Journal of Bio- and Tribo-Corrosion (2022) 831 hetps:/do rg/10.1007/s80735-022-00630-y “nc Corrosion Inhibition of Carob Pod Pulp (Ceratonia siliqua L.) on Carbon Steel Surface C38 in Hydrochloric Acid |. Ghazi"?© . M. Zefzouf? - M. Siniti'-R. Fail? H. Elattari? Received: 10 November 2021 / Revise: 24 December 2021 / Accepted: 4 January 2022 / Published online: 13 January 2022 ‘©The Authors under exclusive licence to Springer Nature Switeriand AG 2022 Abstract ‘The effect of C. siliqua pulp corrosion inhibition on carbon steel has been studied by gravimetric testing and electrochemi- cal methods. In this study, two raw extracts were prepared from the pod pulp of C. siliqua: the first is methanolic and the second is aqueous. The UHPLC/DAD analysis indicated gallic aci'’s presence in the extracts (methanolic and aqueous) of . siliqua as a major compound. The inhibition results achieved revealed that the aqueous extract with gallic acid had a good anticorrosion activity with an inhibition rate of 91.32% at 3 g/l fora temperature of 323 K. Potentiodynamie polarization was, performed in | M HCI without and with different concentrations of C. siliqua extracts clearly proves that inhibitor extracts behave as mixed type. Adsorption of this inkibitor for different extracts studied on the surface of the carbon steel obeys Langmuir adsorption with negative values of AG" ,, suggesting a stable and spontaneous inhibition process. Keywords Carbon steel » Corrosion - Gravimetric «Inhibition » Ceratonia siliqua 1 Introduction ‘The study of carbon steel corrosion in HCI acid solution has grown relevant, owing to the numerous industrial applica- tions of acid solutions, particularly in pickling, rescaling, and cleaning of steel surfaces [!]. Therefore, steels and its alloys dissolve considerably when exposed to acid solutions or aggressive environments. Therefore, these acids cause the degradation of metals, which leads to the problem of corro- sion, which is a very common problem, dificult to eliminate completely. Stee! dissolution and consumption are controlled using inhibitors, In general, inhibitors are organic molecules that contain oxygen, sulfur, and nitrogen atoms [210]. The 1. Ghazi and M.Zefzouti have contributed equally to this Work. 2 Gna ingss0100@ hotmail fe Research Team “Thermodynamic Catalysis and Surfaces” Department of Chemisry. Faculty of Science, University ‘of Chouaib Doukkali, BP: 20, 24000 Eladida, Morooce Laboratory of Coordination and Analytical Chemisty Department of Chemistry. Faulty of Science, University fof Chowaib Doukkali, BP: 20, 24000 El Jada, Moraceo Laboratory of Bioorganic Chemisty, Department ‘of Chemisty, Faculty of Seienee, University of Chousi Doukkali, BP: 20, 24000 El Jadida, Morocco presence of attractive interactions between the corroding, surface of metal and the adsorbate is required for adsorption. Adsorption can be classified as physisorption, chemisorp- tion, or a mixture of both depending on the type of forces involved [11-14]. Functional groups, steric factor, and aro- ‘maticity are all factors that influence the adsorption behavior of organic molecules [15]. A large number of organic syn- thetic inhibitors are highly toxic and, therefore, have nega tive consequences on humans and the environment [16] and can cause temporary or permanent damage to organ systems such as kidneys or liver. or disrupt the enzyme system in the body [17]. Nowadays, research interests are directed towards the application of green inhibitors (i.e., environmentally friendly compounds). Therefore, the inhibitor used must be cost effective and also readily available. Furthermore, due to recent environmental awareness and restrictions, the inhibitor must be non-toxic and biodegradable [18]. As a result, plant extracts are increasingly being considered as 4 source of corrosion inhibitors. They are used for metal protection in acidic environments to replace the toxic chemi- cals currently used [19]. The inhibitory performance of plant extracts is generally linked to the presence in these extracts of primary metabolites such as sugars, proteins, or lipids but above all, to the presence of secondary metabolites such as, alkaloids, polyphenols, and terpenoids. These metabolites, contain polar functions with oxygen, sulfur, nitrogen atoms springer31_Page 20f23 Journal of io-and Tibo-Coresion (2022) 831 and double- or triple-conjugated bonds with aromatic rings, ‘which are the principal adsorption centers in their chemical structures (20, 21). Several studies have been published on the use of vari ‘ous plant parts such as leaves [22], fruits (23], seeds [24], and flowers [25]. They have been extracted by simple low= cost procedures and studied as corrosion inhibitors in dif- ferent media; for example, Prabha etal, [26] have studied the corrosion inhibition of mild steel by aqueous extract of Andrographis paniculata. A leguminous plant of Retama ‘monosperma Was used as a corrosion inhibitor of carbon steel in 1 M HCI solution by El Hamdani etal. [27]. Kathi ravan et al, [28] studied the inhibitory action of aqueous. extract of Ruellia tuberosa leaves on copper corrosion in 0.5 MHI. Carob (C. siligua) isa tree that has been popular in the Mediterranean region. Itis a member of the Legume family (Fabaceae) [29]. After the seeds have been removed. from the fruit pod, carob powder is obtained [30]. The pulp (90%) and seeds (10%) are the main components of carob pod by weight (31]. In fact, the pulp of carob has been used. for centuries in human nutrition, ie., to prepare cakes, bread and flakes [32, 33] chocolate, cookies and as a substitute for cocoa, cereal bars, ice ereams [34, 35], as well as in animal feed (horses, ruminants) (36] alongside other feeds such as barley flour [37]. The pods, after removal oftheir seeds, are used mainly in the food industry [38] as an antioxidant due to their rich polyphenols composition. Numerous clinical studies have highlighted the effectiveness of carob powder in the treatment of acute childhood diarthea [39]. According to Rejeb [40]. the pulp is recommended against pulmonary tuberculosis and bronchial affections. This plant is known in therapeutics for its hypocholesterolemic effect, antiproif- erative, antidiarrheal, and digestive disorders [41]. The high fiber content of carob suggests that it could reduce blood cholesterol levels [42 The carob pods have a high concen- tration of condensed tannins (16-20%), which are composed of lavan-3-ol groups and their galloyl esters [43. 44], gallic acid [45, 46], (+)-catechin, (~}-epicatechingallate, (~)-epi- Hlocatechingallate, and quercetin glycosides [47] ‘As for gallic acid, 3.4.5-trihydroxy benzoic acid is a tri phenolic acid, colorless, or slightly yellow. is widely pre- sent in the plant kingdom as a secondary metabolite and. ‘widely present in free form or as a derivative in various food sources such as nuts, tea, grapes, and sumac (Rhus coriaria L.) [48-50], Other sources include gallnuts, oak bark, honey, various berries, pomegranate, mango and other red fruits, beverages [51-54], and vegetables especially in black radish and onions [55]. Gallic acid is found in plant tissues as an ester and various esters with sugar glycosides, polyols and. phenols [56]. It is a proposed reductant in dilute chemical decontamination formulations due to its inherent stability against radiation degradation [57]. Gallic acid significantly slows down-scale formation and, thus, has been shown to be © springer an effective scale inhibitor at very low concentrations [58] Ithas a wide range of applications in the health, food, and pharmaceutical industries, in the manufacture of inks, paints, dyes, and also in cinematography [59 In fact, it seems to have an antiasthmatic effect (60] and inhibits the formation ‘of esophageal cancer in rats (61) It has @ eytotoxie activity against cancer cells (leukemia, prostate cancer, lung cancer) [62]. Kratz et al. [63] showed that gallic acid had anti-viral activity against the herpes virus HSV-2, Purther, Umar el [64] revealed that gallic acid is used as a therapeutic com- Pound and an inhibitor against five key non-structural pro- teins in the recent coronavirus epidemic caused by the novel coronavirus SARS-CoV-2. In addition, gallic acid has been shown to be a protective antioxidant for plants against envi- ronmental aggression (‘emperature, light) or pathogens. Itis used in routine tess asa reference substance in antioxidant activities [65] and also shows a higher antiradical activity than ascorbic acid or oxalic acid (66), It is more recommended that gallic acid itself can also be useful as a corrosion inhibitor in the decontamination process: this can avoid the addition of another component in the formulation as a corrosion inhibitor [67]. Galle acid is used as a non-toxie corrosion inhibitor for steel structures instead of toxic lead oxide (or ed oxide). The possibility of covering the steel surface with an insoluble gallie acid-iron complex can be one of the reasons for corrosion inhibition [68]. In gold electroless plating studies with a 1,2-hydroqui- none fraction, galic acid due to its high reduetion potential ‘was found to adsorb onto the metal surface and function 4s a corrosion inhibitor [69]. Obot et al. [70] studied the corrosion-inhibiting effect of tannic acid in the presence of gallic acid at the mild steeV/HCI acid solution interface: indeed, the inhibition effect of tannie acid is enhanced by its combination with gallic acid. As well as a suitable inhibitory characteristic of gallic acid was found to be equally effec~ tive in the inhibition properties of henna extract by Ostovari etal. [17]. The objective of this research was to investigate the effects of inhibition of C. siliqua pulp of extracts (ague- ous and methanolic) both without and with gallic acid on carbon steel corrosion C38 in 1 M HCl. The performance of inhibition is analyzed by weight loss, potentiodynamic polarization, as well as impedance spectroscopy. The inhibi- tor's adsorption isotherm on carbon steel was determined. 2 Materials and Methods 2.1 Preparation of Specimens and Solutions ‘Throughout the experiments, carbon steel was employed. The specimens of carbon sel used in this study are rectangular in shape (4% 1 cm?) and contain the following composition:Journal of Bio- and Tribo-Corrosion (2022) 831 Page3of23_ 31 (C=0.38%, Mn=0.68%, Si=0.23%, $=0.02%, P=0.001%) and the remainder of iron, Analytical Grade 37% HCI was diluted with distilled water to prepare the aggressive HC1 acid solution | M. All ofthe studies were done in 1 M HCL solution in the absence and presence of various inhibitor concentrations (0.5; 1; 15:2; 2.5; and 3 gf 2.2 Preparation of Plant Extracts ‘The dried carob pods of C. siliqua were collected in July 2017 in the northwest of Morocco (Gharb-Chrarda ouez~ zane). The samples were deposited in the Bioorganic Chemistry Laboratory at Chouaity Doukkali University in EL Jadida. In the laboratory, the pulp was separated from the seed of the pods; the different parts of C. siliqua pulp were crushed in a fine powder mortar. 2.2.1 Methanol and Water Extracts ‘The vegetable material to be extracted was weighed (60 g) and placed in the Cartridge of Soxhlet. The distilled metha- nol (250 ml) was introduced to the flask, which was then heated to begin the extraction process until the plant was Genistein totally exhausted, A 46 h time was spent extracting the plant with methanol. For the preparation of the aqueous extract, the same quan tity of crushed pulp (60 g) was extracted until exhaustion, for a period of 28 h by following the same extraction technique (Soxhlet). ‘The resulting liquid extracts were then concentrated using a rotary evaporator to give 29.42 g and 30.14 g of metha- nolic and aqueous extracts, respectively. These two extracts of the plant were used to prepare the concentrations men- tioned above, Figure 1 depicts the chemical structures of some active components found in C. siliqua extracts (metha- nolic and aqueous). 2.3 UMPLC/DAD analysis The studied extracts were subjected to UHPLC-DAD analysis. The phenolic compounds were identified as previously explained by Puigventos et al. [72] Liquid chromatography system (Dionex Ultimate 3000, CA, USA), equipped with an autosampler (WPS 3000 TSL), a quaternary pump (HPG 3400 RS), and a column oven (TCC 3000). A Kinetex C18 reversed phase column om J a ee ; ie. or Ty : oy Gallic acid .4.5-triydroxybenzoic acid) Fig.1| Some secondary metabolites separate from C siligua extracts [71] 131_ Page 4of23 Journal of io-and Tibo-Coresion (2022) 831 (2504.6 mm, 2.6 4m particles) provided by Thermo Fisher Seientific (CA, USA) was used for the proposed ‘method. The solvent was used to create a gradient separa- tion A (0.1% formie acid aqueous solution) and solvent B (methanol) as follows: 0-3 min, linear gradient from 5 to 25% B; 3-6 min, at 25% B; 6-9 min, from 25 to 37% B; 9-13 min, at 37% B; 13-18 min, from 37 to 54% B; 18-22 min, at 54%B; 22-26 min, from 54 to 95%B: 26-29 min, at 95% B; 29-29.15 min, back to initial con- ditions at 5% B; and from 29.15 to 36 min, at 5% B. The mobile phase flow rate was I ml/min. The DAD detector Dionex Ultimate 3000 was detected at 280 nm. Retention times and UV spectra were compared to standards to iden- tify the compounds investigated in the extracts (aqueous and methanolic). All eleven standards used for analyses were obtained from Sigma-Aldrich (Berin, Germany); stock solution: gallie acid, eatechine, Chlorogenic acid, Epicathechine, vanillin, x-Coumaric acid, Sinapic acid, naringine, Rutin, quercetin, and kaemplerol. Three series and repetition of stock solution standars at S concentra- tion levels were used (10, 50, 100, 150 and 200 mg/t) for this quantitative analysis. 2.4 Gravimetric Method ‘The specimens were abraded using an emery papers collec- tion (grades 360: 400; 600; 1200; 1500: 2000), then fully cleaned with acetone and distilled water and dried. At ‘a constant temperature regulated by a water thermostat, the specimens were immersed in (30 ml) vials containing acid 1M HCI without and with varying concentrations of the inhibitor being studied. The specimens were abducted after Gh, rinsed, dried, and precisely weighed. The experiments were then carried out at various temperatures. Equation (1) is used to compute the weight loss A,, (mg): 4, by = = My w where m is the starting weight before immersion and m, is the final weight after immersion, Equation (2) is used to get the corrosion rate (w: vw(mg/em? h) = ,/s4 @ Sis the geometrical surface area (Cm?), and 1 is the corrosion test period (h), ‘The inhibitory efficieney £ (%) was estimated using the following formula (3): EG) = [079 ~ Wg] X 100, ° ‘where wg and Wg, are, respectively, the corrosion rates with- cout and with ©: siliqua inhibitor. © springer 2.5 Electrochemical Method The samples of steel 1 em? are prepared as described above (Section gravimetric determination) and were first immersed into the solution for 30 min to establish a steady-state open-circuit potential. Platinum electrode and a saturated calomel (SCE) electrode were used as auxiliary and reference electrodes, respectively. The material used is potentiostat/galvanostat/PRA, SP 200 EC-Lab Research Grad type. EC-Lab software was used to examine the data The effect of inhibitor on stel corrosion was determined bby measuring corrosion rate indifferent concentrations of the pulp of C siligua. For the evaluation of inhibitor co centration effects on inhibition efficiency (the protection of corrosion), experiments were carried out in the pres- ence and absence of HCI I M of various concentrations of| inhibitor. At normal temperature (25 °C), the cell was eft exposed to the air. Curves of potentiodynamie polarization in the potential range between + 10 (V) relative t0 the Eycy ‘were obtained after measuring the potential in an open circuit at a scan rate of 1 (mY 5“). Values of corrosion current densities were obtained by extrapolating the tafel lines (anodic and cathodic). The efficiency of inhibition BC is defined as follows: E(%) = [1-8/0 J] > 100, my where if, and ih, reflect values for current densities of corrosion without and with inhibitor, respectively, Spec- twoscopy of electrochemical impedance technical (EIS) was carried out in the presence of open-cireuit potential atthe frequency ranges between 100 (kHz) and 10 (mHlz), with a 10 mV change in signal amplitude. The following equation is used to calculate inhibition efficiency E(%) E(%) = [iw — Ry/R"] x 100, 6) where RI and R?, are resistance to charge transfer in the presence and abserice ofthe inhibitor, respectively. 2.6 Fourier Transform Infrared Spectroscopic (FTIR) Analysis Fourier transform infrared spectroscopy (FTIR) was stud~ ied in the frequency range 400-4000 Cm" for the solu- tion of | MHCI+3 gil of C. siligua and specimen before and after the corrosion test by using a SHIMADZU FTIR 8400S spectrometer with a Smart iTR Attachment and diamond attenuated Total Reflectance (ATR) crystal. The immersed was for 24 h in 298 K. The experimental data are analyzed by OMNIC softwareJournal of Bio- and Tribo-Corrosion (2022) 831 PageSof 2331 2.7 X-ray Diffraction Analysis X-ray diffraction (XRD) analysis was performed with a BRUKER X D8 ADVANCE-ECO. Metal specimens pre- pared were immersed in solutions for a period of 6 h at 303 K, and the patterns of the phases/films on the prepared steel surface before and afer immersion in I MHI, without and with 3 g/l of C. siliqua aqueous extract in the absence and presence of gallic acid were identified using PANalyti- cal HighScore plus, The XRD patterns were recorded in the angular range of 20 from 10° to 70° with step size 0.06° and scan step time 1.0 (5). 2.8 Scanning Electron Microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) analysis The metal specimens prepared were immersed for a period of 6h in 1 M HCL without and with 3 g/l of C siligua aque- ous extract at 303 K in the absence and presence of gal- lic acid and then were removed carefully and thoroughly washed with distitled water and then dried properly. SEM images were taken using HITACHI $-570 model scanning electron microscope and the compositional alteration of the elemental exposed surface was examined via energy dis- persive X-ray spectroscopy (EDS) using X-FLASH 6/10 BRUKER with an accelerating voltage of 20 kV. 3 Results and Discussion 3.1 UHPLC/DAD Analysis ‘A method coupling chromatography with ultra-high-perfor- ‘mance liquids (UHPLC) with diode-array detector (DAD) ‘was optimized for the separation and identification of phe- nolic compounds in the extracts (aqueous and methanolic) of C. siliqua, The results showed that regression curves of each compound phenolic were discovered to be linear with R? greater than 0.99, In the present study, the analysis by UHPLC/DAD/ ESI-MS showed some similarity of the chromatographic profiles obtained for methanolic (a) and aqueous (b) extracts. In particular, we can note the predominance in the two extracts of the peak eluted at 6.5 min (Fig. 2 and Table 1), As can be seen from the three chromatograms (Fig. 2), the major compound in the two studied extracts is gallic acid (peak 1); the content of this phenolic acid in methanol extract and the aqueous extract is $7.71 and 54.61 mgig of extract, respectively. When we compared our results with the literature, we found it similar, Fadel et al. [73] reported that the pulps and seeds of C. sifiqua growing in Morocco are rich on many phenolic compounds such as gallic acid (17.8% and 5.01%, respectively). Also, Yajedd et al. (74] revealed that the C siliqua growing in Algeria contained five phenolic acids among them gallic acid (27.84%). Recently, Goulas and Georgiou [75] determined the presence of gallic acid in the Carob fruits growing in Cyprus. Peak numbers correspond to those represented in Table | 3.2 Weight Loss Method Table 2 describes the corrosion rate obtained using th tech- nique of mass loss at various concentrations of different C. siliqua pulp exirats ina solution HCI for 6 hat temperatures ranging from 298 to 323 k. Table 2 shows that the corrosive attack of acid on the carbon steel at all temperatures studied in the absence ofthe inhibitor is to high for all the extracts studied, because of the very aggressive nature of the chlo- ride ions. Table 2 demonstrates thatthe corrosion rate ofthe cat= bon steel in HCL M., without and with C sitigua extracts obeys the Arrhenius-type reaction, because it increases with increasing the temperature of the solution. A remarkable decrease in the rate of corrosion of the carbon steel was observed with the addition of an inereasing quantity of C siliqua extracts, at each of the studied temperatures. The existence of heteroatoms like oxygen and x-electrons in the heterocyclic ring system in the molecules of C. siligua may account forthe good inhibitive performance observed in this study Which facilitates the coordination interaction with iron ‘atoms and leads toa high tendeney for protonation in acidie medium, Table 3 lists the values forthe inhibition efficiency of carbon steel corrosion in HCI. The data obtained in this lable show that, forall the extracts studied, the efficiency of inhibition inereased as the inhibitor concentration was raised. This suggests that some ofthe inhibiting molecules in the extracts have been adsorbed to the metal surface at a high concentration, leading to higher coverage and, thus, protect- ing the surface from further corrosion attacks. These results are in agreement with the studies carried out on the extract from the Petersianshus macrocarpus plant in 1 M HCl {76} Moreover, for extracts (methanolic and aqueous). the effi ciency decreases when the temperature is increased. This phenomenon can be explained by desorption of the mol- ecules [77]. which can be attributed to the breakdown of| the physical interactions at high temperature between the adsorbed molecules of the extract and the metal surface ‘The same results were obtained by the extract of Ceraronia siliqua used in nitric aid as a corrosion inhibitor of eopper and brass [78], as well as inthe study conducted by Chetira etal. [79] on the extract of Origanum elongatum used as a green corrosion inhibitor of steel in acid medium, the same adsorption behavior was obtained. ‘The value of the inhibition efficiency reached 90.17% at 298 K and 3 gl for the aqueous extract of C. siligua, indicat- ing thatthe adsorption of molecules is lower in C. siliqua springer31_ Page 60f23 Journal of i and Tibo-Corrsion (2022) 831 | i ed i ee 4 rBnae| TOE ee Rian wee es | ee j 2 } | 4 a | | | ; li ys | Fig.2. Chromatographie profiles of methanolic extract (a), aqueous extract of siiqua (b, and sock solution standards (e) recorded at 280 nm ‘methanolic extracts than in aqueous extracts, It is clear that from Table 3 in extracts (methanolic and aqueous) with gal- lic acid, the values of inhibition efficiencies £(%) increase as the temperature rises (298-323 k). This further confirms the increase in inhibitory effectiveness as concentration of the extract rises. This can be related to the increase in protective springer inhibitory film formed on the carbon steel surface at higher temperatures. The highest inhibition efficiency was 91.32% at 323 k and 3 gil for the aqueous extract of C.siliquay indi- cating that gallic acid can be attributed as the main constitu- ent, responsible for the inhibitory action against corrosion. In effect, gallic acid was also found to be a good corrosionJournal of Bio- and Tribo-Corrosion (2022) 831 Page70f23_ 31 Table 1 UHPLCD-DAD analysis of Csiiqua extracts and stock solution of tandars aD ‘Standards UHPLC-DAD _ Methanolic Aqueous Linear equation ® Aug (00) mg/g extracts RSD 1 647 Galicacid 2m 87712004 S4614008 =10SA0T— $61.69 0.996 2 1098 Catechine 2 7 . 106S44¢~ 185759 0,998 3 1205 Chlorogenic acid 280,327 - _ 108.332 229663 0,998 4 13.68 —_Epicathechine 279 - : 106.25¢— 1365.1 0.996 5 1386 Vannlic acid 261, 300 7 : y=l07592e— 24738 0.904 6 1859 x.Coumaricacid 310 7 . y=109.988r— 32984 0.995 7 18.94 Sinapic acid su 7 . y=106585¢— 15576 0.995 8 2051 Naringine 284,320 : . ¥=106,101x~ 1164 0996 9 2169 Rutin 257, 356 7 : y=lO7I83¢— 21163 0.904 10 2662 Quercetin 255, 368 7 ] y=l14.660%— 49477 0997 M2756 Koempferol 266, 366 7 . y= 106325"— 1365.1 0.996 Table2 Carbon stel's corrosion rate obtained by gravimetric in HCL TM without and with various concentrations of C. signa exteact at 298 to 323 ke aextract of methanol without gallie acid; b-extract of aqueous without gallic acid; c-extraet of methanol with gallie ‘extract of aqueous with gale acid Table3 Inhibition efficiency of carbon steel in HCL 1M solu- on alter altions of corrosion inhibitor at dillrent temperatures: ‘extract of methanol without gallie acid; bextract of aqueous with ‘out gallic acid; c= extract of methanol with galic acid: extract of aqueous with gli acid cen mek 33K 33K 323K Ce) 28K 303K 313K 3K Bone (O.SS4——02625—«O8SB | L.AIAS a Blane . 2 2 2 os 00837 NIST 2916 as791 OS on SATB 41s S785 1 00395 0.1062 .1979 ses 70.82 5954 60.08 30.17 15 00354 = 0s9s ITS 07604 15 7385 659 687 4624 2 00333 0791s 06x95 734 6986 69.34 51.25 25 00291 00687 01228, owI2 2S 785 7382 7521 Sind 3 02s 0.05 oulod 065833 8153 x05 ne 5346 Blane 0.4608 S723. «1.2377 1.8259 Blane - - - a os 0.421 02193697 asHRD OS 09.16, 61.68 4.46 Assi 1 0.1299 © 02181 0S8% osm? 7181 6189 5495 S08 1s 0402 ls?S- Ss os2e2 ass 739 123 132 $677 2 0.1017 0167904963009 7793 70.66 399 6161 25 00s O1SID 08D RSS Ba.8s 73.45 65.35 eo 3 00s ONS 3T3B wa 90.17 80st 8 6476 Blane 0.2687 = 0.9021 1.2479 1.6062 Blane . Ss . 2 os 0182s 0514662082 39582 42.95 025 7 1 bass 04s ose oat 4265 sot 55.09 «ast 15 0.1306 03937 OaTOR SMI LS 4804 5636 27 68.74 2 O27 0347903735462 52.69 6143 6962 7713 23 0.1229 030830386284 34.26 6382 as 2 3 0.1208 0285402604 at 55.08 68.36 013 sug Blane 02187 0243703079 LRT Blane 7 . - - 05 0.108 0.229916 osa7S OS 4476 4957 S185 63.86 1 11S O16 070803396 4856 5297 S707 TT 1s 00979 oz OsS$ OTE 55.23 581 6597 701 2 o0si2 0089 0.1083. 0.2858 2 6287 6323 7278 so. 25 0.075 a7 On 0246s 25 6571 68.36 74.86 8557 3 0.0687 007080072923 6858 Joos S168 91.32 springer31_ Page 8of23 Journal of io-and Tibo-Coresion (2022) 831 inhibitor of aluminum 6061 in alkaline solutions by the study conducted by Ali et al. [80] 3.3 Electrochemical Polarization Results ‘The polarization curves without and with C. siliqua extracts at different concentrations in HCL I M at 303 K are shown in Fig. 3. Based on the results obtained, it can be noted that the addition of C. sitiqua extracts leads to a decrease in densities of anodic and cathodic currents and displaces the corrosion potential (E.y,) owards the more negative values (cathodic) ‘The evolution of the loglayq) = flEgqn) curves according to the concentration of C. siliqua extracts is substantially identical. The cathodic polarization curves ate represented by straight lines indicating that the reaction of hydrogen reduction at the surface is performed by a pure activation mechanism [81]. The values of the electrochemical param eters obtained by the polarization curves without and with different C. siliqua extracts are veported in Table 4. Based on the results obtained from the table above, it can be noted that the corrosion potential Ezor, Values for all C. siliqua extracts change slightly with concentration, indieat- ing that these extracts inhibit cathodic and anodi and, therefore, these C. siliqua extracts can be classified as c reactions Fig.2. Polarization curves of as seein 1M HCI containing diferent concentrations of C siiguaextrct: a extract of methanol without galic acid; extract of aqueous without gal- ‘cid € exact of methanol with gale acids d extract of, aqueous with gallic acid ‘mixed type but preferably as cathodic inhibitor against cor rosion of carbon steel C38 in a solution of HCL M. The same observations were obtained by the work of El Ham dani et al. [27] that tested the alkaloid extract of Retama ‘monosperma as an inhibitor for the corrosion of carbon steel in HCI 1 M solution. In addition, corrosion current densities (igg,) decrease when concentration of all extracts increases. This deerease i likely due to adsomption of C.sili- «qua extracts on the metal surface [82]. The study in Table 4 showed that B, values are approximately constant in the pres- cence of different C. siligua extracts while values change, this shows that anodic and cathodic reactions are carried ‘out but thatthe effect on cathodic reactions is greater. These results are completely in accord withthe work carried out on the extract of Artemesia herba albamedium used as corro- sion inhibitor of stainless steel in solution 1 M HPO, [83] Itis also noted from the results thatthe inhibitory efficacy () increases with the increase in the concentration of siliqua extracts. The highest inhibition value was obtained for the concentration of 3 g/l (90.44%) and (91.27%) for extracts (methanolic and aqueous) with gall acid, resp tively. The values of inhibition efficiencies, calculated from polarization studies, show the same trend as those obtained from weight loss measurements. A comparison of our results, © springerJournal of Bio- and Tribo-Corrosion (2022) 831 Page9of23_ 31 Table 4 Electrochemical parameters for various concentrations of C. siigua extract obtained via polarization curves: s-extract of methanol without galle acid; b-extract of aqueous without gallic acid e-extact ‘of methanol with gallic aid d-estract of aqueous with galic acid CED Ee (OW ag Py vlee) fy (mvdeod s) ‘Blane M080 675064 OLS 05 378353. 3IT8M 52.96 233. 1769) 1 40220294251 S645 482 166.9 15 409536282833 Sed 422 Mars 2 -AI8313 26684 OSI 48.1 135.7 25 -403.765 257.903 61.83 44.9 1521 3 436604 221.374 6723. S18 Isa b Blone 313208 938576 - 752 UTS os 487.688 4804 669 162.1 1 3e2914 59.2774 166.8 15 -852314 368.664 60.72 949 bs 2 362.610 349.341 62.78 74.4 1307 409.536 261,968 72.09 66.4 152.1 3 “419674 49.541 8407 638 US © Blane 315256 136396 — 66 28 05 344327 166907 43.77 196 1354 1 “380.192 655963 S191 849 169.2 1S 365322 BSS 7843 24 1437 2 410303 230.692.8308 59.5, 1334 25° 425814 174901 87.17 588 178 2 -43243 13038 od 84 1st 4 Blane 338818 1061.61 — 92 1596 OS 409752716297 3283. 892 1433 1 “419.102 502.708 5265. 77.2 2083 15 420889 191.656 81.94 66:4 165.1 2 437587 165246 84.34 7H 1872 25° 439.762 107219 $9.9 80.2 1543 3487644 92.708 91.27 838 156.6 ‘with those of other similar studies on the corrosion-inhibit- ing effect of plant extracts shows that our extracts are clearly more effective; Thus, El Attar etal [84] recently carried out a study on the corrosion-inhibiting effect of the essential oil of Dysphania ambrosioides on steel in | M HCl, and they found an inhibition efficiency of 90.20% at 4 gf 3.4 Electrochemical Impedance Spectroscopy Results [Nyquist diagrams ofthe steel immersed in the HCI acid solu- tion without and with varied quantities added of C.sitiqua extracts are shown in Fig. 4. The resulting impedance dia- gram are not perfect semicircles, and this is attributed to the difference in frequency dispersion [85], due tothe dissimilarity of the electrochemical system. This dissimilarity results from adsorption ofthe inhibitor, impurities, rnughness, dislocations, and formation of porous layers [86, 87]. When the coneentra- tion of all C. siliqua extracts inereases from 0.5 10 3 g/l itis ‘noted that the increase in the size ofthe capacitive loop is well marked, which can be attributed to the load transfer process, and the impedance value obtained in the ease of the control is lower than that obtained in the ease of C. siliqua extracts. This result reflects the influence of these extracts on the process at the steeV/acid interface. The electrochemical parameter's val- ues and inhibitory efficiency for different concentrations of . siliqua extracts for corrosion of steel in HCL | M obtained by electrochemical impedance spectroscopy are presented in ‘Table 5. The impedance results are simulated by the equivalent electrical circuit representative of the adsorption mechanism, illustrated in Fig. 5. This circuit consists of the constant phase element (CPE) which represents the frequency distributed in double capacitive layer, used to report the previously described inhomogeneities, the electrolyte resistance (R,) which repre- sents the ohmic fallin the electrolyte when a current passes between the working and reference electrode, and the load transfer resistance (R.,) Note that (C.) (double-layer capacity) and (Ry) are introduced in parallel to show that at the interface level, the establishment of the double layer (modification of the dis- tribution of electrical loads at the interface) and the transfer, of load (electron transfer due to electrochemical reactions) are carried out simultaneously. Examination of the results in ‘Table 5 indicates thatthe load transfer resistance (R,,) values become more important with the increase in the concentra tion of C. siligua extracts. The inhibitory efficiency E(%) of all the extracts studied, calculated from these parameters, evolves in the same way as the load transfer resistance, and reached a value of 89.32% and 92.04% for extracts (metha- nolic and aqueous) of C. siliqua with gallic acid, respec- tively. The results also show that the double-layer capac- ity (C,,) decreases steadily as the inhibitor concentration rises. The same observation was carried out by GHAZI etal [88] on the adsorption of the Peganum harmala methanolic extract on steel surface in | M HCI. Better protection pro- ‘vided by an inhibitor is associated with a decrease in metal capacity [89]. This decline is linked to the adsorption of ‘organic molecules on the surface of the steel [90]. Indeed, the thickness of the organic layer grows as the inhibitor adsorbs more, and the double layer’s capacity decreases [91]. This trend is in agreement with the Helmholtz model, ssiven by the following equation: xa. 6 where dis the protective layer’ thickness, «is the protective layers dielectric constant, isthe environmental permitiv- ity (8.854 10!*F em), and Ais the electrode surface. The inhibitor's adsorption to the steels surface, there~ fore, reduces the mediums dielectric constant ¢, and/or springer31_ Page 100123 Journal of io-and Tibo-Coresion (2022) 831 Fig.4. Nyquist dagrams of sel oe « 1 M HCI containing dierent . D =o concentrations of C:siliqua “0 so = extract: a extract of methanol - =e out ale ai extract of =", anieous without gli acd € =a extract of methanol with alc tok dex of aqusus with vw sales © a increases the double layers thickness. The impedance AG, {qua extracts obtained with mass loss measurements and polarization measurements. 3.5 Adsorption Isotherm An isotherm is a function that describes the adsorbed quantity versus the concentration at a constant tempera- ture, The pace of adsorption isotherms a a given tempera- ture depends on the adsorbent/adsorbent interactions and in particular on the nature of the adsorbed species and the nature of the metal surface, An adsorption isotherm such as Langmuir is used in this study to describe the inhibi- tion mechanism of C, siliqua extracts, Langmuir's adsorp- tion isotherm is expressed by the following mathematical relationship: a © springer ‘whore Cais the inhibitor’ concentration inthe electrolyte Ky iste constant of esulibrium ofthe adsorption process fs the degree of surface coverage Ris the perfect gas con- stant=8.314 I/K/mol; Ts the temperature and Cyag is the ‘water concentration and AG, isthe standard-free adsorp: tion energy. Figure 6 illustrates this procedure and shows C.y/@ sersus of concentration for different temperatures, Itean be seen that this representation gives straight lines with correlation coefficients greater than 0.98 and slope values, are equal to I forall C.siligua extracts. This shows that the adsorption of these extracts om the steel surface in HCI acid medium follows Langmuies isotherm of adsorption The same results were observed in the testing of enna extract used asa mild steel corrosion inhibitor in HCL 1 M. 71 “The equilibrium constants values (Ky) were given in Table 6, (Ky) is related to the Tree adsorption energy standard (AG.,) by the following equation:Journal of Bio- and Tribo-Corrosion (2022) 831 Page 11 0f23_ 31 Table § Electrochemical parameters for different concentrations of C. siligna extract oblainesl by electrochemical impedance meta in | M HCE sextet of methanol without galk acid b-extact of aqueous without gale acid: c-extract of methanol with gallic aid; extract of aqueous with gale aid CS ae ane 2399 a Osu lon as ss is ns 2 mas ds Be : 98 os ross 1 2299 is 1325 2 3 ds 37 3 so78 os 1 Is ds 3 1 lane : os a 1 3539 is nn 2 58 2s 1st 3 2.08 Rs cee Ret Fig5 glen elec ct AGiy, = “RTELn( Cio Kus) » From this equation, (AG.,,) values at all studied tem- peratures can be calculated. In this equation, Cypo is used in Bf, Ky in Vg. so the adsorption (AG-,,) unit depends only on the R xT faetor (Kl/mol). The values obtained from (AG...) are given in Table 6. (AM) and (AS,,) values are determined from the following equation: AH, ~ TAS, 0) Figure 7 demonstrates the change in (AG,,.) versus 7 ‘The resulting lines have the slope (AS%,.). while (AH, its ordinate atthe origi. The adsorption parameters collected in Table 6, clarify the chemical interaction between natural extract with the metal surface. In general, Wo types of adsorption might be considered: physical adsorption or chemical adsorption, and sometimes both atthe same time (AG,,,) values are negative at the temperatures studied for all: sifiqua extracts, indicating that the C. siligua adsorption process occurs spontaneously [92]. Exother- mic adsorption (A/Y,<0) may involve physical adsorption and/or chemisorption, While an endothermic adsorption process (AH',, > 0) is attributed to chemisorptions [93] Physisorption differs from chemisorption in an exother- rile process by taking into account the absolute value of (Aff). When the value is less than 40 Kimo, it is physisorption and ifthe value of (AH) is close to 100 KI? mol, it is a chemisorptions [94]. In this work, the values of (AMF,,) obtained for extracts (aqueous and methanolic) of C.siliqua show that exothermie adsorption ean occur, so physical adsorption has been detected. However, the calculated values of (AAf,) for extracts (aqueous and ethanolic) of C.siliqua with presence of gallic acid are 20.985 and 13.547 ki/mol, respectively, indicating the chemisorbed nature on metalic surface. The higher value of (AM) for aqueous extract of C. silqua with gallic acid indicates that itis more adsorbed than the metha- nolic extract of C.sitiqua with gallic acid on the metallic surface. This corresponds to the findings of wei measurements, polarization curves, and impedance. The values of (AS...) obtained for extracts (aqueous and meth- aolic) of C sifiqua with gallie acid are high and postive, reflecting an increase in the disorder that occurs during the formation of the metal complen/adsorbed species (95). The evolution of (AG, versus temperature is linear forall the extracts studied, indicating a good correlation between the thermodynamic parameters. 3.6 Kinetic/Thermodynamics Considerations ‘Temperature is a significant factor in the study of metal dissolution. For example, the rate of eorrosion in acidic solutions grows exponentially as the temperature rises. ‘The mechanism of action of an inhibitor can be achieved by comparing the apparent activation energies (E,) in the presence and absence of C. siliqua extracts. The Arrhenius Formula is presented by springer31 Page 120123 Journal of io-and Tibo-Coresion (2022) 831 Fig.6. Langmuir’ isotherm of tasorption of C.sitiqua extract ‘on carbon steet in HCL M at ferent temperatures: a extract ‘of methanol without gai aid: Dextract of aqueous without sali aid: eextact of meth nol with gle acid extract of aqueous with gall acid asf B fa poe MB 88 “i912 0.9857 T with A is Arrhenius factor (pre-exponential). © springer for the C. siliqua extracts are given in Fig. 8. These are straight lines, thus, showing that the aw of Arrhenius applies to describe the kinetics of the adsorption ofJournal of Bio- and Tribo-Corrosion (2022) 831 Page 13012331 Fig.7 Variation of AG, versus ro) TF: wextact of methanol without sali aid: b extract of aqueous without gallic acids e extract of methanol with gai aid: 7 act of aqueous with galic “we mses 26° nt) inhibitor onthe surface of the stel. Activation enthalpy (AH; and the activation entropy (AS") in the transition state forthe intermediate complex of corrosion from car- ton stel in HCI, without and with different concentrations OFC. sliqua extracts, were achieved by ulilizing the fol- Jowing transition state equation: toe (F) = (eG) + ‘The variation of Ln(w/T) versus the inverse of the tem- perature (1000/7) is presented by straight lines (Fig. 9), where (AH“/R) is the slope of the line and log (R/hN) +A5;/R is the ordinate at the origin. These two expres- sions make it possible to calculate the activation parameters, (AH%) and (AS!) of which values are collected in Table 7. Its noted from Table 7 that the values of (E,) are more than that of blank and increase with the concentration for extracts (aqueous and methanolic) of C. siliqua. When (E,) with inhibitor presence is greater than the blank value, this phenomenon is commonly seen as a result of physisorp- ion, this result is consistent with the literature data [96] Analysis of temperature's influence on protection efficien- cies E(%) (Table 3) shows that inhibition efficiencies for extracts (aqueous and methanolic) of C. siligua decrease ‘with temperature increase. This is related (© a decline in the AH 3303K7 ass) 2303R. (ay adsorption of these extracts at higher temperatures. This con- firms that physical adsorption could be the sort of adsorption fon the metal surface. These results appear to be consistent with other research that showed that an increase in (E,) with inhibitor concentration was associated with the physisorp- tion mechanism [97]. However, in our study, the data show that the values of (E,) are lower than that of blank in the event of extracts (aqueous and methanolic) of C. siligua in the presence of gallic acid. The concentration rises leads to 4a decrease in activation energy. This decrease is attributed to the substantial increase in the adsorption capability of the imhibitor on a metallic surface with the decrease in corrosion rate [98], this indicates that the inhibitory action of these C, siliqua extracts occurs by chemical adsorption. For extracts {aqueous and methanolic) of C.siliqua, itis observed that the (AS) values evolve towards more positive values. This leads to more disorderly behavior. Moreover, in the case of extracts (aqueous and methanolic) of C. sifiqua in the gal- lie acid presence, the values evolve towards more negative values (more ordered behavior). This ean be explained by the involvement of the constituents of these extracts in the activated complex of the corrosion reaction, which leads to 44 more ordered system [99]. For all studied concentrations, of C.siliqua extracts, the mean value of the E, — AH; differ- ence is around 2.57 ki/mol, which corresponds to the mean value of Rx T, indicating that the corrosion reaction is @ springer31 Page of 23, Journal of io-and Tibo-Coresion (2022) 831 Fig.8. Anmenius straight lines 1 at different temperatures: a extract of methanol without sali aid; b exit of aqueous Without gale acids « extract of methanol with gli aid extract of aqueous with gall : c d : . wot monomolecular reaction [100]. These results are in agree- ‘ment with the studies carried out on the plant extracts [101, 102}. 3.7 Fourier Transform Infrared Spectroscopy (FTIR) Studies The FTIR spectra of 1 M HCI+3 g/l of the methanol and aqueous extracts of C. siiqua before and after the corrosion tests are presented in Fig. 10. A summary of these results is given in Table 8. The spectra revealed that all extracts hhad nearly identical peaks; however, after the corrosion test, the intensities reduced or increased when these com- pounds reacted with the metal and acid to generate corro- sion proxiucts [103]. A broad band at 3300/3327 em’! and 3334/3328 em” can be attributed to the stretching vibration (O-H) beforefatier the corrosion test forthe methanolic and aqueous extracts respectively. In the methanolie extract, a small peak at 2932 cm! was observed for the pure extract corresponding to stretching vibration (C-H) in the -CH, group. Such a peak can be attributed tothe stretching vibra- tion of the carbonyl groups (C=O), and its intensity was shifted from 1635 to 1627 er after testing for the metha- nolic extract and from 1632 to 1633 em“ for the aqueous © springer extract indicates the formation of an iron-plant extract complex [104]. Before the corrosion test inthe methanol extract, a peak appears at 1050 cm which could be attrib- uted to stretching vibrations (C-O) in the primary alcohol However. this peak was increased for the pure extract and its intensity decreased after the corrosion test. The stetch- ing vibration (C-O) in tertiary alcohol was observed at 1193 emr! before the test in the methanolic extract and disappeared in the FTIR spectra after the corrosion test ‘whereas in the extract aqueous, two peaks appear at 1160, and 1033 cm"; can be related to the stretching vibration of (C-O) and disappear after the corrosion test: and reveals, tha oxygen atoms ean act as active adsorption centers. Dou ble peaks around 500/1000 cm”! are related to stretching vibrations (C-H) in aromatic rings for three tests. Thus, the results showed that C. siligua extracts contain organic mol- ecules rich in oxygen atoms as well as aromatic rings, such as phenols, which meet the basic requirements of a good inhibitor [105]. 3.8 X-ray Diffraction Studies ‘The X-ray diffraction (XRD) patterns of the prepared steel surface before andl after immersion in | M HCI, without andJournal of Bio- and Tribo-Corrosion (2022) 831 Fig. Variation of Lntw/7) in vom Page 15012331 the inverse ofthe temperature without and with C:sligua extract exit of methanol without gallie acids b extract of aqueous without gli aide extract of methanol with gale cid extract of aqueous with wali aid | with the aqueous extract of C. siligua in the absence and presence of gallic acid are shown in Fig. 11 Similarly, the peak list of the XRD patterns of the pre- pared steel before and after immersion in 1 M HCI without and with the aqueous extract of C. siliqua in the absence and presence of gallic acid are highlighted in Table 9, while Table 10 shows the identified Patterns list of the phases obtained from the XRD Patterns of the steel without HCL and steel immersed in 1 M HCI both in the absence and presence of the aqueous extract of C. sifiqua without and with gallic acid By analyzing the specira obtained, we note the presence of two lines in the spectrum recorded without immersion of HC! acid (20=45,0435° and 65.1878°), the identifica- tion of these two lines is done by comparing the experi- ‘mental data with the reference data that constitute the code file. This study shows that the diffraction lines are those characteristics of iron, which does the main element con- stitute the Carbon steel sample according to the standard file (COD 96-900-6598), while during the immersion of the steel in HCI in the absence of the extract, the intensity corresponding to the peak of iron towards (20=65.2577°) was decreased (8.16%): 80, we note the appearance of iron oxide (Fe,,Oz.) at 65.2577° according to the standard file (COD 96-900-2332) as well as the appearance of peaks at (21.9281° and 33.7206") suggesting the presence of iron oxides (Fe,0,) according to the standard file (COD 96-900- 3081), ic. corrosion products resulting from the deterio- ration and degradation of the steel sample. The presence of inhibitor without gallic acid indicates a lower presence of corrosion products in HCI; however, the introduction of the extract with gallie acid reveals the complete absence of the iron oxides. This observation is due tothe inhibitive effect ofthe extract of C siligua with gallie acid. Therefore, the extract effectively alded the passivation of the steel and ‘minimized the chemical reaction involving the diffusion of the anodic and cathodic species [106] 3.9 Scanning Electron Microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) Studies ‘Scanning electron microscope (SEM) images were taken in order to study the surface morphology of carbon steel in the absence and presence of inhibitor. SEM/EDS micrographs “obtained for carbon steel surface before and after immersion in 1 M HCI, without and with 3 gil of C. siliqua aqueous extract in the absence and presence of allie acid are shown, in Fig. 12. springer31_ Page 160f23 Journal of io-and Tibo-Coresion (2022) 831 ee co ‘A (mglenPin') (Kimo) AH, (imo) AS, /kimol) iE, — AH, siliqua extract in | M HCI: ik desir of methanol witout lane S07 IO 7139 mms oie oe ae os 59710" oo 89.0678 29.1004 methanol wit guise! 505 x 10" 9162 9.0029 279209 extract of aqueous with gale 1.3 498x108 v191 393056 217609 oid 2 3.08 x 10" 9095 s83778 28138 as 880% 108 9397 91,3958 125269 3 799 10° 10003 7st S08676 Blane 587x107 628 487025 os 441610" 6527 e269 1 1 x 10° 6276 60.1792 42810 6597 63.396 184 10° ool 14288 -37.0398 5463 10! 7312 10. “288719 371108 S37 1.926 e224 23x10! 4995 473679 -93.4052 590% 10" 3633 a0 =143.0829 1 7.46 x 10° 37.15. 141.1293, ee 31x 10° 34.51 50.8749 2 110x108 m8 =176.1803 2s 8.22 10° 26.62 178.6121 3 132 10) n26 =193.776 Blanc 639% 10° wo 57.6316 65.8400 os 233x107 178 $5159 -innsima \ 1963 10 3502 wti6 =152.2609 1s 354% 105 78 35.2006 =1373§q0 2 5.36 x 10" 39.25 36.6764 143.8895, 25 415 x10" 0 30500 165.1617 3 8x 108 18.68 w6.105 -2138576 Fig. 10. FTIR spectrum of C » siliqua extract pare before and aller corrosion test: extract of ‘methanol: b exact of aqueous The surface morphology of the carbon steel sample ‘was examined by SEM/EDS after 6 h of immersion in | M HCI in the extract-free solution and also when the extract ‘was introduced. Figure 12a shows a freshly polished (as- received) surface of the steel that is very smooth and not cor- roded but with minor scratches due to polishing operation, ‘The associated SEM of Fig. 12b (without extract) reveals a © springer surface that is rapidly attacked and heavily damaged with evidence of cracks, pits, and/or cavities which simply affirms metallic dissolution in the stated medium due to the pitting action of chloride ions. By comparison of SEM images, it ccan be noted from Fig. 12c. d that it exhibits a reduction in corrosion attack. This reduction is more observed in SEM images of samples immersed in the presence of gallic acidJournal of Bio- and Tribo-Corrosion (2022) 831 Page 170f23_ 31 Table Characteristic peaks obtained from FTIR spectra for 1 M HCI+C. siligua solution before and after corrosion test a-extact of methanol: bextra of aqueots TMHCI+3 pt inhibitor before ext TMHCI+3 eiiah jt after test Pure extract ‘Frequency em") Functional group Frequency (en) 328792 0-H sieching 330041 29323, CH seething - 163405 stretching 1635.06 = : 1193.13 134706 1080.6 925.08 2 665.49 - 599.1 CH bending 595.11 >. Frequency em") Fnetional group Frequency (en) Functional group Frequency (en Functional soup, OH sreiching 8327.64 O-H stretching C=0 stretching 1627.65, (C= stretching CO stretching - e CO stretching ms €- suetching =CH bending ons HH bending Functional group Frequency em") Funetonal group (0-H stretching 331621 0-H sretching 333499 O-Hswetching 332801 s 2939582 CH sretching . - . (C0 stretching 1633.09 strctching 1632.77 stretching ‘1638.89 . 1422.66 CC stretching 7 . = : 134347 CH bend - . - - 110341 160.11 CO srething . : 1086.77 1033.68, 0 sretching . 599.18 =C-H bening 59894 =C-H bending 59.19 6 7 Table Peak list obtained from the XRD Patterns of the steck ‘swan te without HCk; b-without inhibitor: e-peseace of inkibitor without, = llc avis e-the preseaceof inhibitor with gle acid Dox [2TH] —_Heightfou] — FWHMTeit dhapacing Rel cl ram) AL In. 6] i 450835 8857.41 O2401_—=«« 201104100 a oe 65.1878 114796 03601142997 1296, 210281 2x35 03601403082 - 337206 2732 O96 —24SSBE— LL 45.0542 146192 02401 201059 100 65.2577 115496 02401 LAH BLI6 . 633.5928 230703266566 .74 ee ee a 1383559 otsol 2.00979 100 65.3034 88521 03001 LAT. 64 Fig.11_ XRD patterns ofthe set surface before and after immersion 45.0428 13,305.49 0.2401 2.01108 100 ini MHC in the absence and presence of aqueous extract of C sili 02401 A867 TAL ‘qua without and with gallic aid (Fig. 12d) which is consistent with the previous tests that show a lower corrosion rate for the samples immersed in the presence of this additive, ‘The EDS analysis results of the carbon steel surface before and after immersion in 1 M HCI in the absence and presence of C. siligua aqueous extract without and with gal- c acid are shown in Fig. 12. Specifically, an EDS spectrum highlights the major elemental constituents at the surface 65.2548 985.28 1 of the material: whether a polished, corroded, or inhibited ‘material’s surfaces. The associated EDS of the as-received spectrum of the abraded sample in Fig. 12a highlights the elements constituting carbon steel sample (Fe, Mn, and C) with a high atomic content of iron to 88.63% (Table |), in addition to oxygen low signal to 1.80% related to the air formed oxide film [107]. The attached EDS spectrum of Fig. 12b displays a signal for Cl to 0.61% special for the constituent of acid solution, as well as the presence of the springer31 Page 180f 23 Journal of io-and Tibo-Coresion (2022) 831 Table 10 Identified patterns Into the paces baie Reade Sane Compan mine stacor Chil forma fr the XRD Pater of he sexi awit HCE bio — Sgapoeion 99 hw a 0359 = ini cesnse of ahr ggg 1 Gite o 61 Ca of inhibitor with gallic acid 96-900-0662 66 Iron ° 1 Fer 969003081 5 Tox o ois Fea Ou 96900-2352 2 Mapetite o om9 ior 965000650 81 em ° 0406 Fein 96501-8235 6 onde o oasis Feaae 969000662 70 on ° 097 Fen 96152-4200 18 ‘Niketan o oon Nig Peer 96151-4236 § Manganese vide 0 ous Muss Oren 96151-8107 1 Bixby ° 10068 Mite Onn oxygen peak with a higher atomic percentage in this ease, ‘hich indicates the formation of non-protective corrosion products [108] on the corroded surface. These features may be explained by a serious attack of steel immersed in 1 M HCI solution, The addition of inhibitor decreases the atomic content of oxygen which indicates a reduetion in corrosion attack. This decrease is more apparent with the addition of gallic acid, and also intensity of CI peak disappeared at the same time which is consistent with previous findings indi cating that this additive is more efficient in increasing cor- rosion resistance. Therefore, it could be concluded that the covered surface inereases and the dissolution of earbon steel decreases. These results suggest the formation of inhibitive and protective film on the steel surface that subdued and overpowered the charge and mass exchange by acting as a blockade and, consequently made the inhibited surface dis- play enhanced properties [109] 4 Conclusion This work was devoted to the examination of the corrosion protection of C38 in | M HCI acid medium by using of extracts (aqueous and methanolic) of the pulp of C. sifi- ‘qua, without and with addition of gallic acid, The inhibitory properties of these extracts were studied by gravimetric and electrochemical methods (spectroscopy of electrochemical © springer impedance and polarization curves). The following findings Were reached of this study: 1. A maximum efficiency is obtained for the aqueous extract of C. siligua with gallic acid at a concentration of 3 g Mand the efficiency was 91.32% at 323 K. 2. The influence of temperature on the kinet has helped understand the mode of action of C. siligua inhibitor. of corrosion 3. The polarization curves showed a decrease in current density versus concentration 4. The impedance diagrams showed that this is a process of load transfer on a heterogeneous surface for all the concentrations studied. Based on the polarization results, the studied inbil tor operate as inhibitor of mixed type but the effect on cathodic reactions is greater. 6. The adsorption model obeys Langmuir's isotherm of adsorption, 7. The FTIR spectra analysis confirms the adsorption of C, siliqua extracts molecules on the carbon steel surface. 8. EDX, SEM, and XRD confirm the corrosion of carbon steel in | M HCI and its inhibition by C. siliqua aqueous extract with gallic acid 9. The main constituent responsible for corrosion inhibi- tion characteristic of C. siliqua extract is found to be gallic acidJournal of Bio- and Tribo-Corrosion (2022) 831 Page 190f23 31 Fig. 12. SEM and EDS images micrographs forthe surface of wali aid © springer31_ Page 200123 Journal of i and Tibo-Corrsion (2022) 831 Table 11 Percentage of atomic contents of elements obained from EDX spectra System Percentage of elements detected (@) mC Ma a ‘Afterpolishing S863 899058 1AD Withoutextrct S853. IBAS 064 2134 O61 With extract inthe 5866 2306058773 = absence of gallic seid Withextrct in S807 -2394 O87 ITA = presence of gale aid Acknowledgements The authors gratefully acknowledge the CUR CA2D of Chouaib Doukkali University (El Jadida-Moroeco) for its ‘support. Funding ‘There were no research Grants fr this work fram any fund- ing agencies, Data Availablity All data generated or analyzed during this study are included in this published article (and its supplementary information files). Declarations Conflict of interest ‘The authors declare there is no conict of interest egaring the publication ofthis article. References | EBL Bakr, EL Aoutir Y, Bourazmi H, Harmaoui A, Sebhuout J Ben Ali A, Oudda H, Guenbour A, Tabyaoui M, Ramil Y,Essass EM Y (2017) The roles of 34-diamino-S-phenyl-4 HI 2-tri- azole (TR) on the corrosion inhibition of steel in HCI media. J “Mater Enviton Soi 833343, 2, Absallah M, El-Datfawy AM, Sobhi M, Elwaty AHM, Shaaban [MRR (2014) Corrosion Inhibition of carbon ste in sulphur ac solutions by novel bisaminothiazole derivatives: chemical, lec- trochemical and DFT stues. Int] Electrochem Sci 2186-2207 Soba M, Abdalla M, Hafez E (2013) Some poly sorbate com- pouunds as cortosion inhibitors foe csehon steel in hydrochloric ‘cid. J Adv Chem $:830-838, ipso. ony 10 24297Fje.v 53 2619 4. AMallah M, Asghar BH, Zaafarany I, Sobhi M (2013) Synthesis fof some aromatic nitro compounds and its applications as inii- {ors for corosion of earbon see in hydrochloric acid solution Protect Metals Phys Chem Surf 49:4N8-4. hp. org/10. 1134/820702051 3040187 Foula AS, Abdallah M, Medhat M (2012) Some Schiff base ‘compouinds 3 inhibitors For eorrasion of carbon steel in acidic ‘media. Protect Metals Phys Chem Sur 48:477-4N6, hits: ‘org/10.11S4/S20702051 12040083 6. Issaati 8, Dovadi T, Zzouaoui A, Chataa S, Khan MA, Bouct G(20I1) Novel thiophene symmicirical schi hase eompounds as corrosion inhibitor for mild steel i acc mea. Coros Sc '53:1484-1488, hops//do.ong/10.1016).corsei.2011.01.022 © springer 8 20. 21 [Abdalla M, Zaafarany 1, Khairou KS, Sobi M (2012) Ini- bition of carbon stet corrosion by iron (ID) and imidazole in sulturie acid. TnI Electochem Sei 1564-1579 Zaafarany 1A 2014) Corrosion inhibition of 1018 carbon steal in hydeochlorie acid using Schiff base compounds. at I Corros Scale Inhibit 3:012-027. hitpsi/dos.org/10.17678) 2305-6894-2014-3-1-012-027 Moretti G, Guidi F, Fabris F (2013) Cortosion inhibition ofthe mild stel in 0.5 M HC by 2-butyl-hexahydropyrsole [1,2-b] [1,2] oxazole, Coreos Sci 76:206-218. https:1/dot. 03/10. 1016j.corsei2013.06.044 Fouda AS, Abdallah M, Attia A (2010) Inhibition of carbon steel corrosion by some eyanoacetohydrazide derivatives in HCI solution. Chem Eng Commun 197:1091-1108. hups/doi ‘org/10.1080/0008644903412044 Belghiti ME, Tighadouini S, Karzazi Y, Dafali A, Hammouti B, Radi S, Solmaz R (2016) New hydrazine derivatives as ‘corrosion inhibitors for mild steel protection in phosphoric fcid medium, Par A: experimental study. Mater Environ Sei 7337-346 Verma CB, Quraishi MA, Singh A (2015) 2-Aminobenzene- sdicarhonitiles as green corrosion inhibitor for mild steel in IM HCI: electrochemical, thermodynamic, surface and {quantum chemical investigation. J Taiwan Inst Chom Eng 49:229-239. hups/fdoi.ong/10. 1016) ice 2014.11.029 Boumhara K, Tabyaoui M, Jama C, Bentiss F (2015) Arte- misia Mesatantica essential oil as green inhibitor for carbon Stool corrosion in IM HCI solution: electrochemical snd XPS. investigations. Ind Eng Chem 29'146-185, hups/ido.org/10. 116i jee-2015.03.02% Kabel KI, Zakaria K, Abbas MA, Khamis EA (2015) Assess ment of corrosion inhibitive behavior of 2-aminothiophenol atives on carbon stel in IM HCL.J Ind Eng Chem 23:57- Jib. ong/10. 1016/5 JIEC.2014,07.082 Al Lusi $8, Azad S, Tabi AH (2011) Therma proper tis of amino melamine formaldehyde as corrosion inhibitor for stool in sulfuric soi solution. 1 Mater Environ Sei 2: 148-155 Ramananda MS (2013) A green approach: a corrosion inhibi tion of mild steel by adhatoda vasica plaat extract in 0.5 M. H,SO, 1 Mater Environ Sei 4119-126 Ostoviri A, Hoseinieh SM, Peikari M, Shadizadeh SR, Hashemi $1 (2009) Corrosion inhibition of mid steel in TM HCI solution by henna extract: a comparative study of the inhibition by henna and its constituents (lawsone, Gallic acid, a-b-Glucose and tanni acid). Corros Sei 51:1935-1949. hitpssfdo.ong/ 10.1016) corsei.2000.05 024 Lobe N, George N, Justus N, Nneka E, Peter E (2016) Aque ‘ous extracts of Pemtaclethra macrophlta entham roots as «eco-friendly corrosion inhibition for mild steel in 0.5 M KOH medium. Int J Mater Chem 6:12-18, htpsildoiorg/ 10.5923), {jme.20160001.03, Ali D, Ghasem B, Bahram R, Mohammad (2019) Potential of Borage flower aqueous extract as an environmentally sustainable corrosion inhibitor fr acid corrosion of mild tek: electrochem cal and theoretical studies. J Mol Lig 277:895-D11. hips: ‘ore/10.1016),mollg.2019.01.008 Sharma KS, Acknez M, Gatg Jyoti $ (2010) Corrosion i bition and adsorption properties of Azadirachua indica mature leaves extract as green inhibitor for mild ste! in HINO. Green ‘Chem Lett Rey 3:7-15. hitps:f/doi.org/10. 10800175 1825090 3447100 Murthy ZVP, Vijayaragavan K (2014) Mild stel corosion ih: tion by acid extract of leaves of Hibiscus sabarifa as a green corrosion inhibitor and sorption behavior. Green Chem Lett Rev 7208-219, hnips:fdoiorg10,1O80/17518253.2014:924592 66.Journal of Bio- and Tribo-Corrosion (2022) 831 Page 21 of 2331 22, Haldhar R, Prasad D, Mandal N, Benhiba F, Buhadur I, Dagdag © 2021) Amticorrosive properties of a green and sustainable inhibitor from leaves extract of Cannabis sativa plant: experi- ‘mental and theoretical approsch, Colloids Surt A 614126211, lagps:fdi.ore/ 10.1016) colsura.2021.126211 23, Janaina CR, José ACPG, Eliane D 2014) Aqueous extracts of ‘mango and orange pee! as green inhibitors for carbon steel in laydrochlori aid solution, Matee Res 17:1581-1587 hips. ‘org/10.13901516-1439.285014 24, Rajesh H, Dwarika P, Indra B, Omar D, Avni B (2021) Evalua- tion of Glaviasa superba seeds extract as corosion inhibition for low carbon steel in sulfuric acc medium: a combined exper ‘mental and computational statis. 3 Mol Lig 323:114988, ips oi oe/ 10.1016 mollg,2020, 114958 25. Sangeetha M, Rajendran 8, Sathiyahama J, Umasankareswar T, Krishnaveni A. Joany RM (2015) Corrosion inhibition by flower extract: an overview: Int J Nano Cort Sci Eng 214-21 26. Prabha AS, Kavitha KG, Shrine B, Rajendran S (2020) Inhibition ‘of corrosion of mill steel in similatd ol well water by an aque- us extract of Andru graphis paniculata, Indian J Chem Technol 27452460 27. El Hamdani N, Fail R, Tovrabi M, Jama C, Bentss F (2015) Alkaloids extract of Retama monosperma (L.) Boiss Seeds used as novel eco-friendly inhibitor for earhon steel cormosion in 1 M Isolation: electrachemical and surface sues. Appl Surf Sci 357-194-1305. hups:fdoi.ony/0.10164.apsuse-2015.09.159 28. Kathiravan S. Jyothi S, Ayyannan G, Ravichandran J. Raja G (2021) Inhibitory ation of aqueous RuelliatuberosaL. leaves extract onthe cofrsion of copper HCL solution, J Indian Chem Soe 98:100207. hip: ors/ 1010164 jies.2021. 100207 29, Benmansour N, Cheri HEI HanbaliF. Akssira M 2020) Stuy ‘of the biological activites of the sees ofthe plat Cenaonia sili ‘qua L. recovered in the Bejaia region. Med Technol 4520-521 bps. 10.2681 5/2572-OMXvoltisslpS20-521 30, Santos LM, Tulio LT, Campos LF, Dorneles MR, Kriiger CCH 2015) Glycemic response to Carob (Ceraronia sidigua L) in cathy subjects and with then vito hydrolysis index. Nate Hosp 31:482-487.hupsfAdoiorg/10-330Soh,2015.31.1.8011 31, Zhu B, Zayed MZ, Zhu H, Zhao J, Shao-Ping L 2019) Fun tional polysaccharides of carob uit review, Chin Med 140 32, Salih G.Jilal A (2020) Uiilisation alimentaire de la pulpe de carouhe: formulation et test consommateur Rev Mar Sek Agron Versi249-252 33, Avallone R, Plessi M, Baraldi M, Monzani A (1997) Determi- ation of chemical composition of earub (Cerazonia siliqua): protein, fat, carbohydrates, and tannins. J Food Compos Anal 10:166-172. fps) .og/ 10.1006. 1997.0528 34, Marakis $ (1996) Carob bean in food and feed: current status ‘and future potentialsa critical appraisal. J Food Sci Technol 33:365-383 35. Loeb H, Vandenplas Y, Worse P, Guesry P (1989) Tannin-riet carob pou! forthe treatment of acute onset diare. J Pediatr Gastroenterol Nate $:480-485 36, Batlle 1, Tous J (1997) Promoting the conservation and use of underutilized and neglected crops caro tre, Ceratona siiqua LL). International Plant Genetic Resources Institute (IPGRI), Rome 31. Ait Chitt M, Belmir M, Lazrak A 2007) Production des plantes ‘Seetionnées et grettées du eaoubier. Transfert de technologie en Agriculture 153:1-4 38, Stay H, Abourouh M (2006) Apport des espéces 3 usages mul tiples pour le développement durable: cas du pin pignon et du ccobbier, Centte de Recherche Forestére Haut-Comnissarat aux Eauy et Forts et la Lutte Conte la Desertification, Rabat 1-9 239, Serati-BejiR, Mekki-Zouiten L, Tekaya-Manoubi L, Louesat MH, Guemira F, Ben Mansour A (2000) Can earab powder be used with oral rehydration solution forthe treatment of acute siaerhea, Med Trop 60:125-128 440, Rejcb MN (1993) Le caroubicr en Tunisie: Situations et per spectves d’amélioration. Quel avcnir pour Faméliortion des plantes? Edit, AUPELF-UREF. John Libbey Eurotext, Pats, pp 79-85 41. Berrougui H (2007) Le caroubier (Ceraroniasiiqua L.), une richeste nationale aux vertus médicinales, Maghreb Canada Express 5 42, Ruiz-Roso B, Quintela IC, Fuente EDL, Haya J, Pérez-Olleros L (2010) Insoluble carob fer ich in polyphenols lowers total and LLDL cholesterol in hypercholesteolemic suject. Plant Foods Hum Nate 68:50-60. psdoi.onp/10.1007/11130-009-0153-9, 443, Nasar-Abbas SM, Hums Z, Thi-Hluone V, Khan MK, Esbenshade H,Jayesena V (2016) Carob kibble: a bioutive-rchTood ingredi= cent. Compr Rev Food Sei Pood Saf 15:63-72. haps org/10. TI S41-4337.12177 44, Marakis S, Marakis G, Lambraki M (1997) Tannins of eight ‘carob varieties fom the Island of Lethal, Greece, Chim Chron New Series 26:57-66 45, Dhahir BM, Hameed IH, Jaber AR (2017) Prospective and roto spective study of fractures acconfing to trauma mechanism and Iype of bone fracture, Res J Param Tech 10:1994-2002, bps doi. or/10.59S8/0974-360X.2017.00692.8, 46, Eldahshan OA (2011) Isolation and structure elucidation of phe noc compounds of caro leaves grown in Egypt. Curr Res J Biol Sei 352-5 447. Sakakibara H, Honda Y, Nakagawa S, Asha H, Kanazava K (2003) Simultaneous determination of al polyphenols in vegeta bles, ruts, and teas. J Agric Food Chem 51:571-S81 hpi ore/10.1031/10200261 48, Samanidou V, Tsagiannidis A, Sarakasianos 1 (2012) Simlta- neous determination of polyphenols and major purine akalols in Greek Siderits species, herbal extract, green tea, black tea, and coffee by high-performance liquid chromatography-diode amy detection. J Sep Sei 35:608-615.htpslidi.or/10.10021 jsse-201 100894 49, Schmivzer V, Slatnar A, Veberie R, Stampar F, Solar A 2011) Roasting affects phenolic composition and antioxidative activity of hazelats (Corus aellana L.-J Food Sei 76:14-19. hips oi.or/10.11114,1750-3841.2010.01898. 50. Shahrzad S, Aoyagi K, Winter A, Koyama A, Bitsch I (2001) Pharmacokinetics of gallic aid and ils relative bioaailability from tea in healthy humans. Nutr 131:1207-1210.htps/dos, ‘org/10.1093ja/t31.4.1207 51. Danian E, BacchettiT, Paella L, Tiano L, Carloni P (2014) Antioxidant activity of different white tea: comparison of hot And cold tea infusions. 1 Food Compos Anal 33:59-66. https: doi.or/ 10.1016) 2013.09.010 52. QuW, Breksa APIIL Pan Z, Ma H 2012) Quantitative determi- nation of major polyphenol constituents in pomegranate prod ucts, Food Chem 132s1585-1591. htps/doi.org/10.101 64.006 hem.201 111.106 53. Tako E, Beebe SE, Reed S, Hart J, Giahn RP (2014) Polyphe- nolie compounds appear to Fimit the nutritional benefit of bio fortified higher iron black bean (Phaseolus vulgaris L) 3. Nutr 13:28, hntps:do.org/10-1186/1475-2801-13-28, 54, LiJ, He X. Li M, Zhao W, Lis L, Kong X (2015) Chemical fingerprint and quantitative analysis fo quality contol of poly- ‘phenols extracted from pomegranate peel by HPLC. Food Chem 176:7-11. htps:fdoi.onp/L0 1016 foodchem, 2014, 12.030 55. Nowak R, Olech M, Nowacka N (2014) Chapter 97-plant poly- ‘phenols as chemopreventive agents. Plyphen Human Health springer31 Page 220f 23 Journal of i and Tibo-Corrsion (2022) 831 56, 37, 38 30, o, 61 6 64, 66, a. 68 6, ™ Dis 2:1289-1307, haps. on 10.101 6/8978-0-12-398456, 2.00086-6 Haddock EA. Gupta RK, AL-Shafi SMK, Layden K, Haslam E, “Magnolato B (1982) The metabolism of gale acid and hexs- haydroxydiphenic acid in plans: biogenetic and molecule tax ‘omic considerations. Phytochemistry 21: 1049-1062, hp. ‘ors/10.101 6/3008 1-9422(00)82415- Kumbhar AG, Kishore K, Venkateswaran G, Balaji ¥ (2003) Dissolution of ickel ferrite and rae earths containing magnetite incitrc acid-EDTA-gllic acid formolation. Hydeometallurgy (68:17 181 psf ora/10.1016/S0304-386X(02)00202-5 Boumagoura M, Ghizellaoui S, Rhouati S, Cheap-Charpenticr H, Horner © (2021) Caleium carbonate sealing prevention by a teen chemical inhibitor, gallic cid. Water Envieon 3 35:998- 1006. eps:fdoi.onp/10.111 1h, 12690 Saced 8, Aslam 8, Mehmood T, Nascer R, Nawaz S, Mujahid H, Fieyal §, Anjum AA, Sultan A (2021) Production of gallic acid under solid-state fermentation by ulzing wast from food processing industries, Waste Biomass Valor 12:158-163 ip! {oi ors/10.1007/s12649-020-00080-2 [Nishimura T, Wang LY, Kusano K. Kitanaka $ (2005) Flavonoids iat mimic human ligands from the whole plants of Euphorbia nal. Chem Pharm Bull $3:305-308, bps one, 12487 ph. 305 Hale AL (2003) Screening potato genotypes for antioxidant activity, identification ofthe responsible compounds, and dif fercntating Russet Norkotah sins using AFLP and mierosstel- lite marker analysis, Ofice of Graduate studies of Texas A&M University. Genetics, 260 ‘You BR, Park WH (2010) Gallic acid-induced lung cancer cell death is related to glutathione depletion as well as reactive oxy- ‘en species increase, Toxicol In Vitro 24:1356-1362, hips ‘org/10.101 64.8. 2010.04.008) Kratz IM, Andrighett-Frohner CR, Leal PC, Nunes RJ, Yunes RA, Trybala B, Berpstrim . Barai CRM, Simies CMO (2008) Evaluation of antiHSV.2 activity of gale acid and penyl gal- late. Biol Pharm Bull 31:903-907. hip. ong/ 10-1248. 31.908) ‘Umar HL, Siraj B, Ajayi A, Jimob T, Chukwuemeka PO (2021) “Molecular docking sti of some selected gale acid deriv tives against five non-structural proteins of novel coronavi us. J Genet Eng Biotechnol 19:16, htps:(/doi.org/10.11867 SA3141-021-00120-7 Erlund | (2004) Review ofthe flavonoids quercetin, hesperctin, aad naringenin, Dietary sources, bioactivites, bioavailability, and epidemiology. Nutr Res 24°851-874. huips:/doi.org/0. 10164. autres.2004.07.005 Murray AP. Rodriguez S, Frontera MA, Tomas MA, Mulet MC (2004) Antioxidant metabolites from Limoniu brasiliense Boiss.) Kuntze. Z Naturforsch 59:477 480, bitps/d0. 019/10. 15 15/zne-2008-7-808 Keny SJ. Kumbhar AG, Thinaharan C, Venkateswaran G (2008) Gallic acid as a corrosion inhibitor of carton ste! in chemical ‘decontamination formulation. Corros Sek 50:41] 419. hips? {doi og/10. 1016, corse. 2007 06.024 Favre M, LANDOLT D, (1993) The influence of Gallic acid om the reduction of rust on painted steel surfaces. Corres Sci 34214811494. hups:fdoomp10.1016/0010-938X(03)90243-A Otani Y, Horivehi A. Yamaguchi A, Oyaian K, Yuasa M (2006) [Nom cyanide electoless gold plating using polyphenols as redu ing agents. J Electrochem Soe 153:63-66. hitpsdoi.org/1. 14g/12133716 (Obot TB, Madtankuma A (2015) Enhanced corrosion inhtition effect of tanni acid inthe presence of galic acid at mild steely LC acid solution interface. IInd Eng Chem 25:108-111. hpi! di org/ 10,1016) jee 2014.10.019 © springer 2. 14 18. 16. 7. 78 79 0. SI 2. 83. 4 ss. 8, Azab A (2017) Carob (Ceratonia siliguay: health, medicine and chemistry, Eur Chem Bull 610:456-469,bnip/do.org/10 I7628iech 2017.6.456-469) Puigventos L, Navarto M, Alechaga, E, Nine” O, Sain J Hernandez-Cassou S, Puignou L (2018) Determination of poy Phenolic profiles by liquid chromatography-clectrospray-tan- ‘dem mass spectrometey forthe authentication of fruit exacts Anal Bioanal Chem 407:597-608, hitp/oi.org/10. 1007) 50216-014-8208-2 Fadel F, Fattouch 8, Tahrouch S, Lahmar R, Benddou A, Hat A011) The phenolic compounds of Cerarona siligua pulps and seeds. J Mater Environ Sei 2:285-292 ‘djedd 8, Chaalal M, Richard G, Kati DE, Lépez-Nicolis R, Fauconnier ML, Louaileche H (2017) Assessment of anti- oxidant potential of phenolic compounds fractions of Algerian CCeratoni siliqua L. pos during ripening stages. Int Food Res J 24:2041-2049) Goulas V, Georgiou F (2020) Uitization of carob fruit as sources ‘of phenolic compounds with antioxidant potential extraction ‘optimization and application in food models. Foods 920, hp! oi. ore/10. 3390700560 10020 [Akalezi CO, Enenchaku CK, Oguzie FE (2013) Inhibition of cid ‘corrosion of mil stel hy biomass exact from the petersioths tmacrocarpus plant, J Mate Environ Sci 4:217-226 Elljjaji F, Belkhmima RA, Zerga B, Sfsira M, Taleb M, Eo ‘Touhami M, Hammout B (2014) Tim and temperature elcids- tion on see corrosion inhibition by 3-methyI-L-prap-2-ynylqu- noxalin-2(1H)-one in molar hydrochloric acid: part 2. Mater Environ Sei 5:263-270 Fouda AS, Shalai K, Kress AA (2015) Ceratonia siligua extract asa green corrosion inhibitor for copper and Bassin nitric acid solutions. Green Chem Lett Rev 8:17-29. huipsdoi.or/ 1. 10S0/17318253.2015.1073797 ‘Chetis K, Neila R, Benabbouba T, Sinii M, Reid H, El Attar H (2021) Origanum Elongatum asa green corrosion inhibitor for (C38 see in an acidic mestium. J Fail Anal and Preven 21:1683- 1696, hnpsfidi.or/10, 1007/1 1668-021-01218-3, Al EH, Himdan TA, Ahmed ZW (2019) Gallic acd as corrosion inhibitor for aluminum 6061 i alkali solutions. bn AL-HEiam ‘Pure Appl Sei 32:17-27. psd. ong/10.30526732.1 1983 Bammou L, Belkiaouda M, Salghi R, Benali O, Zatrouk A. Zarrok H, Hammouti B (2014) Corrosion inhibition of steel in sulfuric acidic solution by the Chenopodium Ambrosioides ‘extracts. J Assoe Arab Univ Basic Appl Sci 16:83-90. hips ‘oi.or 10.1016), jaubas.2013. 11.001 Hussin MH, Kassim MJ, Razali NN, Dahon NH, Nasshorudin D (2016) The effect of Tinasporaerispa extracts asa natural ind stel corrosion inhibitor in IM HCI solution. Arab J Chem 9:616-624, ipso ore/10.1016).arabje.201 1.07.02 Boudalia M, Fernindez-Domene RM, Tabysoui MH, Bellaou- chou A, Guenbour A, Gareia-Anton J (2019) Green approach to corrosion inhibition of stainless see i phosphoric acid of Ariemesia erba albamedium using plant extract, J Market Res 83573-3773. hnpsffoiora/10.1016.jm-2019.09.045 Mirinioui A, EL Atari H, Fail R, Zetzouh M, Jorio § (2021) Dysphania ambrosioides essential oi: an eco-friendly inhibi- tor for mild stel corrosion in hydrochloric and sulfure acid medium. 3 Bio Tribo Corros 7150. hitpsf/do.org/10.1007/ ‘S40735-021-00584-7 (ChebliH, Batah A, Asdadi A, Zaattani M,IdrissiHassani LM, Bounimi S, Chebli B, Salphi R (2017) Corrosion inhibition of stool in 1M hydrochloric acid medium by Thymus leptobotrss essential oils. Appl J Eavieon Eng Sei 3131-143. haps ‘org/10.48422/1MIST PRSM/ajces-v32.8997 Batah A, Anejar A, Belkhaouda M, Bammow L, BazziL, Ham- mouti B (2016) Effect of nitrphenyl derivatives on the carbonJournal of Bio- and Tribo-Corrosion (2022) 831 Page 23012331 7 88 89, 90, 91 92 98 94, 97 98, steel corrosion behavior in acidic medium: experimental and theoretical studies. Appl J Environ Sei 2-56-71 htps/doi ong! 10.48422/1MIST.PRSM/sjees-¥212.7102 Benabbouha T, Nila R, Sinii M, Chefira K, EI Atari H, [Rchid H (2020) The beown algae Cystosera Baccata extract as ‘rien corrosion inhibitor om carbon set in acidic media, SN ‘Appl Sei 2:662. tps. ora/10.1007/s42452-020.2492-y Gazi I JoroS,Siniti M, Fall R, lata H 2021) Experimental and theoretical studies on corosion inhibitory ation of arma (L) seeds extract on carbon see in IM HC. Mortoccan J Chern 9:542-563. hutps://doiorg/10-48317/IMIST PRSM/morjchem- WOi3. 22928 About 5, Chellouli M, Zovathi M, Benzidia B, Hammouch H, CChebalse D, Deemaj A, Erramli H, Bttach N, Hajjaji N 2018) [New formulation based on Ceratonia siligquaL. seo oil 38 & sreen corrosion inhibitor of iron in acidic medium. Anal Bioan Electrochem 10:789-804 LLebrini M, Robert F, Roos C (2011) Alkaloids extract rom Pali courea guianensis plantas corrosion inhibitor for C38 stee in {IM tydrochlorc acid medium. Int J Electrochem Sei 6:847-859 ‘Morad MS (2008) Inhibition of iron corrosion in acid solutions by Cefarexyl behaviour near and atthe corosion potenti. Cor ss Sei 50:436-448, hpi one/0.1016) ors 2007.08 018 EtAtari H, Lahmadi K, El brit A, Sinii M (2015) The adsorp- tion and corrosion inhibition of non-ionic surfactant on carbon ‘see srfice in hydrochloric acid. J Mater Chem 5:77-83. hs: oi ore/ 10.5923) jjme-20150508.04 Sacod MM, Ahmed M (2006) Effect of temperature on kinetics ‘nd adsorption profile of endothermie chemisorption process ‘Tin II -PAN loads! PUF system, Sep Sei Technol 41:705-722 bps 10, 108090 1496390500527003 Martinez S, Stern I (2002) Thermodynamic characterization of ‘metal dissofution and inhibitor adsorption processes inthe low athon stoelmimosatanninsulfrie acid systom. Appl Surf Sch 100:83-89, hips ong/10.1016/S0169-8832(02}00546.9 Cang H, Fei Z, Shao J, Shi W, Xu Q (2013) Corrosion inhib on of mid stel by aloes extract in HCI solution medium. Ln J Electrochem Sci 8:720-734 bot IB. Obi-Egbedi NO, Eseola AO (2011) Anticorros potential of 2-mesityl-IH-imidazo [4 5-1] [1,10] phenanthro- Tine on mild stee in sulfuric acid solution: experimental and theoretical stud: na Eng Chem Res 50:2008-2110. hips: ore/10.1021/ie102034¢ Bouknana D, Hammouti B, Messali M, Aouniti A, Sbaa M (2014) Olive pomace extract (OPE) as corrosion inhibitor for ‘eel in HCI medium. Asian Pac 1 Trop Dis 4:963-974. his: {do og/ 10. 1016/82222-1$08(14)60767-2 Eddy NO, Ebenso EE, Ibok UI (2010) Adsorption, synersis- tic inhibitive effect and quantum chemical studies of ampicilin (AMP) and halides forthe eotrosion of mild steel in H,$0,. J Appl Electrochem 40:445-456. ps://doi.org/10. 10077 $10800.009.0015-7, 99, Yago EA, Anaee RA, Abdulmajeed MH, Tomi THR, Kadhim MM (2019) Aminotrizole derivative as anti-corrosion material for Trai kerosene tanks: electrochemical, computational andthe surface study. ChemiseySelect 49883-9892, hips/doiorp/0 1002/set.201902398 Enran KM (2015) Effects of concentration and temperature on the corrosion properties ofthe Fe-Ni-Ma alloy in HC! solutions Res Chem Intermed 41:3583-3596,hitps//doiorg/10.1007/ SI164013-1873.9 Fouda AS, Mohamed OA, Elabbasy HM (2021) Ferula hermonis plant extract as safe corrosion inhibitor for zine in hydrochloric ‘cid soation, J B= Tribo-Corros 7:13, ipso. omp/101007F $40735.021-00570-2 Benabbovka T, Siniti M, El Atti H, Chefiea K, Chibi F Nola R, Rehid H (2018) Red Algae Halopiysincurvus extract, a2 green corrosion inhibitor of carbon stecl in hydrochle- te acid. J Bio- Tribo.Corros 4:39, hripsf/doiorg/ 10.1007) $40735.018-0161.0 Flores-De los Rios JP, Sinchez-Carrillo M, Nava-Dino CG, (Chacén-Nava JG, Gonzilez-Roderiguez JG, Huape-Padila E, Neri-Plores MA, Martncs-Villafaie A (2018) Opuntia ficus- indica exrat as green corosin inhibitor for earbon steel in IM. HCI solution Spectose.htpsdoi.one/10.115S/2015/714692 Handy A, EL-Gendy N 2013) Thermodynamic, adsorption and clectrochemical studies for corrosion inhibition of earbon see! ‘by henna extract in acid medium. Eeypt J Pet 22:17-25. hips: oi or/10.1016)ejpe.2012.06.002 Flores-De los Rios JP, Sinchoz-Carrillo M, Nava-Dino CG, Chacén-Nava J, Escobedo-Brotado MA, Monreal-Romero HA, Bautista-Margulis RG, Neri-Flores MA, Martinez-Vil- Tafae A (2015) Corrosion inhibition of mid sce! using Ago voideae extract in IM HCI solution. Int J Electrochem Sei 10:10210-10222 ‘Okjemute 0, Ochuko GU, Basil OO (2021) Corrosion inhibition for alloy 3D8L, (UINS $30403) in H2SO4 IM solution hy Cen trosema pubescens leaves extract. Appl Sart Sei Adv 3:100061 Inups:fdo.ony/10.1016f apsady-2021. 100061 Deyab MA (2014) Hydrogen generation by tin corrosion in lactic acid solution promoted by sodium perchlorate. J Power Sources 268:765-770, hips. ore 10,1016, jpowsou. 2014.06.14 Fazal MA, Rubaiee S, Al-Zahrai A (2019) Overview of the imeractons between auiomeaive materials an biodiesel obtained from different feedstocks, Fuel Process Technol 196:106178, htpssfdoiore/10.1016.fuproc.2019. 106178 ‘Chai TK, Moana KN, Tandon HC (2016) Study of new this zole based pyritine derivatives as penta corrosion inhibitors For mild see: theoretical and experimental approach. J. Corr, Int. inips:/doi.org/10.1155201609532809 1 tos. los. 106. ur. 10s. Publisher's Note Springer Nature remains neutral with regard {jurisdictional claims in published maps and institutional aiitions. springer