Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

The use of Robinia pseudoacacia L fruit extract as a green corrosion inhibitor in the protection of copper-based objects

The use of Robinia pseudoacacia L fruit extract as a green corrosion inhibitor in the protection... The most important inhibitors used in bronze disease are BTA and AMT. While these inhibitors control corrosion, they are toxic and cancerous. In this study, the acacia fruit extract (200 ppm to 1800 ppm) was used to the prevention of corrosion inhibition of bronze alloy in corrosive sodium chloride solution 0.5 M, for 4 weeks consecutively. The Bronze alloy used in this research, was made based on the same percentage as the ancient alloys (Cu‑ 10Sn). IE% was used to obtain the inhibitory efficiency percentage and Rp can be calculated from the resistance of polarization. SEM–EDX was used to evaluate the surfaces of alloy as well as inhibitory. The experiment was conducted in split plot design in time based on the RCD in four replications. ANOVA was performed and comparison of means square using Duncan’s multiple range test at one percent probability level. The highest rate of corrosion inhibition (93.5%) was obtained at a concentration of 1800 ppm with an increase in the concentration of the extract, corrosion inhibition also increased, i.e., more bronze was prevented from burning. Also, the highest corrosion inhibitory activity of Acacia extract (79.66) was in the second week and with increasing duration, this effect has decreased. EDX analysis of the control sample matrix showed that the amount of chlorine was 8.47%wt, while in the presence of corrosive sodium chloride solution, after 4 weeks, the amount of chlorine detected was 3.20%wt. According to the morphology (needle and rhombus) of these corrosion products based on the SEM images, it can be said, they are the type of atacamite and paratacamite. They have caused bronze disease in historical bronze works. The green inhibitor of Acacia fruit aqueous extract can play an effective role in inhibiting corrosion of bronze, but at higher concentrations, it became fungal, which can reduce the role of Acacia fruit aqueous extract and even ineffective. To get better performance of green inhibitors, more tests need to be done to improve and optimize. Keywords: Corrosion, Bronze disease, Green inhibitors, Acacia, Potentiostat, SEM–EDX Introduction to the inhibitor (materials would be expensive if access There are some growing concerns about the use of green is limited), and its environmental friendliness. Inhibi- inhibitors because some of these inhibitors are not only tors are volatile, inactive (anodic), precipitated, cathodic, toxic to living organisms but also cause environmen- organic and inorganic compounds that prevent corrosion tal damage although some be helpful and nontoxic, through adsorbing ions or molecules from the metal sur- they are less effective. When choosing an inhibitor, it is face, increasing or decreasing anodic or cathodic reac- important to consider the cost of the inhibitor, access tion, reducing penetration rate of reactants on the metal surface and the electrical resistance of metal surface [1–3]. *Correspondence: Bfazeli@uoz.ac.ir Inhibitors are generally substances, which reduce the Research Department of Agronomy and Plant Breeding, Agricultural level of chemical reactions at appropriate concentrations. Research Institute, University of Zabol, Zabol, Iran Corrosion inhibitors are active chemical species, which Full list of author information is available at the end of the article © The Author(s) 2021. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/. The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 2 of 14 help slow down, delay or prevent corrosion, via different potential to be a corrosion inhibitor for Cu in acidic envi- mechanisms, such as adsorption onto the metal surface ronment [24]. that blocks active surface sites [4, 5]. These substances The Acacia plant, scientifically named Robinia pseudo - can inhibit the growth of biological agents and stop the acacia L from the Papilionaceae family, is one of the two- physiological processes. The inhibitor at low concentra - celled plants whose beautiful and ornamental flowers tions in corrosive medium delays the corrosion of metals cultivated by beekeepers to produce fragrant honey. The [6, 7]. These substances can be solid, liquid, or gas and flowers have a soothing, stomach tonic effect and astrin - used in closed, gaseous, and aqueous mediums [8, 9]. gent and biliary properties [25]. The Acacia plant (robina Corrosion inhibitors reduce the rate of corrosion in psudoacacia) is a fast-growing tree. It has a broad crown several ways: (i) reduce the adsorption of ions/molecules with leaves consisting of 11–23 dark green oval leaflets. on the metal surface; (ii) increase or decrease the anodic In the roots, bark, and seeds of the Robinia pseudoacacia and/or cathodic reaction; to the metal surface, (iv) reduce L tree, there is a substance called Description Robin, and the electrical resistance of the metal surface [10]. in the leaves and flowers, there is also a glucoside called The effective techniques possible for protection are Description Robinin. Robinia pseudoacacia L wood is modification of metal, design, corrosive environment, hard and durable. For these reasons, it is of industrial and metal environment potential, surface, and the use of commercial importance and is used to build columns and inhibitors. Inhibitors are categorized into methods such scaffolding for mines, as well as to make sofas and chairs as mechanism (anodic, cathodic and mixed inhibitors), [25]. environment (acid, alkali and neutral inhibitors) and The corrosion inhibitory abilities of tannins, alkaloids, mode of protection (chemical, adsorption, film forming amino acids and organic dyes of plant origin are consid- and vapor phase inhibitors) [11]. ered. Although significant research has been devoted to The inhibitory effect of BTA (Benzotriazole) and AMT the inhibition of corrosion by plant extracts, reports on (5-amino-2-mercapto-1, 3, 4-thiadiazole) on historical the exact mechanisms of the adsorption and identifica - bronze art works has been proved previously [12–15]. tion process of the active substance are still scarce [10]. While these inhibitors have high efficiency, they have Therefore, in this study, following various other studies toxic and cancerous impacts on the environment. For this [26], chloride medium has been used to study the cor- reason, green inhibitors such as honey, fig juice [16], the rosion process and based on previous research, it was extract of salvia [17] and green tea extract [18] have been indicated that the general compounds of the Robinia examined and evaluated in recent years. pseudoacacia L fruit extract contain the natural sug- Most organic corrosion inhibitors have heteroatoms. P, ars of ramenoz, arabinose, and galactose, as well as glu- O, N, and S are known as active centers (O < N < S < P) for conic acid, 4 methoxygluconic and rubinin [27–29] and the adsorption process on the metal surface and have a the application of anti-corrosion effect of Robinia pseu - higher electron density. These elements act as corrosion doacacia L fruit extract on mild steel [30–32], the aim inhibitors. The use of organic compounds containing oxy - of this experiment, Robinia pseudoacacia L fruit extract gen, sulfur and especially nitrogen to reduce corrosion was used to evaluate the inhibitory effect on bronze alloy attack on steel has been studied in detail. Most organic (Cu-10Sn). inhibitors are adsorbed by displacing water molecules on the metal surface and forming a compact barrier. Addi- Material and methods tionally, the availability of non-bonded electrons (single Preparation of plant and extract pair) and p in inhibitor molecules facilitates the transfer Robinia pseudoacacia L fruit was obtained from the of electrons from the inhibitor to the metal [10]. Agricultural and Natural Resources Research and Train- Rosemary leaves were investigated as corrosion inhib- ing Center of Isfahan (Fig. 1). itors for the Al + 2.5  Mg alloy in a 3% NaCl solution at Fruit samples collected were dried on a clean cloth and 25 °C [19], and El-Etre studied natural honey as a corro- ground under appropriate conditions. 30  g of the result- sion inhibitor for copper [20] and studied opuntia extract ing powder was soaked in 100  ml of double distilled on aluminum [21]. The inhibitive influence of the extract water and shaken in a shaker for 24  h at room tempera- of khillah (Ammi visnaga) seeds on the corrosion of SX ture. The obtained liquids were passed through sterile fil - 316 steel in HCl solution was determined utilizing weight ter paper (Watman paper No. 1) and finally the extract loss amounts as well as the potentiostatic method.  Delo- and powder were separated. The remaining particles in nix regia extracts inhibited the corrosion of aluminum in the extract were separated using a refrigerated centrifuge hydrochloric acid extracts [22]. Antibacterial drugs were (2500  rpm) at 4  °C for 20  min. The extract was dewa - used as corrosion inhibitors for bronze surfaces in acidic tered using a vacuum rotary device. The obtained extract solutions [23]. The results indicate that Myrrh extract has was turned into powder and stored in a dark glass at a P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 3 of 14 Fig. 1 The characteristic of Robinia pseudoacacia L. plant temperature of 4 °C. During the experiment, dilutions of This alloy was used for the effect of corrosion inhibitors 200 to 1800  ppm (Part per Million) were prepared from in the potentiostat device, the weight loss method. the extract [33]. After preparing the coupons with a percentage of (Cu- 10Sn), the coupons were completely polished using sand- paper with grades 400 to 2200 to create a completely Experimental design smooth surface. Then, the coupons were rinsed with dis - The Acacia fruit extract (200, 400, 600, 800, 1000, 1200, tilled water and degreased by alcohol. The samples were 1400, 1600, and 1800 ppm) was used to the prevention of placed in an oven at 120  °C for 1  h. The coupons were corrosion inhibition of bronze alloy in corrosive sodium immersed in Robinia pseudoacacia L with concentrations chloride solution 0.5  M, for 4  weeks consecutively. The of 1000  ppm for 24 and 48  h. After removing the cou- experiment was conducted in split plot design in time pons, they were dried at room temperature for 1  h and based on a randomized complete design in four replica- photographed to examine the change in appearance color tions. Different concentrations of plant extracts were on the coupon surfaces. included in the main plots and the duration of applica- Sodium chloride (0.5  M) was used to make a control tion of the plant extract was in the sub-plots [34]. solution. This solution was poured into a special con - The Bronze alloy used in this research, was made based tainer at volume of 100  ml. After calibrating, the device on the same percentage as the ancient alloys (Cu-10Sn) begins plotting the polarization curve. In the polariza- (The alloy used in the research, according to the ancient tion curve, the corrosion potential of the control solu- alloys, with 10% tin and 90% copper, was made by cast- tion (Sodium chloride M 0.5) was recorded -243  mV ing and finally analyzed to make electrodes and coupons). (Millivolts). Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 4 of 14 The Acacia fruit extract was separately mixed and treated the inhibitor solution, − 222  mV indicates a shift toward with a corrosive solution of sodium chloride 0.5  M with 21  mV to positive values, which indicates that the type of pH = 5.5, so that its corrosion power could be examined by inhibitor is combinatorial (mixed-type inhibitor (Some the potentiostat device (Table 1) [35]. The corrosion poten - anodic and some cathodic)) (Fig.  2). In addition to the tial of the control solution was obtained − 243  mV. Based change in the potential of corrosion, a slight flow (Slight on the corrosion potential of the sample at the presence of current drop) is seen in the anodic branch. If the potential increases continuously, the curve will be anodic polarization and if the potential decreases continu- ously, the curve will be cathodic polarization. If polariza- Table 1 Analysis of variance of the effect of the aqueous extract tion causes a slight change to the positive or negative, the of Acacia fruit and duration of treatment on the corrosion inhibition of bronze curve will be of the combined (mixed-type inhibitor) polar- ization type [35, 36]. It is related that Potentiodynamic if Source df SS MS F any compounds suppress has both the anodic and cathodic ** Concentration of extract 8 33,320.9 4165.11 134.50 process, it behaves as mixed-type inhibitors [37]. r 3 197.9 65.96 Error r* Concentration of extract 24 743.2 30.97 Calculating the corrosion efficiency using potentiostat ** Week (period of time) 3 11,575.7 3858.58 157.28 device calculations ** Concentration of extract *week 24 16,934.4 705.60 28.76 IE% was used to obtain the inhibitory efficiency percentage Error r* Concentration of extract 81 1987.2 24.53 (Formula 1). In this formula, Icorr is density of the corro- *week 0 sion flow with inhibitory and I is corrosion flow without Total 143 64,759.3 inhibition. CV(r* concentration) 8.12 CV(r* concentration *week) 7.23 I corr − Icorr IE = × 100 (1) ** I corr Significant at one percent level df: Degrees of freedom; SS: sum of Squares; MS: mean sum of squares; F ratio: each F ratio is computed by dividing the MS value by another MS value. The MS value for the denominator depends on the experimental design Fig. 2 Tafel polarization curve of Robinia pseudoacacia L fruit extract at 1200 ppm (A), 1400 ppm (B), 1600 ppm (C) and 1800 ppm (D) in the presence of a corrosive solution of sodium chloride 0.5 Mm P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 5 of 14 The corrosion current density (The corrosion current W inhibitor IE = 1 − × 100 (5) density is determined at a constant pH value of solu- W blank tion using no buffering additives and it was calculated In order to perform the experiment using the classic for the obvious specimen surface area) [38] can be cal- method, the prepared electrodes were cut with a percent- culated from the polarization resistance and the Stern- age of (Cu-10Sn) as round coupons with a diameter of Geary constant and also Rp can be calculated from the 0.73 cm and a thickness of 2 mm. resistance of polarization (Eq. 2) [39]. The coupons were polished using sandpaper with grades of 400, 800, and 2200. The coupons were Rp = corr degreased in alcohol and rinsed in distilled water. The rinsed samples were heated at 80 °C for 1 h in an oven. Then, coupons were placed in a desiccator for 1  h. b ∗ b a c B = (2) Finally, the coupons were weighed to be immersed in 2.303(b + b ) a c Robinia pseudoacacia L fruit extract. The inhibitory ba = slope of the anodic Tafel reaction, when plotted efficiency of the coupons were calculated each week for on base 10 logarithmic paper in V/decade, bc = slope 4 week consecutively (Formula 5). Hence, one of the cou- of the cathodic Tafel reaction when plotted on base 10 pons were removed from the control solution and Rob- logarithmic paper in V/decade, and B = Stern-Gear y inia pseudoacacia L fruit extract each week, after one constant, V. month of immersion (From the first week to the end). In these experiments, corrosion flow density (For - mula 3), corrosion rate, and equivalent weight with Determine the inhibitory efficiency of the Robinia the presence and absence of inhibitor were calculated pseudoacacia L fruit by standard (ASTM (American Society for Testing and In this paper, the potentiostat device, (SAMA 500 elec- Materials), G 102-98) [40, 41]. tro-analyzer system model (SAMA Research Center, Iran), was used to perform experiments to determine the Icorr icorr = (3) inhibitory efficiency of the Robinia pseudoacacia L fruit. It included three electrodes, a platinum auxiliary elec- i corrosion flow density (μ A/cm ); I : corrosion corr: corr trode, a reference electrode of saturated chloride mer- flow (µA); A = contact surface (cm ). cury (calomel) and a bar working electrode [44, 45] with Corrosion rate is calculated based on the following length of 7.5 cm and diameter of 0.73 cm with compound equation of Cu-10Sn). It was polished with sandpaper (grade from 400 to 2200). Each of these experiments was repeated i corr CR = K 1 EW (4) four times. To calibrate the device, the LSV (Liner sweep voltammetry) Tafel-plot technique was used. Addi- −3 tionally, the classical weight loss method, and finally, CR = corrosion rate (mpy); K1 = 3.27 × 10 (mm g/ SEM–EDX (Scanning Electron Microscope-Energy Dis- µA cm yr); ρ = density (g/cm ). persive X-rays), manufactured by Philips Company of the Netherlands. The XL30 model was used to evaluate the surfaces of alloy as well as inhibitory efficiency of the Calculating the classic weight loss Robinia pseudoacacia L fruit [46, 47]. The weight loss method is the simplest method for studying corrosion inhibitors due to the lack of need for device (except for using the digital scale). In this Scanning Electron Microscope (SEM) method, the weight variations of the metal sample are To accelerate corrosion, the samples were transferred calculated before and after exposure to the corrosive to the humidity compartment. Coupons were placed in medium (in the absence and presence of inhibitor). The a relative humidity of 95 ± 2 and a temperature of 25 to time taken for this experiment is long, but as results 30  °C. The samples underwent sodium chloride 0.5  mM of this method are more real than those of the electro- spray based on the standards of ASTMG85 and ISO9227. chemical method, it is still used [42, 43]. The classic Four weeks later, the samples were removed from the weight loss can be calculated based on the IE formula humidifier compartment and examined to evaluate the (Formula 5). In this formula, Wcorr is the weight loss effect of the inhibitor on the coupon surfaces by using of the sample in the presence of the inhibitor and W0 SEM–EDX device. is the weight loss of the sample in the absence of the To determine the size and morphology of the nanopar- inhibitor. ticles produced using electron microscopy, the reaction Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 6 of 14 mixture was centrifuged three times for 15  min at a pseudoacacia L fruit extract was − 213 mV at 1600 ppm speed of 12,000  rpm. Then, a few drops of the resulting that it is showed displacement of 30  mV, compared to precipitate were dried on a piece of aluminum foil at the corrosion solution (Fig.  2C). A slight drop (Slight room temperature and after drying, the SEM photo was current drop) is also observed in the anodic branch. The taken using an electron microscope device (Philips SEM corrosion potential of the Robinia pseudoacacia L fruit machine (model CMC-300 kV, Netherlands)). extract was − 213 mV at 1800 ppm that it is showed dis- placement of 30  mV, compared to the corrosion solu- Statistical analysis of data tion (Fig.  2D). A slight drop (Slight current drop) is also After data collection, analysis of variance was performed observed in the anodic branch. using student statistic 9 software as well as comparison of means square using Duncan’s multiple range test at one The inhibitory efficiency of Robinia pseudoacacia L fruit percent probability level. extract The analysis of variance were shown that the main effects Results (different concentrations of aqueous acacia extract and Polarization evaluation of Tafel acacia extracts duration of treatment) as well as the interaction of the The Tafel polarization of Robinia pseudoacacia L fruit extract and duration were effective on corrosion inhi - extract in 1200  ppm at the presence of sodium chloride bition (P < 0.01) (Table  1). Mean comparison showed 0.5  M, was shown that the inhibitory corrosion poten- that the highest rate of corrosion inhibition (93.5%) tial is − 216 mV. Based on the control solution, inhibitor was obtained at a concentration of 1800  ppm and with chart has a shift of direction to positive values (Fig.  2A). increasing concentration of the extract, corrosion inhibi- In addition to changes in the corrosion potential, the flow tion also increased, i.e., more bronze was prevented from in both the anodic and cathodic branches was decreased. burning (Fig.  3). Also, the highest corrosion inhibitory The Tafel polarization of Robinia pseudoacacia L fruit activity of Acacia extract (79.66) was in the second week extract at 1400  ppm was shown showed that the inhibi- and with increasing duration, this effect has decreased tory solution corrosion potential is − 216  mV, which (Fig. 4). compared to control solution, it has a shift of direction Some traits like corrosion flow, corrosion potential, to positive values (Fig.  2(B)). The corrosion has also had electrolyte resistance, flow density, cathodic and anodic a slight drop (Slight current drop) in the anodic and slope coefficients, and corrosion rate of Robinia pseu - cathodic branches. The corrosion potential of the Robinia doacacia L fruit investigated using Potentiostat device Fig. 3 Mean square of different concentrations of the aqueous extract of Acacia fruit on preventing corrosion inhibition of bronze (Similar letters indicate no significant differences in the treatments under study). Y is equal to the regression equation P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 7 of 14 Fig. 4 The duration effect of Acacia fruit extract on bronze prevents corrosion inhibition (Similar letters indicate no significant differences in the treatments under study). Y is equal to the regression equation (Table 2). As the result, the relationship between poten- The results of the analysis of variance showed that tial, current intensity and corrosion diagram obtained the effect of different concentrations of acacia aque - based on the use of the anodic and cathodic hypertro- ous extract on bronze weight reduction rate was signifi - phy, measuring the potential difference between this cant (P < 0.01). In the study of the weight reduction rate electrode and the reference electrode, as well as meas- method, the results showed that the least weight reduc- uring the anodic and cathodic current intensity. The tion rate occurred at a concentration of 1800  ppm of weight reduction rates of  Robinia pseudoacacia  L fruit Acacia extract (Fig.  5), in general, the alloy weight loss extract were calculated using the data that they were was least with increasing the concentration of Acacia derived from the Potentiostat device (Table 2). extract (Fig. 6). These results are the same as results that The Weight-reduction rate method is the simplest in were obtained by device. the study of corrosion inhibition due to the lack of need for a device. This experiment takes a long time, but Use of SEM to evaluate the performance of acacia fruit because the results of this method are more realistic extract on the surface of coupons than the electrochemical method, it is still used. An aqueous extract of Acacia fruit can prevent corro- sion of bronze using increasing the concentration but Table 2 Calculation of corrosion flow, corrosion potential, electrolyte resistance, flow density, cathodic and anodic slope coefficients , and corrosion rate of Robinia pseudoacacia L fruit with a Potentiostat device Concentration Robinia -E (mv) R (ohm) B (v/dec) B (v/dec) I corrosion (A) i corrosion (A/cm ) Corrosion corr P a c pseudoacacia L (W/V) rate (mpy) –5 –5 Blank 243 800.5 0.060 0.066 2.716*10 6.497*10 28.381 –5 –5 200 ppm 211 1244 0.061 0.084 1.748*10 4.181*10 18.264 –5 –5 400 ppm 228 1315 0.072 0.079 1.653*10 3.955*10 17.276 –5 –5 600 ppm 214 1268 0.061 0.068 1.714*10 4.102*10 17.091 –5 –5 800 ppm 219 1508 0.082 0.090 1.442*10 30,449*10 15.066 –5 –5 1000 ppm 222 1765 0.059 0.072 1.232*10 2.947*10 12.873 –5 –5 1200 ppm 216 1573 0.067 0.095 1.382*10 3.306*10 14.441 –5 –5 1400 ppm 214 1734 0.077 0.108 1.254*10 2.99*10 13.100 –5 –5 1600 ppm 219 1218 0.076 0.104 1.785*10 4.27*10 18.652 –5 –5 1800 ppm 213 1029 0.121 0.117 2.113*10 5.054*10 22.077 Anodic and cathodic slopes were plotted on the anodic and cathodic branches and finally the device automatically calculated these slopes Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 8 of 14 Fig. 5 The weight reduction rates based on 1800 ppm concentration of Robinia pseudoacacia L from 1 to 4 weeks floatation Fig. 6 Different concentrations effect of aqueous extract of acacia fruit on the weight reduction rate of bronze (Similar letters indicate no significant differences in the studied treatments) to confirm the role of the extract, electron microscopy the bronze level and corrosion. The examination of the was used. After removing the coupons from the control surface of the control coupon revealed that it had green (no extract) and aqueous extracts of Acacia fruit, the and localized corrosion products (Fig.  7). However, it coupons were examined under a microscope to check was observed that the surface of the same coupons were P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 9 of 14 Fig. 7 A Coupons in a corrosive solution of sodium chloride 0.5 after 30 days of immersion. ×60 magnification; B coupons in a corrosive solution of sodium chloride 0.5 after 30 days of immersion. ×40 magnification covered after being placed in corrosive solution and works. These corrosion products are concentrated in acacia extract (Fig.  8), and no trace of corrosion prod- the grain boundaries. ucts were observed on the surface of the alloy (Fig. 9). Although the aqueous extract of acacia fruit creates a SEM was used to evaluate and accurately perform this uniform layer, which covers the surface of the alloy and inhibitor on the surface of these coupons. In the SEM prevents the formation of corrosion products on the sur- images of the control coupon (Fig.  10), the corrosion face of these coupons (Fig.  8) the SEM images showed products in the grain boundaries were identified and that grain corrosion was induced in this alloy in the pres- showed the high impact of the corrosive environment ence of acacia extract (Fig.  10). At higher concentrations on this alloy. According to the morphology (needle and of this extract, i.e. from 1000 to 1800 ppm, after immer- rhombus) of these corrosion products, can said that sion of the samples in the presence of acacia extract and they are the type of atacamite and paratacamite that 0.5 M sodium chloride solution, the presence and growth they have caused bronze disease in historical bronze of fungi have been observed, which can cause poor per- formance of acacia extract in the long run. Fig. 8 A Coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1000 ppm after 30 days of immersion. ×60 magnification; B coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1800 ppm after 30 days of immersion. ×40 magnification (B) Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 10 of 14 Fig. 9 A Coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1000 ppm after 30 days of immersion. ×20 magnification; B coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1800 ppm after 30 days of immersion. ×20 magnification Fig. 10 A SEM analysis of control sample versus Sodium chloride 0.5 M corrosive solution; B SEM analysis of coupon surface containing inhibitor at the presence of Sodium chloride 0.5 M corrosive solution EDX analysis of the control sample matrix showed treatment. These fungi can reduce and even ineffective that the amount of chlorine, which is the most impor- the role of Acacia fruit aqueous extract. Green inhibi- tant factor in the destruction of bronze disease, was tors can play an effective role in preventing corrosion. 8.47wt (Fig.  11). Based on the EDX results on the sam- However, to get better performance of these inhibitors, ple containing acacia extract, it can be concluded that more tests need to be done to improve and optimize their the amount of chlorine detected was 3.20wt in the pres- performance. ence of corrosive sodium chloride solution after 4 weeks. These results indicate that the amount of chlorine in the Discussion presence of inhibitor was least (Fig. 12). So far, different results have been reported regarding The green inhibitor of Acacia fruit aqueous extract can the use of plants extract on the prevention of corrosion. play an effective role in inhibiting corrosion of bronze, The extract of Salvia officinalis and its efficiency in cor - but the fungus has grown in the green inhibitor at higher rosion inhibitory investigated in 0.5  M Nacl. The results concentrations and with increasing the duration of indicated that the extract of Salvia officinalis acted as a P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 11 of 14 Fig. 11 EDX analysis of control sample versus Sodium chloride 0.5 M corrosive solution Fig. 12 EDX analysis of coupon surface containing inhibitor at the presence of Sodium chloride 0.5 M corrosive solution Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 12 of 14 cathodic inhibitor and the inhibitory efficiency increased polarized sodium chloride solution [2]. Perhaps the rea- with increasing sage extract concentration. The results of son for not increasing the inhibition of Acacia extract by the weight loss test reported between 32 and 41% [17]. increasing the concentration of the extract to 1800  ppm In this study, the Potentiostat device method and the and the inhibition oscillation between cathode and classic method of weight loss used to determine the effi - anodic is also because the role of cathodic and anodic ciency of corrosion inhibitory. The results shown that inhibition after oscillation in polarized sodium chloride this efficiency in the Potentiostat device method was 92% solution has decreased. However, it can have another but in the classical method was equal to 55% that more reason, such as less absorption power on the bronze has been mentioned than research [17]. Because aca- (Cu-10Sn). cia contained flavonoids and phenolic compounds with In this research, on the bronze surface, there were a complex structure and high molecular weight, it was active cathodic sites in contact with corrosive species, expected to prevent corrosion, but it did not. which results in a vigorous dissolution of bronze. Bronze The inhibitory effect of two natural honeys (oak and surface can be protected against the charge and mass acacia) with a mixture of black horseradish juice on the transfer which causes corrosion by adsorption of the corrosion of tin in aqueous media and sodium chloride green organic components. This result is similar to the solution by weight loss methods and polarization tech- previous research [50]. niques has been studied. The results showed that the The Corrosion Inhibition by Beet Root (BR) Extract yield of acacia honey was lower than oak honey and by was conducted and the results shown that the BR extract 2+ adding black horseradish juice to both honeys, their yield with 50 ppm Zn had about 98% inhibition efficiency to increased. The inhibition efficiency (IE) of all inhibitors carbon steel immersed in well water (a mixed-type effect 2+ examined obtained from both methods used a decrease existed between BR extract and Zn ) [51]. The results in order: chestnut honey with black radish juice > acacia herein indicated that the type of inhibitor was mixed- honey with black radish juice > chestnut honey > aca- type inhibitor. cia honey [48]. It has been found that acacia extract has The acacia leaves extract was used as an eco-friendly less effect than black horseradish extract. In the present inhibitor on mild steel in acidic media and it easily study, acacia extract had a positive effect at 1000  ppm, extractable, extremely inexpensive, environmentally safe but with increasing acacia extract, the corrosion inhibi- and effective in slowing mild steel corrosion which is not tory effect decreased. formerly used in corrosion studies. Hence, the acacia Natural honey has been studied as a corrosion inhibi- leaves extract can be used as a potential corrosion inhibi- tor of carbon steel in high-salt environments. The inhibi - tor in the acidic environment for mild steel [50]. In the tory efficiency has been calculated through weight loss present study, acacia extract had a positive effect but the and static potential polarization technique. The results corrosion inhibitory effect decreased with increasing aca - have introduced natural honey as a suitable inhibitor for cia extract. corrosion of steel in high-salt environments. However, this beneficial effect has been limited to a certain level Conclusion and after a while, due to the growth and development of Given the investigations on Robinia pseudoacacia L fungi, its inhibitory efficiency has been reduced [20]. It is fruit using potentiostat device, it was revealed that Rob- indicated that, after some time, the inhibition efficiency inia pseudoacacia L fruit had inhibitory efficiency at decreased due to the growth of fungi in the medium. 1800  ppm with a corrosion rate of 12.78% is 55% for Because they said that the effect of fungi on the inhibi - bronze alloy with percentage of (Cu-10Sn) and has a tion efficiency of natural honey is markedly decreased in mixed inhibitory effect. In the classic weight reduc - high saline water and also the high concentration of NaCl tion rate, (in which the results are more real than those may retard the growth of fungi [49]. In the present study, in electrochemical methods), the inhibitory efficiency acacia extract had a fungal growth of 1800  ppm, which of Robinia pseudoacacia L fruit was determined to be over time reduced the inhibitory effect. 92%. SEM images derived from the surface of coupons Inhibition of organic compounds such as honey and at the presence of Robinia pseudoacacia L and a corro- rosemary (Salvia rosmarinus L.) on four metals, alu- sive solution of sodium chloride 0.5  M shown a kind of minum, copper, iron and zinc in sodium chloride and segregation on the surface of coupons in the presence sodium sulfate solution has been investigated. The results of a corrosive solution. Based on the experiments per- showed that the inhibitors had no effect on aluminum in formed, it is necessary to add other natural compounds sodium chloride and sodium sulfate solutions. The rea - to this inhibitor for better efficiency so that appropriate son why honey is not inhibited is that honey plays a small and optimal conditions for this type of inhibitor can be cathodic inhibitory role in aluminum when placed in defined. P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 13 of 14 5. Al‑Moubaraki AH, Al‑Howiti AA, Al‑Dailami MM, Al‑ Ghamdi EA. Role of One of the points that should be considered during the aqueous extract of celery (Apium graveolens L.) seeds against the cor‑ restoration process is not to change the structure and rosion of aluminium/sodium hydroxide systems. J Environ Chem Eng. appearance of the historical monument. Since corro- 2017;5(5):4194–205. https:// doi. org/ 10. 1016/j. jece. 2017. 08. 015. 6. Olajire AA. Corrosion inhibition of offshore oil and gas production sion in a metal monument, especially copper and bronze, facilities using organic compound inhibitors‑a review. J Mol Liq. has a special place and importance from a historical, 2017;248:775–808. https:// doi. org/ 10. 1016/j. molliq. 2017. 10. 097. structural and sometimes aesthetic point of view. Based 7. Barreto LS, Tokumoto MS, Guedes IC, Melo HG, Amado FDR, Capelossi VR. Evaluation of the anticorrosion performance of peel garlic extract as on our result, it seems necessary to pay more attention corrosion inhibitor for ASTM 1020 carbon steel in acidic solution. Matéria. to the rate of color changes after the application of new 2017. https:// doi. org/ 10. 1590/ s1517‑ 70762 01700 03. 0186. materials. 8. Groysman A. Corrosion for everybody. Springer; 2009. https:// doi. org/ 10. 1007/ 978‑ 90‑ 481‑ 3477‑9 9. Ogawa A, Takakura K, Hirai N, Kanematsu H, Kuroda D, Kougo T, et al. Biofilm formation plays a crucial rule in the initial step of carbon steel cor ‑ Abbreviations rosion in air and water environments. Materials. 2020;13(4):923. https:// AMT: 5‑Amino ‑2‑mercapto ‑1,3,4‑thiadiazole; ANOVA: Analysis of variance; doi. org/ 10. 3390/ ma130 40923. ASTM: American Society for Testing and Materials; BTA: Benzotriazole; EDX: 10. Rani B, Basu BBJ. Green inhibitors for corrosion protection of metals and Energy Dispersive X‑rays; LSV: Liner sweep voltammetry; mV: Millivolts; PPM: alloys: an overview. International Journal of corrosion. 2012. https:// doi. Part Per Million; RCD: Randomized complete design; SEM–EDX: Scanning org/ 10. 1155/ 2012/ 380217. Electron Microscope‑Energy Dispersive X ‑rays. 11. Palanisamy G. Corrosion inhibitors. Corrosion inhibitors: Ambrish Singh, IntechOpen; 2019. p. 1–24. https:// doi. org/ 10. 5772/ intec hopen. 80542 Acknowledgements 12. Faltermeier RB. A corrosion inhibitor test for copper‑based artifacts. Stud‑ We thereby appreciate Dr. Vatan Khah, Dr. Emami and Dr. Abed Esfahani, who ies in conservation. 2013;44(2):121–8. https:// doi. org/ 10. 1179/ sic. 1999. helped us in this research. 44.2. 121. 13. Artesani A, Di Turo F, Zucchelli M, Traviglia A. Recent advances in protec‑ Authors’ contributions tive coatings for cultural heritage–an overview. Coatings. 2020;10(3):217. VP and BFN designed the research and wrote the paper. Both authors read https:// doi. org/ 10. 3390/ coati ngs10 030217. and approved the final manuscript. 14. Faltermeier RB, Archaeology UoLIo. AMT: A New Corrosion Inhibitor? : University College; 1992. p. 44 Pages. Funding 15. Kumara SA, Sankar A, Kumarb SR, Vijayanc M. Asparagus racemosus root Not applicable. extract as corrosion inhibitor for mild steel in acid medium. Int J Comput Eng Sci. 2013;3(1):40–5. Availability of data and materials 16. Pourzarghan V, Sarhaddi‑Dadian H, Bakhshandefard H. Feasibility study All the data is embedded in the manuscript. of natural honey use as corrosion inhibitor in protecting the bronze artifacts. Mediter Archaeol Archaeom. 2017;17(3):301–9. https:// doi. org/ Declarations 10. 5281/ zenodo. 10489 35. 17. Vatankhah GR, Bakhshandehfard HR, Golozar MA, Sabzalian MR. Salvia Ethics approval and consent to participate officinalis extract as a natural corrosion inhibitor for copper alloy artifacts No human or animals were used in the present research. treatment. Sci J Maremat & Me’mari‑ e Iran. 2011;1(1):41–54. 18. Vatankhah GR, Bakhshandehfard HR, Golozar MA, Sabzalian MR. Green Consent for publications tea extract (Camellia sinensis): a non‑toxic plant inhibitor for controlling All authors read and approved the final manuscript for publication. corrosion in historical copper artifacts. Sci J Maremat & Me’mari‑ e Iran (quarterly). 2013;1(4):85–96. Competing interests 19. Kliškić M, Radošević J, Gudić S, Katalinić V. Aqueous extract of Rosmarinus All authors declare no conflict of interest exists. officinalis L. as inhibitor of Al–Mg alloy corrosion in chloride solution. J Appl Electrochem. 2000;30(7):823–30. https:// doi. org/ 10. 1023/A: 10040 Author details 41530 105. Department of Historical Works Restoration, Faculty of Art and Architecture, 20. El‑Etre A. Natural honey as corrosion inhibitor for metals and alloys. I. University of Zabol, Zabol, Iran. Research Department of Agronomy and Plant Copper in neutral aqueous solution. Corrosion Sci. 1998;40(11):1845–50. Breeding, Agricultural Research Institute, University of Zabol, Zabol, Iran. https:// doi. org/ 10. 1016/ S0010‑ 938X(98) 00082‑1. 21. El‑Etre A. Inhibition of aluminum corrosion using Opuntia extract. Cor ‑ Received: 16 April 2021 Accepted: 4 June 2021 ros Sci. 2003;45(11):2485–95. https:// doi. org/ 10. 1016/ S0010‑ 938X(03) 00066‑0. 22. Abiola OK, Oforka NC, Ebenso EE, Nwinuka NM. Eco‑friendly corrosion inhibitors: the inhibitive action of Delonix regia extract for the corrosion of aluminium in acidic media. Anti‑ Corros Methods Mater. 2007;54(4):219– References 24. https:// doi. org/ 10. 1108/ 00035 59071 07623 57. 1. Verma C, Ebenso EE, Quraishi M. Ionic liquids as green and sustain‑ 23. Rotaru I, Varvara S, Gaina L, Muresan LM. Antibacterial drugs as cor‑ able corrosion inhibitors for metals and alloys: an overview. J Mol Liq. rosion inhibitors for bronze surfaces in acidic solutions. Appl Surf Sci. 2017;233:403–14. https:// doi. org/ 10. 1016/j. molliq. 2017. 02. 111. 2014;321:188–96. https:// doi. org/ 10. 1016/j. apsusc. 2014. 09. 201. 2. Yee Y. Green inhibitors for corrosion control: a Study on the inhibitive 24. Al‑Nami S, Fouda AE‑AS. Corrosion Inhibition Eec ff t and Adsorption effects of extracts of honey and rosmarinus officinalis L.(Rosemary): MS Activities of methanolic myrrh extract for Cu in 2 M HNO3. Int J Electro‑ thesis, University of Manchester, Institute of Science and Technology; chem Sci. 2020;15:1187–205. https:// doi. org/ 10. 20964/ 2020. 02. 23. 2004. 25. Liu Z, Hu B, Bell TL, Flemetakis E, Rennenberg H. Significance of mycor ‑ 3. Saeed MT, Saleem M, Niyazi AH, Al‑Shamrani FA, Jazzar NA, Ali M. Carrot rhizal associations for the performance of N2‑fixing Black Locust (Robinia (Daucus carota L.) peels extract as an herbal corrosion inhibitor for mild pseudoacacia L.). Soil Biol Biochem. 2020;145:107776. https:// doi. org/ 10. steel in 1M HCl solution. Modern Appl Sci. 2020;14(2):97–112.1016/j. soilb io. 2020. 107776. 4. Miralrio A, Espinoza VA. Plant extracts as green corrosion inhibitors 26. Scott DA. Ancient metals: microstructure and metallurgy: Lulu. com; for different metal surfaces and corrosive media: a review. Processes. 2011. 2020;8(8):942. https:// doi. org/ 10. 3390/ pr808 0942. Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 14 of 14 27. Karamalla K, Siddig N, Osman M. Analytical data for Acacia senegal var 41. Tan X, Zhi Q, Yang R, Wang F, Yang J, Liu Z. Eec ff ts of milling on the cor ‑ senegal gum samples collected between 1993 and 1995 from Sudan. rosion behavior of Al2NbTi3V2Zr high‑ entropy alloy system in 10% nitric Food hydrocolloids. 1998;12(4):373–8. https:// doi. org/ 10. 1016/ S0268‑ acid solution. Mater Corros. 2017;68(10):1080–9. https:// doi. org/ 10. 1002/ 005X(98) 00005‑8.maco. 20170 9472. 28. Mohamed AM, Ariffin MAM, Smaoui H, Osman MH. Performance evalua‑ 42. Tang L, Li X, Li L, Mu G, Liu G. The effect of 1‑(2‑pyridylazo)‑2‑naphthol on tion of concrete with Arabic gum biopolymer. Mater Today. 2020. https:// the corrosion of cold rolled steel in acid media: Part 2: Inhibitive action in doi. org/ 10. 1016/j. matpr. 2020. 04. 576. 0.5 M sulfuric acid. Mater Chem Phys. 2006;97(2–3):301–7. https:// doi. org/ 29. Raja PB, Sethuraman MG. Natural products as corrosion inhibitor for met‑10. 1016/j. match emphys. 2005. 08. 014. als in corrosive media—a review. Mater Lett. 2008;62(1):113–6. https:// 43. Pourfarzad H, Shabani‑Nooshabadi M, Ganjali MR, Olia MH. Inhibition of doi. org/ 10. 1016/j. matlet. 2007. 04. 079. acid corrosion of glass ampoule in Pb/HBF4/PbO2 reserve batteries using 30. Buchweishaija J, Mhinzi G. Natural products as a source of environmen‑ nanobis [3‑(trimethoxysilyl) propyl] amine. J Mol Liq. 2020;302: 112578. tally friendly corrosion inhibitors: the case of gum exudate from Acacia https:// doi. org/ 10. 1016/j. molliq. 2020. 112578. seyal var seyal. Portugaliae Electrochimica Acta. 2008;26(3):257–65. 44. de Rooij M. Electrochemical methods: fundamentals and applications. 31. Nasab SG, Yazd MJ, Semnani A, Kahkesh H, Rabiee N, Rabiee M, et al. Anti‑ Corros Methods Mater. 2003. https:// doi. org/ 10. 1108/ acmm. 2003. Natural corrosion inhibitors. Synth Lect Mech Eng. 2019;14(1):1–96. 12850 eae. 001. https:// doi. org/ 10. 2200/ S0091 0ED1V 01Y20 1903M EC018. 45. Bard AJ, Faulkner LR. Fundamentals and applications. Electrochem Meth‑ 32. Mohyaldinn ME, Lin W, Gawi O, Ismail MC, Ahmed QA, Ayoub MA, et al., ods. 2001;2(482):580–632. editors. Experimental Investigation of a New Derived Oleochemical Cor‑ 46. Pourzarghan V, Vatankhah G, Bakhshandeh‑Fard HR. Investigation and rosion Inhibitor. Key Engineering Materials; 2019: Trans Tech Publ. https:// feasibility of using honey as a corrosion inhibitor in the protection of his‑ doi. org/ 10. 4028/ www. scien tific. net/ KEM. 796. 112 torical bronze objects. Isfahan: Master Thesis on Restoration of Historical 33. Fazeli‑Nasab B, Sirousmehr A, Mirzaei N, Solimani M. Evaluation of total Works of Art University of Isfahan; 2010. phenolic, flavenoeid content and antioxidant activity of Leaf and Fruit 47. Goyal M, Vashist H, Kumar S, Bahadur I, Benhiba F, Zarrouk A. Acid cor‑ in 14 different genotypes of Ziziphus mauritiana L. in south of Iran. Eco ‑ rosion inhibition of ferrous and non‑ferrous metal by nature friendly Phytochem J Med Plants. 2017;4(4):1–14. ethoxycarbonylmethyltriphenylphosphonium bromide (ECMTPB): 34. Goss‑Sampson M. Statistical analysis in JASP: A guide for students: JASP; experimental and MD simulation evaluation. J Mol Liq. 2020;315: 113705. 2019. https:// doi. org/ 10. 6084/ m9. figsh are. 99807 44https:// doi. org/ 10. 1016/j. molliq. 2020. 113705. 35. Allen JB, Larry RF. Electrochemical methods fundamentals and applica‑ 48. Radojčić I, Berković K, Kovač S, Vorkapić‑Furač J. Natural honey and black tions: John Wiley & Sons; 2001. ISBN: 0‑471‑04372‑9 radish juice as tin corrosion inhibitors. Corros Sci. 2008;50(5):1498–504. 36. Li Y, Xu N, Guo X, Zhang G. Inhibition effect of imidazoline inhibitor on https:// doi. org/ 10. 1016/j. corsci. 2008. 01. 013. the crevice corrosion of N80 carbon steel in the CO2‑saturated NaCl solu‑ 49. El‑Etre A, Abdallah M. Natural honey as corrosion inhibitor for metals and tion containing acetic acid. Corros Sci. 2017;126:127–41. https:// doi. org/ alloys. II. C‑steel in high saline water. Corros Sci. 2000;42(4):731–8. https:// 10. 1016/j. corsci. 2017. 06. 021.doi. org/ 10. 1016/ S0010‑ 938X(99) 00106‑7. 37. Wang H‑L, Liu R‑B, Xin J. Inhibiting effects of some mercapto ‑triazole 50. Yüce AO. Corrosion inhibition behavior of Robinia pseudoacacia leaves derivatives on the corrosion of mild steel in 1.0 M HCl medium. Corros extract as a eco‑friendly inhibitor on mild steel in acidic media. Met Mater Sci. 2004;46(10):2455–66. https:// doi. org/ 10. 1016/j. corsci. 2004. 01. 023. Int. 2020;26(4):456–66. https:// doi. org/ 10. 1007/ s12540‑ 019‑ 00509‑7. 38. Rybalka K, Beketaeva L, Davydov A. Determination of corrosion current 51. Selvi JA, Rajendran S, Sri VG, Amalraj AJ, Narayanasamy B. Corrosion density by the rate of cathodic depolarizer consumption. Russ J Electro‑ inhibition by beet root extract. Port Electrochim Acta. 2009;27(1):1–11. chem. 2016;52(3):268–72. https:// doi. org/ 10. 1134/ S1023 19351 60300 95.https:// doi. org/ 10. 4152/ pea. 20090 1001. 39. Standard A. Standard practice for calculation of corrosion rates and related information from electrochemical measurements. Annu Book Publisher’s Note ASTM Stand ASTM Int West Conshohocken PA. 2006;3:G102–89. https:// Springer Nature remains neutral with regard to jurisdictional claims in pub‑ doi. org/ 10. 1520/ G0102‑ 89R15 E01. lished maps and institutional affiliations. 40. Dean S. Calculation of alloy equivalent weight. Mater Perform. 1987;26(12):51–2. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Heritage Science Springer Journals

The use of Robinia pseudoacacia L fruit extract as a green corrosion inhibitor in the protection of copper-based objects

Heritage Science , Volume 9 (1) – Jun 18, 2021

Loading next page...
 
/lp/springer-journals/the-use-of-robinia-pseudoacacia-l-fruit-extract-as-a-green-corrosion-2I9q0av7Be

References (54)

Publisher
Springer Journals
Copyright
Copyright © The Author(s) 2021
eISSN
2050-7445
DOI
10.1186/s40494-021-00545-w
Publisher site
See Article on Publisher Site

Abstract

The most important inhibitors used in bronze disease are BTA and AMT. While these inhibitors control corrosion, they are toxic and cancerous. In this study, the acacia fruit extract (200 ppm to 1800 ppm) was used to the prevention of corrosion inhibition of bronze alloy in corrosive sodium chloride solution 0.5 M, for 4 weeks consecutively. The Bronze alloy used in this research, was made based on the same percentage as the ancient alloys (Cu‑ 10Sn). IE% was used to obtain the inhibitory efficiency percentage and Rp can be calculated from the resistance of polarization. SEM–EDX was used to evaluate the surfaces of alloy as well as inhibitory. The experiment was conducted in split plot design in time based on the RCD in four replications. ANOVA was performed and comparison of means square using Duncan’s multiple range test at one percent probability level. The highest rate of corrosion inhibition (93.5%) was obtained at a concentration of 1800 ppm with an increase in the concentration of the extract, corrosion inhibition also increased, i.e., more bronze was prevented from burning. Also, the highest corrosion inhibitory activity of Acacia extract (79.66) was in the second week and with increasing duration, this effect has decreased. EDX analysis of the control sample matrix showed that the amount of chlorine was 8.47%wt, while in the presence of corrosive sodium chloride solution, after 4 weeks, the amount of chlorine detected was 3.20%wt. According to the morphology (needle and rhombus) of these corrosion products based on the SEM images, it can be said, they are the type of atacamite and paratacamite. They have caused bronze disease in historical bronze works. The green inhibitor of Acacia fruit aqueous extract can play an effective role in inhibiting corrosion of bronze, but at higher concentrations, it became fungal, which can reduce the role of Acacia fruit aqueous extract and even ineffective. To get better performance of green inhibitors, more tests need to be done to improve and optimize. Keywords: Corrosion, Bronze disease, Green inhibitors, Acacia, Potentiostat, SEM–EDX Introduction to the inhibitor (materials would be expensive if access There are some growing concerns about the use of green is limited), and its environmental friendliness. Inhibi- inhibitors because some of these inhibitors are not only tors are volatile, inactive (anodic), precipitated, cathodic, toxic to living organisms but also cause environmen- organic and inorganic compounds that prevent corrosion tal damage although some be helpful and nontoxic, through adsorbing ions or molecules from the metal sur- they are less effective. When choosing an inhibitor, it is face, increasing or decreasing anodic or cathodic reac- important to consider the cost of the inhibitor, access tion, reducing penetration rate of reactants on the metal surface and the electrical resistance of metal surface [1–3]. *Correspondence: Bfazeli@uoz.ac.ir Inhibitors are generally substances, which reduce the Research Department of Agronomy and Plant Breeding, Agricultural level of chemical reactions at appropriate concentrations. Research Institute, University of Zabol, Zabol, Iran Corrosion inhibitors are active chemical species, which Full list of author information is available at the end of the article © The Author(s) 2021. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/. The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 2 of 14 help slow down, delay or prevent corrosion, via different potential to be a corrosion inhibitor for Cu in acidic envi- mechanisms, such as adsorption onto the metal surface ronment [24]. that blocks active surface sites [4, 5]. These substances The Acacia plant, scientifically named Robinia pseudo - can inhibit the growth of biological agents and stop the acacia L from the Papilionaceae family, is one of the two- physiological processes. The inhibitor at low concentra - celled plants whose beautiful and ornamental flowers tions in corrosive medium delays the corrosion of metals cultivated by beekeepers to produce fragrant honey. The [6, 7]. These substances can be solid, liquid, or gas and flowers have a soothing, stomach tonic effect and astrin - used in closed, gaseous, and aqueous mediums [8, 9]. gent and biliary properties [25]. The Acacia plant (robina Corrosion inhibitors reduce the rate of corrosion in psudoacacia) is a fast-growing tree. It has a broad crown several ways: (i) reduce the adsorption of ions/molecules with leaves consisting of 11–23 dark green oval leaflets. on the metal surface; (ii) increase or decrease the anodic In the roots, bark, and seeds of the Robinia pseudoacacia and/or cathodic reaction; to the metal surface, (iv) reduce L tree, there is a substance called Description Robin, and the electrical resistance of the metal surface [10]. in the leaves and flowers, there is also a glucoside called The effective techniques possible for protection are Description Robinin. Robinia pseudoacacia L wood is modification of metal, design, corrosive environment, hard and durable. For these reasons, it is of industrial and metal environment potential, surface, and the use of commercial importance and is used to build columns and inhibitors. Inhibitors are categorized into methods such scaffolding for mines, as well as to make sofas and chairs as mechanism (anodic, cathodic and mixed inhibitors), [25]. environment (acid, alkali and neutral inhibitors) and The corrosion inhibitory abilities of tannins, alkaloids, mode of protection (chemical, adsorption, film forming amino acids and organic dyes of plant origin are consid- and vapor phase inhibitors) [11]. ered. Although significant research has been devoted to The inhibitory effect of BTA (Benzotriazole) and AMT the inhibition of corrosion by plant extracts, reports on (5-amino-2-mercapto-1, 3, 4-thiadiazole) on historical the exact mechanisms of the adsorption and identifica - bronze art works has been proved previously [12–15]. tion process of the active substance are still scarce [10]. While these inhibitors have high efficiency, they have Therefore, in this study, following various other studies toxic and cancerous impacts on the environment. For this [26], chloride medium has been used to study the cor- reason, green inhibitors such as honey, fig juice [16], the rosion process and based on previous research, it was extract of salvia [17] and green tea extract [18] have been indicated that the general compounds of the Robinia examined and evaluated in recent years. pseudoacacia L fruit extract contain the natural sug- Most organic corrosion inhibitors have heteroatoms. P, ars of ramenoz, arabinose, and galactose, as well as glu- O, N, and S are known as active centers (O < N < S < P) for conic acid, 4 methoxygluconic and rubinin [27–29] and the adsorption process on the metal surface and have a the application of anti-corrosion effect of Robinia pseu - higher electron density. These elements act as corrosion doacacia L fruit extract on mild steel [30–32], the aim inhibitors. The use of organic compounds containing oxy - of this experiment, Robinia pseudoacacia L fruit extract gen, sulfur and especially nitrogen to reduce corrosion was used to evaluate the inhibitory effect on bronze alloy attack on steel has been studied in detail. Most organic (Cu-10Sn). inhibitors are adsorbed by displacing water molecules on the metal surface and forming a compact barrier. Addi- Material and methods tionally, the availability of non-bonded electrons (single Preparation of plant and extract pair) and p in inhibitor molecules facilitates the transfer Robinia pseudoacacia L fruit was obtained from the of electrons from the inhibitor to the metal [10]. Agricultural and Natural Resources Research and Train- Rosemary leaves were investigated as corrosion inhib- ing Center of Isfahan (Fig. 1). itors for the Al + 2.5  Mg alloy in a 3% NaCl solution at Fruit samples collected were dried on a clean cloth and 25 °C [19], and El-Etre studied natural honey as a corro- ground under appropriate conditions. 30  g of the result- sion inhibitor for copper [20] and studied opuntia extract ing powder was soaked in 100  ml of double distilled on aluminum [21]. The inhibitive influence of the extract water and shaken in a shaker for 24  h at room tempera- of khillah (Ammi visnaga) seeds on the corrosion of SX ture. The obtained liquids were passed through sterile fil - 316 steel in HCl solution was determined utilizing weight ter paper (Watman paper No. 1) and finally the extract loss amounts as well as the potentiostatic method.  Delo- and powder were separated. The remaining particles in nix regia extracts inhibited the corrosion of aluminum in the extract were separated using a refrigerated centrifuge hydrochloric acid extracts [22]. Antibacterial drugs were (2500  rpm) at 4  °C for 20  min. The extract was dewa - used as corrosion inhibitors for bronze surfaces in acidic tered using a vacuum rotary device. The obtained extract solutions [23]. The results indicate that Myrrh extract has was turned into powder and stored in a dark glass at a P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 3 of 14 Fig. 1 The characteristic of Robinia pseudoacacia L. plant temperature of 4 °C. During the experiment, dilutions of This alloy was used for the effect of corrosion inhibitors 200 to 1800  ppm (Part per Million) were prepared from in the potentiostat device, the weight loss method. the extract [33]. After preparing the coupons with a percentage of (Cu- 10Sn), the coupons were completely polished using sand- paper with grades 400 to 2200 to create a completely Experimental design smooth surface. Then, the coupons were rinsed with dis - The Acacia fruit extract (200, 400, 600, 800, 1000, 1200, tilled water and degreased by alcohol. The samples were 1400, 1600, and 1800 ppm) was used to the prevention of placed in an oven at 120  °C for 1  h. The coupons were corrosion inhibition of bronze alloy in corrosive sodium immersed in Robinia pseudoacacia L with concentrations chloride solution 0.5  M, for 4  weeks consecutively. The of 1000  ppm for 24 and 48  h. After removing the cou- experiment was conducted in split plot design in time pons, they were dried at room temperature for 1  h and based on a randomized complete design in four replica- photographed to examine the change in appearance color tions. Different concentrations of plant extracts were on the coupon surfaces. included in the main plots and the duration of applica- Sodium chloride (0.5  M) was used to make a control tion of the plant extract was in the sub-plots [34]. solution. This solution was poured into a special con - The Bronze alloy used in this research, was made based tainer at volume of 100  ml. After calibrating, the device on the same percentage as the ancient alloys (Cu-10Sn) begins plotting the polarization curve. In the polariza- (The alloy used in the research, according to the ancient tion curve, the corrosion potential of the control solu- alloys, with 10% tin and 90% copper, was made by cast- tion (Sodium chloride M 0.5) was recorded -243  mV ing and finally analyzed to make electrodes and coupons). (Millivolts). Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 4 of 14 The Acacia fruit extract was separately mixed and treated the inhibitor solution, − 222  mV indicates a shift toward with a corrosive solution of sodium chloride 0.5  M with 21  mV to positive values, which indicates that the type of pH = 5.5, so that its corrosion power could be examined by inhibitor is combinatorial (mixed-type inhibitor (Some the potentiostat device (Table 1) [35]. The corrosion poten - anodic and some cathodic)) (Fig.  2). In addition to the tial of the control solution was obtained − 243  mV. Based change in the potential of corrosion, a slight flow (Slight on the corrosion potential of the sample at the presence of current drop) is seen in the anodic branch. If the potential increases continuously, the curve will be anodic polarization and if the potential decreases continu- ously, the curve will be cathodic polarization. If polariza- Table 1 Analysis of variance of the effect of the aqueous extract tion causes a slight change to the positive or negative, the of Acacia fruit and duration of treatment on the corrosion inhibition of bronze curve will be of the combined (mixed-type inhibitor) polar- ization type [35, 36]. It is related that Potentiodynamic if Source df SS MS F any compounds suppress has both the anodic and cathodic ** Concentration of extract 8 33,320.9 4165.11 134.50 process, it behaves as mixed-type inhibitors [37]. r 3 197.9 65.96 Error r* Concentration of extract 24 743.2 30.97 Calculating the corrosion efficiency using potentiostat ** Week (period of time) 3 11,575.7 3858.58 157.28 device calculations ** Concentration of extract *week 24 16,934.4 705.60 28.76 IE% was used to obtain the inhibitory efficiency percentage Error r* Concentration of extract 81 1987.2 24.53 (Formula 1). In this formula, Icorr is density of the corro- *week 0 sion flow with inhibitory and I is corrosion flow without Total 143 64,759.3 inhibition. CV(r* concentration) 8.12 CV(r* concentration *week) 7.23 I corr − Icorr IE = × 100 (1) ** I corr Significant at one percent level df: Degrees of freedom; SS: sum of Squares; MS: mean sum of squares; F ratio: each F ratio is computed by dividing the MS value by another MS value. The MS value for the denominator depends on the experimental design Fig. 2 Tafel polarization curve of Robinia pseudoacacia L fruit extract at 1200 ppm (A), 1400 ppm (B), 1600 ppm (C) and 1800 ppm (D) in the presence of a corrosive solution of sodium chloride 0.5 Mm P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 5 of 14 The corrosion current density (The corrosion current W inhibitor IE = 1 − × 100 (5) density is determined at a constant pH value of solu- W blank tion using no buffering additives and it was calculated In order to perform the experiment using the classic for the obvious specimen surface area) [38] can be cal- method, the prepared electrodes were cut with a percent- culated from the polarization resistance and the Stern- age of (Cu-10Sn) as round coupons with a diameter of Geary constant and also Rp can be calculated from the 0.73 cm and a thickness of 2 mm. resistance of polarization (Eq. 2) [39]. The coupons were polished using sandpaper with grades of 400, 800, and 2200. The coupons were Rp = corr degreased in alcohol and rinsed in distilled water. The rinsed samples were heated at 80 °C for 1 h in an oven. Then, coupons were placed in a desiccator for 1  h. b ∗ b a c B = (2) Finally, the coupons were weighed to be immersed in 2.303(b + b ) a c Robinia pseudoacacia L fruit extract. The inhibitory ba = slope of the anodic Tafel reaction, when plotted efficiency of the coupons were calculated each week for on base 10 logarithmic paper in V/decade, bc = slope 4 week consecutively (Formula 5). Hence, one of the cou- of the cathodic Tafel reaction when plotted on base 10 pons were removed from the control solution and Rob- logarithmic paper in V/decade, and B = Stern-Gear y inia pseudoacacia L fruit extract each week, after one constant, V. month of immersion (From the first week to the end). In these experiments, corrosion flow density (For - mula 3), corrosion rate, and equivalent weight with Determine the inhibitory efficiency of the Robinia the presence and absence of inhibitor were calculated pseudoacacia L fruit by standard (ASTM (American Society for Testing and In this paper, the potentiostat device, (SAMA 500 elec- Materials), G 102-98) [40, 41]. tro-analyzer system model (SAMA Research Center, Iran), was used to perform experiments to determine the Icorr icorr = (3) inhibitory efficiency of the Robinia pseudoacacia L fruit. It included three electrodes, a platinum auxiliary elec- i corrosion flow density (μ A/cm ); I : corrosion corr: corr trode, a reference electrode of saturated chloride mer- flow (µA); A = contact surface (cm ). cury (calomel) and a bar working electrode [44, 45] with Corrosion rate is calculated based on the following length of 7.5 cm and diameter of 0.73 cm with compound equation of Cu-10Sn). It was polished with sandpaper (grade from 400 to 2200). Each of these experiments was repeated i corr CR = K 1 EW (4) four times. To calibrate the device, the LSV (Liner sweep voltammetry) Tafel-plot technique was used. Addi- −3 tionally, the classical weight loss method, and finally, CR = corrosion rate (mpy); K1 = 3.27 × 10 (mm g/ SEM–EDX (Scanning Electron Microscope-Energy Dis- µA cm yr); ρ = density (g/cm ). persive X-rays), manufactured by Philips Company of the Netherlands. The XL30 model was used to evaluate the surfaces of alloy as well as inhibitory efficiency of the Calculating the classic weight loss Robinia pseudoacacia L fruit [46, 47]. The weight loss method is the simplest method for studying corrosion inhibitors due to the lack of need for device (except for using the digital scale). In this Scanning Electron Microscope (SEM) method, the weight variations of the metal sample are To accelerate corrosion, the samples were transferred calculated before and after exposure to the corrosive to the humidity compartment. Coupons were placed in medium (in the absence and presence of inhibitor). The a relative humidity of 95 ± 2 and a temperature of 25 to time taken for this experiment is long, but as results 30  °C. The samples underwent sodium chloride 0.5  mM of this method are more real than those of the electro- spray based on the standards of ASTMG85 and ISO9227. chemical method, it is still used [42, 43]. The classic Four weeks later, the samples were removed from the weight loss can be calculated based on the IE formula humidifier compartment and examined to evaluate the (Formula 5). In this formula, Wcorr is the weight loss effect of the inhibitor on the coupon surfaces by using of the sample in the presence of the inhibitor and W0 SEM–EDX device. is the weight loss of the sample in the absence of the To determine the size and morphology of the nanopar- inhibitor. ticles produced using electron microscopy, the reaction Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 6 of 14 mixture was centrifuged three times for 15  min at a pseudoacacia L fruit extract was − 213 mV at 1600 ppm speed of 12,000  rpm. Then, a few drops of the resulting that it is showed displacement of 30  mV, compared to precipitate were dried on a piece of aluminum foil at the corrosion solution (Fig.  2C). A slight drop (Slight room temperature and after drying, the SEM photo was current drop) is also observed in the anodic branch. The taken using an electron microscope device (Philips SEM corrosion potential of the Robinia pseudoacacia L fruit machine (model CMC-300 kV, Netherlands)). extract was − 213 mV at 1800 ppm that it is showed dis- placement of 30  mV, compared to the corrosion solu- Statistical analysis of data tion (Fig.  2D). A slight drop (Slight current drop) is also After data collection, analysis of variance was performed observed in the anodic branch. using student statistic 9 software as well as comparison of means square using Duncan’s multiple range test at one The inhibitory efficiency of Robinia pseudoacacia L fruit percent probability level. extract The analysis of variance were shown that the main effects Results (different concentrations of aqueous acacia extract and Polarization evaluation of Tafel acacia extracts duration of treatment) as well as the interaction of the The Tafel polarization of Robinia pseudoacacia L fruit extract and duration were effective on corrosion inhi - extract in 1200  ppm at the presence of sodium chloride bition (P < 0.01) (Table  1). Mean comparison showed 0.5  M, was shown that the inhibitory corrosion poten- that the highest rate of corrosion inhibition (93.5%) tial is − 216 mV. Based on the control solution, inhibitor was obtained at a concentration of 1800  ppm and with chart has a shift of direction to positive values (Fig.  2A). increasing concentration of the extract, corrosion inhibi- In addition to changes in the corrosion potential, the flow tion also increased, i.e., more bronze was prevented from in both the anodic and cathodic branches was decreased. burning (Fig.  3). Also, the highest corrosion inhibitory The Tafel polarization of Robinia pseudoacacia L fruit activity of Acacia extract (79.66) was in the second week extract at 1400  ppm was shown showed that the inhibi- and with increasing duration, this effect has decreased tory solution corrosion potential is − 216  mV, which (Fig. 4). compared to control solution, it has a shift of direction Some traits like corrosion flow, corrosion potential, to positive values (Fig.  2(B)). The corrosion has also had electrolyte resistance, flow density, cathodic and anodic a slight drop (Slight current drop) in the anodic and slope coefficients, and corrosion rate of Robinia pseu - cathodic branches. The corrosion potential of the Robinia doacacia L fruit investigated using Potentiostat device Fig. 3 Mean square of different concentrations of the aqueous extract of Acacia fruit on preventing corrosion inhibition of bronze (Similar letters indicate no significant differences in the treatments under study). Y is equal to the regression equation P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 7 of 14 Fig. 4 The duration effect of Acacia fruit extract on bronze prevents corrosion inhibition (Similar letters indicate no significant differences in the treatments under study). Y is equal to the regression equation (Table 2). As the result, the relationship between poten- The results of the analysis of variance showed that tial, current intensity and corrosion diagram obtained the effect of different concentrations of acacia aque - based on the use of the anodic and cathodic hypertro- ous extract on bronze weight reduction rate was signifi - phy, measuring the potential difference between this cant (P < 0.01). In the study of the weight reduction rate electrode and the reference electrode, as well as meas- method, the results showed that the least weight reduc- uring the anodic and cathodic current intensity. The tion rate occurred at a concentration of 1800  ppm of weight reduction rates of  Robinia pseudoacacia  L fruit Acacia extract (Fig.  5), in general, the alloy weight loss extract were calculated using the data that they were was least with increasing the concentration of Acacia derived from the Potentiostat device (Table 2). extract (Fig. 6). These results are the same as results that The Weight-reduction rate method is the simplest in were obtained by device. the study of corrosion inhibition due to the lack of need for a device. This experiment takes a long time, but Use of SEM to evaluate the performance of acacia fruit because the results of this method are more realistic extract on the surface of coupons than the electrochemical method, it is still used. An aqueous extract of Acacia fruit can prevent corro- sion of bronze using increasing the concentration but Table 2 Calculation of corrosion flow, corrosion potential, electrolyte resistance, flow density, cathodic and anodic slope coefficients , and corrosion rate of Robinia pseudoacacia L fruit with a Potentiostat device Concentration Robinia -E (mv) R (ohm) B (v/dec) B (v/dec) I corrosion (A) i corrosion (A/cm ) Corrosion corr P a c pseudoacacia L (W/V) rate (mpy) –5 –5 Blank 243 800.5 0.060 0.066 2.716*10 6.497*10 28.381 –5 –5 200 ppm 211 1244 0.061 0.084 1.748*10 4.181*10 18.264 –5 –5 400 ppm 228 1315 0.072 0.079 1.653*10 3.955*10 17.276 –5 –5 600 ppm 214 1268 0.061 0.068 1.714*10 4.102*10 17.091 –5 –5 800 ppm 219 1508 0.082 0.090 1.442*10 30,449*10 15.066 –5 –5 1000 ppm 222 1765 0.059 0.072 1.232*10 2.947*10 12.873 –5 –5 1200 ppm 216 1573 0.067 0.095 1.382*10 3.306*10 14.441 –5 –5 1400 ppm 214 1734 0.077 0.108 1.254*10 2.99*10 13.100 –5 –5 1600 ppm 219 1218 0.076 0.104 1.785*10 4.27*10 18.652 –5 –5 1800 ppm 213 1029 0.121 0.117 2.113*10 5.054*10 22.077 Anodic and cathodic slopes were plotted on the anodic and cathodic branches and finally the device automatically calculated these slopes Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 8 of 14 Fig. 5 The weight reduction rates based on 1800 ppm concentration of Robinia pseudoacacia L from 1 to 4 weeks floatation Fig. 6 Different concentrations effect of aqueous extract of acacia fruit on the weight reduction rate of bronze (Similar letters indicate no significant differences in the studied treatments) to confirm the role of the extract, electron microscopy the bronze level and corrosion. The examination of the was used. After removing the coupons from the control surface of the control coupon revealed that it had green (no extract) and aqueous extracts of Acacia fruit, the and localized corrosion products (Fig.  7). However, it coupons were examined under a microscope to check was observed that the surface of the same coupons were P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 9 of 14 Fig. 7 A Coupons in a corrosive solution of sodium chloride 0.5 after 30 days of immersion. ×60 magnification; B coupons in a corrosive solution of sodium chloride 0.5 after 30 days of immersion. ×40 magnification covered after being placed in corrosive solution and works. These corrosion products are concentrated in acacia extract (Fig.  8), and no trace of corrosion prod- the grain boundaries. ucts were observed on the surface of the alloy (Fig. 9). Although the aqueous extract of acacia fruit creates a SEM was used to evaluate and accurately perform this uniform layer, which covers the surface of the alloy and inhibitor on the surface of these coupons. In the SEM prevents the formation of corrosion products on the sur- images of the control coupon (Fig.  10), the corrosion face of these coupons (Fig.  8) the SEM images showed products in the grain boundaries were identified and that grain corrosion was induced in this alloy in the pres- showed the high impact of the corrosive environment ence of acacia extract (Fig.  10). At higher concentrations on this alloy. According to the morphology (needle and of this extract, i.e. from 1000 to 1800 ppm, after immer- rhombus) of these corrosion products, can said that sion of the samples in the presence of acacia extract and they are the type of atacamite and paratacamite that 0.5 M sodium chloride solution, the presence and growth they have caused bronze disease in historical bronze of fungi have been observed, which can cause poor per- formance of acacia extract in the long run. Fig. 8 A Coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1000 ppm after 30 days of immersion. ×60 magnification; B coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1800 ppm after 30 days of immersion. ×40 magnification (B) Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 10 of 14 Fig. 9 A Coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1000 ppm after 30 days of immersion. ×20 magnification; B coupon in the presence of Robinia pseudoacacia L inhibitor with a concentration of 1800 ppm after 30 days of immersion. ×20 magnification Fig. 10 A SEM analysis of control sample versus Sodium chloride 0.5 M corrosive solution; B SEM analysis of coupon surface containing inhibitor at the presence of Sodium chloride 0.5 M corrosive solution EDX analysis of the control sample matrix showed treatment. These fungi can reduce and even ineffective that the amount of chlorine, which is the most impor- the role of Acacia fruit aqueous extract. Green inhibi- tant factor in the destruction of bronze disease, was tors can play an effective role in preventing corrosion. 8.47wt (Fig.  11). Based on the EDX results on the sam- However, to get better performance of these inhibitors, ple containing acacia extract, it can be concluded that more tests need to be done to improve and optimize their the amount of chlorine detected was 3.20wt in the pres- performance. ence of corrosive sodium chloride solution after 4 weeks. These results indicate that the amount of chlorine in the Discussion presence of inhibitor was least (Fig. 12). So far, different results have been reported regarding The green inhibitor of Acacia fruit aqueous extract can the use of plants extract on the prevention of corrosion. play an effective role in inhibiting corrosion of bronze, The extract of Salvia officinalis and its efficiency in cor - but the fungus has grown in the green inhibitor at higher rosion inhibitory investigated in 0.5  M Nacl. The results concentrations and with increasing the duration of indicated that the extract of Salvia officinalis acted as a P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 11 of 14 Fig. 11 EDX analysis of control sample versus Sodium chloride 0.5 M corrosive solution Fig. 12 EDX analysis of coupon surface containing inhibitor at the presence of Sodium chloride 0.5 M corrosive solution Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 12 of 14 cathodic inhibitor and the inhibitory efficiency increased polarized sodium chloride solution [2]. Perhaps the rea- with increasing sage extract concentration. The results of son for not increasing the inhibition of Acacia extract by the weight loss test reported between 32 and 41% [17]. increasing the concentration of the extract to 1800  ppm In this study, the Potentiostat device method and the and the inhibition oscillation between cathode and classic method of weight loss used to determine the effi - anodic is also because the role of cathodic and anodic ciency of corrosion inhibitory. The results shown that inhibition after oscillation in polarized sodium chloride this efficiency in the Potentiostat device method was 92% solution has decreased. However, it can have another but in the classical method was equal to 55% that more reason, such as less absorption power on the bronze has been mentioned than research [17]. Because aca- (Cu-10Sn). cia contained flavonoids and phenolic compounds with In this research, on the bronze surface, there were a complex structure and high molecular weight, it was active cathodic sites in contact with corrosive species, expected to prevent corrosion, but it did not. which results in a vigorous dissolution of bronze. Bronze The inhibitory effect of two natural honeys (oak and surface can be protected against the charge and mass acacia) with a mixture of black horseradish juice on the transfer which causes corrosion by adsorption of the corrosion of tin in aqueous media and sodium chloride green organic components. This result is similar to the solution by weight loss methods and polarization tech- previous research [50]. niques has been studied. The results showed that the The Corrosion Inhibition by Beet Root (BR) Extract yield of acacia honey was lower than oak honey and by was conducted and the results shown that the BR extract 2+ adding black horseradish juice to both honeys, their yield with 50 ppm Zn had about 98% inhibition efficiency to increased. The inhibition efficiency (IE) of all inhibitors carbon steel immersed in well water (a mixed-type effect 2+ examined obtained from both methods used a decrease existed between BR extract and Zn ) [51]. The results in order: chestnut honey with black radish juice > acacia herein indicated that the type of inhibitor was mixed- honey with black radish juice > chestnut honey > aca- type inhibitor. cia honey [48]. It has been found that acacia extract has The acacia leaves extract was used as an eco-friendly less effect than black horseradish extract. In the present inhibitor on mild steel in acidic media and it easily study, acacia extract had a positive effect at 1000  ppm, extractable, extremely inexpensive, environmentally safe but with increasing acacia extract, the corrosion inhibi- and effective in slowing mild steel corrosion which is not tory effect decreased. formerly used in corrosion studies. Hence, the acacia Natural honey has been studied as a corrosion inhibi- leaves extract can be used as a potential corrosion inhibi- tor of carbon steel in high-salt environments. The inhibi - tor in the acidic environment for mild steel [50]. In the tory efficiency has been calculated through weight loss present study, acacia extract had a positive effect but the and static potential polarization technique. The results corrosion inhibitory effect decreased with increasing aca - have introduced natural honey as a suitable inhibitor for cia extract. corrosion of steel in high-salt environments. However, this beneficial effect has been limited to a certain level Conclusion and after a while, due to the growth and development of Given the investigations on Robinia pseudoacacia L fungi, its inhibitory efficiency has been reduced [20]. It is fruit using potentiostat device, it was revealed that Rob- indicated that, after some time, the inhibition efficiency inia pseudoacacia L fruit had inhibitory efficiency at decreased due to the growth of fungi in the medium. 1800  ppm with a corrosion rate of 12.78% is 55% for Because they said that the effect of fungi on the inhibi - bronze alloy with percentage of (Cu-10Sn) and has a tion efficiency of natural honey is markedly decreased in mixed inhibitory effect. In the classic weight reduc - high saline water and also the high concentration of NaCl tion rate, (in which the results are more real than those may retard the growth of fungi [49]. In the present study, in electrochemical methods), the inhibitory efficiency acacia extract had a fungal growth of 1800  ppm, which of Robinia pseudoacacia L fruit was determined to be over time reduced the inhibitory effect. 92%. SEM images derived from the surface of coupons Inhibition of organic compounds such as honey and at the presence of Robinia pseudoacacia L and a corro- rosemary (Salvia rosmarinus L.) on four metals, alu- sive solution of sodium chloride 0.5  M shown a kind of minum, copper, iron and zinc in sodium chloride and segregation on the surface of coupons in the presence sodium sulfate solution has been investigated. The results of a corrosive solution. Based on the experiments per- showed that the inhibitors had no effect on aluminum in formed, it is necessary to add other natural compounds sodium chloride and sodium sulfate solutions. The rea - to this inhibitor for better efficiency so that appropriate son why honey is not inhibited is that honey plays a small and optimal conditions for this type of inhibitor can be cathodic inhibitory role in aluminum when placed in defined. P ourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 13 of 14 5. Al‑Moubaraki AH, Al‑Howiti AA, Al‑Dailami MM, Al‑ Ghamdi EA. Role of One of the points that should be considered during the aqueous extract of celery (Apium graveolens L.) seeds against the cor‑ restoration process is not to change the structure and rosion of aluminium/sodium hydroxide systems. J Environ Chem Eng. appearance of the historical monument. Since corro- 2017;5(5):4194–205. https:// doi. org/ 10. 1016/j. jece. 2017. 08. 015. 6. Olajire AA. Corrosion inhibition of offshore oil and gas production sion in a metal monument, especially copper and bronze, facilities using organic compound inhibitors‑a review. J Mol Liq. has a special place and importance from a historical, 2017;248:775–808. https:// doi. org/ 10. 1016/j. molliq. 2017. 10. 097. structural and sometimes aesthetic point of view. Based 7. Barreto LS, Tokumoto MS, Guedes IC, Melo HG, Amado FDR, Capelossi VR. Evaluation of the anticorrosion performance of peel garlic extract as on our result, it seems necessary to pay more attention corrosion inhibitor for ASTM 1020 carbon steel in acidic solution. Matéria. to the rate of color changes after the application of new 2017. https:// doi. org/ 10. 1590/ s1517‑ 70762 01700 03. 0186. materials. 8. Groysman A. Corrosion for everybody. Springer; 2009. https:// doi. org/ 10. 1007/ 978‑ 90‑ 481‑ 3477‑9 9. Ogawa A, Takakura K, Hirai N, Kanematsu H, Kuroda D, Kougo T, et al. Biofilm formation plays a crucial rule in the initial step of carbon steel cor ‑ Abbreviations rosion in air and water environments. Materials. 2020;13(4):923. https:// AMT: 5‑Amino ‑2‑mercapto ‑1,3,4‑thiadiazole; ANOVA: Analysis of variance; doi. org/ 10. 3390/ ma130 40923. ASTM: American Society for Testing and Materials; BTA: Benzotriazole; EDX: 10. Rani B, Basu BBJ. Green inhibitors for corrosion protection of metals and Energy Dispersive X‑rays; LSV: Liner sweep voltammetry; mV: Millivolts; PPM: alloys: an overview. International Journal of corrosion. 2012. https:// doi. Part Per Million; RCD: Randomized complete design; SEM–EDX: Scanning org/ 10. 1155/ 2012/ 380217. Electron Microscope‑Energy Dispersive X ‑rays. 11. Palanisamy G. Corrosion inhibitors. Corrosion inhibitors: Ambrish Singh, IntechOpen; 2019. p. 1–24. https:// doi. org/ 10. 5772/ intec hopen. 80542 Acknowledgements 12. Faltermeier RB. A corrosion inhibitor test for copper‑based artifacts. Stud‑ We thereby appreciate Dr. Vatan Khah, Dr. Emami and Dr. Abed Esfahani, who ies in conservation. 2013;44(2):121–8. https:// doi. org/ 10. 1179/ sic. 1999. helped us in this research. 44.2. 121. 13. Artesani A, Di Turo F, Zucchelli M, Traviglia A. Recent advances in protec‑ Authors’ contributions tive coatings for cultural heritage–an overview. Coatings. 2020;10(3):217. VP and BFN designed the research and wrote the paper. Both authors read https:// doi. org/ 10. 3390/ coati ngs10 030217. and approved the final manuscript. 14. Faltermeier RB, Archaeology UoLIo. AMT: A New Corrosion Inhibitor? : University College; 1992. p. 44 Pages. Funding 15. Kumara SA, Sankar A, Kumarb SR, Vijayanc M. Asparagus racemosus root Not applicable. extract as corrosion inhibitor for mild steel in acid medium. Int J Comput Eng Sci. 2013;3(1):40–5. Availability of data and materials 16. Pourzarghan V, Sarhaddi‑Dadian H, Bakhshandefard H. Feasibility study All the data is embedded in the manuscript. of natural honey use as corrosion inhibitor in protecting the bronze artifacts. Mediter Archaeol Archaeom. 2017;17(3):301–9. https:// doi. org/ Declarations 10. 5281/ zenodo. 10489 35. 17. Vatankhah GR, Bakhshandehfard HR, Golozar MA, Sabzalian MR. Salvia Ethics approval and consent to participate officinalis extract as a natural corrosion inhibitor for copper alloy artifacts No human or animals were used in the present research. treatment. Sci J Maremat & Me’mari‑ e Iran. 2011;1(1):41–54. 18. Vatankhah GR, Bakhshandehfard HR, Golozar MA, Sabzalian MR. Green Consent for publications tea extract (Camellia sinensis): a non‑toxic plant inhibitor for controlling All authors read and approved the final manuscript for publication. corrosion in historical copper artifacts. Sci J Maremat & Me’mari‑ e Iran (quarterly). 2013;1(4):85–96. Competing interests 19. Kliškić M, Radošević J, Gudić S, Katalinić V. Aqueous extract of Rosmarinus All authors declare no conflict of interest exists. officinalis L. as inhibitor of Al–Mg alloy corrosion in chloride solution. J Appl Electrochem. 2000;30(7):823–30. https:// doi. org/ 10. 1023/A: 10040 Author details 41530 105. Department of Historical Works Restoration, Faculty of Art and Architecture, 20. El‑Etre A. Natural honey as corrosion inhibitor for metals and alloys. I. University of Zabol, Zabol, Iran. Research Department of Agronomy and Plant Copper in neutral aqueous solution. Corrosion Sci. 1998;40(11):1845–50. Breeding, Agricultural Research Institute, University of Zabol, Zabol, Iran. https:// doi. org/ 10. 1016/ S0010‑ 938X(98) 00082‑1. 21. El‑Etre A. Inhibition of aluminum corrosion using Opuntia extract. Cor ‑ Received: 16 April 2021 Accepted: 4 June 2021 ros Sci. 2003;45(11):2485–95. https:// doi. org/ 10. 1016/ S0010‑ 938X(03) 00066‑0. 22. Abiola OK, Oforka NC, Ebenso EE, Nwinuka NM. Eco‑friendly corrosion inhibitors: the inhibitive action of Delonix regia extract for the corrosion of aluminium in acidic media. Anti‑ Corros Methods Mater. 2007;54(4):219– References 24. https:// doi. org/ 10. 1108/ 00035 59071 07623 57. 1. Verma C, Ebenso EE, Quraishi M. Ionic liquids as green and sustain‑ 23. Rotaru I, Varvara S, Gaina L, Muresan LM. Antibacterial drugs as cor‑ able corrosion inhibitors for metals and alloys: an overview. J Mol Liq. rosion inhibitors for bronze surfaces in acidic solutions. Appl Surf Sci. 2017;233:403–14. https:// doi. org/ 10. 1016/j. molliq. 2017. 02. 111. 2014;321:188–96. https:// doi. org/ 10. 1016/j. apsusc. 2014. 09. 201. 2. Yee Y. Green inhibitors for corrosion control: a Study on the inhibitive 24. Al‑Nami S, Fouda AE‑AS. Corrosion Inhibition Eec ff t and Adsorption effects of extracts of honey and rosmarinus officinalis L.(Rosemary): MS Activities of methanolic myrrh extract for Cu in 2 M HNO3. Int J Electro‑ thesis, University of Manchester, Institute of Science and Technology; chem Sci. 2020;15:1187–205. https:// doi. org/ 10. 20964/ 2020. 02. 23. 2004. 25. Liu Z, Hu B, Bell TL, Flemetakis E, Rennenberg H. Significance of mycor ‑ 3. Saeed MT, Saleem M, Niyazi AH, Al‑Shamrani FA, Jazzar NA, Ali M. Carrot rhizal associations for the performance of N2‑fixing Black Locust (Robinia (Daucus carota L.) peels extract as an herbal corrosion inhibitor for mild pseudoacacia L.). Soil Biol Biochem. 2020;145:107776. https:// doi. org/ 10. steel in 1M HCl solution. Modern Appl Sci. 2020;14(2):97–112.1016/j. soilb io. 2020. 107776. 4. Miralrio A, Espinoza VA. Plant extracts as green corrosion inhibitors 26. Scott DA. Ancient metals: microstructure and metallurgy: Lulu. com; for different metal surfaces and corrosive media: a review. Processes. 2011. 2020;8(8):942. https:// doi. org/ 10. 3390/ pr808 0942. Pourzarghan and Fazeli‑Nasab Herit Sci (2021) 9:75 Page 14 of 14 27. Karamalla K, Siddig N, Osman M. Analytical data for Acacia senegal var 41. Tan X, Zhi Q, Yang R, Wang F, Yang J, Liu Z. Eec ff ts of milling on the cor ‑ senegal gum samples collected between 1993 and 1995 from Sudan. rosion behavior of Al2NbTi3V2Zr high‑ entropy alloy system in 10% nitric Food hydrocolloids. 1998;12(4):373–8. https:// doi. org/ 10. 1016/ S0268‑ acid solution. Mater Corros. 2017;68(10):1080–9. https:// doi. org/ 10. 1002/ 005X(98) 00005‑8.maco. 20170 9472. 28. Mohamed AM, Ariffin MAM, Smaoui H, Osman MH. Performance evalua‑ 42. Tang L, Li X, Li L, Mu G, Liu G. The effect of 1‑(2‑pyridylazo)‑2‑naphthol on tion of concrete with Arabic gum biopolymer. Mater Today. 2020. https:// the corrosion of cold rolled steel in acid media: Part 2: Inhibitive action in doi. org/ 10. 1016/j. matpr. 2020. 04. 576. 0.5 M sulfuric acid. Mater Chem Phys. 2006;97(2–3):301–7. https:// doi. org/ 29. Raja PB, Sethuraman MG. Natural products as corrosion inhibitor for met‑10. 1016/j. match emphys. 2005. 08. 014. als in corrosive media—a review. Mater Lett. 2008;62(1):113–6. https:// 43. Pourfarzad H, Shabani‑Nooshabadi M, Ganjali MR, Olia MH. Inhibition of doi. org/ 10. 1016/j. matlet. 2007. 04. 079. acid corrosion of glass ampoule in Pb/HBF4/PbO2 reserve batteries using 30. Buchweishaija J, Mhinzi G. Natural products as a source of environmen‑ nanobis [3‑(trimethoxysilyl) propyl] amine. J Mol Liq. 2020;302: 112578. tally friendly corrosion inhibitors: the case of gum exudate from Acacia https:// doi. org/ 10. 1016/j. molliq. 2020. 112578. seyal var seyal. Portugaliae Electrochimica Acta. 2008;26(3):257–65. 44. de Rooij M. Electrochemical methods: fundamentals and applications. 31. Nasab SG, Yazd MJ, Semnani A, Kahkesh H, Rabiee N, Rabiee M, et al. Anti‑ Corros Methods Mater. 2003. https:// doi. org/ 10. 1108/ acmm. 2003. Natural corrosion inhibitors. Synth Lect Mech Eng. 2019;14(1):1–96. 12850 eae. 001. https:// doi. org/ 10. 2200/ S0091 0ED1V 01Y20 1903M EC018. 45. Bard AJ, Faulkner LR. Fundamentals and applications. Electrochem Meth‑ 32. Mohyaldinn ME, Lin W, Gawi O, Ismail MC, Ahmed QA, Ayoub MA, et al., ods. 2001;2(482):580–632. editors. Experimental Investigation of a New Derived Oleochemical Cor‑ 46. Pourzarghan V, Vatankhah G, Bakhshandeh‑Fard HR. Investigation and rosion Inhibitor. Key Engineering Materials; 2019: Trans Tech Publ. https:// feasibility of using honey as a corrosion inhibitor in the protection of his‑ doi. org/ 10. 4028/ www. scien tific. net/ KEM. 796. 112 torical bronze objects. Isfahan: Master Thesis on Restoration of Historical 33. Fazeli‑Nasab B, Sirousmehr A, Mirzaei N, Solimani M. Evaluation of total Works of Art University of Isfahan; 2010. phenolic, flavenoeid content and antioxidant activity of Leaf and Fruit 47. Goyal M, Vashist H, Kumar S, Bahadur I, Benhiba F, Zarrouk A. Acid cor‑ in 14 different genotypes of Ziziphus mauritiana L. in south of Iran. Eco ‑ rosion inhibition of ferrous and non‑ferrous metal by nature friendly Phytochem J Med Plants. 2017;4(4):1–14. ethoxycarbonylmethyltriphenylphosphonium bromide (ECMTPB): 34. Goss‑Sampson M. Statistical analysis in JASP: A guide for students: JASP; experimental and MD simulation evaluation. J Mol Liq. 2020;315: 113705. 2019. https:// doi. org/ 10. 6084/ m9. figsh are. 99807 44https:// doi. org/ 10. 1016/j. molliq. 2020. 113705. 35. Allen JB, Larry RF. Electrochemical methods fundamentals and applica‑ 48. Radojčić I, Berković K, Kovač S, Vorkapić‑Furač J. Natural honey and black tions: John Wiley & Sons; 2001. ISBN: 0‑471‑04372‑9 radish juice as tin corrosion inhibitors. Corros Sci. 2008;50(5):1498–504. 36. Li Y, Xu N, Guo X, Zhang G. Inhibition effect of imidazoline inhibitor on https:// doi. org/ 10. 1016/j. corsci. 2008. 01. 013. the crevice corrosion of N80 carbon steel in the CO2‑saturated NaCl solu‑ 49. El‑Etre A, Abdallah M. Natural honey as corrosion inhibitor for metals and tion containing acetic acid. Corros Sci. 2017;126:127–41. https:// doi. org/ alloys. II. C‑steel in high saline water. Corros Sci. 2000;42(4):731–8. https:// 10. 1016/j. corsci. 2017. 06. 021.doi. org/ 10. 1016/ S0010‑ 938X(99) 00106‑7. 37. Wang H‑L, Liu R‑B, Xin J. Inhibiting effects of some mercapto ‑triazole 50. Yüce AO. Corrosion inhibition behavior of Robinia pseudoacacia leaves derivatives on the corrosion of mild steel in 1.0 M HCl medium. Corros extract as a eco‑friendly inhibitor on mild steel in acidic media. Met Mater Sci. 2004;46(10):2455–66. https:// doi. org/ 10. 1016/j. corsci. 2004. 01. 023. Int. 2020;26(4):456–66. https:// doi. org/ 10. 1007/ s12540‑ 019‑ 00509‑7. 38. Rybalka K, Beketaeva L, Davydov A. Determination of corrosion current 51. Selvi JA, Rajendran S, Sri VG, Amalraj AJ, Narayanasamy B. Corrosion density by the rate of cathodic depolarizer consumption. Russ J Electro‑ inhibition by beet root extract. Port Electrochim Acta. 2009;27(1):1–11. chem. 2016;52(3):268–72. https:// doi. org/ 10. 1134/ S1023 19351 60300 95.https:// doi. org/ 10. 4152/ pea. 20090 1001. 39. Standard A. Standard practice for calculation of corrosion rates and related information from electrochemical measurements. Annu Book Publisher’s Note ASTM Stand ASTM Int West Conshohocken PA. 2006;3:G102–89. https:// Springer Nature remains neutral with regard to jurisdictional claims in pub‑ doi. org/ 10. 1520/ G0102‑ 89R15 E01. lished maps and institutional affiliations. 40. Dean S. Calculation of alloy equivalent weight. Mater Perform. 1987;26(12):51–2.

Journal

Heritage ScienceSpringer Journals

Published: Jun 18, 2021

Keywords: Corrosion; Bronze disease; Green inhibitors; Acacia; Potentiostat; SEM–EDX

There are no references for this article.