CN115161519B - 一种高表面质量铝合金镀层钢板及其制造方法 - Google Patents
一种高表面质量铝合金镀层钢板及其制造方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 47
- 239000010959 steel Substances 0.000 title claims abstract description 47
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- 238000007747 plating Methods 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910000765 intermetallic Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017073 AlLi Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 3
- 238000005098 hot rolling Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017150 AlTi Inorganic materials 0.000 claims description 2
- 229910002555 FeNi Inorganic materials 0.000 claims description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 208000012868 Overgrowth Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
一种高表面质量铝合金镀层钢板及其制造方法，钢板镀层合金元素按质量百分比计包括Ti0.11％～2.50％、Mn0.5％～7.0％、Li0.05％～3％、Cu0.1％～5.0％、Fe0.05％～3.0％、Ni0.1％～10.0％、V0.01％～0.5％、Zr0.5％～1.0％、Cr0.1％～2.0％、Mg0.5％～5％、Zn1％～10％其中的一种或几种，以及Si 3％～15.0％；其余为Al和不可避免的杂质。本发明的有益效果是采用该方法生产的铝合金镀层钢板表面质量高，能够在多种严酷的条件下使用，且镀层钢板具备极好的耐腐蚀性能。
Description
技术领域
本发明属于合金镀层技术，尤其涉及一种高表面质量铝合金镀层钢板及其制造方法。
背景技术
现有的铝硅镀层钢板是在镀铝的基础上添加Si元素约10％制成，虽然提高了热浸镀的可镀性能，但是镀层表面会出现非常明显的铝花，严重影响了铝合金镀层钢板的表面质量，同时镀层的耐腐蚀性能改善有限，为了进一步提高铝硅镀层的耐腐蚀性能，需要进一步优化镀层的化学成分、微观组织结构。
为减少和消除镀铝钢板表面的铝花，现在采用两种技术：1)采用光整工艺，将镀铝板表面的铝花压平，但是铝花的形貌依然存在，严重影响美观程度和使用效果；2)采用小铝花技术，该技术目前掌握在国外公司的手里，且装置价格昂贵。
现有技术镀铝钢板表面的铝花一般在3-5mm。
发明内容
本发明的目的是提供一种高表面质量铝合金镀层钢板及其制造方法，本发明采用添加合金元素和优化热浸镀工艺相结合的的方法来减小镀层表面铝花，提高镀层表面的均一性，提高铝合金镀层韧性和耐腐蚀性能，细化镀层组织，同时也可以进一步提高镀层的成型性能。采用该方法生产的铝合金镀层钢板，能够在多种严酷的条件下使用，且镀层钢板具备极好的耐腐蚀性能。
为实现上述目的，本发明采用以下技术方案实现：
一种高表面质量铝合金镀层钢板，钢板镀层合金元素按质量百分比计包括Ti0.11％～2.50％、Mn 0.5％～7.0％、Li 0.05％～3％、Cu 0.1％～5.0％、Fe 0.05％～3.0％、Ni 0.1％～10.0％、V 0.01％～0.5％、Zr 0.5％～1.0％、Cr 0.1％～2.0％、Mg0.5％～5％、Zn 1％～10％其中的一种或几种，以及Si 3％～15.0％；其余为Al和不可避免的杂质。
还包括Re 0.01％～0.20％。
所述钢板化学成分按质量百分比计包括：C 0.0005％～0.40％、Si 0.001％～2.0％、Mn0.08％～5.50％、P≤0.08％、S≤0.05％、Al 0.01％～3.00％、Ti≤0.10％、B≤0.007％、Cr≤0.80％；其余为Fe和不可避免的杂质。
还包括以下元素中的一种或几种：Mo 0.03％～1.00％、Cu≤1.50％、Ni 0.3％～1.5％、Nb≤0.10％；
镀层凝固后包含有富铝相、富硅相以及镀层与钢基体反应形成的合金层，同时依据添加合金元素的不同，还含有不同的金属间化合物包括：Al3Li、AlTi、AlLi、FeNi、FeCr、Al2CuLi、Al2Cu、Al6CuLi3、Al2CuMg以及Al3Zr中的一种或几种；镀层组织结构细小，韧性良好。析出相的种类、数量、分布以及相互作用情况决定合金镀层的性能。
一种高表面质量铝合金镀层钢板的制造方法，工艺过程为冶炼、铸造、热轧、酸洗、冷轧、热浸镀，具体包括如下方法：
1)热轧工艺：1240±50℃加热，保温190±50分钟，1100±50℃粗轧，1050±50℃精轧，880±50℃终轧，450～800℃卷取；
2)热浸镀工艺：冷轧基板热浸镀，加热退火温度控制在700～900℃，入锌锅温度为630～700℃，锌锅温度为630～690℃；(入锌锅温度是带钢的温度；锌锅温度是镀液的温度)
3)镀后冷却工艺：出锌锅、气刀后立即以10±2℃/s的冷却速度将镀层温度冷却到610±5℃，然后立即以20±5℃/s的速度冷却到500±10℃，随后10±5℃/s的速度冷却到290±20℃，进入转向辊，风冷至120℃以下，进入水冷。
在镀层中加入Si 3％～15.0％、Ti 0.11％～2.50％、Mn 0.5％～7.0％、Re0.01％～0.20％、Li 0.05％～3％、Cu 0.1％～5.0％、Fe 0.05％～3.0％、Ni 0.1％～10.0％、V 0.01％～0.5％、Zr 0.5％～1.0％、Cr 0.1％～2.0％合金元素，可以提供更多的形核质点，使得铝合金镀层表面变成小铝花或者零铝花的效果，从而消除表面铝花提高表面质量；可以使得钢基体与镀液反应的过程中形成的合金层过度生长增厚，原因在于合金元素溶于镀液中，在镀液中的Al与钢基体中的Fe发生反应的过程中，合金元素需要通过扩散排出，由于溶质的拖拽作用，降低反应速度，同时排出的溶质元素在合金层的附近区域形成较高的浓度梯度，阻碍了其它区域的Al元素向合金层的扩散，也阻碍了后续合金元素向溶液的排出；可以形成不同的金属间化合物，细化镀层的微观组织，控制镀层表面的锌花大小，同时使得镀层组织更加均匀的分布，提高镀层的耐腐蚀性能，提高镀层的塑韧性。
在镀层中加入Mg0.5～5％，Zn1～10％，可以大幅度的提高镀层的耐腐蚀性能。
在镀层中加入Si3～15.0％、Ti0.11～2.50％、Mn0.5～7.0％、Re0.01～0.20％、Li0.05～3％、Cu0.1～5.0％、Fe0.05～3.0％、Ni0.1～10.0％、V0.01～0.5％、Zr0.5～1.0％、Cr0.1～2.0％合金元素，在镀层形成过程中，合金元素的原子能够与镀层中的空位强烈结合，形成稳定的空位-溶质原子复合体，阻碍空位的迁移，减少镀层表面由于空位移动到表面形成的缺陷，提高镀层表面质量。
锌锅温度为630～690℃，可以在出锌锅后获得良好的表面质量，避免锌流波纹等缺陷产生。
出锌锅、气刀后立即以10±2℃/s的冷却速度将镀层温度冷却到610±5℃，目的是在锌锅温度到610±5℃这个温度段以较缓慢的温度冷却，合金元素有充足的时间析出，提供足够多的形核质点，降低或者消除铝花；然后立即以20±5℃/s的速度冷却到500±10℃，在这个温度段快速冷却，避免铝花的过度生长，降低铝花的尺寸；随后10±5℃/s的速度冷却到290±20℃，进入转向辊，风冷至120度以下，进入水冷，在290±20℃进入转向辊，镀层有一定的硬度，避免辊印和划伤的产生。
镀层中元素的作用
Al：Al是铝合金镀层的主要元素，能够为钢板在存储、使用及成型后的零件提供良好的防护，在镀层组织中形成富铝相，同时与镀层中的其它合金元素形成金属间化合物。
Si：Si在金属间化合物层中富集，形成紧凑的抑制层组织，降低合金层的厚度，提高镀层韧性，可以细化镀层的组织，提高镀层性能，与Mg元素形成Mg2Si等金属间化合物。
Ti：Ti的加入可以提供更多的形核质点，降低铝花尺寸，可以提高镀层的耐腐蚀性能，另外Ti可以形成氧化钛的保护膜，该保护膜与基体结合力强，保护性能好，且可以自行修复破损。同时加入Si和Ti，可以生成更加紧致的抑制层，提高镀层生长的均匀性。
Re：稀土元素可以提供更多的形核质点，降低铝花尺寸，具有特殊的电子层排布结构以及物理化学性质，在铝合金镀层中添加微量稀土元素可以改善合金的强韧性，提高合金的耐腐蚀抗力，并减轻杂质危害的影响，提高镀层的耐腐蚀性能，细化晶粒，提高镀层表面质量。
Mn：可以提供更多的形核质点，降低铝花尺寸，提高镀层的耐腐蚀性能，细化晶粒，提高镀层的韧性。
Ni：可以提供更多的形核质点，降低铝花尺寸，提高镀层的耐腐蚀性能，形成氧化膜保护镀层。
Cr：可以提供更多的形核质点，降低铝花尺寸，提高镀层的耐腐蚀性能，形成氧化膜保护镀层。
Zr：添加Zr所形成的弥散相β('Al3Zr)粒子能有效抑制再结晶，调制晶粒大小以及改变强化相尺寸和分布状况等。β'粒子与铝基体呈共格关系，平均错配度在0.3～0.5％之间。提高镀层的耐腐蚀性能，形成氧化膜保护镀层。
Li、Cu：提高镀层的韧性、细化镀层组织，与镀层元素形成金属间化合物：Al3Li、AlLi、Al2CuLi、Al2Cu、Al6CuLi3、Al2CuMg等，可以提供更多的形核质点，降低铝花尺寸，
Mg、Zn，可以大幅度的提高镀层的耐腐蚀性能
钢中元素的作用
C作为主要合金元素对钢的强度贡献最大，Mn及Si次之。Mn/Si的比例应大于4，目的是保证钢板在热浸镀铝硅退火过程中生成的氧化膜不会影响热浸镀性能。为保证淬透性，添加了Ti、Cr及B。添加Cu改进钢的耐蚀性能，进而阻止H的渗入，提高了钢的耐延迟断裂性能。Mo、Nb的加入，起到强化钢基体和细化晶粒的效果，Si、Al的加入可以抑制渗碳体的形成。
与现有的技术相比，本发明的有益效果是：
一种高表面质量铝合金镀层钢板及其制造方法，本发明采用添加合金元素和优化热浸镀工艺相结合的的方法来消除镀层表面铝花，提高镀层表面的均一性，提高铝合金镀层韧性和耐腐蚀性能，细化镀层组织，同时也可以进一步提高镀层的成型性能。采用该方法生产的铝合金镀层钢板表面质量高，能够在多种严酷的条件下使用，且镀层钢板具备极好的耐腐蚀性能。
具体实施方式
下面结合具体实施例对本发明的实施方式进一步说明：
实施例见附表1、2、3；其中附表1为实施例镀层的化学元素组成，附表2为实施例钢的化学成分，附表3为实施例钢的工艺参数及性能。
表1实施例镀层的化学元素组成
表2实施例钢的化学成分
| C | Si | Mn | Al | Ni | Cu | Cr | Mo | B | Nb | Ti | Fe | |
| 1 | 0.0008 | 0.005 | 0.08 | 0.02 | 0 | 0 | 0 | 0 | 0 | 0.03 | 0 | 余量 |
| 2 | 0.001 | 0.01 | 0.12 | 0.03 | 0 | 0 | 0 | 0 | 0 | 0.02 | 0 | 余量 |
| 3 | 0.003 | 0.02 | 0.15 | 0.05 | 0 | 0 | 0.15 | 0 | 0 | 0 | 0 | 余量 |
| 4 | 0.012 | 0.03 | 0.20 | 0.03 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 余量 |
| 5 | 0.021 | 0.04 | 0.22 | 0.04 | 0 | 0.2 | 0 | 0 | 0 | 0 | 0.06 | 余量 |
| 6 | 0.044 | 0.05 | 0.18 | 0.03 | 0 | 0 | 0.05 | 0 | 0 | 0 | 0.04 | 余量 |
| 7 | 0.065 | 0.10 | 0.30 | 0.02 | 0 | 0 | 0.03 | 0 | 0 | 0 | 0 | 余量 |
| 8 | 0.090 | 1.90 | 1.0 | 0.05 | 0 | 0.5 | 0.40 | 0.20 | 0 | 0 | 0 | 余量 |
| 9 | 0.19 | 0.4 | 1.5 | 0.5 | 0.5 | 0.8 | 0.50 | 0 | 0 | 0 | 0.02 | 余量 |
| 10 | 0.21 | 0.6 | 2.0 | 0.10 | 0 | 0 | 0 | 0 | 0.005 | 0.08 | 0 | 余量 |
| 11 | 0.24 | 1.0 | 2.5 | 0.8 | 0 | 0 | 0.80 | 0.40 | 0.002 | 0 | 0 | 余量 |
| 12 | 0.31 | 1.5 | 3.5 | 0.1 | 0.2 | 0 | 0 | 0 | 0.003 | 0.03 | 0 | 余量 |
| 13 | 0.35 | 0.5 | 5 | 3.0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 余量 |
| 14 | 0.40 | 0.8 | 1.3 | 0.5 | 1.0 | 0 | 0 | 0 | 0 | 0 | 0 | 余量 |
表3实施例钢的工艺参数及性能
实施例钢板的镀层表面质量优良，可以达到小铝花的效果，实施例铝花尺寸均小于2mm。
Claims (3)
1.一种高表面质量铝合金镀层钢板，其特征在于，钢板镀层合金元素按质量百分比计包括Ti 0.11%～2.50%、Mn 0.5%～7.0%、Li 0.05%～3%、Cu 0.1%～5.0%、Fe 0.05%～3.0%、Ni 0.1%～10.0%、V 0.01%～0.5%、Zr 0.5%～1.0%、Cr 0.1%～2.0%、Mg 0.5%～5%、Zn 1%～10%其中的一种或几种，以及Si 14%～15.0%；其余为Al和不可避免的杂质；
所述钢板化学成分按质量百分比计包括：C 0.0005%～0.40%、Si 0.001%～2.0%、Mn0.08%～5.50%、P≤0.08%、S≤0.05%、Al 0.01%～3.00%、Ti≤0.10%、B≤0.007%、Cr ≤0.80%；其余为Fe和不可避免的杂质；
镀层凝固后包含有富铝相、富硅相以及镀层与钢基体反应形成的合金层，同时依据添加合金元素的不同，还含有不同的金属间化合物包括：Al3Li、AlTi、AlLi、FeNi、FeCr、Al2CuLi、Al2Cu、Al6CuLi3、Al2CuMg以及Al3Zr中的一种或几种；
一种高表面质量铝合金镀层钢板的制造方法，具体包括如下方法：
1）热轧工艺：1240±50℃加热，保温190±50分钟，1100±50℃粗轧，1050±50℃精轧，880±50℃终轧，450～800℃卷取；
2）热浸镀工艺：冷轧基板热浸镀，加热退火温度控制在700～900℃，入锌锅温度为630～700℃，锌锅温度为630～690℃；
3）镀后冷却工艺：出锌锅、气刀后以10±2℃/s的冷却速度将镀层温度冷却到610±5℃，然后以20±5℃/s的速度冷却到500±10℃，随后10±5℃/s的速度冷却到290±20℃，进入转向辊，风冷至120℃以下，进入水冷；
在镀层形成过程中，合金元素的原子能够与镀层中的空位强烈结合，形成稳定的空位-溶质原子复合体，阻碍空位的迁移，减少镀层表面由于空位移动到表面形成的缺陷，提高镀层表面质量。
2.根据权利要求1所述的一种高表面质量铝合金镀层钢板，其特征在于，钢板镀层合金元素还包括RE 0.01%～0.20%。
3.根据权利要求1所述的一种高表面质量铝合金镀层钢板，其特征在于，钢板化学成分还包括以下元素中的一种或几种：Mo 0.03%～1.00%、Cu≤1.50%、Ni 0.3%～1.5%、Nb≤0.10%。
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| CN111893377A (zh) * | 2020-07-13 | 2020-11-06 | 首钢集团有限公司 | 一种1900MPa级高强韧性热冲压用铝硅镀层钢板及其制备方法 |
| CN113528940A (zh) * | 2021-06-16 | 2021-10-22 | 首钢集团有限公司 | 一种铝硅合金系镀层热成形钢及其制备方法 |
| CN113564466A (zh) * | 2021-07-13 | 2021-10-29 | 鞍钢股份有限公司 | 一种高耐蚀铝锌镁镀层钢板及其制造方法 |
| CN114369758A (zh) * | 2021-12-10 | 2022-04-19 | 首钢集团有限公司 | 一种高强高韧性热冲压钢基体及其制备方法和应用 |
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