Interactions of polymer–small molecule complex with cupric (II) ions in aqueous ethanol solution

Acar, Nermin; Tulun, Tülay

doi:10.1016/s0014-3057(01)00026-x

Cited by 18 publications

(10 citation statements)

References 18 publications

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“…1 By physically mixing transition-metals cations and coordinating polymers, it has been possible to obtain materials with properties different from those of the individual bulk components. 2,3 Recently, the importance of developing macromolecular complexes was highlighted because of their optical, magnetic, electronic and solution properties. 4 For instance, the conducting and thermal properties of poly(4-vinylpyridine) (P4VP) are significantly changed when the polymer is complexed with copper ions.…”

Section: Introductionmentioning

confidence: 99%

Protective effect of poly(4-Vinylpyridine) containing surface films to the corrosion of copper

Giacomelli¹,

Giacomelli²,

Schmidt³

et al. 2005

J. Braz. Chem. Soc.

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Neste trabalho investigou-se a capacidade de filmes de poli(4-vinilpiridina) (P4VP) em melhorar as propriedades de corrosão do cobre em H 2 SO 4 0,1 mol L -1 . Filmes que formam o complexo macromolecular Cu(P4VP) 2 (SCN) 2 foram obtidos por métodos eletroquímicos ou espontaneamente (por imersão) em soluções contendo 3% de ácido acético, KSCN 0,1 mol L -1 e P4VP. As características morfológicas dos filmes e o seu efeito sobre a corrosão do cobre foram analisados por técnicas de microscopia e eletroquímicas, respectivamente. Um aumento acentuado na resistência à corrosão de amostras de cobre recobertas por filmes de P4VP gerados espontaneamente foi observado em comparação às amostras não recobertas. A melhor condição para a obtenção destes filmes consiste na imersão do cobre em soluções contendo P4VP 0,1 mol L -1 durante 3 -4 h. Empregando-se esta metodologia, registraram-se eficiências de inibição (EI) de 94 -98%. Para filmes gerados eletroquimicamente, a EI foi de 70 -85%.We report here on the ability of poly(4-vinylpyridine) (P4VP) films to improve the copper corrosion properties in 0.1 mol L -1 H 2 SO 4 . Films formed by Cu(P4VP) 2 (SCN) 2 macromecularcomplex were electrochemically or spontaneously (by immersion) grown onto copper surfaces in 3% acetic acid, 0.1 mol L -1 KSCN and P4VP containing solutions. Imaging and electrochemical techniques were employed to characterize the film morphology and evaluate its effect on the copper corrosion, respectively. A substantial increase in corrosion resistance of copper samples spontaneously coated by P4VP films was found in comparison to the uncoated ones. The optimum conditions for spontaneous growth comprise a 3 -4 h immersion period in a 0.1 mol L -1 P4VP containing solution. Inhibition efficiencies (IE) of 94 -98% were recorded by employing this methodology. For electrochemically grown P4VP films, the IE was 70 -85%. Keywords: poly(4-vinylpyridine), corrosion, copper IntroductionThe use of d-block metals to produce coordination complexes in polymer blends has been studied over the past few decades. 1 By physically mixing transition-metals cations and coordinating polymers, it has been possible to obtain materials with properties different from those of the individual bulk components. 2,3 Recently, the importance of developing macromolecular complexes was highlighted because of their optical, magnetic, electronic and solution properties. 4 For instance, the conducting and thermal properties of poly(4-vinylpyridine) (P4VP) are significantly changed when the polymer is complexed with copper ions. 5 The technological applications of the P4VP/ copper system include reactive blending, 6 catalyst, 7-9 cation exchange resins and membranes designed to preconcentrate metals from dilute solutions 10 or remove them from wastewater, 11 solid-state electrochemical cells, 12 circuit manufacturing on microscopic smoothly polymeric surfaces 13 and anti-corrosion methods. 14 Poly(4-vinylpyridine)/cupric salts complexes can be synthesized by physical mixing methods, and their therma...

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Section: Introductionmentioning

confidence: 99%

Protective effect of poly(4-Vinylpyridine) containing surface films to the corrosion of copper

Giacomelli¹,

Giacomelli²,

Schmidt³

et al. 2005

J. Braz. Chem. Soc.

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“…At these potentials a competition between transpassivation and repassivation occurs. 17 Moreover, when the localized corrosion phenomenon takes place, it is related to the nucleation and growth of an unstable Cu(SCN) 2 layer in equilibrium with Cu(SCN) 3 -.…”

Section: Resultsmentioning

confidence: 99%

“…2,3 Since the development of synthetic procedures with the objective of obtaining new polymers, blends and composites with specific properties and technologic applications has been one of the prime targets in the new materials research field, 4 the mixture of transition-metals and polymers is, indeed, a very promising strategy to achieve several desired material features. Recently, Schmelz and Rehahn emphasized the importance in developing transition-metal coordination polymers because of their optical, magnetic, electronic and solution properties.…”

Section: Introductionmentioning

confidence: 99%

“…7 The polymer poly(4-vinylpyridine) (P4VP) exhibited different thermal and conducting properties as a [P4VP]/copper iodide binary mixture; the electrical conductivity changes drastically with the increase in the amount of copper iodide in the blends. 8 Specifically, the couple P4VP/copper has been focused elsewhere 1,3,6,10-15 due its great potential for applications such as in reactive blending, 6 catalyst for determination and oxidation of ascorbic acid 9 and the technically important oxidative polymerization of 2,6-dimethylphenol 1 in addition to the selective conversion of 2,3,6-trimethylphenol and related compounds to p-benzoquinones, 10 cation exchange resins designed to remove or preconcentrate metals from dilute solutions by binding them to soluble polymers, 11 solid-state electrochemical cells, 12 anti-corrosion methods 13 and circuit manufacturing on microscopic smoothly polymeric surfaces or production of polymeric films on metallic surfaces. 14 Consequently, the importance in obtaining P4VP/copper films onto copper surfaces for technological development is clear.…”

Section: Introductionmentioning

confidence: 99%

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Interaction of poly(4-vinylpyridine) with copper surfaces: electrochemical, thermal and spectroscopic studies

Giacomelli¹,

Giacomelli²,

Santana

et al. 2004

J. Braz. Chem. Soc.

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A interação do polímero poli(4-vinilpiridina) (P4VP) e íons tiocianato com cobre em soluções ácidas foi estudada através de voltametria cíclica, termogravimetria, análise elementar e espectroscopia na região do infravermelho. Observou-se que os íons Cu(I) eletrogerados em ca. -0,45 V/ECS na superfície do eletrodo promovem uma reação de complexação com P4VP e SCN -, ambos presentes em solução. O complexo polimérico eletroativo resultante cresce sobre a superfície do eletrodo como um filme e o centro metálico é oxidado para Cu(II) numa etapa subseqüente em ca. -0,23 V/ECS. De acordo com os resultados termogravimétricos, o complexo obtido é menos estável do que o P4VP puro, conforme indicado pelo abaixamento da temperatura inicial de degradação de ca. 400 ºC (P4VP) para ca. 200 ºC (complexo). A análise elementar do filme revelou uma composição química de 2:1:2 para P4VP:Cu:SCN -e os espectros na região do infravermelho indicaram que tal complexo polimérico é formado por um centro metálico de cobre coordenado pelos átomos de nitrogênio dos anéis piridínicos e íons tiocianato.The interaction of poly(4-vinylpyridine) (P4VP) and thiocyanate ions with copper in acid solutions was studied by cyclic voltammetry, thermogravimetry, elemental analysis and infrared spectroscopy. It is shown that at ca. -0.45 V/SCE the electrogenerated Cu(I) ions at the surface of a copper electrode induce a complexing reaction with P4VP and SCN -both present in solution. The resulting electroactive polymer-complex grows onto the electrode surface as a film, and the metallic center is further oxidized to Cu(II) in a subsequent step at ca. -0.23 V/SCE. According to thermogravimetric results, the polymer-complex is less thermally-stable than P4VP as evidenced by the lowering in the initial temperature of degradation from ca. 400 ºC (P4VP) to ca. 200 ºC (complex). The elemental analysis revealed a chemical composition of 2:1:2 for P4VP:Cu:SCN, and the infrared spectra indicated that the complex comprises a copper metallic center coordinated with nitrogen pyridinic rings (P4VP) and thiocyanate ions.

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“…Polymer–metal complexes are now of great interest. Different polymers are commonly used in industry to produce a large variety of useful items for everyday personal and industrial uses as well 1, 2. It has been demonstrated that the thermophysical properties of polymeric ligands can be modified by coordination to transition‐metal complexes 3–6.…”

Section: Introductionmentioning

confidence: 99%

Effects of some solvents on the thermal and free‐volume properties of poly(4‐vinylpyridine) complexes

Mazroua¹,

Gomaa²

2008

J of Applied Polymer Sci

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Modified poly(4-vinylpyridine) (P4VP) and its complexes were prepared with different solvents such as benzene, toluene, and xylene as well as potassium chloride (KCl) and copper chloride (CuCl 2 ). Fourier transform infrared spectroscopy, thermal analysis, and positron annihilation spectroscopy were used to investigate the properties of the modified P4VP and its complexes. It was concluded that complexes were formed between the polymer and solvents via quaternization of nitrogen in the ring with the solvents and also with KCl and CuCl 2 Á2H 2 O. Furthermore, the modified P4VP-CuCl 2 complexes were more stable than the modified P4VP-KCl complexes, and these complexes were more stable than the P4VP-solvent complexes. Ortho-positronium components (s 3 , I 3 ) were used to estimate the nanoscale free-volume hole size (V f ) and the free-volume fraction (f %). The free-volume hole size and its fractions depended on the addition of solvents and metals to the polymer.

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Interactions of polymer–small molecule complex with cupric (II) ions in aqueous ethanol solution

Cited by 18 publications

References 18 publications

Protective effect of poly(4-Vinylpyridine) containing surface films to the corrosion of copper

Protective effect of poly(4-Vinylpyridine) containing surface films to the corrosion of copper

Interaction of poly(4-vinylpyridine) with copper surfaces: electrochemical, thermal and spectroscopic studies

Effects of some solvents on the thermal and free‐volume properties of poly(4‐vinylpyridine) complexes

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