WO2017219368A1 - 锰系磷化剂、金属件及其表面磷化处理方法 - Google Patents

锰系磷化剂、金属件及其表面磷化处理方法 Download PDF

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WO2017219368A1
WO2017219368A1 PCT/CN2016/087140 CN2016087140W WO2017219368A1 WO 2017219368 A1 WO2017219368 A1 WO 2017219368A1 CN 2016087140 W CN2016087140 W CN 2016087140W WO 2017219368 A1 WO2017219368 A1 WO 2017219368A1
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parts
phosphating
manganese
metal member
solution
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PCT/CN2016/087140
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French (fr)
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王饶玲
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深圳市恒兆智科技有限公司
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Priority to PCT/CN2016/087140 priority Critical patent/WO2017219368A1/zh
Publication of WO2017219368A1 publication Critical patent/WO2017219368A1/zh

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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

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  • the present invention relates to the field of metal surface treatment technology, and in particular to a manganese phosphating agent, a metal member and a surface phosphating treatment method thereof.
  • the surface treatment technology of the workpiece is usually applied.
  • 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 some metal parts need to be phosphated.
  • Phosphating treatment generally uses a phosphating agent to pretreat a metal member to form a passivation layer on the surface of the metal member for subsequent surface treatment, thereby increasing the bonding force, corrosion resistance, lubricity, and the like of the subsequent film.
  • a phosphating agent for example, automotive transmission gears and other transmissions require a manganese film on their surface and a lubricant to improve their lubricity, wear resistance and noise reduction.
  • most of the existing phosphating agents are zinc-based and zinc-manganese, and they are insufficient in abrasion resistance and lubricity.
  • a pure manganese phosphating agent having a dense crystal layer, a film thickness, a high hardness, and a high corrosion resistance, and a phosphating treatment method on the surface of the metal member and a phosphating treatment are provided.
  • metallic parts are provided.
  • a manganese-based phosphating agent for forming a film on a surface of a metal member comprising 1800 parts by weight, including the following parts by weight: 40-80 parts of phosphoric acid, 3.5-7 parts of magnesium oxide, 10-20 Parts of calcium nitrate, 84-150 parts of nitric acid solution 375-500 parts of manganese salt, 10-20 nickel nitrate and the balance of water.
  • a method for phosphating a surface of a metal member comprising the steps of: formulating a manganese phosphating agent as described above; dissolving the manganese phosphating agent in water to prepare a phosphating solution, wherein the phosphating solution
  • the manganese phosphating agent has a mass concentration of 15-20%, and the metal member is immersed in the phosphating solution to control the total acidity of the phosphating solution to be 30-70 pt.
  • the metal parts are washed and dried.
  • the above-mentioned manganese phosphating agent is compounded by a manganese salt, a nitrate salt and various additives, and the formed film layer has a dense crystal, a film thickness, a high hardness, and a strong corrosion resistance.
  • the manganese phosphating agent can be widely used for metal anti-corrosion and antifriction lubrication of bearings, gears, screw fasteners and the like.
  • Embodiments of the present invention provide a manganese phosphating agent for forming a film on a surface of a metal member, comprising 1800 parts by weight, including the following parts by weight: 40-80 parts of phosphoric acid, 3.5-7 parts of oxidation Magnesium, 10-20 parts of calcium nitrate, 84-150 parts of nitric acid solution 375-500 parts of manganese salt, 10-20 nickel nitrate and balance water.
  • the parts by weight of the phosphoric acid are preferably 50 to 70 parts by weight.
  • the magnesium oxide is preferably from 4 to 6 parts by weight.
  • the calcium nitrate is used in an amount of 12 to 16 parts by weight.
  • the parts by weight of the nitric acid solution are preferably from 100 to 12 parts by weight.
  • the mass concentration of the nitric acid solution is preferably from 40 to 65%, more preferably 45%.
  • the nickel nitrate has a weight fraction of 12-16 parts.
  • the manganese salt is preferably manganese acid phosphate in a part by weight of 400 to 450 parts.
  • the manganese phosphating agent preferably has a total acidity of 40 to 60 pt, and cerium is used, and the manganese phosphating agent has a mass concentration of 15 to 20.
  • nitric acid is preferred in this embodiment.
  • the parts by weight are 100-120 parts.
  • the phosphoric acid stabilizes the bath pH and is the main film-forming component.
  • Manganese salt is the main film-forming component. Magnesium oxide, calcium nitrate, and nickel nitrate can increase the corrosion resistance and wear resistance of the phosphate film.
  • the manganese-based phosphating film has a large thickness, a small number of pores, and a phosphating grain is densely granulated, and can be widely used for anti-corrosion, cold working, bearing and the like.
  • the manganese phosphating agent is compounded by a manganese salt, a nitrate and various additives.
  • the metal workpiece is immersed in an acidic treatment liquid prepared from the phosphating solution, and the metal interacts with the acid and the salt to form a layer of a water-insoluble protective black film on the surface of the workpiece. Crystallization of the film Dense, with film thickness, high hardness, strong corrosion resistance and so on.
  • the embodiment of the present invention further provides a metal component surface phosphating treatment method, comprising the steps of: preparing a manganese phosphating agent as described above; dissolving the manganese phosphating agent in water to prepare a phosphating solution, The mass concentration of the manganese phosphating agent in the phosphating solution is 15-20%, the metal member is immersed in the phosphating solution, and the total acidity of the phosphating solution is controlled to be 30-70 pt. After the predetermined daytime treatment, the metal is washed. Pieces, dry.
  • the total acidity of the phosphating solution is preferably 40 to 60 pt.
  • the metal member is immersed in the phosphating solution for 8-12 minutes.
  • the metal workpiece is degreased and pickled, and after the metal member is immersed in the phosphating solution, the metal member is further saponified or immersed in the rust inhibitor or immersed in the lubricant.
  • the phosphating treatment temperature is 92-98 °C.
  • the total acidity measurement method is as follows: Pipette 10 mL of manganese phosphating agent test solution into a 250 mL Erlenmeyer flask, and add 2-3 drops of phenolphthalein indicator solution. Use O.lmol/L sodium hydroxide standard droplets until the solution is pink, which is the end point. The milliliters of sodium hydroxide standard solution consumed is the total acidity of the bath.
  • Embodiments of the present invention also provide a metal member which is processed by a surface phosphating treatment method of a metal member as described above to form a film on the surface of the metal member.
  • the film protects and lubricates metal parts with high hardness and high corrosion resistance.
  • the components are mixed in the following parts by weight (total amount is 1800 parts by weight): 40 parts of phosphoric acid, 3.5 parts of magnesium oxide, 10 parts of calcium nitrate, 84 parts of nitric acid solution, 375 parts of manganese salt, 10 parts of nickel nitrate and The balance of water, stirred, mixed evenly, formulated as a phosphating agent.
  • Phosphating treatment method preparing the manganese phosphating agent according to the above method; taking the iron piece as an example, the iron piece is immersed in the phosphating solution, and the total acidity of the phosphating solution is controlled to be 40-60 pt, at 95 At a temperature of 8 minutes, after washing for 8 minutes, the metal parts are washed and dried. During the treatment, phosphating agent can be added to ensure the effect of the working fluid.
  • ingredients are mixed in the following parts by weight (total amount is 1800 parts by weight): 60 parts of phosphoric acid, 4 parts of magnesium oxide
  • Phosphating treatment method preparing the manganese phosphating agent according to the above method; taking the iron member as an example, the iron member is immersed in the phosphating solution, and the total acidity of the phosphating solution is controlled to be 40-60 pt, at 95 At a temperature of 8 minutes, after washing for 8 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 surface of the workpiece was observed, and it was found that the surface of the workpiece had a black film layer, the color was uniform, and the film was fine, and the nail was able to draw a clear imprint, and the thickness of the phosphating film layer was about 10-30 ⁇ ( Micron), suitable for metal anti-corrosion and anti-friction lubrication of bearings, gears, screw fasteners, etc.
  • ingredients are mixed in the following parts by weight (total amount is 1800 parts by weight): 70 parts of phosphoric acid, 5 parts of magnesium oxide
  • Phosphating treatment method preparing the manganese phosphating agent according to the above method; taking the iron member as an example, the iron member is immersed in the phosphating solution, and the total acidity of the phosphating solution is controlled to be 40-60 pt, at 98 At a temperature of 10 minutes, after washing 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 surface of the workpiece is observed, and a black film layer is found on the surface of the workpiece, the color is uniform, the film is fine, and the nail can be used to draw a clear imprint, and the thickness of the phosphating film layer is about 10-30 ⁇ ( Micron), suitable for metal anti-corrosion and anti-friction lubrication of bearings, gears, screw fasteners, etc.
  • ingredients are mixed in the following parts by weight (total amount is 1800 parts by weight): 80 parts of phosphoric acid, 7 parts of magnesium oxide
  • Phosphating treatment method preparing the manganese phosphating agent according to the above method; taking the iron member as an example, the iron member is immersed in the phosphating solution, and the total acidity of the phosphating solution is controlled to be 40-60 pt, at 98 At temperature, after 12 minutes After the clock is processed, the metal parts are washed and dried. During the treatment, phosphating agent can be added to ensure the effect of the working fluid.
  • the surface of the workpiece is observed, and a black film layer is found on the surface of the workpiece, the color is uniform, and the film is fine, and the nail can be used to draw a clear imprint.
  • the thickness of the phosphating film layer is about 10-30 ⁇ ( Micron), suitable for metal anti-corrosion and anti-friction lubrication of bearings, gears, screw fasteners, etc.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

一种锰系磷化剂、金属件及其表面磷化处理方法。锰系磷化剂用于在金属件表面形成皮膜，以1800重量份计，其包括如下重量份数的成分：40-80份磷酸，3.5-7份氧化镁，10-20份的硝酸钙，84-150份硝酸溶液，375-500份锰盐、10-20硝酸镍和余量水。上述锰系磷化剂形成的膜层结晶为层叠半球状，能够极好的储存润滑油，其膜厚，硬度高，耐蚀性强。

Description

锰系磷化剂、 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， 具体涉及一种锰系磷化剂、 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技术。 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钝化层， 以便进行后续的表面处理， 增加后续膜的结合力和防腐力、 润滑性等。 例如， 汽车变速箱齿轮及其他传动件需要在其表面形成锰系皮膜， 再涂润滑剂， 以提 高其润滑性， 耐磨性和减少噪音。 然而， 现有的磷化剂大多使用锌系， 锌锰系 ， 在耐磨性、 润滑性等方面表现不足。
技术问题
[0004] 有鉴于此， 提供一种膜层结晶致密、 膜厚， 硬度高， 耐蚀性强的纯锰系磷化剂 ， 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] 一种锰系磷化剂， 用于在金属件表面形成皮膜， 以 1800重量份计， 包括如下重 量份数的成分： 40-80份磷酸， 3.5-7份氧化镁， 10-20份的硝酸钙， 84-150份硝酸 溶液 375-500份锰盐、 10-20硝酸镍和余量水。
[0006] 一种金属件表面磷化处理方法， 其包括下列步骤： 配制如上所述的锰系磷化剂 ； 将锰系磷化剂溶于水中配制成磷化溶液， 所述磷化溶液中锰系磷化剂的质量 浓度为 15-20%， 将金属件浸入磷化溶液中， 控制磷化溶液的总酸度为 30-70pt， 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 的皮膜。
发明的有益效果
有益效果
[0008] 上述锰系磷化剂由锰盐、 硝酸盐和多种添加剂复配而成， 形成的膜层结晶致密 ， 具膜厚， 硬度高， 耐蚀性强等特点。 该锰系磷化剂可广泛应用于金属防腐蚀 及轴承、 齿轮、 螺丝紧固件等减摩润滑。
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锰系磷化剂， 用于在金属件表面形成皮膜， 以 1800重量 份计， 包括如下重量份数的成分： 40-80份磷酸， 3.5-7份氧化镁， 10-20份的硝酸 钙， 84- 150份硝酸溶液 375-500份锰盐、 10-20硝酸镍和余量水。
[0011] 具体地， 所述磷酸的重量份数优选为 50-70份。 所述氧化镁的重量份数优选为 4- 6份。 所述硝酸钙的重量份数为 12-16份。 所述硝酸溶液的重量份数优选为 100-12 0份。 所述硝酸溶液的质量浓度优选为 40-65%， 更优选为 45%。 所述硝酸镍的重 量份数为 12-16份。 所述锰盐优选为酸式磷酸锰， 重量份数为 400-450份。 所述锰 系磷化剂的总酸度优选为 40-60pt， 使用吋， 所述锰系磷化剂的质量浓度为 15-20 。
[0012] 在上述锰系磷化剂中， 通过控制各成分配比平衡， 以达到较佳成膜效果。 例如 ， 当硝酸含量低， 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， 所以本实施例优选硝酸的重量份数 为 100-120份。 其中， 磷酸稳定槽液 PH值并且为主要成膜成分。 锰盐为主要成膜 成分。 氧化镁， 硝酸钙， 硝酸镍可以增加磷化膜的耐蚀性和耐磨性。
[0013] 本实施例中， 锰系磷化膜厚度大、 孔隙少， 磷化晶粒呈密集颗状， 可广泛应用 于防腐蚀及冷加工、 轴承等减摩润滑。 锰系磷化剂是由锰盐、 硝酸盐和多种添 加剂复配而成。 将金属工件浸入由该磷化液配成的酸性处理液中， 金属与酸及 盐相互作用， 在工件表面生成一层不溶于水的保护性黑色膜层。 该膜层结晶致 密， 具有膜厚， 硬度高， 耐蚀性强等特点。
[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 上所述的锰系磷化剂； 将锰系磷化剂溶于水中配制成磷化溶液， 所述磷化溶液 中锰系磷化剂的质量浓度为 15-20%， 将金属件浸入磷化溶液中， 控制磷化溶液 的总酸度为 30-70pt， 经过预定吋间处理后， 水洗金属件， 干燥。
[0015] 在金属件浸入磷化溶液吋， 控制磷化溶液的总酸度优选为 40-60pt。 表面处理吋 ， 锰系磷化剂温度控制在 92-98°C。 金属件浸入磷化溶液的吋间优选为 8-12分钟 。 优选地， 在金属件浸入磷化溶液前， 先对金属工件进行除油， 酸洗处理， 在 金属件浸入磷化溶液处理之后， 进一步对金属件进行皂化处理或者浸入防锈剂 或者浸入润滑剂中处理， 所述磷化处理温度为 92-98°C。
[0016] 总酸度计量方式为： 用移液管吸取 10mL锰系磷化剂试液于 250mL锥形烧瓶中 ， 加 2-3滴酚酞指示液。 用 O.lmol/L的氢氧化钠标准液滴定至溶液呈粉红色， 即 为终点， 所消耗氢氧化钠标准液毫升数即为该槽液的总酸度。
[0017] 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， 在金属件表面形成皮膜。 皮膜可对金属件进行保护、 润滑， 且硬度 高， 耐蚀性强。
[0018] 以下通过具体实例说明本发明实施例的锰系磷化剂及其处理方法等方面。
[0019] 实施例 1
[0020] 按照下列重量份数混合各成分 （总量为 1800重量份） ： 40份磷酸， 3.5份氧化镁 ， 10份的硝酸钙， 84份硝酸溶液， 375份锰盐、 10份硝酸镍和余量水， 搅拌， 混 合均匀， 配制成磷化剂。
[0021] 磷化处理方法： 按照上述方法配制好锰系磷化剂； 金属件以铁件为例， 将铁件 浸入磷化溶液中， 控制磷化溶液的总酸度为 40-60pt， 在 95度温度下， 经过 8分钟 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。
[0022] 经过上述磷化溶液处理后， 观察工件表面， 发现工件表面有一层黑色膜层， 颜 色均匀， 皮膜细致， 用指甲能画出明显的印迹， 磷化膜层厚度约为 10-30μηι (微 米） ， 适合金属防腐蚀及轴承、 齿轮、 螺丝紧固件等减摩润滑。 [0023] 实施例 2
[0024] 按照下列重量份数混合各成分 （总量为 1800重量份） ： 60份磷酸， 4份氧化镁
， 12份的硝酸钙， 100份硝酸溶液， 400份锰盐、 12份硝酸镍和余量水， 搅拌， 混合均匀， 配制成磷化剂。
[0025] 磷化处理方法： 按照上述方法配制好锰系磷化剂； 金属件以铁件为例， 将铁件 浸入磷化溶液中， 控制磷化溶液的总酸度为 40-60pt， 在 95度温度下， 经过 8分钟 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。
[0026] 经过上述磷化溶液处理后， 观察工件表面， 发现工件表面有一层黑色膜层， 颜 色均匀， 皮膜细致， 用指甲能画出明显的印迹， 磷化膜层厚度约为 10-30μηι (微 米） ， 适合金属防腐蚀及轴承、 齿轮、 螺丝紧固件等减摩润滑。
[0027] 实施例 3
[0028] 按照下列重量份数混合各成分 （总量为 1800重量份） ： 70份磷酸， 5份氧化镁
， 15份的硝酸钙， 120份硝酸溶液， 450份锰盐、 15份硝酸镍和余量水， 搅拌， 混合均匀， 配制成磷化剂。
[0029] 磷化处理方法： 按照上述方法配制好锰系磷化剂； 金属件以铁件为例， 将铁件 浸入磷化溶液中， 控制磷化溶液的总酸度为 40-60pt， 在 98度温度下， 经过 10分 钟处理后， 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。
[0030] 经过上述磷化溶液处理后， 观察工件表面， 发现工件表面有一层黑色膜层， 颜 色均匀， 皮膜细致， 用指甲能画出明显的印迹， 磷化膜层厚度约为 10-30μηι (微 米） ， 适合金属防腐蚀及轴承、 齿轮、 螺丝紧固件等减摩润滑。
[0031] 实施例 4
[0032] 按照下列重量份数混合各成分 （总量为 1800重量份） ： 80份磷酸， 7份氧化镁
， 20份的硝酸钙， 140份硝酸溶液， 500份锰盐、 20份硝酸镍和余量水， 搅拌， 混合均匀， 配制成磷化剂。
[0033] 磷化处理方法： 按照上述方法配制好锰系磷化剂； 金属件以铁件为例， 将铁件 浸入磷化溶液中， 控制磷化溶液的总酸度为 40-60pt， 在 98度温度下， 经过 12分 钟处理后， 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。
[0034] 经过上述磷化溶液处理后， 观察工件表面， 发现工件表面有一层黑色膜层， 颜 色均匀， 皮膜细致， 用指甲能画出明显的印迹， 磷化膜层厚度约为 10-30μηι (微 米） ， 适合金属防腐蚀及轴承、 齿轮、 螺丝紧固件等减摩润滑。
[0035] 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

权利要求书
[权利要求 1] 一种锰系磷化剂， 用于在金属件表面形成皮膜， 其特征在于， 以 1800 重量份计， 包括如下重量份数的成分： 40-80份磷酸， 3.5-7份氧化镁 ， 10-20份的硝酸钙， 84-150份硝酸溶液 375-500份锰盐、 10-20硝酸镍 和余量水。
[权利要求 2] 如权利要求 1所述的锰系磷化剂， 其特征在于， 所述磷酸的重量份数 为 50-70份。
[权利要求 3] 如权利要求 1所述的锰系磷化剂 其特征在于， 所述氧化镁的重量份 数为 4-6份。
[权利要求 4] 如权利要求 1所述的锰系磷化剂 其特征在于， 所述硝酸钙的重量份 数为 12-16份， 所述硝酸镍的重： ：份数为 12-16份。
[权利要求 5] 如权利要求 1所述的锰系磷化剂 其特征在于， 所述锰盐为酸式磷酸 锰， 重量份数为 400-450份。
[权利要求 6] 如权利要求 1所述的锰系磷化剂 其特征在于， 所述硝酸溶液的重量 份数为 100-120份， 所述硝酸溶液的质量浓度为 40-65%。
[权利要求 7] 如权利要求 1所述的锰系磷化剂， 其特征在于， 所述磷化剂的总酸度 为 30-70pt。
[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 1- 7任一项所述的锰系磷化剂； 将锰系磷化剂溶于水中配制成磷化溶液 ， 所述磷化溶液中锰系磷化剂的质量浓度为 15-20%， 将金属件浸入 磷化溶液中， 控制磷化溶液的总酸度为 30-70pt， 经过预定吋间处理 后， 水洗金属件， 干燥。
[权利要求 9] 如权利要求 8所述的金属件表面磷化处理方法， 其特征在于， 在金属 件浸入磷化溶液前， 先对金属工件进行除油， 酸洗处理， 在金属件浸 入磷化溶液处理之后， 进一步对金属件进行皂化处理或者浸入防锈剂 或者浸入润滑剂中处理， 所述磷化处理温度为 92-98°C。
[权利要求 10] 一种金属件， 其特征在于， 所述金属件表面通过如权利要求 7所述的 金属件表面磷化处理方法形成有皮膜。
PCT/CN2016/087140 2016-06-24 2016-06-24 锰系磷化剂、金属件及其表面磷化处理方法 WO2017219368A1 (zh)

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