Green Corrosion Inhibitor for Protection of Conserved Some Archaeological Iron Spears Heads from Military Museum, Al-Qala, Egypt

doi:10.21203/rs.3.rs-2441753/v1

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Green Corrosion Inhibitor for Protection of Conserved Some Archaeological Iron Spears Heads from Military Museum, Al-Qala, Egypt

https://doi.org/10.21203/rs.3.rs-2441753/v1

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Archaeological iron artifacts are often covered with a crust, containing organic fibers, mineral particles, dirt, etc. Before conservation, this crust must be carefully removed. With traditional mechanical and chemical methods, there is an obvious risk of over-cleaning. These methods also increase the risk of the oxidized or primary corrosion layer breaking away which will lead to loss of information about the form of the object and other important surface details. The same archaeological iron spears from Military Museum, Al-Qala, Egypt were selected for the study. The aim of this case study is concerned with preserving and controlling the corrosion of steel spears heads. Due to the restriction of the archeological parts preservation and corrosion control are achieved by environmentally friendly chemicals. This inhibitor is of attentiveness since there has been a growth in ecological consciousness and a variation in guidelines that control the toxicity of systematic corrosion inhibitors. So, natural products are becoming the main source of environmentally friendly corrosion inhibitors. Furthermost their extracts comprise the required features of the traditional corrosion inhibitors such as oxygen, carbon, nitrogen, and sulfur. These elements are contributed to the adsorption process on the metal surfaces and arrangement a protective layer, which shields the metal surface against environmental corrosion. Progress of green chemical knowledge compromises a new artificial approach for ionic liquids. These compounds are well-thought-out as new safe corrosion inhibitors which act in different corrosive conditions. Finally, exploiting the successfully obtained results, we used this inhibitor to protect the selected objects.

Conservation

Environmentally Friendly Inhibitors

Corrosion Control

Spears Heads

Surface Characterization

Archaeological Iron Spears

Iron and steel, except for stainless steel and other similar alloys, are readily attacked by oxygen when in the presence of moisture forming rust [1–3]. Rust is a term used to describe non-specific corrosion products which form on the surface of degraded iron. Unlike iron, the surface layers of iron corrosion products are not protective [4]. They tend to accelerate the corrosion of the metal by forming localized corrosion cells [5]. A variety of iron oxides and oxyhydroxides can form depending on the pH, oxygen concentration, relative humidity (RH), and contaminants. The corrosion process is not a chemical reaction, but it is mainly an electrochemical reaction [6]. North has claimed that if the pH at the metal surface rises above 10 the iron will be passive and will not corrode even if the potential rises [7]. Whether the pH at the metal surface does rise to 10 is uncertain since hydroxide ions diffusing in towards the surface will be precipitated by the iron ions present and hydrogen evolution at the metal will not occur fast enough to affect the pH noticeably [8]. Even if this pH rise does occur, it is unlikely that passivity will result, for several reasons. Firstly, experimental passivation potentials are much higher (approximately 0.0 v at pH 10, than those measured [9]. Secondly, inhibition by hydroxide is due to the formation of a ferric oxide film on the metal surfaces and this usually requires the presence of oxygen at the surface [10]. Careful use of suitable conservation treatment is, therefore, necessary to preserve the material and the valuable scientific information that the artifacts carry [11]. Cleaning is usually the first step of many in conservation work. It is also one of the most difficult operations undertaken when preserving metal artifacts [12]. Any cleaning must be carried out with great respect and consideration of the original object’s form, function, and material [13]. The protection of metals or metal alloys from the deterioration process could be approached by separating the metal structures from the belligerent environment [14]. This phenomenon could be happened by employing coatings or by forming a protected film by using chemical molecules or compensating for the release of electrons [15]. However, corrosion is considered as oxidation of metallic structures since the corroded structure is formed. Corrosion control could be achieved by using organic and/or inorganic compounds [16]. The mode of action of these inhibitors comprises the adsorption of the chemical molecules on the metallic structure to segregate it from its adjacent environment to prevent oxidation-reduction development by forming a thin protective layer [17]. Most of the famous corrosion inhibitors are toxic, so we must lead the use of some new safe corrosion inhibitors. We call that the corrosion inhibitors act perfect when they are added in low doses to care for the surface against a corrosive atmosphere [18–21]. The exploit of inhibitors molecules happens to owe to their adsorption process on the surface in the type of neutral particles as an alternative to hydrogen ions as described in the following equation [22]:

Inhibitor + n H_ads → Inhibitor _ads + H₂

(1)

This action prevents the most cathodic reactions as seen in the following equations:

-2H⁺ + 2e ⁻ → H₂	(2)
-O₂ + 4H⁺ + 4e ⁻ → 2H₂O	(3)
-2H⁺ + 2e ⁻ → H_ads → 2H₂	(4)

This study aims to get deeper sight into the morphology and mineralogy of corrosion products of the selected iron artifacts, the cause, and mechanism of the corrosion process to control and stop it and to identify the types of corrosion products as well as their constituting elements to carry out scientific treatment and conservation to avoid the further deterioration [23].

2.1. Materials

2.1.1. Description of Iron Spears and Their Condition

Same archaeological iron spears from Military Museum, Al-Qala, Egypt were selected for studying; there are descriptions and documentation as cited in the following Table 1:

Table 1

Description and documented dimensions of the objects under study
Item	Dimensions
Spearhead No.1	6.1X0.7Cm
Spearhead No.2	9.2X1.3Cm
Spearhead No.2	9.5X1.2Cm
Spearhead No.4	10.3X1.2Cm
Spearhead No.5	11.3X1.3Cm

The selected objects suffered from the deterioration aspects, such as thick red/brown layers of corrosion products, these aspects of deterioration disfigured them and left them ugly see Figs. 1a,b.

Examinations and analysis were conducted to identify the type of iron alloy used in the spear’s heads and to identify methods of manufacturing and detecting the nature of corrosion products. This has been achieved by using metallographic microscopy, SEM with EDS, carbon-sulfur analyzer, and XRD [24]. The metallographic examination was accomplished on an un-etched polished cross-section through an OLYMPUS-PMTVC2D03043JAPAN metallographic microscope. The same sample was carefully investigated using the JEOL model JSM-53000 scanning electron microscope (SEM) with an energy dispersive spectrometer (EDS). The carbon and sulfur contents in the iron alloys used in the spear’s heads were determined using the Carbon/Sulfur analyzer ELTRA CS-2000. The XRD analysis was undertaken with D8 advanced X-Ray diffractometer X. (Bruker, Germany) to identify corrosion products that formed on the iron surface.

2.2. Methods

2.2.1. Corrosion Techniques

To do the requisite electrochemical experimentation, Autolab Potentiostat/Galvanostat PGSTAT302N was utilized in conjunction with an Autolab computer and a conventional three-electrode Pyrex glass cell that was operated at room temperature. Results show that the reference electrode was silver/silver chloride, the counter electrode was platinum foil, and the working electrodes were mild steel with a 1 cm² surface area exposed in 3.5% sodium chloride in the absence and presence of various loads of polyaniline as a defensive layer against corrosion. The open circuit potential (OCP) was measured and recorded in a logbook before each experiment. It has an alternating current voltage of 10 mV and an amplitude of 10 mV, with a frequency ranging from 0.01 to 105 Hz. At the OCP facility, electrochemical impedance spectra were measured. In the same experimental setup as the electrochemical impedance experiments, potentiodynamic polarization measurements were also performed. Following the EIS technique, potentiodynamic polarization curves were obtained to examine the influence of polyaniline concentration on polarization. When conducting polyaniline concentration measurements at room temperature, all polarization measurements were carried out in the potential range from − 1600 to 200 mV and at 1 mVs^− 1 for varied polyaniline) concentrations. The intersection of the linear anodic and cathodic branches of the Tafel plots was used to calculate the corrosion current density and corrosion potential of the corrosion system. When evaluating the compound's inhibitory impact, researchers employed the Tafel extrapolation method, which is detailed in detail below. The Nova 1.10 software was required to match all the impedance data to a suitable equivalent circuit. After electrochemical investigation, a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDS) was used to characterize the mild steel surface of the objects to determine the morphological and chemical information of the mild steel surface, with and without the optimal concentration of polyaniline. Perkin Elmer model 1430 spectrophotometer at room temperature was used to record the FT-IR measurements used to get the bonding information of polyaniline with mild steel surface in the range 4000–200 cm^− 1. After much deliberation, it was decided to use an X-ray diffractometer with Cu K radiation to evaluate samples from the sculptures' corrosion products and an X-ray fluorescence NITON/XL8138 to analyze the samples' elemental composition before proceeding with the evaluation (USA) [25].

3.1. Surface Characterization

The metallographic and scanning electron microscopes were used to investigate the chosen artifacts from the archaeological site. The X-ray diffraction method (XRD) was used to investigate the corrosion products, and the X-ray fluorescence method (XRF) was used to study the metallic component. The results of the examination and analysis may be broken down into the following categories [26]. The un-etched sample was examined under metallography and SEM with EDS to identify the type of iron alloy used in the spearheads as presented in Figs. 2a,b. The appearance of deteriorated spots scattered across the metal surface of both of the objects has been observed during examinations of them, as can be seen in Figs. 2a,b.

An investigation using an SEM revealed the degraded characteristics of the items, which were distributed over the metal in the manner seen in Figs. 3a,b. This provided evidence that the findings of the metallographic examination were correct. Two small samples were taken from the spears heads and examined by SEM, as it is shown in Figs. 4a,b. The scans SEM&EDS, and the identified elements are given in Figs. 5,6.

The samples were obtained from the corrosion products coating the items and evaluated by utilizing a Philips X-ray Diffractometer with Cu Kα radiation. The first sample was collected from the circular ring, and the second sample was taken from the rectangular item. The discovered chemicals are presented in Table 2,3. The carbon and sulfur contents in the iron alloys used in the spear’s heads were determined using the Carbon/Sulfur analyzer ELTRA CS-2000, it has been shown that the alloy contains 0.93 wt % carbon and 0.15 wt % sulfur. The corrosion products which formed on the iron surface were identified using x-ray diffraction as shown in Figs. 7, 8, and Tables 2,3. The XRD examination of the corrosion products revealed, to a small extent, the existence of hematite (Fe₂O₃), magnetite (Fe₃O₄), and feroxyhyte (FeO(OH)). However, most of the material is composed of quartz (SiO₂) and calcite (CaCO₃). The sandy soil that was dug to find the items was a significant contributing factor in the artifacts' extreme corrosion [27].

Table 2

shows the results of XRD analysis of corrosion products that formed on spears heads surface.
Ref. Code	Mineral Name	Chemical Formula
01-073-6522	Goethite	FeO(OH)
00-003-0863	Magnetite	Fe₃O₄
00-002-1366	Pyrite	FeS₂
00-002-0127	Lepidocrocite	Fe₂O₃·H₂O
01-088-2359	Hematite	Fe₂O₃
00-053-0854	Vivianite	(Fe, Mg, Mn)₃ (PO₄)₂·8H₂O
01-075-8320	Quartz	SiO₂
01-073-8408	Ferrihydrite	Fe (1.44) O (0.32) OH (3.68)

Table 3

shows the results of XRD analysis of corrosion products that formed on spears heads surface.
Ref. Code	Mineral Name	Chemical Formula
01-075-8320	Quartz	SiO₂
01-076-2891	Magnesioferrite	Mg (0.306) Fe (0.694) Mg (0.694) Fe (1.306) O (4)

3.2. Electrochemical Measurements

3.2.1. Open Circuit Potential Measurements

It was important to keep a continual vigilance over the open circuit potential values until they acquired a steady-state potential to effectively carry out the subsequent electrochemical experiments. Only then were we able to ensure that the tests would be successful? The results of this investigation are depicted in Fig. 9. Figure 9 illustrates the potential values for both uncontrolled and inhibited 3.5% NaCl solutions. The concentration of this solution increases from 10 ppm up to 100 ppm, starting at the lower end and working its way up. There was a direct correlation between the rise in the concentration of the solution and the accompanying increase in the value of the possible outcomes. When the concentration was 10 ppm, the open circuit potential values ranged from − 460 millivolts (mV) to -150 millivolts (mV), with the lower values suggesting a more severe situation. According to Fig. 9, the findings of 100 ppm are used to get to the conclusion that the open circuit potential has shifted from − 150 mV to -220 mV. This conclusion was reached because of the change. This shows that the shift is proceeding in the direction of a potentially bad outcome. An excellent illustration of this phenomenon may be seen in the propensity of organic molecules to form bigger aggregates when they are present in higher concentrations than they are in the water. This tendency gives a useful example of the phenomenon. There is a theory that the molecules of the inhibitor gather in specific sections of the treated surface, exposing those regions to greater corrosion and so allowing the corrosion process to continue. This theory is supported by observations that have been made. Because of the information that has been provided in this article, it has been determined that the ideal concentration of this inhibitor in the electrolyte for treating this alloy is 100 ppm [28].

3.2.2. Potentiodynamic Polarization curves

Figure 10 shows the potentiodynamic polarization results for both uninhibited and inhibited 3.5% NaCl with increasing polyaniline concentrations for both uninhibited and inhibited 3.5% NaCl with progressive polyaniline concentrations. These results are displayed for both uninhibited and inhibited 3.5% NaCl with increasing polyaniline concentrations. These results were accomplished by subjecting the solution to a treatment that involved increasing concentrations of polyaniline. Iron's anodic dissolution in an infinite NaCl solution lead to the creation of FeCl₂, which is adsorbed on the surface of mild steel when the solution is heated to high temperatures [29]. This process takes place when the iron is exposed to an electric current. Because the creation of FeCl₃ is a direct result of the limiting current reaching its plateau, the current density begins to grow almost immediately after the limiting current hits its plateau. Depending on the specifics of the situation, this results in either an increase in the bulk solution's solubility of iron or an increase in the amount of iron that is oxidized to Fe³⁺. The quantity of FeCl₃ that can diffuse into the bulk of the mild steel anode may be used to influence the rate at which the iron atoms are dissolved anodically [30]. The inhibitory mechanism at work in this scenario can be explained by the attachment of polyaniline to the surface of the electrode while the electrode is in the presence of polyaniline. This would have to take place while the electrode is in the presence of polyaniline. The adsorption process occurs at a rate comparable to that of a snail when there are only a few molecules of polyaniline present. When there are significant quantities of polyaniline, the result is that an inhibitor is not there to protect the metal surface. Because of this, the disintegration of bronze occurs on the surface of the metal in areas where polyaniline has not been adsorbed onto it. When the concentration of the polyaniline is raised, a considerable layer is created. This layer inhibits any further dissolving from taking place, thus the concentration must be raised again. According to the findings, increasing the concentration of polyaniline results in a decrease in the current density values. This indicates that polyaniline is a potent inhibitor of mild steel in the saline medium. It would appear from Fig. 10 that this behavior is favorable and becomes clear after an inhibitor concentration of 100 ppm is achieved [31]. This conclusion is supported by the fact that this behavior is shown to become apparent. Looking at Fig. 10 makes it abundantly clear that the concentration has been increased to 100 ppm, and that because of this alteration, there has been a slight decrease in potential values between the levels of 50 and 100 ppm. Moreover, this modification has caused a slight increase in the range of the potential values. It has been determined that an inhibitory concentration of at least 100 ppm must be present to forestall the corrosion process which is the focus of the present investigation. The results of this experiment were comparable to those obtained from the open circuit potential measurements that had been carried out in the past. During this study, potentiodynamic polarizations were performed, and the results of those studies were obtained, along with the calculations for the following parameters: corrosion potential (Ecorr), Tafel slope (ba and bc), corrosion current density (Icorr), corrosion rate (CR), inhibition efficiency (IE %), and polarization resistance (Rp) [32]. According to these findings, a concentration of 100 ppm of inhibitor was required to achieve the lowest possible corrosion rate while still allowing the reactor system to function at its highest possible efficiency. This was the case even though the inhibitor was applied evenly throughout the system. When it comes to using in the field, the inhibitory effects of 92% are extremely encouraging study results. The high efficiency of the electrode is probably due to the adsorption of polyaniline on the surface of the electrode. This is because the electrode has a high electron density due to the presence of nitrogen and oxygen atoms. This is caused by the high electron density that exists within the electrode due to the presence of nitrogen and oxygen atoms. This may be the reason for the high level of productivity [33].

3.2.3. Electrochemical impedance spectroscopy

Figure 6 depicts the shape of a characteristic semicircle (Cdl), which is formed during the initial film formation process and can be observed at high to intermediate frequencies for various concentrations of polyaniline in a 3.5 % sodium chloride solution. This shape can be observed at different frequencies depending on the specific concentration of polyaniline. This form may be seen at a variety of frequencies depending on the amount of polyaniline present in the system. In a solution of sodium chloride with a concentration of 3.5 %, the Cdl can be detected at frequencies ranging from high to moderate for a variety of different polyaniline concentrations [34]. This can happen for several different reasons. The data demonstrated that when the concentration of polyaniline was increased, the diameter of the semicircle grew until it reached 100 ppm, indicating that the passive coating that was produced on the metal surface was more protective since it takes place because of an increase in the concentration of polyaniline. In keeping with what had been discovered before, the fact that a tiny spike appeared at a lower frequency demonstrates that the diffusion-limited process started at the interface between the metal and the solution which brings new results lends credence to the prior ones that were uncovered. When attempting to understand the dynamics of the process by which species travel from the bulk of the solution to the surface, the Warburg impedance W is an essential component that must not be ignored [35]. This is because it is a vital component that should not be neglected. Researchers number 55 noticed that there was a decrease in adhesion and diffusion when there was a rise in the thickness of the layer that contained corrosion products. Figure 7 depicts the Bode plots and Bode phase for a variety of polyaniline concentrations in a solution containing 3.5 % NaCl. The concentration-specific Bode graphs are also given in this report. In addition, the Bode phase is shown in Figure 7 for a variety of various polyaniline concentrations in a solution that contains 3.5 % NaCl. One of the types of figures that may be seen in statistical literature is called a Bode plot (log f vs. log lZl). Image 7 depicts both capacitive and resistive regions for intermediate frequency ranges; however, this figure only depicts a capacitive area for high-frequency ranges and a resistive region for low-frequency ranges. Throughout our research, we realized that the values of the impedance grew in a manner that was exactly proportional to the concentration of the solution that was utilized. This was one of our key findings [36]. As can be observed in Figure 8, an increase in the concentration of polyaniline results in shifting to a lower frequency that is accompanied by an increase in the phase angle. The phase angle achieves its maximum value at a concentration of 100 ppm, after which it continues to fall steadily until it reaches a concentration of 100 ppm. According to the findings, the formation of a protective layer surrounding the molecule is suggested by an increase in the maximum phase at the intermediate frequencies. This rise may be seen as an indication of the development of the layer. The occurrence of this phenomenon is caused by an increase in the concentration of polyaniline [37]. A similar circuit model to the one shown in Figure 9 was created by Randle in the 1980s and is depicted here for your viewing pleasure. The circuit demonstrated that achieving the desired results could be attained by connecting the charge transfer resistance (Rct) in series with the Warburg impedance (Zw) in series. Additionally, doubling the layer capacitance could be accomplished by connecting the solution resistance (Rs) in series with the parallel combination of (Cdl), and the desired results could be attained by connecting the solution resistance (Rs) in series with the Warburg impedance (Zw). It was demonstrated that each of these relationships led to the consequences that were anticipated. To construct an equivalent circuit, the data were "fitted" to the data by using the Nova software. For your convenience and as a point of reference, the impedance characteristics of the equivalent circuit, which was created specifically for this purpose. Rct will go up when the concentration of polyaniline is raised until it reaches the ideal concentration [38]. This demonstrates that corrosion inhibition has been much improved. It is necessary to first understand how accumulated charges in the double layer increase with increasing polyaniline concentration 57 to be able to explain the increase in adsorption of inhibitor molecules on the corroding surface as a function of increasing polyaniline concentration. This is to explain the increase in the adsorption of inhibitor molecules on the corroding surface as a function of increasing polyaniline concentration. This is because it is a result of increased concentrations of polyaniline. Because of this increase in collected charges, there is a subsequent increase in the film thickness, as well as an increase in the efficiency of the inhibition. Both effects are a direct result of the growth in the total number of charges. The results that were acquired from the potentiodynamic polarization curves, together with those that were obtained from the impedance measurements, were consistent with one another [39]. Even though the EIS is a well-known approach for proving adsorption phenomena in addition to corrosion mechanisms, this was nonetheless the case. Figs 10 and 11 show, for illustrative purposes, the relationships between the concentration of polyaniline and the polarization resistance and capacitance of the film, which were calculated from EIS studies. Figures 10 and 11 also depict the relationships between the concentration of polyaniline and the corrosion rate and inhibition efficiency, which were calculated from polarization measurements [40].

3.3. Inhibition mechanism

According to the information provided by the manufacturer, the process of adsorption that takes place on the metal surface is included in the mechanism of action of corrosion inhibitors, in addition to the prevention of subsequent attacks. These two facets are inextricably intertwined with one another. It is well known that the organic compounds that are found on the surfaces of metallic ions have the potential to form complexes with the ions that are already present in the metal itself. According to the chemical structure, chelation centers, which are denoted by lone pairs of electrons on the nitrogen and oxygen atoms in the molecule, can be in a variety of locations across the chemical structure of the corrosion inhibitor [41]. These lone pairs of electrons on the nitrogen and oxygen atoms in the molecule are what makeup chelation centers. It is possible to determine the inhibition efficiency of polyaniline against the corrosion of mild steel in 3.5% NaCl by examining the number of active sites, the mode of interaction with dissolute Fe³⁺ ions from the metal surface, as well as the ability of the dissolute Fe³⁺ ions to react chemically with polyaniline and form a stable complex of Fe-polyaniline. This is achieved by blocking the path of the aggressive solution that would otherwise lead to the surface of the metal [42]. IR spectra were taken in the presence of 100 ppm polyaniline of a metal surface coated with a corrosion product to validate the possibility of polyaniline -M complex formation on the surface of the metal surface coated with a corrosion product. This was done to validate the possibility of polyaniline-M complex formation on the surface of the metal surface coated with a corrosion product. These spectra were acquired from a corrosion product that had been applied to a metal surface [43]. In addition to polarization and impedance testing on mild steel, it was discovered that applying polyaniline to the material produces an adsorbed coating on the surface of the material, which prevents the material from corroding. This discovery was made in conjunction with the testing of polarization and impedance. This discovery is consistent with the findings that were published in the past. The process of chemisorption is brought on by the transfer of electrons from the aromatic ring to the empty d-orbital of the iron atoms on the metal surface [44]. This transfer of electrons is what is known as charge sharing. Electrostatic contact with the metal surface is what causes the polyaniline molecule to physically adsorb onto the surface. Chemisorption, on the other hand, is the result of charge transfer between the Fe³⁺ poly aniline complex and the metal surface. Physical adsorption of polyaniline is caused by electrostatic interaction with the metal surface, whereas chemisorption is caused by charge sharing between polyaniline and the metal surface via N [45]. Physical adsorption of polyaniline is caused by electrostatic interaction with the metal surface, whereas chemisorption is caused by charge sharing. Electrostatic contact with the metal surface is what causes the physical adsorption of polyaniline, whereas charge sharing is what causes chemisorption. To determine the type of bonding that takes place on a metallic surface, it is necessary to examine the FTIR spectra of both the polyaniline powder and the film that is produced on the surface of the mild steel [46]. This may be accomplished by utilizing a strategy that combines the two approaches. In addition to this, it is essential to have a conversation about the changes that take place in the spectrum of the polyaniline powder when metal ions encounter it. On the right is a representation of the infrared spectra of (a) pure polyaniline powder in the wavenumber 500–4000 cm^− 1, and (b) the infrared spectra of the film formed on the mild steel surface after immersion in 3.5% NaCl solution with an optimal concentration of 100 ppm polyaniline at the optimal concentration. Both spectra can be seen in the wavenumber range of 500–4000 cm^− 1. The wavenumber range of 500 to 4000 cm^− 1 is where any of these spectra can be observed. Because of the shift in the band, it is now able to differentiate between the two spectral lines based on the major differences in the features that they share [47]. The peaks in the spectrum include those that are in the band 3447 − 3283 cm^− 1. These peaks correspond to the stretching vibrations of the O-H and N-H bonds. The change from the ketone to the enol form caused these vibrations to be concentrated into a narrow band at a frequency of 3508 cm^− 1 because of the transition. In addition, the spectrum exhibits a distinct band at 3080 cm^− 1, which corresponds to the H-C = frequency, as well as a distinct and strong band at 1700 cm^− 1, which corresponds to the C frequency [48]. Even if the synthesis of Fe-polyaniline complexes on the surface of the metal is exceedingly unlikely to occur, it is impossible to rule out the possibility of their being there entirely. This is because the chance of their formation is so low. It has been found, based on the data obtained from the FTIR spectrum analysis, that the production of a protective layer is due to composites constructed of Fe³⁺- polyaniline and Fe- polyaniline. This conclusion was reached. As a direct result of these discoveries, there is a possibility that the adsorption of polyaniline will take place between the atoms of iron, oxygen, and nitrogen. The findings of the study were used to validate and corroborate the conclusions of the study, which were based on the findings of the study on adsorption [49].

Cleaning is one of the most common operations in conservation. The choice of method for cleaning depends on what is required from the object, what is made of, and what condition it is in. As these spears' heads have the same condition and it will be uneasily to remove the concretion layer and the hard crust covering them by mechanical tools, the chemical treatment was chosen assisted by skilled mechanical cleaning. The treatment procedures included the following steps [50]. Firstly, chemical cleaning techniques include using soapy solutions to dissolve grease and remove surface dirt. Secondly, the spearheads were soaked in a 5% solution of Citric Acid mixed with 1%Thiourea to soluble the corrosion; this can be subsequently washed away. This was done with regular checks and removing loosened corrosion products with nylon and iron brushes, this procedure was followed by washing these parts with deionized water [51]. This step resulted in dissolving and removing the soluble corrosion products. After that, all the treated spears heads again were soaked in a 2% solution of sodium hydroxide (NaOH) to equilibrate the Acidic condition from the last step, assisted by gentle mechanical cleaning with nylon and iron brushes from time to time to dissolve the rest of acid and the corrosion [52]. Finally, this procedure was followed by washing spears' heads with deionized water. Repeated washing with hot deionized water to ensure flushing capillaries to remove any chemical residues and drying with a soft and clean cloth. Applying the corrosion inhibitor will guarantee the complete protection of the artifacts and in the long run, this will ensure that the interfaces between component materials will not harbor contaminants and harmful compounds [Figs. 12a-e] [53].

In this investigation, the spear's head from the Al-Qala museum, Cairo, Egypt date back to the 19th century. The degree of deterioration was determined for the spears by employing visual inspection [54]. It was based on an estimation of corrosion depth, surface condition and the part of the cross-section converted into corrosion products. Small fragments from the spears were analyzed by using metallographic microscopy and scanning electron microscopy combined with energy dispersive spectrometry (SEM&EDS), small samples from the objects were analyzed by using an Inspect S 50 (FEI), to know their chemical composition, to show the microstructure and surface characterization of the objects. The spears are mainly made of iron; the analytical results are presented in Tables 1 and 2. The corrosion products were analyzed by X-ray diffraction (XRD). A list of identified corrosion products is shown in Table 3. Naturally, the corrosion products are dependent on the surrounding [55]. Metallographic and Scanning Electron microscopic examinations declared that the spear's heads suffered from deterioration spots such as pitting surfaces, micro-cracks, and grieve corrosion (Figs. 8–12). There is a natural tendency for most pure metals to return to their more stable, corroded states. Because of this, metal objects need to be protected from environmental conditions and pollutants which encourage corrosion. In some cases, as the metal corrodes the oxide film that forms acts as an insulating barrier, which slows the rate of corrosion to an acceptable level via the formation of oxide coatings from protective layers, called passivation layers. When iron corrodes, however, it does not usually form a protective film [56]. As the iron objects were partially protected from aeration by patches of oxide, etc., certain areas became anodic and other cathodes, so that the corroding metal behave in the presence of an electrolyte as if it were several tiny galvanic cells. Iron continues to corrode until no metal is left unless some other protective coating is applied to protect it from the elements. Metallographic examination showed that there are particulars of charcoal between the grains of iron metal (Figs. 8, 9, and 10), in the case of charcoal-reduced iron, the incidence of significant impurities are likely to be so low that little useful information would be gained by chemical microanalysis [57]. In pre-modern cultures, iron was extracted from its abundant ores by heating with charcoal (carbon) in a small furnace, perhaps 1 m high. While the reduction of iron ores to iron is straightforward, the high melting point of iron (1550 ^oC) makes its liquefaction very difficult. The non-metallic part of the ore, however, forms “slag” a glassy material, which liquefies around 1200 ^oC and enables the particles of iron to coalesce as a heterogeneous lump or ‘bloom’. If this bloom is allowed to remain in contact with carbon for some hours, or even days, then an alloy of iron and carbon, steel, is formed. If the steel is allowed to cool in the air after being worked hot, then its hardness is comparable to bronze, but of course, steel is far cheaper than bronze [58]. Under air cooling, equilibrium conditions will prevail. The carbon that was dissolved in the iron above 900 ^oC comes out of the solution as a lamellar arrangement of iron carbide and ferrite with a distinctive microscopic appearance called pearlite. On the other hand, if steels are quenched, their hardness increases enormously. Its resistance to indentation can measure the hardness of a metal by a given load. This can be reported using the Vickers Pyramid Hardness (VPH) scale, whose units are kg/mm². Hardness values between 300 VPH and 700 VPH are easily obtained, even with medieval alloys, compared with perhaps 120 VPH for modern mild (low-carbon) steel. This is because, when steel is quenched, then martensitic, a material of lathlike microscopically appearance and great hardness, may form [59–61]. By using a Carbon/Sulfur analyzer, it has been shown that the alloy contains 0.93%wt carbon and 0.15%wt sulfur. Through the above-mentioned results, the iron alloy used in the spears heads is steel, whereas the main forms of iron alloys used throughout history are cast iron, wrought iron, and steel. Wrought iron contains little carbon (not more than 0.35%), steel has a moderate carbon content (between 0.6% and 2%) and cast irons have a high carbon content greater than 2% but generally less than 5% [62, 63]. Until the mid-19th century, the use of wrought iron was generally limited to relatively small items such as tie rods, straps, and nails. The microstructure of wrought iron is easily recognized, consisting primary of ductile α–iron (ferrite) matrix with slag inclusion (a glassy material that is deliberately added or worked into the iron during manufacture), mostly FeO and SiO₂ [64, 65]. Wrought iron melts at 1535°C [66] and is remarkably malleable and generally ductile (unless it has been overworked and not annealed by re-heating), with similar strengths in tension and compression [67], the more wrought iron is worked the stronger it becomes [68]. Corrosion products identified by XRD analyses are composed of Hematite (Fe₂O₃), Feroxyhite FeO(OH), and Magnetite (Fe₃O₄). Dust particles can be also recognized which include Quartz (SiO₂) and Calcite (CaCO₃) accumulated above the corrosion layers. Iron exposed to the atmosphere develops a moderately protective film of oxides and hydroxide forms [69]. There is an inner layer of magnetite along with other amorphous iron corrosion products, and an outer layer of iron hydroxide oxides [70]. The appearance of martensite as a micro constituent does not, of course, prove the deliberate employment of steel on the part of the smith. He may well have quenched everything he made because it might improve the tool or weapon, and was unlikely to do much harm, at the low carbon contents likely to be found. As described above, the smelting process resulted in a heterogeneous ‘bloom' consisting of a spongy matrix of metal and slag [71]. In the production of steel, the diffusion of carbon from charcoal was likely to produce a bloom with a carbon content that varied considerably from one area to another of the bloom. It was up to the smith to forge out a homogenous plate of the metal relatively free from slag impurities (slag is released from the bloom during forging). The quality of the final product was therefore highly dependent on the skills of the smith. XRD diffraction data showed that the composition of the corrosion products of the metallic parts of the spears mainly consists of Quartz, Calcite, Feroxyhyte, Magnetite, and Hematite in a minor amount, moisture and oxygen are required for metals to corrode see Fig. 6, Table 3. The corrosion products of the spear’s heads were removed by using a 5% solution of Citric Acid mixed with 1%Thiourea to soluble the corrosion; this can be subsequently washed away. This was done with regular checks and removing loosened corrosion products with nylon and iron brushes, this procedure was followed by washing these parts with deionized water [72]. This step resulted in dissolving and removing the soluble corrosion products, after that, all the treated spears heads again were soaked in a 2% solution of sodium hydroxide (NaOH) to equilibrate the Acidic condition from the last step, assisted by gentle mechanical cleaning with nylon and iron brushes from time to time to dissolve the rest of Acid and the corrosion. While citric acid is relatively safe on most objects, care should be taken to ensure that cast iron, cast steel, spring steel, or combinations of these are not left unattended for long periods, because these metals will actively corrode. Prolonged gas evolution (which you will see as bubbling) indicates that the iron surface is corroding. With harder alloys, this can also cause hydrogen embrittlement in which the hydrogen is generated within the metal and the stress of the gas pressure cracks the metal [73]. Gas evolution can also result in pitted, weakened, or destroyed objects. Because some mechanical cleaning techniques can be quite severe, they should be used very carefully, especially with small or fragile objects. Techniques that can be used with care include simple wire brushing [74]. This is often very effective in removing loose or flaking rust. Wire brushes are available in a range of bristle materials, for example, steel and brass, and grades, for example, coarse to fine, so take care to select one appropriate for the object. If in doubt regarding the type of iron or the duration of acid treatment, more time should be spent removing corrosion products by mechanical means [75]. Once the worst deposits are removed, a short treatment in citric acid should clean the object, with a reduced risk of damage. Some forms of corrosion leave spots on the object, which cannot be removed by citric acid. These can usually be picked off mechanically [76].

Investigations and analysis of which were performed for the iron archaeological artifacts using Metallography microscopy, scanning electron microscopy & Energy Dispersive Spectrometry, X-Ray Diffraction, and Carbon/Sulfur analyzer to allow precise identification of specific phases containing chloride responsible for iron archaeological artifact degradation. Indeed, the presence of adsorbed Cl seems to be confirmed and certainly plays an important role in the corrosion mechanism and degradation of objects after excavation. Because some of the major contributors to the deterioration of metals are oxygen, water, Chlorine ion, and airborne pollutants, it is important to provide an environment that offers protection against these factors. It can be achieved by removing oxygen, water, chlorine ion, and airborne pollutants from the local storage environment, storing, and displaying iron objects in environments where: The temperature is stable, avoiding airborne pollutants and relative humidity is less than 45%. The iron objects mustn't seal in plastic bags because the bags seal in moisture as well. This raises the relative humidity inside the bag, providing a microclimate that is favorable to corrosion also avoid polyvinyl chloride/PVC bags; they can give off hydrogen chloride, an acidic gas which will corrode most metals, we can select polyethylene bags and punch holes in the bag. The findings of this study revealed that a solution containing 3.5% sodium chloride and polyaniline both inhibit the corrosion of mild steel and that the effectiveness of the inhibition is directly proportional to the concentration, with the level of inhibition reaching approximately 98% at 100 ppm. Additionally, the results demonstrated that the effectiveness of the inhibition is directly proportional to the concentration (ppm). The results of the impedance tests suggest that the double layer capacitance of the protective film is falling, while its charge transfer resistance is growing. Based on the findings of this investigation, it appears that the protective film is likely to be rather thick and dense in comparison to other forms of protective film.

Competing Interests

The authors declare that there is no conflict of interest

Conflicts of Interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Data availability Statement

All data generated or analyzed during this study are included in this published article

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Funding:

This work was supported by own

Acknowledgments

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Author Contribution:

Mohamed M. Megahed and Ashraf M. El-Shamy analyzed the data and wrote the manuscript. Noha H. El-Ashery and Saleh M. Saleh handling the experimental work and helping in the analysis of data

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Green Corrosion Inhibitor for Protection of Conserved Some Archaeological Iron Spears Heads from Military Museum, Al-Qala, Egypt

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Abstract

Figures

1. Introduction

2. Materials And Methods

2.1. Materials

2.1.1. Description of Iron Spears and Their Condition

2.2. Methods

2.2.1. Corrosion Techniques

3. Results And Discussions

3.1. Surface Characterization

3.2. Electrochemical Measurements

3.2.1. Open Circuit Potential Measurements

3.2.2. Potentiodynamic Polarization curves

3.2.3. Electrochemical impedance spectroscopy

3.3. Inhibition mechanism

4. Conservation Process

5. Explanation Of The Results

Conclusion

Declarations

References

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