WO2019006627A1 - 无铬钝化剂、铝件及其表面钝化处理方法 - Google Patents
无铬钝化剂、铝件及其表面钝化处理方法 Download PDFInfo
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- WO2019006627A1 WO2019006627A1 PCT/CN2017/091562 CN2017091562W WO2019006627A1 WO 2019006627 A1 WO2019006627 A1 WO 2019006627A1 CN 2017091562 W CN2017091562 W CN 2017091562W WO 2019006627 A1 WO2019006627 A1 WO 2019006627A1
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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
- C23C22/44—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 fluorides or complex fluorides
Definitions
- the present invention relates to the field of metal surface treatment technology, and in particular, to a chromium-free passivating agent, an aluminum member, and a surface passivation 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 parts of the aluminum parts need to be inactivated.
- the passivation treatment generally uses a passivating agent to pretreat the aluminum member to form a film layer on the surface of the aluminum member for subsequent surface treatment, thereby increasing the bonding force and corrosion resistance of the subsequent film.
- Conventional passivation generally requires passivation of chromium ions, which does not meet environmental requirements and the process requirements of some businesses.
- a chromium-free passivating agent with good corrosion resistance and strong bonding force, and a surface passivation treatment method for aluminum parts and an aluminum member obtained by passivation treatment are provided, and the passivation agent is environmentally friendly. Non-toxic, easy to process, washed after passivation.
- a chromium-free passivating agent for surface pretreatment of aluminum parts comprising 1000 parts by weight, including the following parts by weight: 5-30 parts of fluorozirconic acid, 2-10 parts of sodium nitrate, 1 -5 parts ammonium metavanadate, 0.1-0.5 parts sodium bromide and
- a method for surface passivation treatment of aluminum parts comprising the steps of: formulating a chromium-free passivating agent as described above; formulating a chromium-free passivating agent into a passivation solution having a mass percentage of 4-20% Control the passivation solution to a pH of 3-5; pass the passivation solution onto the surface of the aluminum part by dipping or spraying, washing with water, and drying.
- the film formed by the above chromium-free passivating agent has good corrosion resistance, can be used as a coating treatment bottom layer, and is processed by an aluminum piece, directly rolled up, not washed with water, and is very convenient to use, and the passivating agent does not contain damage.
- the environment's chromium ions and other heavy metals are green products that comply with the EU ROHS Directive.
- Embodiments of the present invention provide a chromium-free passivating agent for surface pretreatment of aluminum parts, comprising 1000 parts by weight, including the following parts by weight: 5-30 parts of fluorozirconic acid, 2-10 parts Sodium nitrate, 1-5 parts ammonium metavanadate, 0.1-0.5 parts sodium bromide and the balance water.
- the fluorozirconic acid is preferably 10 to 30 parts by weight.
- the sodium nitrate is preferably from 4 to 8 parts by weight.
- the parts by weight of the ammonium metavanadate is preferably 2-4 parts by weight.
- the parts by weight of the sodium bromide are preferably 0.2 to 0.4 parts by weight.
- the passivating agent has a rhodium ratio of 4 to 20% by weight, a pH of preferably 3-5, and a weak acidity.
- a preferable film forming effect is achieved by controlling the balance of the respective distribution ratios.
- fluorozirconic acid is the main component of the membrane layer
- sodium nitrate is the oxidant
- ammonium metavanadate and sodium bromide are the promoters
- ammonium metavanadate is the auxiliary film-forming agent to make the membrane layer firm and uniform.
- Embodiments of the present invention also provide a method for surface passivation treatment of aluminum parts, comprising the steps of: formulating a chromium-free passivating agent as described above; formulating a chromium-free passivating agent into a mass percentage of 4- 20% of the passivation solution; control the passivation solution to a pH of 3-5; the passivation solution is applied by dipping or spraying onto the surface of the aluminum part, washed with water, and dried.
- the mass percentage of the passivating agent in the passivating agent solution is preferably 5-15%, and the ruthenium is sprayed onto the surface of the aluminum member, and the impregnation method may also be employed.
- the treatment temperature is normal temperature, such as 20-25 °C.
- the surface of the aluminum member is further subjected to passivation, oxidation resistance or coating treatment.
- the drying temperature is controlled at about 80 degrees, and should not be too high to prevent cracks in the film layer.
- Embodiments of the present invention also provide an aluminum member that is treated by a surface passivation treatment method of an aluminum member as described above to form passivation on the surface of the aluminum member. Passivation protects the aluminum part and can be used as a coating treatment layer for subsequent coating and other treatments.
- the passivating agent of this embodiment can also be applied to other materials. For example, it can be widely applied to surface treatment processes of automobile, furniture, electronic instruments, household appliances, CPU radiators, sports equipment, and the like. Of course, the aluminum products in these products can be processed by the passivating agent of the embodiment to form Passivation.
- the ingredients are mixed according to the following parts by weight: 5 parts by weight of fluorozirconic acid, 2 parts of sodium nitrate, based on 1000 parts by weight,
- Treatment method preparing a chromium-free passivating agent; formulating a chromium-free passivating agent into a passivation solution having a mass percentage of 20%; controlling the pH of the passivating agent solution to be 4; at normal temperature, The surface of the aluminum part is immersed in the passivation solution
- the ingredients are mixed in the following parts by weight: 10 parts by weight of fluorozirconic acid, 4 parts of sodium nitrate, based on 1000 parts by weight
- Processing method preparing a chromium-free passivating agent; formulating a chromium-free passivating agent into a passivation solution having a mass percentage of 15%; controlling the pH of the passivating agent solution to be 4; at normal temperature, The surface of the aluminum part is immersed in the passivation solution
- the components are mixed according to the following parts by weight: 15 parts by weight of fluorozirconic acid, 6 parts of sodium nitrate, 3 parts of ammonium metavanadate, 0.3 parts of sodium bromide and the balance water, stirred, mixed Uniform, formulated as a passivating agent.
- Processing method preparing a chromium-free passivating agent; formulating a chromium-free passivating agent into a passivation solution having a mass percentage of 10%; controlling the pH of the passivating agent solution to be 3.5; at normal temperature, The surface of the aluminum part was immersed in a passivation solution, treated for 8 minutes, washed with water, and dried at 80 degrees.
- the ingredients are mixed in the following parts by weight: 20 parts by weight of fluorozirconic acid, 8 parts of sodium nitrate, based on 1000 parts by weight
- Treatment method preparing a chromium-free passivating agent; formulating a chromium-free passivating agent into a passivation solution having a mass percentage of 10%; controlling the pH of the passivating agent solution to be 3; at normal temperature, The surface of the aluminum part is immersed in the passivation solution
- the ingredients are mixed in the following parts by weight: 30 parts by weight of fluorozirconic acid, 10 parts of sodium nitrate, based on 1000 parts by weight
- Treatment method preparing a chromium-free passivating agent; formulating a chromium-free passivating agent into a passivation solution having a mass percentage of 6%; controlling the pH of the passivating agent solution to be 3; at normal temperature, The surface of the aluminum part is immersed in the passivation solution
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
一种无铬钝化剂，用于铝件表面预处理，以1000重量份计，包括如下重量份数的成分：5-30份氟锆酸，2-10份硝酸钠，1-5份偏钒酸铵，0.1-0.5份溴化钠和余量水。还公开了一种铝件表面钝化处理方法及一种铝件。
Description
无铬钝化剂、 铝件及其表面钝化处理方法 技术领域
[0001] 本发明涉及金属表面处理技术领域， 具体涉及一种无铬钝化剂、 铝件及其表面 钝化处理方法。
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， 某些用途的铝件还需要进行钝 化处理。
[0003] 钝化处理一般采用钝化剂对铝件进行预处理， 以在铝件表面形成膜层， 以便进 行后续的表面处理， 增加后续膜的结合力和防腐力。 传统钝化一般钝化处理含 铬离子， 不能满足环保需求跟一些商家的工艺要求。
技术问题
[0004] 有鉴于此， 提供一种耐蚀性好、 结合力强的无铬钝化剂， 以及铝件表面钝化处 理方法和经过钝化处理后制得的铝件， 此钝化剂环保无毒， 工艺简便， 钝化后 水洗。
问题的解决方案
技术解决方案
[0005] 一种无铬钝化剂， 用于铝件表面预处理， 以 1000重量份计， 包括如下重量份数 的成分： 5-30份氟锆酸， 2-10份的硝酸钠， 1-5份偏钒酸铵， 0.1-0.5份溴化钠和余
[0006] 一种铝件表面钝化处理方法， 其包括下列步骤： 配制如上所述的无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 4-20%的钝化溶液； 控制钝化剂溶液的 PH值 为 3-5; 将钝化溶液通过浸渍或喷淋于铝件表面， 水洗， 烘干。
[0007] 以及， 一种铝件， 其表面具有通过如上所述的铝件表面钝化处理方法形成的钝 化。
发明的有益效果
有益效果
[0008] 上述无铬钝化剂形成的膜层耐蚀性好， 可作为涂装处理底层， 处理铝件吋， 直 接滚涂上去， 不用水洗， 使用起来非常方便， 该钝化剂不含损害环境的铬离子 及其它重金属， 是一种绿色环保产品， 符合欧盟 ROHS指令。
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无铬钝化剂， 用于铝件表面预处理， 以 1000重量份计， 包括如下重量份数的成分： 5-30份氟锆酸， 2-10份的硝酸钠， 1-5份偏钒酸铵， 0. 1-0.5份溴化钠和余量水。
[0011] 具体地， 所述氟锆酸的重量份数优选为 10-30份。 所述硝酸钠的重量份数优选 为 4-8份。 所述偏钒酸铵的重量份数优选为 2-4份。 所述溴化钠的重量份数优选为 0.2-0.4份。 所述钝化剂使用吋的配比为 4-20wt%， PH值优选为 3-5， 呈弱酸性。
[0012] 在上述无铬钝化剂中， 通过控制各成分配比平衡， 以达到较佳成膜效果。 例如 ， 氟锆酸为膜层主要成分， 硝酸钠为氧化剂， 偏钒酸铵、 溴化钠为促进剂， 偏 钒酸铵为辅助成膜剂使膜层坚固和均匀。
[0013] 本发明实施例还提供一种铝件表面钝化处理方法， 其包括下列步骤： 配制如上 所述的无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 4-20%的钝化溶液； 控 制钝化剂溶液的 PH值为 3-5; 将钝化溶液涂通过浸渍或喷淋于铝件表面， 水洗， 烘干。
[0014] 具体地， 钝化剂溶液中钝化剂的质量百分含量优选为 5-15%， 处理吋， 喷淋到 铝件表面上去， 也可采用浸渍方式。 处理温度为常温， 如 20-25°C。 另外， 在形 成钝化后， 进一步对铝件表面进行钝化、 抗氧化或涂装处理。 烘干温度控制在 8 0度左右， 不宜过高， 防止膜层出现裂痕。
[0015] 本发明实施例还提供一种铝件， 其通过如上所述的铝件表面钝化处理方法进行 处理， 在铝件表面形成钝化。 钝化可对铝件进行保护， 可作为涂装处理底层， 便于后续涂装等处理。 除铝型材外， 本实施例的钝化剂还可应用于其它材料，
例如可广泛地应用于汽车、 家俱、 电子仪器、 家用电器、 CPU散热器、 运动器材 等产品部件的表面处理工艺， 当然这些产品中的铝制品可以采用本实施例的钝 化剂进行处理， 形成钝化。
[0016] 以下通过具体实例说明本发明实施例的无铬钝化剂及其处理方法等方面。
[0017] 实施例 1
[0018] 按照下列重量份数混合各成分： 以 1000重量份计， 5份氟锆酸， 2份的硝酸钠，
1份偏钒酸铵， 0.1份溴化钠和余量水， 搅拌， 混合均匀， 配制成钝化剂。
[0019] 处理方法： 配制好无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 20%的钝 化溶液； 控制钝化剂溶液的 PH值为 4; 在常温下， 将铝件表面浸渍于钝化溶液中
， 处理 10分钟， 水洗， 在 80度下烘干。
[0020] 经过上述钝化剂溶液处理后， 发现工件耐腐蚀性大大提高， 中性盐雾测试达 16 小吋以上， 油漆涂装后附着力以沸水煮 2小吋百格测试， 实验等级为 1。
[0021] 实施例 2
[0022] 按照下列重量份数混合各成分： 以 1000重量份计， 10份氟锆酸， 4份的硝酸钠
， 2份偏钒酸铵， 0.2份溴化钠和余量水， 搅拌， 混合均匀， 配制成钝化剂。
[0023] 处理方法： 配制好无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 15%的钝 化溶液； 控制钝化剂溶液的 PH值为 4; 在常温下， 将铝件表面浸渍于钝化溶液中
， 处理 10分钟， 水洗， 在 80度下烘干。
[0024] 经过上述钝化剂溶液处理后， 发现工件耐腐蚀性大大提高， 中性盐雾测试达 24 小吋以上， 油漆涂装后附着力以沸水煮 2小吋百格测试， 无任何脱落， 等级为 0
[0025] 实施例 3
[0026] 按照下列重量份数混合各成分： 以 1000重量份计， 15份氟锆酸， 6份的硝酸钠 ， 3份偏钒酸铵， 0.3份溴化钠和余量水， 搅拌， 混合均匀， 配制成钝化剂。
[0027] 处理方法： 配制好无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 10%的钝 化溶液； 控制钝化剂溶液的 PH值为 3.5; 在常温下， 将铝件表面浸渍于钝化溶液 中， 处理 8分钟， 水洗， 在 80度下烘干。
[0028] 经过上述钝化剂溶液处理后， 发现工件耐腐蚀性大大提高， 中性盐雾测试达 34
小吋以上， 油漆涂装后附着力以沸水煮 2小吋百格测试， 无任何脱落， 等级为 0 [0029] 实施例 4
[0030] 按照下列重量份数混合各成分： 以 1000重量份计， 20份氟锆酸， 8份的硝酸钠
， 4份偏钒酸铵， 0.4份溴化钠和余量水， 搅拌， 混合均匀， 配制成钝化剂。
[0031] 处理方法： 配制好无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 10%的钝 化溶液； 控制钝化剂溶液的 PH值为 3; 在常温下， 将铝件表面浸渍于钝化溶液中
， 处理 8分钟， 水洗， 在 80度下烘干。
[0032] 经过上述钝化剂溶液处理后， 发现工件耐腐蚀性大大提高， 中性盐雾测试达 48 小吋以上， 油漆涂装后附着力以沸水煮 2小吋百格测试， 无任何脱落， 等级为 0
[0033] 实施例 5
[0034] 按照下列重量份数混合各成分： 以 1000重量份计， 30份氟锆酸， 10份的硝酸钠
， 5份偏钒酸铵， 0.5份溴化钠和余量水， 搅拌， 混合均匀， 配制成钝化剂。
[0035] 处理方法： 配制好无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 6%的钝 化溶液； 控制钝化剂溶液的 PH值为 3; 在常温下， 将铝件表面浸渍于钝化溶液中
， 处理 8分钟， 水洗， 在 80度下烘干。
[0036] 经过上述钝化剂溶液处理后， 发现工件耐腐蚀性大大提高， 中性盐雾测试达 40 小吋以上， 油漆涂装后附着力以沸水煮 2小吋百格测试， 无任何脱落， 等级为 0 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] 一种无铬钝化剂， 用于铝件表面预处理， 其特征在于， 以 1000重量份 计， 包括如下重量份数的成分： 5-30份氟锆酸， 2-10份的硝酸钠， 1-5 份偏钒酸铵， 0.1-0.5份溴化钠和余量水。
[权利要求 2] 如权利要求 1所述的无铬钝化剂， 其特征在于， 所述氟锆酸的重量份 数为 10-30份。
[权利要求 3] 如权利要求 1所述的无铬钝化剂， 其特征在于， 所述硝酸钠的重量份 数为 4-8份。
[权利要求 4] 如权利要求 1所述的无铬钝化剂， 其特征在于， 所述偏钒酸铵的重量 份数为 2-4份。
[权利要求 5] 如权利要求 1所述的无铬钝化剂， 其特征在于， 所述溴化钠的重量份 数为 0.2-0.4份。
[权利要求 6] 如权利要求 1所述的无铬钝化剂， 其特征在于， 所述钝化剂使用配比 为 4-20wt<¾。
[权利要求 7] 如权利要求 1所述的无铬钝化剂， 其特征在于， 所述钝化剂以氢氧化 钠或硝酸控制 PH值为 3-5。
[权利要求 8] 一种铝件表面钝化处理方法， 其包括下列步骤： 配制如权利要求 1-7 任一项所述的无铬钝化剂； 将无铬钝化剂配制成质量百分含量为 4-20 <¾的钝化溶液； 控制钝化剂溶液的 PH值为 3-5; 将钝化溶液通过浸渍 或者喷淋于铝件表面， 水洗， 烘干。
[权利要求 9] 一种铝件， 其特征在于， 所述铝件表面通过如权利要求 8所述的铝件 表面钝化处理方法形成有钝化。
[权利要求 10] 如权利要求 9所述的铝件， 其特征在于， 在形成钝化后， 进一步对铝 件表面进行钝化、 抗氧化或涂装处理。
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| US20070068602A1 (en) * | 2005-09-28 | 2007-03-29 | Coral Chemical Company | Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings |
| CN102766862A (zh) * | 2012-08-21 | 2012-11-07 | 湖南大学 | 一种处理液及用其制备具有自修复性能的铝合金表面钒锆复合转化膜的方法 |
| CN103276385A (zh) * | 2013-05-17 | 2013-09-04 | 华南理工大学 | 一种在铝合金表面制备高耐蚀性有色钝化膜的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070068602A1 (en) * | 2005-09-28 | 2007-03-29 | Coral Chemical Company | Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings |
| CN102766862A (zh) * | 2012-08-21 | 2012-11-07 | 湖南大学 | 一种处理液及用其制备具有自修复性能的铝合金表面钒锆复合转化膜的方法 |
| CN103276385A (zh) * | 2013-05-17 | 2013-09-04 | 华南理工大学 | 一种在铝合金表面制备高耐蚀性有色钝化膜的方法 |
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