磷酸鹽處理一般用於金屬表面作為改善耐蝕、抗磨耗及後續塗裝之附著性，而其中又以磷酸錳鍍層之硬度最高，且具較高耐蝕及抗磨耗性能，但目前大部分磷酸鹽之研究集中於磷酸鋅處理，有關磷酸錳析鍍探討則較少發現。本研究利用鍍層與基材重量變化量測，驗證磷酸錳反應機構，電子微探儀 (EPMA) 及掃描式電子顯微鏡（SEM），能量散佈光譜儀 (EDS) 、線掃描及面掃描對鍍層進行成分分析，穿透式電子顯微鏡（TEM）及X光繞射儀 (XRD )來觀察及分析鍍層表面、橫截面形態及晶體結構；另外使用開路電位（OCP）及電化學交流阻抗(EIS) 量測來評估磷酸錳表面電位特性及極化阻抗值，並藉由熱重 (TGA) 及熱差 (DSC)瞭解熱處理後脫水行為及相變化情形，其目的在探討不同析鍍條件(如溫度、外加電位及鍍液中鎳離子濃度)生成之磷酸錳鍍層及後續熱處理溫度，對其微觀組織對其電化學性質之影響。
實驗結果顯示，磷酸錳反應主要由陽極之金屬溶解及陰極之氫離子還原所控制，於酸性磷酸錳鍍液中，基材重量損失高於析鍍增加重量，在90℃溫度條件下，基材表面上析出之磷酸錳結晶鍍層，比在70、80 及100℃所生成之磷酸錳鍍層為厚，其組成主要為(Mn,Fe)5H2(PO4)4‧4H2O，並為雙層結構。
外加陽極電位於90℃所生成之鍍層厚度比在開路電位及陰極電位下所生成的鍍層厚度為厚，且皆為為雙層結構，其內層厚度大於外層，而極化阻抗較低。相反的，使用外加陰極電位下所生成之雙層結構鍍層，內層厚度小於外層，極化阻抗值隨陰極電位增加而有提昇之趨勢。
溶液中鎳離子的存在會影響磷酸錳鍍層表面形態及所含鎳、鉻、鉬及釩等合金元素之成分佈，且析鍍過程會發生鎳置換鐵之反應；當鍍液中鎳離子濃度提高時，會增加磷酸錳成核數目及縮小磷酸錳結晶顆粒尺寸。在90℃開路電位條件下生成之磷酸錳鍍層雙層結構，內層為富鐵結晶差之組織，外層則為富錳之結晶顆粒所組成。磷酸錳內外層中鎳含量皆會隨著鍍液中鎳離子濃度提高而有增加趨勢，但鉻、鉬及釩等合金元素含量僅於內層（富鐵層）有增加現象，使用鎳離子濃度為2000 ppm之析鍍條件時，鎳離子會在磷酸錳層中間附近還原成細條狀。
磷酸錳層在325℃下會歷經吸附水流失及結晶水損失的兩階段脫水過程，當溫度超過340℃時，磷酸錳結晶會分解並形成結晶性差的Fe0.5Mn2.5(PO4)2化合物。結晶水的損失會影響磷酸錳鍍層之極化阻抗值；當熱處理溫度在300℃以下時，磷酸錳層會隨熱處理溫度增加而提高其極化阻抗值，當溫度高於300℃，熱處理會誘發磷酸錳鍍層產生垂直於基材與鍍層界面之裂縫及降低其阻抗值。
本研究中90℃為最佳析鍍溫度，利用外加陰極電位及鍍液中添加鎳離子方法，可加快陰極氫離子的還原，進而促進磷酸錳成核及增加析鍍速度，並使結晶顆粒尺寸縮小。所生成之磷酸錳鍍層雙層結構，當施以300℃及30分鐘熱處理，會因脫水但不破壞其鍍層完整性，而獲得最高之極化阻抗值。

Phosphate coatings are commonly used to improve the corrosion and wear resistance as well as the adhesive properties prior to the apply of paintings on metal surface. Manganese phosphate coating has the highest hardness and superior corrosion and wear resistances of general phosphate coatings. However, most researches have focused on the investigation of zinc phosphate coating instead of manganese phosphate coating.
The aim of this study is to investigate the influence of various deposition parameters (such as, temperature of phosphating solution, applied potential and Ni2+ ion concentration in phosphating solution) and heat treatment on the microstructure and electrochemical behavior of manganese phosphating. In this study, the weight change of coating and substrate were used to interpretate the manganese phosphating mechanism. The surface morphology, cross-section micrograph and chemical composition of manganese phosphate coating were examined by using an electron probe micro analysis (EPMA) and a scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS), line scan and mapping. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were also conducted for phase identification of the coated specimen. In addition, the open circuit potential (OCP) and the electrochemical impedance spectra (EIS) of the coated steels were measured the potential characteristic and polarization resistance of manganese phosphating surface. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)) were performed for the as-coated specimen to investigate the dehydration behavior and phase change under heat treatment.
Experimental results show that manganese phosphating mechanism is controlled by the anodic reaction of metal dissolution and cathodic reaction of hydrogen ion reduction. It is also found that the weight loss of substrate was more than the weight gain for phosphate coating deposited from acidic manganese phosphating solution. The manganese phosphate coating formed a thicker layer with crystalline (Mn,Fe)5H2(PO4)4‧4H2O at 90 ℃, which is not observed for coatings formed at 70, 80 or 100℃.
The phosphate coatings consisted of a two-layered structure under applied potential and OCP condition was thus conducted at 90℃. The phosphate coating formed under anodic applied potential was also found thicker and with lower polarization resistance than those formed under OCP and cathodic polarization condition. However, the polarization resistance of phosphate coating deposited a thinner inner layer increases with cathodic potential during phosphating treatments.
The surface morphology and distributions of Ni, Cr, Mo and V in phosphate layer is affected by the presence of Ni2+ ions in coating solution. And it also occurred in the displacement of iron with Ni2+ during the phosphating process Phosphate layer with more grains and smaller particle size is observed for phosphating with higher Ni2+ ion concentration in the solution. This referred to the increase of nucleation sites on substrate surface as the Ni2+ ion concentration in the phosphating solution increases. At 90℃, the deposit consisted of two-layered structure with the inner layer containing a higher Fe content with poor crystalline while a Mn-rich crystal compound in the outer layer. As Ni2+ ion in the phosphating solution increased, Ni contents in the deposited layers are also increased both in the inner and outer layers of the coating, while the contents of Cr, Mo and V are only increased in the inner layer. In some cases, Ni particles are found in the phsophating layer, such as Ni strips are located near the center of the phosphate layer with the phosphating solution contained 2000 ppm Ni2+ ions.
Thermogrammetrtic analysis data show that manganese phosphate coating undergo a two-step dehydration process which cause the sequential loss of adsorptive and structural water at temperatures below 325℃. Decomposition of the phosphate coating occurred at 340℃ resulted in the formation of Fe0.5Mn2.5(PO4)2 with poor crystallinity. The polarization resistance of the phosphate coating was also observed to be increased with increased heated temperatures as below 300℃, which could be due to the loss of structural water. At temperatures higher than 300℃, cracks which are perpendicular to the substrate/coating interface were found and the impedance of phsphating layer was also observed to be decreased.
From this study, it is concluded that the optimum phosphating temperature for manganese phosphate is 90℃. Under applied cathodic potential and with Ni2+ ion in phosphating solution could increase the hydrogen ion reduction, manganese phosphate nucleation, rate of deposition and thus decrease the crystalline particle size. The layer was not destroyed by dehydration with heat treatment at 300℃ for 30 minutes. The two-layered manganese phosphate coating has highest polarization resistance.

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