PHOSPHONIC ACID MONOLAYERS FOR CORROSION PROTECTION OF COPPER: EQCM AND EIS INVESTIGATIONS

2019 ◽  
Vol 27 (06) ◽  
pp. 1950166
Author(s):  
AYSEL YURT ◽  
ESRA SOLMAZ

Preparation, characterization and application of protective phosphonic acid monolayers formed by 1-Aminohexyl phosphonic acid (AHP), 1,4-butanediphosphonic acid (BDPA), 1-amino-1,3-dimethylbutyl phosphonic acid (ADBP) on copper surface as anticorrosive self-assembled molecular monolayers (SAMs) have been investigated by atomic force microscopy (AFM) analysis, electrochemical impedance spectroscopy (EIS) and in situ electrochemical quartz crystal microbalance (EQCM) techniques. Film formation and growth were monitored by EQCM and the step-by-step construction of monolayer was investigated through measurement of the frequency change, which corresponds to mass change due to the adsorption of molecules. Observed increase in electrode mass suggests that SAMs formed on copper surface by the adsorption of phosphonic acids. Results clearly demonstrate that adsorbed amounts of phosphonic acids were strongly influenced by immersion time and molecular structure. Quantum chemical calculations were performed by semi-empirical PM6 method, in order to explain the relationship between molecular structure and adsorption mechanism. Quantum chemical parameters of phosphonic acids propound that adsorption of molecules on copper surface has a chemical mechanism. Corrosion protection ability of SAMs against the acidic corrosion of copper has been evaluated in 0.1[Formula: see text]M H2SO4 solution. It was found that phosphonic acid SAMs act as protective barrier and the protection efficiencies increased in the following order: [Formula: see text].

2019 ◽  
Vol 91 (3) ◽  
pp. 509-521 ◽  
Author(s):  
Clément Coquery ◽  
Claire Negrell ◽  
Nicolas Caussé ◽  
Nadine Pébère ◽  
Ghislain David

Abstract Two grades of chitosan [chitosan 30000 g mol−1 (N-chitosan 30) and 250000 g mol−1 (N-chitosan 250)] were functionalized by the Kabachnik–Fields reaction. To obtain the highest phosphonic ester grafting rate (55% and 40% for the N-chitosan 30 and N-chitosan 250, respectively), the pH must be kept constant during the reaction (pH=5). Then, a partial hydrolysis of the ester functions was carried out in HCl medium to generate phosphonic acid functions up to 25% and 20% for the N-chitosan 30 and N-chitosan 250, respectively. It was shown that the grafting of phosphonic acids on chitosan significantly reduced the dynamic viscosity. Afterwards, electrochemical impedance measurements were performed in an aqueous solution (pH=5) in the presence of either N-chitosans or P-chitosans (3 wt.%). The two native N-chitosans were little adsorbed onto the carbon steel surface and the corrosion protection was low. In contrast, the impedance results in the presence of the 30000 g mol−1 phosphorylated chitosan (P-chitosan 30) evidenced the beneficial effect of grafted phosphonic acid on its adsorption on the steel surface. The lower efficiency of the 250000 g mol−1 (P-chitosan 250) was attributed to its high molecular weight which made difficult the interactions between the phosphonic groups and the metallic surface.


2020 ◽  
Vol 117 (6) ◽  
pp. 610
Author(s):  
Nadia Hammouda ◽  
Kamel Belmokre

Organic coatings are widely employed in the corrosion protection of most metal surfaces, particularly steel. They provide a barrier against corrosive species present in the environment, due to their high resistance to oxygen, water and ions transport. This study focuses on the evaluation of corrosion protection performance of epoxy paint on the carbon steel surface in chloride environment (3% NaCl) by Electrochemical Impedance Spectroscopy (EIS). The electrochemical behavior of painted surface was estimated by EIS parameters that contained paint film resistance, paint film capacitance and double layer capacitance. On the basis of calculation using EIS spectrums it was observed that pore resistance (Rpore) decreased with the appearance of doubled layer capacitance (Cdl) due to the electrolyte penetration through the film. This was further confirmed by the decrease of diffusion resistance (Rd) which was also the indicator of the deterioration of paint film protectiveness. Microscopic analyses have shown that oxidation dominates the corroded surfaces.


2019 ◽  
Vol 6 (438) ◽  
pp. 21-29
Author(s):  
Zh.B. Satpaeva ◽  
◽  
O.A. Nurkenov ◽  
K.M. Turdybekov ◽  
L.K. Abulyaissova ◽  
...  

Metals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 337
Author(s):  
Ewa Wierzbicka ◽  
Marta Mohedano ◽  
Endzhe Matykina ◽  
Raul Arrabal

REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) regulations demand for an expedient discovery of a Cr(VI)-free alternative corrosion protection for light alloys even though the green alternatives might never be as cheap as current harmful technologies. In the present work, flash- plasma electrolytic oxidation coatings (FPEO) with the process duration < 90 s are developed on AZ31B alloy in varied mixtures of silicate-, phosphate-, aluminate-, and fluoride-based alkaline electrolytes implementing current density and voltage limits. The overall evaluation of the coatings’ anticorrosion performance (electrochemical impedance spectroscopy (EIS), neutral salt spray test (NSST), paintability) shows that from nine optimized FPEO recipes, two (based on phosphate, fluoride, and aluminate or silicate mixtures) are found to be an adequate substitute for commercially used Cr(VI)-based conversion coating (CCC). The FPEO coatings with the best corrosion resistance consume a very low amount of energy (~1 kW h m−2 µm−1). It is also found that the lower the energy consumption of the FPEO process, the better the corrosion resistance of the resultant coating. The superb corrosion protection and a solid environmentally friendly outlook of PEO-based corrosion protection technology may facilitate the economic justification for industrial end-users of the current-consuming process as a replacement of the electroless CCC process.


Organics ◽  
2021 ◽  
Vol 2 (2) ◽  
pp. 107-117
Author(s):  
Mattia Forchetta ◽  
Valeria Conte ◽  
Giulia Fiorani ◽  
Pierluca Galloni ◽  
Federica Sabuzi

Owing to the attractiveness of organic phosphonic acids and esters in the pharmacological field and in the functionalization of conductive metal-oxides, the research of effective synthetic protocols is pivotal. Among the others, ω-bromoalkylphosphonates are gaining particular attention because they are useful building blocks for the tailored functionalization of complex organic molecules. Hence, in this work, the optimization of Michaelis–Arbuzov reaction conditions for ω-bromoalkylphosphonates has been performed, to improve process sustainability while maintaining good yields. Synthesized ω-bromoalkylphosphonates have been successfully adopted for the synthesis of new KuQuinone phosphonate esters and, by hydrolysis, phosphonic acid KuQuinone derivatives have been obtained for the first time. Considering the high affinity with metal-oxides, KuQuinones bearing phosphonic acid terminal groups are promising candidates for biomedical and photo(electro)chemical applications.


Coatings ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 113
Author(s):  
Jacob Ress ◽  
Ulises Martin ◽  
Juan Bosch ◽  
David M. Bastidas

The protection of mild steel by modified epoxy coating containing colophony microencapsulated corrosion inhibitors was investigated in this study. The corrosion behavior of these epoxy coatings containing colophony microcapsules was studied by electrochemical analysis using cyclic potentiodynamic polarization and electrochemical impedance spectroscopy. The microcapsule coating showed decreased corrosion current densities of 2.75 × 10−8 and 3.21 × 10−8 A/cm2 along with corrosion potential values of 0.349 and 0.392 VSCE for simulated concrete pore solution and deionized water with 3.5 wt.% NaCl, respectively, indicating improved corrosion protection in both alkaline and neutral pH. Electrochemical impedance spectroscopy analysis also showed charge transfer resistance values over one order of magnitude higher than the control sample, corroborating the electrochemical corrosion potential and current density testing results. Overall, the use of colophony microcapsules showed improved corrosion protection in simulated concrete pore solution and DI water solutions containing chloride ions.


Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1321
Author(s):  
Yasunobu Asawa ◽  
Aleksandra V. Arsent’eva ◽  
Sergey A. Anufriev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
...  

Bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1′-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7′(8′)-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2−. The attempted reaction of [7,7′(8′)-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2− with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3′-Gd(1,2-C2B9H11)2]− as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.


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