WO2024093998A1 - Niobium-titanium alloy precision strip and manufacturing method therefor - Google Patents

Niobium-titanium alloy precision strip and manufacturing method therefor Download PDF

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Publication number
WO2024093998A1
WO2024093998A1 PCT/CN2023/128464 CN2023128464W WO2024093998A1 WO 2024093998 A1 WO2024093998 A1 WO 2024093998A1 CN 2023128464 W CN2023128464 W CN 2023128464W WO 2024093998 A1 WO2024093998 A1 WO 2024093998A1
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niobium
slab
titanium alloy
manufacturing
strip
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PCT/CN2023/128464
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French (fr)
Chinese (zh)
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朱宝辉
刘彦昌
沈立华
王培军
韩伟松
胡革全
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宁夏中色金航钛业有限公司
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Publication of WO2024093998A1 publication Critical patent/WO2024093998A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/28—Control of flatness or profile during rolling of strip, sheets or plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/56—Elongation control
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum

Definitions

  • the present invention relates to the technical field of niobium-titanium alloy preparation, and in particular to a niobium-titanium alloy precision strip and a method for manufacturing the same.
  • Niobium-titanium alloy sheets are generally warm-rolled by the sheet method to produce sheets with a thickness of not less than 2 mm. They are mostly used for stamping or wire cutting of thin-walled rings and for making gaskets for connecting superconducting acceleration cavities. Since this type of sheet will be processed in size and surface later, the processing accuracy and surface quality requirements are relatively low. For niobium-titanium alloy strips, since their rolling deformation resistance is lower than that of titanium alloys, but much higher than that of pure niobium, the thickness of the strip cannot be made very thin during processing.
  • niobium-titanium alloy precision strips is as a key material for the preparation of low-temperature superconducting magnets.
  • the wall thickness is not only required to be very thin, but also the dimensional accuracy and surface quality of the strips are required to be high.
  • other indicators of the niobium-titanium alloy strips are not ideal, such as wall thickness deviation ⁇ 0.05mm, surface roughness ⁇ 0.8 ⁇ m and flatness (H/L) ⁇ 6%. Therefore, even if the thickness is processed to 0.6mm, there will be problems such as surface bulging, edge waves and low dimensional accuracy control.
  • the purpose of the present invention is to provide a niobium-titanium alloy precision strip and a manufacturing method thereof to solve the problems of surface bulging, edge wave and low dimensional accuracy.
  • the niobium-titanium alloy precision strip prepared by the present invention has a thickness of ⁇ 0.6mm, high dimensional accuracy, good surface quality and stable performance.
  • a niobium-titanium alloy precision strip the components of which, by mass percentage, are: Ti 46-57% and Nb 42-53%, with the remainder being impurities; the thickness of the niobium-titanium alloy precision strip is ⁇ 0.6mm.
  • the present invention also provides a method for manufacturing the niobium-titanium alloy precision strip described in the above scheme, comprising the following steps: step:
  • Preparing a slab splitting the ingot to obtain a slab, and forging the slab;
  • Slab warm rolling heating the forged slab and then performing several rounds of warm rolling to obtain a strip blank, wherein the total processing rate of the warm rolling is 60-80%;
  • the cold-rolled billet is cold-rolled by using a special roller, which is a special-shaped roller with a large middle diameter, a small edge diameter and a smooth transition, and a niobium-titanium alloy precision strip is obtained after cold rolling.
  • a special roller which is a special-shaped roller with a large middle diameter, a small edge diameter and a smooth transition, and a niobium-titanium alloy precision strip is obtained after cold rolling.
  • the niobium-titanium alloy precision strip prepared by the manufacturing method provided by the present invention controls the processing rate by warm rolling of the slab, and then adopts a special micro-convex roller for cold rolling, and also finely controls the pass deformation and the total deformation of the cold rolling, thereby obtaining a thinner thickness, which is less than 0.6 mm, and in the best case can be less than 0.09 mm, and the wall thickness deviation is ⁇ 0.02 mm, the flatness (H/L) is ⁇ 2%, the tensile strength is ⁇ 460 MPa, the non-proportional elongation strength is ⁇ 420 MPa, and the elongation is ⁇ 15%. It has the advantages of high dimensional accuracy, good surface quality and stable performance, and fully meets the precision requirements for the preparation of low-temperature superconducting magnets.
  • the present invention provides a niobium-titanium alloy precision strip, wherein the composition of the niobium-titanium alloy precision strip, by mass percentage, is as follows: Ti 46-57%, C ⁇ 0.04%, N ⁇ 0.02%, H ⁇ 0.0045%, O ⁇ 0.10%, Fe ⁇ 0.010%, Ta ⁇ 0.10%, other impurity elements ⁇ 0.03%, and the balance is Nb; the thickness of the niobium-titanium alloy precision strip is ⁇ 0.6 mm, preferably 0.12 mm or 0.09 mm, the wall thickness deviation is preferably ⁇ 0.01 mm (typically the thickness difference between the middle position and the edge of the strip), the surface roughness is preferably ⁇ 0.4 ⁇ m, the flatness (H/L) is preferably ⁇ 2% (for the algorithm of flatness, refer to the unevenness measurement method in GB/T3630-2017), the tensile strength is preferably ⁇ 460 MPa, the specified non-proportional elongation strength is preferably ⁇ 420 MPa
  • the present invention also provides a method for manufacturing the niobium-titanium alloy precision strip described in the above scheme, comprising the following steps:
  • Preparing a slab splitting the ingot to obtain a slab, and forging the slab;
  • Slab warm rolling The forged slab is heated and then subjected to several rounds of warm rolling to obtain a strip blank.
  • the total processing rate of the warm rolling is 60-80% (i.e., the deformation of the warm rolling of the adjacent two rounds is large, which can It can roll the coarse grains into small ones and avoid the existence of coarse and uneven grains);
  • Cold rolling The cold-rolled billet is subjected to coil-type cold rolling by using a special rolling roller, wherein the special rolling roller is a slightly convex rolling roller with a middle diameter slightly larger than an edge diameter and a smooth transition, and a niobium-titanium alloy precision strip is obtained after cold rolling.
  • the special rolling roller is a slightly convex rolling roller with a middle diameter slightly larger than an edge diameter and a smooth transition, and a niobium-titanium alloy precision strip is obtained after cold rolling.
  • the preparation of the slab is preferably: the ingot is first subjected to forging at a temperature of 1050-1150°C, kept warm for 4-6 hours, a forging ratio of 4-8, and a final forging temperature ⁇ 800°C, and then the slab is forged at a temperature of 800-1000°C, kept warm for 1-3 hours, a forging ratio of 2-6, and a final forging temperature ⁇ 750°C; the number of fires forging the slab is preferably 2-4 fires, and the specifications of the obtained slab are preferably: thickness 30-40mm ⁇ width 300-650mm.
  • the process also includes preparing an ingot before preparing the slab: configuring pure titanium and pure niobium in a weight ratio of Ti: 46-57% and Nb: 43-54%, pressing an electrode block, welding the electrode blocks together with a primary electrode, and then performing three vacuum consumable arc furnace smelting to obtain a niobium-titanium ingot.
  • the temperature of the heated slab is preferably 400-550°C, and it is preferably kept warm for 0.7-1.5 hours. After that, it is preferably subjected to 1-3 rounds of warm rolling, and the deformation amount per pass is preferably 12%-30%.
  • the total processing rate is preferably 60-80%, and the thickness of the strip after warm rolling is preferably greater than 1.2 mm (that is, the deformation amount of the two adjacent warm rolling rounds is large, and coarse grains can be rolled into fine ones, thus avoiding the existence of coarse and uneven grains).
  • the warm-rolled slab is preferably subjected to alkali washing and/or pickling to remove surface oxide scale, then washed with water, and then surface polished until there are no defects visible to the naked eye on the surface.
  • the cold rolling conditions are preferably: the number of cold rolling is preferably 3 to 5 times, the deformation amount during cold rolling is preferably 9% to 25% (the deformation amount of two adjacent cold rollings), the total processing rate is preferably 35% to 60% (the deformation amount of the billet after rolling and before cold rolling between two annealings), and the thickness of the strip formed after cold rolling is preferably less than or equal to 0.6mm.
  • the deformation amount per pass and the total processing rate deformation are both large, the purpose is to refine the grains, and the deformation amount is the deformation amount of cold rolling.
  • the cold rolling thickness reaches 0.6mm, and the deformation amount per pass and the total processing rate are greatly affected by the thickness of the strip, and each process Strict process control is required, otherwise, it is easy to cause cracking or breaking of the strip during cold rolling.
  • the thickness of the strip obtained by cold rolling is preferably less than 0.12 mm.
  • intermediate annealing is performed by vacuum heat treatment before the cold rolling.
  • degreasing treatment is preferably performed before vacuum annealing; intermediate vacuum annealing must be performed between two rolling passes (one rolling pass is from the initial rolling pass after annealing to the last rolling pass that must be softened annealed for work hardening), and finished product vacuum annealing treatment must be performed after finished product rolling in order to adjust the mechanical properties.
  • a degreasing treatment is also performed after completing a rolling process: the plate and strip materials that need to be heat treated after cold rolling are degreasing; the degreasing treatment is preferably ultrasonic cleaning degreasing or degreasing agent cleaning.
  • intermediate softening and finished product heat treatment are provided after the degreasing treatment: the intermediate softening and finished product heat treatment are both vacuum annealing heat treatment.
  • the intermediate annealing temperature is preferably 750-900°C, the holding time is preferably 1-3 hours, and the vacuum degree is preferably not less than 1 ⁇ 10 -1 Pa; the finished product annealing temperature is preferably 300-450°C, the holding time is preferably 1-3 hours, and the vacuum degree is preferably not less than 5 ⁇ 10 -2 Pa).
  • the middle diameter of the special roller is preferably slightly larger than the diameter of the middle of the edge by 0.1 to 0.6 mm (by using special micro-convex rollers for cold rolling, a strip with nearly consistent thickness at the edge and middle is formed, so that the wall thickness deviation of the strip is ⁇ 0.02 mm).
  • Pure titanium billet and pure niobium are mixed in the following ratios: Ti: 50% and Nb: 50%; the electrode blocks are pressed, the electrode blocks are welded together with primary electrodes, and then smelted in a vacuum consumable arc furnace three times.
  • the ingot surface is coated, the forging temperature is 1100°C, the temperature is kept for 6 hours, the forging ratio is 8, the final forging temperature is 850°C, the slab forging temperature is 850 ⁇ 900°C, the temperature is kept for 2 ⁇ 3 hours (specifically 3 times Forging, the holding time is 3, 2.5 and 2h respectively), the forging ratio is 3-4 (specifically 3 forgings, the forging ratios are 4, 3.8 and 3 respectively), the final forging temperature is 800°C, the slab specifications are thickness 30mm ⁇ width 630mm ⁇ length ⁇ 700mm, and the slab forging times are 3 times.
  • the temperature is 450-500°C
  • the temperature is kept for 1 hour
  • the total processing rate is 60-70%
  • the final rolling thickness is 1.8mm.
  • the annealing temperature is 800°C, the temperature is maintained for 1 hour, and the vacuum degree is not less than 1 ⁇ 10 -1 Pa.
  • the finished product annealing temperature is 350°C, kept at this temperature for 2 hours, with a vacuum degree of not less than 5 ⁇ 10 -2 Pa, and cooled along with the furnace.
  • the finished annealed strip is trimmed and rewound into a coiled product.
  • Cold rolling adopts flat roll rolling.
  • problems such as surface bulging, edge waves (flatness (H/L) is about 6%), large wall thickness deviation (the thickness of the middle position of the strip is 0.69mm, the edge thickness is 0.59mm, and the wall thickness deviation is 0.1mm) and so on appear. Even the strip breaks, making it difficult to continue rolling.
  • both the roller and the deformed metal will produce certain deformation during the rolling process, that is, although the roller is relatively rigid, it still produces elastic deformation, and the rolled metal will produce plastic and elastic deformation. Therefore, when flat roll rolling is used, the elastic deformation of the middle part of the roller is the largest due to the distance between the middle part of the roller and the fixed support point, resulting in the smallest thickness reduction in the middle part of the plate and strip in the width direction, which is equivalent to concave roll rolling, resulting in an increase in thickness deviation in the middle and edge positions.
  • the flat roll can be ground and polished to a certain convexity, which can balance the corresponding elastic deformation during the rolling deformation process and thus become flat roll rolling, thereby greatly reducing the thickness deviation in the middle and edge positions of the plate and strip.
  • Pure titanium billet and pure niobium are mixed in the following ratios: Ti: 55% and Nb: 45%; the electrode blocks are pressed, the electrode blocks are welded together with primary electrodes, and then smelted in a vacuum consumable arc furnace three times.
  • the surface of the ingot is coated, the forging temperature is 1100°C, the insulation time is 6 hours, the forging ratio is 6, the final forging temperature is 800°C, the slab forging temperature is 900-950°C, the insulation time is 2-3 hours, the forging ratio is 3-4, the final forging temperature is 750°C, the specifications of the slab are thickness 30mm ⁇ width 530mm ⁇ length ⁇ 600mm, and the slab forging times is 3 times.
  • the temperature is 450-500°C (specifically, for example, 480, 450, and 400°C), and the temperature is kept for 1 hour.
  • the total processing rate is 60-75% (specifically, for example, 75, 70, and 65%), and the final rolling thickness is 1.25mm.
  • the annealing temperature is 750°C, the temperature is maintained for 1 hour, and the vacuum degree is not less than 1 ⁇ 10 -1 Pa.
  • the pass processing rate and total processing rate are strictly controlled, with the pass deformation amount of 12% to 20% and the total processing rate of 45% to 60%.
  • the work roll with crown (0.2 to 0.5 mm) is used for three cold rolling processes to finally process the finished product to a thickness of 0.12 ⁇ 0.012 mm (the thickness of the three rolling processes is 0.48 mm, 0.22 mm and 0.12 mm respectively).
  • the finished product annealing temperature is 350°C, kept at this temperature for 3 hours, with a vacuum degree of not less than 5 ⁇ 10 -2 Pa, and cooled along with the furnace.
  • the finished annealed strip is trimmed and rewound into a coiled product.
  • Nb-47Ti niobium titanium alloy precision strip specifications: thickness 0.09mm ⁇ width 300mm ⁇ length ⁇ 30000mm, preparation method:
  • Pure titanium billet and pure niobium are prepared in the following mass ratios: Ti: 47% and Nb: 53%; the electrode blocks are pressed, the electrode blocks are welded together with primary electrodes, and then smelted in a vacuum consumable arc furnace three times.
  • the ingot surface is coated, the forging temperature is 1150°C, the insulation time is 6 hours, the forging ratio is 5, the final forging temperature is 800°C, the slab forging temperature is 850-900°C, the insulation time is 1-3 hours, the forging ratio is 3-4, the final forging temperature is 750°C, the slab specifications are: thickness 40mm ⁇ width 350mm ⁇ length ⁇ 800mm, and the slab forging times is 2 times.
  • the temperature is 450-500°C
  • the temperature is kept for 1 hour
  • the total processing rate is 70-80%
  • the final rolling thickness is 1.2mm.
  • the annealing temperature is 850°C, the temperature is kept for 1 hour, and the vacuum degree is not less than 1 ⁇ 10 -1 Pa.
  • the pass deformation is 12% to 20%, and the total processing rate is 35% to 60% (the cold rolling pass deformation and total processing rate are controlled within the above range. If it is too small, the shaping cannot be fully exerted and the process requirements cannot be met. If it is too large, cracks or fracture defects are prone to occur).
  • the finished product annealing temperature is 450°C, kept at this temperature for 2 hours, with a vacuum degree of not less than 5 ⁇ 10 -2 Pa, and cooled along with the furnace.
  • the finished annealed strip is trimmed and rewound into a coiled product.

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Abstract

The present application relates to the technical field of niobium-titanium alloy preparation, and in particular to a niobium-titanium alloy precision strip and a manufacturing method therefor. The niobium-titanium alloy precision strip provided by the present application comprises the following components in mass percent: 46-57% of Ti and 43-54% of Nb, and the thickness of the niobium-titanium alloy precision strip is less than or equal to 0.6 mm. The manufacturing method for the niobium-titanium alloy precision strip provided by the present application comprises the following steps: cogging a cast ingot to obtain a slab, and forging the slab; heating the forged slab, and then performing warm rolling in multiple number of times of heating to obtain a strip blank, wherein a total processing rate of the warm rolling is 60-80%; and performing surface treatment on the warm-rolled slab to remove a surface oxide scale to obtain a cold-rolled blank; and performing roll-like cold-rolling on the cold-rolled stock by using a dedicated roller, wherein the dedicated roller is a profiled roller having a large middle diameter and a small edge diameter and having smooth transition, and the niobium-titanium alloy precision strip is obtained after cold-rolling.

Description

铌钛合金精密带材及其制造方法Niobium-titanium alloy precision strip and manufacturing method thereof
本申请要求于2022年10月31日提交中国专利局、申请号为202211347689.6、发明名称为“铌钛合金精密带材及其制造方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed with the China Patent Office on October 31, 2022, with application number 202211347689.6 and invention name “Niobium-titanium alloy precision strip and its manufacturing method”, the entire contents of which are incorporated by reference in this application.
技术领域Technical Field
本发明涉及铌钛合金制备技术领域，尤其涉及铌钛合金精密带材及其制造方法。The present invention relates to the technical field of niobium-titanium alloy preparation, and in particular to a niobium-titanium alloy precision strip and a method for manufacturing the same.
背景技术Background technique
铌钛合金板材一般采用片式法温轧制备厚度不小于2mm的板材，多用于冲压或线切割加工壁厚较薄的环件，用于制作超导加速腔体连接的垫圈。这种板材由于后续还要进行尺寸和表面加工，加工精度和表面质量要求相对不高。对于铌钛合金带材，由于其轧制变形抗力比钛合金低，但是又比纯铌高很多，导致带材加工时厚度无法做到很薄。Niobium-titanium alloy sheets are generally warm-rolled by the sheet method to produce sheets with a thickness of not less than 2 mm. They are mostly used for stamping or wire cutting of thin-walled rings and for making gaskets for connecting superconducting acceleration cavities. Since this type of sheet will be processed in size and surface later, the processing accuracy and surface quality requirements are relatively low. For niobium-titanium alloy strips, since their rolling deformation resistance is lower than that of titanium alloys, but much higher than that of pure niobium, the thickness of the strip cannot be made very thin during processing.
铌钛合金精密带材的用途之一是用在低温超导磁体制备的关键材料，壁厚尺寸不仅要求非常薄，而且对带材的尺寸精度和表面质量要求也较高。现有技术中，虽然已经存在的铌钛合金带材的壁厚达到0.6mm，但是铌钛合金带材其他指标均不理想，比如壁厚偏差≤±0.05mm、表面粗糙度≤0.8μm以及平面度(H/L)≤6％，所以即使加工至厚度为0.6mm，也会存在表面起包、边部波浪和尺寸精度控制不高等问题。One of the uses of niobium-titanium alloy precision strips is as a key material for the preparation of low-temperature superconducting magnets. The wall thickness is not only required to be very thin, but also the dimensional accuracy and surface quality of the strips are required to be high. In the prior art, although the wall thickness of the existing niobium-titanium alloy strips has reached 0.6mm, other indicators of the niobium-titanium alloy strips are not ideal, such as wall thickness deviation ≤±0.05mm, surface roughness ≤0.8μm and flatness (H/L) ≤6%. Therefore, even if the thickness is processed to 0.6mm, there will be problems such as surface bulging, edge waves and low dimensional accuracy control.
发明内容Summary of the invention
本发明的目的在于提供铌钛合金精密带材及其制造方法，以解决表面起包、边部波浪和尺寸精度控制不高的问题。本发明制备的铌钛合金精密带材厚度≤0.6mm，且尺寸精度高，表面质量好，性能稳定。The purpose of the present invention is to provide a niobium-titanium alloy precision strip and a manufacturing method thereof to solve the problems of surface bulging, edge wave and low dimensional accuracy. The niobium-titanium alloy precision strip prepared by the present invention has a thickness of ≤0.6mm, high dimensional accuracy, good surface quality and stable performance.
一种铌钛合金精密带材，所述铌钛合金精密带材的成分，按质量百分比计：Ti 46～57％和Nb 42～53％，其他为杂质；所述铌钛合金精密带材的厚度≤0.6mm。A niobium-titanium alloy precision strip, the components of which, by mass percentage, are: Ti 46-57% and Nb 42-53%, with the remainder being impurities; the thickness of the niobium-titanium alloy precision strip is ≤0.6mm.
本发明还提供了上述方案所述铌钛合金精密带材的制造方法，包括以下 步骤：The present invention also provides a method for manufacturing the niobium-titanium alloy precision strip described in the above scheme, comprising the following steps: step:
制备板坯：对铸锭进行开坯得到板坯，并对所述板坯进行锻造；Preparing a slab: splitting the ingot to obtain a slab, and forging the slab;
板坯温轧：加热所述锻造后的板坯，再进行若干火次温轧，得到带材坯料，所述温轧的总加工率为60～80％；Slab warm rolling: heating the forged slab and then performing several rounds of warm rolling to obtain a strip blank, wherein the total processing rate of the warm rolling is 60-80%;
表面处理：对所述温轧后的板坯进行表面处理，以去除表面氧化皮，得到冷轧坯料；Surface treatment: performing surface treatment on the slab after warm rolling to remove surface oxide scale to obtain a cold-rolled billet;
冷轧：利用专用轧辊对所述冷轧坯料进行冷轧，专用轧辊为中间直径大、边缘直径小且平滑过度的异形辊，冷轧后得到铌钛合金精密带材。Cold rolling: The cold-rolled billet is cold-rolled by using a special roller, which is a special-shaped roller with a large middle diameter, a small edge diameter and a smooth transition, and a niobium-titanium alloy precision strip is obtained after cold rolling.
本发明取得的有益效果：采用本发明提供的制造方法制备的铌钛合金精密带材，通过板坯温轧控制加工率，再采用专用微凸型轧辊冷轧，而且还精细化控制冷轧的道次变形量和总变形量，从而得到较薄的厚度，厚度小于0.6mm，较佳情况还可以达到小于0.09mm，且壁厚偏差≤±0.02mm，平面度(H/L)≤2％，抗拉强度≥460MPa，规定非比例延伸强度≥420MPa，延伸率≥15％，具有尺寸精度高、表面质量好以及性能稳定等优点，完全满足低温超导磁体制备的精密要求。The beneficial effects achieved by the present invention are as follows: the niobium-titanium alloy precision strip prepared by the manufacturing method provided by the present invention controls the processing rate by warm rolling of the slab, and then adopts a special micro-convex roller for cold rolling, and also finely controls the pass deformation and the total deformation of the cold rolling, thereby obtaining a thinner thickness, which is less than 0.6 mm, and in the best case can be less than 0.09 mm, and the wall thickness deviation is ≤±0.02 mm, the flatness (H/L) is ≤2%, the tensile strength is ≥460 MPa, the non-proportional elongation strength is ≥420 MPa, and the elongation is ≥15%. It has the advantages of high dimensional accuracy, good surface quality and stable performance, and fully meets the precision requirements for the preparation of low-temperature superconducting magnets.
具体实施方式Detailed ways
本发明提供了一种铌钛合金精密带材，所述铌钛合金精密带材的成分，按质量百分比计：Ti 46～57％，C≤0.04％，N≤0.02％，H≤0.0045％，O≤0.10％，Fe≤0.010％，Ta≤0.10％，其他杂质元素≤0.03％，余量为Nb；所述铌钛合金精密带材的厚度≤0.6mm，优选为0.12mm或0.09mm，壁厚偏差优选≤±0.01mm(典型的为带材中间位置和边缘之间的厚度差)，表面粗糙度优选≤0.4μm，平面度(H/L)优选≤2％(平面度的算法参见GB/T3630-2017中不平度测量方法)，抗拉强度优选≥460MPa，规定非比例延伸强度优选≥420MPa，延伸率优选≥15％，组织均匀。The present invention provides a niobium-titanium alloy precision strip, wherein the composition of the niobium-titanium alloy precision strip, by mass percentage, is as follows: Ti 46-57%, C≤0.04%, N≤0.02%, H≤0.0045%, O≤0.10%, Fe≤0.010%, Ta≤0.10%, other impurity elements≤0.03%, and the balance is Nb; the thickness of the niobium-titanium alloy precision strip is ≤0.6 mm, preferably 0.12 mm or 0.09 mm, the wall thickness deviation is preferably ≤±0.01 mm (typically the thickness difference between the middle position and the edge of the strip), the surface roughness is preferably ≤0.4 μm, the flatness (H/L) is preferably ≤2% (for the algorithm of flatness, refer to the unevenness measurement method in GB/T3630-2017), the tensile strength is preferably ≥460 MPa, the specified non-proportional elongation strength is preferably ≥420 MPa, the elongation is preferably ≥15%, and the structure is uniform.
本发明还提供了上述方案所述铌钛合金精密带材的制造方法，包括以下步骤：The present invention also provides a method for manufacturing the niobium-titanium alloy precision strip described in the above scheme, comprising the following steps:
制备板坯：对铸锭进行开坯得到板坯，并对所述板坯进行锻造；Preparing a slab: splitting the ingot to obtain a slab, and forging the slab;
板坯温轧：加热所述锻造后的板坯，再进行若干火次温轧，得到带材坯料，所述温轧的总加工率为60～80％(即该相邻两火次的温轧变形量大，能 够将粗大晶粒轧制细小，避免粗大、不均匀晶粒存在)；Slab warm rolling: The forged slab is heated and then subjected to several rounds of warm rolling to obtain a strip blank. The total processing rate of the warm rolling is 60-80% (i.e., the deformation of the warm rolling of the adjacent two rounds is large, which can It can roll the coarse grains into small ones and avoid the existence of coarse and uneven grains);
表面处理：对所述温轧后的板坯进行表面处理，以去除表面氧化皮，得到冷轧坯料；Surface treatment: performing surface treatment on the slab after warm rolling to remove surface oxide scale to obtain a cold-rolled billet;
冷轧：利用专用轧辊对所述冷轧坯料进行卷式法冷轧，专用轧辊为中间直径略大于边缘直径且平滑过渡的微凸型轧辊，冷轧后得到铌钛合金精密带材。Cold rolling: The cold-rolled billet is subjected to coil-type cold rolling by using a special rolling roller, wherein the special rolling roller is a slightly convex rolling roller with a middle diameter slightly larger than an edge diameter and a smooth transition, and a niobium-titanium alloy precision strip is obtained after cold rolling.
在本发明中，所述制备板坯优选为：对铸锭先进行开坯锻造，开坯温度为1050～1150℃，保温4～6小时，锻造比为4～8，终锻温度≥800℃，再进行板坯锻造，温度为800～1000℃，保温1～3小时，锻造比为2～6，终锻温度≥750℃；所述板坯锻造的火次优选为2～4火次，得到的板坯的规格优选为：厚度30～40mm×宽度300～650mm。In the present invention, the preparation of the slab is preferably: the ingot is first subjected to forging at a temperature of 1050-1150°C, kept warm for 4-6 hours, a forging ratio of 4-8, and a final forging temperature ≥800°C, and then the slab is forged at a temperature of 800-1000°C, kept warm for 1-3 hours, a forging ratio of 2-6, and a final forging temperature ≥750°C; the number of fires forging the slab is preferably 2-4 fires, and the specifications of the obtained slab are preferably: thickness 30-40mm×width 300-650mm.
在本发明中，优选还包括在所述制备板坯前制备铸锭：将纯钛和纯铌按照Ti：46～57％和Nb：43～54％重量比配置，压制电极块，电极块组合焊接一次电极，然后进行3次真空自耗电弧炉熔炼，得到铌钛铸锭。In the present invention, it is preferred that the process also includes preparing an ingot before preparing the slab: configuring pure titanium and pure niobium in a weight ratio of Ti: 46-57% and Nb: 43-54%, pressing an electrode block, welding the electrode blocks together with a primary electrode, and then performing three vacuum consumable arc furnace smelting to obtain a niobium-titanium ingot.
在本发明中，所述加热板坯的温度优选为400～550℃，优选保温0.7～1.5小时，之后优选进行1～3火次温轧，道次变形量优选为12％～30％，总加工率优选为60～80％，温轧后的带材坯料的厚度优选大于1.2mm(即该相邻两火次温轧变形量大，能够将粗大晶粒轧制细小，避免粗大、不均匀晶粒存在)。In the present invention, the temperature of the heated slab is preferably 400-550°C, and it is preferably kept warm for 0.7-1.5 hours. After that, it is preferably subjected to 1-3 rounds of warm rolling, and the deformation amount per pass is preferably 12%-30%. The total processing rate is preferably 60-80%, and the thickness of the strip after warm rolling is preferably greater than 1.2 mm (that is, the deformation amount of the two adjacent warm rolling rounds is large, and coarse grains can be rolled into fine ones, thus avoiding the existence of coarse and uneven grains).
在本发明中，对所述温轧板坯优选进行碱洗和/或酸洗，以去除表面氧化皮，之后水洗清洁，再进行表面修磨，至表面无肉眼可见的缺陷。In the present invention, the warm-rolled slab is preferably subjected to alkali washing and/or pickling to remove surface oxide scale, then washed with water, and then surface polished until there are no defects visible to the naked eye on the surface.
在本发明中，所述碱洗优选采用质量配比为85～95％NaOH和15～5％NaNO3的混合熔融液(保持熔融液温度优选为420～480℃)；所述酸洗优选采用体积配比为HF：HNO3：H2O＝5～10：30～40：余量的混合液。In the present invention, the alkali washing preferably uses a mixed molten liquid with a mass ratio of 85-95% NaOH and 15-5% NaNO3 (the molten liquid temperature is preferably maintained at 420-480°C); the acid washing preferably uses a mixed liquid with a volume ratio of HF: HNO3 : H2O =5-10:30-40:the remainder.
在本发明中，所述冷轧的条件优选为：所述冷轧的次数优选为3～5次，所述冷轧时的道次变形量优选为9％～25％(相邻两次冷轧的变形量)，总加工率优选为35％～60％(两次退火之间轧后与冷轧前坯料的变形量)，冷轧后形成的带材的厚度优选小于等于0.6mm。本发明中，道次变形量和总加工率变形量均较大，目的在于细化晶粒，且该变形量为冷态轧制的变形量。冷轧厚度达到0.6mm，道次变形量及总加工率受到带材厚度的影响较大，各工 艺控制要求严格，否则，很容易在冷轧时造成带材的开裂或断带。In the present invention, the cold rolling conditions are preferably: the number of cold rolling is preferably 3 to 5 times, the deformation amount during cold rolling is preferably 9% to 25% (the deformation amount of two adjacent cold rollings), the total processing rate is preferably 35% to 60% (the deformation amount of the billet after rolling and before cold rolling between two annealings), and the thickness of the strip formed after cold rolling is preferably less than or equal to 0.6mm. In the present invention, the deformation amount per pass and the total processing rate deformation are both large, the purpose is to refine the grains, and the deformation amount is the deformation amount of cold rolling. The cold rolling thickness reaches 0.6mm, and the deformation amount per pass and the total processing rate are greatly affected by the thickness of the strip, and each process Strict process control is required, otherwise, it is easy to cause cracking or breaking of the strip during cold rolling.
在本发明中，所述冷轧得到的带材的厚度优选小于0.12mm。In the present invention, the thickness of the strip obtained by cold rolling is preferably less than 0.12 mm.
在本发明中，优选还包括在所述冷轧前采用真空热处理进行中间退火。In the present invention, it is preferred that intermediate annealing is performed by vacuum heat treatment before the cold rolling.
在本发明中，所述真空退火前优选先进行除油处理；两个轧程(从退火后初始道次轧制到加工硬化必须软化退火的最后一道次轧制之间为一个轧程)之间必须进行中间真空退火，成品轧制后为了调控力学性能必须进行成品真空退火处理。In the present invention, degreasing treatment is preferably performed before vacuum annealing; intermediate vacuum annealing must be performed between two rolling passes (one rolling pass is from the initial rolling pass after annealing to the last rolling pass that must be softened annealed for work hardening), and finished product vacuum annealing treatment must be performed after finished product rolling in order to adjust the mechanical properties.
在本发明中，优选还包括在完成一个轧程之后进行除油处理：对冷轧后需要进行热处理的板带材进行除油处理；所述除油处理优选为超声波清洗除油或除油剂清洗。In the present invention, it is preferred that a degreasing treatment is also performed after completing a rolling process: the plate and strip materials that need to be heat treated after cold rolling are degreasing; the degreasing treatment is preferably ultrasonic cleaning degreasing or degreasing agent cleaning.
在本发明中，优选还包括在所述除油处理后设置中间软化和成品热处理：所述中间软化和成品热处理均采用真空退火热处理。(中间退火温度优选为750～900℃，保温时间优选为1～3小时，真空度优选不低于1×10-1Pa；成品退火温度优选为300～450℃，保温时间优选为1～3小时，真空度优选不低于5×10-2Pa)。In the present invention, it is preferred that intermediate softening and finished product heat treatment are provided after the degreasing treatment: the intermediate softening and finished product heat treatment are both vacuum annealing heat treatment. (The intermediate annealing temperature is preferably 750-900°C, the holding time is preferably 1-3 hours, and the vacuum degree is preferably not less than 1×10 -1 Pa; the finished product annealing temperature is preferably 300-450°C, the holding time is preferably 1-3 hours, and the vacuum degree is preferably not less than 5×10 -2 Pa).
在本发明中，所述专用轧辊的中间直径优选略大于边缘中间的直径0.1～0.6mm(通过采用专用微凸型轧辊冷轧，形成边缘和中间厚度接近一致的带材，使带材的壁厚偏差≤±0.02mm)。In the present invention, the middle diameter of the special roller is preferably slightly larger than the diameter of the middle of the edge by 0.1 to 0.6 mm (by using special micro-convex rollers for cold rolling, a strip with nearly consistent thickness at the edge and middle is formed, so that the wall thickness deviation of the strip is ≤±0.02 mm).
为了进一步说明本发明，下面结合实施例对本发明的方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with embodiments, but they should not be understood as limiting the scope of protection of the present invention.
实施例1Example 1
Nb-50Ti铌钛合金精密带材，规格为：厚度0.6mm×宽度600mm×长度20000mm(>＝20000mm的任意长度，不做具体限定)，制备方法为：Nb-50Ti niobium-titanium alloy precision strip, specifications: thickness 0.6mm×width 600mm×length 20000mm (any length >= 20000mm, not specifically limited), preparation method:
(1)铸锭制备(1) Ingot preparation
纯钛坯和纯铌按照以下配比：Ti：50％和Nb：50％；压制电极块，电极块组合焊接一次电极，然后进行3次真空自耗电弧炉熔炼出 Pure titanium billet and pure niobium are mixed in the following ratios: Ti: 50% and Nb: 50%; the electrode blocks are pressed, the electrode blocks are welded together with primary electrodes, and then smelted in a vacuum consumable arc furnace three times.
(2)制备板坯(2) Preparation of slab
铸锭表面进行涂层，锻造开坯温度为1100℃，保温6小时，锻造比为8，终锻温度为850℃，板坯锻造温度为850～900℃，保温2～3小时(具体的3次 锻造，保温时间依次分别为3、2.5和2h)，锻造比为3～4(具体的3次锻造，锻造比依次分别为4、3.8和3)，终锻温度为800℃，板坯规格为厚度30mm×宽度630mm×长度≥700mm，板坯锻造火次为3火次。The ingot surface is coated, the forging temperature is 1100℃, the temperature is kept for 6 hours, the forging ratio is 8, the final forging temperature is 850℃, the slab forging temperature is 850～900℃, the temperature is kept for 2～3 hours (specifically 3 times Forging, the holding time is 3, 2.5 and 2h respectively), the forging ratio is 3-4 (specifically 3 forgings, the forging ratios are 4, 3.8 and 3 respectively), the final forging temperature is 800℃, the slab specifications are thickness 30mm×width 630mm×length ≥700mm, and the slab forging times are 3 times.
(3)板坯温轧(3) Slab warm rolling
采用3火次加热，温度为450～500℃，保温1小时，总加工率为60～70％，最终轧制厚度为1.8mm。Three heating steps are used, the temperature is 450-500°C, the temperature is kept for 1 hour, the total processing rate is 60-70%, and the final rolling thickness is 1.8mm.
(4)表面处理(4) Surface treatment
对板坯进行碱洗(配比为95％NaOH+5％NaNO3)和酸洗(配比为HF：HNO3：H2O＝10：40：50)，水洗清洁后进行表面修磨。The slab was alkali washed (with a ratio of 95% NaOH+5% NaNO 3 ) and pickled (with a ratio of HF:HNO 3 :H 2 O=10:40:50) and then surface ground after water washing.
(5)中间真空退火(5) Intermediate vacuum annealing
退火温度为800℃，保温1小时，真空度不低于1×10-1Pa。The annealing temperature is 800°C, the temperature is maintained for 1 hour, and the vacuum degree is not less than 1×10 -1 Pa.
(6)冷轧(6) Cold rolling
严格控制道次变形量和总加工率，道次变形量为12％～18％，总加工率为40％～50％。采用带凸度(具体的为0.3～0.6mm的0.3、0.4、0.5、0.6mm的平辊)的工作轧辊经过2个轧程的冷轧，最终加工至成品厚度为0.6±0.02mm(2个轧程的厚度分别为1.0mm和0.6mm)。Strictly control the deformation amount and total processing rate of each pass, with the deformation amount of each pass being 12% to 18% and the total processing rate being 40% to 50%. Use working rolls with crown (specifically 0.3 to 0.6mm flat rolls of 0.3, 0.4, 0.5, 0.6mm) to undergo two cold rolling passes, and finally process to a finished product thickness of 0.6±0.02mm (the thickness of the two rolling passes is 1.0mm and 0.6mm respectively).
(7)成品热处理(7) Finished product heat treatment
成品退火温度为350℃，保温2小时，真空度不低于5×10-2Pa，随炉冷却。The finished product annealing temperature is 350°C, kept at this temperature for 2 hours, with a vacuum degree of not less than 5×10 -2 Pa, and cooled along with the furnace.
(8)精整(8) Finishing
对成品退火后的带材进行切边、复绕成卷状成品。The finished annealed strip is trimmed and rewound into a coiled product.
(9)成品性能检测(9) Finished product performance testing
检测数据参见表格1。The test data is shown in Table 1.
对比例1Comparative Example 1
在实施例1基础上，改变以下步骤的控制：Based on Example 1, the control of the following steps is changed:
冷轧采用平辊轧制，当轧制厚度减薄到0.6mm左右时就出现了表面起包、边部波浪(平面度(H/L)约为6％)、壁厚偏差较大(带材中间位置厚度0.69mm，边缘厚度为0.59mm，壁厚偏差0.1mm)等问题，甚至产生断带，导致轧制难于继续进行。 Cold rolling adopts flat roll rolling. When the rolling thickness is reduced to about 0.6mm, problems such as surface bulging, edge waves (flatness (H/L) is about 6%), large wall thickness deviation (the thickness of the middle position of the strip is 0.69mm, the edge thickness is 0.59mm, and the wall thickness deviation is 0.1mm) and so on appear. Even the strip breaks, making it difficult to continue rolling.
由于基于轧辊和变形金属在轧制过程中都会产生一定的变形，即轧辊虽然刚性比较高，但仍然要产生弹性变形，而被轧制的金属会产生塑形和弹性变形。所以，当采用平辊轧制时就会由于轧辊中间部位远离固定支撑点而发生的弹性变形量最大导致板带材中间部位的压下厚度在宽度方向上也最小，即相当于凹辊轧制，从而产生中间位置和边缘位置厚度偏差增大的现象。为了解决这个问题，可以采用对平辊磨抛一定的凸度，在轧制变形过程中正好平衡相应的弹性变形从而变成平辊轧制，从而可以极大的降低板带材中间位置和边缘位置的厚度偏差。Because both the roller and the deformed metal will produce certain deformation during the rolling process, that is, although the roller is relatively rigid, it still produces elastic deformation, and the rolled metal will produce plastic and elastic deformation. Therefore, when flat roll rolling is used, the elastic deformation of the middle part of the roller is the largest due to the distance between the middle part of the roller and the fixed support point, resulting in the smallest thickness reduction in the middle part of the plate and strip in the width direction, which is equivalent to concave roll rolling, resulting in an increase in thickness deviation in the middle and edge positions. In order to solve this problem, the flat roll can be ground and polished to a certain convexity, which can balance the corresponding elastic deformation during the rolling deformation process and thus become flat roll rolling, thereby greatly reducing the thickness deviation in the middle and edge positions of the plate and strip.
实施例2Example 2
Nb-55Ti铌钛合金精密带材，规格为：厚度0.12mm×宽度500mm×长度20000mm(>＝20000mm的任意长度，不做具体限定)，制备方法为：Nb-55Ti niobium-titanium alloy precision strip, specifications: thickness 0.12mm×width 500mm×length 20000mm (any length >= 20000mm, not specifically limited), preparation method:
(1)铸锭制备(1) Ingot preparation
纯钛坯和纯铌按照以下配比：Ti：55％和Nb：45％；压制电极块，电极块组合焊接一次电极，然后进行3次真空自耗电弧炉熔炼出 Pure titanium billet and pure niobium are mixed in the following ratios: Ti: 55% and Nb: 45%; the electrode blocks are pressed, the electrode blocks are welded together with primary electrodes, and then smelted in a vacuum consumable arc furnace three times.
(2)制备板坯(2) Preparation of slab
铸锭表面进行涂层，锻造开坯温度为1100℃，保温6小时，锻造比为6，终锻温度为800℃，板坯锻造温度为900～950℃，保温2～3小时，锻造比为3～4，终锻温度为750℃，板坯的规格为厚度30mm×宽度530mm×长度≥600mm，板坯锻造火次为3火次。The surface of the ingot is coated, the forging temperature is 1100℃, the insulation time is 6 hours, the forging ratio is 6, the final forging temperature is 800℃, the slab forging temperature is 900-950℃, the insulation time is 2-3 hours, the forging ratio is 3-4, the final forging temperature is 750℃, the specifications of the slab are thickness 30mm×width 530mm×length ≥600mm, and the slab forging times is 3 times.
(3)板坯温轧(3) Slab warm rolling
采用3火次加热，温度为450～500℃(具体的依次为例如480、450、400℃)，保温1小时，总加工率为60～75％(具体的依次例如75、70、65％)，最终轧制厚度为1.25mm。Three heating steps are used, the temperature is 450-500°C (specifically, for example, 480, 450, and 400°C), and the temperature is kept for 1 hour. The total processing rate is 60-75% (specifically, for example, 75, 70, and 65%), and the final rolling thickness is 1.25mm.
(4)表面处理(4) Surface treatment
对板坯进行碱洗(配比为88％NaOH+12％NaNO3)和酸洗(配比为HF：HNO3：H2O＝6：32：62)，水洗清洁后进行表面修磨。The slab was alkali washed (with a ratio of 88% NaOH+12% NaNO 3 ) and pickled (with a ratio of HF:HNO 3 :H 2 O=6:32:62), and then surface ground after water washing.
(5)中间真空退火(5) Intermediate vacuum annealing
退火温度为750℃，保温1小时，真空度不低于1×10-1Pa。The annealing temperature is 750°C, the temperature is maintained for 1 hour, and the vacuum degree is not less than 1×10 -1 Pa.
(6)冷轧 (6) Cold rolling
严格控制道次加工率和总加工率，道次变形量为12％～20％，总加工率为45％～60％。采用带凸度(0.2～0.5mm)的工作轧辊经过3个轧程的冷轧最终加工至成品厚度为0.12±0.012mm(3个轧程的厚度分别为0.48mm、0.22mm和0.12mm)。The pass processing rate and total processing rate are strictly controlled, with the pass deformation amount of 12% to 20% and the total processing rate of 45% to 60%. The work roll with crown (0.2 to 0.5 mm) is used for three cold rolling processes to finally process the finished product to a thickness of 0.12 ± 0.012 mm (the thickness of the three rolling processes is 0.48 mm, 0.22 mm and 0.12 mm respectively).
(7)成品热处理(7) Finished product heat treatment
成品退火温度为350℃，保温3小时，真空度不低于5×10-2Pa，随炉冷却。The finished product annealing temperature is 350°C, kept at this temperature for 3 hours, with a vacuum degree of not less than 5×10 -2 Pa, and cooled along with the furnace.
(8)精整(8) Finishing
对成品退火后的带材进行切边、复绕成卷状成品。The finished annealed strip is trimmed and rewound into a coiled product.
(9)成品性能检测(9) Finished product performance testing
检测数据参见表格1。The test data is shown in Table 1.
实施例3Example 3
Nb-47Ti铌钛合金精密带材，规格为：厚度0.09mm×宽度300mm×长度≥30000mm，制备方法为：Nb-47Ti niobium titanium alloy precision strip, specifications: thickness 0.09mm × width 300mm × length ≥ 30000mm, preparation method:
(1)铸锭制备(1) Ingot preparation
纯钛坯和纯铌按照以下质量配比：Ti：47％和Nb：53％；压制电极块，电极块组合焊接一次电极，然后进行3次真空自耗电弧炉熔炼出 Pure titanium billet and pure niobium are prepared in the following mass ratios: Ti: 47% and Nb: 53%; the electrode blocks are pressed, the electrode blocks are welded together with primary electrodes, and then smelted in a vacuum consumable arc furnace three times.
(2)制备板坯(2) Preparation of slab
铸锭表面进行涂层，锻造开坯温度为1150℃，保温6小时，锻造比为5，终锻温度为800℃，板坯锻造温度为850～900℃，保温1～3小时，锻造比为3～4，终锻温度为750℃，板坯规格为：厚度40mm×宽度350mm×长度≥800mm，板坯锻造火次为2火次。The ingot surface is coated, the forging temperature is 1150℃, the insulation time is 6 hours, the forging ratio is 5, the final forging temperature is 800℃, the slab forging temperature is 850-900℃, the insulation time is 1-3 hours, the forging ratio is 3-4, the final forging temperature is 750℃, the slab specifications are: thickness 40mm×width 350mm×length ≥800mm, and the slab forging times is 2 times.
(3)板坯温轧(3) Slab warm rolling
采用3火次加热，温度为450～500℃，保温1小时，总加工率为70～80％，最终轧制厚度为1.2mm。Three heating steps are used, the temperature is 450-500°C, the temperature is kept for 1 hour, the total processing rate is 70-80%, and the final rolling thickness is 1.2mm.
(4)表面处理(4) Surface treatment
对板坯进行碱洗(配比为85％NaOH+15％NaNO3)和酸洗(配比为HF：HNO3：H2O＝10：40：50)，水洗清洁后进行表面修磨。The slab was alkali washed (with a ratio of 85% NaOH+15% NaNO 3 ) and pickled (with a ratio of HF:HNO 3 :H 2 O=10:40:50), and then surface ground after water washing.
(5)中间真空退火 (5) Intermediate vacuum annealing
退火温度为850℃，保温1小时，真空度不低于1×10-1Pa。The annealing temperature is 850°C, the temperature is kept for 1 hour, and the vacuum degree is not less than 1×10 -1 Pa.
(6)冷轧(6) Cold rolling
严格控制道次加工率和总加工率，道次变形量为12％～20％，总加工率为35％～60％(冷轧道次变形量及总加工率控制在上述区间内，太小则塑形不能充分发挥，达不到工艺要求，太大则容易出现裂纹或断裂缺陷)。采用带凸度(0.1～0.4mm)的工作轧辊经过4个轧程最终加工至成品厚度为0.09±0.01mm(4个轧程的厚度分别为0.48mm、0.24mm、0.14mm和0.09mm)。Strictly control the pass processing rate and total processing rate, the pass deformation is 12% to 20%, and the total processing rate is 35% to 60% (the cold rolling pass deformation and total processing rate are controlled within the above range. If it is too small, the shaping cannot be fully exerted and the process requirements cannot be met. If it is too large, cracks or fracture defects are prone to occur). Use a working roll with a crown (0.1 to 0.4mm) and go through 4 rolling processes to finally process the finished product to a thickness of 0.09±0.01mm (the thickness of the 4 rolling processes are 0.48mm, 0.24mm, 0.14mm and 0.09mm respectively).
(7)成品热处理(7) Finished product heat treatment
成品退火温度为450℃，保温2小时，真空度不低于5×10-2Pa，随炉冷却。The finished product annealing temperature is 450°C, kept at this temperature for 2 hours, with a vacuum degree of not less than 5×10 -2 Pa, and cooled along with the furnace.
(8)精整(8) Finishing
对成品退火后的带材进行切边、复绕成卷状成品。The finished annealed strip is trimmed and rewound into a coiled product.
(9)成品性能检测(9) Finished product performance testing
检测数据参见表格1。The test data is shown in Table 1.
表1实施例1～3制备的铌钛合金精密带材的性能测试数据
Table 1 Performance test data of niobium-titanium alloy precision strips prepared in Examples 1 to 3
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。 Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims (21)

  1. 一种铌钛合金精密带材，其特征在于，所述铌钛合金精密带材的成分，按质量百分比计：Ti 46～57％和Nb 42～53％，其他为杂质；所述铌钛合金精密带材的厚度≤0.6mm。A niobium-titanium alloy precision strip, characterized in that the components of the niobium-titanium alloy precision strip, by mass percentage, are: Ti 46-57% and Nb 42-53%, and the rest are impurities; the thickness of the niobium-titanium alloy precision strip is ≤0.6mm.
  2. 根据权利要求1所述的铌钛合金精密带材，其特征在于，所述铌钛合金精密带材的厚度为0.09mm～0.6mm。The niobium-titanium alloy precision strip according to claim 1 is characterized in that the thickness of the niobium-titanium alloy precision strip is 0.09 mm to 0.6 mm.
  3. 根据权利要求1所述的铌钛合金精密带材，其特征在于，所述铌钛合金精密带材的成分，按质量百分比计：Ti 46～57％，C≤0.04％，N≤0.02％，H≤0.0045％，O≤0.10％，Fe≤0.010％，Ta≤0.10％，其他杂质元素≤0.03％，余量为Nb。The niobium-titanium alloy precision strip according to claim 1 is characterized in that the composition of the niobium-titanium alloy precision strip, by mass percentage, is as follows: Ti 46-57%, C≤0.04%, N≤0.02%, H≤0.0045%, O≤0.10%, Fe≤0.010%, Ta≤0.10%, other impurity elements≤0.03%, and the balance is Nb.
  4. 根据权利要求3所述的铌钛合金精密带材，其特征在于，所述铌钛合金精密带材的厚度为0.09mm～0.12mm或0.12mm～0.6mm，壁厚偏差≤±0.02mm。The niobium-titanium alloy precision strip according to claim 3 is characterized in that the thickness of the niobium-titanium alloy precision strip is 0.09 mm to 0.12 mm or 0.12 mm to 0.6 mm, and the wall thickness deviation is ≤ ±0.02 mm.
  5. 根据权利要求4所述的铌钛合金精密带材，其特征在于，所述铌钛合金精密带材的表面粗糙度≤0.4μm，平面度≤2％，抗拉强度≥460MPa，规定非比例延伸强度≥420MPa，延伸率≥15％。The niobium-titanium alloy precision strip according to claim 4 is characterized in that the surface roughness of the niobium-titanium alloy precision strip is ≤0.4 μm, the flatness is ≤2%, the tensile strength is ≥460 MPa, the specified non-proportional elongation strength is ≥420 MPa, and the elongation is ≥15%.
  6. 权利要求1～5任一项所述铌钛合金精密带材的制造方法，其特征在于，包括以下步骤：The method for manufacturing the niobium-titanium alloy precision strip according to any one of claims 1 to 5 is characterized in that it comprises the following steps:
    制备板坯：对铸锭进行开坯得到板坯，并对所述板坯进行锻造；Preparing a slab: splitting the ingot to obtain a slab, and forging the slab;
    板坯温轧：加热所述锻造后的板坯，再进行若干火次温轧，得到带材坯料，所述温轧的总加工率为60～80％；Slab warm rolling: heating the forged slab and then performing several rounds of warm rolling to obtain a strip blank, wherein the total processing rate of the warm rolling is 60-80%;
    表面处理：对所述温轧后的板坯进行表面处理，以去除表面氧化皮，得到冷轧坯料；Surface treatment: performing surface treatment on the slab after warm rolling to remove surface oxide scale to obtain a cold-rolled billet;
    冷轧：利用专用轧辊对所述冷轧坯料进行冷轧，专用轧辊为中间直径大、边缘直径小且平滑过度的异形辊，冷轧后得到铌钛合金精密带材。Cold rolling: The cold-rolled billet is cold-rolled by using a special roller, which is a special-shaped roller with a large middle diameter, a small edge diameter and a smooth transition, and a niobium-titanium alloy precision strip is obtained after cold rolling.
  7. 根据权利要求6所述的制造方法，其特征在于，所述制备板坯为：对铸锭先进行开坯锻造，开坯温度为1050～1150℃，保温4～6小时，锻造比为4～8，终锻温度≥800℃，再进行板坯锻造，温度为800～1000℃，保温1～3小时，锻造比为2～6，终锻温度≥750℃；所述板坯锻造的火次为2～4火次，所述锻造后的板坯的规格为厚度30～40mm×宽度300～650mm。 The manufacturing method according to claim 6 is characterized in that the preparation of the slab is: the ingot is first subjected to forging at a temperature of 1050-1150°C, kept warm for 4-6 hours, a forging ratio of 4-8, and a final forging temperature ≥800°C, and then the slab is forged at a temperature of 800-1000°C, kept warm for 1-3 hours, a forging ratio of 2-6, and a final forging temperature ≥750°C; the slab is forged 2 to 4 times, and the specifications of the forged slab are 30-40 mm in thickness × 300-650 mm in width.
  8. 根据权利要求7所述的制造方法，其特征在于，还包括在所述制备板坯前制备铸锭：将纯钛和纯铌按照Ti：46～57％和Nb：42～53％重量比配置，压制电极块，电极块组合焊接一次电极，然后进行3次真空自耗电弧炉熔炼，得到铌钛铸锭。The manufacturing method according to claim 7 is characterized in that it also includes preparing an ingot before preparing the slab: pure titanium and pure niobium are configured according to a weight ratio of Ti: 46-57% and Nb: 42-53%, an electrode block is pressed, the electrode block is combined and welded with a primary electrode, and then three vacuum consumable arc furnace smeltings are performed to obtain a niobium-titanium ingot.
  9. 根据权利要求6所述的制造方法，其特征在于，所述板坯温轧为：加热板坯的温度为400～550℃，保温0.7～1.5小时，之后进行1～3火次温轧，道次变形量为12％～30％，温轧后带材坯料的厚度大于1.2mm。The manufacturing method according to claim 6 is characterized in that the slab warm rolling is: heating the slab to a temperature of 400 to 550°C, keeping it warm for 0.7 to 1.5 hours, and then performing 1 to 3 rounds of warm rolling, with a deformation amount of 12% to 30% per pass, and the thickness of the strip after warm rolling is greater than 1.2 mm.
  10. 根据权利要求6所述的制造方法，其特征在于，所述表面处理为：对温轧板坯进行碱洗和/或酸洗，以去除表面氧化皮，之后水洗清洁。The manufacturing method according to claim 6 is characterized in that the surface treatment is: alkali washing and/or pickling the warm-rolled slab to remove the surface oxide scale, and then washing with water for cleaning.
  11. 根据权利要求10所述的制造方法，其特征在于，所述碱洗采用质量配比为85～95％NaOH和15～5％NaNO3的混合液；所述酸洗采用质量配比为HF：HNO3：H2O＝5～10：30～40：余量的混合液。The manufacturing method according to claim 10 is characterized in that the alkali washing adopts a mixed solution with a mass ratio of 85-95% NaOH and 15-5% NaNO 3 ; the acid washing adopts a mixed solution with a mass ratio of HF:HNO 3 :H 2 O=5-10:30-40:the remainder.
  12. 根据权利要求6所述的制造方法，其特征在于，所述冷轧的条件为：冷轧的次数为3～5次，冷轧时道次变形量为9％～25％，总加工率为35％～60％，冷轧得到的带材的厚度小于等于0.6mm。The manufacturing method according to claim 6 is characterized in that the cold rolling conditions are: the number of cold rolling is 3 to 5 times, the deformation amount per pass during cold rolling is 9% to 25%, the total processing rate is 35% to 60%, and the thickness of the strip obtained by cold rolling is less than or equal to 0.6 mm.
  13. 根据权利要求12所述的制造方法，其特征在于，所述冷轧得到的带材的厚度为小于等于0.12mm。The manufacturing method according to claim 12 is characterized in that the thickness of the strip obtained by cold rolling is less than or equal to 0.12 mm.
  14. 根据权利要求12所述的制造方法，其特征在于，所述冷轧得到的带材的厚度为小于等于0.09mm。The manufacturing method according to claim 12 is characterized in that the thickness of the strip obtained by cold rolling is less than or equal to 0.09 mm.
  15. 根据权利要求12所述的制造方法，其特征在于，还包括在所述冷轧前采用真空热处理进行中间退火。The manufacturing method according to claim 12 is characterized in that it also includes intermediate annealing by vacuum heat treatment before the cold rolling.
  16. 根据权利要求12所述的制造方法，其特征在于，两次所述冷轧之间进行除油处理和中间真空退火，成品轧制后进行成品真空退火处理。The manufacturing method according to claim 12 is characterized in that degreasing treatment and intermediate vacuum annealing are performed between the two cold rolling processes, and the finished product is subjected to vacuum annealing after the finished product is rolled.
  17. 根据权利要求12所述的制造方法，其特征在于，还包括在所述冷轧后进行除油处理：对冷轧后需要进行热处理的板带材进行除油处理，所述除油处理为超声波清洗除油或除油剂清洗。The manufacturing method according to claim 12 is characterized in that it also includes degreasing treatment after the cold rolling: degreasing treatment is performed on the plate and strip materials that need to be heat treated after cold rolling, and the degreasing treatment is ultrasonic cleaning degreasing or degreasing agent cleaning.
  18. 根据权利要求16所述的制造方法，其特征在于，还包括在所述除油处理后进行中间软化和成品热处理：所述中间软化和成品热处理均采用真空退火热处理。 The manufacturing method according to claim 16 is characterized in that it also includes intermediate softening and finished product heat treatment after the degreasing treatment: the intermediate softening and finished product heat treatment both adopt vacuum annealing heat treatment.
  19. 根据权利要求18所述的制造方法，其特征在于，所述中间软化的真空退火热处理为：中间退火温度为750～900℃，保温时间为1～3小时，真空度不低于1×10-1Pa。The manufacturing method according to claim 18 is characterized in that the intermediate softening vacuum annealing heat treatment is: the intermediate annealing temperature is 750-900°C, the holding time is 1-3 hours, and the vacuum degree is not less than 1×10 -1 Pa.
  20. 根据权利要求18所述的制造方法，其特征在于，所述成品热处理的真空退火热处理为：成品退火温度为300～450℃，保温时间为1～3小时，真空度不低于5×10-2Pa。The manufacturing method according to claim 18 is characterized in that the vacuum annealing heat treatment of the finished product heat treatment is: the finished product annealing temperature is 300-450°C, the insulation time is 1-3 hours, and the vacuum degree is not less than 5×10 -2 Pa.
  21. 根据权利要求6所述的制造方法，其特征在于，所述专用轧辊中间的直径比边缘的直径大0.1～0.6mm。 The manufacturing method according to claim 6 is characterized in that the diameter in the middle of the special rolling roller is 0.1 to 0.6 mm larger than the diameter at the edge.
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CN113322386A (en) * 2021-04-19 2021-08-31 西部超导材料科技股份有限公司 Preparation method of large-size NbTi alloy ingot
CN113414551A (en) * 2021-06-25 2021-09-21 中国航发北京航空材料研究院 Preparation method of deformed high-temperature alloy wide and thin strip
CN114406607A (en) * 2021-12-21 2022-04-29 江西铜业集团铜板带有限公司 Preparation method of ultrathin red copper thin strip and ultrathin red copper thin strip
CN115652139A (en) * 2022-10-31 2023-01-31 宁夏中色金航钛业有限公司 Niobium-titanium alloy precision strip and manufacturing method thereof

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