WO2018218436A1 - 改性磷化剂、金属件及其表面磷化处理方法 - Google Patents
改性磷化剂、金属件及其表面磷化处理方法 Download PDFInfo
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- WO2018218436A1 WO2018218436A1 PCT/CN2017/086360 CN2017086360W WO2018218436A1 WO 2018218436 A1 WO2018218436 A1 WO 2018218436A1 CN 2017086360 W CN2017086360 W CN 2017086360W WO 2018218436 A1 WO2018218436 A1 WO 2018218436A1
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
Definitions
- Modified phosphating agent, metal parts and surface phosphating treatment method thereof Modified phosphating agent, metal parts and surface phosphating treatment method thereof
- the present invention relates to the technical field of metal surface treatment, and in particular to a modified phosphating agent, a metal member and a surface phosphating treatment method thereof.
- the surface of the workpiece is usually treated.
- the surface treatment of aluminum, iron and their alloys goes deep into all walks of life.
- most of the work needs to be pretreated before surface treatment, for example, cleaning, decontamination and degreasing, and metal parts for certain purposes also need to be phosphatized, passivated and the like.
- Phosphating treatment generally uses a phosphating agent to pretreat a metal member to form a film layer on the surface of the metal member for subsequent surface treatment, thereby increasing the bonding force and corrosion resistance of the subsequent film.
- phosphating is required on the surface of the metal part to prevent corrosion of the surface of the workpiece and increase the adhesion between the workpiece and the coating.
- the existing phosphating agents have high energy consumption, many precipitates, short service life and low anti-corrosion performance, and complicated operation (preservation is required before phosphating, and phosphating solution needs to be quantitatively added with phosphating agent, and strict Control acidity).
- a modified phosphating agent with fine structure, strong adhesion, good corrosion resistance, low processing temperature, low energy consumption and simple operation, and a phosphating treatment method and phosphating of a metal part are provided. Metal parts produced after processing.
- a modified phosphating agent for forming phosphating on a surface of a metal member comprising 1000 parts by weight, including the following parts by weight: 5-30 parts of phosphoric acid, 3-10 parts of zinc oxide, 0.5 - 3 parts of molybdenum salt, 0.5-5 parts of bismuth nitrate
- the balance is water.
- a method for phosphating a surface of a metal part comprising the steps of: formulating a modified phosphating agent as described above, brushing, dipping or spraying the metal phosphating agent solution through a predetermined daytime treatment; After, washing metal parts , dry.
- the modified phosphating agent forms a film structure with fine adhesion, good adhesion and good corrosion resistance. After processing the metal parts, the temperature is low, the energy consumption is low, and the operation is simple, and the steel surface can be used as a phosphating before spraying on the steel surface. Processing.
- Embodiments of the present invention provide a modified phosphating agent for surface pretreatment of metal parts, comprising 1000 parts by weight, including the following parts by weight: 5-30 parts of phosphoric acid, 3-10 parts of oxidation Zinc, 0.5-3 parts of molybdenum salt, 0.5 to 5 parts of cerium nitrate, the balance being water.
- the modified phosphating agent further includes 0.2-3 parts of nickel nitrate and 0.5-5 parts of calcium nitrate.
- the cerium nitrate is in an amount of from 1 to 3 parts by weight
- the nickel nitrate is in an amount of from 0.5 to 2 parts by weight
- the calcium nitrate is in an amount of from 1 to 3 parts by weight.
- the purity of the phosphoric acid is ⁇ 85%
- the weight fraction of the phosphoric acid is preferably 10-20 parts.
- the molybdenum salt is preferably sodium molybdate or ammonium heptamolybdate, and the molybdenum salt is in an amount of from 1 to 2 parts by weight.
- the zinc oxide is 5-8 parts by weight.
- a preferable film forming effect is achieved by controlling the balance of the respective distribution ratios. For example, when the phosphoric acid content is low, the film formation is too slow and too thin, and even film formation is not possible. On the contrary, if the reaction is too fast, the film formation is too fast, the formed film is dissolved again, and the film is not strong enough, so the phosphoric acid is preferred in this embodiment.
- the parts by weight are 10-20.
- zinc oxide and phosphoric acid function to provide a main component of the phosphate film.
- Molybdenum salt is used as a secondary component of the accelerator and the film layer.
- Nickel nitrate is used to improve the corrosion resistance of the film layer.
- the barium salt and the calcium salt fill the pores of the phosphate film, increase the hardness of the film, and the wear resistance of the film layer. Corrosion resistance and adhesion are significantly improved.
- the phosphating agent formed by the modified phosphating agent has fine phosphating structure, strong adhesion, good corrosion resistance, low treatment temperature, low energy consumption and simple operation, and can be used as a treatment for phosphating before spraying on the steel surface.
- Embodiments of the present invention also provide a method for phosphating a surface of a metal member, which comprises the following steps: In the modified phosphating agent described above, the metal material is brushed, immersed or sprayed with the modified phosphating agent solution, and after a predetermined daytime treatment, the metal member is washed with water and dried.
- the temperature of the modified phosphating agent is controlled at 10 ° C to 50 ° C, preferably at about 35 ° C.
- the metal member is immersed in the crucible solution for a period of preferably 5-15 minutes.
- the embodiment of the present invention also provides a metal member which is treated by the surface phosphating treatment of the metal member as described above to form phosphating on the surface of the metal member. Phosphating protects metal parts and is bright in color.
- the modified phosphating agent of the embodiment of the present invention, a treatment method thereof and the like will be described by way of specific examples.
- the ingredients are mixed in the following parts by weight (total amount of 1000 parts by weight): 5 parts of phosphoric acid, 3 parts of zinc oxide
- Treatment method preparing the modified phosphating agent; taking the cold-rolled plate as an example, the cold-rolled plate is immersed in the phosphating solution, the temperature is controlled at 35 ° C, after 10 minutes of immersion treatment, the metal is washed. Pieces, dry. During the treatment, phosphating agent can be added to ensure the effect of the working fluid. The phosphating drying temperature should not be too high, and should be controlled at room temperature to 120 ° C to prevent cracks in the film layer due to excessive temperature.
- the components are mixed in the following parts by weight (total amount of 1000 parts by weight): 10 parts of phosphoric acid, 5 parts of zinc oxide, 1 part of ammonium heptamolybdate, 1 part of cerium nitrate, 0.2 part of nickel nitrate, 0.5 parts of calcium nitrate, the balance is water, stirred, evenly mixed, and formulated into a phosphating agent.
- Treatment method preparing a modified phosphating agent; taking a cold-rolled plate as an example, the cold-rolled plate is immersed in a phosphating solution, and the temperature is controlled at 35 ° C. After 10 minutes of immersion treatment, the metal is washed. Pieces, dry. During the treatment, phosphating agent can be added to ensure the effect of the working fluid.
- the phosphating drying temperature should not be too high, and should be controlled at room temperature to 120 ° C to prevent cracks in the film layer due to excessive temperature.
- the components are mixed in the following parts by weight (total amount of 1000 parts by weight): 20 parts of phosphoric acid, 8 parts of zinc oxide, 2 parts of molybdenum salt, 2 parts of cerium nitrate, 1 part of nickel nitrate, 1 part Calcium nitrate, the balance is water, stirred, evenly mixed, and formulated into a phosphating agent.
- Treatment method preparing the modified phosphating agent; taking the cold-rolled plate as an example, the cold-rolled plate is immersed in the phosphating solution, the temperature is controlled at 35 ° C, after 10 minutes of immersion treatment, the metal is washed. Pieces, dry. During the treatment, phosphating agent can be added to ensure the effect of the working fluid. The phosphating drying temperature should not be too high, and should be controlled at room temperature to 120 ° C to prevent cracks in the film layer due to excessive temperature.
- the components are mixed in the following parts by weight (total amount 1000 parts by weight): 25 parts of phosphoric acid, 9 parts of zinc oxide, 2 parts of sodium molybdate, 3 parts of cerium nitrate, 2 parts of nickel nitrate, 3 Part of calcium nitrate, the balance is water, stirred, evenly mixed, formulated as a phosphating agent.
- Processing method preparing a modified phosphating agent; taking a cold-rolled plate as an example, the cold-rolled plate is immersed in a phosphating solution, and the temperature is controlled at 35 ° C. After 10 minutes of immersion treatment, the metal is washed. Pieces, dry. During the treatment, phosphating agent can be added to ensure the effect of the working fluid.
- the phosphating drying temperature should not be too high, and should be controlled at room temperature to 120 ° C to prevent cracks in the film layer due to excessive temperature.
- the components are mixed in the following parts by weight (total amount 1000 parts by weight): 30 parts of phosphoric acid, 10 parts of zinc oxide, 3 parts of ammonium heptamolybdate, 5 parts of cerium nitrate, 3 parts of nickel nitrate, 5 parts of calcium nitrate, the balance is water, stirred, evenly mixed, and formulated into a phosphating agent.
- Treatment method preparing a modified phosphating agent; metal parts are taken as a cold-rolled sheet, and the cold-rolled sheet is immersed in a phosphating agent. In the liquid, the temperature is controlled at 35 ° C. After soaking for 10 minutes, the metal parts are washed and dried. During the treatment, phosphating agent can be added to ensure the effect of the working fluid.
- the phosphating drying temperature should not be too high, and should be controlled at room temperature to 120 ° C to prevent cracks in the film layer due to excessive temperature.
- the phosphating is fine.
- the copper sulfate test is more than 60S in the daytime. After spraying, it is tested according to the adhesion of 2 small boiling water, and the adhesion is evaluated to 0.
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Abstract
一种改性磷化剂，以1000重量份计，包括如下重量份数的成分：5-30份磷酸，3-10份的氧化锌，0.5-3份的钼盐，0.5-5份的硝酸钡和余量的水。改性磷化剂使用寿命长，使用温度为10-50℃，用于金属件表面预处理形成彩色的磷化层，且结构细致，附着力牢固。还公开了一种金属件表面磷化处理方法，以及通过表面磷化处理方法得到的金属件。
Description
改性磷化剂、 金属件及其表面磷化处理方法 技术领域
[0001] 本发明涉及金属表面处理技术领域， 具体涉及一种改性磷化剂、 金属件及其表 面磷化处理方法。
背景技术
[0002] 为提高产品表面性能或者外观， 通常对工件表面处理。 例如， 铝、 铁及其合金 的表面处理工艺深入各行各业中。 而且， 大多数工作在进行表面处理前还需要 经过预处理， 例如， 进行清洗， 除污除油， 某些用途的金属件还需要进行磷化 ， 钝化等处理。
[0003] 磷化处理一般采用磷化剂对金属件进行预处理， 以在金属件表面形成膜层， 以 便进行后续的表面处理， 增加后续膜的结合力和防腐力。 例如， 对金属件进行 喷涂处理之前， 需要在金属件表面形成磷化， 以在工件处理吋对其表面进行防 腐， 增加工件和涂层之间的附着力。 然而， 现有的磷化剂能耗高， 沉淀多， 使 用寿命短且防腐性能不强， 操作复杂 （磷化前需要表调， 磷化液中需要定吋定 量添加磷化剂， 还需要严格控制酸度） 。
技术问题
[0004] 有鉴于此， 提供一种结构细致、 附着力牢固、 防腐性好、 处理温度低、 能耗低 且操作简单的改性磷化剂， 以及金属件表面磷化处理方法和经过磷化处理后制 得的金属件。
问题的解决方案
技术解决方案
[0005] 一种改性磷化剂， 用于在金属件表面形成磷化， 以 1000重量份计， 包括如下重 量份数的成分： 5-30份磷酸， 3-10份的氧化锌， 0.5-3份的钼盐， 0.5-5份的硝酸钡
， 余量为水。
[0006] 一种金属件表面磷化处理方法， 其包括下列步骤： 配制如上所述的改性磷化剂 ， 将金属件刷、 浸或喷该改性磷化剂溶液， 经过预定吋间处理后， 水洗金属件
， 干燥。
[0007] 以及， 一种金属件， 其表面具有通过如上所述的金属件表面磷化处理方法形成 的磷化。
发明的有益效果
有益效果
[0008] 上述改性磷化剂形成的膜层结构细致， 附着力牢固、 防腐性好， 在对金属件进 行处理吋， 温度低、 能耗低且操作简单， 可作为钢铁表面喷涂前磷化的处理。
本发明的实施方式
[0009] 以下将结合具体实施例对本发明进行详细说明。
[0010] 本发明实施例提供一种改性磷化剂， 用于金属件表面预处理， 以 1000重量份计 ， 包括如下重量份数的成分： 5-30份磷酸， 3-10份的氧化锌， 0.5-3份的钼盐， 0. 5-5份的硝酸钡， 余量为水。
[0011] 具体地， 改性磷化剂还包括 0.2-3份的硝酸镍和 0.5-5份硝酸钙。 所述硝酸钡的重 量份数为 1-3份， 所述硝酸镍的重量份数为 0.5-2份， 所述硝酸钙的重量份数为 1-3 份。 所述磷酸的纯度≥85%， 所述磷酸的重量份数优选为 10-20份。 所述钼盐优选 为钼酸钠或七钼酸铵， 所述钼盐的重量份数为 1-2份。 所述氧化锌的重量份数为 5 -8份。
[0012] 在上述改性磷化剂中， 通过控制各成分配比平衡， 以达到较佳成膜效果。 例如 ， 当磷酸含量低， 成膜则过慢过薄， 甚至不能成膜， 反之则反应过快导致成膜 过快， 刚成的膜又会被溶解， 膜不够牢固， 所以本实施例优选磷酸的重量份数 为 10-20。 其中， 氧化锌和磷酸的作用在于提供磷化膜的主要成分。 钼盐作为促 进剂和膜层的次要成分， 硝酸镍用于提高膜层的耐蚀性， 钡盐和钙盐填补磷化 膜的孔隙， 增加膜的硬度， 对于膜层的耐磨性， 防腐性， 附着力都有显著的提 高。
[0013] 本实施例中， 改性磷化剂形成的磷化结构细致、 附着力牢固、 防腐性好、 处理 温度低、 能耗低且操作简单， 可作为钢铁表面喷涂前磷化的处理。
[0014] 本发明实施例还提供一种金属件表面磷化处理方法， 其包括下列步骤： 配制如
上所述的改性磷化剂， 将金属件刷、 浸或喷该改性磷化剂溶液， 经过预定吋间 处理后， 水洗金属件， 干燥。
[0015] 在金属件浸入磷化剂溶液表面处理吋， 改性磷化剂温度控制在 10°C-50°C， 优选 为控制在 35°C左右。 金属件浸入磷化剂溶液的吋间优选为 5-15分钟。 本发明实施 例还提供一种金属件， 其通过如上所述的金属件表面磷化处理方法进行处理， 在金属件表面形成磷化。 磷化可对金属件进行保护， 且色泽光亮。 以下通过具 体实例说明本发明实施例的改性磷化剂及其处理方法等方面。
[0016] 实施例 1
[0017] 按照下列重量份数混合各成分 （总量为 1000重量份） ： 5份磷酸， 3份的氧化锌
， 0.5份的钼酸钠， 0.5份的硝酸钡和余量为水， 搅拌， 混合均匀， 配制成磷化剂
[0018] 处理方法： 配制好改性磷化剂； 金属件以冷轧板为例， 将冷轧板浸入磷化剂溶 液中， 控制温度在 35°C， 经过 10分钟浸泡处理后， 水洗金属件， 干燥。 在处理过 程中， 可及吋添加磷化剂， 以保证工作液的效果。 磷化干燥温度不宜过高， 应 控制在常温至 120摄氏度， 防止因为温度过高导致膜层出现裂痕。
[0019] 经过上述磷化剂溶液处理后， 观察工件表面， 发现工件表面呈彩色， 颜色均匀 ， 磷化细致， 硫酸铜点滴试验吋间约 20S， 喷涂处理后按照 2小吋沸水附着性测 试， 附着力评定 1级。
[0020] 实施例 2
[0021] 按照下列重量份数混合各成分 （总量为 1000重量份） ： 10份磷酸， 5份的氧化 锌， 1份的七钼酸铵， 1份的硝酸钡， 0.2份的硝酸镍， 0.5份硝酸钙， 余量为水， 搅拌， 混合均匀， 配制成磷化剂。
[0022] 处理方法： 配制好改性磷化剂； 金属件以冷轧板为例， 将冷轧板浸入磷化剂溶 液中， 控制温度在 35°C， 经过 10分钟浸泡处理后， 水洗金属件， 干燥。 在处理过 程中， 可及吋添加磷化剂， 以保证工作液的效果。 磷化干燥温度不宜过高， 应 控制在常温至 120摄氏度， 防止因为温度过高导致膜层出现裂痕。
[0023] 经过上述磷化剂溶液处理后， 观察工件表面， 发现工件表面呈彩色， 颜色均匀 ， 磷化细致， 硫酸铜点滴试验吋间大于 60S， 喷涂处理后按照 2小吋沸水附着性
测试， 附着力评定 0级。
[0024] 实施例 3
[0025] 按照下列重量份数混合各成分 （总量为 1000重量份） ： 20份磷酸， 8份的氧化 锌， 2份的钼盐， 2份的硝酸钡， 1份的硝酸镍， 1份硝酸钙， 余量为水， 搅拌， 混合均匀， 配制成磷化剂。
[0026] 处理方法： 配制好改性磷化剂； 金属件以冷轧板为例， 将冷轧板浸入磷化剂溶 液中， 控制温度在 35°C， 经过 10分钟浸泡处理后， 水洗金属件， 干燥。 在处理过 程中， 可及吋添加磷化剂， 以保证工作液的效果。 磷化干燥温度不宜过高， 应 控制在常温至 120摄氏度， 防止因为温度过高导致膜层出现裂痕。
[0027] 经过上述磷化剂溶液处理后， 观察工件表面， 发现工件表面呈彩色， 颜色均匀 ， 磷化细致， 硫酸铜点滴试验吋间大于 60S， 喷涂处理后按照 2小吋沸水附着性 测试， 附着力评定 0级。
[0028] 实施例 4
[0029] 按照下列重量份数混合各成分 （总量为 1000重量份） ： 25份磷酸， 9份的氧化 锌， 2份的钼酸钠， 3份的硝酸钡， 2份的硝酸镍， 3份硝酸钙， 余量为水， 搅拌 ， 混合均匀， 配制成磷化剂。
[0030] 处理方法： 配制好改性磷化剂； 金属件以冷轧板为例， 将冷轧板浸入磷化剂溶 液中， 控制温度在 35°C， 经过 10分钟浸泡处理后， 水洗金属件， 干燥。 在处理过 程中， 可及吋添加磷化剂， 以保证工作液的效果。 磷化干燥温度不宜过高， 应 控制在常温至 120摄氏度， 防止因为温度过高导致膜层出现裂痕。
[0031] 经过上述磷化剂溶液处理后， 观察工件表面， 发现工件表面呈彩色， 颜色均匀 ， 磷化细致， 硫酸铜点滴试验吋间大于 60S， 喷涂处理后按照 2小吋沸水附着性 测试， 附着力评定 0级。
[0032] 实施例 5
[0033] 按照下列重量份数混合各成分 （总量为 1000重量份） ： 30份磷酸， 10份的氧化 锌， 3份的七钼酸铵， 5份的硝酸钡， 3份的硝酸镍， 5份硝酸钙， 余量为水， 搅 拌， 混合均匀， 配制成磷化剂。
[0034] 处理方法： 配制好改性磷化剂； 金属件以冷轧板为例， 将冷轧板浸入磷化剂溶
液中， 控制温度在 35°C， 经过 10分钟浸泡处理后， 水洗金属件， 干燥。 在处理过 程中， 可及吋添加磷化剂， 以保证工作液的效果。 磷化干燥温度不宜过高， 应 控制在常温至 120摄氏度， 防止因为温度过高导致膜层出现裂痕。
[0035] 经过上述磷化剂溶液处理后， 观察工件表面， 发现工件表面呈彩色， 颜色均匀
， 磷化细致， 硫酸铜点滴试验吋间大于 60S， 喷涂处理后按照 2小吋沸水附着性 测试， 附着力评定 0级。
[0036] 需要说明的是， 本发明并不局限于上述实施方式， 根据本发明的创造精神， 本 领域技术人员还可以做出其他变化， 这些依据本发明的创造精神所做的变化， 都应包含在本发明所要求保护的范围之内。
Claims
[权利要求 1] 一种改性磷化剂， 用于在金属件表面形成磷化， 其特征在于， 以 1000 重量份计， 包括如下重量份数的成分： 5-30份磷酸， 3-10份的氧化锌 ， 0.5-3份的钼盐， 0.5-5份的硝酸钡和余量为水。
[权利要求 2] 如权利要求 1所述的改性磷化剂， 其特征在于， 还包括 0.2-3份的硝酸 镍和 0.5-5份硝酸钙。
[权利要求 3] 如权利要求 1所述的改性磷化剂， 其特征在于， 所述磷酸的纯度≥85%
[权利要求 4] 如权利要求 1所述的改性磷化剂， 其特征在于， 所述钼盐为钼酸钠或 七钼酸铵， 所述钼盐的重量份数为 1-2份。
[权利要求 5] 如权利要求 1所述的改性磷化剂， 其特征在于， 所述磷酸的重量份数 为 10-20份。
[权利要求 6] 如权利要求 1所述的改性磷化剂， 其特征在于， 所述氧化锌的重量份 数为 5-8份。
[权利要求 7] 如权利要求 2所述的改性磷化剂， 其特征在于 所述硝酸钡的重量份 数为 1-3份， 所述硝酸镍的重量份数为 0.5-2份 所述硝酸钙的重量份 数为 1-3份。
[权利要求 8] 一种金属件表面磷化处理方法， 其包括下列步骤： 配制如权利要求 I
7任一项所述的改性磷化剂， 将金属件刷、 浸或喷该改性磷化剂溶液 ， 经过预定吋间处理后， 水洗金属件， 干燥。
[权利要求 9] 一种金属件， 其特征在于， 所述金属件表面通过如权利要求 8所述的 金属件表面磷化处理方法形成有磷化。
[权利要求 10] 如权利要求 9所述的金属件， 其特征在于， 所述金属件为冷轧板、 热 轧板或角钢等钢铁。
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| CN201780090679.XA CN110691863A (zh) | 2017-05-27 | 2017-05-27 | 改性磷化剂、金属件及其表面磷化处理方法 |
| PCT/CN2017/086360 WO2018218436A1 (zh) | 2017-05-27 | 2017-05-27 | 改性磷化剂、金属件及其表面磷化处理方法 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3681148A (en) * | 1967-03-10 | 1972-08-01 | Collardin Gmbh Gerhard | Process for the application of thin,continuous phosphate layers on metal surfaces |
| CN101109081A (zh) * | 2007-04-30 | 2008-01-23 | 余取民 | 磷化后可免水洗的常温钡盐改性磷化液 |
| CN102747356A (zh) * | 2012-07-30 | 2012-10-24 | 长沙学院 | 一种常温锰钙系磷化液 |
-
2017
- 2017-05-27 CN CN201780090679.XA patent/CN110691863A/zh not_active Withdrawn
- 2017-05-27 WO PCT/CN2017/086360 patent/WO2018218436A1/zh active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3681148A (en) * | 1967-03-10 | 1972-08-01 | Collardin Gmbh Gerhard | Process for the application of thin,continuous phosphate layers on metal surfaces |
| CN101109081A (zh) * | 2007-04-30 | 2008-01-23 | 余取民 | 磷化后可免水洗的常温钡盐改性磷化液 |
| CN102747356A (zh) * | 2012-07-30 | 2012-10-24 | 长沙学院 | 一种常温锰钙系磷化液 |
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