技术领域technical field
本发明涉及一种磷化液，尤其是涉及一种适用于金属工件涂漆前表面磷化处理的磷化液及其制备方法，同时还公开了该磷化液的使用方法。The invention relates to a phosphating solution, in particular to a phosphating solution suitable for phosphating the surface of metal workpieces before painting and a preparation method thereof, and also discloses a using method of the phosphating solution.
背景技术Background technique
磷化是常用的前处理技术，原理上应属于化学转换膜处理，主要应用于钢铁表面磷化，有色金属(如铝、锌)件也可应用磷化。磷化的目的主要是给基体金属提供保护，在一定程度上防止金属被腐蚀；用于涂漆前打底，提高漆膜层的附着力与防腐蚀能力；在金属冷加工工艺中起减摩润滑作用。金属的磷化处理是钢铁在磷酸二氢盐、氧化剂、助剂等构成的磷化液中进行处理并在其表面生成几微米厚的磷化膜的过程，包括锌系锌钙系、锰系和铁系等类型。磷化膜主要用做涂料的底层，金属冷加工时的润滑层，及金属表面保护层等，可以起到防锈，减磨耐磨，润滑，增进涂料与金属基底附着力等多种作用。磷化可明显提高涂层的附着力、防护能力，是保证涂装质量的关键技术，是汽车、家电、机械生产的必要工艺。目前普遍使用的磷化技术是锌系中温磷化，磷化温度高，易产生酸雾，槽液不稳定，同时沉渣较多，磷化膜厚重，涂装后涂膜的附着力较低，耐蚀性也较差，所使用的亚硝酸盐和重金属离子污染环境。近年来，随着磷化技术的进步，国内外正在积极开发快速磷化工艺，其磷化温度低、能耗少、沉渣少、晶粒细、膜薄、涂膜的附着力和耐蚀性有很大提高。目前国内磷化技术普遍存在的问题是：磷化温度高、磷化液使用寿命短、水洗难度大以及造成水体污染等问题，不仅给环境治理带来负担而且消耗大量的水、磷酸盐等资源。Phosphating is a commonly used pretreatment technology. In principle, it should belong to chemical conversion film treatment. It is mainly used for phosphating on the surface of steel, and non-ferrous metals (such as aluminum, zinc) can also be phosphating. The purpose of phosphating is mainly to provide protection for the base metal and prevent the metal from being corroded to a certain extent; it is used as a primer before painting to improve the adhesion and anti-corrosion ability of the paint film layer; it plays an anti-friction lubrication role in the metal cold processing process effect. Phosphating treatment of metals is a process in which iron and steel are treated in a phosphating solution composed of dihydrogen phosphate, oxidants, additives, etc., and a phosphating film with a thickness of several microns is formed on the surface, including zinc-based zinc-calcium, manganese-based and iron types. Phosphating film is mainly used as the bottom layer of paint, lubricating layer during metal cold working, and metal surface protection layer, etc., which can play various functions such as rust prevention, wear reduction, lubrication, and improvement of adhesion between paint and metal substrate. Phosphating can significantly improve the adhesion and protection ability of the coating. It is a key technology to ensure the quality of coating and a necessary process for the production of automobiles, home appliances and machinery. At present, the commonly used phosphating technology is zinc-based medium-temperature phosphating. The phosphating temperature is high, acid mist is easily generated, the bath solution is unstable, and there are more sediments, the phosphating film is thick, and the adhesion of the coating film after coating is low. The corrosion resistance is also poor, and the nitrite and heavy metal ions used pollute the environment. In recent years, with the progress of phosphating technology, rapid phosphating process is being actively developed at home and abroad, which has low phosphating temperature, less energy consumption, less sediment, fine grain, thin film, adhesion and corrosion resistance of coating film There is a great improvement. At present, the common problems of domestic phosphating technology are: high phosphating temperature, short service life of phosphating solution, difficult washing and water pollution, which not only bring burden to environmental governance but also consume a lot of water, phosphate and other resources .
从磷化膜的形成过程原理可知，溶液的酸度、氧化剂、催化剂是影响磷化速度的重要因素，对磷化质量起着决定性的作用，因此磷化液组分含量的配置和调整必须高度给予重视，尤其是氧化剂、催化剂的组分配置起着关键作用，广大科研和企业也在积极对氧化剂、催化剂的配方制备进行试验研究。From the principle of the formation process of the phosphating film, it can be known that the acidity of the solution, the oxidant, and the catalyst are important factors affecting the phosphating speed and play a decisive role in the phosphating quality. Pay attention, especially the composition of oxidants and catalysts plays a key role, and the majority of scientific research and enterprises are also actively conducting experimental research on the formulation preparation of oxidants and catalysts.
发明内容Contents of the invention
本发明的目的在于提供一种不仅具有成膜快速、漆膜结合力强、耐蚀性好、可通过涂刷或喷淋进行操作、操作简单、成本低等优点，而且适用于大型工件或 户外设备的磷化液及其制备方法。The purpose of the present invention is to provide a paint film that not only has the advantages of fast film formation, strong paint film adhesion, good corrosion resistance, can be operated by brushing or spraying, simple operation, and low cost, but also is suitable for large workpieces or outdoors. A phosphating solution for equipment and a preparation method thereof.
该磷化液的原料组成按重量份为：磷酸二氢锌80-150份，氧化锌10-30份，磷酸30-50份，碳酸锰2-5份，氟硅酸钠2-4份，硫酸羟胺1-5份，三唑化合物4-8份，柠檬酸钠2-3份，多聚磷酸盐10-15份，氟化钠1-3份，过二硫酸铵1-2份，钼酸钠3-8份，氯酸钾1-2份，六亚甲基四胺1-3份，环三偏磷酸钠3-5份，其制备方法为：先在耐酸容器或磷化槽内用适量水将氧化锌10-30份完全溶解，充分搅拌后再加入磷酸30-50份继续搅拌，加热至100-120℃保温2小时进行充分反应，待充分反应后加入磷酸二氢锌80-150份、碳酸锰2-5份，氟硅酸钠2-4份，硫酸羟胺1-5份，三唑化合物4-8份，氟化钠1-3份，过二硫酸铵1-2份，钼酸钠3-8份，氯酸钾1-2份，六亚甲基四胺1-3份，环三偏磷酸钠3-5份搅拌均匀，最后加入多聚磷酸盐10-15份、柠檬酸钠2-3份，然后再加入适量水进行PH值调整搅拌均匀后即可。The raw materials of the phosphating solution are composed by weight: 80-150 parts of zinc dihydrogen phosphate, 10-30 parts of zinc oxide, 30-50 parts of phosphoric acid, 2-5 parts of manganese carbonate, 2-4 parts of sodium fluorosilicate, 1-5 parts of hydroxylamine sulfate, 4-8 parts of triazole compound, 2-3 parts of sodium citrate, 10-15 parts of polyphosphate, 1-3 parts of sodium fluoride, 1-2 parts of ammonium peroxodisulfate, molybdenum 3-8 parts of sodium chlorate, 1-2 parts of potassium chlorate, 1-3 parts of hexamethylenetetramine, 3-5 parts of sodium cyclic trimetaphosphate, the preparation method is: first use appropriate amount of Water dissolves 10-30 parts of zinc oxide completely, stir well, then add 30-50 parts of phosphoric acid and continue stirring, heat to 100-120°C and keep it warm for 2 hours to fully react, after fully reacting, add 80-150 parts of zinc dihydrogen phosphate , 2-5 parts of manganese carbonate, 2-4 parts of sodium fluorosilicate, 1-5 parts of hydroxylamine sulfate, 4-8 parts of triazole compounds, 1-3 parts of sodium fluoride, 1-2 parts of ammonium peroxodisulfate, molybdenum 3-8 parts of sodium chlorate, 1-2 parts of potassium chlorate, 1-3 parts of hexamethylenetetramine, 3-5 parts of sodium cyclic trimetaphosphate, stir well, and finally add 10-15 parts of polyphosphate, sodium citrate 2-3 parts, and then add an appropriate amount of water to adjust the pH value and stir evenly.
相比于现有的磷化液组成和制备方法，上述磷化液具有以下优势，Compared with the existing phosphating solution composition and preparation method, the above-mentioned phosphating solution has the following advantages,
1)采用的氧化剂、促进剂包括碳酸锰，氟硅酸钠，硫酸羟胺，三唑化合物，柠檬酸钠，多聚磷酸盐，氟化钠，过二硫酸铵，钼酸钠，氯酸钾，六亚甲基四胺，环三偏磷酸钠，经试验验证，该组分配置可以使得制备得出的磷化液成膜快速、漆膜结合力强、耐蚀性好等特点；1) The oxidants and accelerators used include manganese carbonate, sodium fluorosilicate, hydroxylamine sulfate, triazole compounds, sodium citrate, polyphosphate, sodium fluoride, ammonium peroxodisulfate, sodium molybdate, potassium chlorate, hexaethylene Methyltetramine, sodium cyclic trimetaphosphate, it has been verified by experiments that the configuration of this component can make the prepared phosphating solution film-forming quickly, with strong paint film adhesion and good corrosion resistance;
2)例如，采用硫酸羟胺的少量适量组分可以最大程度上减少磷酸的使用量，从而降低成本减少污染，更为重要的是其能加快基底腐蚀反应速度使得Fe被氧化成Fe2+二价铁离子，从而快速消耗大量氢离子，促进磷化液中离解出大量PO43-，与Zn2+，Fe2+反应而在工件表面快速沉积处磷化膜晶核并快速生长；2) For example, the use of a small amount of hydroxylamine sulfate can minimize the use of phosphoric acid, thereby reducing costs and pollution, and more importantly, it can accelerate the corrosion reaction rate of the substrate so that Fe is oxidized to Fe2+ divalent Iron ions, so as to quickly consume a large amount of hydrogen ions, promote the dissociation of a large amount of PO43- in the phosphating solution, and react with Zn2+ , Fe2+ to rapidly deposit and grow the phosphating film crystal nucleus on the surface of the workpiece;
3)采用氟化钠1-3份、氟硅酸钠2-4份、硫酸羟胺1-5份的活化促进剂的配置不但可以加速磷化晶核形成，使得晶核致密耐腐蚀性增强，还可以加快磷化液整体的磷化速度，促进磷化层细致；3) The configuration of activation accelerators with 1-3 parts of sodium fluoride, 2-4 parts of sodium fluorosilicate, and 1-5 parts of hydroxylamine sulfate can not only accelerate the formation of phosphating crystal nuclei, but also make the crystal nuclei dense and corrosion-resistant. It can also speed up the overall phosphating speed of the phosphating solution and promote the fineness of the phosphating layer;
4)采用的氧化剂由过二硫酸铵1-2份、钼酸钠3-8份、氯酸钾1-2份等组分形成，起在酸性溶液中具有很强的氧化性，尤其是钼酸钠与磷化液主要成分之间具有很好的协调效应，可有效降低处理温度，提高成膜速度，还可以起到缓蚀剂以及降低磷化膜厚度的作用；4) The oxidant used is composed of 1-2 parts of ammonium peroxodisulfate, 3-8 parts of sodium molybdate, 1-2 parts of potassium chlorate and other components, which have strong oxidizing properties in acidic solutions, especially sodium molybdate It has a good coordination effect with the main components of the phosphating solution, which can effectively reduce the treatment temperature, increase the film forming speed, and also act as a corrosion inhibitor and reduce the thickness of the phosphating film;
5)添加适量的六亚甲基四胺，主要是将其作为缓冲金属材料腐蚀剂使用， 还可起到对磷化液PH值调节的作用；添加适量的环三偏磷酸钠，其作用在于生成复合化合物来分解可能存在的重金属，用做分散剂和稳定剂；5) Adding an appropriate amount of hexamethylenetetramine is mainly used as a buffer metal material corrosion agent, and can also play a role in adjusting the pH value of the phosphating solution; adding an appropriate amount of cyclic sodium trimetaphosphate, its function is to generate Compound compounds to decompose possible heavy metals, used as dispersants and stabilizers;
6)添加适量的三唑化合物，主要是其能在金属表面发生吸附或形成配合物，在钼酸钠与金属形成的钝化膜上又形成杂环化合物的新吸附层，构成了一层三维网络结构的化合物膜，杂环化合物在微孔处的吸附有效地堵塞了金属离子的扩散通道，同时也阻止了CI-向金属内渗透，从而在具有钼酸钠组分的情况下有效地降低了对金属工件的腐蚀速度；6) Add an appropriate amount of triazole compound, mainly because it can adsorb or form a complex on the metal surface, and form a new adsorption layer of heterocyclic compounds on the passivation film formed by sodium molybdate and metal, forming a layer of three-dimensional In the compound film with network structure, the adsorption of heterocyclic compounds at the micropores effectively blocks the diffusion channels of metal ions, and also prevents the penetration of CI- into the metal, thereby effectively reducing the The corrosion rate of metal workpieces;
7)而在制备磷化液的最后阶段加入多聚磷酸盐10-15份、柠檬酸钠2-3份可以充分发挥其作为晶核调整剂和降渣剂的作用，经试验验证，相比于以往技术，该方法可以降低磷化渣形成5-10％以上。7) Adding 10-15 parts of polyphosphate and 2-3 parts of sodium citrate in the final stage of preparing the phosphating solution can give full play to its role as a crystal nucleus regulator and slag reducing agent. Compared with the prior art, this method can reduce the formation of phosphating slag by more than 5-10%.
需要说明的是，氧化剂、促进剂是实现低温磷化不可缺少的条件，其溶液酸度、氧化剂、催化剂是影响磷化速度的重要因素，对磷化质量起着决定性的作用，氧化剂、促进剂的浓度低则磷化速度慢，太低则不成膜，反之浓度过高，磷化速度快，会出现反应过程过快，不易形成合适厚度等情况，因此上述组分配置比例的形成确定需要经过创造性的考虑和试验验证才能最终确定。It should be noted that oxidants and accelerators are indispensable conditions for low-temperature phosphating. The acidity of the solution, oxidants, and catalysts are important factors affecting the phosphating speed and play a decisive role in the quality of phosphating. If the concentration is low, the phosphating speed will be slow, if the concentration is too low, the phosphating speed will be fast, and the reaction process will be too fast, and it will not be easy to form a suitable thickness. Creative consideration and experimental verification can be finalized.
本发明还公开了一种磷化液的使用方法，包括将待处理工件进行磷化前处理和磷化处理两个步骤，The invention also discloses a method for using the phosphating solution, which includes two steps of performing phosphating pretreatment and phosphating treatment on the workpiece to be treated,
其中磷化前处理主要包括：The pre-phosphating treatment mainly includes:
1)除油：将待处理工件浸泡在丙酮溶液中，使用超声波清洗器清洗10-15min，将油污进行充分清洗；1) Degreasing: Soak the workpiece to be treated in acetone solution, use an ultrasonic cleaner to clean it for 10-15 minutes, and fully clean the oil stain;
2)碱洗：将待处理工件浸泡在恒温水浴锅中保持60℃，浸洗15-20min，碱洗液为50g/L的Na2PO4、50g/L的Na2CO3，和20g/L的N2SiO3的混合溶液，pH值为7，恒温水浴锅保持温度在60℃作用，时间大约15-20min；2) Alkaline cleaning: Soak the workpiece to be treated in a constant temperature water bath at 60°C for 15-20 minutes. The alkaline washing solution is 50g/L Na2 PO4 , 50g/L Na2 CO3 The mixed solution of N2 SiO3 in L, the pH value is 7, and the constant temperature water bath is kept at 60°C for about 15-20 minutes;
3)酸洗：所用酸洗液为150mL/L的H2SO4、50mL/L的HF和30mL/L的三乙醇胺的混合溶液，控制温度在25℃左右，酸洗时间约为2min；3) Pickling: The pickling solution used is a mixed solution of 150mL/L H2 SO4 , 50mL/L HF and 30mL/L triethanolamine, the temperature is controlled at about 25°C, and the pickling time is about 2 minutes;
4)水洗：先用去离子水冲洗干净，但在物体表面尤其是表面凹处、小孔部位仍残留酸液，容易再次产生生锈，需要在水洗之后进行中和处理，主要使用20-40g/L的碳酸钠溶液，处理1-2min，然后进行二次去离子水冲洗，冷风吹干后待用；4) Washing: first rinse with deionized water, but acid remains on the surface of the object, especially in the recesses and small holes on the surface, which is prone to rust again, and needs to be neutralized after washing, mainly using 20-40g /L of sodium carbonate solution, treated for 1-2min, then rinsed with deionized water twice, and dried with cold air before use;
所述磷化处理包括：使用耐酸刷直接将按照上述权利要求1方法制备所得磷化液在工件上均匀涂刷一层磷化液膜，或者使用喷枪喷淋一层磷化液膜，或者进行浸泡处理，然后干燥即可，工件表面形成的磷化膜结晶致密，磷化表面无挂灰、反白现象产生，膜层本身无脆性，即达到工艺要求。The phosphating treatment includes: directly using an acid-resistant brush to evenly paint a layer of phosphating liquid film on the workpiece with the obtained phosphating liquid prepared according to the method of claim 1 above, or use a spray gun to spray a layer of phosphating liquid film, or carry out Soaking treatment, and then drying. The phosphating film formed on the surface of the workpiece is crystallized and dense. The phosphating surface has no dust or whitening phenomenon, and the film itself is not brittle, which means it meets the process requirements.
与现有技术相比，本发明磷化液的优点在于，具有成膜快速、漆膜结合力强、耐蚀性好、可通过涂刷或喷淋进行操作、操作简单、成本低等优点，该配制的磷化液不但减少了磷化液沉渣，保证磷化膜的质量，膜层均匀细腻，应用范围广范，成本低，使用方便，有利于工业化生产。Compared with the prior art, the advantages of the phosphating solution of the present invention are that it has the advantages of rapid film formation, strong paint film binding force, good corrosion resistance, operation by brushing or spraying, simple operation, and low cost. The prepared phosphating solution not only reduces the phosphating solution sediment, but also ensures the quality of the phosphating film, the film layer is uniform and fine, the application range is wide, the cost is low, the use is convenient, and it is beneficial to industrial production.
具体实施方式detailed description
以下实施例用于说明本发明，但不用来限制本发明的范围。The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
所述磷化液的原料组成按重量份为：磷酸二氢锌80-150份，氧化锌10-30份，磷酸30-50份，碳酸锰2-5份，氟硅酸钠2-4份，硫酸羟胺1-5份，三唑化合物4-8份，柠檬酸钠2-3份，多聚磷酸盐10-15份，氟化钠1-3份，过二硫酸铵1-2份，钼酸钠3-8份，氯酸钾1-2份，六亚甲基四胺1-3份，环三偏磷酸钠3-5份，其制备方法为：先在耐酸容器或磷化槽内用适量水将氧化锌10-30份完全溶解，充分搅拌后再加入磷酸30-50份继续搅拌，加热至100-120℃保温2小时进行充分反应，待充分反应后加入磷酸二氢锌80-150份、碳酸锰2-5份，氟硅酸钠2-4份，硫酸羟胺1-5份，三唑化合物4-8份，氟化钠1-3份，过二硫酸铵1-2份，钼酸钠3-8份，氯酸钾1-2份，六亚甲基四胺1-3份，环三偏磷酸钠3-5份搅拌均匀，最后加入多聚磷酸盐10-15份、柠檬酸钠2-3份，然后再加入适量水进行PH值调整搅拌均匀后即可。The raw materials of the phosphating solution are composed by weight: 80-150 parts of zinc dihydrogen phosphate, 10-30 parts of zinc oxide, 30-50 parts of phosphoric acid, 2-5 parts of manganese carbonate, and 2-4 parts of sodium fluorosilicate , 1-5 parts of hydroxylamine sulfate, 4-8 parts of triazole compound, 2-3 parts of sodium citrate, 10-15 parts of polyphosphate, 1-3 parts of sodium fluoride, 1-2 parts of ammonium peroxodisulfate, 3-8 parts of sodium molybdate, 1-2 parts of potassium chlorate, 1-3 parts of hexamethylenetetramine, and 3-5 parts of sodium cyclic trimetaphosphate. Dissolve 10-30 parts of zinc oxide with appropriate amount of water, stir well, then add 30-50 parts of phosphoric acid and continue stirring, heat to 100-120°C for 2 hours to fully react, after fully reacting, add 80-150 parts of zinc dihydrogen phosphate 2-5 parts of manganese carbonate, 2-4 parts of sodium fluorosilicate, 1-5 parts of hydroxylamine sulfate, 4-8 parts of triazole compounds, 1-3 parts of sodium fluoride, 1-2 parts of ammonium peroxodisulfate, 3-8 parts of sodium molybdate, 1-2 parts of potassium chlorate, 1-3 parts of hexamethylenetetramine, 3-5 parts of sodium cyclic trimetaphosphate, stir well, and finally add 10-15 parts of polyphosphate, citric acid 2-3 parts of sodium, and then add an appropriate amount of water to adjust the pH value and stir evenly.
相比于现有的磷化液组成和制备方法，上述磷化液具有以下优势，Compared with the existing phosphating solution composition and preparation method, the above-mentioned phosphating solution has the following advantages,
1)采用的氧化剂、促进剂包括碳酸锰，氟硅酸钠，硫酸羟胺，三唑化合物，柠檬酸钠，多聚磷酸盐，氟化钠，过二硫酸铵，钼酸钠，氯酸钾，六亚甲基四胺，环三偏磷酸钠，经试验验证，该组分配置具有特殊作用，可以使得制备得出的磷化液成膜快速、漆膜结合力强、耐蚀性好等特点；1) The oxidants and accelerators used include manganese carbonate, sodium fluorosilicate, hydroxylamine sulfate, triazole compounds, sodium citrate, polyphosphate, sodium fluoride, ammonium peroxodisulfate, sodium molybdate, potassium chlorate, hexaethylene Methyltetramine, sodium cyclic trimetaphosphate. It has been verified by experiments that the configuration of this component has a special effect, which can make the prepared phosphating solution film-forming fast, with strong paint film adhesion and good corrosion resistance;
2)例如，采用硫酸羟胺的少量适量组分可以最大程度上减少磷酸的使用量，从而降低成本减少污染，更为重要的是其能加快基底腐蚀反应速度使得FE被氧化成Fe2+二价铁离子，从而快速消耗大量氢离子，促进磷化液中离解出大量 PO43-，与Zn2+，Fe2+反应而在工件表面快速沉积处磷化膜晶核并快速生长；2) For example, the use of a small amount of hydroxylamine sulfate can minimize the use of phosphoric acid, thereby reducing costs and reducing pollution. More importantly, it can accelerate the corrosion reaction rate of the substrate so that FE is oxidized to Fe2+ divalent Iron ions, so as to quickly consume a large amount of hydrogen ions, promote the dissociation of a large amount of PO43- in the phosphating solution, and react with Zn2+ , Fe2+ to rapidly deposit and grow the phosphating film crystal nucleus on the surface of the workpiece;
3)采用氟化钠1-3份、氟硅酸钠2-4份、硫酸羟胺1-5份的活化促进剂的配置不但可以加速磷化晶核形成，使得晶核致密耐腐蚀性增强，还可以加快磷化液整体的磷化速度，促进磷化层细致；3) The configuration of activation accelerators with 1-3 parts of sodium fluoride, 2-4 parts of sodium fluorosilicate, and 1-5 parts of hydroxylamine sulfate can not only accelerate the formation of phosphating crystal nuclei, but also make the crystal nuclei dense and corrosion-resistant. It can also speed up the overall phosphating speed of the phosphating solution and promote the fineness of the phosphating layer;
4)采用的氧化剂由过二硫酸铵1-2份、钼酸钠3-8份、氯酸钾1-2份等组分形成，起在酸性溶液中具有很强的氧化性，尤其是钼酸钠与磷化液主要成分之间具有很好的协调效应，可有效降低处理温度，提高成膜速度，还可以起到缓蚀剂以及降低磷化膜厚度的作用；4) The oxidant used is composed of 1-2 parts of ammonium peroxodisulfate, 3-8 parts of sodium molybdate, 1-2 parts of potassium chlorate and other components, which have strong oxidizing properties in acidic solutions, especially sodium molybdate It has a good coordination effect with the main components of the phosphating solution, which can effectively reduce the treatment temperature, increase the film forming speed, and also act as a corrosion inhibitor and reduce the thickness of the phosphating film;
5)添加适量的六亚甲基四胺，主要是将其作为缓冲金属材料腐蚀剂使用，还可起到对磷化液PH值调节的作用；添加适量的环三偏磷酸钠，其作用在于生成复合化合物来分解可能存在的重金属，用做分散剂和稳定剂；5) Adding an appropriate amount of hexamethylenetetramine is mainly used as a buffer metal material corrosion agent, and can also play a role in adjusting the pH value of the phosphating solution; adding an appropriate amount of sodium trimetaphosphate, its function is to generate Compound compounds to decompose possible heavy metals, used as dispersants and stabilizers;
6)添加适量的三唑化合物，主要是其能在金属表面发生吸附或形成配合物，在钼酸钠与金属形成的钝化膜上又形成杂环化合物的新吸附层，构成了一层三维网络结构的化合物膜，杂环化合物在微孔处的吸附有效地堵塞了金属离子的扩散通道，同时也阻止了CI-向金属内渗透，从而在具有钼酸钠组分的情况下有效地降低了对金属工件的腐蚀速度；6) Add an appropriate amount of triazole compound, mainly because it can adsorb or form a complex on the metal surface, and form a new adsorption layer of heterocyclic compounds on the passivation film formed by sodium molybdate and metal, forming a layer of three-dimensional In the compound film with network structure, the adsorption of heterocyclic compounds at the micropores effectively blocks the diffusion channels of metal ions, and also prevents the penetration of CI- into the metal, thereby effectively reducing the The corrosion rate of metal workpieces;
7)而在制备磷化液的最后阶段加入多聚磷酸盐10-15份、柠檬酸钠2-3份可以充分发挥其作为晶核调整剂和降渣剂的作用，经试验验证，相比于以往技术，该方法可以降低磷化渣形成5-10％以上。7) Adding 10-15 parts of polyphosphate and 2-3 parts of sodium citrate in the final stage of preparing the phosphating solution can give full play to its role as a crystal nucleus regulator and slag reducing agent. Compared with the prior art, this method can reduce the formation of phosphating slag by more than 5-10%.
需要说明的是，氧化剂、促进剂是实现低温磷化不可缺少的条件，其溶液酸度、氧化剂、催化剂是影响磷化速度的重要因素，对磷化质量起着决定性的作用，氧化剂、促进剂的浓度低则磷化速度慢，太低则不成膜，反之浓度过高，磷化速度快，会出现反应过程过快，不易形成合适厚度等情况，因此上述配置比例的形成需要经过创造性的考虑和经过试验验证才能最终确定。磷化液的总酸度TA为50-90点，酸度比(TA/FA)为5-15点的范围内。It should be noted that oxidants and accelerators are indispensable conditions for low-temperature phosphating. The acidity of the solution, oxidants, and catalysts are important factors affecting the phosphating speed and play a decisive role in the quality of phosphating. If the concentration is low, the phosphating speed will be slow, if the concentration is too low, there will be no film formation. On the contrary, if the concentration is too high, the phosphating speed will be fast, the reaction process will be too fast, and it will be difficult to form a suitable thickness. Therefore, the formation of the above configuration ratio requires creative consideration. And it can only be finally determined after experimental verification. The total acidity TA of the phosphating solution is 50-90 points, and the acidity ratio (TA/FA) is within the range of 5-15 points.
给出以下实施例及对比数据以证明本申请的技术效果Provide the following examples and comparative data to prove the technical effect of the present application
实施例1Example 1
所述磷化液的原料组成按重量份为：磷酸二氢锌100份，氧化锌15份，磷酸40份，碳酸锰2份，氟硅酸钠2份，硫酸羟胺4份，三唑化合物4份，柠檬 酸钠2份，多聚磷酸盐10份，氟化钠2份，过二硫酸铵2份，钼酸钠5份，氯酸钾1份，六亚甲基四胺1份，环三偏磷酸钠3份，The raw materials of the phosphating solution are composed in parts by weight: 100 parts of zinc dihydrogen phosphate, 15 parts of zinc oxide, 40 parts of phosphoric acid, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 4 parts of triazole compound 2 parts of sodium citrate, 10 parts of polyphosphate, 2 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, 5 parts of sodium molybdate, 1 part of potassium chlorate, 1 part of hexamethylenetetramine 3 parts sodium phosphate,
其制备方法为：先在耐酸容器或磷化槽内用适量水将氧化锌15份完全溶解，充分搅拌后再加入磷酸40份继续搅拌，加热至100-120℃保温2小时进行充分反应，待充分反应后加入磷酸二氢锌100份、碳酸锰2份，氟硅酸钠2份，硫酸羟胺4份，三唑化合物4份，氟化钠2份，过二硫酸铵2份，钼酸钠5份，氯酸钾1份，六亚甲基四胺1份，环三偏磷酸钠3份搅拌均匀，最后加入多聚磷酸盐10份、柠檬酸钠2份，然后再加入适量水进行PH值调整搅拌均匀后即可。Its preparation method is as follows: first dissolve 15 parts of zinc oxide in an acid-resistant container or phosphating tank with an appropriate amount of water, stir thoroughly, then add 40 parts of phosphoric acid and continue stirring, heat to 100-120 ° C for 2 hours to fully react, wait After fully reacting, add 100 parts of zinc dihydrogen phosphate, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 4 parts of triazole compound, 2 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, sodium molybdate 5 parts, 1 part of potassium chlorate, 1 part of hexamethylenetetramine, 3 parts of sodium cyclic trimetaphosphate, stir evenly, finally add 10 parts of polyphosphate, 2 parts of sodium citrate, and then add appropriate amount of water to adjust the pH value Just mix well.
实施例2Example 2
所述磷化液的原料组成按重量份为：磷酸二氢锌100份，氧化锌15份，磷酸40份，碳酸锰2份，氟硅酸钠3.5份，硫酸羟胺4份，三唑化合物4份，柠檬酸钠2份，多聚磷酸盐10份，氟化钠3份，过二硫酸铵2份，钼酸钠5份，氯酸钾2份，六亚甲基四胺1份，环三偏磷酸钠3份，可以看出，相比于实施例1，增加了活化剂组分配置。The raw materials of the phosphating solution are composed in parts by weight: 100 parts of zinc dihydrogen phosphate, 15 parts of zinc oxide, 40 parts of phosphoric acid, 2 parts of manganese carbonate, 3.5 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 4 parts of triazole compound 2 parts of sodium citrate, 10 parts of polyphosphate, 3 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, 5 parts of sodium molybdate, 2 parts of potassium chlorate, 1 part of hexamethylenetetramine 3 parts of sodium phosphate, it can be seen that compared with Example 1, the configuration of the activator component has been increased.
其制备方法为：先在耐酸容器或磷化槽内用适量水将氧化锌15份完全溶解，充分搅拌后再加入磷酸40份继续搅拌，加热至100-120℃保温2小时进行充分反应，待充分反应后加入磷酸二氢锌100份、碳酸锰2份，氟硅酸钠3.5份，硫酸羟胺4份，三唑化合物4份，氟化钠3份，过二硫酸铵2份，钼酸钠5份，氯酸钾2份，六亚甲基四胺1份，环三偏磷酸钠3份搅拌均匀，最后加入多聚磷酸盐10份、柠檬酸钠2份，然后再加入适量水进行PH值调整搅拌均匀后即可。Its preparation method is as follows: first dissolve 15 parts of zinc oxide in an acid-resistant container or phosphating tank with an appropriate amount of water, stir thoroughly, then add 40 parts of phosphoric acid and continue stirring, heat to 100-120 ° C for 2 hours to fully react, wait After full reaction, add 100 parts of zinc dihydrogen phosphate, 2 parts of manganese carbonate, 3.5 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 4 parts of triazole compound, 3 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, sodium molybdate 5 parts, 2 parts of potassium chlorate, 1 part of hexamethylenetetramine, 3 parts of sodium cyclic trimetaphosphate, stir evenly, finally add 10 parts of polyphosphate, 2 parts of sodium citrate, and then add appropriate amount of water to adjust the pH value Just mix well.
实施例3Example 3
所述磷化液的原料组成按重量份为：磷酸二氢锌100份，氧化锌15份，磷酸40份，碳酸锰2份，氟硅酸钠2份，硫酸羟胺4份，三唑化合物6份，柠檬酸钠2份，多聚磷酸盐10份，氟化钠2份，过二硫酸铵2份，钼酸钠8份，氯酸钾2份，六亚甲基四胺1份，环三偏磷酸钠3份，可以看出，相比于实施例1，增加了氧化剂组分配置。The raw materials of the phosphating solution are composed in parts by weight: 100 parts of zinc dihydrogen phosphate, 15 parts of zinc oxide, 40 parts of phosphoric acid, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 6 parts of triazole compound 2 parts of sodium citrate, 10 parts of polyphosphate, 2 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, 8 parts of sodium molybdate, 2 parts of potassium chlorate, 1 part of hexamethylenetetramine 3 parts of sodium phosphate, it can be seen that compared with Example 1, the configuration of the oxidizing agent component has been increased.
其制备方法为：先在耐酸容器或磷化槽内用适量水将氧化锌15份完全溶解，充分搅拌后再加入磷酸40份继续搅拌，加热至100-120℃保温2小时进行充分反应，待充分反应后加入磷酸二氢锌100份、碳酸锰2份，氟硅酸钠2份，硫酸羟 胺4份，三唑化合物6份，氟化钠2份，过二硫酸铵2份，钼酸钠8份，氯酸钾2份，六亚甲基四胺1份，环三偏磷酸钠3份搅拌均匀，最后加入多聚磷酸盐10份、柠檬酸钠2份，然后再加入适量水进行PH值调整搅拌均匀后即可。Its preparation method is as follows: first dissolve 15 parts of zinc oxide in an acid-resistant container or phosphating tank with an appropriate amount of water, stir thoroughly, then add 40 parts of phosphoric acid and continue stirring, heat to 100-120 ° C for 2 hours to fully react, wait After fully reacting, add 100 parts of zinc dihydrogen phosphate, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 6 parts of triazole compound, 2 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, sodium molybdate 8 parts, 2 parts of potassium chlorate, 1 part of hexamethylenetetramine, 3 parts of sodium cyclic trimetaphosphate, stir evenly, finally add 10 parts of polyphosphate, 2 parts of sodium citrate, and then add appropriate amount of water to adjust the pH value Just mix well.
实施例4Example 4
所述磷化液的原料组成按重量份为：磷酸二氢锌100份，氧化锌15份，磷酸40份，碳酸锰2份，氟硅酸钠2份，硫酸羟胺4份，三唑化合物4份，柠檬酸钠2份，多聚磷酸盐10份，氟化钠2份，过二硫酸铵2份，钼酸钠5份，氯酸钾1份，六亚甲基四胺2份，环三偏磷酸钠5份，可以看出，相比于实施例1，调整了六亚甲基四胺和环三偏磷酸钠组分配置。The raw materials of the phosphating solution are composed in parts by weight: 100 parts of zinc dihydrogen phosphate, 15 parts of zinc oxide, 40 parts of phosphoric acid, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 4 parts of triazole compound 2 parts of sodium citrate, 10 parts of polyphosphate, 2 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, 5 parts of sodium molybdate, 1 part of potassium chlorate, 2 parts of hexamethylenetetramine 5 parts of sodium phosphate, it can be seen that compared with Example 1, the configuration of hexamethylenetetramine and sodium cyclic trimetaphosphate components has been adjusted.
其制备方法为：先在耐酸容器或磷化槽内用适量水将氧化锌15份完全溶解，充分搅拌后再加入磷酸40份继续搅拌，加热至100-120℃保温2小时进行充分反应，待充分反应后加入磷酸二氢锌100份、碳酸锰2份，氟硅酸钠2份，硫酸羟胺4份，三唑化合物4份，氟化钠2份，过二硫酸铵2份，钼酸钠5份，氯酸钾1份，六亚甲基四胺2份，环三偏磷酸钠5份搅拌均匀，最后加入多聚磷酸盐10份、柠檬酸钠2份，然后再加入适量水进行PH值调整搅拌均匀后即可。Its preparation method is as follows: first dissolve 15 parts of zinc oxide in an acid-resistant container or phosphating tank with an appropriate amount of water, stir thoroughly, then add 40 parts of phosphoric acid and continue stirring, heat to 100-120 ° C for 2 hours to fully react, wait After fully reacting, add 100 parts of zinc dihydrogen phosphate, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 4 parts of hydroxylamine sulfate, 4 parts of triazole compound, 2 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, sodium molybdate 5 parts, 1 part of potassium chlorate, 2 parts of hexamethylenetetramine, 5 parts of sodium cyclic trimetaphosphate, stir evenly, finally add 10 parts of polyphosphate, 2 parts of sodium citrate, and then add appropriate amount of water to adjust the pH value Just mix well.
实施例5Example 5
所述磷化液的原料组成按重量份为：磷酸二氢锌80份，氧化锌10份，磷酸30份，碳酸锰2份，氟硅酸钠2份，硫酸羟胺2.5份，三唑化合物6份，柠檬酸钠2份，多聚磷酸盐10份，氟化钠1.5份，过二硫酸铵2份，钼酸钠5份，氯酸钾2份，六亚甲基四胺2份，环三偏磷酸钠4份，The raw materials of the phosphating solution are composed in parts by weight: 80 parts of zinc dihydrogen phosphate, 10 parts of zinc oxide, 30 parts of phosphoric acid, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 2.5 parts of hydroxylamine sulfate, 6 parts of triazole compound , 2 parts of sodium citrate, 10 parts of polyphosphate, 1.5 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, 5 parts of sodium molybdate, 2 parts of potassium chlorate, 2 parts of hexamethylenetetramine, cyclic trimide 4 parts sodium phosphate,
其制备方法为：先在耐酸容器或磷化槽内用适量水将氧化锌10份完全溶解，充分搅拌后再加入磷酸30份继续搅拌，加热至100-120℃保温2小时进行充分反应，待充分反应后加入磷酸二氢锌80份、碳酸锰2份，氟硅酸钠2份，硫酸羟胺2.5份，三唑化合物6份，氟化钠1.5份，过二硫酸铵2份，钼酸钠5份，氯酸钾2份，六亚甲基四胺2份，环三偏磷酸钠4份搅拌均匀，最后加入多聚磷酸盐10份、柠檬酸钠2份，然后再加入适量水进行PH值调整搅拌均匀后即可。The preparation method is as follows: first dissolve 10 parts of zinc oxide in an acid-resistant container or phosphating tank with an appropriate amount of water, stir thoroughly, then add 30 parts of phosphoric acid and continue stirring, heat to 100-120 ° C for 2 hours to fully react, wait After full reaction, add 80 parts of zinc dihydrogen phosphate, 2 parts of manganese carbonate, 2 parts of sodium fluorosilicate, 2.5 parts of hydroxylamine sulfate, 6 parts of triazole compound, 1.5 parts of sodium fluoride, 2 parts of ammonium peroxodisulfate, sodium molybdate 5 parts, 2 parts of potassium chlorate, 2 parts of hexamethylenetetramine, 4 parts of sodium cyclic trimetaphosphate, stir evenly, finally add 10 parts of polyphosphate, 2 parts of sodium citrate, and then add appropriate amount of water to adjust the pH value Just mix well.
将上述实施例1-5得到的磷化液对同一金属工件进行磷化处理，环境参数：室温20℃，常压，湿度70％，其效果参数比较如下：The phosphating solution that above-mentioned embodiment 1-5 obtains is carried out phosphating treatment to same metal workpiece, environmental parameter: room temperature 20 ℃, normal pressure, humidity 70%, its effect parameter is compared as follows:
同时，目前我国的工业生产中只重视生产环节而无视实践操作施工应用，使得好的产品得不到好的应用，进而无法实现相应的技术效果，因此本发明还公开了一种磷化液的使用方法，包括将待处理工件进行磷化前处理和磷化处理两个步骤，磷化前处理主要包括：At the same time, the current industrial production in our country only pays attention to the production link and ignores the practical operation and construction application, so that good products cannot be used well, and the corresponding technical effects cannot be realized. Therefore, the invention also discloses a phosphating solution. The method of use includes two steps of phosphating pre-treatment and phosphating treatment of the workpiece to be treated. The pre-phosphating treatment mainly includes:
1)除油：将待处理工件浸泡在丙酮溶液中，使用超声波清洗器清洗10-15min，将油污进行充分清洗；1) Degreasing: Soak the workpiece to be treated in acetone solution, use an ultrasonic cleaner to clean it for 10-15 minutes, and fully clean the oil stain;
2)碱洗：将待处理工件浸泡在恒温水浴锅中保持60℃，浸洗15-20min，碱洗液为50g/L的Na2PO4、50g/L的Na2CO3，和20g/L的N2SiO3的混合溶液，pH值为7，恒温水浴锅保持温度在60℃作用，时间大约15-20min，采用超声波清洗和碱液除油的目的是为了更好地去除试样表面粘附的冷加工碎屑、油脂和污垢；2) Alkaline cleaning: Soak the workpiece to be treated in a constant temperature water bath at 60°C for 15-20 minutes. The alkaline washing solution is 50g/L Na2 PO4 , 50g/L Na2 CO3 The mixed solution of N2 SiO3 in L, the pH value is 7, the temperature of the constant temperature water bath is kept at 60°C, and the time is about 15-20min. The purpose of ultrasonic cleaning and lye degreasing is to better remove the surface of the sample Adhered cold working debris, grease and dirt;
3)酸洗：所用酸洗液为150mL/L的H2SO4、50mL/L的HF和30mL/L的三乙醇胺的混合溶液，控制温度在25℃左右，酸洗时间约为2min。该酸洗液以硫酸为主酸，配合以氢氟酸和三乙醇胺添加溶合，采用该配制组分的酸性溶液主要用于高合金钢和不锈钢的处理，其能够快速有效地去除工件表面的氧化物。3) Pickling: The pickling solution used is a mixed solution of 150mL/L H2 SO4 , 50mL/L HF and 30mL/L triethanolamine, the temperature is controlled at about 25°C, and the pickling time is about 2 minutes. The pickling solution is mainly sulfuric acid, combined with hydrofluoric acid and triethanolamine, the acid solution is mainly used for the treatment of high-alloy steel and stainless steel, it can quickly and effectively remove the surface of the workpiece oxide.
4)水洗：先用去离子水冲洗干净，但在物体表面尤其是表面凹处、小孔部位仍残留酸液，容易再次产生生锈，需要在水洗之后进行中和处理，主要使用20-40g/L的碳酸钠溶液，处理1-2min，然后进行二次去离子水冲洗，冷风吹干后待用；4) Washing: first rinse with deionized water, but acid remains on the surface of the object, especially in the recesses and small holes on the surface, which is prone to rust again, and needs to be neutralized after washing, mainly using 20-40g /L of sodium carbonate solution, treated for 1-2min, then rinsed with deionized water twice, and dried with cold air before use;
所述磷化处理包括：使用耐酸刷直接将上述实施例1-5方法制备所得磷化液在工件上均匀涂刷一层磷化液膜，或者使用喷枪喷淋一层磷化液膜，或者进行浸泡处理，然后干燥即可，工件表面形成的磷化膜结晶致密，磷化表面无挂灰、反白现象产生，膜层本身无脆性，即达到工艺要求。The phosphating treatment includes: using an acid-resistant brush to directly apply the obtained phosphating solution prepared by the method of the above-mentioned embodiment 1-5 to evenly brush a layer of phosphating solution film on the workpiece, or use a spray gun to spray a layer of phosphating solution film, or Soaking treatment, and then drying, the phosphating film formed on the surface of the workpiece is crystallized and dense, the phosphating surface is free of dust and whitening, and the film itself is not brittle, that is, it meets the process requirements.
尽管上文对本发明的具体实施方式给予了详细描述和说明，但是应该指明的是，我们可以依据本发明的构想对上述实施方式进行各种等效改变和修改，其所产生的功能作用仍未超出说明书所涵盖的精神时，均应在本发明的保护范围之内。以上所述，仅为本发明的较佳实施例，并不用以限制本发明，凡是依据本发明的技术实质对以上实施例所作的任何细微修改、等同替换和改进，均应包含在本发明技术方案的保护范围之内。Although the specific embodiments of the present invention have been described and illustrated in detail above, it should be pointed out that we can make various equivalent changes and modifications to the above-mentioned embodiments according to the concept of the present invention, and the functional effects produced by it are still the same. Anything beyond the spirit covered by the description shall be within the protection scope of the present invention. The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any minor modifications, equivalent replacements and improvements made to the above embodiments according to the technical essence of the present invention shall be included in the technical aspects of the present invention. within the scope of protection of the program.
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| CN201711110115.6ACN107620057B (en) | 2015-12-10 | 2015-12-10 | A kind of application method of the phosphating solution for metal processing |
| CN201510900020.9ACN105483682B (en) | 2015-12-10 | 2015-12-10 | A kind of phosphating solution for metal treatment and preparation method thereof |
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