面在快速转动的冷却辊的表面处降温很快。现有技术中，若要保持喷嘴的温度，需要不断流过喷嘴的金属液对喷嘴有加热作用，甚至采用复杂的火焰幕熔潭保护技术使喷嘴失去的热量与金属液对喷嘴的热量补充相平衡，技术难度高，效果差。而本发明的喷嘴具有熔潭保护体，可以很好地解决现有喷嘴中存在的技术问题。
在本发明中，前唇73和后唇72是相对于冷却辊运动方向而言的，开启冷却辊后，处于静止状态时冷却辊的最低点转动到喷嘴附近最先通过的是前唇73，之后通过的是喷嘴后唇74。
熔潭容纳部78的形状与钢液喷出嘴缝71后形成的熔潭形状接近或相同。优选地，后唇72的内壁自上到下是倾斜设置的且后唇72的壁厚自上到下逐渐减小。更优选地，后唇72的内壁为直线型倾斜设置或弧线型倾斜设置。前唇73的下端面的形状与对应的冷却辊10的表面形状相同；后唇72的下端面的形状与对应的冷却辊10的表面形状相同；第一侧唇74的下端面的形状与对应的冷却辊10的表面形状相同；第二侧唇75的下端面的形状与对应的冷却辊10的表面形状相同。 也就是说熔潭保护体的下端面与冷却辊面平行，前唇主要是阻挡冷却辊高速转动时将辊面带动的气体卷入熔潭，因此前唇73的厚度不小于所述第一喷嘴本体侧壁79’的厚度即可，优选二者厚度相同。后唇72主要作用是对熔潭的自由面的刮压和对层流钢液的横向扰动的修正作用，因此后唇72相应形状应该与熔潭后端自由面相近，优选地，后唇72的内壁自上到下是倾斜设置的且后唇72的壁厚自上到下逐渐减小；更优选地，后唇72的内壁为直线型倾斜设置或弧线型倾斜设置；进一步地，后唇72上端部的厚度不小于第三喷嘴本体侧壁79”的厚度。这样可以减小熔体对后唇72的冲击，更好地对熔潭自由面的进行刮压和对层流钢液的横向扰动进行修正，从而形成厚度均匀、表面粗糙度低的薄带材9。
前唇73的高度(即从喷嘴本体下底面至前唇下端面的距离)不低于后唇的高度(从喷嘴本体下底面至后唇下端面的距离)；优选地，所述前唇的高度高于所述后唇的高度。前唇73的下端面与冷却辊10表面的垂直距离不低于0.05mm(比如0.06mm、0.08mm、0.1mm、0.15mm、0.2mm、0.25mm、0.3mm、0.35mm、0.4mm)，前唇距离辊面过近容易划伤辊子；后唇72的下端面与冷却辊10表面的垂直距离不低于0.1mm(比如0.11mm、0.15mm、0.2mm、0.25mm、0.3mm、0.35mm、0.4mm)；更优选地，后唇72的下端面与冷却辊10表面的垂直距离为0.1-0.3mm。后唇过低容易直接与凝固的带材接触，在带材自由面形成划痕，若后唇过高，比如与辊嘴间距相同，则喷嘴后唇起不到对对熔潭自由面的刮压并对层流钢液的横向扰动的修正作用。第一侧唇74和第二侧唇75的下端面距离冷却辊10正下方表面的距离不低于0.05mm。
本发明的喷嘴在使用时，优选，嘴缝71与冷却辊面的垂直距离为0.25mm。
下面针对本发明合金超薄带材的制备进行详细说明。
实施例1
在本发明所述的铁基非晶合金的化学成分范围内，分别选取6种不同的铁基非晶合金成分，序号为1-6，用平面流铸造工艺制造纳米晶合金宽带，主要工艺参数如下：
(1)采用纯铁、硼铁、硅铁、铌铁、磷铁、铜锭、铝锭、锡锭作为母合金熔炼的原材料，按照表1中各合金表达式准备原料，在氩气保护下的感应炉或其它方式的冶炼炉1中将原材料熔化并进行过热处理以形成成分均匀的钢液。熔炼温 度为1400℃，熔炼时间为30min，钢水化清后在1550℃下进行过热处理，过热时间20min，得到均匀的钢液。
(2)然后将熔炼后的钢液倒入中间包中，镇静温度为1280℃。钢液温度达到设定温度后加入以氧化硅和稀土作为净化剂主体，以氧化钙和硅锰合金作为稳定剂的净化剂，进行钢液净化，在净化剂中，各组分含量为20wt％的氧化硅、15wt％的氧化钙、15wt％的硅锰合金，余量为稀土。镇静时间为30min，实时监控钢液内O、S、N含量，经过多次镇静打渣，最终将O、S、N含量均控制在10ppm以下。
(3)将中间包中的钢液浇入喷嘴包中，然后钢液从位于喷嘴包底部的喷嘴的嘴缝喷至位于喷嘴下方旋转的冷却辊表面，并迅速冷却成为铁基非晶合金超薄宽带，其中，喷嘴为本发明的熔潭内嵌式喷嘴，嘴缝长度L为51-201mm，嘴缝宽度W为0.2-0.3mm，嘴缝横向(沿嘴缝长度方向)宽度偏差不大于±0.02mm；喷嘴前唇下端面与其正下方的冷却辊的垂直距离为0.05mm，喷嘴后唇下端面与其正下方的冷却辊的垂直距离为0.15mm，嘴缝与其正下方的冷却辊的垂直距离为0.25mm；冷却辊的线速度为25m/s，喷带温度为1300-1350℃，喷带粘度10.0-13.2mPa·S，喷带表面张力为0.6-1.75N/m，冷却辊表面粗糙度Ra为0.00030-0.00050mm，冷却辊表面横向(即辊的宽度方向或嘴缝的长度方向)平整度为0.003-0.018mm。
(4)然后在线自动卷取机构对超薄非晶宽带进行收取，从而得到带材卷。
(5)将超薄非晶宽带放入在常规热处理炉内，560℃处理30min。用X射线衍射仪(XRD)及投射电镜表征微观结构，用常规磁性测试设备测试本发明合金带材的磁性能。
各序号合金的某些具体工艺参数和非晶合金宽带的性能分别如表1和表4中1-6所示。
利用本实施例的工艺所制造的铁基纳米晶合金宽带厚度在0.01～0.02mm之间，宽带厚度的横向偏差不大于±0.0015mm,叠片系数大于0.80，饱和磁通密度大于1.7T，在频率为50Hz、最大磁通密度为1.3T条件下的铁损小于0.20W/kg。
由图5可以看出，制备的合金成分为Fe82.5Si4B8P4Nb0.7Cu0.75Al0.02Sn0.03的全玻璃棒表面光滑又金属光泽，XRD只有一个宽大的馒头峰，是典型的非晶结构，带材厚度达到0.05mm时，仍然保持典型的非晶态，说明该体系具有强非晶形成能力， 可以制备淬态结构均一的非晶条带。
由图6可以看出，Fe82.5Si4B8P4Nb0.7Cu0.75Al0.02Sn0.03非晶条带经560℃退火30分钟等温退火后形成典型的纳米双相复合结构，大量直径约为17nm的α-Fe纳米粒子均匀分布在非晶基体上。
实施例2
本发明微量表面活性元素Al和Sn的加入，可以大幅度降低喷带时熔体的表面张力而不降低熔体的粘度，通过协调熔体表面张力及粘度的相互作用来调整熔潭的形状和尺寸来提高熔潭稳定性，从而达到改善带材自由面平整度的目的，并减小了开包难度，极大提高了带材生产的工艺及产品质量稳定。在本发明所述的铁基非晶合金的化学成分范围内，分别选取6种不同的铁基非晶合金成分，序号为7-12(其中序号7和11的合金为对比例)，用平面流铸造工艺制造纳米晶合金宽带，主要工艺参数如下：
(1)采用纯铁、硼铁、硅铁、铌铁、磷铁、铜锭、铝锭、锡锭作为母合金熔炼的原材料，按照表1中各合金表达式准备原料，在氩气保护下的感应炉或其它方式的冶炼炉1中将原材料熔化并进行过热处理以形成成分均匀的钢液。熔炼温度为1400℃，熔炼时间为30min，钢水化清后在1550℃下进行过热处理，过热时间20min，得到均匀的钢液。
(2)然后将熔炼后的钢液倒入中间包中，镇静温度为1280℃。钢液温度达到设定温度后加入以氧化硅和稀土作为净化剂主体，以氧化钙和硅锰合金作为稳定剂的净化剂，进行钢液净化，各组分含量为20wt％的氧化硅、15wt％的氧化钙、15wt％的硅锰合金，余量为稀土。镇静时间为30min，实时监控钢液内O、S、N含量，经过多次镇静打渣，最终将O、S、N含量均控制在10ppm以下，
(3)将中间包中的钢液浇入喷嘴包中，然后钢液从位于喷嘴包底部的喷嘴的嘴缝喷至位于喷嘴下方旋转的冷却辊表面，并迅速冷却成为铁基纳米晶合金超薄宽带，其中，喷嘴为本发明的熔潭内嵌式喷嘴，嘴缝长度为151mm，嘴缝宽度为0.02mm，嘴缝横向宽度偏差不大于±0.02mm；喷嘴前唇下端面与其正下方的冷却辊的垂直距离为0.05mm，喷嘴后唇下端面与其正下方的冷却辊的垂直距离为0.15mm，嘴缝与其正下方的冷却辊的垂直距离为0.25mm；冷却辊的线速度为25m/s，喷带温度为1300℃，喷带粘度10.0-13.2mPa·S，喷带表面张力为0.6-1.75N/m， 冷却辊表面粗糙度Ra为0.00030-0.00050mm，冷却辊表面横向(即辊的宽度方向)平整度为0.003-0.018mm。
(4)然后在线自动卷取机构对超薄非晶宽带进行收取，从而得到带材卷。
(5)将超薄非晶宽带放入在常规热处理炉内，560℃处理30min。用X射线衍射仪(XRD)及投射电镜表征微观结构，用常规磁性测试设备测试本发明合金带材的磁性能。
各序号合金的具体工艺参数和非晶合金宽带的性能分别如表1和表4中7-12所示。
通过对本实施例热处理前后带材微观结构的观察可以看出，该体系具有强非晶形成能力，可以制备淬态结构均一的非晶条带；经等温退火后可形成典型的纳米双相复合结构，大量α-Fe纳米粒子均匀分布在非晶基体上。
综合实施例可以看出，Al和Sn对纳米晶超薄宽带的制备及性能能影响较大。这表现在如下两个方面：1.熔体方面，适量Al和Sn元素的添加大幅降低了熔体的表面张力，对熔体粘度影响不大，所以在温度熔潭的同时大大降低了喷带时开包难度；2.磁性能方面，适量Al和Sn元素的添加对饱和磁感及损耗影响不大，但是过量添加会导致带材变脆及损耗变大。
实施例3
本发明采用熔潭内嵌式喷嘴喷带，极大的提高了熔潭稳定性，改善了带材自由面表面质量，采用超窄嘴缝控制单位时间内通过喷嘴的钢液流量，同时采用高精度在线修磨装置，改善带材贴辊面表面质量，三个参数相互协调进一步提高超薄宽带的质量。在本发明所述的铁基非晶合金的化学成分范围内，分别选取6种不同的铁基非晶合金成分，序号为13-18，用平面流铸造工艺制造纳米晶合金宽带，主要工艺参数如下：
(1)采用纯铁、硼铁、硅铁、铌铁、磷铁、铜锭、铝锭、锡锭作为母合金熔炼的原材料，按照表1中各合金表达式准备原料，在氩气保护下的感应炉或其它方式的冶炼炉1中将原材料熔化并进行过热处理以形成成分均匀的钢液。熔炼温度为1400℃，熔炼时间为30min，钢水化清后在1550℃下进行过热处理，过热时间20min，得到均匀的钢液。
(2)然后将熔炼后的钢液倒入中间包中，镇静温度为1280℃。钢液温度达到 设定温度后加入以氧化硅和稀土作为净化剂主体，以氧化钙和硅锰合金作为稳定剂的净化剂，进行钢液净化，各组分含量为20wt％的氧化硅、15wt％的氧化钙、15wt％的硅锰合金，余量为稀土。镇静时间为30min，实时监控钢液内O、S、N含量，经过多次镇静打渣，最终将O、S、N含量均控制在10ppm以下，
(3)将中间包中的钢液浇入喷嘴包中，然后钢液从位于喷嘴包底部的喷嘴的嘴缝喷至位于喷嘴下方旋转的冷却辊表面，并迅速冷却成为铁基纳米晶合金超薄宽带，其中，喷嘴为本发明的熔潭内嵌式喷嘴，嘴缝长度为150mm，嘴缝宽度为0.05-0.2mm，嘴缝横向宽度偏差不大于±0.02mm；喷嘴前唇下端面与其正下方的冷却辊的垂直距离为0.05mm，喷嘴后唇下端面与其正下方的冷却辊的垂直距离为0.15mm，嘴缝与其正下方的冷却辊的垂直距离为0.25mm；冷却辊的线速度为25m/s，喷带温度为1320℃，喷带粘度10.0mPa.S，喷带表面张力为0.6-1.75N/m，冷却辊表面粗糙度Ra为0.00030-0.00050mm，冷却辊表面横向(即辊的宽度方向)平整度为0.003-0.018mm。
(4)然后在线自动卷取机构对超薄非晶宽带进行收取，从而得到带材卷。
(5)将超薄非晶宽带放入在常规热处理炉内，560℃处理30min。
用X射线衍射仪(XRD)及投射电镜表征微观结构，用常规磁性测试设备测试本发明合
各序号合金的具体工艺参数和非晶合金宽带的性能分别如表2、表4和表5中13-18所示。
综合实施例可以看出，喷带设备及工艺对超薄宽带的制备也有很大影响。这表现在如下两个方面：1.损耗方面，带材损耗随带厚迅速降低。2.带厚方面，喷嘴嘴缝宽度直接决定了带材厚度。3.表面质量方面，熔潭内嵌式喷嘴的使用大大降低了带材表面张力的粗糙度，从而有效提高了叠片系数，并且间接的减小了带材厚度。
实施例4
采用平面流铸造制备的非晶条带，带厚主要由喷嘴嘴缝宽度尺寸、熔潭稳定性及冷却辊表面质量三个因素决定。非晶合金带材制造时，喷嘴缝的尺寸决定了母合金钢液的流量，因此，喷嘴缝的横向宽度均匀性是非晶宽带横向厚度均匀性的关键之一。熔潭内层流钢液的横向扰动及熔潭不稳定性会增大带材自由面的粗 糙度和划痕的深度，从而间接影响带材的厚度。冷却辊表面粗糙度会直接反映到带材的贴辊面，也会影响带材的平整度，从而间接地影响带材的厚度。因此，本实施例设置了8个对比试验(商业化非晶合金Fe78Si9B13、商业化纳米晶合金Fe73.5Cu1Nb3Si13.5B9，本发明成分Fe82.5Si4B8P4Nb0.7Cu0.75Al0.02Sn0.03)，序号为19-26，除某些工艺参数参见表3外，其他工艺参见实施例1。重点考察喷嘴形状和结构、嘴缝宽带、辊面粗糙度对带材质量及性能的影响。综合实施例可以看出：1.嘴缝尺寸直接决定了单位时间内流经喷嘴的钢液，因此超窄嘴缝是制备超薄带的前提；2.使用超窄嘴缝进行喷带时，熔体表面张力必须小，才能顺利开包；3.合金成分具有强非晶形成能力才能制备宽带；4.采用熔潭内嵌式喷嘴可以有效减少熔潭内层流钢液的横向扰动及熔潭不稳定性会增大带材自由面的粗糙度和划痕的深度，有效改善带材自由面的质量。5.采用市售的高精度在线修磨装置，改善带材贴辊面表面质量，从而改善带材贴辊面的质量。本发明通过优化成分设计，突破了原有纳米晶软磁合金带在合金成分上的限制，开发出了具有强非晶形成能力的纳米晶合金体系，通过微量表面活性元素Al和Sn的加入，大大降低了熔体的表面张力，喷带时开包难度大大降低。辅以熔潭内嵌式喷嘴及辊面的在线修磨，提高了带材的表面质量，成功制备了超薄纳米晶宽带。本发明采用改进的平面流铸造方法，对非晶、纳米晶宽带的工业化生产具有重要意义。结果参见表5。
以上实施方式仅用于说明本发明，而并非对本发明的限制，有关技术领域的普通技术人员，在不脱离本发明的精神和范围的情况下，还可以做出各种变化和变型，因此所有等同的技术方案也属于本发明的范畴，本发明的专利保护范围应由权利要求限定。
Figure PCTCN2016083738-appb-000001
Figure PCTCN2016083738-appb-000002
Figure PCTCN2016083738-appb-000003
Figure PCTCN2016083738-appb-000004
Figure PCTCN2016083738-appb-000005

Claims (27)

  1. 一种铁基纳米晶合金超薄宽带，其特征在于，所述合金超薄宽带的组分表达式为FexSiaBbPcNbdCueMf，其中所述表达式中M为Sn和/或Al；所述表达式中x、a、b、c、d、e和f分别表示各对应组分的原子百分比含量且满足以下条件：0.5≤a≤10，0.5≤b≤12，0.5≤c≤8，0.1≤d≤3，0.1≤e≤1，0.001≤f≤0.05且x+a+b+c+d+e+f＝100。
  2. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述组分Fe的原子百分比含量x的取值范围为82≤x≤83。
  3. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述组分Si的原子百分比含量a的取值范围为1≤a≤6。
  4. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述组分B的原子百分比含量b的取值范围为2≤b≤7。
  5. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述组分P的原子百分比含量c的取值范围为2≤c≤5。
  6. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述组分Nb的原子百分比含量d的取值范围为0.5≤d≤0.75。
  7. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述组分Cu的原子百分比含量e的取值范围为0.5≤e≤0.75。
  8. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述组分M的原子百分比含量f的取值范围为0.01≤f≤0.05。
  9. 根据权利要求1所述的铁基纳米晶合金超薄宽带，其特征在于，所述超薄宽带的宽度为50～200mm，厚度为0.001～0.02mm，横向厚度偏差小于±0.0015mm，叠片系 数大于0.80，饱和磁通密度大于1.7T，且在频率为50Hz、最大磁通密度为1.5T条件下铁损小于0.30W/kg。
  10. 权利要求1-9任一所述的铁基纳米晶合金超薄宽带的制造方法，包括如下步骤：
    步骤一，按照权利要求1-9任一所述合金超薄宽带的组分表达式准备原料，然后在保护气体气氛下采用感应熔炼将所述原料熔化并进行过热处理，以形成成分均匀的钢液；
    步骤二，将所述钢液浇入中间包镇静并进行钢液净化处理；
    步骤三，将所述中间包中的钢液浇入喷嘴包中，然后所述钢液从设置于喷嘴包底面的喷嘴的嘴缝流至位于所述喷嘴下方旋转的冷却辊表面，并迅速冷却成为铁基非晶合金超薄宽带；
    步骤四，将所述铁基非晶合金超薄宽带进行热处理，从而得到铁基纳米晶合金超薄宽带。
  11. 根据权利要求10所述的制造方法，其特征在于，在所述步骤四中，所述热处理的时间为5-120min，所述热处理的温度为400-600℃。
  12. 根据权利要求10所述的制造方法，其特征在于，在所述步骤三中，冷却后得到的所述铁基非晶合金超薄宽带随即被卷取机同步卷取成宽带卷。
  13. 根据权利要求10所述的制造方法，其特征在于，在所述步骤一中，所述过热处理的温度不低于1500℃，过热处理的时间不少于10min。
  14. 根据权利要求10所述的制造方法，其特征在于，在所述步骤二中，所述钢液镇静的温度为1250-1300℃，所述净化处理是向所述钢液中加入净化剂并多次打渣以去除钢液中的夹杂物；优选地，所述净化剂包括：氧化硅20-35wt％；氧化钙7-20wt％；硅锰合金10-20wt％；余量为稀土。
  15. 根据权利要求10所述的制造方法，其特征在于，在所述步骤三中，所述喷嘴为熔潭内嵌式喷嘴，包括：
    喷嘴本体，形成有钢液容纳部，用于接收并缓冲来自所述喷嘴包的钢液；
    嘴缝，设置于所述喷嘴本体的下底面上，用于将所述喷嘴本体内的钢液喷出；以及
    熔潭保护体：设置于所述喷嘴本体的下方并与所述喷嘴本体连接，形成有熔潭容纳部，用于保护所述钢液喷出所述嘴缝后形成的熔潭。
  16. 根据权利要求15所述的制造方法，其特征在于，在所述熔潭内嵌式喷嘴中，所述喷嘴本体包括第一喷嘴本体侧壁、第二喷嘴本体侧壁、第三喷嘴本体侧壁、第四喷嘴本体侧壁，所述第一喷嘴本体侧壁、第二喷嘴本体侧壁、第三喷嘴本体侧壁以及第四喷嘴本体侧壁依次连接以形成封闭的喷嘴本体周壁，所述喷嘴本体周壁和所述喷嘴本体下底面围成上底面开口的所述钢液容纳部；所述第一喷嘴本体侧壁和所述第三喷嘴本体侧壁与所述嘴缝的长度方向平行。
  17. 根据权利要求15所述的制造方法，其特征在于，所述嘴缝的宽度为0.05～0.3mm，优选地，所述嘴缝的横向宽度偏差小于±0.025mm。
  18. 根据权利要求16所述的制造方法，其特征在于，在所述熔潭内嵌式喷嘴中，所述熔潭保护体包括：
    前唇，自所述第一喷嘴本体侧壁下端面垂直向下延伸；
    后唇，自所述第三喷嘴本体侧壁下端面垂直向下延伸；
    第一侧唇，自所述第二喷嘴本体侧壁下端面垂直向下延伸；
    第二侧唇，自所述第四喷嘴本体侧壁下端面垂直向下延伸；
    所述前唇、所述第一侧唇、所述后唇以及所述第二侧唇依次连接以形成下底面开口的所述熔潭容纳部。
  19. 根据权利要求16所述的制造方法，其特征在于，所述熔潭容纳部的形状与钢液喷出所述嘴缝后形成的熔潭形状相同或相近。
  20. 根据权利要求18所述的制造方法，其特征在于，所述后唇的内壁自上到下是倾斜设置的且所述后唇的壁厚自上到下逐渐减小；优选地，所述后唇的内壁为直线型倾斜设置或弧线型倾斜设置。
  21. 根据权利要求18所述的制造方法，其特征在于，所述前唇的高度不低于所述后唇的高度；优选地，所述前唇的高度高于所述后唇的高度。
  22. 根据权利要求18所述的制造方法，其特征在于，所述前唇的下端面与所述冷却辊的垂直距离不低于0.05mm；所述后唇的下端面与所述冷却辊表面表面的垂直距离不低于0.1mm；更优选地，所述后唇的下端面与所述冷却辊表面的垂直距离为0.1-0.3mm。
  23. 根据权利要求15所述的制造方法，其特征在于，所述嘴缝与所述冷却辊面的垂直距离为0.25mm。
  24. 根据权利要求10所述的制造方法，其特征在于，在所述步骤三中，所述喷嘴制带时采用后喷法进行制带。
  25. 根据权利要求10所述的制造方法，其特征在于，在所述步骤三中，所述喷嘴制带时，所述钢液自所述喷嘴流出的温度为1300～1350℃。
  26. 根据权利要求10所述的制造方法，其特征在于，在所述步骤三中，所述冷却辊的横向平整度小于0.02mm；所述冷却辊的表面粗糙度Ra始终小于0.0005mm；优选地，所述冷却辊外表面的线速度为25～35m/sec。
  27. 一种喷嘴为熔潭内嵌式喷嘴，其特征在于，包括：
    喷嘴本体，形成有钢液容纳部，用于接收并缓冲来自所述喷嘴包的钢液；
    嘴缝，设置于所述喷嘴本体的下底面上，用于将所述喷嘴本体内的钢液喷出；以及
    熔潭保护体：设置于所述喷嘴本体的下方并与所述喷嘴本体连接，形成有熔潭容纳部，用于保护所述钢液喷出所述嘴缝后形成的熔潭。
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