稀土促进的钢铁表面磷酸盐转化膜形成

探讨了在硝酸盐-锌系磷化过程中稀土化合物、溶液酸碱度、时间对磷化膜外观、膜重和耐蚀性的影响.结果表明,把少量稀土化合物(REC)添加到磷化液中可显著提高磷化膜的耐蚀性和磷化速度,其较佳的投加量为30 mg/L～55 mg/L.      

冷轧A3钢薄板的稀土复合锌系低温磷化

为配制出成膜质量更佳的涂装用磷化液,从锌系磷化膜形成机理出发,分析了改善其低温成膜效果的可能途径;通过高效促进剂和磷化工艺参数的优选,开发出一种实用性强的钢铁工件涂漆前处理--含稀土复合促进剂的低温锌系磷化新工艺.研究表明:家电外壳广泛采用的冷轧A3钢薄板经此LZP快速磷化液处理后,所得防锈涂装底层实用效果良好.在含1.0～2.0g/L 稀土促进剂的磷化液中,A3钢薄板经40℃、3～4min喷淋处理后可获得厚约3μm的磷化膜,其结晶细小致密、与基体结合力强、抗蚀性好.磷化后经在线涂漆,对应漆膜抗冲击性、耐蚀性和附着性能良好.     

铝合金稀土硝酸盐磷化的电化学行为

采用电化学测试和扫描电镜等方法研究了硝酸铈对6061 铝合金磷化过程及磷化膜形貌的影响。结果表明,硝酸铈的加入改变了铝合金基体与磷化液之间液固界面间的初始电位;硝酸铈吸附在铝合金表面上形成凝胶,成为磷酸盐晶体形成的良好晶核,磷化晶粒细化,生成较为致密的磷化膜,膜的耐蚀性得到提高。硝酸铈使铝合金达到最高电位的时间缩短,阴极极化电流密度增大,磷化速度加快。硝酸铈在整个铝合金磷化过程中起到了成核和促进的作用。在本实验条件下,最佳硝酸盐含量为20 mg/L～40 mg/L。     

铝合金表面无铬磷酸盐稀土转化膜的成膜机理及耐蚀性研究

从磷化成膜过程的电化学行为和稀土对磷化膜生长过程的影响两方面,对6061铝合金表面一种不合铬的复合磷酸盐膜的成膜机理进行了研究,并利用极化曲线对其耐蚀性进行了初步探究.结果表明:磷化成膜过程主要分为4个阶段,即基体侵蚀期、晶体初步形成期、基体再溶解和晶体形成期、基体溶解和晶体生长达到平衡期;稀土化合物的引入,提高了磷化...     

Fe2+对铝合金无铬磷化的影响

通过电化学、X射线衍射、能谱仪、扫描电镜等分析方法研究了铝合金在含Fe2 磷化液中的磷化过程.结果表明,在磷化液中加入Fe2 后可使磷化膜均匀、致密,促进磷化膜的形成,磷化膜的主要成分为Zn3(PO4)2·4H2O和Zn2Fe(PO4)2·4H2O.     

Mn~(2+)对镀锌板磷化的影响

通过开路电位-时间曲线和扫描电镜(SEM)的方法研究了镀锌板在含有不同浓度Mn2+磷化液中的磷化成膜过程。结果表明,在磷化液中添加Mn2+,磷化初始电位降低,有利于磷化膜的形成;当Mn(NO3)2含量为0.6g/L时,所生成的磷化膜结晶细化,均匀致密。     

高酸度磷化液成膜机理探讨

有关高酸度磷化液的成膜机理目前尚无定论,作者通过对高酸度磷化液进行反复的实验,主要从时间、温度、促进剂等因素对高酸度磷化液所形成的磷化膜的耐蚀性的影响进行了讨论,并在此基础上初步探讨了高酸度磷化液的成膜机理, 形成的磷化膜为非晶型的磷酸铁盐.     

"绿色"磷化工艺研究

介绍一种不含硝酸盐及亚硝酸盐的磷化液,试验结果表明该磷化液性能稳定,磷化过程及磷化废液对环境无任何污染,磷化膜耐蚀性能良好.     

氧化钇对6061铝合金磷化膜性能的影响

采用电化学测试、扫描电镜(SEM)、百格试验等方法研究了氧化钇(Y2O3)对6061铝合金磷化膜性能的影响.结果表明,Y2O3加入磷化液中,使得6061铝合金表面所生成的磷化膜晶粒均匀,致密;与不含Y2O3的磷化液中形成的磷化膜相比,当Y2O3含量为20 mg/L时,所形成的磷化膜点滴腐蚀时间延长,腐蚀电位增大30 mV,腐蚀电流减小0.15 mA,百格试验和全浸泡试验结果显示,加入Y2O3可以增强磷化膜与有机涂层间的结合力.     

油套管接箍锰系磷化工艺研究

通过正交试验设计方法确定了锰系磷化工艺的工艺参数,研究了磷化液酸比、磷化时间和磷化温度等工艺参数对磷化膜成膜的影响,分析了各工艺参数对磷化成膜的作用机理.用经过磷化处理的接箍进行上、卸扣试验,结果表明,得到的磷化膜具有良好的抗粘扣性能.     

Effect of silicate pretreatment, post-sealing and additives on corrosion resistance of phosphated galvanized steel

Sodium silicate （water glass） pretreatment before phosphating, silicate post-sealing after phosphating and adding silicate to a traditional phosphating solution were respectively carried out to obtain the improved phosphate coatings with high corrosion resistance and coverage on hot-dip galvanized（HDG） steel. The corrosion resistance, morphology and chemical composition of the coatings were investigated using neutral salt spray（NSS） tests, scanning electron microscopy（SEM） and energy dispersive spectroscopy（EDS）. The results show that pretreatment HDG steel with silicate solutions, phosphate coatings with finer crystals and higher coverage are formed and the corrosion resistance is enhanced. Adding silicate to a traditional phosphating solution, the surface morphology of the coatings is nearly unchanged. The corrosion resistance of the coatings is mainly dependent on phosphating time. Phosphating for a longer time （such as 5 min）, the corrosion resistance, increasing with concentration of silicate, is improved significantly. Post-sealing the phosphated HDG steel with silicate solutions, the pores among the zinc phosphate crystals are sealed with the films containing Si, P, O and Zn and the continuous composite coatings are formed. The corrosion resistance of the composite coatings, related to the pH value, contents of hydrated gel of silica and Si2O^2- 5 and post-sealing time, is increased markedly. The improved coatings with optimal corrosion resistance are obtained for phosphating 5 min and post-sealing with 5 g/L silicate solution for 10 min.     

热镀锌层上磷酸锌转化膜的生长与耐蚀性

热镀锌钢板在pH3.0、45℃的磷酸锌溶液中磷化2～600s,用扫描电镜、能谱仪和X射线衍射仪分析磷化膜的组织形貌和成分,并探讨膜层的生长行为。结果表明:磷酸锌晶体在锌晶粒内及晶界处均可成核,开始是以接近平行的片状生长,并逐渐向多方向生长成扇骨状的晶片。随着磷酸锌晶体的成核和生长,磷化膜的覆盖率增加,但晶体之间的孔隙难以完全消除;长大的磷酸锌晶片容易折断脱落,导致磷化后期膜层的质量增量减小;磷化膜主要由Zn3(PO4)2.4H2O组成。热镀锌钢板经磷化处理后,耐蚀性显著提高,磷化膜的耐蚀性随磷化时间和膜层覆盖率的增加而提高。     

钼酸盐后处理提高热镀锌上磷化膜耐蚀性的探讨

将磷化后的热镀锌钢板用钼酸盐后处理,以提高磷化膜的耐蚀性。用SEM、EDS、电化学极化测量和盐雾试验研究了钼酸盐后处理对磷化膜组成和耐蚀性的影响。结果表明,经钼酸盐处理后,磷化膜上磷酸锌晶体间的孔隙被钼酸盐膜填补,从而在锌层表面形成了由磷化膜和钼酸盐膜构成的连续完整致密的复合膜;复合膜的极化电阻Rp显著增大,腐蚀电流密度显著减小,耐蚀性大大增强。磷化300s、后处理50s时复合膜的耐蚀性最优,Rp比单磷化膜的增加了一个数量级。     

Zinkphosphat-Überzüge aus übersättigten Bädern

Zinc phosphate coatings from supersaturated baths The author studied the properties of supersaturated phosphating solutions containing zinc phosphate being used for phosphating steel. The study included the influence of the solution variables, and in particular of the ferrous ion concentration, on the supersaturation and the coating properties. The accelerating effect of supersaturation is so strong that heavy, dense, and fine grain coatings are obtained without oxidants and at temperatures as low as + 10° C. Some aspects of the kinetics and the mechanism of coating formation in supersaturated solutions are discussed. Supersaturated phosphating solutions with zinc phosphate may find practical application, particularly where a high degree of protection is desired.     

The mechanism of inhibition by zinc phosphate in an epoxy coating

Epoxy coatings containing different volume fractions of zinc phosphate have been successfully prepared and their inhibitive properties have been studied by electrochemical impedance spectroscopy (EIS) and immersion tests. The results show that zinc phosphate can improve the protection ability of epoxy coatings and its best volume fraction is 30%. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) results indicate that the presence of zinc phosphate can form an inhibiting film which is composed of the phosphating film of FePO₄, Fe₂O₃, and FeO, as well as the shielding film of zinc phosphate on the steel surface.     

The growth of zinc phosphate coatings on 6061-Al alloy

Zinc phosphate coating was formed on 6061-Al alloy through a phosphating bath containing mainly ZnO, H₃PO₄, NaF. Yttrium oxide (Y₂O₃) was used as an accelerator of phosphatization to replace nitrite. The morphology, composition and the growth process of the zinc phosphate coating were investigated by SEM, EDX, XRD, FTIR and electrochemical measurements. The phosphate coating formed is composed of hopeite and metallic zinc. The formation and morphology of the zinc phosphate coating were strongly influenced by the presence of yttrium oxide (Y₂O₃) in the phosphating bath. The formed zinc phosphate coatings exhibited high corrosion resistance in 3% NaCl solution as shown by polarization measurement.     

铝合金无铬磷化处理

    研制一种不含铬的低温快速磷化液并用X射线衍射及能谱、扫描电镜、电化学等方法研究了游离酸度、温度和所含物质对其磷化效果的影响及磷化膜的晶相、形貌、耐蚀性.结果表明,该磷化液在35℃～45℃、5 min～8 min时,能在6061铝合金上形成一层致密均匀的磷化膜,膜重4 g/m²～6g/m²,作为油漆底层具有良好的应用前景.     

Über den Reaktionsmechanismus und die Wirkungsweise von Komplex- und Chelatbildnern bei der Herstellung von Konversionsüberzügen aus Phosphaten und Oxalaten

The reaction mechanism and mode of action of chelating and complexing agents during the preparation of conversion coatings of phosphates and oxalates Complexing and chelating agents act as anodic depolarizers of the primary pickling reaction in phosphating and oxalating solutions. It has been shown on the example of the accelerating effect of fluorides which form soluble and little dissociated ferrous cryolites that fluorides have a double function in zinc phosphate solutions. They dissolve iron at a rate exceeding by a factor of at least ten the rate in any other acid and on the other hand bind and mask the ferrous ions formed, so that complex compounds of the ferrous cryolite type are formed. Reaction with phosphoric acid and the phosphate ions of zinc phosphate in the phosphating bath yields vivianite, phosphophyllite and hopeite; these poorly soluble orthophosphates constitute the phosphate layers and during their formation free hydrofluoric acid is regenerated. This acid thus acts similiar to a catalyst. Other complexing and chelating agents such as pyrophosphates or polyphosphates act in the same way. A reaction mechanism of this same type is at the base of the formation of oxalate coating in the presence of activating fluorides. Optimum reaction conditions for the formation of the coating are simultaneous cathodic and anodic depolarizatioin (by the use of oxidising agents) and the presence of complexing and chelating agents (as accelerators, grains refining agents and activators).     

添加稀土引致的磷化膜变化与促进机制

用能谱与SEM分析，发现加入稀土硝酸盐(REN)后明显提高了无定形晶体Zn2Fe(PO4)2在磷化膜表面的覆盖率，而使得膜的耐蚀性能提高.此时膜内相关元素含量比例发生了变化：P增大,Zn减小，可见磷对膜耐蚀性的贡献比锌大.讨论认为，稀土硝酸盐是一个有良好载氧能力的催化剂，具有良好的成核促进作用和阴极去极化作用，从而能加速磷化并使膜的耐腐蚀性能提高.      

磷化膜电化学测试技术的研究进展

综述了用线性极化法和电化学阻抗法测磷化膜孔隙率以定量评价磷化膜耐蚀性能的电化学方法,着重介绍了简便快速检测磷化膜性能的改进型电化学阻抗法,分析了测试溶液对磷化膜孔隙率的影响,展望了电化学测试技术在磷化工业中的应用前景.