论文研究-硫酸盐介质中青铜腐蚀的电化学阻抗谱（EIS）研究：实验设计方法

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Journal of Materials Science and Chemical Engineering, 2017, 5, 44-54

http://www.scirp.org/journal/msce

ISSN Online: 2327-6053

ISSN Print: 2327-6045

DOI:

10.4236/msce.2017.510004 Oct. 31, 2017 44 Journal of Materials Science and Chemical Engineering

Electro-Chemical Impedance Spectral (EIS)

Study of Patinated Bronze Corrosion in Sulfate

Media: Experimental Design Approach

Aymen Chaabani

1,2

, Safa Aouadi

1,2

, Nébil Souissi

, X. Ramón Nóvoa

Preparatory Institute For Engineering Studies El Manar, University of Tunis El Manar, Farhat Hached University Campus of El

Manar, Tunisia

Faculty of Sciences of Bizerte, University of Carthage, Jarzouna, Tunisia

ENCOMAT Group, E.E.I., University of Vigo, Vigo, Spain

Abstract

The aim of the present investigation was to model the experimental cond

tions of tin

bronze patination using full factorial experimental design. In this

sense, a full factorial design approach was developed to model the corrosion

behavior of patinated tin bronze alloy in sulfate electrolyte. Three experime

tal factors (the immersion time i

n the chloride electrolyte, the potential limit

for the anodic sweep Elim, and the potential scan rate) were chosen to identify

the significant factor on the patina growth process at the bronze substrate.

The experimental responses were the kinetic paramet

ers extracted from the

electro-chemical spectra (EIS) for eight different experiments. An

equivalent

electrical circuit containing an electrolyte resistance (

), a double layer cap

citance (

CPE

), a charge transfer resistance (

) and Gerischer element (

was developed to model the patinated bronze corrosion process. The ele

tro-

chemical spectra (EIS) show that the corrosion process of the patinated

bronze alloy occurred from a chemical reaction is followed by an electr

chemical one. Analysis of the exp

erimental responses showed that while the

scan rate is the most influent factor for the corrosion potential (

corr

), the

electrolyte resistance (

), and the double layer capacitance

CPE

variation,

the potential limit is the significant factor for charge transfer resistance

, r

ciprocal of the admittance parameter

and the effective transfer rate of the

chemical reaction

variation.

Keywords

Bronze, Corrosion, Experimental Design, Electrochemical Impedance

Spectroscopy, Gerischer Impedance

How to cite this paper:

Chaabani, A.,

Aouadi

, S., Souissi, N. and Nóvoa, X.R.

(201

7) Electro-Chemical Impedance Spec-

tral (EIS) Study of Pat

inated Bronze Corro-

sion in Sulfate Media: Experimental Design

Approach

Journal of

Materials Science and

Chemical Eng

ineering

, 44-54.

https://doi.org/10.4236/msce.2017.510004

Received:

September 25, 2017

Accepted:

October 28, 2017

Published:

October 31, 2017

7 by authors and

Scientific

Research Publishing Inc.

This work is licensed under the Creative

Commons

Attribution International

License (CC BY

4.0).

http://creativecommons.org/licenses/by/4.0/

Open Access

A. Chaabani et al.

DOI:

10.4236/msce.2017.510004 45 Journal of Materials Science and Chemical Engineering

1. Introduction

Cu-Sn alloys were used since antiquity to produce sculptures, coins and arte-

facts. These materials exhibit good mechanical and esthetical properties.

Numerous analytical techniques were used to study tin bronze corrosion me-

chanisms [1] [2] [3]. Electrochemical investigations were also undertaken

[4]-[8]. We used the cyclic voltammetry technique to explore archaeological

Punic bronze corrosion behavior in chloride electrolyte [9] and we compared

also modern and archaeological materials voltammetric behaviors [10] recently,

we showed [11] that the bronze corrosion reaction order with respect to chloride

ions varied as the halide content changed. In fact, for [Cl

−

] < 0.5 M, the reaction

order was about 0.22 suggesting that the Cu10Sn bronze alloy dissolution was

not strongly dependent with Cl

−

ions which could act as corrosion initiator. For

[Cl

−

] > 0.5 M the bronze mechanism alloy was controlled by copper oxidation.

Two determining steps were evidenced where the cuprous chloride formation

was followed by

CuCl

−

complex.

We used also electro-chemical impedance spectroscopy to characterize the

corrosion behavior of archaeological bronze in 0.1 M chloride medium interface.

Indeed, a simple electrical equivalent circuit was used to explain the material

reactivity.

As the corrosion ability of materials depends on various conditions, then, the

large number of experimental factors to consider remained the major obstacle

for the experimenter to understand the alteration mechanisms. Nowadays, the

chemometric approach is considered as powerful tool for studying the corrosion

and protection process. Many works introduced the use of experimental designs

for understand metals corrosion and inhibition [12]-[18]. Among them, only

de Lago

et al.

[19] used the experimental design to study the effect of 2-amino-

5-mercapto-1,3,4-thiadiazole (AMT) as inhibitor for bronze protection in artifi-

cial rainwater.

However, the experimental design use for studying bronze corrosion, to the

best of our knowledge, was not yet investigated.

The aim of the present investigation was to model the experimental condi-

tions of tin bronze patination using full factorial experimental design. The main

interests for application of an artificial patina are rebuilding of historical arti-

facts, works of arts and for the purpose of scientific research.

2. Methodology

2.1. Electrochemical Test

High-purity Cu and Sn metals (Goodfellow copper rod > 99.999 wt. % and Sn

Johnson-Matthey tin slug > 99.9985 wt. %) and Cu-10 wt. % Sn alloy (5.60 at. %

Sn) were used in this study. The bronze was prepared from the pure copper and

tin through a procedure detailed elsewhere [20]. The working electrodes made

from this alloy were embedded into a chemically inert resin with an exposed area

(only one face) of 0.33 cm

. Before use, the electrodes were mechanically polished

A. Chaabani et al.

DOI:

10.4236/msce.2017.510004 46 Journal of Materials Science and Chemical Engineering

with abrasive paper up to 2500 SiC grade, washed with distilled water and dried

in a room temperature.

The electrochemical experiments were carried out in a standard three-electrode

cell, with a large size graphite sheet as counter electrode and a saturated calomel

electrode (SCE) as reference electrode. The electrochemical impedance spec-

troscopy (EIS) measurements were performed with an Autolab® PGSTAT 20 po-

tentiostat equipped with an impedance analysis module. Software NOVA was

used for the instrumentation control, data treatment as well as spectra fitting.

The chloride patina was electrochemically formed at the Cu10Sn bronze using

potentiodynamic technique (anodic potential sweep) according to the experi-

mental design described here above.

2.2. Experimental Design Approach

The full factorial design was used to study the influence of different experimen-

tal factors on the chloride patina formation at the bronze substrate. The patina

layer was artificially electrodeposited at the Cu10Sn alloy using potentiodynamic

technique. After a preliminary investigation, three experimental variables were

chosen:

: first factor representing the immersion time in the chloride electrolyte,

: second factor representing the potential limit for the anodic sweep,

lim

: third factor representing the potential scan rate,

Table 1 summarizes the experimental field.

The total number of the experiments to be carried out was 2

[13]-[19], where

n is the number of experimental variables. Therefore, the experimental design

consisted of eight experiments.

The experimental design as well as the experimental matrix is listed in

Table 2.

The experimental responses studied were the electrochemical parameters ob-

tained after fitting of the the EIS spectra for the different experiments.

corr

: the corrosion potential, the rest potential at which the EIS spectra were

taken.

: the electrolyte resistance,

: the charge transfer resistance,

CPE

: the constant phase element associated to the double layer capacitance,

: the effective transfer rate of the chemical reaction (Gerischer type imped-

ance, see below),

- 1/

: the admittance parameter (Gerischer type impedance, see below).

Table 1. Experimental field.

Factors

(immersion time)

(min)

(limit potential)

(V/SCE)

(scan rate)

(mV·s

−1

)

−1

30 0.1 1

60 1 10

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论文研究 - 硫酸盐介质中青铜腐蚀的电化学阻抗谱（EIS）研究：实验设计方法

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论文研究 - 硫酸盐介质中青铜腐蚀的电化学阻抗谱（EIS）研究：实验设计方法

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