CN109530438B - 一种光辐射空间用Zn-Ag复合镀层纯钛极薄带及其生产方法 - Google Patents

一种光辐射空间用Zn-Ag复合镀层纯钛极薄带及其生产方法 Download PDF

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CN109530438B
CN109530438B CN201811317322.3A CN201811317322A CN109530438B CN 109530438 B CN109530438 B CN 109530438B CN 201811317322 A CN201811317322 A CN 201811317322A CN 109530438 B CN109530438 B CN 109530438B
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pure titanium
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陶军晖
戴伟
李�杰
汪川惠
陈温雅
薛宇婷
姜无忧
唐玉
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Hubei University of Education
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B1/00Metal-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
    • B21B1/40Metal-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 foils which present special problems, e.g. because of thinness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B15/00Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B15/00Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B15/0007Cutting or shearing the product
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B37/00Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/74Temperature control, e.g. by cooling or heating the rolls or the product
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • C23C4/08Metallic material containing only metal elements
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129Flame spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B15/00Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B2015/0057Coiling the rolled product

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Abstract

一种光辐射空间用Zn‑Ag复合镀层纯钛极薄带及其生产方法,包括纯极钛薄带和Zn‑Ag复合镀层;所述纯极钛薄带包括Ti,其中Ti含量纯度达99.9%;采用超音速火焰喷涂的方法在纯钛冷轧极薄带表面形成一层致密Zn‑Ag复合镀层;Zn在Ti与Ag之间形成过渡层,可使得Zn‑Ag复合镀层的整体稳定性得到提高;Zn与Ag的重量比例为1:8~9;Zn及Ag粉末粒径范围为0.8~0.9μm。Zn‑Ag复合镀层纯钛极薄带的表面硬度为75~85HV,粗糙度为0.05~0.07μm,镜面反射率不低于99.9%;在室外常规大气条件下放置960d后,表面失光率不超过0.2%,表面腐蚀面积不超过0.2%;电阻率为6~8μΩ·cm,热导率为75~90w/m·℃;在350~400℃下保持960d后,表面氧化面积不超过0.1%,硬度值变化不超过0.1%。

Description

一种光辐射空间用Zn-Ag复合镀层纯钛极薄带及其生产方法
技术领域
本发明涉及一种光辐射空间用Zn-Ag复合镀层纯钛极薄带及其生产方法。
背景技术
纯钛是一种银白色的过渡金属,其特征为重量轻、强度高、具金属光泽,将其制造成极薄带可用于光辐射空间的基础材料使用。目前,纯钛极薄带作为光辐射空间原料存在电导率低、耐高热性差、耐腐蚀性不高、成本较高等不足,以无法满足人们的需求。
发明内容
针对以上所述,本发明的目的在于提供一种光辐射空间用Zn-Ag复合镀层纯钛极薄带及其生产方法,以解决上述问题的至少一个方面。
根据本发明的一方面,提供一种光辐射空间用Zn-Ag复合镀层纯钛极薄带的生产方法,包括以下步骤:
步骤一,纯钛厚度规格为1.8~2.0mm;其化学成份按重量百分数计为Ti含量纯度达99.9%。
步骤二,纯钛极薄带原料制作;
(1)、采用真空自耗熔炼炉进行纯钛的熔炼,经混料、压制电极、电极和残料焊接成自耗电极、熔炼、浇注成板坯;
(2)、将板坯加热,加热温度在1400~1500℃,均热时间为90~100min;
(3)、进行粗轧,并控制粗轧结束温度不低于1350℃;
(4)、进行精轧,并控制终轧温度在900~950℃;
(5)、进行层流超快冷冷却,终冷温度为50~100℃,冷却速度:200~250℃/s;
(6)、进行卷取,制得热轧板卷;
步骤三,纯钛极薄带热轧原料的精整及打包;
(1)、精整切边:按标准规格切取纯钛板,并切除钛板周围毛边,切割余量3~4mm;
(2)、打包:用捆带进行周向和径向打包。
步骤四,Zn-Ag复合镀层纯钛极薄带的制造;
(1)、对纯钛极薄带热轧原料卷进行9或10道次冷轧轧制,冷轧总压下率为95~98%,轧制后的纯钛极薄带冷轧原料的厚度为0.10~0.15mm;
(2)、冷轧原料经常规脱脂后开卷、分条、去毛刺;
(3)、进行卷取;
(4)、机械性能检测:对纯钛极薄带取样按国标进行力学性能检验,力学性能满足表面硬度75~85HV;
(5)、对纯钛极薄带热轧原料表面进行常规喷丸,使板表面无氧化层残留;
(6)、进行常规电解脱脂;
(7)、采用超音速火焰喷涂的方法进行Zn-Ag涂层喷涂,Zn与Ag的重量比例为1:8~9;Zn及Ag粉末粒径范围为0.8~0.9μm,并采用行星球磨机混合均匀;喷涂速度为500~600m/s,喷涂温度300~350℃,沉积率为0.55~0.65kg/h;
(8)、在氮气含量达99.999%的气氛中进行退火,退火温度为320~370℃,保温时间为25~30min;
(9)、空冷至室温,进行风冷、水洗并烘干;
(10)、消毒风干、无菌包装。
根据本发明的另一方面,提供一种根据上述方法制成的光辐射空间用Zn-Ag复合镀层纯钛极薄带,包括纯钛极薄带和Zn-Ag复合镀层;所述纯钛极薄带包括Ti,其中Ti含量纯度达99.9%;采用超音速火焰喷涂的方法在纯钛冷轧极薄带表面形成一层致密Zn-Ag复合镀层;Zn在Ti与Ag之间形成过渡层,可使得Zn-Ag复合镀层的整体稳定性得到提高;Zn与Ag的重量比例为1:8~9;Zn及Ag粉末粒径范围为0.8~0.9μm。
进一步,Zn-Ag复合镀层纯钛极薄带的表面硬度为75~85HV,粗糙度为0.05~0.07μm,镜面反射率不低于99.9%;在室外常规大气条件下放置960d后,表面失光率不超过0.2%,表面腐蚀面积不超过0.2%;电阻率为6~8μΩ·cm,热导率为75~90w/m·℃;在350~400℃下保持960d后,表面氧化面积不超过0.1%,硬度值变化不超过0.1%。
本发明的有益效果:
1)、采用纯钛的冷轧极薄带作为超音速喷涂原料,是因为其在较薄规格下仍然能够保证极薄带的力学性能,并且纯钛不含其它合金元素,因而保证了原料的成本较低,此外,不含其它合金元素也可以保证纯钛极薄带基材较好的表面质量和超音速喷涂性能,而且,不含其它合金元素的纯钛具有较好的柔韧性不宜发生脆断而使其具有良好的焊接及冲压成型性能;
2)、采用廉价的Zn来代替部分贵金属Ag,并采用超音速火焰喷涂的方法在纯钛冷轧极薄带表面形成了一层致密Zn-Ag复合镀层;
3)、纯钛极薄带表面所形成的致密Zn-Ag复合镀层兼顾了Zn和Ag镀层的优点,使纯钛冷轧极薄带从根本上解决了其表面获得了电导率高、耐高热性好、耐腐蚀性能好的特性;
4)、Zn在Ti与Ag之间所形成的过渡层可使得Zn-Ag复合镀层的整体稳定性得到很大的提高;
5)、超音速火焰喷涂过程速度快,原料浪费少,温度低能耗少,镀层厚度可精确控制。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例一,根据本发明的一方面,提供一种光辐射空间用Zn-Ag复合镀层纯钛极薄带的生产方法,包括以下步骤:
步骤一,制备纯钛极薄带热轧原料;
步骤二,将纯钛进行熔炼成板坯,将板坯进行加热、粗轧、精轧、冷却和卷取,得到纯钛热轧板卷;
步骤三,将纯钛热轧板卷切边和打包,得到纯钛极薄带热轧原料卷;
步骤四,将纯钛极薄带热轧原料卷冷轧轧制、脱脂、分条、去毛刺、卷制、机械性能检测、喷丸、电解脱脂、Zn-Ag涂层喷涂、退火、风冷、烘干、消毒风干和包装,得到Zn-Ag复合镀层纯钛极薄带。
步骤一中,纯钛厚度规格为1.8~2.0mm;其化学成份按重量百分数计为Ti含量纯度达99.9%,其余为不可避免的杂质。
步骤二中,纯钛极薄带原料制作;
1)、采用真空自耗熔炼炉进行纯钛的熔炼,经混料、压制电极、电极和残料焊接成自耗电极、熔炼(熔炼温度1900~2000℃)、浇注成板坯;
2)、将板坯加热,加热温度在1400~1500℃,均热时间为90~100min;
3)、进行粗轧,并控制粗轧结束温度不低于1350℃;
4)、进行精轧,并控制终轧温度在900~950℃;
5)、进行层流超快冷冷却(在线淬火),终冷温度为50~100℃,冷却速度:200~250℃/s;
6)、进行卷取,制得热轧板卷;
步骤三,纯钛极薄带热轧原料的精整及打包;
1)、精整切边:按标准规格切取纯钛板,并切除钛板周围毛边,切割余量3~4mm;
2)、打包:用捆带进行周向和径向打包。
步骤四中,Zn-Ag复合镀层纯钛极薄带的制造;
1)、对纯钛极薄带热轧原料卷进行9或10道次冷轧轧制,冷轧总压下率为95~98%,轧制后的纯钛极薄带冷轧原料的厚度为0.10~0.15mm;
2)、冷轧原料经常规脱脂后开卷、分条、去毛刺;
3)、进行卷取;
4)、机械性能检测:对纯钛极薄带取样按国标进行力学性能检验,力学性能满足表面硬度75~85HV;
5)、对纯钛极薄带热轧原料表面进行常规喷丸,使板表面无氧化层残留;
6)、进行常规电解脱脂;
7)、采用超音速火焰喷涂(high-velocity oxygen-fuel)的方法进行Zn-Ag涂层喷涂,Zn与Ag的重量比例为1:8~9;Zn及Ag粉末粒径范围为0.8~0.9μm,并采用行星球磨机(采用玛瑙罐及玛瑙磨球)混合均匀;喷涂速度为500~600m/s,喷涂温度300~350℃,沉积率为0.55~0.65kg/h;
8)、在氮气含量达99.999%的气氛中进行退火,退火温度为320~370℃,保温时间为25~30min;
9)、空冷至室温,进行风冷、水洗并烘干;
10)、消毒风干、无菌包装。
实施例二,根据本发明的另一方面,提供一种光辐射空间用Zn-Ag复合镀层纯钛极薄带,包括纯钛极薄带和Zn-Ag复合镀层;所述的纯钛薄层包括Ti,其中Ti含量纯度达99.9%;所述的Zn-Ag涂层位于纯钛薄层表面,其中Zn与Ag的重量比例为1:8~9;Zn及Ag粉末粒径范围为0.8~0.9μm。
表1本发明各实施例的Zn-Ag复合镀层纯钛极薄带热轧原料化学成分(wt%)
实施例 Ti 其它杂质
1 99.90 0.10
2 99.99 0.01
3 99.91 0.09
4 99.92 0.08
5 99.97 0.03
6 99.95 0.05
在表1中,选取6个Zn-Ag复合镀层纯钛极薄带热轧原料进行成分分析,其中,Zn-Ag复合镀层纯钛极薄带热轧原料中的Ti含量在99%.9以上。
表2本发明各实施例的Zn-Ag复合镀层纯钛极薄带热轧原料熔炼工艺
实施例 熔炼温度(℃)
1 1910
2 1960
3 1970
4 1900
5 1920
6 2000
在表2中,Zn-Ag复合镀层纯钛极薄带热轧原料在熔炼中的温度为1900~2000℃。
表3本发明各实施例的Zn-Ag复合镀层纯钛极薄带热轧原料热轧工艺
Figure GDA0002495605210000061
表4本发明各实施例的Zn-Ag复合镀层纯钛极薄带冷轧原料冷轧工艺
Figure GDA0002495605210000062
Figure GDA0002495605210000071
表5本发明各实施例的Zn-Ag复合镀层纯钛极薄带力学性能
Figure GDA0002495605210000072
表6本发明各实施例的Zn-Ag复合镀层纯钛极薄带超音速火焰喷涂Zn与Ag重量比及粒径范围
Figure GDA0002495605210000073
表7本发明各实施例的Zn-Ag复合镀层纯钛极薄带超音速火焰喷涂工艺
Figure GDA0002495605210000074
表8为本发明各实施例的Zn-Ag复合镀层纯钛极薄带退火工艺
Figure GDA0002495605210000075
表9本发明各实施例的各实施例的Zn-Ag复合镀层纯钛极薄带的耐腐蚀性能和弹性模量
Figure GDA0002495605210000081
从表5和表9中可以看出,本发明申请的Zn-Ag复合镀层纯钛极薄带,其表面硬度为75~85HV,粗糙度为0.05~0.07μm,镜面反射率不低于99.9%;在室外常规大气条件下放置960d后,表面失光率不超过0.2%,表面腐蚀面积不超过0.2%;电阻率为6~8μΩ·cm,热导率为75~90w/m·℃;在350~400℃下保持960d后,表面氧化面积不超过0.1%,硬度值变化不超过0.1%,本发明的Zn-Ag复合镀层纯钛极薄带的性能各项指标均优于对比例纯钛极薄带,产品性能完全满足使用要求,且其焊接及加工成型性能良好可作为光辐射空间高端设备安全可靠的结构材料。
以上所述的仅是本发明的一些实施方式。对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出至少一个变形和改进,这些都属于本发明的保护范围。

Claims (2)

1.一种光辐射空间用Zn-Ag复合镀层纯钛极薄带的生产方法,包括以下步骤:
步骤一,纯钛厚度规格为1.8~2.0mm;其化学成份按重量百分数计为Ti含量纯度达99.9%;
步骤二,纯钛极薄带原料制作;
(1)、采用真空自耗熔炼炉进行纯钛的熔炼,经混料、压制电极、电极和残料焊接成自耗电极、熔炼、浇注成板坯;
(2)、将板坯加热,加热温度在1400~1500℃,均热时间为90~100min;
(3)、进行粗轧,并控制粗轧结束温度不低于1350℃;
(4)、进行精轧,并控制终轧温度在900~950℃;
(5)、进行层流超快冷冷却,终冷温度为50~100℃,冷却速度:200~250℃/s;
(6)、进行卷取,制得热轧板卷;
步骤三,纯钛极薄带热轧原料的精整及打包;
(1)、精整切边:按标准规格切取纯钛板,并切除钛板周围毛边,切割余量3~4mm;
(2)、打包:用捆带进行周向和径向打包;
步骤四,Zn-Ag复合镀层纯钛极薄带的制造;
(1)、对纯钛极薄带热轧原料卷进行9或10道次冷轧轧制,冷轧总压下率为95~98%,轧制后的纯钛极薄带冷轧原料的厚度为0.10~0.15mm;
(2)、冷轧原料经常规脱脂后开卷、分条、去毛刺;
(3)、进行卷取;
(4)、机械性能检测:对纯钛极薄带取样按国标进行力学性能检验,力学性能满足表面硬度75~85HV;
(5)、对纯钛极薄带热轧原料表面进行常规喷丸,使板表面无氧化层残留;
(6)、进行常规电解脱脂;
(7)、采用超音速火焰喷涂的方法进行Zn-Ag涂层喷涂,Zn与Ag的重量比例为1:8~9;Zn及Ag粉末粒径范围为0.8~0.9μm,并采用行星球磨机混合均匀;喷涂速度为500~600m/s,喷涂温度300~350℃,沉积率为0.55~0.65kg/h;
(8)、在氮气含量达99.999%的气氛中进行退火,退火温度为320~370℃,保温时间为25~30min;
(9)、空冷至室温,进行风冷、水洗并烘干;
(10)、消毒风干、无菌包装。
2.根据权利要求1所述方法制成的光辐射空间用Zn-Ag复合镀层纯钛极薄带,其特征在于:包括纯钛极薄带和Zn-Ag复合镀层;所述纯钛极薄带包括Ti,其中Ti含量纯度达99.9%;采用超音速火焰喷涂的方法在纯钛冷轧极薄带表面形成一层致密Zn-Ag复合镀层;Zn在Ti与Ag之间形成过渡层,可使得Zn-Ag复合镀层的整体稳定性得到提高;Zn与Ag的重量比例为1:8~9;Zn及Ag粉末粒径范围为0.8~0.9μm;所述Zn-Ag复合镀层纯钛极薄带的表面硬度为75~85HV,粗糙度为0.05~0.07μm,镜面反射率不低于99.9%;在室外常规大气条件下放置960d后,表面失光率不超过0.2%,表面腐蚀面积不超过0.2%;电阻率为6~8μΩ·cm,热导率为75~90w/m·℃;在350~400℃下保持960d后,表面氧化面积不超过0.1%,硬度值变化不超过0.1%。
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