Effect of additives on the properties of phosphate conversion coating on electrogalvanized steel sheet

Ni²⁺ and Mn²⁺ ions have been added separately to the phosphate solution to minimize the porosity of the phosphate conversion coating on electrogalvanized steels. Results showed that the Ni²⁺ or Mn²⁺ in the solution reduced the grain size and porosity of the phosphate coating; thereby, the corrosion resistance was enhanced. However, Ni²⁺ and Mn²⁺ played a different role in the coating formation. Ni²⁺ in the solution was reduced by Zn to form Ni, which enhanced the dissolution of Zn to promote the nucleation of hopeite grains. Mn²⁺ in the solution facilitated the nucleation by increasing the impingement of reacting species.     

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating (MPCC) was fabricated on AZ31 magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg²⁺ and PO^3?₄ ions. The MPCC on AZ31 Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about 2.5 µm after 20 min of phosphating treatment. The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds. The MPCC showed a significant protective effect on AZ31 Mg alloy. The corrosion current of MPCC was reduced to about 3% of that of the uncoated surface and the time for the deterioration process during immersion in 0.5 mol/L NaCl solution improved from about 10 min to about 24 h.     

Characterization and corrosion behavior of ceramic coating on magnesium by micro-arc oxidation

In this study, the commercial pure magnesium was coated in different aqueous solutions of Na₂SiO₃ and Na₃PO₄ by the micro-arc oxidation method (MAO). Coating thickness, phase composition, surface and cross sectional morphology and corrosion resistance of coatings were analyzed by eddy current method, X-ray diffraction (XRD), scanning electron microscope (SEM) and tafel extrapolation method, respectively. The average thickness of the coatings ranged from 52 to 74 μm for sodium silicate solution and from 64 to 88 μm for sodium phosphate solution. The dominant phases on the coatings were detected as spinal Mg₂SiO₄ (Forsterite) and MgO (Periclase) for sodium silicate solution and Mg₃(PO₄)₂ (Farringtonite) and MgO (Periclase) for sodium phosphate solution. SEM images reveal that the coating is composed of two layers as of a porous outer layer and a dense inner layer. The corrosion results show the coating consisting Mg₂SiO₄ is more resistant to corrosion than that containing Mg₃(PO₄)₂.     

Characterization of calcium-modified zinc phosphate conversion coatings and their influences on corrosion resistance of AZ31 alloy

Two kinds of phosphate conversion coatings, including zinc phosphate coating and zinc-calcium phosphate coating, were prepared on the surface of AZ31 alloy in phosphate baths. The morphologies of these coatings were observed using scanning electron microscopy. Their chemical compositions and structures were characterized using energy-dispersive X-ray spectrum, X-ray photoelectron spectroscopy and X-ray diffraction. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization technique. The results show that the flowerlike Zn-Ca phosphate conversion coatings are mainly composed of hopeite (Zn₃(PO₄)₂·4H₂O). They have a quite different morphology from the dry-riverbed-like Zn phosphate coatings that consist of MgO, MgF₂, Zn or ZnO and hopeite. Both of the zinc and zinc-calcium phosphate coatings can remarkably reduce the corrosion current density of the substrates. The Zn-Ca coating exhibits better corrosion resistance than the Zn coating. Introduction of calcium into the phosphate baths leads to the full crystallinity of the Zn-Ca coating.     

Studies on the Influence of Hexadecylamine on Chromate Phosphate Coating on Aluminium

The effect of hexadecylamine (HDA) on a Chromate phosphate coating on aluminium was studied using an optimized Chromate phosphate bath, The addition of HDA was found to decrease the coating weight, but to enhance the coating quality and corrosion resistance. The inhibitory effect of HDA helps in regulating the excessive attack on the metal and its ability to reduce Cr⁶⁺ to Cr³⁺ compensates the possible time delay for the initiation of coating deposition due to the inhibition.     

AZ31B镁合金表面火焰喷涂Al-Mg_2Si涂层的耐腐蚀性能

为提高AZ31B镁合金表面的耐腐蚀性能,用火焰喷涂方法在镁合金表面制备Al-Mg_2Si复合涂层。采用XRD、SEM和EDS分析涂层的物相组成、微观组织及元素分布;通过电化学试验测试样品在3.5%NaCl溶液中的腐蚀电位、腐蚀电流密度;通过3.5%NaCl溶液浸泡试验测试样品的腐蚀速率;并测试涂层的显微硬度。结果表明:涂层中的主要物相有Mg_2Si、Al,组织比较致密,元素分布均匀。Tafel极化曲线测试表明,Al-Mg_2Si涂层样品与AZ31B镁合金样品相比腐蚀电位从-1.489 V正移到-1.366 V,腐蚀电流密度从2.817×10~(-3) A/cm~2降低到1.198×10~(-3) A/cm~2。浸泡试验结果表明,喷涂Al-Mg_2Si的镁合金的腐蚀速率明显低于没有喷涂的镁合金。显微硬度测试表明,涂层的显微硬度集中分布在259~308 HV0.05之间,镁合金为50~60 HV0.05。因此在AZ31B镁合金表面火焰喷涂Al-Mg_2Si涂层可以提高其耐腐蚀性能,表面硬度显著提高。     

Understanding corrosion via corrosion product characterization: II. Role of alloying elements in improving the corrosion resistance of Zn–Al–Mg coatings on steel

Corrosion products are identified on Zn, ZnMg and ZnAlMg coatings in cyclic corrosion tests with NaCl or Na₂SO₄ containing atmospheres. For Mg-containing alloys the improved corrosion resistance is achieved by stabilization of protective simonkolleite and zinc hydroxysulfate. At later stages, the formation of layered double hydroxides (LDH) is observed for ZnAlMg. According to thermodynamic modeling, Mg²⁺ ions bind the excess of carbonate or sulfate anions preventing the formation of soluble or less-protective products. A preferential dissolution of Zn and Mg at initial stages of corrosion is confirmed by in situ dissolution measurement. The physicochemical properties of different corrosion products are compared.     

The Corrosion Behaviour of Electrochemical Zn Coated with Conversion Chromate and Phosphate Films in Concrete

The corrosion behaviour of electrochemical Zn coatings with and without chromate (VI, III) and phosphate (amorphous and crystalline) films in aerated 0.1 M NaOH + 0.1 M NaCl solution and concrete, immersed into water has been studied. The estimated corrosion rate in 0.1 M NaOH + 0.1 M NaCl solution is minimal cf. Zn chromatised in Cr³⁺ solution. The value of j_cor of Zn chromatised in Cr⁶⁺ solution is 1.5 times as high as that in Cr³⁺. The experiments carried out in concrete immersed into water (pH 12.5) have shown that all the chromate films studied do not extend the operating time of the sample. The best corrosion protection is provided by crystalline phosphate film.     

Corrosion behaviour in alkaline medium of zinc phosphate coated steel obtained by cathodic electrochemical treatment

The present work evaluated the ability of zinc phosphate coating, obtained by cathodic electrochemical treatment, to protect mild steel rebar against the localized attack generated by chloride ions in alkaline medium. The corrosion behaviour of coated steel was assessed by open circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopy. The chemical composition and the morphology of the coated surfaces were evaluated by X-ray diffraction and scanning electron microscopy. Cathodically phosphated mild steel rebar have been studied in alkaline solution with and without chloride simulating the concrete pore solution. For these conditions, the results showed that the slow dissolution of the coating generates the formation of calcium hydroxyzincate (Ca(Zn(OH)₃)₂·2H₂O). After a long immersion time in alkaline solution with and without Cl⁻, the coating is dense and provides an effective corrosion resistance compared to mild steel rebar.     

镁锂合金表面锌锰磷化膜的制备与性能表征

采用化学转化法在镁锂合金表面制备了外观深灰色、结构均匀致密、耐蚀性能良好的锌锰磷酸盐转化膜,并研究了磷化温度对磷化膜性能的影响。采用扫描电子显微镜(SEM)、能谱(EDS)仪、X射线光电子能谱(XPS)和X射线衍射(XRD)仪对膜层的表面形貌、化学组成及结构进行了表征。采用动电位极化曲线、电化学交流阻抗(EIS)和腐蚀失重实验对磷化膜的耐蚀性进行了研究。结果表明,锌锰磷化膜主要由Zn、Zn3(PO4)2、MnHPO4、Mn3(PO4)2组成。锌锰磷酸化膜起到了保护镁锂合金的作用,提高了镁锂合金的耐蚀性,当磷化温度为45℃时,磷化膜的腐蚀电流密度最低,腐蚀速率最小,耐蚀性能最好。     

Cu2+对钢铁磷化膜表面形貌的影响及其机理

采用扫描电镜和电化学工作站、盐雾实验研究了铜离子对钢铁磷化膜表面形貌、生成机制、防腐蚀性能的影响。结果表明:未加入铜离子时,磷化膜由片状的ZPO(Zn3(PO4)2.4H2O)组成;加入铜离子后,磷化膜由花瓣状的ZPO和团簇状的CuO组成。未加入铜离子时,磷化膜中ZPO的生成机制为由花瓣状至片状;加入铜离子后,磷化膜中ZPO的生成机制为由片状至花瓣状。铜离子对磷化膜的影响存在一个临界浓度6～8 g/L。在临界浓度下,随着磷化液中Cu2+的增多,磷化膜的耐腐蚀性能逐步提高;当磷化液中Cu2+的浓度超过临界浓度后,Cu2+会阻碍ZPO的形成,并且耐腐蚀性能下降。     

A Black Phosphate Conversion Coating on Steel Surface Using Antimony(III)-Tartrate as an Additive

A novel black phosphate conversion coating was formed on steel surface through a Zn-Mn phosphating bath containing mainly ZnO, H₃PO₄, Mn(H₂PO₄)₂, and Ca(NO₃)₂, where antimony(III)-tartrate was used as the blackening agent of phosphatization. The surface morphology and composition of the coating were characterized by scanning electron microscopy, energy dispersion spectroscopy, and x-ray photoelectron spectroscopy. Corrosion resistance of the coating was studied by potentiodynamic polarization curves and electrochemical impedance spectroscopy. The pH value of the solution had significant influence on the formation and corrosion resistance of the coating. The experimental results indicated that the Sb plays a vital role in the blackening of phosphate conversion coating. The optimal concentration of antimony(III)-tartrate in the phosphating bath used in this experiment was 1.0 g L^?1, as higher values reduced the corrosion resistance of the coating. In addition, by saponification and oil seals, the corrosion duration of the black phosphate coating in a copper sulfate spot test can be as long as 20 min.     

Investigation of wear and corrosion resistance of nanocomposite coating formed on AZ31B Mg alloy by plasma electrolytic oxidation

Ceramic-WC coatings were prepared on AZ31 B Mg alloy by plasma electrolytic oxidation (PEO) from a phosphate based bath containing suspended tungsten carbide nanoparticles at various process times. Scanning electron microscope results indicated that increase of coating time and incorporation of tungsten carbide into the ceramic coating during the PEO process led to a decrease in the number and diameter of coating pores. Phase analysis showed that the nanocomposite coating was composed of MgO, Mg₃(PO₄)₂ and WC. Tribological properties and corrosion behaviour of uncoated AZ31 B Mg alloy and ceramic coatings were evaluated using a pin-on-disc tribometer and potentiodynamic polarisation technique in 3.5% NaCl solution, respectively. The wear and electrochemical tests showed that wear and corrosion resistance of ceramic-WC nanocomposite coatings were better than ceramic only ones. In addition, wear and corrosion behaviour of coatings improved with increasing the coating time.     

Electrochemical properties and structure of vanadium-based conversion coatings on electro-galvanised steel

The corrosion resistance of vanadium-based conversion coatings on electro-galvanised steel (EG) was examined in terms of the different valence species V⁵⁺ and V⁴⁺ as the raw material in the treatment solution. The effects of mixing phosphoric acid with the vanadium-based conversion coating have also been investigated. Corrosion performance was tested by neutral salt spray test and the mechanism of corrosion resistance was analysed by electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. It was found that conversion coatings formed from V⁵⁺ or V⁴⁺ did not clearly show different corrosion behaviour, but that the addition of phosphoric acid to the solution including V⁵⁺ improved corrosion protection. These results indicate that mixing phosphoric acid lowers the pH of the solution and improves corrosion resistance. The role of phosphoric acid is also explained by the formation of hydrogen bonds at the interface between the vanadium species and EG substrate.     

The effects of 8-hydroxyquinoline on corrosion performance of a Mg-rich coating on AZ91D magnesium alloy

A Mg-HQ-rich primer was prepared by adding 45% pure magnesium particles and 5% 8-hydroxyquinoline in epoxy coating. The Mg-HQ-rich primer showed obviously better protection for AZ91D alloy than 50% Mg-rich primer. The additive 8-HQ combines with Mg²⁺ in the coating, forming a insoluble complex, MgQ₂, instead of Mg(OH)₂ on Mg particles. The MgQ₂ layer may retard dissolution of magnesium particles and prolong the cathodic protection effect of Mg-HQ-rich primer. Additionally, the corrosion products may also block the defects in the primer and the active sites on the substrate surface, thereby further increase the corrosion resistance of the Mg-HQ-rich primer.     

Effect on Corrosion Resistance of Ce-Rich-Sealed Ni-P Coatings on Cf/Al Composite Surface

In this study, Ni-P coatings and sealing of the coatings by Ce-rich solution on Cf/Al composite surface for enhanced corrosion resistance are investigated. The corrosion resistance of uncoating sample in 3.5 wt.% NaCl solution was investigated and a comparison with Ni-P and Ce-sealed Ni-P coatings is given. Effect of Ce-sealing on Ni-P coating is discussed. The results of electrochemical measurements of corrosion performance of Cf/Al composites show that sealing of Ni-P coatings with Ce-rich solution can improve the corrosion resistance. The Ce-rich-sealed Ni-P coating has higher corrosion resistance than the coating without Ce, and the electroless plated Ni-P coating on composite surface has higher corrosion resistance than the bare sample, as evidenced by EIS and potentiodynamic polarization measurements. The microstructure of the Cf/Al composites and the two kinds of coatings (i.e., Ni-P coating and Ce-sealed Ni-P coating) were examined by scanning electron microscopy, energy dispersive spectroscopy, and transmission electron microscopy. The Ce-sealed Ni-P coatings on Cf/Al composite surface have a total thickness of ~11 μm of which 10 μm is the thickness of the Ni-P coating and ~1 μm is the thickness of the Ce-rich sealing. It shows that the selected area electron diffraction ring pattern of Ce-rich sealing on Ni-P plated composite is consistent with Ce₆O₁₁ or CeO₂. X-ray photoelectron spectroscopy results show that Ce⁴⁺ was the dominant oxidation state for Ce-rich sealing on Ni-P plated composite. The Ce-sealing treatment on Ni-P coating has improved the corrosion resistance over and above the corrosion resistance offered by the Ni-P mono-coating to the bare substrate.     

Effects of coolant chemistry on corrosion of 3003 aluminum alloy in automotive cooling system

In this work, effects of coolant chemistry, including concentrations of chloride ions and ethylene glycol and addition of various ions, on corrosion of 3003 Al alloy were investigated by electrochemical impedance spectroscopy measurements and scanning electron microscopy characterization. In chloride‐free, ethylene glycol–water solution, a layer of Al‐alcohol film is proposed to form on the electrode surface. With the increase of ethylene glycol concentration, more Al‐alcohol film is formed, resulting in the increase in film resistance and charge‐transfer resistance. In the presence of Cl^? ions, they would be involved in the film formation, decreasing the stability of the film. In 50% ethylene glycol–water solution, the threshold value of Cl^? concentration for pitting initiation is within the range of 100 ppm to 0.01 M. When the ethylene glycol concentration increases to 70%, the threshold Cl^? concentration for pitting is from 0.01 to 0.1 M. In 100% ethylene glycol, there is no pitting of 3003 Al alloy even at 0.1 M of Cl^?. Even a trace amount of impurity cation could affect significantly the corrosion behavior of 3003 Al alloy in ethylene glycol–water solution. Addition of Zn²⁺ is capable of increasing the corrosion resistance of Al alloy electrode, while Cu²⁺ ions containing in the solution would enhance corrosion, especially pitting corrosion, of Al alloy. The effect of Mg²⁺ on Al alloy corrosion is only slight.     

淫羊藿苷含量对Mg/UMAO/CS/IC涂层性能的影响

为了研究淫羊藿苷含量对镁/超声微弧氧化/壳聚糖/淫羊藿苷（Mg/UMAO/CS/IC）涂层性能的影响,并提高纯镁的耐蚀性,采用电泳沉积（EPD）和UMAO技术在纯镁基体上制备Mg/UMAO/CS/IC涂层。采用扫描电子显微镜（SEM）、X射线衍射（XRD）、原子力显微镜（AFM）和傅立叶变换红外光谱（FTIR）对涂层的特征进行分析。对不同样品在模拟体液中进行了电化学阻抗和动电位极化的腐蚀行为研究。结果表明：当IC含量为0.4 g/L时CS/IC层具有较好的封孔效果。添加不同IC含量的Mg/UMAO/CS/IC涂层均由Mg、MgO、CS和Mg₂SiO₄组成。不同IC含量涂层的自腐蚀电流密度（i_corr）比Mg至少都低一个数量级,能为镁基底提供更有效的保护。IC含量为0.4 g/L时Mg/UMAO/CS/IC涂层的耐蚀性更好,自腐蚀电流密度（1.667×10^-6 A/cm²）最小。Mg/UMAO/CS/IC涂层可有效解决纯镁在临床骨内固定应用上降解过快的问题。     

磷酸盐浓度对5083铝合金微弧氧化膜组织与耐腐蚀性能的影响

为研究电解液浓度对微弧氧化的影响规律,在磷酸钠电解液中采用恒压模式对5083铝合金进行微弧氧化,采用场发射扫描电镜、划痕仪以及电化学工作站等研究了电解质浓度对膜层生长速率、组织成分、膜基结合强度以及耐腐蚀性能的影响。结果表明:随着磷酸钠浓度的增大,氧化膜厚度线性增加,膜层表面的"火山堆积"状形貌特征愈发明显,但浓度过大时氧化膜出现局部不均匀堆积及较大孔洞,其对氧化膜成分影响不明显;氧化膜与基体结合良好,且随着浓度增加结合强度出现先增后减的趋势。当磷酸钠浓度为10 g/L时,氧化膜的自腐蚀电流最低,为2.96×10~(–8) A/cm~2,比铝合金基体降低了1个数量级,表现出良好的耐腐蚀性能。     

Effect of Caand Mg on corrosion and scaling of galvanized steel pipe in simulated geothermal water

In this paper, the effects of scaling ions (Ca²⁺ and Mg²⁺) on corrosion and scaling processes of galvanized steel pipe in geothermal water are presented. Spherical corrosion products and needle-shaped scale coexisted on the pipe surface. The concentration of Zn²⁺ and OH⁻ affected the nuclei formation of scale. The corrosion products and scale were identified as Zn(OH)₂, ZnO, CaCO₃ and MgCO₃, respectively. When scale formed on the galvanized steel pipe, the corrosion rate slowed down and the pitting region became smaller.