交流阻抗谱研究钙磷陶瓷电沉积层的结构

用交流阻抗技术研究了不同电沉积时间的钙磷陶瓷沉积层。结果表明，沉积时间不同的陶瓷沉积层的交流阻抗谱存在显著的差别。采用双层结构物理模型，对不同沉积时间陶瓷沉积层的交流阻抗谱进行计算机拟合，得到的等效电路各元件拟合值显示：电极表面钙磷陶瓷为内密外疏型梯度沉积层。在陶瓷电沉积过程中，钙磷晶粒同时沉积于距电极表面不同距离的部位，沉积层厚度增加的同时内层密度也在逐渐增加，整个 只层的梯度结构处于动态变化之中。     

Electrochemical corrosion behaviour of plasma electrolytic oxidation coatings on AM50 magnesium alloy formed in silicate and phosphate based electrolytes

PEO coatings were produced on AM50 magnesium alloy by plasma electrolytic oxidation process in silicate and phosphate based electrolytes using a pulsed DC power source. The microstructure and composition of the PEO coatings were analyzed by scanning electron microscopy (SEM) and X-ray Diffraction (XRD). The corrosion resistance of the PEO coatings was evaluated using open circuit potential (OCP) measurements, potentiodynamic polarisation tests and electrochemical impedance spectroscopy (EIS) in 0.1 M NaCl solution. It was found that the electrolyte composition has a significant effect on the coating evolution and on the resulting coating characteristics, such as microstructure, composition, coating thickness, roughness and thus on the corrosion behaviour. The corrosion resistance of the PEO coating formed in silicate electrolyte was found to be superior to that formed in phosphate electrolyte in both the short-term and long-term electrochemical corrosion tests.     

Electrochemical behavior of cobalt oxide coatings on cold-rolled steel in alkaline sodium sulfate

The electrochemical behavior of a coating of cobalt oxide on cold-rolled steel in alkaline sodium sulfate was studied using the electrochemical techniques of open-circuit potential measurements and electrochemical impedance spectroscopy. The coating was prepared at different annealing temperatures ranging from 350 to 750 °C and characterized by SEM, EDX and XRD. Below 550 °C the composition of the coating was basically of Co₃O₄. At 750 °C CoO was formed and big cracks appeared on the film exposing an inner layer of iron oxides. Analysis of the EIS data is very difficult because of the complexity of the interface structure. It can be inferred that the charge transfer resistance of the coatings prepared at 350 and 450 °C were higher than those for the coatings prepared at temperatures above 550 °C.     

锌锰系电解磷化膜工艺的研究

在锌锰系电解磷化液中,采用外加电流的方法对工件进行磷化处理,研究了电解磷化工艺对磷化膜性能的影响规律,通过硫酸铜点滴和盐雾试验,电化学方法及扫描电子显微镜和X-射线衍射仪等对电解磷化膜耐蚀性能、微观形貌和膜层成分进行了研究。结果表明,经过电解磷化后,可得到结晶致密的针形结构的电解磷化膜,膜层主要由Mn2Zn(PO4)2、Fe3(PO4)2和MnHPO4.3H2O等成分组成,电解磷化膜经过24 h中性盐雾试验无锈蚀。     

Effect of transition layer on the performance of hydroxyapatite/titanium nitride coating developed on Ti-6Al-4V alloy by magnetron sputtering

A gradient transition multilayer hydroxyapatite/titanium nitride (HA/TiN) coating was prepared on the Ti-6Al-4V alloy by magnetron sputtering. The composition, surface topography, microstructure, adhesion strength and electrochemical properties of the as-deposited coatings were characterized by SEM/EDS, AFM, XRD, FT-IR and electrochemical workstation. The experimental results showed that the single TiN coating deposited at a partial pressure of nitrogen (N₂) of 0.08?Pa had the best internal stress and tribological performance, and its volume loss was only 0.89% of that of Ti-6Al-4V alloy. The introduction of the TiN transition layer greatly improved the wear resistance of the Ti-6Al-4V alloy, and the adhesion strength of the HA layer to the substrate increased from 6.50?±?0.5?N to 11.70?±?1.2?N, an increase of 56%. The HA/TiN coating surface consisted of uniform hemispherical particles with dense structure and invisible defects (micro-cracks and pores). For the HA surface layer, the crystal structure and active hydroxyl (-OH) group was restored after heat treatment. Potentiodynamic polarization experiments indicated that the HA/TiN coating achieved the lowest corrosion current density and the most positive corrosion potential compared to the single TiN layer and Ti-6Al-4V alloy. In summary, it can be conclude that the gradient transition layer can well improve the mechanical properties and electrochemical behavior of the titanium alloy, and largely ensuring the stability of the surface bioactive coating.     

Phenol electropolymerization on phosphated mild steel via zinc electrodeposition

Phenol electropolymerization to polyoxyphenylene coatings on phosphated steel and phosphated galvanized steel, normally impossible under the conditions allowing effective coating formation on either steel or zinc, is activated by cathodic deposition of zinc. A critical zinc amount has been found to be necessary to suppress electrochemical processes competitive with electropolymerization and induce coating formation with nearly 100% efficiency. SEM analysis showed that this critical amount of zinc corresponded to the formation of a low number of zinc nuclei emerging at the surface of the phosphate layer, on which, however, polyoxyphenylene was formed as a continuous coating. A.c. impedance tests showed that initial barrier properties are worse for coatings grown on zinc-plated phosphated samples than for those grown on steel from the same solutions. However, the long term corrosion resistance is much better in the former case, the improvement being largely associated with zinc cathodic protection     

Drying and property studies on protective coatings formed by spontaneous surface polymerization

Drying studies on a protective coating formed by spontaneous polymerization on aluminum are described. The polymer coating studied here was formed from styrene, n-phenyl maleimide (NPMI), bismaleimide (BMI), and 2-(methacryloyloxy) ethyl acetoacetate (MEA). The coating successfully changed into an adherent film through drying in the presence of a coalescing solvent. Drying at a high temperature (> 170°C) enhanced the performance of the coating in terms of corrosion resistance and adhesion. It was found that the drying process involved removal of surface water on the substrate followed by formation of a dense protective layer associated with thermal crosslinking of g -diketone functional groups in the coating. The reaction mechanism, glass transition temperature, adhesion strength to aluminum, and corrosion resistance of these coatings are reported. The resultant coatings show excellent adhesion strength in a torsional test and very good resistance under the ASTM B-117 accelerated salt fog test.     

电沉积制备羟基磷灰石-碳化硅复合涂层

采用电沉积技术在碳/碳复合材料表面制备出羟基磷灰石-碳化硅复合涂层,通过扫描电镜、x.射线衍射仪、能谱仪、傅里叶红外光谱仪研究了电解液浓度与电流密度对复合涂层形貌与组成的影响,采用粘接拉伸法测试羟基磷灰石-碳化硅涂层、羟基磷灰石涂层与基体的结合强度.结果表明:随着电解液浓度的降低,涂层的组成由磷酸氢钙转变为羟基磷灰石,晶体从大尺寸的片状逐渐转变为纳米级球状.随着电流密度的升高,涂层的钙、磷摩尔比逐渐升高,晶体向疏松的针状转变.选取适当的工艺参数,羟基磷灰石-碳化硅与基体结合强度高于羟基磷灰石涂层.     

Mechanisms of non-toxic anticorrosive pigments in organic waterborne coatings

Investigations have been carried out concerning the mechanism of the behaviour of non-toxic anticorrosive pigments belonging to the group of phosphates, ferrites and ion exchange pigments in waterborne systems. The mechanism controlling the protective effectiveness of organic coatings is complex and results from simultaneous activity of various agents, from among which the kind of the corrosion inhibitor and the structure of the coating are of fundamental importance. The effect of pigments on the protective properties of coatings was tested by means of electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) as well as the salt spray and Prohesion tests. For the investigation of the structure of coatings the porosymetric method and modulated-force thermomechanical analysis (mf TMA) were applied. The results of these investigations have shown that calcium zinc phosphate and zinc ferrite are the most effective. These pigments take part in the passivation of steel, which has been proved by the results of electrochemical investigations and by the presence of the passive layers as has been found out by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDXA) and scanning electron microscopy (SEM). Calcium zinc phosphate and zinc ferrite affect the structure of the coatings, increasing the glass transition temperature (Tg) of the coatings. Zinc phosphate and calcium-exchanged silica do not act in compliance with electrochemical mechanism neither do they improve the barrier properties of the binder.     

Construction of multilayer coatings for flame retardancy of ramie fabric using layer‐by‐layer assembly

Complex multilayer coatings composed of α‐zirconium phosphate (ZrP), polyethylenimine (PEI), and ammonium polyphosphate (APP) were constructed via layer‐by‐layer assembly method for flame retardant ramie fabric. Bicomponent PEI/ZrP layers served as insulating barrier coating, and bicomponent PEI/APP layers served as intumescent coating. The flame retardancy of the coated ramie fabric was strongly dependent on the nature of the coatings and the layer‐by‐layer assembly patterns. The coated ramie fabric with inside PEI/ZrP layers and outside PEI/APP layers possessed the most uniform and consistent coating surface morphology, as well as the highest content of N and P elements, resulting in an excellent improvement in flame retardancy of ramie fabrics. When this kind of coated ramie fabric was heated, the inner PEI/ZrP layer effectively prevent oxygen and heat from penetrating into the substrate, and the outer PEI/APP layer exposed to air with good expansion during combustion. The synergistic effect was formed during the combustion process and could impart ramie fabrics with high flame retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45556.     

Study on corrosion resistance and roughness of micro-plasma oxidation ceramic coatings on Ti alloy by EIS technique

Micro-plasma oxidation (MPO) technique has been developed quickly in recent years. The produced ceramic coatings are reported to possess fine properties and promising application prospects in many fields. The aim of this work is to study the corrosion resistance and the roughness of the micro-plasma oxidation ceramic coatings on Ti alloy by electrochemical impedance spectroscopy (EIS) technique. Compound ceramic coatings were prepared on Ti-6Al-4V alloy by pulsed bi-polar micro-plasma oxidation in NaAlO₂ solution. The phase composition and element distribution in the coating were investigated by X-ray diffractometry and electron probe micro-analyzer. EIS of the coatings was measured through CHI604 electrochemical analyzer in 3.5% NaCl solution. The ceramic coating is composed of a large amount of Al₂TiO₅ and a little α-Al₂O₃ and rutile TiO₂. The coating is of double-layer structure with the loose outer layer and the dense inner layer. The thickness of the coatings is reduced when the working frequency or the cathode pulse current density is increased, while the thickness is increased when the frequency or the anode current density is increased. The established “equivalent circuit” of the coatings is consistent with the double-layer structure. The electric charge transfer resistance (R_t) in the equivalent circuit can be used to assess the corrosion resistance of the coatings, which is consistent with the result of the polarizing curves test. And the empirical exponent (n₁) of the constant phase element (Q₁) in the equivalent circuit can be used to assess the surface roughness of the coatings, which is consistent with the surface SEM analysis of the coatings.     

Formation and characteristics of Al−Zn hydrotalcite coatings on galvanized steel

In this study, a process for depositing hydrotalcite (HT) coatings on galvanized steel was developed and the resulting coatings were characterized. Results showed that coatings formed spontaneously on galvanized surfaces upon exposure to ambient temperature alkaline aluminate solutions. Anodic polarization and electrochemical impedance spectroscopy experiments showed clear evidence of surface passivation. Scanning electron microscopy showed the formation of a continuous and conformal surface film comprised on a compact mass of crystallites. X-ray diffraction confirmed that the coating contained an Al−Zn hydrotalcite compound. Coating formation was enhanced by oxidizer and ammonium salt additions. Coatings formed by using best practices were deposited in less than 10 minutes and demonstrated good surface coverage and good organic coating adhesion. HT coatings formed by using best practices showed excellent organic coating adhesion compared to zinc phosphate control coatings. In salt spray testing, the presence of a hydrotalcite conversion coating under an epoxy neat resin was found to delay the onset of red rusting compared to control samples that were epoxy coated, but not conversion coated.     

固渗+EB-PVD法制备炭/炭复合材料防氧化复合涂层研究

制备出了SiC/SiC-Al2O3-Y2O3炭/炭复合材料防氧化复合涂层,该复合涂层的内层SiC基涂层采用料浆固渗法制备,SiC-Al2O3-Y2O3外层涂层采用大功率电子束物理气相沉积法。研究表明,电子束物理气相沉积法能达到较好的沉积效果,在制备过程中形成了柱状晶结构的涂层,使得涂层具有更高的应变容限,涂层非常均匀致密。用SEM、XPS和EDS等分析方法分析了涂层的防氧化机理。结果表明:在制备过程和氧化过程中,涂层内会发生复杂的物理和化学变化,生成硅酸盐氧化物,显示出电子束物理气相沉积法在制备炭/炭复合材料防氧化涂层方面独特的优势。     

Hydroxyapatite coating on selectively passivated and sensitively polymer-protected surgical grade stainless steel

Surgical grade stainless steel (316L SS) is a widely used implant material in orthopedic surgeries. However, the release of metallic ions evidenced from the 316L SS implants in vivo conditions is a big challenge. In order to minimize the release of metallic ions, coating the 316L SS implant with a biocompatible material like hydroxyapatite [HAP, Ca₁₀(PO₄)₆(OH)₂] is one of the suitable methods. In this paper, the hydroxyapatite coating on borate passivated through poly-ortho-phenylenediamine (PoPD)-coated 316L SS by a dip coating method has been reported. The coatings were characterized by electrochemical techniques such as potentiodynamic polarization, electrochemical impedance spectroscopy, and cyclic voltammetry. Surface characterization studies of the coatings such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were also carried out. The leach out characteristics of the coatings was determined at the impressed potential. The mechanical property of the coatings was evaluated by Vicker’s microhardness test. The Cr-rich passive film formed underneath the PoPD layer showed a higher protective efficiency. The ability to form apatite on the post-passivated PoPD-coated 316L SS specimen was examined by immersing it in the simulated body fluid. The enhanced corrosion resistivity of the HAP coating on the post-passivated PoPD-coated 316L SS was due to an effective barrier of PoPD followed by the passive film underneath the PoPD.     

Studying the corrosion protection properties of an epoxy coating containing different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments

Epoxy/polyamide coatings were loaded with different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments. Moreover, a coating containing zinc phosphate (ZP) was prepared as a reference sample. The coatings were applied on St-37 steel substrates and then were exposed to 3.5 wt% NaCl solution up to 35 days. The corrosion inhibition properties of the pigments extracts were studied on bare steel samples by a potentiodynamic polarization technique after 24 h immersion. The morphological properties and corrosion resistance of the coatings were investigated by scanning electron microscope (SEM), optical microscope, electrochemical impedance spectroscopy (EIS) and salt spray tests.     

The effect of mixture of mercaptobenzimidazole and zinc phosphate on the corrosion protection of epoxy/polyamide coating

The protective performance of solvent-borne epoxy/polyamide coatings formulated with zinc phosphate anticorrosion pigment was improved through the addition of 2-mercaptobenzimidazole as an organic corrosion inhibitor. In addition to determining the optimum percentage of mercaptobenzimidazole, the electrochemical impedance spectroscopy data could show the influence of inhibitor concentration on the epoxy behavior within 35 days of immersion in 3.5 wt% NaCl solution. The improved corrosion protection and adhesion strength in the presence of the pigment and inhibitor were connected to the deposition of a protective layer at the coating/substrate interface which might limit active zones for electrochemical reactions. The precipitation was confirmed using electrochemical impedance spectroscopy, polarization curves and SEM/EDX surface analysis.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Development and characterization of silver and zinc doped bioceramic layer on metallic implant materials for orthopedic application

A successful electrodeposition method for preparing silver and zinc modified bioactive calcium phosphate layers onto surgical grade titanium alloy material (Ti6Al4V) was developed. The coatings were deposited on the Ti6Al4V surface by pulse current at 70 °C from an electrolyte containing adequate amounts of calcium nitrate, ammonium dihydrogen phosphate, zinc nitrate and silver nitrate. The corrosion resistivity of the bioceramic coatings was assessed in conventional Ringer׳s solution in a three electrode open cell by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results revealed the pure bioactive calcium phosphate (CaP) coated implant materials to possess the highest resistivity to corrosion, while the silver and zinc doped CaP layer showed at least one order of magnitude lower corrosion resistance. These modified CaP coatings can be further considered as antimicrobial coatings with enhanced biocompatibility. The morphology and structure of the coatings were characterized by Scanning electron microscopy (SEM), Energy-dispersive X-ray Spectroscopy (EDX) and X-ray diffraction (XRD) that confirmed the pulse current deposited CaP layer to consist of a mixture of different calcium phosphate phases such as hydroxyapatite (HAp), monetite (dicalcium phosphate, CaHPO₄) as well as other Ca-containing components, portlandite (Ca(OH)₂) and parascholzite (CaZn₂(PO₄)₂(H₂O)₂).     

Biomimetic Preparation and Characterization of Bioactive Coatings on Alumina and Zirconia Ceramics

For the preparation of bioactive coatings on alumina and zirconia ceramic surfaces a fast biomimetic method using a supersaturated solution containing Na⁺, Ca²⁺, Cl⁻, HCO₃⁻, and PO₄³⁻ ions was used. The coatings were analysed with the use of an X-ray diffraction spectrometer and a transmission electron microscope equipped with an energy-dispersive spectroscopy detector. After the precipitation both coatings were composed of poorly crystallized, nanosized, plate-like particles with the octacalcium phosphate (OCP) crystal structure. The adhesion of the coatings was improved by a heat treatment at 1050°C for 1 h. During this heat treatment the calcium phosphate layer, deposited from a supersaturated solution onto the surface of the substrates, was sintered to form a dense coating. At the same time the OCP crystal structure was transformed into that of hydroxyl apatite, the coating's crystallinity was increased, and the particles grew isotropically up to 300 nm in size. The bioactivity of the coated ceramic was confirmed before and after the heat treatment using a simple simulated body fluid test.     

New single-step electrosynthesis process of homogeneous and strongly adherent polypyrrole films on iron electrodes in aqueous medium

Homogeneous and strongly adherent polypyrrole (PPy) films were electrochemically synthesized on iron electrodes in sodium tartrate (Na₂C₄O₆H₄ 0.2 M) aqueous solution. This one step pyrrole electropolymerization process has been successfully achieved under different electrochemical techniques, such as potentiodynamic, galvanostatic and potentiostatic modes. During the first stage of the electrochemical process the tartrate counterion slows down the iron dissolution by leading to the formation of a passivation layer on the working electrode surface, and the pyrrole electropolymerization takes place. The electrosynthesized polymer deposit has been characterized by several microscopic and spectroscopic techniques. Any iron traces have been detected by X-ray photoelectron spectroscopy (XPS) on the outer side of the PPy films, which confirms the compactness and the homogeneity of the polymeric coating. Scanning electronic microscopy (SEM) imaging showed uniform and compact PPy coatings with cauliflower-like structure. Infra-red (IR) and Raman spectroscopies proved that the obtained PPy films have the same vibrational properties as those electrodeposited on noble Pt plates.