WO2022007505A1 - 一种用以替代热扩散电镀线磷化的清洗方法 - Google Patents

一种用以替代热扩散电镀线磷化的清洗方法 Download PDF

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WO2022007505A1
WO2022007505A1 PCT/CN2021/094556 CN2021094556W WO2022007505A1 WO 2022007505 A1 WO2022007505 A1 WO 2022007505A1 CN 2021094556 W CN2021094556 W CN 2021094556W WO 2022007505 A1 WO2022007505 A1 WO 2022007505A1
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cleaning
tank
phosphorus
znso
free
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PCT/CN2021/094556
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English (en)
French (fr)
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刘祥
姚利丽
李呐
冯国兵
苗为钢
华欣
魏于博
封恒
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江苏兴达钢帘线股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/081—Iron or steel solutions containing H2SO4
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/20—Regeneration of process solutions of rinse-solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a cleaning method for replacing phosphating of thermal diffusion electroplating lines, and belongs to the technical field of electroplating line cleaning technology.
  • the Zn on the surface of the steel wire will be oxidized to ZnO after the intermediate frequency heating. Because ZnO is a hard and low plastic material, it is not easy to deform in the subsequent production and cause the steel wire to be drawn and broken. Therefore, After thermal diffusion, the steel wire needs to be pickled to remove surface oxides.
  • the intermediate frequency post-cleaning process of the thermal diffusion plating line is phosphating, that is, using phosphoric acid to wash off ZnO and other oxides on the surface of the steel wire.
  • industrial phosphate wastewater contains high phosphorus concentration, which is expensive in terms of treatment cost and regeneration process.
  • phosphorus-containing substances are a basic nutrient salt.
  • the technical problem to be solved by the present invention is to overcome the defects of the prior art and provide a phosphorus-free cleaning solution with low cost and no pollution, which is used to replace the phosphating cleaning method of thermal diffusion electroplating lines.
  • the technical scheme adopted in the present invention is:
  • a cleaning method for replacing the phosphating of thermal diffusion electroplating lines The steel wire is cleaned with a phosphorus-free cleaning solution.
  • the phosphorus-free cleaning solution is composed of H 2 SO 4 , ZnSO 4 and pure water.
  • the phosphorus-free cleaning solution is placed in a cleaning tank.
  • An adjustment tank is set between the galvanizing tank and the phosphorus-free cleaning tank. The galvanizing tank and the phosphorus-free cleaning tank, the galvanizing tank and the adjustment tank, and the phosphorus-free cleaning tank and the adjustment tank are connected by pipes.
  • the solution in the phosphorus-free cleaning tank is directly refluxed to the galvanizing tank, and at the same time, the new solution in the galvanizing tank is supplemented by the adjustment tank into the phosphorus-free cleaning tank.
  • the initial cleaning solution in the phosphorus-free cleaning tank directly takes part of the solution of the galvanizing tank, and then adds new H 2 SO 4 and pure water to the adjustment tank to make the cleaning solution pH 1 ⁇ 2, ZnSO 4 concentration 100 ⁇ 160g/L.
  • Appropriate addition of ZnSO 4 avoids excessive pickling or dirty water, and the cleaning solution is replenished frequently if the concentration is too high, which is unfavorable for pickling.
  • the cleaning tank will directly return part of the cleaning solution to the galvanizing tank, and then circulate the new solution through the adjustment tank.
  • the pH and ZnSO 4 concentration of the phosphorus-free cleaning solution can be kept in a relatively stable state by adjusting the function of the tank according to actual needs.
  • the time for the steel wire to pass through the cleaning solution is controlled within 1.5 to 3.5 seconds to avoid dirty cleaning or over-pickling.
  • the present invention provides a cleaning method for replacing the phosphating of thermal diffusion electroplating lines.
  • the H 2 SO 4 /ZnSO 4 cleaning solution with a certain pH and concentration is used to replace phosphoric acid to clean the ZnO on the surface of the steel wire.
  • the electroplated steel wire obtained by the above cleaning solution is tested for ZnO on its surface to meet the requirements of subsequent wet drawing.
  • the steel wire processed by this cleaning solution is similar to conventional phosphating in the effect of electroplating, wet drawing or plying process. ,;
  • the raw materials of the cleaning solution are cheap and easy to obtain, and the cleaning level can reach conventional phosphating, which saves the cost of electroplating production, and does not produce industrial waste water.
  • the concentration of H 2 SO 4 /ZnSO 4 solution can be supplemented and updated after reaching a certain value. At the same time, part of the old liquid can be directly returned to the galvanizing tank for recycling, which avoids the loss of Zn.
  • Fig. 1 is a kind of process flow schematic diagram of the cleaning technology that replaces thermal diffusion electroplating line phosphating of the present invention
  • Fig. 2 is different cleaning process steel wire surface ZnO content in the embodiment
  • FIG. 3 shows the adhesion of different customer sizing materials for samples of cords with different cleaning processes in the embodiment.
  • the thermal diffusion electroplating process is copper plating first, then galvanizing, and then thermal diffusion, and phosphating is used to clean the surface of the steel wire after thermal diffusion.
  • the above cleaning solution can directly replace the phosphoric acid in the phosphating tank at room temperature without adding new cleaning equipment. After the steel wire is thermally diffused, it goes through a phosphorus-free cleaning solution to remove the surface ZnO.
  • the electroplating line is a 42-head production line, and the steel wire specification is ⁇ 1.20mm.
  • Part of the solution from the galvanizing tank was pumped into the adjustment tank, diluted with water in the adjustment tank, and 50% H 2 SO 4 was added to prepare a H 2 SO 4 /ZnSO 4 cleaning solution with a pH of 1.0 and a ZnSO 4 concentration of 130g/L , After the preparation is completed, the solution is pumped into the phosphorus-free cleaning tank of the electroplating line, and the steel wire is immersed in the cleaning solution after being cooled by thermal diffusion water.
  • pH measurement was carried out every day, and ZnSO 4 concentration was measured every three days. pH adjustment is additionally added every 12h 50% H 2 SO 4 five kilograms.
  • the replacement cycle is normally about 15 days.
  • the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 130g/L
  • the steel wire cleaning time is 2s
  • the ZnO content on the surface of the steel wire is detected to be 26.5mg/m 2 , which meets the requirements of wet drawing.
  • This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 1.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 130g/L, the cleaning time of the steel wire is 2s, and the content of ZnO on the surface of the steel wire is 32.3 mg/m 2 . , to meet the needs of wet drawing.
  • This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 2.0, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 130 g/L, the cleaning time of the steel wire is 2 s, and the ZnO content on the surface of the steel wire is 36.9 mg/m 2 . , to meet the needs of wet drawing.
  • This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 1.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 102 g/L, the cleaning time of the steel wire is 2 s, and the ZnO content on the surface of the steel wire is detected to be 30.7 mg/m 2 , to meet the needs of wet drawing.
  • This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 1.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 160 g/L, the cleaning time of the steel wire is 2 s, and the ZnO content on the surface of the steel wire is detected as 33.5 mg/m 2 , to meet the needs of wet drawing.
  • This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 1.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 130 g/L, the cleaning time of the steel wire is 1.5 s, and the ZnO content on the surface of the steel wire is 37.0 mg/m. 2 , to meet the needs of wet drawing.
  • This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 1.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 130g/L, the cleaning time of the steel wire is 3.5s, and the content of ZnO on the surface of the steel wire is 38.6 mg/m. 2 , to meet the needs of wet drawing.
  • This example is the same as Example 1, except that when the pH of the cleaning solution is 0.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 130g/L, the cleaning time of the steel wire is 2s, and the content of ZnO on the surface of the steel wire is 89.2 mg/m 2 . , is not conducive to wet drawing. If the pH is too low, the surface of the steel wire is prone to acidity after cleaning, resulting in secondary oxidation or dissolution of zinc.
  • This example is the same as Example 1, except that when the pH of the cleaning solution is 2.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 130g/L, the cleaning time of the steel wire is 2s, and the content of ZnO on the surface of the steel wire is 110.5 mg/m 2 , is not conducive to wet drawing. The pH is too high for pickling.
  • Example 2 This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 1.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 225g/L, the cleaning time of the steel wire is 0.5s, and the content of ZnO on the surface of the steel wire is 76.2 mg/m. 2. It is not conducive to wet drawing. The cleaning time is too short and the cleaning is not clean.
  • Example 2 This example is the same as Example 1, the difference is that when the pH of the cleaning solution is 1.5, the concentration of ZnSO 4 is H 2 SO 4 /ZnSO 4 of 225g/L, the cleaning time of the steel wire is 4s, and the cleaning time is too long, which will easily lead to the difference between the percentage of copper and zinc in the coating The original design is out of balance, and the zinc is excessively dissolved.
  • Figure 2 is a graph of the detection data of ZnO on the steel wire surface produced by different cleaning processes.
  • S and P are H 2 SO 4 /ZnSO 4 and phosphating process, respectively. It can be seen from the figure that the average content of ZnO on the steel wire surface of the two processes is basically the same, which also shows that the cleaning effect of the H 2 SO 4 /ZnSO 4 process can reach the level of the phosphating process.
  • Table 1 shows the wet drawing yield and ply breakage rate of samples produced by different cleaning processes. It can be seen from Table 1 that the wet drawing yields of the two steel wires are similar, and the H 2 SO 4 /ZnSO 4 washing process steel wire is not seen during the drawing process. There are broken wires. It can be seen that the electroplated steel wire cleaned by H 2 SO 4 /ZnSO 4 can adapt to the existing wet drawing lubricant, and the drawing effect is not lower than that of the phosphating process steel wire. During the plying process, the ton of flat broken wires of the H 2 SO 4 /ZnSO 4 process cord is 0.7 times/ton, which is not higher than that of the phosphating process cord. It can be seen that the plying process performance can reach the level of the phosphating process.
  • Figure 3 shows the vulcanization test of 6 rubber compounds for two cleaning process cords, respectively.
  • the six rubber compounds correspond to A, B, C, D, E and F respectively.
  • the left side of the spectrum is the adhesion pull-out force, that is bar graph area, the right spectrum of H 2 SO 4 / ZnSO 4 phosphating process with conventional processes cords cord adhesion percentage difference ((F S -F P) / F P * 100%), That is, the line graph area.
  • the ratio of the difference in the adhesion of the six kinds of rubbers between the H 2 SO 4 /ZnSO 4 washing process cord and the phosphating process cord is between -6% and 16%, and it is more positive and more, so H 2 SO 4 / ZnSO 4 phosphating process with washing cord adhesion values significantly lower compared to no signs in multiple sizes, which also shows the H 2 SO 4 / ZnSO 4 scrubbing process of the cords of the compound The applicability is not lower than that of the phosphating process cord.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

本发明公开了一种用以替代热扩散电镀线磷化的清洗方法，采用无磷清洗液清洗钢丝，无磷清洗液由H 2SO 4、ZnSO 4和纯水组成，无磷清洗液放置在清洗槽内，在镀锌槽与无磷清洗槽之间设置调节槽，镀锌槽与无磷清洗槽、镀锌槽与调节槽之间以及无磷清洗槽与调节槽之间以管道连接，当清洗槽内ZnSO 4浓度过高时，清洗槽内溶液直接回流至镀锌槽，同时通过调节槽补充添加镀锌槽中新液进清洗槽。本发明的一种用以替代热扩散电镀线磷化的清洗方法，能够替代含磷清洗液，成本低廉且不产生污染。

Description

一种用以替代热扩散电镀线磷化的清洗方法 技术领域
本发明涉及一种用以替代热扩散电镀线磷化的清洗方法，属于电镀线清洗工艺技术领域。
背景技术
钢帘线生产过程中的电镀工序，钢丝经中频加热后表面部分Zn会氧化为ZnO，由于ZnO是一种硬而塑性低的物质，后道生产中不易变形而造成钢丝拉拔断丝，因此热扩散后钢丝需经酸洗去除表面氧化物质。热扩散电镀线中频后清洗工艺为磷化，即利用磷酸洗去钢丝表面ZnO及其它少许氧化物。但工业磷酸盐废水含磷浓度高，无论是处理成本或是再生工艺花费都较高昂，且含磷物质作为一种基本营养盐，水体中过量的磷会造成富营养化滋生大量藻类和浮游生物，使水体质量恶化。工业含磷废水的排放是磷排放主要方式之一，而电镀磷化废水是工业含磷废水的一种，因此随着国家对环保要求的逐步提高以及可持续发展战略考虑，含磷工艺的使用应尽量避免。
发明内容
本发明要解决的技术问题是，克服现有技术的缺陷，提供一种成本较低且不产生污染的无磷清洗液，用以替代热扩散电镀线磷化的清洗方法。
为解决上述技术问题，本发明采用的技术方案为：
一种用以替代热扩散电镀线磷化的清洗方法，采用无磷清洗液清洗钢丝，无磷清洗液由H 2SO 4、ZnSO 4和纯水组成，无磷清洗液放置在清洗槽内，在镀锌槽与无磷清洗槽之间设置调节槽，镀锌槽与无磷清洗槽、镀锌槽与调节槽以及无磷清洗槽与调节槽之间以管道连接，当无磷清洗槽内ZnSO 4浓度过高时，无磷清洗槽内溶液直接回流至镀锌槽，同时通过调节槽补充添加镀锌槽中新液进无磷清洗槽。
无磷清洗槽内初始清洗液直接取用镀锌槽的部分溶液，然后在调节槽中添加新的H 2SO 4和纯水，使清洗液达到pH在1～2，ZnSO 4浓度为100～160g/L。适当ZnSO 4的加入避免了酸洗过度或水洗不净，浓度太高清洗液补充频繁，不利酸洗。
清洗液在生产工作中，当ZnSO 4的浓度达到200～220g/L时，清洗槽将部分清洗液直接回流至镀锌槽，再通过调节槽循环补充新液。生产过程中可根据实际需要，通过调节槽的作用，使无磷清洗液的pH和ZnSO 4浓度保持在较稳定的状态。
可选择将无磷清洗槽1/2体积的旧液排入镀锌槽，并补充1/2体积的新液。
钢丝经过清洗液的时间控制在1.5～3.5s，以避免清洗不净或过酸洗。
试验期间每天进行pH的检测，ZnSO 4浓度为每三天检测一次。
本发明的有益效果：本发明提供一种用以替代热扩散电镀线磷化的清洗方法，用一定pH和浓度的H 2SO 4/ZnSO 4清洗液取代磷酸，用以清洗钢丝表面ZnO，经过上述清洗液得到的电镀钢丝，对其表面ZnO进行检测，满足后道湿式拉拔的要求，此清洗液处理的钢丝无论是在电镀、湿拉或合股工序所能达到的效果与常规磷化相近，；清洗液原料价廉易得，清洗水平可以达到常规磷化，节约了电镀生产成本，且不产生工业废水，清洗后的H 2SO 4/ZnSO 4溶液浓度达到一定值后可补充更新，同时部分旧液可直接回到镀锌槽回收利用，此方法避免了Zn的流失。
附图说明
图1为本发明一种替代热扩散电镀线磷化的清洗技术的工艺流程示意图；
图2为实施例中不同清洗工艺钢丝表面ZnO含量；
图3为实施例不同清洗工艺帘线样品的不同客户胶料粘合力。
具体实施方式
下面结合附图对本发明作进一步描述，以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
如图1所示，热扩散电镀工艺为先镀铜、后镀锌、再经过热扩散，磷化在热扩散之后用于清洗钢丝表面氧化物质。而上述清洗液在常温状态可直接替换掉磷化槽的磷酸，无需增加新的清洗设备。钢丝热扩散后经过无磷清洗液，用以去除表面ZnO。
实施例1
电镀线为42根头生产线，处理钢丝规格为Φ1.20mm。将镀锌槽的部分溶液泵入调节槽，在调节槽中加水稀释，并添加50％H 2SO 4配制成pH为1.0、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4清洗液，配制完成后溶液泵入电镀线无磷清洗槽中，钢丝经过热扩散水冷却后浸入清洗液。试验期间每天进行pH的检测，ZnSO 4浓度为每三天检测一次。pH的调节为每12h补充添加50％H 2SO 4五千克。当ZnSO 4浓度检测在200～220g/L时，同时打开调节槽与清洗槽以及清洗槽与镀锌槽的管道开关，将约1/2体积的旧液排入镀锌槽，并补充1/2体积的新液，更换周期正常为15天左右。
当清洗液pH为1.0、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4，钢丝清洗时间2s，检测钢丝表面ZnO含量为26.5mg/m 2，满足湿式拉拔需求。
实施例2
本实施例与实施例1相同，区别在于当清洗液pH为1.5、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4，钢丝清洗时间2s，检测钢丝表面ZnO含量为32.3mg/m 2，满足湿式拉拔需求。
实施例3
本实施例与实施例1相同，区别在于当清洗液pH为2.0、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4，钢丝清洗时间2s，检测钢丝表面ZnO 含量为36.9mg/m 2，满足湿式拉拔需求。
实施例4
本实施例与实施例1相同，区别在于当清洗液pH为1.5、ZnSO 4浓度为102g/L的H 2SO 4/ZnSO 4，钢丝清洗时间2s，检测钢丝表面ZnO含量为30.7mg/m 2，满足湿式拉拔需求。
实施例5
本实施例与实施例1相同，区别在于当清洗液pH为1.5、ZnSO 4浓度为160g/L的H 2SO 4/ZnSO 4，钢丝清洗时间2s，检测钢丝表面ZnO含量为33.5mg/m 2，满足湿式拉拔需求。
实施例6
本实施例与实施例1相同，区别在于当清洗液pH为1.5、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4，钢丝清洗时间1.5s，检测钢丝表面ZnO含量为37.0mg/m 2，满足湿式拉拔需求。
实施例7
本实施例与实施例1相同，区别在于当清洗液pH为1.5、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4，钢丝清洗时间3.5s，检测钢丝表面ZnO含量为38.6mg/m 2，满足湿式拉拔需求。
对比实施例8
本实施例与实施例1相同，区别在于当清洗液pH为0.5、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4，钢丝清洗时间2s，检测钢丝表面ZnO含量为89.2mg/m 2，不利于湿式拉拔。pH太低，在清洗后容易出现钢丝表面带酸现象，造成锌的二次氧化或溶解。
对比实施例9
本实施例与实施例1相同，区别在于当清洗液pH为2.5、ZnSO 4浓度为130g/L的H 2SO 4/ZnSO 4，钢丝清洗时间2s，检测钢丝表面ZnO含量为110.5mg/m 2，不利于湿式拉拔。pH值太高，不利于酸洗。
对比实施例10
本实施例与实施例1相同，区别在于当清洗液pH为1.5、ZnSO 4浓度为225g/L的H 2SO 4/ZnSO 4，钢丝清洗时间0.5s，检测钢丝表面ZnO含量为76.2mg/m 2，不利于湿式拉拔。清洗时间过短，清洗不净。
对比实施例11
本实施例与实施例1相同，区别在于当清洗液pH为1.5、ZnSO 4浓度为225g/L的H 2SO 4/ZnSO 4，钢丝清洗时间4s，清洗时间过长易导致镀层铜锌百分比与原有设计失衡，锌出现过度溶解现象。
实施例12
在钢丝连续批量处理后验证此清洗技术的钢丝对后道生产及帘线粘合力的影响。采用无磷清洗技术的钢丝与同期磷化工艺的钢丝进行对比，对二者表面ZnO进行检测，检测合格后流向湿拉合股工序生产1.20→0.22→3922规格帘线，同时跟踪无磷清洗工艺钢丝与磷化清洗的钢丝湿拉合股工序的断丝率以及合股成绳后钢丝帘线的粘合力进行对比，并验证无磷清洗工艺得到的钢丝帘线对不同客户胶料是否具有普适性。具体数据见图2、图3和表1。
图2是不同清洗工艺生产的钢丝表面ZnO检测数据图谱。其中S和P分别为H 2SO 4/ZnSO 4和磷化工艺。由图可知，两种工艺钢丝表面ZnO含量均值基本相当，这也说明了以H 2SO 4/ZnSO 4工艺的清洗效果可以达到磷化工艺的水平。
表1为不同清洗工艺生产样品的湿拉成品率和合股断丝率，由表1可知两种钢丝湿拉成品率相近，且H 2SO 4/ZnSO 4洗工艺钢丝在拉拔过程中未见有断丝。可见经过H 2SO 4/ZnSO 4清洗的电镀钢丝可以适应现有湿拉润滑剂，且拉拔效果不低于磷化工艺钢丝。合股过程中H 2SO 4/ZnSO 4工艺帘线的吨平断丝为0.7次/吨，不高于磷化工艺帘线，可见合股工艺性能可以达到磷化工艺水平。
图3为两种清洗工艺帘线分别进行了6中胶料的硫化试验，六种胶料分别对应于A、B、C、D、E和F，谱图左侧为粘合抽出力，即 柱形图区域，谱图右侧为H 2SO 4/ZnSO 4工艺帘线与常规磷化工艺帘线的粘合力差值百分比((F S-F P)/F P*100％)，即折线图区域。由图3可知，H 2SO 4/ZnSO 4洗工艺帘线与磷化工艺帘线六种胶料粘合力差值比例在-6％～16％之间，且居正偏多，因此H 2SO 4/ZnSO 4洗与磷化工艺帘线粘合力值相比在多种胶料下无明显偏低的迹象，这也说明H 2SO 4/ZnSO 4洗工艺帘线对胶料的适用性不低于磷化工艺帘线。
表1 实施例清洗液样品湿拉成品率及合股断丝率
Figure PCTCN2021094556-appb-000001
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (6)

  1. 一种用以替代热扩散电镀线磷化的清洗方法，其特征在于：采用无磷清洗液清洗钢丝，无磷清洗液由H 2SO 4、ZnSO 4和纯水组成，无磷清洗液放置在清洗槽内，在镀锌槽与无磷清洗槽之间设置调节槽，镀锌槽与无磷清洗槽、镀锌槽与调节槽以及无磷清洗槽与调节槽之间以管道连接，当无磷清洗槽内ZnSO 4浓度过高时，无磷清洗槽内溶液直接回流至镀锌槽，同时通过调节槽补充添加镀锌槽中新液进无磷清洗槽。
  2. 根据权利要求1所述的一种用以替代热扩散电镀线磷化的清洗方法，其特征在于：无磷清洗槽内初始清洗液直接取用镀锌槽的部分溶液，然后在调节槽中添加新的H 2SO 4和纯水，使清洗液达到pH为1～2，ZnSO 4浓度为100～160g/L。
  3. 根据权利要求1所述的一种用以替代热扩散电镀线磷化的清洗方法，其特征在于：无磷清洗液在生产工作中，当ZnSO 4的浓度达到200～220g/L时，无磷清洗槽将部分清洗液直接回流入镀锌槽，再通过调节槽循环补充新液。
  4. 根据权利要求3所述的一种用以替代热扩散电镀线磷化的清洗方法，其特征在于：无磷清洗槽将1/2体积的旧液排入镀锌槽，并补充1/2体积的新液。
  5. 根据权利要求1所述的一种用以替代热扩散电镀线磷化的清洗方法，其特征在于：钢丝经过清洗液的时间控制在1.5～3.5s。
  6. 根据权利要求1所述的一种用以替代热扩散电镀线磷化的清洗方法，其特征在于：生产期间每天进行pH的检测，ZnSO 4浓度为每三天检测一次。
PCT/CN2021/094556 2020-07-09 2021-05-19 一种用以替代热扩散电镀线磷化的清洗方法 WO2022007505A1 (zh)

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