[go: up one dir, main page]

WO2020206610A1 - 一种锆基非晶薄带材连续制备的方法 - Google Patents

一种锆基非晶薄带材连续制备的方法 Download PDF

Info

Publication number
WO2020206610A1
WO2020206610A1 PCT/CN2019/081934 CN2019081934W WO2020206610A1 WO 2020206610 A1 WO2020206610 A1 WO 2020206610A1 CN 2019081934 W CN2019081934 W CN 2019081934W WO 2020206610 A1 WO2020206610 A1 WO 2020206610A1
Authority
WO
WIPO (PCT)
Prior art keywords
alloy
casting
roll
zirconium
based amorphous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/081934
Other languages
English (en)
French (fr)
Inventor
袁国
张晨阳
张元祥
王洋
康健
李振磊
王黎筠
王国栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University China
Original Assignee
Northeastern University China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeastern University China filed Critical Northeastern University China
Publication of WO2020206610A1 publication Critical patent/WO2020206610A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B22D11/0622—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent

Definitions

  • the invention belongs to the field of amorphous alloy preparation, and specifically relates to a method for continuously preparing a zirconium-based amorphous alloy thin strip by using a double-roll method.
  • Amorphous alloy also known as Metallic Glass or Glassy Alloy
  • Metallic Glass or Glassy Alloy is a new, special, and crystalline alloy material prepared by applying modern rapid solidification metallurgical technology. Due to the unique atomic structure arrangement and metal bond composition of amorphous alloys, amorphous alloys have better mechanical, physical and chemical properties than traditional crystalline metal materials. This makes amorphous alloys have a wide range of application prospects in aerospace, weapon industry, precision instruments, biomedicine and power transmission.
  • the main production methods of amorphous strip include single-roll melt quenching method, double-roll melt quenching method and casting mold casting method.
  • the most widely used and industrialized production is the single-roll melt quenching method, referred to as the single-roll method.
  • the iron-based amorphous strip produced by the single-roll method has excellent soft magnetic properties, which can replace silicon steel and permalloy to make transformer cores, thereby greatly improving transformer efficiency, reducing iron loss of distribution transformers, and reducing volume and weight.
  • the single-roll production process limits the thickness (about 20-50 ⁇ m) and width (less than 220mm) of the strip.
  • the twin-roll melt quenching method is referred to as the twin-roll method.
  • the United States Patent discloses a continuous housing device and method for bulk amorphous alloy plates.
  • the device in the patent uses multiple sets of small-diameter cooling rolls to cool the alloy strip, because the row of rolls can only apply small Contact pressure, the cooling rate of the system can only reach less than 10°C/s, the thickness of the prepared sheet is 0.1-10mm, and it is limited to the forming of the Zr-based amorphous alloy containing Be with strong forming ability, which will also reduce the amorphous life and stability.
  • Chinese Patent Publication No. CN1486800A discloses a continuous casting and rolling technology for bulk amorphous alloys. The molten metal in the crucible is poured into two relatively rotating water-cooled rolls, and the bulk amorphous sheet is prepared by double-roller casting. , Bars, etc., but the patent does not see specific process protection nodes and technical implementation schemes.
  • a relatively large rolling force can be applied to the roll gap position to achieve a large cooling rate.
  • its cooling capacity is greater than that of the single-roll method, and it can be used to prepare amorphous alloy plates and strips with large thickness specifications.
  • the mold pull casting method is a kind of master alloy after melting in a crucible, heat preservation, and casting into a water-cooled hole through a flow nozzle, and pulling force on the formed amorphous alloy at a certain speed to realize the amorphous alloy Continuous casting method.
  • CN101543885A discloses a device and method for horizontal continuous casting of bulk amorphous alloys.
  • the cooling of the alloys mainly relies on water-cooled copper molds, and the solidified castings are continuously output by the pulling rod driven by the motor.
  • the purpose of the present invention is to provide a continuous preparation of zirconium-based amorphous alloys using a double-roll method
  • the thin strip method uses common industrial sponge zirconium and other raw materials, based on the characteristics of the thin strip casting and rolling process that can provide a continuous and stable solidification environment, and the amorphous formation process has a short flow, fast cooling speed and continuous preparation process.
  • the method of the present invention is used It can efficiently and continuously prepare zirconium-based amorphous thin strips and promote the application of zirconium-based amorphous alloys.
  • a method for continuous preparation of zirconium-based amorphous thin strips is carried out according to the following steps:
  • the alloy melt is introduced into the tundish through the preheated draft tube.
  • the temperature of the tundish is 100-300°C higher than the melting point of the alloy, so that the alloy is uniformly heated in the tundish, and the superheat of the alloy is controlled to 100-300 during casting. °C;
  • Amorphous thin strip forming process Open the stopper, and evenly distribute the alloy melt through the preheated flow nozzle to the roll gap of the casting roll, so that the alloy is rapidly cooled and cast-rolled; during the casting-rolling process, the alloy passes through The casting roll is rapidly cooled by heat transfer, and its cooling rate is 500-75000°C/s.
  • the casting-rolling speed to 0.01-3m/s and the casting-rolling force
  • the casting-rolling force per 1cm width of the cast strip is 2-15kN.
  • the width of the roll gap opening of the casting roll is set to 0.1 ⁇ 2mm to control the temperature of the alloy ribbon exit roll and control the alloy exit roll temperature to be less than the crystallization temperature Tx of the alloy;
  • a double-roll method is used to continuously and quickly prepare a zirconium-based amorphous alloy thin strip with a thickness of 0.1-2 mm.
  • the master alloy smelting process and the uniform temperature storage process are all carried out under a high vacuum of ⁇ 0.1Pa or a high-purity argon atmosphere with a volume purity of ⁇ 99.999%;
  • the rolling process is carried out under an argon atmosphere with a volume purity of ⁇ 99.9%.
  • the alloy raw materials are directly used for smelting, or the smelted master alloy is used for melting.
  • the method for continuous preparation of the zirconium-based amorphous thin strip is achieved by the flow port size at the lower end of the flow nozzle, the roll gap value, the casting speed, the copper casting roll, the steel casting roll, and the cooling water volume of the casting roll.
  • the casting-rolling process parameters control the solidification cooling rate to reach 500-75000°C/s.
  • the flow outlet at the lower end of the flow nozzle is designed to be rectangular or a row of circles, the width of the rectangle is 0.2 to 1 mm, and the diameter of the circle is 0.5 to 2 mm; It is divided into three types: direct injection roll gap method, single-side pouring method or double-side pouring method; the material of the flow port is SiO 2 or BN which is not easy to react with the alloy melt.
  • the preheating temperature range of the flow nozzle is 900-1200°C
  • the preheating temperature range of the draft tube is 900-1000°C.
  • the alloy molten pool on the upper part of the casting roll is controlled to be highly stable by controlling the alloy flow rate, and the surface of the alloy molten pool is aligned along the diameter direction of the casting roll.
  • the width is controlled within 20mm.
  • the casting roll is made of copper or steel alloy with good thermal conductivity, the casting roll diameter is 220mm-510mm, and the roll surface roughness Ra ⁇ 10 ⁇ m.
  • the cooling water inlet temperature of the casting roll is controlled at 5-12°C, and the outlet water temperature is controlled at 5-15°C.
  • the water temperature rise interval is less than 3°C. .
  • the present invention makes full use of thin strip continuous casting technology to continuously prepare bulk amorphous alloys.
  • the preparation process of alloy thin strips is formed in one step, and the process is short; the cooling and solidification process of the alloy has good heat conduction under pressure, and its cooling speed is fast, and industrial raw materials are used It can be used to prepare amorphous alloy ribbons.
  • the invention adopts the deep roll gap casting or side casting method in combination with the double-roll casting and rolling technology, and the alloy molten pool is narrow, the cooling rate is large, and the deformation is small.
  • the principle, structure and method have not yet been reported in public.
  • the present invention carries out sufficient technical practice, and realizes the continuous casting and rolling process of zirconium-based amorphous strip with a length of more than 12 m and a thickness of 0.2-0.75 mm.
  • the present invention provides a method for continuously and quickly preparing a zirconium-based amorphous alloy ribbon with a thickness of 0.1-2 mm using industrial raw materials. Its composition is: (Zr a Hf b Cu c Al d Ni e Ti f Y g ) 100-x O x , a, b, c, d, e, f, g, x are atomic percentages, where 30 ⁇ a ⁇ 75; 0 ⁇ b ⁇ 2; 10 ⁇ c ⁇ 45; 0 ⁇ d ⁇ 25; 0 ⁇ e ⁇ 15; 0 ⁇ f ⁇ 20; 0 ⁇ g ⁇ 3; 0.001 ⁇ x ⁇ 1.
  • trace Y element is used to suppress the adverse effect of O element in the raw material and the environment on the formation of matrix amorphous.
  • the completely molten metal melt is spread evenly through the cloth flow nozzle, and then the casting port that matches the roll gap is directly injected into the depth of the roll gap to evenly fill the entire roll gap. And realize the tiny liquid level control.
  • the alloy melt filled into the roll gap is in contact with the casting roll, so that the heat is lost through heat conduction through the roll. And deep pouring can make the alloy get a great cooling rate when it is just injected, thereby inhibiting the formation and growth of crystal nuclei.
  • the pressure generated by casting and rolling can accelerate the heat transfer of the alloy to the outside and increase the cooling rate of the alloy.
  • the reduction of the ratio of the width of the alloy molten pool to the width of the roll gap can reduce its casting deformation, thereby reducing the jamming of the cooled amorphous alloy due to excessive strength, ensuring the casting and rolling The process continues continuously. In addition, more free volume is obtained, so that the amorphous life, stability and amorphous forming ability are significantly improved.
  • the entire casting and rolling process of the present invention takes place in the sealing cover.
  • the sealing cover is filled with Ar gas as a protective gas to ensure that the alloy melt does not come into contact with oxygen during the solidification to a solid, preventing the occurrence of oxidation phenomenon and inhibiting the shape of the alloy. nuclear.
  • Fig. 1 is a structural schematic diagram of a casting and rolling device for continuous preparation of zirconium-based amorphous thin strips of the present invention.
  • 1 vacuum induction melting furnace 2 melting crucible, 3 draft tube, 4 gate valve, 5 tundish, 6 stopper rod, 7 tundish crucible, 8 flow nozzle, 9 casting roll, 10 sealed protective cover, 11 cast belts, 12 rows of rolls, 13 winding equipment.
  • Figure 2 is a schematic diagram of the structure of an amorphous alloy prepared by a two-roll single-side casting method. In the picture: 8 flow nozzles, 9 casting rolls, 14 single-side outlets, 15 alloy melts.
  • Figure 3 is a schematic diagram of the structure of the amorphous alloy prepared by the double-roll double-side casting method.
  • Figure 4 is a schematic diagram of 0.55 mm thick amorphous strip. Among them, (a) unfolded view, (b) take-up view.
  • Figure 5 is a microstructure photograph (a) and XRD graph (b).
  • the abscissa 2 ⁇ represents the diffraction angle (drgee)
  • the ordinate intensity represents the relative intensity (a.u.).
  • Figure 6 is the microstructure photograph (a) and XRD graph (b).
  • the abscissa 2 ⁇ represents the diffraction angle (drgee)
  • the ordinate intensity represents the relative intensity (a.u.).
  • Figure 7 is a microstructure photograph (a) and XRD graph (b).
  • the abscissa 2 ⁇ represents the diffraction angle (drgee)
  • the ordinate intensity represents the relative intensity (a.u.).
  • Figure 8 is a microstructure photograph (a) and XRD graph (b).
  • the abscissa 2 ⁇ represents the diffraction angle (drgee)
  • the ordinate intensity represents the relative intensity (a.u.).
  • Figure 9 is a microstructure photograph (a) and XRD graph (b).
  • the abscissa 2 ⁇ represents the diffraction angle (drgee)
  • the ordinate intensity represents the relative intensity (a.u.).
  • Figure 10 is a microstructure photograph (a) and XRD graph (b).
  • the abscissa 2 ⁇ represents the diffraction angle (drgee)
  • the ordinate intensity represents the relative intensity (a.u.).
  • Figure 11 is a microstructure photograph (a) and XRD graph (b).
  • the abscissa 2 ⁇ represents the diffraction angle (drgee)
  • the ordinate intensity represents the relative intensity (a.u.).
  • the casting and rolling device for continuous preparation of zirconium-based amorphous thin strip of the present invention mainly includes: vacuum induction melting furnace 1, melting crucible 2, draft tube 3, gate valve 4, tundish 5, plug The rod 6, the tundish crucible 7, the flow nozzle 8, the casting roll 9, the sealing protection cover 10, the casting belt 11, the row roll 12, the coiling device 13, etc.
  • the specific structure is as follows:
  • the bottom opening of the vacuum induction melting furnace 1 communicates with the top opening of the tundish 5 through the gate valve 4, and the bottom opening of the tundish 5 communicates with the top opening of the sealed protective cover 10;
  • the vacuum induction melting furnace 1 is provided with a melting crucible 2 and a guide
  • the flow tube 3 and the flow tube 3 are located at one side of the smelting crucible 2, the flow tube 3 is arranged vertically, and its lower port corresponds to the tundish crucible 7 in the tundish 5.
  • the zirconium-based amorphous master alloy melt When the zirconium-based amorphous master alloy melt is obtained by smelting in the vacuum induction melting furnace 1, it is poured into the draft tube 3, and the draft tube 3 moves down through the bottom opening of the vacuum induction melting furnace 1 and the top opening of the tundish 5. , The zirconium-based amorphous master alloy melt enters the tundish crucible 7 through the deflector 3.
  • the stopper rod 6 is vertically inserted through the tundish crucible 7, the lower end of the stopper rod 6 plugs the bottom opening of the tundish 5, and the upper side of the flow nozzle 8 is connected to the bottom opening of the tundish 5, and passes through the sealing protection cover 10 vertically.
  • the top opening of is inserted between the two casting rolls 9.
  • a row roller 12 and a winding device 13 are arranged, and a channel for the casting belt 11 is formed between the opposite row rollers 12.
  • the row rollers 12 are evenly arranged in an arc shape, and the upper part of the row roller 12 Corresponding to the roll gap between the two casting rolls 9, the lower part of the row roll 12 corresponds to the entrance of the winding device 13.
  • the alloy melt in the tundish crucible 7 flows evenly through the flow nozzle 8 to the roll gap between the two casting rolls 9, and is cooled in the roll gap to form a cast strip 11, which passes through The opposite row of rolls 12 below the casting roll 9 is guided through the winding device 13 to form a roll.
  • the structure of the amorphous alloy prepared by the double-roll single-side casting method corresponds to a casting roll 9 with a single-side outlet 14, and the flow nozzle 8
  • the alloy melt 15 flows through the single-side outlet 14 and flows out between the two casting rollers 9 along the corresponding casting roller 9 to form an amorphous strip.
  • the structure of the amorphous alloy prepared by the double-roll double-side casting method As shown in Figure 3, the structure of the amorphous alloy prepared by the double-roll double-side casting method.
  • the two sides of the bottom of the flow nozzle 8 correspond to the casting roll 9 and the two-sided outlets 16 are respectively provided in the flow nozzle 8.
  • the alloy melt 15 flows through the double-sided outlets 16, and merges into the casting roll gap along the corresponding casting roll 9 respectively, and is cast-rolled into an amorphous strip.
  • the composition of the zirconium-based amorphous alloy of the present invention is: (Zr a Hf b Cu c Al d Ni e Ti f Y g ) 100-x O x , a, b, c, d, e, f, g, x are atomic percentages, where: 30 ⁇ a ⁇ 75; 0 ⁇ b ⁇ 2; 10 ⁇ c ⁇ 45; 0 ⁇ d ⁇ 25; 0 ⁇ e ⁇ 15; 0 ⁇ f ⁇ 20; 0 ⁇ g ⁇ 3; 0.001 ⁇ x ⁇ 1.
  • the preparation method is: combining the characteristics of metal double-roll casting and rolling and amorphous continuous cooling and forming, smelting the alloy raw materials or the preliminarily prepared master alloy in a vacuum induction melting furnace 1 to obtain a zirconium-based amorphous master alloy melt.
  • a vacuum induction melting furnace 1 After the temperature control meets the requirements, fill with argon gas and open the gate valve 4 between the vacuum induction melting furnace 1 and the tundish 5, and introduce the zirconium-based amorphous master alloy melt through the preheating runner (duct 3) Inside the tundish 5 protected by high-purity argon.
  • the alloy melt 15 is evenly distributed through the flow nozzle 8 and then injected into the roll gap of the casting roll 9, and is cooled by the water-cooled casting roll 9 to form an amorphous strip.
  • the material is continuously cooled by the discharging roller 12 and introduced into the winding device 13. The entire casting-rolling-cooling-coiling process is completed in the cavity of the casting machine protected by high-purity argon.
  • Alloy composition (Zr 53.5 Hf 1.5 Cu 30 Al 10 Ni 5 ) 99.9 O 0.1 (atomic percentage at.%, the same below);
  • Distribution method deep roll gap cloth flow
  • the cooling rate of alloy melt is 10000°C/s. Its parameters are shown in Table 1 below.
  • Alloy composition (Zr 53.5 Hf 1.5 Cu 30 Al 10 Ni 5 ) 99.9 O 0.1 ;
  • Distribution method deep roll gap cloth flow
  • the alloy melt cooling rate is 20000°C/s. Its parameters are shown in Table 2 below.
  • Casting roll width 110mm Casting force About 50KN Alloy melting point Tl 885°C Strip width 50mm Crystallization temperature Tx 487°C Cast roll cooling water temperature 5°C Glass transition temperature Tg 403°C To To
  • Alloy composition (Zr 53.5 Hf 1.5 Cu 30 Al 10 Ni 5 ) 99.9 O 0.1 ;
  • Distribution method deep roll gap cloth flow
  • the alloy melt cooling rate is 30000°C/s. Its parameters are shown in Table 3 below.
  • the test obtained 0.5mm thick amorphous strip.
  • the microstructure photo and XRD curve are shown in Figure 7. It can be seen from Figure 7 that there is no crystal structure in the cast strip and it is an amorphous alloy.
  • Alloy composition (Zr 53.5 Hf 1.5 Cu 30 Al 10 Ni 5 ) 99.9 O 0.1 ;
  • Distribution method deep roll gap cloth flow
  • the cooling rate of the alloy melt is 55000°C/s. Its parameters are shown in Table 4 below.
  • the test obtained 0.23mm thick amorphous strip.
  • the microstructure photo and XRD curve are shown in Figure 8. It can be seen from Fig. 8 that the cast tape matrix is an amorphous structure with only a few crystal particles.
  • Alloy composition (Zr 63.5 Hf 1.5 Cu 17.5 Al 7.5 Ni 10 ) 99.9 O 0.1 ;
  • Distribution method deep roll gap cloth flow
  • the cooling rate of alloy melt is 15000°C/s. Its parameters are shown in Table 5 below.
  • the test obtained 0.5mm thick amorphous strip.
  • the microstructure photo and XRD curve are shown in Figure 9. It can be seen from Figure 9 that there is no crystal structure in the cast strip and it is an amorphous alloy.
  • Alloy composition (Zr 54 Hf 1 Cu 30 Al 10 Ni 5 ) 98.9 Y 1 O 0.1 ;
  • Flow distribution method unilateral flow distribution
  • the test obtained 0.6mm thick amorphous strip.
  • the microstructure photo and XRD curve are shown in Figure 10. It can be seen from Figure 10 that there is no crystal structure in the cast strip, and it is an amorphous alloy.
  • Alloy composition (Zr 51.5 Hf 1 Cu 17.9 Al 10 Ni 14.6 Ti 5 ) 99.9 O 0.1 ;
  • Distribution method deep roll gap cloth flow
  • the cooling rate of the alloy melt is 12000°C/s. Its parameters are shown in Table 7 below.
  • the test obtained 0.5 mm thick amorphous strip.
  • the microstructure photo and XRD curve are shown in Figure 11. It can be seen from Figure 11 that there is no crystal structure in the cast strip, and it is an amorphous alloy.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)

Abstract

一种锆基非晶合金薄带材连续制备的方法，该方法将合金原料或初步制得的母合金在真空感应熔炼炉（1）中熔炼获得锆基非晶母合金熔体，控温达到要求后，充入氩气并打开真空感应熔炼炉与中间包（5）间的闸板阀（4），将熔体通过导流管（3）导入具有高纯氩气保护的中间包内，中间包的控流塞棒（6）打开后，合金熔体（15）经布流嘴（8）均匀布流后注入铸辊（9）辊缝中，通过水冷铸辊冷却成形为非晶带材，非晶带材经排辊（12）继续冷却并导入卷取设备（13），整个铸轧、冷却、卷取过程在高纯氩气保护的铸机腔体内完成，该方法的非晶合金形成过程流程短、冷却快且制备过程连续化，利用该方法可高效、连续地制备锆基非晶薄带材。

Description

一种锆基非晶薄带材连续制备的方法 技术领域
本发明属于非晶合金制备领域，具体涉及一种使用双辊法连续制备锆基非晶合金薄带材的方法。
背景技术
非晶合金，也称金属玻璃(Metallic Glass)或玻璃合金(Glassy Alloy)，是应用现代快速凝固冶金技术制备获得的一种新型的、特殊的、物质状态明显区别于晶态的合金材料。由于非晶合金独特的原子结构排列及金属键组成，使非晶合金具有相比于传统晶态金属材料更为优异的力学性能、物理性能及化学性能。这使非晶合金在航空航天、兵器工业、精密仪器、生物医疗和电力输送等方面具有广泛的应用前景。
早期非晶合金的制备需要很大的冷却速度(＞10 6K/s)，当时非晶合金只能以粉、丝、薄带等形式存在，极大地削弱非晶合金性能潜力的发挥，限制非晶合金在工业中的应用。因此，自上世纪八十年代末开始，如何提高非晶合金的形成能力，制备大尺寸的非晶合金成为新材料研究领域中重点研究方向之一。从20世纪80年代至今的几十年里，经过大量学者的努力，已经开发出Zr基、Ti基、Fe基、Co基、Ni基、Cu基、Pt基等大量具有大的玻璃形成能力的合金体系；发展水淬法、铜模铸造法、定向凝固法、非晶粉末挤压法等多种块体非晶合金的制备技术。其中，使用单辊法生产的具有优良的软磁性能的非晶薄带在国内已经有大规模、广泛的应用，为我国电力系统的节能减排做出突出贡献。而且，块体非晶合金的制备与应用同样取得长足的发展，因其优异的力学性能，已被作为结构材料生产并应用于电子产品、体育器材、汽车零件等。目前，市场上应用的块体非晶合金产品最主要的生产方式是压铸法，由于其自身条件限制，只能生产小规格产品。而作为结构材料中应用广泛的板带材，依然没有可靠的生产方式。因此，如何实现非晶合金板带材连续、大量、稳定的生产，推动块体非晶合金的广泛应用，是当前非晶产业急需解决的问题之一。
目前，非晶板带的主要生产方法包括单辊熔体急冷法、双辊熔体急冷法和铸型拉铸法。目前应用最广的、已用于工业化生产的是单辊熔体急冷法，简称单辊法。单辊法生产的铁基非晶带材具有优良的软磁性能，能代替硅钢、坡莫合金以制作变压器铁芯，进而大大提高变压器效率，降低配电变压器的铁损，同时减小体积和重量。然而单辊法生产工艺限制带材的厚度(约20～50μm)和宽度(小于220mm)。双辊熔体急冷法简称双辊法。基于双辊法开发多种块体非晶合金的连铸方法。美国专利(公开号US2006/0260782A1)公开一种块体非晶合金板材的连续住在装置和方法，专利中装置采用多组小直径冷却辊冷却合金带材，由于其排辊只能施加较小接触压力，其系统冷速只能达到小于10℃/s，制备的板材厚度为0.1～10mm，且仅限于形成能力强的含Be的Zr基非晶合金的成型，也会降低非晶寿命和稳定性。与之技术思想较为接近的是中国专利(公开号CN 107755652 A)，其利用履带式冷却，连续铸造非晶，其接触力较小，冷速有限，同样会降低非晶寿命和制备非晶的成分设计冗余度。 中国专利(公开号CN1486800A)公开一种块体非晶合金连续铸轧技术，将坩埚中熔化的金属熔体注入两个相对旋转的水冷轧辊中，采用双轧辊铸轧制备块体非晶板材、棒材等，但该专利未见具体工艺保护节点和技术实施方案，同时对熔炼温度、保温措施、控流措施、冷速、铸轧力等详细参数也没有进行公开。而且辊缝位置可以施加相对较大轧制力，以实现较大冷速，在理论上其冷却能力大于单辊法，而且可是制备厚度规格较大的非晶合金板带材。铸型拉铸法，是一种熔炼后的母合金在坩埚中熔化、保温后经流嘴浇铸到水冷的孔型中，并通过以一定速度给成型的非晶合金以拉力，实现非晶合金连续铸造的方法。中国专利(公开号CN101543885A)公开一种块体非晶合金水平连续铸造的装置和方法，合金的冷却主要依靠水冷铜模，凝固的铸坯由电动机驱动的牵引杆拉动不断输出。
发明内容
针对锆基非晶合金制备对原料纯度、真空度要求高，尚未见锆基非晶合金板带材大量生产的问题，本发明的目的在于提供一种使用双辊法连续制备锆基非晶合金薄带材的方法，利用普通工业海绵锆等原料，基于薄带铸轧工艺可以提供连续稳定凝固环境的特点，非晶形成过程流程短、冷速快且制备过程连续化，利用本发明的方法可高效、连续地制备锆基非晶薄带材，促进锆基非晶合金的应用。
本发明的技术方案是：
一种锆基非晶薄带材连续制备的方法，按以下步骤进行：
(1)按设定成分熔炼母合金，其成分为：(Zr aHf bCu cAl dNi eTi fY g) 100-xO x，a、b、c、d、e、f、g、x为原子百分比，其中30≤a≤75；0≤b≤2；10≤c≤45；0≤d≤25；0≤e≤15；0≤f≤20；0≤g≤3；0.001＜x≤1；将合金原料或初步制得的母合金放入熔炼坩埚中熔炼至完全熔化，熔化后继续熔炼，在高于合金熔点200℃以上的温度下熔炼5～20min，使合金充分熔化；
(2)将合金熔体通过预热的导流管导入中间包内，中间包温度高于合金熔点100～300℃，使合金在中间包内均温，浇铸时控制合金过热度为100～300℃；
(3)非晶薄带成形过程：打开塞棒，将合金熔体经过预热的布流嘴均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形；铸轧过程中，合金通过铸辊传热快速冷却，其冷却速度为500～75000℃/s，通过控制铸轧速度为0.01～3m/s、铸轧力大小控制为每1cm宽度铸带的铸轧力为2～15kN，铸辊辊缝开口宽度设置为0.1～2mm，来调控合金薄带出辊温度，并将合金出辊温度控制在小于合金的晶化温度Tx；
(4)合金铸带经排辊再次冷却并导入卷取机成卷；铸带制备过程中，整个铸轧-冷却-卷取过程在高纯氩气保护的铸机腔体内完成。
所述的锆基非晶薄带材连续制备的方法，使用双辊法连续快速的制备0.1～2mm厚度的锆基非晶合金薄带。
所述的锆基非晶薄带材连续制备的方法，母合金熔炼过程和均温存储过程都在＜0.1Pa的高真空或体积纯度≥99.999％的高纯氩气保护氛围下进行的；铸轧过程在体积纯度≥99.9％的 氩气保护氛围下进行。
所述的锆基非晶薄带材连续制备的方法，熔炼坩埚中，直接使用合金原料进行熔炼，或者使用已熔炼好的母合金进行熔化。
所述的锆基非晶薄带材连续制备的方法，通过布流嘴下端的布流口尺寸、铸辊辊缝值、铸轧速度、铜质铸辊、钢质铸辊、铸辊冷却水量的铸轧工艺参数控制凝固冷却速度达到500～75000℃/s。
所述的锆基非晶薄带材连续制备的方法，布流嘴下端的布流口设计为矩形或一排圆形，矩形宽度为0.2～1mm，圆形直径为0.5～2mm；布流方式分为三种：直接注入辊缝法、单侧浇涂法或双侧浇涂法；布流口材质为不易与合金熔体反应的SiO 2或BN。
所述的锆基非晶薄带材连续制备的方法，布流嘴的预热温度范围为900～1200℃，导流管的预热温度范围为900～1000℃。
所述的锆基非晶薄带材连续制备的方法，薄带铸轧过程中，通过控制合金流量控制铸辊上部的合金熔池高度稳定，并将合金熔池表面沿铸辊辊径方向的宽度控制在20mm以内。
所述的锆基非晶薄带材连续制备的方法，铸辊采用导热性好的铜质或钢质合金制备，其铸辊辊径为220mm～510mm，辊面粗糙度Ra≤10μm。
所述的锆基非晶薄带材连续制备的方法，铸辊冷却水进水温度控制在5～12℃，出水温度控制在5～15℃，通过控制水流量，使水升温区间小于3℃。
本发明优点及有益效果是：
1、本发明充分利用薄带连铸技术对块体非晶合金进行连续制备，合金薄带制备过程一步成形，其流程短；合金冷却凝固过程受压力导热好，其冷速快，利用工业原料既可对非晶合金薄带进行制备。
2、对于块体非晶合金连续成形过程，大的冷速和良好的稳定性是必不可少的。而一般铸轧设备因其浇铸方式简单，合金熔池较宽，使得合金在浅过冷液相区的冷速较小，难以形成非晶合金。本发明根据块体非晶凝固的特点，结合双辊铸轧技术，采取深入辊缝浇铸或侧面浇涂法，合金熔池窄、冷速大、变形小。其原理、结构和方法尚未见公开报道，本发明进行充分的技术实践，并且实现12m以上长度、0.2～0.75mm厚度的锆基非晶带材连续铸轧过程。
3、本发明提供一种使用工业原料连续快速的制备0.1～2mm厚度的锆基非晶合金薄带的方法。其成分组成为：(Zr aHf bCu cAl dNi eTi fY g) 100-xO x，a、b、c、d、e、f、g、x为原子百分比，其中30≤a≤75；0≤b≤2；10≤c≤45；0≤d≤25；0≤e≤15；0≤f≤20；0≤g≤3；0.001＜x≤1。加入微量Y元素，用于抑制原料与环境中O元素对基体非晶形成的不利影响。
4、本发明将完全熔融的金属熔体通过布流水口将液流均匀展宽后，将与轧辊辊缝吻合的浇铸口直接注入辊缝深处，均匀地充满整个辊缝。并且实现微小液位控制。充入辊缝的合金熔体与铸辊辊接触，使热量通过轧辊导热流失。且深入浇注可使合金在刚注入时便可得到 极大的冷却速度，从而抑制晶核的形成和长大。此外，铸轧产生的压力可使合金向外传热加速，增加合金冷速。而且，因为合金熔池液面宽度与轧辊间隙宽度比例的减小可减小其铸轧变形量，从而减小因冷却后的非晶合金因为强度过高而出现的卡住现象，保证铸轧过程的连续进行。并且，获得较多的自由体积，使得非晶寿命、稳定性以及非晶成形能力显著提高。
5、本发明整个铸轧过程都发生在密封罩内，密封罩内充Ar气作为保护气体，保证合金熔体凝固到固体的过程中不与氧气接触，防止氧化现象的发生，抑制合金的形核。
附图说明
图1是本发明锆基非晶薄带材连续制备的铸轧装置的结构示意图。图中：1真空感应熔炼炉，2熔炼坩埚，3导流管，4闸板阀，5中间包，6塞棒，7中间包坩埚，8布流嘴，9铸辊，10密封保护罩，11铸带，12排辊，13卷取设备。
图2是双辊单侧浇涂法制备非晶合金的结构示意图。图中：8布流嘴，9铸辊，14单侧出口，15合金熔体。
图3是双辊双侧浇涂法制备非晶合金的结构示意图。图中：8布流嘴，9铸辊，15合金熔体，16双侧出口。
图4是0.55毫米厚非晶带材示意图。其中，(a)展开图，(b)卷取图。
图5是微观组织照片(a)及XRD曲线图(b)。图中，横坐标2θ代表衍射角(drgee)，纵坐标intensity代表相对强度(a.u.)。
图6是微观组织照片(a)及XRD曲线图(b)。图中，横坐标2θ代表衍射角(drgee)，纵坐标intensity代表相对强度(a.u.)。
图7是微观组织照片(a)及XRD曲线图(b)。图中，横坐标2θ代表衍射角(drgee)，纵坐标intensity代表相对强度(a.u.)。
图8是微观组织照片(a)及XRD曲线图(b)。图中，横坐标2θ代表衍射角(drgee)，纵坐标intensity代表相对强度(a.u.)。
图9是微观组织照片(a)及XRD曲线图(b)。图中，横坐标2θ代表衍射角(drgee)，纵坐标intensity代表相对强度(a.u.)。
图10是微观组织照片(a)及XRD曲线图(b)。图中，横坐标2θ代表衍射角(drgee)，纵坐标intensity代表相对强度(a.u.)。
图11是微观组织照片(a)及XRD曲线图(b)。图中，横坐标2θ代表衍射角(drgee)，纵坐标intensity代表相对强度(a.u.)。
具体实施方式
如图1所示，本发明锆基非晶薄带材连续制备的铸轧装置，主要包括：真空感应熔炼炉1、熔炼坩埚2、导流管3、闸板阀4、中间包5、塞棒6、中间包坩埚7、布流嘴8、铸辊9、密封保护罩10、铸带11、排辊12、卷取设备13等，具体结构如下：
真空感应熔炼炉1的底部开口通过闸板阀4与中间包5的顶部开口相通，中间包5的底 部开口与密封保护罩10的顶部开口相通；真空感应熔炼炉1内设置熔炼坩埚2和导流管3，导流管3位于熔炼坩埚2的一侧，导流管3竖向设置，其下端口与中间包5内的中间包坩埚7相对应。当真空感应熔炼炉1中熔炼获得锆基非晶母合金熔体时，倾倒于导流管3内，导流管3下移穿过真空感应熔炼炉1的底部开口与中间包5的顶部开口，锆基非晶母合金熔体经导流管3进入中间包坩埚7内。
塞棒6沿竖向穿设于中间包坩埚7，塞棒6下端塞住中间包5的底部开口，布流嘴8上侧连接中间包5的底部开口，并竖向穿过密封保护罩10的顶部开口插设于两个铸辊9之间。密封保护罩10内的铸辊9下方设置排辊12和卷取设备13，相对设置的排辊12之间形成铸带11的通道，排辊12呈弧形均匀排布，排辊12的上部与两个铸辊9之间的辊缝相对应，排辊12的下部与卷取设备13的进口相对应。当打开塞棒时，中间包坩埚7内的合金熔体经过布流嘴8均匀布流到两个铸辊9之间的辊缝，并在辊缝冷却成形为铸带11，铸带11经过铸辊9下方的相对排辊12导入经过卷取设备13成卷。
如图2所示，双辊单侧浇涂法制备非晶合金的结构，布流嘴8内的底部一侧与一个铸辊9相对应处设有单侧出口14，布流嘴8内的合金熔体15流经单侧出口14，沿所对应的铸辊9经过两个铸辊9之间流出形成非晶带材。
如图3所示，双辊双侧浇涂法制备非晶合金的结构，布流嘴8内的底部相对两侧与铸辊9相对应处分别设有双侧出口16，布流嘴8内的合金熔体15流经双侧出口16，分别沿所对应的铸辊9汇于铸辊辊缝，并铸轧成形为非晶带材。
在具体实施过程中，本发明锆基非晶合金的成分组成为：(Zr aHf bCu cAl dNi eTi fY g) 100-xO x，a、b、c、d、e、f、g、x为原子百分比，其中：30≤a≤75；0≤b≤2；10≤c≤45；0≤d≤25；0≤e≤15；0≤f≤20；0≤g≤3；0.001＜x≤1。其制备方法是：结合金属双辊铸轧和非晶连续冷却成形的特点，将合金原料或初步制得的母合金在真空感应熔炼炉1中熔炼获得锆基非晶母合金熔体。控温达到要求后，充入氩气并打开真空感应熔炼炉1与中间包5间的闸板阀4，将锆基非晶母合金熔体通过预热流道(导流管3)导入具有高纯氩气保护的中间包5内。中间包5的控流塞棒6打开后，合金熔体15经布流嘴8均匀布流后注入铸辊9的辊缝中，通过水冷铸辊9冷却成形为非晶带材，非晶带材经排辊12继续冷却并导入卷取设备13。整个铸轧-冷却-卷取过程在高纯氩气保护的铸机腔体内完成。
下面，结合附图和具体实施例对本发明作进一步的说明。
实施例一
合金成分：(Zr 53.5Hf 1.5Cu 30Al 10Ni 5) 99.9O 0.1(原子百分比at.％，下同)；
布流方式：深入辊缝布流；
制备流程：
a.按原子百分比配50kg原料，将其投入真空感应熔炼炉中，并抽真空至0.05Pa，对合金原料加热至其完全熔化熔化，并于1500℃继续熔炼10min。
b.关闭真空泵，向真空感应熔炼炉内充入体积纯度99.999％的高纯氩气至大气压，打开闸板阀，放下导流管，将合金经导流管(导流管的预热温度为1000℃)导入高纯氩气保护的中间包内。
c.合金在中间包均热后，打开塞棒，将合金熔体经过布流嘴(布流嘴的预热温度为1150℃)均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形，合金熔体冷却速度为10000℃/s。其参数如下表1所示。
表1实验主要参数
铸辊辊速 0.3m/s 熔炼温度 1500℃
辊缝开口宽度 0.5mm 继续熔炼时间 10min
辊径 300mm 中间包温度 1150℃
铸辊宽度 110mm 铸轧力() 约54KN
合金熔点Tl 885℃ 铸带宽度 60mm
晶化温度Tx 487℃ 铸辊冷却水温 5℃
玻璃转变温度Tg 403℃    
试验获得0.55毫米厚非晶带材，如图4所示。其微观组织照片及XRD曲线如图5所示。由图4-图5可以看出，铸带中不存在晶体组织，为非晶态合金。
实施例二
合金成分：(Zr 53.5Hf 1.5Cu 30Al 10Ni 5) 99.9O 0.1；
布流方式：深入辊缝布流；
制备流程：
a.按原子百分比配50kg原料，将其投入真空感应熔炼炉中，并抽真空至0.03Pa，对合金原料加热至其完全熔化熔化，并于1400℃继续熔炼20min。
b.关闭真空泵，向真空感应熔炼炉内充入体积纯度99.999％的高纯氩气至大气压，打开闸板阀，放下导流管，将合金经导流管(导流管的预热温度为950℃)导入高纯氩气保护的中间包内。
c.合金在中间包均热后，打开塞棒，将合金熔体经过布流嘴(布流嘴的预热温度为1000℃)均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形，合金熔体冷却速度为20000℃/s。其参数如下表2所示。
表2实验主要参数
铸辊辊速 0.5m/s 熔炼温度 1400℃
辊缝开口宽度 0.5mm 继续熔炼时间 20min
辊径 300mm 中间包温度 1000℃
铸辊宽度 110mm 铸轧力 约50KN
合金熔点Tl 885℃ 铸带宽度 50mm
晶化温度Tx 487℃ 铸辊冷却水温 5℃
玻璃转变温度Tg 403℃    
试验获得0.5mm厚非晶带材。其微观组织照片及XRD曲线如图6所示。由图6可以看出，铸带基体为非晶态，组织中仅存在极少晶体颗粒。
实施例三
合金成分：(Zr 53.5Hf 1.5Cu 30Al 10Ni 5) 99.9O 0.1；
布流方式：深入辊缝布流；
制备流程：
a.按原子百分比配50kg原料，将其投入真空感应熔炼炉中，并抽真空至0.08Pa，对合金原料加热至其完全熔化熔化，并于1500℃继续熔炼10min。
b.关闭真空泵，向真空感应熔炼炉内充入体积纯度99.999％的高纯氩气至大气压，打开闸板阀，放下导流管，将合金经导流管(导流管的预热温度为900℃)导入高纯氩气保护的中间包内。
c.合金在中间包均热后，打开塞棒，将合金熔体经过布流嘴(布流嘴的预热温度为1150℃)均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形，合金熔体冷却速度为30000℃/s。其参数如下表3所示。
表3实验主要参数
铸辊辊速 0.8m/s 熔炼温度 1500℃
辊缝开口宽度 0.5mm 继续熔炼时间 10min
辊径 500mm 中间包温度 1150℃
铸辊宽度 200mm 铸轧力 约46KN
合金熔点Tl 885℃ 铸带宽度 80mm
晶化温度Tx 487℃ 铸辊冷却水温 12℃
玻璃转变温度Tg 403℃    
试验获得0.5mm厚非晶带材。其微观组织照片及XRD曲线如图7所示。由图7可以看出，铸带中不存在晶体组织，为非晶态合金。
实施例四
合金成分：(Zr 53.5Hf 1.5Cu 30Al 10Ni 5) 99.9O 0.1；
布流方式：深入辊缝布流；
制备流程：
a.按原子百分比配50kg原料，将其投入真空感应熔炼炉中，并抽真空至0.04Pa，对合金原料加热至其完全熔化熔化，并于1500℃继续熔炼10min。
b.关闭真空泵，向真空感应熔炼炉内充入体积纯度99.999％的高纯氩气至大气压，打开闸板阀，放下导流管，将合金经导流管(导流管的预热温度为1000℃)导入高纯氩气保护的中间包内。
c.合金在中间包均热后，打开塞棒，将合金熔体经过布流嘴(布流嘴的预热温度为1150℃)均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形，合金熔体冷却速度为55000℃/s。其参数如下表4所示。
表4实验主要参数
铸辊辊速 2m/s 熔炼温度 1500℃
辊缝开口宽度 0.2mm 继续熔炼时间 10min
辊径 300mm 中间包温度 1150℃
铸辊宽度 110mm 铸轧力 约24KN
合金熔点Tl 885℃ 铸带宽度 80mm
晶化温度Tx 487℃ 铸辊冷却水温 5℃
玻璃转变温度Tg 403℃    
试验获得0.23mm厚非晶带材。其微观组织照片及XRD曲线如图8所示。由图8可以看出，铸带基体为非晶态组织，仅存在少量晶体颗粒。
实施例五
合金成分：(Zr 63.5Hf 1.5Cu 17.5Al 7.5Ni 10) 99.9O 0.1；
布流方式：深入辊缝布流；
制备流程：
a.按原子百分比配50kg原料，将其投入真空感应熔炼炉中，并抽真空至0.06Pa，对合金原料加热至其完全熔化熔化，并于1500℃继续熔炼10min。
b.关闭真空泵，向真空感应熔炼炉内充入体积纯度99.999％的高纯氩气至大气压，打开闸板阀，放下导流管，将合金经导流管(导流管的预热温度为950℃)导入高纯氩气保护的中间包内。
c.合金在中间包均热后，打开塞棒，将合金熔体经过布流嘴(布流嘴的预热温度为1150℃)均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形，合金熔体冷却速度为15000℃/s。其参数如下表5所示。
表5实验主要参数
铸辊辊速 0.5m/s 熔炼温度 1500℃
辊缝开口宽度 0.5mm 继续熔炼时间 10min
辊径 300mm 中间包温度 1150℃
铸辊宽度 110mm 铸轧力 约40KN
铸辊冷却水温 5℃ 铸带宽度 45mm
试验获得0.5mm厚非晶带材。其微观组织照片及XRD曲线如图9所示。由图9可以看出，铸带中不存在晶体组织，为非晶态合金。
实施例六
合金成分：(Zr 54Hf 1Cu 30Al 10Ni 5) 98.9Y 1O 0.1；
布流方式：单侧布流；
制备流程：
a.按原子百分比配50kg原料，将其投入真空感应熔炼炉中，并抽真空至0.02Pa，对合金原料加热至其完全熔化熔化，并于1600℃继续熔炼10min。
b.关闭真空泵，向真空感应熔炼炉内充入体积纯度99.999％的高纯氩气至大气压，打开闸板阀，放下导流管，将合金经导流管(导流管的预热温度为900℃)导入高纯氩气保护的中间包内。
c.合金在中间包均热后，打开塞棒，将合金熔体经过布流嘴(布流嘴的预热温度为1000℃)均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形，合金熔体冷却速度为8000℃/s。其参数如下表6所示。
表6实验主要参数
铸辊辊速 0.5m/s 熔炼温度 1600℃
辊缝开口宽度 0.6mm 继续熔炼时间 10min
辊径 500mm 中间包温度 1000℃
铸辊宽度 110mm 铸轧力 约15KN
铸辊冷却水温 10℃ 铸带宽度 45mm
试验获得0.6mm厚非晶带材。其微观组织照片及XRD曲线如图10所示。由图10可以看出，铸带中不存在晶体组织，为非晶态合金。
实施例七
合金成分：(Zr 51.5Hf 1Cu 17.9Al 10Ni 14.6Ti 5) 99.9O 0.1；
布流方式：深入辊缝布流；
制备流程：
a.按原子百分比配50kg原料，将其投入真空感应熔炼炉中，并抽真空至0.07Pa，对合金原料加热至其完全熔化熔化，并于1500℃继续熔炼10min。
b.关闭真空泵，向真空感应熔炼炉内充入体积纯度99.999％的高纯氩气至大气压，打开闸板阀，放下导流管，将合金经导流管(导流管的预热温度为1000℃)导入高纯氩气保护的 中间包内。
c.合金在中间包均热后，打开塞棒，将合金熔体经过布流嘴(布流嘴的预热温度为1150℃)均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形，合金熔体冷却速度为12000℃/s。其参数如下表7所示。
表7实验主要参数
铸辊辊速 0.5m/s 熔炼温度 1500℃
辊缝开口宽度 0.5mm 继续熔炼时间 10min
辊径 300mm 中间包温度 1150℃
铸辊宽度 110mm 铸轧力 约49KN
铸辊冷却水温 5℃ 铸带宽度 55mm
试验获得0.5毫米厚非晶带材。其微观组织照片及XRD曲线如图11所示。由图11可以看出，铸带中不存在晶体组织，为非晶态合金。
上述实施例仅用于说明本发明的技术特点，而非是对本发明保护范围的限制，其目的是对本发明作详细说明。但凡是据此发明精神实质所做的等效替代，而不脱离本发明技术实质的方案都在本发明的保护范围之内。

Claims (10)

  1. 一种锆基非晶薄带材连续制备的方法，其特征在于，按以下步骤进行：
    (1)按设定成分熔炼母合金，其成分为：(Zr aHf bCu cAl dNi eTi fY g) 100-xO x，a、b、c、d、e、f、g、x为原子百分比，其中30≤a≤75；0≤b≤2；10≤c≤45；0≤d≤25；0≤e≤15；0≤f≤20；0≤g≤3；0.001＜x≤1；将合金原料或初步制得的母合金放入熔炼坩埚中熔炼至完全熔化，熔化后继续熔炼，在高于合金熔点200℃以上的温度下熔炼5～20min，使合金充分熔化；
    (2)将合金熔体通过预热的导流管导入中间包内，中间包温度高于合金熔点100～300℃，使合金在中间包内均温，浇铸时控制合金过热度为100～300℃；
    (3)非晶薄带成形过程：打开塞棒，将合金熔体经过预热的布流嘴均匀布流到铸辊辊缝中，使合金快速冷却铸轧成形；铸轧过程中，合金通过铸辊传热快速冷却，其冷却速度为500～75000℃/s，通过控制铸轧速度为0.01～3m/s、铸轧力大小控制为每1cm宽度铸带的铸轧力为2～15kN，铸辊辊缝开口宽度设置为0.1～2mm，来调控合金薄带出辊温度，并将合金出辊温度控制在小于合金的晶化温度Tx；
    (4)合金铸带经排辊再次冷却并导入卷取机成卷；铸带制备过程中，整个铸轧-冷却-卷取过程在高纯氩气保护的铸机腔体内完成。
  2. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，使用双辊法连续快速的制备0.1～2mm厚度的锆基非晶合金薄带。
  3. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，母合金熔炼过程和均温存储过程都在＜0.1Pa的高真空或体积纯度≥99.999％的高纯氩气保护氛围下进行的；铸轧过程在体积纯度≥99.9％的氩气保护氛围下进行。
  4. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，熔炼坩埚中，直接使用合金原料进行熔炼，或者使用已熔炼好的母合金进行熔化。
  5. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，通过布流嘴下端的布流口尺寸、铸辊辊缝值、铸轧速度、铜质铸辊、钢质铸辊、铸辊冷却水量的铸轧工艺参数控制凝固冷却速度达到500～75000℃/s。
  6. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，布流嘴下端的布流口设计为矩形或一排圆形，矩形宽度为0.2～1mm，圆形直径为0.5～2mm；布流方式分为三种：直接注入辊缝法、单侧浇涂法或双侧浇涂法；布流口材质为不易与合金熔体反应的SiO 2或BN。
  7. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，布流嘴的预热温度范围为900～1200℃，导流管的预热温度范围为900～1000℃。
  8. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，薄带铸轧过程中，通过控制合金流量控制铸辊上部的合金熔池高度稳定，并将合金熔池表面沿铸辊辊径方向的宽度控制在20mm以内。
  9. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，铸辊采用导热性好的铜质或钢质合金制备，其铸辊辊径为220mm～510mm，辊面粗糙度Ra≤10μm。
  10. 根据权利要求1所述的锆基非晶薄带材连续制备的方法，其特征在于，铸辊冷却水进水温度控制在5～12℃，出水温度控制在5～15℃，通过控制水流量，使水升温区间小于3℃。
PCT/CN2019/081934 2019-04-08 2019-04-09 一种锆基非晶薄带材连续制备的方法 Ceased WO2020206610A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910276763.1 2019-04-08
CN201910276763.1A CN109957732B (zh) 2019-04-08 2019-04-08 一种锆基非晶薄带材连续制备的方法

Publications (1)

Publication Number Publication Date
WO2020206610A1 true WO2020206610A1 (zh) 2020-10-15

Family

ID=67025776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/081934 Ceased WO2020206610A1 (zh) 2019-04-08 2019-04-09 一种锆基非晶薄带材连续制备的方法

Country Status (2)

Country Link
CN (1) CN109957732B (zh)
WO (1) WO2020206610A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114559001A (zh) * 2022-03-08 2022-05-31 太原科技大学 一种高温合金双辊铸轧工艺
CN115283629A (zh) * 2022-08-02 2022-11-04 太原科技大学 一种利用双辊铸轧工艺制备镍基高温合金的方法
CN115475618A (zh) * 2022-10-17 2022-12-16 南京工程学院 一种基于可燃非晶条带的多棱柱形四元光催化剂制备方法
CN115478234A (zh) * 2022-09-16 2022-12-16 盘星新型合金材料(常州)有限公司 具有塑性的无Be锆基非晶合金及其制备方法
CN117900396A (zh) * 2024-01-19 2024-04-19 武汉维福利德智能装备制造有限公司 一种基于陀螺仪的非晶合金熔喷装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115971723B (zh) * 2023-02-11 2025-10-28 中国机械总院集团郑州机械研究所有限公司 一种非晶钛基钎料带材及其制备方法、应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1486800A (zh) * 2003-05-09 2004-04-07 燕山大学 大块非晶合金连续铸轧技术
CN102211182A (zh) * 2011-05-13 2011-10-12 青岛云路新能源科技有限公司 一种非晶带的连续生产装置
CN102314985A (zh) * 2011-09-29 2012-01-11 安泰科技股份有限公司 一种铁基非晶合金宽带及其制造方法
CN105803311A (zh) * 2016-03-28 2016-07-27 东北大学 一种基于薄带连铸制备高磁感高强度无取向硅钢的方法
WO2016194167A1 (ja) * 2015-06-03 2016-12-08 日産自動車株式会社 双ロール式縦型鋳造装置及び双ロール式縦型鋳造方法
CN108796191A (zh) * 2018-06-28 2018-11-13 东北大学 一种if钢薄带的制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6682611B2 (en) * 2001-10-30 2004-01-27 Liquid Metal Technologies, Inc. Formation of Zr-based bulk metallic glasses from low purity materials by yttrium addition
CN100447287C (zh) * 2007-02-01 2008-12-31 北京航空航天大学 一种锆基非晶态合金
CN100523266C (zh) * 2007-11-15 2009-08-05 北京航空航天大学 锆基非晶-晶体复相材料及其制备方法
CN102061429B (zh) * 2009-11-13 2012-11-21 比亚迪股份有限公司 一种锆基非晶复合材料及其制备方法
CN102080196B (zh) * 2009-11-30 2012-09-12 比亚迪股份有限公司 一种锆基非晶合金及其制备方法
JP5685761B2 (ja) * 2011-01-31 2015-03-18 株式会社真壁技研 Ｃｕを含まないＺｒ基金属ガラス合金
CN102489677A (zh) * 2011-12-26 2012-06-13 大连理工大学 一种块体非晶合金板材连续铸造装置和方法
EP2759614B1 (de) * 2013-01-25 2019-01-02 ThyssenKrupp Steel Europe AG Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt
CN103938132B (zh) * 2013-08-22 2016-07-06 中国科学院金属研究所 一种具有强玻璃形成能力的锆基非晶合金
CN104745973A (zh) * 2013-12-26 2015-07-01 比亚迪股份有限公司 一种锆基非晶合金及其制备方法
CN103924170B (zh) * 2014-04-03 2016-03-23 东北大学 一种锆基非晶合金的遗传制备方法
US20180073104A1 (en) * 2016-09-13 2018-03-15 Apple Inc. Methods and apparatus for rejuvenation of amorphous alloys and micro-alloying
CN108220827A (zh) * 2018-01-02 2018-06-29 歌尔股份有限公司 锆基非晶合金及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1486800A (zh) * 2003-05-09 2004-04-07 燕山大学 大块非晶合金连续铸轧技术
CN102211182A (zh) * 2011-05-13 2011-10-12 青岛云路新能源科技有限公司 一种非晶带的连续生产装置
CN102314985A (zh) * 2011-09-29 2012-01-11 安泰科技股份有限公司 一种铁基非晶合金宽带及其制造方法
WO2016194167A1 (ja) * 2015-06-03 2016-12-08 日産自動車株式会社 双ロール式縦型鋳造装置及び双ロール式縦型鋳造方法
CN105803311A (zh) * 2016-03-28 2016-07-27 东北大学 一种基于薄带连铸制备高磁感高强度无取向硅钢的方法
CN108796191A (zh) * 2018-06-28 2018-11-13 东北大学 一种if钢薄带的制备方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114559001A (zh) * 2022-03-08 2022-05-31 太原科技大学 一种高温合金双辊铸轧工艺
CN114559001B (zh) * 2022-03-08 2024-04-12 太原科技大学 一种高温合金双辊铸轧工艺
CN115283629A (zh) * 2022-08-02 2022-11-04 太原科技大学 一种利用双辊铸轧工艺制备镍基高温合金的方法
CN115283629B (zh) * 2022-08-02 2024-04-12 太原科技大学 一种利用双辊铸轧工艺制备镍基高温合金的方法
CN115478234A (zh) * 2022-09-16 2022-12-16 盘星新型合金材料(常州)有限公司 具有塑性的无Be锆基非晶合金及其制备方法
CN115475618A (zh) * 2022-10-17 2022-12-16 南京工程学院 一种基于可燃非晶条带的多棱柱形四元光催化剂制备方法
CN115475618B (zh) * 2022-10-17 2023-09-22 南京工程学院 一种基于可燃非晶条带的多棱柱形四元光催化剂制备方法
CN117900396A (zh) * 2024-01-19 2024-04-19 武汉维福利德智能装备制造有限公司 一种基于陀螺仪的非晶合金熔喷装置

Also Published As

Publication number Publication date
CN109957732A (zh) 2019-07-02
CN109957732B (zh) 2020-11-27

Similar Documents

Publication Publication Date Title
CN109822067B (zh) 一种镍基非晶薄带材连续制备的方法
CN109957732B (zh) 一种锆基非晶薄带材连续制备的方法
CN109822066B (zh) 一种铜基非晶薄带材连续制备的方法
CN109825781B (zh) 一种铁基非晶薄带材连续制备的方法
CN110629127B (zh) 一种因瓦合金箔材的制造方法
CN107710352B (zh) 铁基纳米晶合金超薄宽带及其制造方法
CN102069167B (zh) 一种双辊薄带连铸制备取向硅钢等轴晶薄带坯的方法
CN108188362A (zh) CuNiSn系合金及带坯组合外场水平连铸制备方法及装置
CN102069165B (zh) 一种双辊薄带连铸制备无取向硅钢柱状晶薄带坯的方法
CN109967703B (zh) 一种厚度为80～1500μm的宽幅非晶薄带连续大冷速高效制备的方法
CN104775077B (zh) 超细晶因瓦合金薄带及其制备方法
CN106583672B (zh) 一种铜铬系合金水平连铸工艺
CN209811188U (zh) 一种宽幅非晶薄带水平连续制备的铸轧装置
CN100435244C (zh) 一种纳米晶软磁合金超薄带及其制备方法
CN103938127B (zh) 一种铁基非晶宽带的制备方法
CN117000958A (zh) 一种基于平面流铸技术制备无取向硅钢极薄带的方法
CN102568729B (zh) 一种制备块体纳米晶复合稀土永磁材料的方法
CN110142321A (zh) 一种非晶薄壁结构件的连续冲压成型的装置和方法
CN104805382A (zh) 一种非晶纳米晶合金薄带及其制备方法
CN209811186U (zh) 一种宽幅非晶薄带连续大冷速制备的铸轧装置
CN209811187U (zh) 一种非晶薄带材连续制备的铸轧装置
CN120878444A (zh) 一种高磁性能纳米晶软磁薄带的制备方法
CN115482986A (zh) 高磁感200μm级铁基非晶软磁合金带材及其制备方法
CN117286431B (zh) 一种铁基非晶软磁合金铸带及其制备方法
CN202387931U (zh) 非晶带制备装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19924099

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19924099

Country of ref document: EP

Kind code of ref document: A1