技术领域technical field
本发明涉及一种锌合金的表面处理方法，尤其是涉及一种锌合金高耐蚀仿六价铬颜色的表面处理方法。The invention relates to a surface treatment method of a zinc alloy, in particular to a surface treatment method of a zinc alloy with high corrosion resistance imitating the color of hexavalent chromium.
背景技术Background technique
锌合金是以锌为主体加入铝、铜、镁、镉、铅、钛等少量元素组成的合金。锌合金熔点低，流动性好，易熔焊，钎焊和塑性加工。合金成分中杂质元素铅、镉、锡超过标准时，导致铸件老化而发生变形，表现为体积胀大，机械性能特别是塑性显著下降，时间长了甚至破裂。铅、锡、镉在锌合金中溶解度很小，因而集中于晶粒边界而成为阴极，富铝的固溶体成为阳极，在水蒸气（电解质）存在的条件下，促成晶间电化学腐蚀。压铸件因晶间腐蚀而老化。由于锌合金的化学稳定性差，在空气中容易遭到腐蚀，在强酸、强碱中均会受到强烈的浸蚀，因此目前通过镀覆电镀层来达到防腐蚀或者装饰的目的。锌合金压铸件表面致密层只有0.05～0.1μm，且锌合金压铸件硬度低，只是表面层无孔，而表层下的基体多为疏松多孔结构，表层一旦被破坏，就会露出孔隙较多的内层，给电镀造成困难。为了达到电镀层与锌合金基础之间的良好结合力，需要采用氰化镀铜来作为预镀层，氰化物对环境及人类的危害极大，目前已限制氰化物电镀工艺。Zinc alloy is an alloy composed of zinc as the main body and a small amount of elements such as aluminum, copper, magnesium, cadmium, lead, and titanium. Zinc alloy has low melting point, good fluidity, easy welding, brazing and plastic processing. When the impurity elements lead, cadmium, and tin in the alloy composition exceed the standard, the casting will be aged and deformed, manifested as volume expansion, mechanical properties, especially plasticity, will decrease significantly, and even crack after a long time. The solubility of lead, tin, and cadmium in zinc alloy is very small, so they concentrate on the grain boundary and become the cathode, and the aluminum-rich solid solution becomes the anode, which promotes intergranular electrochemical corrosion in the presence of water vapor (electrolyte). Die castings age due to intergranular corrosion. Due to the poor chemical stability of zinc alloy, it is easily corroded in the air, and will be strongly corroded in strong acid and strong alkali. Therefore, the purpose of anti-corrosion or decoration is currently achieved by plating an electroplating layer. The dense layer on the surface of zinc alloy die castings is only 0.05-0.1 μm, and the hardness of zinc alloy die castings is low, but the surface layer is non-porous, and the matrix under the surface layer is mostly loose and porous. Once the surface layer is damaged, more pores will be exposed. Inner layer, causing difficulties for electroplating. In order to achieve a good bonding force between the electroplating layer and the zinc alloy base, cyanide copper plating is required as a pre-plating layer. Cyanide is extremely harmful to the environment and humans, and the cyanide electroplating process has been restricted at present.
中国专利200610167410公开一种锌合金制品及其制备方法，锌合金制品包括锌合金基材和锌合金基材表面上的真空镀膜层，其中，该制品还包括紫外光固化涂层，该紫外光固化涂层位于锌合金基材和真空镀膜层之间。该发明提供的锌合金制品的锌合金基材和真空镀膜层之间具有紫外光固化涂层，该涂层可以有效地降低锌合金基材的表面粗糙度，而且该涂层与真空镀膜层的附着力也比较好，得到的锌合金制品的表面光泽度较高。该发明的锌合金处理方法存在膜层最外层（PVD层）太薄，耐磨性与耐蚀性较差等缺点。Chinese patent 200610167410 discloses a zinc alloy product and its preparation method. The zinc alloy product includes a zinc alloy substrate and a vacuum coating layer on the surface of the zinc alloy substrate. The coating is located between the zinc alloy substrate and the vacuum coating layer. The zinc alloy product provided by the invention has an ultraviolet-cured coating between the zinc alloy substrate and the vacuum coating layer, which can effectively reduce the surface roughness of the zinc alloy substrate, and the coating is compatible with the vacuum coating layer. The adhesion is also relatively good, and the surface gloss of the obtained zinc alloy products is relatively high. The zinc alloy treatment method of the invention has the disadvantages that the outermost layer (PVD layer) of the film layer is too thin, and the wear resistance and corrosion resistance are poor.
中国发明200910166879公开一种压铸锌合金表面疏孔之填充封闭及其制法，该填充封闭包括熔点低于锌合金之单一金属或合金；该制法是在经过脱腊、脱脂、脱油的锌合金表面施以低熔点金属电镀，达到目标厚度之后,经漂洗烘干，再经绝氧升温表融,再经淬冷的制程工序，将锌合金在升温后疏孔内之气体排出，并利用融熔态之表面低熔点金属镀层之表面张力渗透补满锌合金之疏孔，再利用淬冷过程减小合金晶型尺寸、强化结构强度、增加工件表面之密封性、避免疏孔的再生。该发明的锌合金素材胚件封孔方法比较复杂，而且采用金属进行封孔，对锌合金的本身的耐蚀性没有启动提升。Chinese invention 200910166879 discloses a kind of filling and sealing of pores on the surface of die-casting zinc alloy and its preparation method. The filling and sealing includes a single metal or alloy with a melting point lower than that of zinc alloy; The surface of the alloy is electroplated with a low-melting point metal. After reaching the target thickness, it is rinsed and dried, then melted by anaerobic heating, and then quenched. The gas in the porous pores of the zinc alloy after heating is discharged, and used The surface tension of the low-melting-point metal coating on the surface of the molten state penetrates and fills the porous pores of the zinc alloy, and then uses the quenching process to reduce the alloy crystal size, strengthen the structural strength, increase the sealing of the workpiece surface, and avoid the regeneration of the porous pores. The sealing method of the zinc alloy material blank of the invention is relatively complicated, and metal is used for sealing, which does not start to improve the corrosion resistance of the zinc alloy itself.
中国专利200710182088公开一种合金材料的表面处理方法，该方法包括对合金材料进行电泳涂装,其特征在于,该方法还包括在电泳涂装之前先对合金材料进行阳极氧化。该发明提供的合金材料的表面处理方法处理后的合金材料经过油漆涂装后的表面形成的膜层的耐腐蚀性和附着力较好。但是其外观无法达到水电镀6价铬所要求的颜色。Chinese patent 200710182088 discloses a method for surface treatment of an alloy material, the method includes performing electrophoretic coating on the alloy material, and is characterized in that the method also includes performing anodic oxidation on the alloy material before the electrophoretic coating. The surface treatment method of the alloy material provided by the invention has good corrosion resistance and adhesion of the film layer formed on the surface of the alloy material after the paint coating. However, its appearance cannot reach the color required by hydroplating of hexavalent chromium.
发明内容Contents of the invention
本发明的目的在于针对现有的锌合金的表面处理工艺中存在的缺点与不足，提供一种锌合金高耐蚀仿六价铬颜色的表面处理方法。The object of the present invention is to provide a surface treatment method for zinc alloys with high corrosion resistance imitating the color of hexavalent chromium aiming at the shortcomings and deficiencies existing in the existing zinc alloy surface treatment process.
本发明包括以下步骤：The present invention comprises the following steps:
1）将锌合金胚件进行超声波除蜡除油处理；1) Ultrasonic dewaxing and degreasing of zinc alloy blanks;
2）对经过步骤1）处理的锌合金胚件进行阳极氧化处理；2) Carrying out anodic oxidation treatment on the zinc alloy blank treated in step 1);
3）对经过步骤2）处理的锌合金胚件进行电泳涂装、水洗、烘干处理；3) Perform electrophoretic coating, water washing, and drying on the zinc alloy blanks treated in step 2);
4）对经过步骤3）处理的锌合金胚件转入紫外光固化（UV）喷漆线上进行喷UV底漆，流平、UV固化；4) Transfer the zinc alloy blanks treated in step 3) to the ultraviolet curing (UV) painting line for spraying UV primer, leveling and UV curing;
5）对经过步骤4）处理的锌合金胚件挂入物理气相沉积（PVD）炉进行等离子体处理后，进行物理气相沉积镀膜处理；5) Hang the zinc alloy blank treated in step 4) into a physical vapor deposition (PVD) furnace for plasma treatment, and then perform physical vapor deposition coating treatment;
6）对经过步骤5）处理的锌合金胚件转入UV喷漆线上进行喷紫外光固化（UV）中层漆，流平、UV固化，再喷透明UV面漆，流平，UV固化，并在紫外光固化（UV）中层漆中调配出电镀6价铬金属的颜色，完成锌合金高耐蚀仿六价铬颜色的表面处理。6) Transfer the zinc alloy blanks treated in step 5) to the UV painting line for spraying ultraviolet light curing (UV) middle layer paint, leveling, UV curing, and then spray transparent UV topcoat, leveling, UV curing, and The color of electroplated hexavalent chromium metal is formulated in the ultraviolet curing (UV) intermediate paint, and the surface treatment of zinc alloy with high corrosion resistance imitating hexavalent chromium color is completed.
在步骤1）中，所述超声除蜡处理的配方可采用本领域公知的除蜡配方，如广东三浮有限公司除蜡液配方：除蜡剂SF-20420～40ml/L，其余为纯水，除蜡液温度为55～65℃，时间为3～5min；超声波除油液的配方可采用Na3PO48～12g/L、K2CO320～30g/L，其余为纯水，除油液温度为55～65℃，时间为1～2min。In step 1), the formula of the ultrasonic wax removal treatment can be a wax removal formula known in the art, such as the wax removal liquid formula of Guangdong Sanfu Co., Ltd.: wax removal agent SF-20420 ~ 40ml/L, and the rest is pure water , the temperature of the wax removal liquid is 55-65°C, and the time is 3-5 minutes; the formula of the ultrasonic degreasing liquid can be Na3 PO4 8-12g/L, K2 CO3 20-30g/L, and the rest is pure water. The temperature of the degreasing liquid is 55-65°C, and the time is 1-2 minutes.
在步骤2）中，所述锌合金胚件进行阳极氧化处理，阳极处理液的配方可采用氢氧化钠15～20g/L，温度40～45℃，时间5～8min，电流密度6～12A/dm2。In step 2), the zinc alloy blank is subjected to anodic oxidation treatment. The formula of the anodic treatment solution can be sodium hydroxide 15-20g/L, the temperature is 40-45°C, the time is 5-8min, and the current density is 6-12A/L. dm2 .
在步骤3）中，所述电泳涂装的工艺条件可为：电泳液成分：美国PPG公司的PPG-EC-1800电泳漆，该电泳漆中的有机固体的质量分数9%～12%，蒸馏水质量分数88%～91%；电压：30～60V；时间：1.5～2.5min；所述水洗的条件可为在去离子水槽中漂洗1～2min；所述烘干处理的条件可为在150～170℃温度下烘40～60min。In step 3), the process conditions of the electrophoretic coating can be: electrophoretic liquid composition: PPG-EC-1800 electrophoretic paint from PPG Company of the United States, the mass fraction of organic solids in the electrophoretic paint is 9% to 12%, distilled water The mass fraction is 88% to 91%; voltage: 30 to 60V; time: 1.5 to 2.5 minutes; the washing condition can be rinsing in a deionized water tank for 1 to 2 minutes; the drying treatment condition can be at 150 to Bake at 170°C for 40-60 minutes.
在步骤4）中，所述喷UV底漆，流平、UV固化的具体方法可为：喷镀一层UV漆后（漆层厚15～30μm），送入红外线烘干段，进行流平后，在50~70℃下烘干3～10min，再送入紫外线光固化段进行UV照射固化交联10～45s，UV照射固化的能量为500～1000mJ/cm2，UV漆为聚氨酯丙烯酸酯类UV涂料。In step 4), the specific method of spraying UV primer, leveling and UV curing can be: after spraying a layer of UV paint (the thickness of the paint layer is 15-30 μm), send it to the infrared drying section for leveling Finally, dry at 50-70°C for 3-10 minutes, and then send it to the ultraviolet light curing section for UV irradiation curing and crosslinking for 10-45s. The energy of UV irradiation curing is 500-1000mJ/cm2 . The UV paint is polyurethane acrylate UV coatings.
在步骤5）中，所述等离子体处理的工艺条件可为离子源电流0.3～0.5A，偏压80～150V，占空比50%～80%，氩气流速10～100SCCM，氧气流速10～150SCCM，炉内真空压力0.1～0.4Pa，活化时间5～10min，以达到活化表面之目的；所述物理气相沉积镀膜处理的工艺条件可为采用大功率中频脉冲或者大功率直流电源，电源电流为50～300A，电压为400～800V，沉积时间为0.5～10min，偏压20～60V，占空比50%～80%，氩气流速60～200SCCM；物理气相沉积镀膜所采用的靶材可为铬、铟、锡、锑、银等金属中的至少一种。In step 5), the process conditions of the plasma treatment can be ion source current 0.3-0.5A, bias voltage 80-150V, duty cycle 50%-80%, argon flow rate 10-100SCCM, oxygen flow rate 10- 150SCCM, the vacuum pressure in the furnace is 0.1-0.4Pa, and the activation time is 5-10min to achieve the purpose of activating the surface; the process conditions of the physical vapor deposition coating treatment can be high-power intermediate frequency pulse or high-power DC power supply, and the power supply current is 50~300A, voltage 400~800V, deposition time 0.5~10min, bias voltage 20~60V, duty cycle 50%~80%, argon flow rate 60~200SCCM; the target used for physical vapor deposition coating can be At least one of metals such as chromium, indium, tin, antimony, and silver.
在步骤6）中，所述喷紫外光固化（UV）中层漆，流平、UV固化的具体方法可为：喷镀一层UV漆后（漆层厚5～10μm），送入红外线烘干段，进行流平后，在50～70℃下烘干3～10min，再送入紫外线光固化段进行UV照射固化交联10～45s，UV照射固化的能量为500～1000mJ/cm2；UV漆为聚氨酯丙烯酸酯类UV涂料，并加入调色剂进行调色；所述喷UV面漆，流平、UV固化的具体方法可为：喷镀一层UV漆后（漆层厚15～25μm），送入红外线烘干段，进行流平后，在50～70℃下烘干3～10min，再送入紫外线光固化段进行UV照射固化交联10～45s，UV照射固化的能量为500～1000mJ/cm2，UV漆为聚氨酯丙烯酸酯类UV涂料。In step 6), the specific method of spraying ultraviolet curing (UV) middle layer paint, leveling and UV curing can be: after spraying a layer of UV paint (paint layer thickness 5-10 μm), sending it into infrared drying Section, after leveling, drying at 50-70°C for 3-10 minutes, and then sent to the ultraviolet light curing section for UV irradiation curing and crosslinking for 10-45s, the energy of UV irradiation curing is 500-1000mJ/cm2 ; UV paint It is a polyurethane acrylate UV coating, and toner is added for coloring; the specific method of spraying UV topcoat, leveling and UV curing can be: after spraying a layer of UV paint (the thickness of the paint layer is 15-25 μm) , into the infrared drying section, after leveling, drying at 50-70°C for 3-10 minutes, and then sent to the ultraviolet light curing section for UV irradiation curing and crosslinking for 10-45s, the energy of UV irradiation curing is 500-1000mJ /cm2 , the UV paint is polyurethane acrylate UV paint.
本发明没有采用氰化物的电镀来提高基材与镀层之间的结合力，而是采用阳极氧化及电泳技术来确保了锌合金的高耐蚀性、镀层与基材之间的结合力和高装饰性外观要求。The present invention does not use cyanide electroplating to improve the bonding force between the substrate and the coating, but uses anodic oxidation and electrophoresis technology to ensure the high corrosion resistance of the zinc alloy, the bonding force and high bonding force between the coating and the substrate. Decorative appearance requirements.
与现有的锌合金表面处理技术相比，本发明具有以下优点：Compared with the existing zinc alloy surface treatment technology, the present invention has the following advantages:
1）整个工艺流程采用绿色环保的表面处理方法进行处理，没有氰化物的电镀，减少了对环境的污染和人类的危害。1) The entire process is treated with a green and environmentally friendly surface treatment method, and there is no electroplating with cyanide, which reduces environmental pollution and human harm.
2）采用了锌合金的阳极氧化和电泳涂装处理，确保了锌合金的高耐蚀性要求。2) The anodic oxidation and electrophoretic coating treatment of zinc alloy are adopted to ensure the high corrosion resistance requirements of zinc alloy.
3）采用本发明生产的锌合金产品颜色与现有的水电镀6价铬颜色一致。3) The color of the zinc alloy product produced by the present invention is consistent with that of the existing water electroplating hexavalent chromium.
5）采用本发明生产的锌合金产品的抗耐蚀性高，CASS可通过16h，热淬火可通过150℃测试。5) The zinc alloy product produced by the present invention has high corrosion resistance, CASS can pass 16h, and heat quenching can pass 150°C test.
具体实施方式Detailed ways
以下实施例将对本发明作进一步的说明。The following examples will further illustrate the present invention.
实施例1Example 1
实施例1用来说明本发明的一种锌合金高耐蚀仿六价铬颜色的表面处理方法。Embodiment 1 is used to illustrate the surface treatment method of a kind of zinc alloy high corrosion resistance imitating hexavalent chromium color of the present invention.
（1）采用对抛光好的锌合金胚件采用超声波除蜡，其工艺配方为：广东三浮的除蜡剂SF-204 20ml/L，温度65℃，时间5min；超声波除油具体方法可采用Na3PO4 8g/L、K2CO3 30g/L，温度65℃，时间1min。(1) Ultrasonic dewaxing is used for polished zinc alloy blanks. The process formula is: Guangdong Sanfu dewaxing agent SF-204 20ml/L, temperature 65°C, time 5min; the specific method of ultrasonic degreasing can be used Na3 PO4 8g/L, K2 CO3 30g/L, temperature 65°C, time 1min.
（2）然后进行阳极氧化处理，工艺配方可采用氢氧化钠15g/L,温度45℃，时间8min，电流密度6A/dm2。阳极氧化处理处理后再经2道去离子水漂洗1min后进行电泳涂装。电泳涂装工艺配方可采用电解液成分：美国PPG公司PPG-EC-1800电泳漆，固体分质量分数9%，蒸馏水质量分数91%。电压：30V；时间：2.5min。电泳涂装后在去离子水槽中漂洗2min后进行烘干处理，烘干处理工艺为在150℃温度下烘60min。(2) Then carry out anodic oxidation treatment, the process formula can use sodium hydroxide 15g/L, temperature 45 ℃, time 8min, current density 6A/dm2. After the anodic oxidation treatment, the electrophoretic coating is carried out after rinsing with deionized water for 1 minute. The electrophoretic coating process formula can use electrolyte components: PPG company PPG-EC-1800 electrophoretic paint, solid content mass fraction 9%, distilled water mass fraction 91%. Voltage: 30V; Time: 2.5min. After electrophoretic coating, rinse in the deionized water tank for 2 minutes and then perform drying treatment. The drying treatment process is to bake at 150°C for 60 minutes.
（3）将锌合金胚件转挂放入UV喷漆线上进行喷UV底漆，喷镀一层UV漆后（漆层厚约30μm），送入红外线烘干段，进行流平、烘干（70℃×3min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间10s），UV照射固化的能量为1000mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料。(3) Put the zinc alloy blank into the UV painting line to spray UV primer, spray a layer of UV paint (the thickness of the paint layer is about 30μm), and send it to the infrared drying section for leveling and drying (70℃×3min), after leveling and drying, it is sent to the ultraviolet light curing section for UV irradiation curing and crosslinking (time 10s), and the energy of UV irradiation curing is 1000mJ/cm2 . UV paint is polyurethane acrylate UV paint.
（4）将锌合金胚件从UV喷漆线去下来，进行转挂，挂入PVD炉进行等离子体处理，等离子体处理的工艺条件可为离子源电流0.5A，偏压80V，占空比50%，氩气流速100SCCM，氧气流速10SCCM，炉内真空压力0.3Pa，活化时间10min，以达到活化表面之目的；所述PVD镀膜的工艺条件可为采用大功率直流电源，电流为50A，电压为400V，沉积时间为10min，偏压60V，占空比50%，氩气流速60SCCM。PVD镀膜所采用的靶材可为纯铬。(4) Remove the zinc alloy blank from the UV painting line, transfer it, and hang it into the PVD furnace for plasma treatment. The process conditions of the plasma treatment can be ion source current 0.5A, bias voltage 80V, duty cycle 50 %, the argon flow rate is 100SCCM, the oxygen flow rate is 10SCCM, the vacuum pressure in the furnace is 0.3Pa, and the activation time is 10min to achieve the purpose of activating the surface; the process conditions of the PVD coating can be high-power DC power supply, the current is 50A, and the voltage is 400V, the deposition time is 10min, the bias voltage is 60V, the duty cycle is 50%, and the argon flow rate is 60SCCM. The target used for PVD coating can be pure chromium.
（5）将锌合金胚件从PVD炉中取出，进行转挂、转入UV喷漆线上进行喷UV中漆，喷一层UV漆后（漆层厚约5μm），送入红外线烘干段，进行流平、烘干（50℃×10min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间10s），UV照射固化的能量为500mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料，并加入调色剂进行调色，调配出电镀6价铬金属的颜色。然后再进行喷UV面漆，喷一层UV漆后（漆层厚约25μm），送入红外线烘干段，进行流平、烘干（70℃×3min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间45s），UV照射固化的能量为500mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料。(5) Take the zinc alloy blank out of the PVD furnace, transfer it to the UV painting line for spraying UV intermediate paint, spray a layer of UV paint (the thickness of the paint layer is about 5 μm), and send it to the infrared drying section , for leveling and drying (50℃×10min), after leveling and drying, it is sent to the ultraviolet light curing section for UV irradiation curing and crosslinking (time 10s), and the energy of UV irradiation curing is 500mJ/cm2 . The UV paint is polyurethane acrylate UV paint, and toner is added for color matching, and the color of electroplated hexavalent chromium metal is formulated. Then spray UV topcoat. After spraying a layer of UV paint (the thickness of the paint layer is about 25μm), it is sent to the infrared drying section for leveling and drying (70℃×3min). After leveling and drying, it is sent to the The ultraviolet photocuring section carries out UV irradiation curing crosslinking (time 45s), and the energy of UV irradiation curing is 500mJ/cm2 . UV paint is polyurethane acrylate UV paint.
参照卫浴的标准，对锌合金绿色环保全干法产品进行以下测试标准进行测试：Referring to the standards of sanitary ware, the zinc alloy green environmental protection full dry method products are tested according to the following test standards:
1.CASS(防腐蚀测试ASTM B368-09)-----16h；1. CASS (corrosion test ASTM B368-09) ----- 16h;
2.AASS(盐雾测试ASTM G85-9)--------96h；2. AASS (salt spray test ASTM G85-9) --------96h;
3.冷热循环测试(ASME A112.18.1-2005/CSA B125.1-05)---4cycles；3. Cold and hot cycle test (ASME A112.18.1-2005/CSA B125.1-05)---4cycles;
4.落砂测试(ASTM D968-09,Method A)-----12liter;4. Falling sand test (ASTM D968-09, Method A)-----12liter;
5.水浸测试(ASTM D870-02)--------38±2℃×24h；5. Water immersion test (ASTM D870-02)-------38±2℃×24h;
6.耐化学性测试(ASTM D1308-02)--------Na OH 6mol/L;6. Chemical resistance test (ASTM D1308-02)-------Na OH 6mol/L;
7.铅笔硬度(ASTM D3363-05)----中华铅笔2H;7. Pencil hardness (ASTM D3363-05) - Chinese pencil 2H;
8.百割测试(ASTM D3359-09)------3B以上；8. Hundred cut test (ASTM D3359-09)------3B or above;
9.热淬火测试（ASTM B 571）--------150℃。9. Thermal quenching test (ASTM B 571) --------150°C.
结果如下：1.CASS 16h OK；2.AASS96h OK；3.冷热循环测试OK；4.落砂测试OK；5.水浸测试OK，没有颜色变化；6.耐化学性测试OK；7.铅笔硬度中华铅笔5H；8.百割测试5B；9.热淬火测试OK，无气泡、起皮等现象出现。The results are as follows: 1. CASS 16h OK; 2. AASS96h OK; 3. Cooling and heating cycle test OK; 4. Falling sand test OK; 5. Water immersion test OK, no color change; 6. Chemical resistance test OK; 7. Pencil hardness Chinese pencil 5H; 8. Hundred cutting test 5B; 9. Thermal quenching test OK, no bubbles, peeling and other phenomena.
实施例2Example 2
（1）采用对抛光好的锌合金胚件采用超声波除蜡，其工艺配方为：广东三浮的除蜡剂SF-20440ml/L，温度55℃，时间3min；超声波除油具体方法可采用Na3PO4 8g/L、K2CO3 30g/L，温度55℃，时间1min。(1) Ultrasonic dewaxing is used for polished zinc alloy blanks. The process formula is: Guangdong Sanfu dewaxing agent SF-20440ml/L, temperature 55°C, time 3min; the specific method of ultrasonic degreasing can be Na3 PO4 8g/L, K2 CO3 30g/L, temperature 55°C, time 1min.
（2）然后进行阳极氧化处理，工艺配方可采用氢氧化钠20g/L,温度45℃，时间5min，电流密度6A/dm2。阳极氧化处理处理后再经2道去离子水漂洗1min后进行电泳涂装。电泳涂装工艺配方可采用电解液成分：美国PPG公司PPG-EC-1800电泳漆，固体分质量分数12%，蒸馏水质量分数88%。电压：60V；时间：1.5min。电泳涂装后在去离子水槽中漂洗1min后进行烘干处理，烘干处理工艺为在170℃温度下烘40min。(2) Then carry out anodic oxidation treatment, the process formula can use sodium hydroxide 20g/L, temperature 45 ℃, time 5min, current density 6A/dm2. After the anodic oxidation treatment, the electrophoretic coating is carried out after rinsing with deionized water for 1 minute. The electrophoretic coating process formula can use electrolyte components: PPG-EC-1800 electrophoretic paint from American PPG company, the mass fraction of solids is 12%, and the mass fraction of distilled water is 88%. Voltage: 60V; Time: 1.5min. After electrophoretic coating, rinse in a deionized water tank for 1 minute and then dry. The drying process is to dry at 170 ° C for 40 minutes.
（3）将锌合金胚件转挂放入UV喷漆线上进行喷UV底漆，喷镀一层UV漆后（漆层厚15μm），送入红外线烘干段，进行流平、烘干（50℃×10min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间45s），UV照射固化的能量为500mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料。(3) Put the zinc alloy blank into the UV painting line to spray UV primer, spray a layer of UV paint (the thickness of the paint layer is 15 μm), and send it to the infrared drying section for leveling and drying ( 50℃×10min), after leveling and drying, it is sent to the ultraviolet light curing section for UV irradiation curing and crosslinking (time 45s), and the energy of UV irradiation curing is 500mJ/cm2 . UV paint is polyurethane acrylate UV paint.
（4）将锌合金胚件从UV喷漆线去下来，进行转挂，挂入PVD炉进行等离子体处理，等离子体处理的工艺条件可为离子源电流0.3A，偏压150V，占空比80%，氩气流速10SCCM，氧气流速100SCCM，炉内真空压力0.3Pa，活化时间5min，以达到活化表面之目的；所述PVD镀膜的工艺条件可为采用大功率中频电源，电流为300A，电压为800V，沉积时间为0.5min，偏压20V，占空比80%，氩气流速200SCCM。PVD镀膜所采用的靶材可为纯银。(4) Remove the zinc alloy blank from the UV painting line, transfer it, and hang it into a PVD furnace for plasma treatment. The process conditions of the plasma treatment can be ion source current 0.3A, bias voltage 150V, duty cycle 80 %, the argon flow rate is 10SCCM, the oxygen flow rate is 100SCCM, the vacuum pressure in the furnace is 0.3Pa, and the activation time is 5min to achieve the purpose of activating the surface; the process conditions of the PVD coating can be high-power intermediate frequency power supply, the current is 300A, and the voltage is 800V, the deposition time is 0.5min, the bias voltage is 20V, the duty cycle is 80%, and the argon flow rate is 200SCCM. The target material used for PVD coating can be pure silver.
（5）将锌合金胚件从PVD炉中取出，进行转挂、转入UV喷漆线上进行喷UV中漆，喷一层UV漆后（漆层厚约10μm），送入红外线烘干段，进行流平、烘干（70℃×3min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间45s），UV照射固化的能量为1000mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料，并加入调色剂进行调色，调配出电镀6价铬金属的颜色。然后再进行喷UV面漆，喷一层UV漆后（漆层厚约15μm），送入红外线烘干段，进行流平、烘干（50℃×10min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间10s），UV照射固化的能量为1000mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料。(5) Take the zinc alloy blank out of the PVD furnace, transfer it to the UV painting line for spraying UV intermediate paint, spray a layer of UV paint (the thickness of the paint layer is about 10 μm), and send it to the infrared drying section , for leveling and drying (70℃×3min), after leveling and drying, it is sent to the ultraviolet light curing section for UV irradiation curing and crosslinking (time 45s), and the energy of UV irradiation curing is 1000mJ/cm2 . The UV paint is polyurethane acrylate UV paint, and toner is added for color matching, and the color of electroplated hexavalent chromium metal is formulated. Then spray UV topcoat, after spraying a layer of UV paint (the thickness of the paint layer is about 15μm), it is sent to the infrared drying section for leveling and drying (50℃×10min), after leveling and drying, it is sent to the The ultraviolet light curing section performs UV irradiation curing and crosslinking (time 10s), and the energy of UV irradiation curing is 1000mJ/cm2 . UV paint is polyurethane acrylate UV paint.
参照卫浴的标准，对锌合金绿色环保全干法产品进行以下测试标准进行测试：Referring to the standards of sanitary ware, the zinc alloy green environmental protection full dry method products are tested according to the following test standards:
1．CASS(防腐蚀测试ASTM B368-09)-----16h；1. CASS (corrosion test ASTM B368-09) ----- 16h;
2．AASS(盐雾测试ASTM G85-9)--------96h；2. AASS (salt spray test ASTM G85-9) --------96h;
3．冷热循环测试(ASME A112.18.1-2005/CSAB125.1-05)---4cycles；3. Hot and cold cycle test (ASME A112.18.1-2005/CSAB125.1-05)---4cycles;
4．落砂测试(ASTM D968-09,Method A)-----12liter;4. Falling sand test (ASTM D968-09, Method A)-----12liter;
5．水浸测试(ASTM D870-02)--------38±2℃×24h；5. Water immersion test (ASTM D870-02)-------38±2℃×24h;
6．耐化学性测试(ASTM D1308-02)--------Na OH6mol/L;6. Chemical resistance test (ASTM D1308-02)-------Na OH6mol/L;
7．铅笔硬度(ASTM D3363-05)----中华铅笔2H;7. Pencil hardness (ASTM D3363-05)----Chinese pencil 2H;
8．百割测试(ASTM D3359-09)------3B以上；8. Hundred cut test (ASTM D3359-09)------3B or above;
9．热淬火测试（ASTM B571）--------150℃。9. Heat Quenching Test (ASTM B571) --------150℃.
结果如下：1.CASS 16h OK；2.AASS 96h OK；3.冷热循环测试OK；4.落砂测试OK；5.水浸测试OK，没有颜色变化；6.耐化学性测试OK；7.铅笔硬度中华铅笔4H；8.百割测试5B；9.热淬火测试OK，无气泡、起皮等现象出现。The results are as follows: 1. CASS 16h OK; 2. AASS 96h OK; 3. Cooling and heating cycle test OK; 4. Falling sand test OK; 5. Water immersion test OK, no color change; 6. Chemical resistance test OK; 7 .Pencil hardness Chinese pencil 4H; 8. Hundred cut test 5B; 9. Thermal quenching test OK, no bubbles, peeling and other phenomena.
实施例3Example 3
（1）采用对抛光好的锌合金胚件采用超声波除蜡，其工艺配方为：广东三浮的除蜡剂SF-204 30ml/L，温度60℃，时间4min；超声波除油具体方法可采用Na3PO4 10g/L、K2CO325g/L，温度60℃，时间1.5min。(1) Ultrasonic dewaxing is used for polished zinc alloy blanks. The process formula is: Guangdong Sanfu dewaxing agent SF-204 30ml/L, temperature 60°C, time 4min; the specific method of ultrasonic degreasing can be used Na3 PO4 10g/L, K2 CO3 25g/L, temperature 60°C, time 1.5min.
（2）然后进行阳极氧化处理，工艺配方可采用氢氧化钠18g/L,温度42℃，时间6min，电流密度8A/dm2。阳极氧化处理处理后再经2道去离子水漂洗1.5min后进行电泳涂装。电泳涂装工艺配方可采用电解液成分:美国PPG公司PPG-EC-1800电泳漆，固体分质量分数10%，蒸馏水质量分数90%。电压：50V；时间：2min。电泳涂装后在去离子水槽中漂洗1.5min后进行烘干处理，烘干处理工艺为在160℃温度下烘50min。(2) Then carry out anodic oxidation treatment, the process formula can use sodium hydroxide 18g/L, temperature 42 ℃, time 6min, current density 8A/dm2. After anodic oxidation treatment, rinse with deionized water for 1.5 minutes before electrophoretic coating. The electrophoretic coating process formula can use electrolyte components: PPG-EC-1800 electrophoretic paint from PPG Company of the United States, the mass fraction of solids is 10%, and the mass fraction of distilled water is 90%. Voltage: 50V; Time: 2min. After electrophoretic coating, rinse in a deionized water tank for 1.5 minutes and then dry. The drying process is to dry at 160 ° C for 50 minutes.
（3）将锌合金胚件转挂放入UV喷漆线上进行喷UV底漆，喷镀一层UV漆后（漆层厚20μm），送入红外线烘干段，进行流平、烘干（60℃×7min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间30s），UV照射固化的能量为800mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料。(3) Put the zinc alloy blank into the UV painting line to spray UV primer, spray a layer of UV paint (the thickness of the paint layer is 20μm), and send it to the infrared drying section for leveling and drying ( 60℃×7min), after leveling and drying, it is sent to the ultraviolet light curing section for UV irradiation curing and crosslinking (time 30s), and the energy of UV irradiation curing is 800mJ/cm2 . UV paint is polyurethane acrylate UV paint.
（4）将锌合金胚件从UV喷漆线去下来，进行转挂，挂入PVD炉进行等离子体处理，等离子体处理的工艺条件可为离子源电流0.4A，偏压100V，占空比60%，氩气流速50SCCM，氧气流速10SCCM，炉内真空压力0.1Pa，活化时间6min，以达到活化表面之目的；所述PVD镀膜的工艺条件可为采用大功率直流电源，电流为100A，电压为500V，沉积时间为2min，偏压40V，占空比60%，氩气流速100SCCM。PVD镀膜所采用的靶材可为纯锑。(4) Remove the zinc alloy blank from the UV painting line, transfer it, and hang it into the PVD furnace for plasma treatment. The process conditions of the plasma treatment can be ion source current 0.4A, bias voltage 100V, duty cycle 60 %, the argon flow rate is 50SCCM, the oxygen flow rate is 10SCCM, the vacuum pressure in the furnace is 0.1Pa, and the activation time is 6min, so as to achieve the purpose of activating the surface; the process conditions of the PVD coating can be high-power DC power supply, the current is 100A, and the voltage is 500V, the deposition time is 2min, the bias voltage is 40V, the duty cycle is 60%, and the argon flow rate is 100SCCM. The target used for PVD coating can be pure antimony.
（5）将锌合金胚件从PVD炉中取出，进行转挂、转入UV喷漆线上进行喷UV中漆，喷一层UV漆后（漆层厚约8μm），送入红外线烘干段，进行流平、烘干（60℃×5min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间30s），UV照射固化的能量为800mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料，并加入调色剂进行调色，调配出电镀6价铬金属的颜色。然后再进行喷UV面漆，喷一层UV漆后（漆层厚约10μm），送入红外线烘干段，进行流平、烘干（60℃×15min），流平、烘干后送入紫外线光固化段进行UV照射固化交联（时间30s），UV照射固化的能量为800mJ/cm2。UV漆为聚氨酯丙烯酸酯类UV涂料。(5) Take the zinc alloy blank out of the PVD furnace, transfer it to the UV painting line for spraying UV intermediate paint, spray a layer of UV paint (the thickness of the paint layer is about 8 μm), and send it to the infrared drying section , for leveling and drying (60°C×5min), after leveling and drying, it is sent to the ultraviolet light curing section for UV irradiation curing and crosslinking (time 30s), and the energy of UV irradiation curing is 800mJ/cm2 . The UV paint is polyurethane acrylate UV paint, and toner is added for color matching, and the color of electroplated hexavalent chromium metal is formulated. Then spray UV topcoat, after spraying a layer of UV paint (the thickness of the paint layer is about 10μm), it is sent to the infrared drying section for leveling and drying (60℃×15min), after leveling and drying, it is sent to the The ultraviolet light curing section performs UV irradiation curing and crosslinking (time 30s), and the energy of UV irradiation curing is 800mJ/cm2 . UV paint is polyurethane acrylate UV paint.
参照卫浴的标准，对锌合金绿色环保全干法产品进行以下测试标准进行测试：Referring to the standards of sanitary ware, the zinc alloy green environmental protection full dry method products are tested according to the following test standards:
1．CASS(防腐蚀测试ASTM B368-09)-----16h；1. CASS (corrosion test ASTM B368-09) ----- 16h;
2．AASS(盐雾测试ASTM G85-9)--------96h；2. AASS (salt spray test ASTM G85-9) --------96h;
3．冷热循环测试(ASME A112.18.1-2005/CSA B125.1-05)---4cycles；3. Hot and cold cycle test (ASME A112.18.1-2005/CSA B125.1-05)---4cycles;
4．落砂测试(ASTM D968-09,Method A)-----12liter;4. Falling sand test (ASTM D968-09, Method A)-----12liter;
5．水浸测试(ASTM D870-02)--------38±2℃×24h；5. Water immersion test (ASTM D870-02)-------38±2℃×24h;
6．耐化学性测试(ASTM D1308-02)--------Na OH6mol/L;6. Chemical resistance test (ASTM D1308-02)-------Na OH6mol/L;
7．铅笔硬度(ASTM D3363-05)---中华铅笔2H;7. Pencil hardness (ASTM D3363-05)---Chinese pencil 2H;
8．百割测试(ASTM D3359-09)------3B以上；8. Hundred cut test (ASTM D3359-09)------3B or above;
9．热淬火测试（ASTM B571）--------150℃。9. Heat Quenching Test (ASTM B571) --------150℃.
结果如下：1.CASS 16h OK；2.AASS 96h OK；3.冷热循环测试OK；4.落砂测试OK；5.水浸测试OK，没有颜色变化；6.耐化学性测试OK；7.铅笔硬度中华铅笔6H；8.百割测试5B；9.热淬火测试OK,无气泡、起皮等现象出现。The results are as follows: 1. CASS 16h OK; 2. AASS 96h OK; 3. Cooling and heating cycle test OK; 4. Falling sand test OK; 5. Water immersion test OK, no color change; 6. Chemical resistance test OK; 7 .Pencil hardness Chinese pencil 6H; 8. Hundred cutting test 5B; 9. Thermal quenching test OK, no bubbles, peeling and other phenomena.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210270312.5ACN102758237B (en) | 2012-07-31 | 2012-07-31 | High-corrosion-resistance surface treatment method of zinc alloy by hexavalent chrome color emulation |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210270312.5ACN102758237B (en) | 2012-07-31 | 2012-07-31 | High-corrosion-resistance surface treatment method of zinc alloy by hexavalent chrome color emulation |
| Publication Number | Publication Date |
|---|---|
| CN102758237A CN102758237A (en) | 2012-10-31 |
| CN102758237Btrue CN102758237B (en) | 2015-01-28 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210270312.5AExpired - Fee RelatedCN102758237B (en) | 2012-07-31 | 2012-07-31 | High-corrosion-resistance surface treatment method of zinc alloy by hexavalent chrome color emulation |
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| CN (1) | CN102758237B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104099616B (en)* | 2014-07-22 | 2016-03-30 | 宁波威霖住宅设施有限公司 | The chromic surface treatment method of the imitative plating of a kind of zinc alloy high-hardness wear-resistant |
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| CN107159541A (en)* | 2017-04-26 | 2017-09-15 | 句容市江电电器机械有限公司 | A kind of surface of workpiece processing method |
| CN108118381A (en)* | 2018-01-23 | 2018-06-05 | 滁州英诺信电器有限公司 | Coating Materials prints anti-oxidation technique |
| CN109402554A (en)* | 2018-09-30 | 2019-03-01 | 柳州科沃塑业有限公司 | A kind of method for plating metal on surface of plastic products |
| CN110314825A (en)* | 2019-04-29 | 2019-10-11 | 东莞市洪骏实业科技有限公司 | Automatic spraying process based on nano water-based paint application |
| CN112439660A (en)* | 2019-08-30 | 2021-03-05 | 烟台霍富汽车锁有限公司 | Spraying method for surface of automobile door lock |
| CN115369408A (en)* | 2022-06-27 | 2022-11-22 | 重庆市桦悦机电设备有限公司 | Equipment and method for surface treatment of notebook metal case |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1031725A (en)* | 1987-06-24 | 1989-03-15 | 福建师范大学 | The manufacture method of ABS plastic base lead dioxide electrode |
| CN1324412A (en)* | 1998-10-02 | 2001-11-28 | Nkt研究中心有限公司 | Method for metallizing surface of a solid polymer substrate and the product obtd. |
| CN1397993A (en)* | 2001-06-19 | 2003-02-19 | 联华电子股份有限公司 | Formation method of plug metal layer |
| CN1404175A (en)* | 2002-09-16 | 2003-03-19 | 华南师范大学 | Surface treatment method with cog structure on inner surface of cathode current collector of alkaline zinc-manganese battery |
| CN1559618A (en)* | 2003-12-26 | 2005-01-05 | 淮阴工学院 | Nano air purification net and its manufacturing method |
| CN1641857A (en)* | 2004-01-15 | 2005-07-20 | 台湾积体电路制造股份有限公司 | copper metallization process |
| CN1936103A (en)* | 2006-09-26 | 2007-03-28 | 梁刚 | Magnesiumalloy surface modifying method |
| CN101200128A (en)* | 2006-12-15 | 2008-06-18 | 比亚迪股份有限公司 | A kind of zinc alloy product and preparation method thereof |
| CN101597784A (en)* | 2008-06-04 | 2009-12-09 | 比亚迪股份有限公司 | A kind of hole sealing method of anodized film of light metal material |
| CN101922010A (en)* | 2009-06-16 | 2010-12-22 | 比亚迪股份有限公司 | A kind of aluminum alloy surface treatment method |
| CN101423967B (en)* | 2007-10-31 | 2011-05-18 | 比亚迪股份有限公司 | Surface treating method of aluminum alloy material |
| CN102151437A (en)* | 2011-01-28 | 2011-08-17 | 厦门建霖工业有限公司 | PP (polypropylene) filter paper with functions of resisting bacteria, dechlorinating and removing heavy metal ions and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031725A (en)* | 1987-06-24 | 1989-03-15 | 福建师范大学 | The manufacture method of ABS plastic base lead dioxide electrode |
| CN1324412A (en)* | 1998-10-02 | 2001-11-28 | Nkt研究中心有限公司 | Method for metallizing surface of a solid polymer substrate and the product obtd. |
| CN1397993A (en)* | 2001-06-19 | 2003-02-19 | 联华电子股份有限公司 | Formation method of plug metal layer |
| CN1404175A (en)* | 2002-09-16 | 2003-03-19 | 华南师范大学 | Surface treatment method with cog structure on inner surface of cathode current collector of alkaline zinc-manganese battery |
| CN1559618A (en)* | 2003-12-26 | 2005-01-05 | 淮阴工学院 | Nano air purification net and its manufacturing method |
| CN1641857A (en)* | 2004-01-15 | 2005-07-20 | 台湾积体电路制造股份有限公司 | copper metallization process |
| CN1936103A (en)* | 2006-09-26 | 2007-03-28 | 梁刚 | Magnesiumalloy surface modifying method |
| CN101200128A (en)* | 2006-12-15 | 2008-06-18 | 比亚迪股份有限公司 | A kind of zinc alloy product and preparation method thereof |
| CN101423967B (en)* | 2007-10-31 | 2011-05-18 | 比亚迪股份有限公司 | Surface treating method of aluminum alloy material |
| CN101597784A (en)* | 2008-06-04 | 2009-12-09 | 比亚迪股份有限公司 | A kind of hole sealing method of anodized film of light metal material |
| CN101922010A (en)* | 2009-06-16 | 2010-12-22 | 比亚迪股份有限公司 | A kind of aluminum alloy surface treatment method |
| CN102151437A (en)* | 2011-01-28 | 2011-08-17 | 厦门建霖工业有限公司 | PP (polypropylene) filter paper with functions of resisting bacteria, dechlorinating and removing heavy metal ions and preparation method thereof |
| Publication number | Publication date |
|---|---|
| CN102758237A (en) | 2012-10-31 |
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| CP03 | Change of name, title or address | Address after:Tianfeng road in Jimei District of Xiamen City, Fujian Province, No. 69 361000 Patentee after:Runner (Xiamen) Corp. Address before:361000, room 12, building 1208, lotus tower, 859 Lotus Road, Fujian, Xiamen Patentee before:Xiamen Runner Industrial Corp. | |
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| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20150128 | |
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