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CN106042264B - 一种不锈钢树脂复合体的制备方法及其制备的不锈钢树脂复合体 - Google Patents

一种不锈钢树脂复合体的制备方法及其制备的不锈钢树脂复合体 Download PDF

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Publication number
CN106042264B
CN106042264B CN201610352244.5A CN201610352244A CN106042264B CN 106042264 B CN106042264 B CN 106042264B CN 201610352244 A CN201610352244 A CN 201610352244A CN 106042264 B CN106042264 B CN 106042264B
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stainless steel
preparation
resin
aluminium
aqueous solution
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CN106042264A (zh
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章晓
程云
郭强
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BYD Co Ltd
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BYD Co Ltd
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    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明提供了一种不锈钢树脂复合体的制备方法及其制备的不锈钢树脂复合体,该不锈钢树脂复合体的制备方法,包含以下步骤:S1、在不锈钢基材表面热喷涂铝粉,冷却,得到附着有铝的不锈钢;S2、去除侵蚀到不锈钢表层中的铝,得到表层有侵蚀孔的不锈钢基材;S3、将树脂组合物注塑在步骤S2所得的表面有侵蚀孔的不锈钢基材表面,成型后得到不锈钢树脂复合体,提高了树脂和不锈钢的结合力,对合成树脂也没有特别要求,适用范围更广,可以只在需注塑区热喷涂铝粉,不会对不锈钢产品非注塑区域造成影响,不会影响外观,且对环境无污染,工艺简单,更适合大规模生产。

Description

一种不锈钢树脂复合体的制备方法及其制备的不锈钢树脂复 合体
技术领域
本发明涉及一种不锈钢树脂复合体的制备方法及其制备的不锈钢树脂复合体,更具体来说,尤其涉及一种结合力更强的不锈钢与热塑性树脂一体化而形成的不锈钢树脂复合体的制备方法及其制备的不锈钢树脂复合体。
背景技术
在汽车、家用电器制品、工业机器等的零件制造领域中,要求金属与树脂的一体成型技术,目前业界采用粘合剂在常温或加热下将金属与合成树脂一体化的结合。采用上述方法虽然可制备出金属与塑料一体成型的复合体,但按照这些方法得到的复合体金属与塑胶之间结合力较差,且胶粘剂耐酸耐碱性能差,复合体无法进行后续的阳极氧化等表面处理,同时胶粘剂有一定的厚度,对于复杂形状区域不适用,无法实现不锈钢与树脂的无缝结合,因而,一直以来,人们一直在研究是否有更合理的将高强度的工程树脂与金属一体化的方法。
本领域的技术人员通过研究提出了纳米加工处理技术,纳米加工处理技术(NMT)就是金属与塑胶一体化结合技术,其通过将金属表面纳米化处理,让塑胶直接在金属表面上射出成型,使金属与塑胶可以一体化成型。对于金属与塑胶的有效结合,纳米成型技术是一种最好的方式方法,并能取代目前常用的嵌入射出或锌铝、镁铝压铸件,可以提供一种具有价格竞争、高性能的金塑一体化产品。与胶合技术相比,NMT技术具有明显的优势,例如:减少产品的整体重量、强度优异、加工效率高等。NMT技术应用范围涵盖车辆、IT设备及3C产品,可以让产品朝更轻薄、更微型的方向发展。
现有公开的有通过酸性溶液化学腐蚀的方式,在不锈钢表面腐蚀出超微细凹凸形状,再通过注塑将树脂与金属结合到一起,但此种腐蚀方式由于酸性腐蚀液对不锈钢基材的腐蚀较严重,不锈钢基体会腐蚀变薄,影响结构尺寸的稳定性,同时也会造成不锈钢产品非注塑区域的腐蚀,尤其是对外观面的腐蚀,需要增加抛光或CNC对非腐蚀区域进行后续处理,工艺复杂,从而限制了其使用范围,且其制备的不锈钢树脂复合体的不锈钢和树脂的结合力也没有达到理想效果。
发明内容
本发明为了解决现有技术制备不锈钢树脂复合体时易对不锈钢基体造成影响,且不锈钢与树脂的结合力并不理想的技术问题。提供一种不锈钢与树脂的结合力强,且不会影响不锈钢基体的结构尺寸,可不对非注塑区域造成腐蚀,工艺简单易大规模生产,无污染的不锈钢树脂复合体的制备方法及其制备的不锈钢树脂复合体。
本发明的第一个目的是提供一种不锈钢树脂复合体的制备方法,包含以下步骤:
S1、在不锈钢基材表面热喷涂铝粉,冷却,得到附着有铝的不锈钢;
S2、去除侵蚀到不锈钢表层中的铝,得到表层有侵蚀孔的不锈钢基材;
S3、将树脂组合物注塑在步骤S2所得的表面有侵蚀孔的不锈钢基材表面,成型后得到不锈钢树脂复合体。
本发明的第二个目的是提供一种不锈钢树脂复合体,采用上述方法制作而成。
本发明意外发现通过本发明的方法能够在不锈钢基材表面形成独特的不规则的侵蚀孔,与树脂本身具有很好的结合性,提高树脂和不锈钢的结合力,热喷涂工艺能够使铝颗粒侵蚀到不锈钢表层内部,从而占据一定的空间,当去除去铝后,能在不锈钢表层留下大量不规则侵蚀孔,结构独特,不仅结合强度更高,而且树脂注塑成型容易,对合成树脂也没有特别要求,适用范围更广,同时可以选择性对不锈钢表面进行热喷涂,可以只在需注塑区热喷涂铝粉,通过简单的模具遮盖即可实现,不会对非注塑区域造成腐蚀,不会影响外观,对不锈钢的外观基本无影响,且对环境无污染,工艺简单,更适合大规模生产。
具体实施方式
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明提供了一种不锈钢树脂复合体的制备方法,包含以下步骤:
S1、在经过前处理的不锈钢基材表面热喷涂铝粉,冷却,得到附着有铝的不锈钢。对不锈钢基材表面热喷涂铝粉可以对整个不锈钢基材表面,也可以对部分不锈钢基材表面,优选,步骤S1包括在经过前处理的不锈钢基材需结合树脂的表面热喷涂铝粉,冷却,得到部分表面附着有铝的不锈钢,较佳情况下,可以根据设计需要,对需结合树脂层的面进行热喷涂铝粉,不会对非注塑区域造成影响,无需抛光或CNC等后续处理,一般先通过模具将不需结合树脂层的面即不用进行表面改性热喷涂铝粉的面遮盖,例如将不锈钢基材放入设计好的模具中,利用模具遮蔽非注塑区域,再将模具放入热喷涂设备中,在没有遮蔽的不锈钢基材表面热喷涂铝粉。
其中,优选,热喷涂的送粉速率为30-100g/min,进一步优选为60-80g/min。热喷涂的喷涂源到不锈钢基材表面的喷涂距离为300-420mm,进一步优选为340-390mm。热喷涂的温度可以为2000-5000℃,进一步优选为2600-3000℃,可以通过调节热喷涂的煤油流量和氧气流量来实现。使铝颗粒能更多更好的侵蚀到不锈钢表层内部,形成结构更优的不锈钢表面,增强与树脂的结合力。
对于热喷涂工艺的种类,本发明没有限制,优选热喷涂选自电弧喷涂、等离子喷涂和超音速火焰喷涂中的一种或几种,设备和操作技术为本领域技术人员公知。
优选,通过热喷涂工艺在不锈钢基材表面附着的铝的厚度为100-400微米,进一步优选为150-200微米。不仅节约了原料和成本,也有利于后续的碱蚀,对不锈钢树脂复合体的性能进行了进一步优化。
优选,铝粉的颗粒平均直径为30-50微米,铝粉的纯度大于99wt%,可以采用市售。
冷却一般冷却到常温,一般经过热喷涂后,可从设备中取出放置0.5-12h,使其冷却。
步骤S1之后形成的附着铝中,有部分附着在不锈钢表面的,也有部分侵蚀到不锈钢表层中的。
S2、去除侵蚀到不锈钢表层中的铝,得到表层有侵蚀孔的不锈钢基材。如前所述,可以理解的,步骤S1之后形成的附着铝中,有部分附着在不锈钢表面的,也有部分侵蚀到不锈钢表层中的。将侵蚀到不锈钢表层中的铝去除后,该部分铝所占据的空间露出,形成上述侵蚀孔。对于附着在不锈钢表面的铝,可同时去除,也可单独清除。通常,优选同时去除不锈钢表面的铝粉及内部嵌入的铝。
对于上述步骤S2,其目的在于去除侵蚀到不锈钢表层中的铝粉,露出侵蚀孔。根据本发明所公开的内容可以理解的,去除上述铝粉的方法和工艺可以采用现有技术中的各种方法。例如,可以将步骤S1所得的附着有铝的不锈钢浸泡到可溶解铝的溶蚀液中。具体的,可将步骤S1所得的附着有铝的不锈钢浸泡到碱性溶液中,去除附着的铝,得到表层有侵蚀孔的不锈钢基材。通常,碱性溶液不会腐蚀损伤不锈钢基材。对于碱性溶液的pH值,本领域技术人员可根据实际情况进行调整,例如,碱性溶液的pH值可以为10以上,进一步优选浸泡到pH=12-14的碱性溶液中,通过碱液浸泡,除去铝,在不锈钢表层留下大量侵蚀孔洞,优选碱性溶液选自可溶性碳酸盐、可溶性碱、可溶性磷酸盐、可溶性硫酸盐或可溶性硼酸盐中的一种或几种的水溶液,碱性溶液可以选自Na2CO3、NaHCO3、NaOH、Na2HPO4、Na3PO4、Na2SO3、KOH、KHCO3、K2CO3或K3PO4中的一种或几种的水溶液,优选,碱性溶液选自质量浓度为5-20wt%的Na2CO3水溶液、质量浓度为5-20wt%NaHCO3水溶液、质量浓度为5-20wt%NaOH水溶液、质量浓度为5-20wt%Na2HPO4水溶液、质量浓度为5-20wt%Na3PO4水溶液、质量浓度为5-20wt%KOH水溶液、质量浓度为5-20wt%KHCO3水溶液、质量浓度为5-20wt%K2CO3水溶液、质量浓度为5-20wt%Na2SO3水溶液或质量浓度为5-20wt%K3PO4水溶液中的一种或几种。较佳情况下,碱性溶液选自质量浓度为5-20wt%的氢氧化钠水溶液、质量浓度为5-20wt%的氢氧化钾水溶液、质量浓度为5-20wt%的碳酸钠水溶液或质量浓度为5-20wt%的磷酸钠水溶液中的一种或几种,进一步优选,碱性溶液选自质量浓度为5-15wt%的氢氧化钠水溶液、质量浓度为5-15wt%的氢氧化钾水溶液、质量浓度为5-15wt%的碳酸钠水溶液或质量浓度为5-15wt%的磷酸钠水溶液中的一种或几种。上述优选的碱性溶液能够更快更彻底地去除不锈钢表面的铝层及内部嵌入的铝粉颗粒,且不会腐蚀不锈钢基体,得到更好的侵蚀孔洞,孔结构优异,能够使树脂层与不锈钢基材的结合性能更佳,具有更佳的抗拉伸强度,使得不锈钢复合体的一体化结合更好。
优选,浸泡到pH≥10的碱性溶液中的浸泡温度为10-80℃,进一步优选为30-70℃,更进一步优选为40-60℃,浸泡时间为10-120min,进一步优选为10-60min,可以一次浸泡,也可以反复多次浸泡,每次浸渍后用去离子水洗净,反复的次数可以为2-5次。
形成的侵蚀孔一般为不规则侵蚀孔,结构独特,与树脂的结合力强。
S3、将树脂组合物注塑在步骤S2所得的表面有侵蚀孔的不锈钢基材表面,成型后得到不锈钢树脂复合体。具体可以为将干燥后的不锈钢基材转入模具中,与制得的树脂组合物进行一体化处理,成型后可得到本发明提供的不锈钢复合体,在本发明中,能够使金属塑料一体化的成型方式均可用于本发明,注塑的条件可以为喷嘴温度200-350℃,模具温度50-200℃,一般注入的树脂组合物的量为0.1-1000g,制备的复合体表面具有0.1-10mm厚的树脂层。
前处理为本领域技术人员常用的对不锈钢表面进行的前处理工序,一般包括进行机械打磨或研磨去除表面明显的异物,然后对金属表面粘附的加工油等进行脱脂、清洗。优选,前处理包括对不锈钢基材表面进行打磨,例如可以为:先采用100-400目的砂纸或者将其放入抛光机内对不锈钢基材表面打磨使产生微米级的小孔。然后依次进行除油、第一水洗、喷砂、第二水洗、干燥等步骤,用本领域技术人员常用的各种溶剂在超声波中清洗该不锈钢,清洗时间0.5-2h,去除不锈钢表面的油污,所述溶剂可以为乙醇或丙酮。在本发明中,优选用无水乙醇将不锈钢除油后水洗擦拭干净后再进行喷砂,可以增加热喷涂时铝粉在不锈钢表面的侵蚀深度,再用去离子水冲洗干净,最后于60-80℃下烘干。
需前处理的不锈钢本发明没有特别限制,可以使用各种市售的不锈钢;本发明中所述的不锈钢为本领域技术人员常用的各种形状、结构的不锈钢,本发明没有特别限制。不锈钢的各种形状、结构,可通过机械加工完成。
树脂组合物本发明没有特别限制,可以采用本领域技术人员公知的各种能与不锈钢结合的树脂组合物即可,优选树脂组合物为热塑性树脂。优选热塑性树脂为含有主体树脂和聚烯烃树脂的共混物。优选主体树脂为非结晶性的主体树脂,选用非结晶性的主体树脂作为注塑料,其表面光泽、韧性都优于现有技术中的高结晶性树脂,同时配合使用熔点为65℃-105℃的聚烯烃树脂,在成型时不需要在特定模温下注塑,成型工艺简化,同时能保证得到的金属树脂复合体具有更好的机械强度和表面处理特性,从而解决塑料件的表面装饰问题,满足客户的多样化需求。通过在所采用的非结晶主体树脂中,配合使用熔点为65℃-105℃的聚烯烃树脂,能增加树脂流入金属表面纳米级微孔的能力,从而保证所形成的金属与塑料具有良好的附着力、机械强度。优选情况下,以100重量份的热塑性树脂为基准,其中主体树脂的含量为70-95重量份,聚烯烃树脂的含量为5-30重量份。
作为本发明的进一步改进,本发明的发明人还发现,在热塑性树脂中采用流动性改进剂,还能提高树脂的流动能力,进一步提高金属与树脂的附着力和树脂的注塑性能。优选情况下,以100重量份的热塑性树脂为基准,所述热塑性树脂中还含有1-5重量份的流动性改进剂。优选情况下,所述流动性改进剂为环状聚酯。
如前所述,本发明中,所述主体树脂为非结晶性树脂。具体地,优选,主体树脂为聚苯醚(PPO)与聚苯硫醚(PPS)的混合物,优选情况下,PPO与PPS的重量比为3:1-1:3,更优选为2:1-1:1。或者优选主体树脂为聚苯醚(PPO)与聚酰胺(PA)的混合物,优选情况下,PPO与PA的重量比为3:1-1:3,更优选为2:1-1:1。或者优选主体树脂为聚碳酸酯(PC),其可以选自各种直链聚碳酸酯和/或直链聚碳酸酯,本发明没有特殊规定。
本发明中,所采用的聚烯烃树脂的熔点为65℃-105℃。优选情况下,所述聚烯烃树脂可以采用接枝聚乙烯。更优选情况下,所述聚烯烃树脂可以采用熔点为100℃或105℃的接枝聚乙烯。
本发明的树脂组合物还可以含有其他改性添加剂等,本发明没有特别限制,可根据需要设置,例如树脂组合物中还可以含有填料。所述填料为本领域技术人员常用的各种填料,例如可以为各种纤维填料或无机粉末性填料。所述纤维填料可以选自玻璃纤维、碳纤维或芳族聚酰胺纤维中的一种或几种;所述无机粉末性填料可以选自碳酸钙、碳酸镁、二氧化硅、重质硫酸钡、滑石粉、玻璃和粘土中的一种或几种。更优选情况下,为使塑料组合物的横向、纵向均具有与不锈钢基材相近的线性膨胀系数,本发明中,以100重量份的主体树脂为基准,纤维填料含量为50-150重量份,无机粉末性填料的含量为50-150重量份。
根据本发明提供的不锈钢树脂复合体的制备方法,将主体树脂、聚烯烃树脂混合均匀,制备树脂组合物。所述树脂组合物的制备方法采用本领域技术人员常用物理共混的方法得到,即将主体树脂、聚烯烃树脂混合均匀,通过双螺杆挤出机挤出造粒,待用。
根据本发明提供的不锈钢复合体的制备方法,还可以往所述主体树脂中加入填料、流动性改进剂,混合均匀,制得树脂组合物,从而使得树脂组合物的横向、纵向均具有与不锈钢基材相近的线性膨胀系数。
本发明的制备方法简单,较现有的采用胶黏剂的工艺简化了生产流程,缩短了生产时间,而且较现有的表面纳米孔注塑需采用注塑热压再注塑的两步法也大幅降低了工艺复杂度,只需直接注塑即可实现,同时通过本发明的制备方法所制得的不锈钢树脂复合体的树脂层与不锈钢基材之间结合力好,具有较佳的拉伸剪切强度。
本发明同时提供了上述制备方法制备的不锈钢树脂复合体,包括不锈钢基材及树脂层,所述不锈钢基材的表层形成有侵蚀孔,形成所述树脂层的树脂组合物填充于所述侵蚀孔中。其中,树脂组合物为本领域技术人员公知的各种能与不锈钢复合的树脂组合物。
本发明制得的金属树脂复合体可直接使用,也可以根据需要进行一些后续后处理,例如CNC(数控机床加工)、喷涂等,本发明没有限制。
下面通过具体实施例对本发明作进一步的详述。
实施例1
本实施例制备不锈钢树脂复合体;
1、前处理:将1mm厚304不锈钢板,切成15mm*80mm的长方形片,将其放入抛光机内研磨,后用无水乙醇洗净,然后喷砂、用去离子水冲洗干净、80℃下烘干,得到经过前处理的不锈钢片;
2、表面处理:将上述不锈钢片放入模具中,利用模具遮蔽非注塑区域,不锈钢片一端15mm*5mm区域不遮蔽,将模具放入超音速喷涂机中,热喷涂纯度为99.5wt%平均颗粒直径为30微米的纯铝粉体,其中,热喷涂的煤油流量为22L/h,氧气流量为930L/min,送粉速率为75g/min,喷涂距离为370mm,喷涂的铝粉厚度为100微米。将所得样品取出室温下放置2小时,待样品完全冷却后,放入20wt%的氢氧化钠溶液中,恒温30℃浸泡1小时,待样品表面的铝层完全溶解,取出不锈钢样品,水洗,80℃下烘干;
3、成型:将烘干后的不锈钢片插入注射成型模具中,注塑含有20wt%玻璃纤维的聚苯硫醚(PPS)树脂组合物,脱模并冷却后得到牢固结合在一起的不锈钢与树脂组合物的不锈钢树脂复合体样品S1。
实施例2
采用与实施例1相同的方法制备不锈钢树脂复合体样品S2。不同的是步骤2表面处理:将上述不锈钢片放入模具中,利用模具遮蔽非注塑区域,不锈钢片一端15mm*5mm区域不遮蔽,将模具放入超音速喷涂机中,热喷涂纯度为99.5wt%平均颗粒直径为50微米的纯铝粉体,其中,热喷涂的煤油流量为22L/h,氧气流量为930L/min,送粉速率为75g/min,喷涂距离为370mm,喷涂的铝粉厚度为100微米。将所得样品取出室温下放置2小时,待样品完全冷却后,放入20wt%的氢氧化钠溶液中,恒温30℃浸泡1小时,待样品表面的铝层完全溶解,取出不锈钢样品,水洗,80℃下烘干。
实施例3
采用与实施例1相同的方法制备不锈钢树脂复合体样品S3。不同的是步骤2表面处理:将上述不锈钢片放入模具中,利用模具遮蔽非注塑区域,不锈钢片一端15mm*5mm区域不遮蔽,将模具放入超音速喷涂机中,热喷涂纯度为99.5wt%平均颗粒直径为30微米的纯铝粉体,其中,热喷涂的煤油流量为22L/h,氧气流量为930L/min,送粉速率为75g/min,喷涂距离为370mm,喷涂的铝粉厚度为200微米。将所得样品取出室温下放置2小时,待样品完全冷却后,放入20wt%的氢氧化钠溶液中,恒温30℃浸泡1小时,待样品表面的铝层完全溶解,取出不锈钢样品,水洗,80℃下烘干。
实施例4
采用与实施例1相同的方法制备不锈钢树脂复合体样品S4。不同的是步骤2表面处理:将上述不锈钢片放入模具中,利用模具遮蔽非注塑区域,不锈钢片一端15mm*5mm区域不遮蔽,将模具放入超音速喷涂机中,热喷涂纯度为99.5wt%平均颗粒直径为30微米的纯铝粉体,其中,热喷涂的煤油流量为22L/h,氧气流量为930L/min,送粉速率为100g/min,喷涂距离为370mm,喷涂的铝粉厚度为100微米。将所得样品取出室温下放置2小时,待样品完全冷却后,放入20wt%的氢氧化钠溶液中,恒温30℃浸泡1小时,待样品表面的铝层完全溶解,取出不锈钢样品,水洗,80℃下烘干。
实施例5
采用与实施例1相同的方法制备不锈钢树脂复合体样品S5。不同的是步骤2表面处理:将上述不锈钢片放入模具中,利用模具遮蔽非注塑区域,不锈钢片一端15mm*5mm区域不遮蔽,将模具放入超音速喷涂机中,热喷涂纯度为99.5wt%平均颗粒直径为30微米的纯铝粉体,其中,热喷涂的煤油流量为22L/h,氧气流量为930L/min,送粉速率为75g/min,喷涂距离为320mm,喷涂的铝粉厚度为100微米。将所得样品取出室温下放置2小时,待样品完全冷却后,放入20wt%的氢氧化钠溶液中,恒温30℃浸泡1小时,待样品表面的铝层完全溶解,取出不锈钢样品,水洗,80℃下烘干。
对比例1
1、前处理:将1mm厚304不锈钢板,切成15mm*80mm的长方形片,将其放入抛光机内研磨,后用无水乙醇洗净,然后喷砂、用去离子水冲洗干净、80℃下烘干,得到经过前处理的不锈钢片;
2、表面处理:将上述不锈钢片放入20wt%的氢氧化钠溶液中,恒温30℃浸泡1小时,取出不锈钢样品,水洗,80℃下烘干;
3、成型:将烘干后的不锈钢片插入注射成型模具中,注塑含有20wt%玻璃纤维的聚苯硫醚(PPS)树脂组合物,脱模并冷却后得到牢固结合在一起的不锈钢与树脂组合物的不锈钢树脂复合体样品DS1。
对比例2
1、前处理:将1mm厚304不锈钢板,切成15mm*80mm的长方形片,将其放入抛光机内研磨,后用无水乙醇洗净,然后喷砂、用去离子水冲洗干净、80℃下烘干,得到经过前处理的不锈钢片;
2、表面处理:将上述不锈钢片放入10wt%的硫酸溶液中,恒温70℃浸泡1小时,取出不锈钢样品,水洗,80℃下烘干;
3、成型:将烘干后的不锈钢片插入注射成型模具中,注塑含有20wt%玻璃纤维的聚苯硫醚(PPS)树脂组合物,脱模并冷却后得到牢固结合在一起的不锈钢与树脂组合物的不锈钢树脂复合体样品DS2。
性能测试:
不锈钢与树脂的结合力:将实施例1-5及对比例1-2制备的不锈钢树脂复合体S1-S5和DS1、DS2固定于万能材料试验机进行产品拉伸测试,测试结果中剪切断裂力可视为不锈钢与树脂之间的结合力的大小,测试结果如表1。
非注塑区域表观:将实施例1-5及对比例1制备的不锈钢树脂复合体S1-S5和DS1、DS2在标准光照D65条件下进行观察,并取一片未处理不锈钢板S0做对比,眼睛到样品距离为30厘米,观察样品表面对比S0表面有无明显变化,记录出现的缺陷,测试结果如表1。
表1
剪切断裂力/MPa 非注塑区域表观
实施例1 10.12 无明显变化
实施例2 8.84 无明显变化
实施例3 9.28 无明显变化
实施例4 8.556 无明显变化
实施例5 8 无明显变化
对比例1 注塑后脱落 无明显变化
对比例2 8.41 表面有明显腐蚀,粗糙无光泽
本发明制备的不锈钢树脂复合体结合力强,对合成树脂没有特别要求,适用范围更广,同时可以选择性对不锈钢表面进行热喷涂,可以只在需注塑区热喷涂铝粉,通过简单的模具遮盖即可实现,不会对非注塑区域造成腐蚀,不会影响外观,对不锈钢且碱性溶液基体尺寸影响也小,放热小,对不锈钢的外观基本无影响,且对环境无污染,工艺简单,更适合大规模生产。
本领域技术人员容易知道,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。本发明的保护范围由权利要求书确定。

Claims (25)

1.一种不锈钢树脂复合体的制备方法,其特征在于,包含以下步骤:
Sl、在不锈钢基材表面热喷涂铝粉,冷却,得到附着有铝的不锈钢;有部分铝附着在不锈钢的表面,也有部分铝侵蚀到不锈钢的表层中,所述热喷涂的送粉速率为30-100g/min,热喷涂的喷涂源到不锈钢基材表面的喷涂距离为300-420mm,热喷涂温度为2000-5000℃;
S2、去除侵蚀到不锈钢表层中的铝,得到表层有侵蚀孔的不锈钢基材;
S3、将树脂组合物注塑在步骤S2所得的表面有侵蚀孔的不锈钢基材表面,成型后得到不锈钢树脂复合体。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤Sl包括在不锈钢基材需结合树脂的表面热喷涂铝粉,冷却,得到部分表面附着有铝的不锈钢。
3.根据权利要求1所述的制备方法,其特征在于,所述热喷涂选自电弧喷涂、等离子喷涂和超音速火焰喷涂中的一种或几种。
4.根据权利要求1所述的制备方法,其特征在于,所述附着的铝的厚度为100-400微米。
5.根据权利要求1所述的制备方法,其特征在于,所述铝粉的颗粒平均直径为30-50微米,所述铝粉的纯度大于99wt%。
6.根据权利要求1-5中任意一项所述的制备方法,其特征在于,将步骤Sl所得的附着有铝的不锈钢浸泡到溶蚀液中,去除附着的铝,得到表层有侵蚀孔的不锈钢基材。
7.根据权利要求6所述的制备方法,其特征在于,所述溶蚀液为碱性溶液。
8.根据权利要求7所述的制备方法,其特征在于,所述碱性溶液的pH≥10。
9.根据权利要求8所述的制备方法,其特征在于,所述碱性溶液的pH值为12-14;
所述碱性溶液为选自Na2CO3、NaHCO3、NaOH、Na2HPO4、Na3PO4、KOH、KHCO3、K2CO3、Na2SO3和K3PO4中的一种或几种的水溶液。
10.根据权利要求9所述的制备方法,其特征在于,所述碱性溶液选自质量浓度为5-20wt%的Na2CO3水溶液、质量浓度为5-20wt%NaHCO3水溶液、质量浓度为5-20wt%NaOH水溶液、质量浓度为5-20wt%Na2HPO4水溶液、质量浓度为5-20wt%Na3PO4水溶液、质量浓度为5-20wt%KOH水溶液、质量浓度为5-20wt%KHCO3水溶液、质量浓度为5-20wt%K2CO3水溶液、质量浓度为5-20wt%Na2SO3水溶液或质量浓度为5-20wt%K3PO4水溶液中的一种或几种。
11.根据权利要求7-10中任意一项所述的制备方法,其特征在于,所述浸泡的温度为10-800C,浸泡时间为10-120min。
12.根据权利要求1所述的制备方法,其特征在于,所述侵蚀孔为不规则侵蚀孔。
13.根据权利要求1所述的制备方法,其特征在于,所述步骤Sl中,先对不锈钢基材进行前处理;所述前处理包括对不锈钢基材表面进行打磨,然后依次进行除油、第一水洗、喷砂、第二水洗、60-800℃干燥。
14.根据权利要求1所述的制备方法,其特征在于,所述树脂组合物为热塑性树脂组合物。
15.根据权利要求14所述的制备方法,其特征在于,所述热塑性树脂为含有主体树脂和聚烯烃树脂的共混物。
16.根据权利要求15所述的制备方法,其特征在于,所述主体树脂为聚苯醚与聚苯硫醚的混合物,所述聚烯烃树脂的熔点为65℃-105℃。
17.根据权利要求16所述的制备方法,其特征在于,所述主体树脂中聚苯醚与聚苯硫醚的重量比为3:1-1:3。
18.根据权利要求15所述的制备方法,其特征在于,所述主体树脂为聚苯醚与聚酰胺的混合物,所述聚烯烃树脂的熔点为65℃-105℃。
19.根据权利要求18所述的制备方法,其特征在于,所述主体树脂中聚苯醚与聚酰胺的重量比为3:1-1:3。
20.根据权利要求15所述的制备方法,其特征在于,所述主体树脂为聚碳酸酯,所述聚烯烃树脂的熔点为65℃-105℃。
21.根据权利要求15所述的制备方法,其特征在于,以100重量份的热塑性树脂为基准,其中主体树脂的含量为70-95重量份,聚烯烃树脂的含量为5-30重量份。
22.根据权利要求15所述的制备方法,其特征在于,所述聚烯烃树脂为接枝聚乙烯。
23.根据权利要求14所述的制备方法,其特征在于,以100重量份的热塑性树脂为基准,所述热塑性树脂中还含有1-5重量份的流动性改进剂;所述流动性改进剂为环状聚酯。
24.根据权利要求14所述的制备方法,其特征在于,所述树脂组合物中含有填料,所述填料包括纤维填料或无机粉末性填料,所述纤维填料为玻璃纤维、碳纤维或聚酰胺纤维中的一种以上,无机粉末性填料为二氧化硅、滑石粉、氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、玻璃或高岭土中的一种以上。
25.一种不锈钢树脂复合体,其特征在于,采用如权利要求1-24任意一项所述的方法制作而成。
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