CN115386703A - 一种改善冷轧淬火延性钢汽车涂装前处理质量的工艺方法 - Google Patents
一种改善冷轧淬火延性钢汽车涂装前处理质量的工艺方法 Download PDFInfo
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- C21D8/0257—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
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Abstract
本发明涉及一种改善冷轧淬火延性钢汽车涂装前处理质量的工艺方法。该方法包括对冷轧QP钢的连续退火工艺进行改进以及对汽车厂前处理工艺的调整,前者包括采用两相区退火和三段加热,并且明确了各段的具体温度和升温速率,同时还在炉内特定位置进行氮气弱加湿处理;后者对预脱脂、脱脂、水洗I段、水洗II段、水洗III段的pH值、游离碱浓度、促进剂点数、时间、压力、温湿度等关键工艺控制点进行了严格管控,最终彻底解决了冷轧QP钢汽车涂装薄膜前处理工艺中容易出现的锈蚀问题。本发明方法具有工艺简单、容易实现、改造成本低等优点,有利于QP钢在汽车行业的进一步推广应用。
Description
技术领域
本发明涉及钢铁加工技术领域,具体涉及一种改善冷轧淬火延性钢汽车涂装前处理质量的工艺方法。
背景技术
随着汽车轻量化要求的日益提高,超高强钢越来越多的应用于汽车车身结构件中,QP钢就是其中的典型代表。QP钢(Quenching Partitioning)即淬火延性钢,是第三代先进高强钢。相对于第一代和第二代高强钢,QP钢在综合力学性能大幅度提升的同时,还形成了以马氏体+残余奥氏体为主要成分的、兼具高强度和良好塑性、韧性的组织,这对于强度要求较高且形状相对复杂的零件尤其适用,因此QP钢常应用于A/B柱加强板、纵梁加强板等车身结构件。此外,QP钢的焊接性能良好,易通过简单的焊接工艺调整实现良好的焊接效果。
QP钢应用于车身结构件时,需经过汽车厂涂装处理,在涂装前处理过程中QP钢的耐腐蚀能力,直接影响后续涂层附着力及整车防腐性能。随着环保要求逐渐严格,目前各大主机厂的新型薄膜前处理涂装工艺,正在逐渐取代传统的磷化前处理涂装工艺。不同于磷化前处理中大量磷酸液的使用,新型薄膜前处理以有机硅烷为主要原料,生成的三维网状化合物附着在钢件表面,起到增加钢件表面耐蚀性和增加漆层附着力的作用。因此,新型薄膜工艺的废水处理起来更容易,并且无磷化渣产生,易于满足当前日益严格的环保要求。这两种前处理工艺机理上的区别,也导致具体工艺流程存在较大区别。磷化工艺的一般流程为:脱脂—水洗I—水洗II—表调—磷化—水洗,而新型薄膜工艺的一般流程为:脱脂-水洗I-水洗II-水洗III。相对于磷化中的表调工序,薄膜工艺中的水洗III工序更易导致零件表面锈蚀,此外新型薄膜工艺相对于磷化的酸性更弱,形成的膜也更薄,因此其在后续水洗中的防锈能力相对于磷化工艺较弱。综上,新型薄膜工艺虽然在工艺和环保方面有明显的优势,但是防腐能力相对于传统的磷化工艺弱。
某钢厂在设计QP钢时,为了使其具有优良的硬度、强度和热加工性能,在成份中大幅增加了Si、Mn的含量,由于Si、Mn含量较高,使其易在钢板表面氧化富集,一旦生产时控制不好,就会导致表面氧化富集,造成耐蚀性下降。以HC600/980QP产品为例,其化学成分(质量分数,%)如下表所示:
牌号 | C | Si | Mn | P | S | Alt |
HC600/980QP | ≤0.25 | ≤2.5 | ≤3.0 | ≤0.040 | ≤0.015 | ≥0.005 |
正是由于以上多种原因,在实际应用中我们发现,QP钢在新型薄膜涂装前处理工艺中,出水洗后容易出现黄色锈蚀斑点,且在后续的薄膜前处理和电泳处理中均无法消除,对生产造成了很大的不利影响。如何彻底解决上述问题,对第三代超高强钢的推广应用具有至关重要的意义。
发明内容
本发明对现有汽车厂薄膜涂装前处理工艺进行了调整和优化,锁定了导致锈蚀的核心影响因子并提出了精准的控制手段,此外还针对QP钢的冷轧生产工艺进行了改进,从以上两方面着手最终彻底解决了QP钢的涂装质量问题,确保其表面质量完好。为实现上述目的和效果,本发明所采用的技术方案如下:
一种改善冷轧淬火延性钢汽车涂装前处理质量的工艺方法,包括以下步骤:
(a)在QP钢冷轧阶段,对连续退火方式和气氛进行改进;
(b)在QP钢汽车涂装前处理阶段,对预脱脂、脱脂、水洗I、水洗II、水洗III工序进行改进。
进一步的,步骤(a)对连续退火方式的改进包括采用两相区退火,并且将加热分为三段,其中加热一段的温度为145-300℃,加热速率为2-27℃/s;加热二段的温度为595-655℃,加热速率为2-25℃/s;加热三段的温度为780-830℃,加热速率为2-12℃/s;均热段的保温时间控制在20-100s。
进一步的,步骤(a)对连续退火气氛的改进包括采用氮气弱加湿工艺造成钢板轻微内氧化,从而降低钢板表面Si、Mn元素富集,改善QP钢表面耐蚀性。所述氮气弱加湿工艺具体过程如下:将氢气(1-10vol%)与氮气组成的混合气体与饱和水蒸汽(1-5vol%)混合均匀,由此得到的混合湿气输送至连续退火炉内,利用其控制加热段三段或均热段炉内露点为-30℃至0℃,在形成的均匀气氛中完成钢板轻微内氧化。
进一步的,步骤(b)对预脱脂工序的改进包括控制预脱脂液的pH为10.5-11.5,游离碱浓度为12-18g/L,喷淋时间1-2min,喷淋压力0.6-1.0bar,喷淋温度40-50℃,其中预脱脂液是以氢氧化钠和碳酸钠为主体的碱液。
进一步的,步骤(b)对脱脂工序的改进包括控制脱脂液的pH为11-12,游离碱浓度为12-18g/L,喷淋时间1.5-2.5min,喷淋压力0.6-1.0bar,喷淋温度40-50℃,其中脱脂液也是以氢氧化钠和碳酸钠为主体的碱液。
进一步的,步骤(b)中对水洗I工序的改进包括控制促进剂点数5.5-8.5,水洗pH值8-9,水洗时间2-3min,水洗温度30-40℃,水洗湿度为30%-40%。
进一步的,步骤(b)中对水洗II工序的改进包括控制促进剂点数4.5-7.5,水洗pH值7.5-8.5,水洗时间1.5-2.5min,水洗温度30-40℃,水洗湿度30%-40%。
进一步的,步骤(b)中对水洗III工序的改进包括控制促进剂点数3.5-6.5,水洗pH值7-8,水洗时间1-2min,水洗温度30-40℃,水洗湿度30%-40%。
本发明的另一重目的在于提供一种按照上述方法制得的冷轧QP钢汽车板材。
与现有技术相比,本发明的有益效果主要体现在以下几个方面:
(1)彻底解决了冷轧QP钢在薄膜涂装前处理工艺中出水洗后易出现黄色锈蚀斑点且无法消除的问题,从根本上改善了冷轧QP钢的汽车涂装质量,有利于冷轧QP钢在汽车行业更大规模、更深层次推广应用;
(2)从冷轧QP钢生产端连续退火工序进行工艺改进,确保加热段温度在控制范围内的同时,在加热段三段或均热段炉内增加氮气弱加湿气氛,造成钢板轻微内氧化,极大的降低了钢板表面Si、Mn元素富集,改善了QP钢表面耐蚀性;
(3)通过反复分析试验,找到了导致冷轧QP钢锈蚀的核心影响因子:促进剂点数(防锈剂亚硝酸钠浓度)>水洗pH值>浸泡时间>温度>湿度,针对性的提出了精准控制手段,提高了脱脂及脱脂后水洗的稳定性;
(4)通过对三段水洗过程中促进剂点数、pH值等关键参数的分段调整,而不是原有的三段统一参数,彻底解决了冷轧QP钢汽车涂装薄膜前处理工艺中的锈蚀问题;
(5)本发明方法相对简单且容易实现,实施应用后有助于提升企业的效益和竞争力,取得较好的经济和社会效益。
附图说明
图1为本发明采用不同工艺制得的两种冷轧QP钢汽车涂装薄膜前处理后的表面质量实物对照图。
具体实施方式
为使本领域普通技术人员充分理解本发明的技术方案和有益效果,以下结合具体实施例进行进一步说明。
本发明实施过程中涉及到的一些测试方法具体如下:
(1)游离碱(含氢氧化钠、碳酸钠的碱液)检测
用移液管将10mL待测试样移入150mL锥型烧杯中,加入10mL去离子水和2-3滴酚酞指示剂,用0.1mol/L的硫酸水溶液滴定,溶液从紫红色变为无色即为滴定终点,按下式计算脱脂液游离碱浓度(即槽液浓度):
式中:C—H2SO4标准溶液的摩尔质量,mol/L。
V0—移取脱脂液量,mL。
V1—滴定试液所消耗H2SO4标准溶液的体积,mL。
m—厂家提供的脱脂剂摩尔质量,g/mol。
(2)促进剂点数(防锈剂浓度)检测
从新型薄膜槽液中取样100mL,加入10滴质量分数为50%的硫酸溶液,用0.02mol/L的高锰酸钾溶液滴定,直到溶液保持玫瑰红约20秒停止,所消耗的高锰酸钾溶液毫升数即为促进剂点数。
(3)生锈时间检测
按照预脱脂—脱脂—水洗I—水洗II—水洗III的步骤进行QP钢材料的前处理实验,通过肉眼判断板材从离开水洗III水面后到表面出现锈蚀(用纸巾擦拭板材湿膜表面是否有黄色,如有则锈蚀)的时间间隔T(单位分钟),生锈时间为T减去1min。
实施例1
一、QP钢连续退火工序工艺改进
按照现有冷轧QP钢生产工艺(制备板坯、加热、热轧、冷却、卷取、冷轧、连续退火等)生产,在连续退火工序改用以下新的工艺:采用两相区退火,加热分为三段,各加热段具体如下:(1)加热一段:145-300℃,加热速率2-27℃/s;(2)加热二段:595-655℃,加热速率2-25℃/s;(3)加热三段:780-830℃,加热速率2-12℃/s;(4)均热段:保温时间20-100s。
期间同时在连续退火炉沿其长度方向的辐射管加热段三段或均热段进行氮气弱加湿处理,具体过程如下:将氢气(1-10vol%)和氮气组成的混合气体与饱和水蒸汽(1-5vol%)混合,得到的混合湿气从交替布置的炉内喷梁上的喷嘴中溢出,经导流配气板流到带钢上,控制加热段三段或均热段炉内露点为-30℃至0℃,形成均匀的气氛。经过氮气弱加湿处理后,造成钢板轻微内氧化,降低了钢板表面Si、Mn元素富集及氧化,改善了QP钢表面耐蚀性。
经过上述步骤后制得冷轧QP钢产品,然后将其制成汽车零部件。
二、汽车厂前处理工艺调整
整个汽车厂前处理工艺具体如下:首先将冲压好的冷轧QP钢汽车零件放入预脱脂槽及脱脂槽中进行除油处理,然后将脱脂后的工件放在水洗I段进行第一次清洗,再放入水洗II段进行二次清洗,最后放入水洗III段进行三次清洗。在这个过程中,按照下述要求控制各个工序的关键核心参数:
(1)预脱脂工艺关键控制点
预脱脂液pH值 | 游离碱浓度 | 喷淋时间 | 喷淋压力 | 温度 |
11.0±0.5 | 15±3g/L | 1.5±0.5min | 0.8±0.2bar | 45±5℃ |
(2)脱脂工艺关键控制点
脱脂液pH值 | 游离碱浓度 | 喷淋时间 | 喷淋压力 | 温度 |
11.5±0.5 | 15±3g/L | 2.0±0.5min | 0.8±0.2bar | 45±5℃ |
(3)脱脂后水洗I工艺关键控制点
促进剂点数 | 水洗pH值 | 水洗时间 | 温度 | 湿度 |
7.0±1.5 | 8.5±0.5 | 2.5±0.5min | 35±5℃ | 35±5% |
(4)脱脂后水洗II工艺关键控制点
促进剂点数 | 水洗pH值 | 水洗时间 | 温度 | 湿度 |
6.0±1.5 | 8.0±0.5 | 2.0±0.5min | 35±5℃ | 35±5% |
(5)脱脂后水洗III工艺关键控制点
促进剂点数 | 水洗pH值 | 水洗时间 | 温度 | 湿度 |
5.0±1.5 | 7.5±0.5 | 1.5±0.5min | 35±5℃ | 35±5% |
结果表明,按照以上方法彻底解决了冷轧QP钢在汽车涂装薄膜前处理工艺中容易出现锈蚀的问题。
对比例1
一、QP钢连续退火工序工艺
按照现有冷轧QP钢生产工艺进行生产,其中连续退火工序具体如下:采用两相区退火,加热分为三段,各加热段具体如下:(1)加热一段:145-300℃,加热速率2-27℃/s;(2)加热二段:595-655℃,加热速率2-25℃/s;(3)加热三段:780-830℃,加热速率2-12℃/s;(4)均热段:保温时间20-100s。
将氢气(1-10vol%)和氮气的混合气体从交替布置的炉内喷梁上的喷嘴中溢出,经导流配气板流到带钢上,控制加热段三段或均热段炉内露点为-30℃至0℃,形成均匀的气氛。
二、汽车厂前处理工艺
汽车厂前处理工艺流程参照实施例1,各个工序的关键核心参数如下:
(1)脱脂工艺关键控制点
脱脂液pH值 | 游离碱浓度 | 喷淋时间 | 喷淋压力 | 温度 |
11.5±0.5 | 15±3g/L | 3.0±1.0min | 0.8±0.2bar | 45±5℃ |
(2)脱脂后水洗I工艺关键控制点
促进剂点数 | 水洗pH值 | 水洗时间 | 温度 | 湿度 |
7.5±1.5 | 9.0±0.5 | 2.5±0.5min | 40±5℃ | 35±5% |
(3)脱脂后水洗II工艺关键控制点
促进剂点数 | 水洗pH值 | 水洗时间 | 温度 | 湿度 |
7.0±1.5 | 8.5±0.5 | 2.5±0.5min | 40±5℃ | 35±5% |
(4)脱脂后水洗III工艺关键控制点
促进剂点数 | 水洗pH值 | 水洗时间 | 温度 | 湿度 |
7.0±1.5 | 8.5±0.5 | 2.0±0.5min | 40±5℃ | 35±5% |
实施例1和对比例1制得的钢板涂装前处理后的表面质量如图1所示。从图中可以看出,左图(实施例1)钢板表面洁净如新,而右图(对比例1)钢板表面存在明显的黄锈。
Claims (10)
1.一种改善冷轧淬火延性钢汽车涂装前处理质量的工艺方法,其特征在于,该方法包括以下步骤:(a)在QP钢冷轧阶段,对连续退火方式和气氛进行改进;(b)在QP钢汽车涂装前处理阶段,对预脱脂、脱脂、水洗I、水洗II、水洗III工序进行改进。
2.如权利要求1所述的方法,其特征在于:步骤(a)对连续退火方式的改进包括采用两相区退火,并且将加热分为三段;对连续退火气氛的改进包括采用氮气弱加湿工艺,使得钢板轻微内氧化。
3.如权利要求2所述的方法,其特征在于:步骤(a)中加热一段的温度为145-300℃,加热速率为2-27℃/s;加热二段的温度为595-655℃,加热速率为2-25℃/s;加热三段的温度为780-830℃,加热速率为2-12℃/s;均热段的保温时间控制在20-100s。
4.如权利要求2所述的方法,其特征在于:步骤(a)中氮气弱加湿工艺具体如下:将氢气、氮气、饱和水蒸汽混合均匀,所得混合湿气输送至连续退火炉内,利用其控制加热段三段或均热段露点为-30℃至0℃。
5.如权利要求1所述的方法,其特征在于:步骤(b)对预脱脂工序的改进包括控制预脱脂液的pH为10.5-11.5,游离碱浓度为12-18g/L,喷淋时间1-2min,喷淋压力0.6-1.0bar,喷淋温度40-50℃。
6.如权利要求1所述的方法,其特征在于:步骤(b)对脱脂工序的改进包括控制脱脂液的pH为11-12,游离碱浓度为12-18g/L,喷淋时间1.5-2.5min,喷淋压力0.6-1.0bar,喷淋温度40-50℃。
7.如权利要求1所述的方法,其特征在于:步骤(b)中对水洗I工序的改进包括控制促进剂点数为5.5-8.5,水洗pH值为8-9,水洗时间2-3min,水洗温度30-40℃,水洗湿度30%-40%。
8.如权利要求1所述的方法,其特征在于:步骤(b)中对水洗II工序的改进包括控制促进剂点数为4.5-7.5,水洗pH值为7.5-8.5,水洗时间1.5-2.5min,水洗温度30-40℃,水洗湿度30%-40%。
9.如权利要求1所述的方法,其特征在于:步骤(b)中对水洗III工序的改进包括控制促进剂点数为3.5-6.5,水洗pH值为7-8,水洗时间1-2min,水洗温度30-40℃,水洗湿度30%-40%。
10.一种冷轧QP钢汽车板材,其特征在于:该冷轧QP钢汽车板材按照权利要求1-9中的任意一种方法制备得到。
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KR20200065987A (ko) * | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | 열처리 방법, 이를 이용한 강판 제조방법 및 이 제조방법으로 제조된 강판 |
KR20200076478A (ko) * | 2018-12-19 | 2020-06-29 | 주식회사 포스코 | 인산염 처리성이 우수한 냉연강판의 제조방법 |
CN110369244A (zh) * | 2019-04-10 | 2019-10-25 | 汉腾汽车有限公司 | 一种车身涂装环保前处理无磷硅烷工艺 |
CN113718168A (zh) * | 2020-05-25 | 2021-11-30 | 宝山钢铁股份有限公司 | 一种高强度冷轧钢板及其制造方法 |
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