技术领域technical field
本发明属于钛合金材料加工技术领域，特别涉及一种耐蚀钛合金箔材的制备方法。The invention belongs to the technical field of titanium alloy material processing, in particular to a preparation method of corrosion-resistant titanium alloy foil.
背景技术Background technique
双极板是质子交换膜燃料电池(PEMFC)的关键部件，其质量占整个电池堆的70％左右，成本约占其40％。双极板钛合金基材具有优异的耐腐蚀性、更高的比强度，质量轻等优点。双极板大致可分为3类：炭质材料、金属材料及金属与炭质的复合材料；其中，金属材料中铝，镍，钛及不锈钢等金属材料可用于制作双极板，金属双极板易加工，可批量制造，成本低，厚度薄，电池的体积比功率与比能量高。而新型Ti－Ni－Nb近α钛合金，具有优异的耐蚀性，是双极板基板的良好材料，用于制造双极板的钛合金箔材厚度一般为0.05mm～0.15mm，厚度偏差要求不大于±5μm；但Ti－Ni－Nb箔材一般需要在二十辊轧机上进行加工，加工过程复杂，加工周期长，成本高昂。The bipolar plate is a key component of a proton exchange membrane fuel cell (PEMFC), its mass accounts for about 70% of the entire battery stack, and its cost accounts for about 40%. The titanium alloy base material of the bipolar plate has the advantages of excellent corrosion resistance, higher specific strength, and light weight. Bipolar plates can be roughly divided into three categories: carbonaceous materials, metal materials, and composite materials of metal and carbon; among them, metal materials such as aluminum, nickel, titanium and stainless steel can be used to make bipolar plates, and metal bipolar plates The board is easy to process, can be manufactured in batches, has low cost, thin thickness, and the volume specific power and specific energy of the battery are high. The new Ti-Ni-Nb near-alpha titanium alloy has excellent corrosion resistance and is a good material for bipolar plate substrates. The thickness of titanium alloy foil used to manufacture bipolar plates is generally 0.05mm to 0.15mm, and the thickness deviation The requirement is not greater than ±5μm; however, Ti-Ni-Nb foil generally needs to be processed on a 20-high rolling mill, the processing process is complicated, the processing cycle is long, and the cost is high.
中国专利CN113578959A、CN113564500A和CN113578967A分别提供了一种细晶TA15、TC4钛合金箔材和550℃～650℃高温钛合金箔材的制备方法，以上专利均采用了包覆轧制，制造工艺繁琐，制造成本高，制备出的钛合金箔材晶粒细小，按照此方法制备的箔材强度高、塑性低，不利于后期的双极板成形。国内尚未开展双极板用耐蚀Ti－Ni－Nb钛合金箔材的研制和加工制备工作，因此对双极板用耐蚀Ti－Ni－Nb钛合金箔材的加工工艺和热处理工艺进行研究以满足燃料电池对双极板用钛合金基材的需求是一项亟需解决的问题。Chinese patents CN113578959A, CN113564500A and CN113578967A respectively provide a preparation method of fine-grained TA15, TC4 titanium alloy foil and 550°C-650°C high-temperature titanium alloy foil. The above patents all use clad rolling, and the manufacturing process is cumbersome. The manufacturing cost is high, and the grains of the prepared titanium alloy foil are fine. The foil prepared according to this method has high strength and low plasticity, which is not conducive to the later forming of bipolar plates. The development and processing of corrosion-resistant Ti-Ni-Nb titanium alloy foil for bipolar plates has not been carried out in China, so the processing technology and heat treatment process of corrosion-resistant Ti-Ni-Nb titanium alloy foil for bipolar plates are studied It is an urgent problem to be solved to meet the demand of fuel cells for titanium alloy substrates for bipolar plates.
发明内容Contents of the invention
针对上述问题，本发明公开了一种耐蚀钛合金箔材的制备方法，包括：In view of the above problems, the invention discloses a preparation method of corrosion-resistant titanium alloy foil, comprising:
将钛合金热轧板坯料先进行真空退火处理，再进行冷轧；按照上述步骤循环进行n次真空退火处理和n－1轧程冷轧处理后得到钛合金箔材，n为正整数。The titanium alloy hot-rolled plate blank is subjected to vacuum annealing treatment first, and then cold-rolled; the titanium alloy foil material is obtained after vacuum annealing treatment and n-1 rolling process cold rolling treatment are cycled according to the above steps, and n is a positive integer.
进一步地，所述制备方法步骤如下：Further, the steps of the preparation method are as follows:
步骤一，将钛合金热轧板坯料进行第一次真空退火处理；Step 1, performing the first vacuum annealing treatment on the titanium alloy hot-rolled sheet blank;
步骤二，对第一次真空退火后的热轧板坯料进行第一轧程冷轧、平整矫直处理；Step 2, performing cold rolling in the first rolling process and smoothing and straightening treatment on the hot-rolled sheet blank after the first vacuum annealing;
步骤三，对第一轧程后的板材进行剪切、碱洗以及第二次真空退火处理；Step 3, performing shearing, alkali washing and second vacuum annealing treatment on the plate after the first rolling process;
步骤四，对第二次真空退火后的板材进行第二轧程冷轧、平整矫直处理；Step 4, performing second rolling process cold rolling, leveling and straightening treatment on the plate after the second vacuum annealing;
步骤五，对第二轧程后的钛合金板材进行剪切、碱洗以及第三次真空退火处理；Step 5, performing shearing, alkali washing and third vacuum annealing treatment on the titanium alloy plate after the second rolling process;
步骤六，将第三次真空退火后的钛合金板材进行第三轧程冷轧、平整矫直处理；Step 6, subjecting the titanium alloy plate after the third vacuum annealing to cold rolling in the third rolling process, and smoothing and straightening treatment;
步骤七，对第三轧程后的钛合金板材进行剪切、碱洗以及第四次真空退火处理；Step 7, performing shearing, alkali washing and fourth vacuum annealing treatment on the titanium alloy plate after the third rolling process;
步骤八，对第四次真空退火后的钛合金板材进行第四轧程冷轧、平整矫直处理；Step 8, carrying out the fourth rolling process cold rolling, leveling and straightening treatment on the titanium alloy plate after the fourth vacuum annealing;
步骤九，对第四轧程后的钛合金板材进行剪切、碱洗以及第五次真空退火处理后得到耐蚀钛合金箔材；Step 9, performing shearing, alkali washing and fifth vacuum annealing treatment on the titanium alloy plate after the fourth rolling process to obtain a corrosion-resistant titanium alloy foil;
步骤十，若因初始热轧板较厚，步骤九中未得到满足要求的钛合金箔材，可重复步骤八～步骤九。In step ten, if the titanium alloy foil that meets the requirements is not obtained in step nine because the initial hot-rolled plate is relatively thick, repeat steps eight to nine.
进一步地，所述耐蚀钛合金为Ti－Ni－Nb新型近α钛合金；所述钛合金热轧板坯料尺寸为厚度×宽度×长度＝3.5～6mm×100～300mm×200～500mm；Further, the corrosion-resistant titanium alloy is a new type of Ti-Ni-Nb near-alpha titanium alloy; the size of the titanium alloy hot-rolled plate blank is thickness×width×length=3.5～6mm×100～300mm×200～500mm;
进一步地，采用高真空电阻炉进行真空退火处理，真空度为1×10－3Pa～6×10－3Pa，温度均匀性小于等于±5℃，温控精度为小于等于±3℃，保温时间为60min，冷却方式为随炉冷却；所述真空退火处理的温度为650℃～750℃。Further, a high vacuum resistance furnace is used for vacuum annealing treatment, the vacuum degree is 1×10-3 Pa～6×10-3 Pa, the temperature uniformity is less than or equal to ±5°C, the temperature control accuracy isless than or equal to ±3°C, and the heat preservation The time is 60 minutes, and the cooling method is furnace cooling; the temperature of the vacuum annealing treatment is 650°C-750°C.
进一步地，第一轧程冷轧后钛合金板材的厚度为1.4～3mm；Further, the thickness of the titanium alloy plate after cold rolling in the first rolling process is 1.4-3mm;
第二轧程冷轧后钛合金板材的厚度为0.4～1.8mm；The thickness of the titanium alloy plate after cold rolling in the second rolling process is 0.4-1.8mm;
第三轧程冷轧后钛合金板材的厚度为0.2～0.9mm；The thickness of the titanium alloy plate after cold rolling in the third rolling process is 0.2-0.9mm;
第四轧程冷轧后钛合金板材的厚度为0.1～0.4mm。The thickness of the titanium alloy plate after cold rolling in the fourth rolling process is 0.1-0.4 mm.
进一步地，第一轧程总变形量不小于50％，厚度偏差不超过±0.05mm；Further, the total deformation in the first rolling process is not less than 50%, and the thickness deviation is not more than ±0.05mm;
第二轧程总变形量为40％～72％，厚度偏差不超过±0.03mm；The total deformation in the second rolling process is 40% to 72%, and the thickness deviation does not exceed ±0.03mm;
第三轧程总变形量不小于50％，厚度偏差不超过±0.01mm；The total deformation of the third rolling process is not less than 50%, and the thickness deviation is not more than ±0.01mm;
第四轧程总变形量为20％～60％，厚度偏差不超过±0.005mm。The total deformation in the fourth rolling process is 20% to 60%, and the thickness deviation does not exceed ±0.005mm.
进一步地，采用液压张力冷/温轧实验机进行冷轧，冷轧前对坯料进行矫直平整处理。Further, a hydraulic tension cold/warm rolling test machine is used for cold rolling, and the billet is straightened and leveled before cold rolling.
采用上述制备方法制备的耐蚀钛合金箔材的平均晶粒尺寸20～30μm，室温抗拉强度为200～400MPa，延伸率≥30％，箔材的厚度偏差不大于±0.005mm。The average grain size of the corrosion-resistant titanium alloy foil prepared by the above preparation method is 20-30 μm, the tensile strength at room temperature is 200-400 MPa, the elongation is ≥ 30%, and the thickness deviation of the foil is not more than ±0.005 mm.
进一步地，按照上述方法制备的耐蚀钛合金箔材可以在制造双极板基板上应用。Furthermore, the corrosion-resistant titanium alloy foil prepared according to the above method can be used in the manufacture of bipolar plate substrates.
本发明的有益效果：Beneficial effects of the present invention:
本发明在Ti－Ni－Nb钛合金箔材制备过程中，通过循环进行n次真空退火处理和n－1次轧程冷轧处理后得最终箔材，整个过程无需采用包覆叠轧以及复杂昂贵的二十辊轧机，只需采用液压张力冷/温轧实验机即可，整个制备过程操作简单，且大大降低了制备成本；In the preparation process of the Ti-Ni-Nb titanium alloy foil, the present invention obtains the final foil after n times of vacuum annealing treatment and n-1 times of rolling cold rolling treatment. The expensive 20-high rolling mill only needs to use the hydraulic tension cold/warm rolling test machine, the whole preparation process is easy to operate, and the preparation cost is greatly reduced;
本发明中通过将冷轧和热处理方法结合，真空处理的温度均在650℃～750℃之间，冷轧轧程总变形量不同，可有效控制箔材的力学性能和尺寸精度；最终制得的Ti－Ni－Nb钛合金箔材平均晶粒尺寸达到20～30μm，室温抗拉强度可达300MPa～400MPa，延伸率≥30％，箔材厚度的正负偏差小于等于0.005mm；In the present invention, by combining cold rolling and heat treatment methods, the temperature of vacuum treatment is between 650°C and 750°C, and the total deformation of the cold rolling process is different, which can effectively control the mechanical properties and dimensional accuracy of the foil; finally obtained The average grain size of Ti-Ni-Nb titanium alloy foil reaches 20-30μm, the tensile strength at room temperature can reach 300MPa-400MPa, the elongation rate is ≥30%, and the positive and negative deviation of foil thickness is less than or equal to 0.005mm;
本发明提出的制备方法相较于包覆轧制方法操作更加简单，制备的箔材力学性能和抗腐蚀能力均符合标准。Compared with the clad rolling method, the preparation method proposed by the invention is simpler to operate, and the mechanical properties and corrosion resistance of the prepared foil meet the standards.
本发明的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。本发明的目的和其他优点可通过在说明书、权利要求书中所公开的内容实现和获得。Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objects and other advantages of the present invention can be realized and attained by the contents disclosed in the specification and claims.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中，对本发明实施例中的技术方案进行清楚、完整地说明，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are the embodiment of the present invention Some, but not all, embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明针对双极板用耐蚀Ti－Ni－Nb钛合金箔材制备技术空白，提供一种双极板用耐蚀Ti－Ni－Nb钛合金箔材的制备方法，钛合金热轧板坯料为起始坯料的尺寸为厚度×宽度×长度＝3.5～6mm×100～300mm×200～500mm，通过循环进行n次真空退火处理和n－1次轧程冷轧处理后得钛合金箔材。n的取值根据起始坯料的尺寸而定，厚度越厚，n的取值越大。其中，真空退火所采用的设备包括高真空电阻炉，真空度为1×10－3Pa～6×10－3Pa，温度均匀性不大于±5℃，温控精度为不大于±3℃，保温时间为60min，冷却方式为随炉冷却。冷轧过程使用的轧机为液压张力冷/温轧实验机，轧制前对坯料进行矫直平整处理。The present invention aims at the technical blank of preparation of corrosion-resistant Ti-Ni-Nb titanium alloy foil for bipolar plate, and provides a preparation method of corrosion-resistant Ti-Ni-Nb titanium alloy foil for bipolar plate, titanium alloy hot-rolled plate blank The size of the starting blank is thickness×width×length=3.5～6mm×100～300mm×200～500mm, and the titanium alloy foil is obtained after n times of vacuum annealing treatment and n-1 times of rolling process cold rolling treatment. The value of n depends on the size of the starting blank, the thicker the thickness, the larger the value of n. Among them, the equipment used for vacuum annealing includes high vacuum resistance furnace, the vacuum degree is 1×10-3 Pa ~ 6×10-3 Pa, the temperature uniformity is not greater than ±5°C, and the temperature control accuracy is not greater than ±3°C. The holding time is 60 minutes, and the cooling method is furnace cooling. The rolling mill used in the cold rolling process is a hydraulic tension cold/warm rolling test machine, and the billet is straightened and leveled before rolling.
具体包括以下步骤：Specifically include the following steps:
步骤一，将Ti－Ni－Nb钛合金热轧板坯料进行第一次真空退火处理，退火温度为650～750℃，保温时间为60min，随后炉冷。Step 1: The Ti-Ni-Nb titanium alloy hot-rolled sheet blank is subjected to the first vacuum annealing treatment, the annealing temperature is 650-750° C., the holding time is 60 minutes, and then the furnace is cooled.
步骤二，对第一次真空退火后的热轧板坯料进行第一轧程冷轧，分为15个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量大于等于50％，厚度偏差不超过±0.05mm，轧制到厚度为1.4～3mm的板材。Step 2: Carry out cold rolling in the first rolling pass on the hot-rolled slab stock after the first vacuum annealing, which is divided into 15 passes for rolling, and straightening and smoothing after rolling. The total deformation of the rolling pass is greater than or equal to 50 %, the thickness deviation does not exceed ±0.05mm, and rolled to a plate with a thickness of 1.4-3mm.
步骤三，对第一轧程后的板材进行剪切、碱洗以及第二次真空退火处理，退火温度为650～750℃，保温时间为60min，随后炉冷。Step 3: shearing, alkali washing and second vacuum annealing treatment are carried out on the plate after the first rolling process. The annealing temperature is 650-750° C., the holding time is 60 minutes, and then furnace cooling.
步骤四，对第二次真空退火后的板坯进行第二轧程冷轧，分为30个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为40－72％，厚度偏差不超过±0.03mm，轧制到厚度为0.4～1.8mm的板材。Step 4: Carry out cold rolling in the second rolling process for the slab after the second vacuum annealing, which is divided into 30 passes for rolling, and straightening and smoothing after rolling, the total deformation of the rolling process is 40-72% , The thickness deviation does not exceed ±0.03mm, and rolled to a plate with a thickness of 0.4-1.8mm.
步骤五，对第二轧程后的板材进行剪切、碱洗以及第三次真空退火处理，退火温度为650℃～750℃，保温时间为60min，随后炉冷。Step five, shearing, alkali washing and third vacuum annealing treatment are performed on the plate after the second rolling process, the annealing temperature is 650°C-750°C, the holding time is 60min, and then furnace cooling.
步骤六，对第三次真空退火后的板坯进行第三轧程冷轧，分为20个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为大于等于50％，厚度偏差不超过±0.01mm，轧制到厚度为0.2～0.9mm的板材。Step 6: Carry out cold rolling in the third rolling process for the slab after the third vacuum annealing, and divide it into 20 passes for rolling, and perform straightening and leveling treatment after rolling, and the total deformation of the rolling process is greater than or equal to 50% , the thickness deviation does not exceed ±0.01mm, and rolled to a plate with a thickness of 0.2-0.9mm.
步骤七，对第三轧程后的板材进行剪切、碱洗以及第四次真空退火处理，退火温度为650℃～750℃，保温时间为60min，随后炉冷。Step 7: Carry out shearing, alkali washing and fourth vacuum annealing treatment on the plate after the third rolling process. The annealing temperature is 650° C. to 750° C., the holding time is 60 minutes, and then furnace cooling.
步骤八，对第四次真空退火后的板坯进行第四轧程冷轧，第四轧程总变形量为20％～60％，厚度偏差不超过±0.005mm，轧制到厚度为0.1～0.4mm的箔材。Step 8: Carry out cold rolling in the fourth rolling process to the slab after the fourth vacuum annealing, the total deformation in the fourth rolling process is 20% to 60%, the thickness deviation is not more than ±0.005mm, and rolled to a thickness of 0.1 to 60%. 0.4mm foil.
步骤九，对第四轧程后的钛合金板材进行矫直平整、剪切、碱洗以及第五次真空退火处理最后得Ti－Ni－Nb钛合金，退火温度为650℃～750℃。Step 9: Straightening, shearing, alkali washing and fifth vacuum annealing treatment are carried out on the titanium alloy plate after the fourth rolling process to finally obtain Ti-Ni-Nb titanium alloy, and the annealing temperature is 650°C-750°C.
步骤十，若因初始热轧板较厚，步骤九中未得到满足要求的钛合金箔材，可重复步骤八～步骤九。In step ten, if the titanium alloy foil that meets the requirements is not obtained in step nine because the initial hot-rolled plate is relatively thick, repeat steps eight to nine.
以下以3.5mm×265mm×850mm的Ti－Ni－Nb钛合金热轧板坯料为例结合具体实施例对上述方法进行说明。The above method will be described below by taking a 3.5mm×265mm×850mm Ti—Ni—Nb titanium alloy hot-rolled plate blank as an example in combination with specific examples.
实施例1Example 1
步骤一，将尺寸为3.5mm×265mm×850mm的Ti－Ni－Nb钛合金热轧板坯料进行真空退火处理，退火温度为750℃，保温时间为60min，随后炉冷。In step 1, the Ti-Ni-Nb titanium alloy hot-rolled sheet blank with a size of 3.5mm×265mm×850mm is subjected to vacuum annealing treatment, the annealing temperature is 750° C., the holding time is 60 minutes, and then furnace cooled.
步骤二，对真空退火后的热轧板坯料进行第一轧程冷轧，分为15个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为57％，轧制到厚度为1.4mm的板材。Step 2: Carry out cold rolling in the first rolling pass for the hot-rolled slab stock after vacuum annealing, which is divided into 15 passes for rolling. After rolling, straightening and leveling treatment is carried out. to a plate with a thickness of 1.4mm.
步骤三，对第一轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为750℃，保温时间为60min，随后炉冷。Step 3: Carry out shearing, alkali washing, and vacuum annealing treatment on the titanium alloy plate after the first rolling process. The annealing temperature is 750° C., the holding time is 60 minutes, and then furnace cooling.
步骤四，对步骤三中真空退火后的板坯进行第二轧程冷轧，分为30个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为71％，轧制到厚度为0.4mm的板材。Step 4, the slab after the vacuum annealing in the step 3 is carried out the second rolling process cold rolling, is divided into 30 passes and carries out rolling, after rolling, carry out straightening smooth treatment, the total deformation of rolling process is 71%, rolling Made to a plate with a thickness of 0.4mm.
步骤五，对第二轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为750℃，保温时间为60min，随后炉冷。Step 5: Perform shearing, alkali washing, and vacuum annealing on the titanium alloy plate after the second rolling process. The annealing temperature is 750° C., the holding time is 60 minutes, and then furnace cooling.
步骤六，对步骤五中真空退火后的板坯进行第三轧程冷轧，分为20个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为71％，轧制到厚度为0.2mm的箔材。Step 6, the slab after the vacuum annealing in the step 5 is carried out the cold rolling of the third rolling process, is divided into 20 passes and carries out rolling, after rolling, carry out straightening and smoothing treatment, the total deformation of the rolling process is 71%. Foils with a thickness of 0.2 mm were produced.
步骤七，对第三轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为750℃，保温时间为60min，随后炉冷。Step 7: Perform shearing, alkali washing, and vacuum annealing on the titanium alloy plate after the third rolling process. The annealing temperature is 750° C., the holding time is 60 minutes, and then furnace cooling.
步骤八，对步骤七中真空退火后的板料进行第四轧程冷轧，分为15个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为40％，轧制到厚度为0.12mm的箔材。Step 8: Carry out the fourth rolling process cold rolling to the plate after vacuum annealing in the step 7, divide into 15 passes and carry out rolling, carry out straightening and flattening treatment after rolling, the total deformation of the rolling process is 40%, rolling Foils with a thickness of 0.12 mm were produced.
步骤九，对第四轧程后的钛合金箔材进行平整矫直、剪切、碱洗、真空退火处理，退火温度为750℃，保温时间为60min，随后炉冷。Step 9: Perform flattening, shearing, alkali washing, and vacuum annealing on the titanium alloy foil after the fourth rolling process. The annealing temperature is 750° C., the holding time is 60 minutes, and then furnace cooled.
实施例2采用五次真空处理和四次轧程冷轧处理的方式制备Ti－Ni－Nb钛合金箔材。Example 2 A Ti-Ni-Nb titanium alloy foil was prepared by five vacuum treatments and four cold rolling treatments.
步骤一，将尺寸为3.5mm×265mm×850mmTi－Ni－Nb钛合金热轧板坯料进行真空退火处理，退火温度为700℃，保温时间为60min，随后炉冷。Step 1: Vacuum annealing the Ti-Ni-Nb titanium alloy hot-rolled blank with a size of 3.5mm×265mm×850mm, the annealing temperature is 700°C, the holding time is 60min, and then furnace cooled.
步骤二，对真空退火后的热轧板坯料进行第一轧程冷轧，分为15个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为57％，轧制到厚度为1.4mm的板材。Step 2: Carry out cold rolling in the first rolling pass for the hot-rolled slab stock after vacuum annealing, which is divided into 15 passes for rolling. After rolling, straightening and leveling treatment is carried out. to a plate with a thickness of 1.4mm.
步骤三，对第一轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为700℃，保温时间为60min，随后炉冷。Step 3: Carry out shearing, alkali washing, and vacuum annealing treatment on the titanium alloy plate after the first rolling process. The annealing temperature is 700° C., the holding time is 60 minutes, and then furnace cooling.
步骤四，对步骤三中真空退火后的板坯进行第二轧程冷轧，分为15个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为57％，轧制到厚度为0.6mm的板材。Step 4, the slab after the vacuum annealing in the step 3 is carried out the second rolling pass cold rolling, is divided into 15 passes and carries out rolling, after rolling, carry out straightening smooth treatment, the total deformation of the rolling pass is 57%, rolling Made to a plate with a thickness of 0.6mm.
步骤五，对第二轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为700℃，保温时间为60min，随后炉冷。Step 5: Carry out shearing, alkali washing, and vacuum annealing treatment on the titanium alloy plate after the second rolling process. The annealing temperature is 700° C., the holding time is 60 minutes, and then furnace cooling.
步骤六，对步骤五中真空退火后的板坯进行第三轧程冷轧，分为15个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为58％，轧制到厚度为0.25mm的板材。Step 6, the slab after the vacuum annealing in the step 5 is carried out the third rolling pass cold rolling, is divided into 15 passes and carries out rolling, after rolling, carry out straightening smooth treatment, the total deformation of the rolling pass is 58%, rolling Made to a plate with a thickness of 0.25mm.
步骤七，对第三轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为700℃，保温时间为60min，随后炉冷。Step 7: Perform shearing, alkali washing, and vacuum annealing on the titanium alloy plate after the third rolling process. The annealing temperature is 700° C., the holding time is 60 minutes, and then furnace cooling.
步骤八，对步骤七中真空退火后的板料进行第四轧程冷轧，分为26个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为40％，轧制到厚度为0.15mm的箔材。Step 8: Carry out the fourth rolling pass cold rolling to the sheet material after the vacuum annealing in the step 7, divide into 26 passes and carry out rolling, carry out straightening and flattening treatment after rolling, the total deformation of the rolling process is 40%, rolling Foils with a thickness of 0.15 mm were produced.
步骤九，对第四轧程后的钛合金箔材进行平整矫直、剪切、碱洗、真空退火处理，退火温度为700℃，保温时间为60min，随后炉冷。Step 9: Perform flattening, shearing, alkali washing, and vacuum annealing on the titanium alloy foil after the fourth rolling process. The annealing temperature is 700° C., the holding time is 60 minutes, and then furnace cooling.
实施例3采用五次真空处理和四次轧程冷轧处理的方式制备Ti－Ni－Nb钛合金箔材。Example 3 The Ti—Ni—Nb titanium alloy foil was prepared by five vacuum treatments and four cold rolling treatments.
步骤一，将尺寸为3.5mm×265mm×850mmTi－Ni－Nb钛合金热轧板坯料进行真空退火处理，退火温度为650℃，保温时间为60min，随后炉冷。Step 1: Vacuum annealing the Ti-Ni-Nb titanium alloy hot-rolled blank with a size of 3.5mm×265mm×850mm, the annealing temperature is 650°C, the holding time is 60min, and then furnace cooling.
步骤二，对真空退火后的热轧板坯料进行第一轧程冷轧，分为15个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为57％，轧制到厚度为1.4mm的板材。Step 2: Carry out cold rolling in the first rolling pass for the hot-rolled slab stock after vacuum annealing, which is divided into 15 passes for rolling. After rolling, straightening and leveling treatment is carried out. to a plate with a thickness of 1.4mm.
步骤三，对第一轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为650℃，保温时间为60min，随后炉冷。Step 3: Carry out shearing, alkali washing, and vacuum annealing treatment on the titanium alloy plate after the first rolling process. The annealing temperature is 650° C., the holding time is 60 minutes, and then furnace cooling.
步骤四，对步骤三中真空退火后的板坯进行第二轧程冷轧，分为30个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为71％，轧制到厚度为0.4mm的板材。Step 4, the slab after the vacuum annealing in the step 3 is carried out the second rolling process cold rolling, is divided into 30 passes and carries out rolling, after rolling, carry out straightening smooth treatment, the total deformation of rolling process is 71%, rolling Made to a plate with a thickness of 0.4mm.
步骤五，对第二轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为650℃，保温时间为60min，随后炉冷。Step 5: Perform shearing, alkali washing, and vacuum annealing on the titanium alloy plate after the second rolling process. The annealing temperature is 650° C., the holding time is 60 minutes, and then furnace cooling.
步骤六，对步骤五中真空退火后的板坯进行第三轧程冷轧，分为20个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为50％，轧制到厚度为0.2mm的板材。Step 6, the slab after the vacuum annealing in the step 5 is carried out the third rolling pass cold rolling, is divided into 20 passes and carries out rolling, carries out straightening smooth treatment after rolling, and the total deformation of the rolling pass is 50%, rolling Made to a plate with a thickness of 0.2mm.
步骤七，对第三轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为680℃，保温时间为60min，随后炉冷。Step 7: Perform shearing, alkali washing, and vacuum annealing on the titanium alloy plate after the third rolling process. The annealing temperature is 680° C., the holding time is 60 minutes, and then furnace cooling.
步骤八，对步骤七中真空退火后的板料进行第四轧程冷轧，分为30个道次进行轧制，轧制后进行矫直平整处理，轧程总变形量为50％，轧制到厚度为0.1mm的箔材。Step 8: Carry out the fourth rolling process cold rolling to the sheet material after vacuum annealing in the step 7, divide into 30 passes and carry out rolling, carry out straightening and flattening treatment after rolling, the total deformation of the rolling process is 50%, rolling Foils with a thickness of 0.1 mm were produced.
步骤九，对第四轧程后的钛合金箔材进行平整矫直、剪切、碱洗、真空退火处理，退火温度为680℃，保温时间为60min，随后炉冷。Step 9: Perform flattening, shearing, alkali washing, and vacuum annealing treatment on the titanium alloy foil after the fourth rolling process. The annealing temperature is 680° C., the holding time is 60 minutes, and then furnace cooling.
对比例1采用包覆轧制的方法制备耐蚀钛合金箔材Comparative example 1 adopts the method of clad rolling to prepare corrosion-resistant titanium alloy foil
步骤一，将尺寸为3.5mm×265mm×850mm的Ti－Ni－Nb钛合金热轧板坯料，4片一组，组焊后用钢板包覆表面，制成包覆轧制包，钢板与每片钛合金坯料的厚度比为20：1；Step 1, the Ti-Ni-Nb titanium alloy hot-rolled plate blanks with a size of 3.5mm×265mm×850mm are made into a group of 4 pieces, and after assembly and welding, the surface is covered with a steel plate to make a clad rolling package, and the steel plate and each The thickness ratio of the sheet titanium alloy blank is 20:1;
步骤二，将所得包覆轧制包放入保护气氛加热炉中，随炉加热至850℃，随后保温120min，将热处理完的坯料从炉中取出后，使用二辊热轧实验机分为13个道次轧制到厚度为1.4mm的板材；Step 2: Put the obtained clad rolling ladle into a protective atmosphere heating furnace, heat it with the furnace to 850°C, and then keep it warm for 120 minutes. After the heat-treated billet is taken out from the furnace, it is divided into 13 Each pass is rolled to a plate with a thickness of 1.4mm;
步骤三，对步骤二轧制后的钛合金板材进行剪切，4片一组，组焊后用钢板包覆表面，制成包覆轧制包，钢板与每片钛合金坯料的厚度比为20：1；Step 3, shearing the titanium alloy plate after step 2 rolling, 4 pieces in a group, covering the surface with steel plate after assembly and welding to make a coated rolling package, the thickness ratio of the steel plate to each titanium alloy blank is 20:1;
步骤四，将步骤三中所得包覆轧制包放入保护气氛加热炉中，随炉加热至850℃，随后保温120min，将热处理完的坯料从炉中取出后，使用二辊热轧实验机分为10个道次轧制到厚度为0.7mm的板材；Step 4: Put the clad rolling ladle obtained in Step 3 into a protective atmosphere heating furnace, heat it with the furnace to 850°C, and then keep it warm for 120 minutes. After the heat-treated billet is taken out of the furnace, use a two-roll hot rolling test machine Divided into 10 passes and rolled to a plate with a thickness of 0.7mm;
步骤六，对步骤四中0.7mm的热轧板，进行真空退火处理，退火温度为650℃，保温时间为60min，随后炉冷。Step 6: Carry out vacuum annealing treatment on the 0.7mm hot-rolled sheet in step 4, the annealing temperature is 650° C., the holding time is 60 minutes, and then furnace cooling.
步骤七，对真空退火后的热轧板坯料进行第一轧程冷轧，分为15个道次进行轧制，轧制前先进行矫直平整处理，轧程总变形量为57％，轧制到厚度为0.3mm的板材。Step 7: Carry out cold rolling in the first rolling process to the hot-rolled slab stock after vacuum annealing, which is divided into 15 passes for rolling. Before rolling, straightening and leveling treatment is carried out. The total deformation of the rolling process is 57%. Made to a plate with a thickness of 0.3mm.
步骤八，对第一轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为680℃，保温时间为60min，随后炉冷。Step 8: Perform shearing, alkali washing, and vacuum annealing on the titanium alloy plate after the first rolling process. The annealing temperature is 680° C., the holding time is 60 minutes, and then furnace cooling.
步骤九，对步骤八中真空退火后的板坯进行二轧程冷轧，分为20个道次进行轧制，轧制前先进行矫直平整处理，轧程总变形量为50％，轧制到厚度为0.15mm的箔材。Step 9, carry out two-pass cold rolling to the slab after vacuum annealing in step 8, divide into 20 passes and carry out rolling, carry out straightening and flattening treatment earlier before rolling, the total deformation of the rolling process is 50%, rolling Foils with a thickness of 0.15 mm were produced.
步骤十，对第二轧程后的钛合金板材进行剪切、碱洗、真空退火处理，退火温度为680℃，保温时间为60min，随后炉冷。In step ten, the titanium alloy plate after the second rolling process is subjected to shearing, alkali washing, and vacuum annealing. The annealing temperature is 680° C., and the holding time is 60 minutes, followed by furnace cooling.
步骤十一，对步骤十中真空退火后的板坯进行三轧程冷轧，分为15个道次进行轧制，轧制前先进行矫直平整处理，轧程总变形量为25％，轧制到厚度为0.1mm的箔材。In step eleven, the slab after vacuum annealing in step ten is subjected to three-pass cold rolling, which is divided into 15 passes for rolling. Before rolling, straightening and leveling treatment is carried out, and the total deformation of the rolling process is 25%. Rolled to a foil thickness of 0.1mm.
步骤十二，对第三轧程后的钛合金箔材进行平整矫直、剪切、碱洗、真空退火处理，退火温度为680℃，保温时间为60min，随后炉冷。In step 12, the titanium alloy foil after the third rolling process is subjected to flattening, shearing, alkali washing, and vacuum annealing. The annealing temperature is 680° C., and the holding time is 60 minutes, followed by furnace cooling.
将实施例1－3和对比例1得到的Ti－Ni－Nb钛合金箔材进行抗拉强度、延伸率和腐蚀电流测试，并对晶粒尺寸和箔材厚度偏差进行测量；腐蚀电流测试方法依据国家标准GB/T20042.6－2011；厚度、力学性能测试方法分别依据标准YB/T4432－2014和GB/T228.1－2010；The Ti-Ni-Nb titanium alloy foil obtained in Examples 1-3 and Comparative Example 1 is subjected to tensile strength, elongation and corrosion current tests, and the grain size and foil thickness deviation are measured; corrosion current test method According to the national standard GB/T20042.6-2011; the test methods of thickness and mechanical properties are respectively based on the standards YB/T4432-2014 and GB/T228.1-2010;
其测试结果如表1所示：The test results are shown in Table 1:
表1Table 1
从上表可以看出，按照本发明实施例方法制备的耐蚀箔材，其平均晶粒尺寸20～30μm，室温抗拉强度为300MPa～360MPa，延伸率≥30％，箔材厚度偏差不大于±0.005mm，腐蚀电流不大于2.5×10－7A/cm2；对比例中使用包覆叠轧制备的钛合金箔材室温抗拉强度高、塑性低，尺寸公差大于±0.005mm，腐蚀电流大于2.5×10－7A/cm2，耐蚀性较差。It can be seen from the above table that the corrosion-resistant foil prepared according to the method of the embodiment of the present invention has an average grain size of 20-30 μm, a room temperature tensile strength of 300MPa-360MPa, an elongation of ≥30%, and a foil thickness deviation of not more than ±0.005mm, the corrosion current is not more than 2.5×10-7 A/cm2 ; in the comparative example, the titanium alloy foil prepared by cladding and rolling has high room temperature tensile strength and low plasticity, and the dimensional tolerance is greater than ±0.005mm, the corrosion The current is greater than 2.5×10-7 A/cm2 , and the corrosion resistance is poor.
尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Although the present invention has been described in detail with reference to the aforementioned embodiments, those of ordinary skill in the art should understand that: it can still modify the technical solutions described in the aforementioned embodiments, or perform equivalent replacements for some of the technical features; and these The modification or replacement does not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.
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| CN202210807065.1ACN115351080A (en) | 2022-07-07 | 2022-07-07 | A kind of preparation method of corrosion-resistant titanium alloy foil material |
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| CN116550754A (en)* | 2023-05-19 | 2023-08-08 | 攀钢集团攀枝花钢铁研究院有限公司 | High-plasticity corrosion-resistant titanium alloy foil and preparation method and application thereof |
| CN116637949A (en)* | 2023-06-16 | 2023-08-25 | 西北工业大学重庆科创中心 | Preparation method of high-temperature high-strength titanium alloy foil tape |
| CN116673328A (en)* | 2023-06-06 | 2023-09-01 | 太原理工大学 | Composite forming process and method for preparing near alpha high-temperature titanium alloy foil |
| CN117363929A (en)* | 2023-10-11 | 2024-01-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Corrosion-resistant high-plasticity titanium alloy foil for wide bipolar plate and industrial preparation method thereof |
| CN117960787A (en)* | 2024-04-01 | 2024-05-03 | 西安钢研功能材料股份有限公司 | Preparation method of micron-sized kovar alloy soft foil |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143241A (en)* | 1999-02-09 | 2000-11-07 | Chrysalis Technologies, Incorporated | Method of manufacturing metallic products such as sheet by cold working and flash annealing |
| CN103084389A (en)* | 2012-11-06 | 2013-05-08 | 陈建兴 | Cold rolling titanium foil material process |
| CN110328244A (en)* | 2019-07-09 | 2019-10-15 | 东北大学 | A kind of Straight pull is cold/hydraulic tensioning system and its control method of warm-rolling experimental machine |
| FR3085968A1 (en)* | 2018-09-13 | 2020-03-20 | Constellium Issoire | ALMGMN ALLOY PRODUCT HAVING IMPROVED CORROSION RESISTANCE |
| CN113462999A (en)* | 2020-03-30 | 2021-10-01 | 国核宝钛锆业股份公司 | Method for manufacturing titanium foil for bipolar plate |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143241A (en)* | 1999-02-09 | 2000-11-07 | Chrysalis Technologies, Incorporated | Method of manufacturing metallic products such as sheet by cold working and flash annealing |
| CN103084389A (en)* | 2012-11-06 | 2013-05-08 | 陈建兴 | Cold rolling titanium foil material process |
| FR3085968A1 (en)* | 2018-09-13 | 2020-03-20 | Constellium Issoire | ALMGMN ALLOY PRODUCT HAVING IMPROVED CORROSION RESISTANCE |
| CN110328244A (en)* | 2019-07-09 | 2019-10-15 | 东北大学 | A kind of Straight pull is cold/hydraulic tensioning system and its control method of warm-rolling experimental machine |
| CN113462999A (en)* | 2020-03-30 | 2021-10-01 | 国核宝钛锆业股份公司 | Method for manufacturing titanium foil for bipolar plate |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116550754A (en)* | 2023-05-19 | 2023-08-08 | 攀钢集团攀枝花钢铁研究院有限公司 | High-plasticity corrosion-resistant titanium alloy foil and preparation method and application thereof |
| CN116673328A (en)* | 2023-06-06 | 2023-09-01 | 太原理工大学 | Composite forming process and method for preparing near alpha high-temperature titanium alloy foil |
| CN116673328B (en)* | 2023-06-06 | 2024-01-02 | 太原理工大学 | Composite forming process and method for preparing near alpha high-temperature titanium alloy foil |
| CN116637949A (en)* | 2023-06-16 | 2023-08-25 | 西北工业大学重庆科创中心 | Preparation method of high-temperature high-strength titanium alloy foil tape |
| CN117363929A (en)* | 2023-10-11 | 2024-01-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Corrosion-resistant high-plasticity titanium alloy foil for wide bipolar plate and industrial preparation method thereof |
| CN117960787A (en)* | 2024-04-01 | 2024-05-03 | 西安钢研功能材料股份有限公司 | Preparation method of micron-sized kovar alloy soft foil |
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