Citation: Marianne Seter, Gaetan M. A. Girard, Winnie W. Lee, Glen Deacon, Peter Junk, Bruce Hinton, Maria Forsyth. The influence of organic structure and rare earth metal cation on the corrosion efficiency observed on AS1020 steel compared with La(4OHCin)3[J]. AIMS Materials Science, 2015, 2(1): 1-15. doi: 10.3934/matersci.2015.1.1
| [1] | Aleksander Panichkin, Alma Uskenbayeva, Aidar Kenzhegulov, Axaule Mamaeva, Akerke Imbarova, Balzhan Kshibekova, Zhassulan Alibekov, Didik Nurhadiyanto, Isti Yunita . Assessment of the effect of small additions of some rare earth elements on the structure and mechanical properties of castings from hypereutectic chromium white irons. AIMS Materials Science, 2023, 10(3): 517-540. doi: 10.3934/matersci.2023029 |
| [2] | Roman I. Bogdanov, Yaakov B. Unigovski, Emmanuel M. Gutman, Iliya V. Ryakhovskikh, Roni Z. Shneck . Stress corrosion cracking of pipeline steels in near-neutral pH solutions: the role of mechanochemical and chemomechanical effects. AIMS Materials Science, 2019, 6(6): 1065-1085. doi: 10.3934/matersci.2019.6.1065 |
| [3] | A. A. Ayoola, N. Auta-Joshua, B. M. Durodola, O. J. Omodara, E. A. Oyeniyi . Combating A36 mild steel corrosion in 1 M H2SO4 medium using watermelon seed oil inhibitor. AIMS Materials Science, 2021, 8(1): 130-143. doi: 10.3934/matersci.2021009 |
| [4] | Felicia Ullstad, Jay R. Chan, Harry Warring, Natalie Plank, Ben Ruck, Joe Trodahl, Franck Natali . Ohmic contacts of Au and Ag metals to n-type GdN thin films. AIMS Materials Science, 2015, 2(2): 79-85. doi: 10.3934/matersci.2015.2.79 |
| [5] | Igor A Chaves, Robert E Melchers, Barbara Jardim do Nascimento, Jordan Philips, Mark Masia . Effects of inter-cavity corrosion on metallic wall ties in masonry structures. AIMS Materials Science, 2022, 9(2): 311-324. doi: 10.3934/matersci.2022019 |
| [6] | Kanishka Jha, Ravinder Kataria, Jagesvar Verma, Swastik Pradhan . Potential biodegradable matrices and fiber treatment for green composites: A review. AIMS Materials Science, 2019, 6(1): 119-138. doi: 10.3934/matersci.2019.1.119 |
| [7] | Madhuri Sharon, Farha Modi, Maheshwar Sharon . Titania based nanocomposites as a photocatalyst: A review. AIMS Materials Science, 2016, 3(3): 1236-1254. doi: 10.3934/matersci.2016.3.1236 |
| [8] | Yulia M. Panchenko, Andrey I. Marshakov, Ludmila A. Nikolaeva, Victoria V. Kovtanyuk . Prediction of first-year corrosion losses of copper and aluminum in continental regions. AIMS Materials Science, 2018, 5(4): 624-649. doi: 10.3934/matersci.2018.4.624 |
| [9] | Faiz Uddin Ahmed Shaikh, Mohamed Maalej, Salah Al Toubat . Ductile fibre reinforced cementitious composites (DFRCC) for improved corrosion durability of reinforced concrete columns. AIMS Materials Science, 2017, 4(5): 1078-1094. doi: 10.3934/matersci.2017.5.1078 |
| [10] | Muhammad Awwaluddin, Djoko Hadi Prajitno, Wisnu Ari Adi, Maman Kartaman, Tresna P. Soemardi . Mechanical properties and corrosion behavior of novel β-type biomaterial Zr-6Mo-4Ti-xY alloys in simulated body fluid Ringer's lactate solution for implant applications. AIMS Materials Science, 2020, 7(6): 887-901. doi: 10.3934/matersci.2020.6.887 |
In order to ameliorate the deterioration of metal substrates from the effects of harsh environments, environmentally friendly inhibitors are an ideal alternative to the carcinogenic and toxic chromates [1,2,3,4]. Such inhibitors are able to reinforce the metal oxide film or alternatively deposit complexes onto the metal substrate [4,5,6]. There is an increased demand for more environmentally friendly and cost effective protection against corrosion; such alternatives include inorganic compounds, e.g. nitrates, molybdates, and rare earths, and organic compounds such as carboxylates, phosphonates, phosphates and sulphonates [7,8,9]. Over the past decade Forsyth and co-workers have developed a range of rare earth organic compounds that show promise as environmentally friendly corrosion inhibitors for steel substrates, in particular lanthanum 4-hydroxycinnamate [ 10,11,12,13,14,15,16 ].
Recently, lanthanum 4-hydroxycinnamate in solution has shown remarkable corrosion inhibition properties with mild steel substrates [15]. This compound performs better as an inhibitor of steel at higher concentrations and under alkaline conditions. Under acidic pH conditions dissociation of the lanthanum 4-hydroxycinnamate, (La(4OHCin)3, occurs where the predominant species are lanthanum chloride [LaCl4]- and 4-hydroxylcinnamic acid as separate entities in solution. This leads to a rather low mixed inhibition effect compared with the strong anodic inhibition observed at higher pH values when the complex [LaL4]- is present [15]. The observation that slight cathodic inhibition was more evident under acidic conditions (except for high concentrations, i.e 1000 ppm where the inhibition was via both anodic and cathodic processes), and that this correlated with an excess of the LaCl4- species, strongly suggests that the speciation of La(4OHCin)3 is critical to the anodic nature and high efficiency of the inhibition and confirms the synergy of the organic and REM components previously suggested by Forsyth et al. [17].
It was certainly interesting to discover that this inhibitor might be capable of functioning well over a wide pH range, and that the inhibition mechanism could also vary over that range.
The study of the speciation for La(4OHCin)3 and its influence on the corrosion inhibition efficiency for steel substrates over a wide range of environmental conditions has provided an in depth perception of the working mechanism of the inhibitor. The aim of this current work was to investigate the influence of the position of substitution of the aromatic ring of the organic component of the inhibitor, and the influence of the rare earth metal coordinated by the cinnamate ion. This included analysis of lanthanum 2-hydroxycinnamate (La(2OHCin) 3), lanthanum 3-hydroxycinnamate (La (3OHCin) 3), praseodymium 4-hydroxycinnamate (Pr(4OHCin)3) and cerium 4-hydroxycinnamate (Ce(4OHCin)3). These studies could lead to more clever choices of inhibitor combinations, and a better understanding of the influence of chemical structure and bonding which could allow design of improved inhibition properties for this type of inhibitor compound.
The x-hydroxy cinnamic acid, where x is 2, 3 and 4, and the lanthanum, praseodymium, and cerium chlorides were purchased from Sigma Aldrich. The rare earth 4-hydroxycinnamates were prepared according to already published methodology [18] while the La(2OHCin) 3 and La (3OHCin) 3 were prepared by similar metathesis synthesis between the corresponding sodium salts and lanthanum chloride, refer to Electronic Supplementary Information (ESI) for experimental details, including the powder X-ray diffraction pattern for La (3OHCin) 3. All test solutions were prepared using reagent grade sodium chloride (Chem Supply), sodium hydroxide (Merck) and hydrochloric acid (Merck) solutions. The use of deionised water for the preparation of all solutions was adopted. The working electrodes used for the potentiodynamic polarisation experiments were machined from a cylindrical mild steel rod, Australian standard AS1020, to a 1.0 cm diameter (0.78 cm2). These electrodes were coated with an epoxy resin and attached to a teflon holder. The steel coupons used for the constant immersion corrosion tests were prepared also from a 2.0 cm diameter mild steel rod, AS1020, to a thickness of 0.3 cm.
The working electrodes for use in the potentiodynamic polarisation studies and the corrosion test coupons were abraded with silicon carbide paper to a P4000 grit finish from P320 grit. They were washed with tap water followed by DI water, and dried using nitrogen gas. Potentiodynamic polarisation and corrosion tests were carried out immediately after specimen preparation, which aided reproducibility.
The test solutions were prepared by dissolving the appropriate weights of each rare earth x-hydroxy cinnamate in 1 L to make concentrations of 400 and 600 ppm in 0.01 M sodium chloride solution. The pH of the solutions was adjusted using 0.01 M hydrochloric acid solution to achieve pH 2.5. The unadjusted pH of the prepared solution was pH 5.5. The solutions were exposed to a temperature-controlled laboratory atmosphere at approximately 22 °C.
Using potentiodynamic polarization experiments it is possible to determine the inhibitive nature of the rare earth cinnamates at different concentrations and solution pH in an open-to-air environment.
All polarisation experiments were carried out open-to-air using 100 mL of inhibitor solution in a standard three-electrode system consisting of a saturated calomel reference electrode, a titanium mesh counter electrode, and the working electrode. The cell assembly was located in a Faraday cage to prevent electrical interference. The exposed area of the working electrode was 0.78 cm2. After immersion the open circuit potential (OCP) was monitored for 12 hours, and then the potentiodynamic polarisation experiment was carried out at a scanning rate of 0.1667 mV s-1. The scans started at 200 mV more negative than Ecorr and continued through Ecorr for a range of 1.0 V in the positive direction. Polarisation curves were replicated in triplicate to assess reproducibility. All electrochemical measurements were conducted using a Biologic VMP multichannel potentiostat with EC-Lab v 10.32 software used for analysis. The current density (icorr) values were calculated using Tafel extrapolation methods. Where anodic and cathodic curves were near linear and symmetrical within +/− 50 mV from Ecorr, both Tafel slopes were extrapolated until the lines intersected at Ecorr. Where polarisation occurred for the cathodic reaction under acidic conditions, the slope for the cathodic region was extrapolated until it intersected the Ecorr value.
A Jeol 270 MHz spectrometer was used to collect 139La (38.2 MHz) NMR spectra. A double pulse spin echo experiment was used with a 180° pulse duration of 26.4 μs followed by a 90° pulse duration of 13.2 μs. Spectra were collected using 4096 transients, a 0.36 s acquisition time, and a 0.30 s relaxation delay. Each spectrum had the subsequent processing parameters applied using MestReNova 7.0.3: smoothing via Whittaker Smoother method, phase correction, and baseline correction. Peak widths at half height were measured. All NMR spectra are reported as their corresponding chemical shifts δ. A solution of 0.01 M lanthanum chloride inD2O was used as an external standard to reference the 139La chemical shifts.
NMR experiments were run at room temperature in 10 mm NMR tubes for the 400 ppm lanthanum x-hydroxycinnamate solutions at pH 5.5.
An Agilent Technologies LC/MSD TOF with acetonitrile as the mobile phase with a flow rate of 25 μL min-1 was used to collect mass spectrometry data. All inhibitor solutions were directly injected into the spectrometer, with nitrogen gas used for nebulisation. Data were collected using Agilent MassHunter Workstation Data Acquisition software and analysed using Agilent MassHunter Qualitative Analysis software.
Typical potentiodynamic polarisation curves for the inhibitors at 400 ppm and 600 ppm at pH 2.5 and 5.5 revealed that they all suppressed the anodic reaction to some degree (Figures 1-4). At these concentrations for pH 2.5, only a slight shift of Ecorr was observed toward more noble potentials, except for La(2OHCin) 3 which showed a slight cathodic shift in the potential. This is most likely due to the dissociation of the inhibitor into its rare earth chloride and cinnamate ions, a similar trend was seen in previous work for La(4OHCin)3 at pH 2.5 [15]. According to Table 1 and 3, Ecorr and icorr values calculated from the potentiodynamic polarisation curves for the inhibitors at concentrations of 400 and 600 ppm and pH 2.5 show that La(4OHCin)3 was by far the best inhibitor under these conditions with icorr being reduced compared to control solution values ( Figure 1 ). Interestingly, the Pr(4OHCin)3 and La (3OHCin) 3 showed comparable behaviour, to the results for the La(4OHCin)3. In contrast however, the Ecorr and icorr values calculated for the La(2OHCin) 3 and Ce(4OHCin)3 are very poor, being almost the same as for the control solution values.
Figure 1. Potentiodynamic polarisation curves for rare earth cinnamates in 0.01 M
NaCl solution at 400 ppm and pH 2.5. Polarisation curves are compared to a control
experiment consisting of 0.01M NaCl solution at pH 2.5.
Figure 2. Potentiodynamic polarisation curves for rare earth cinnamates in a 0.01M
NaCl solution at 400 ppm and pH 5.5. Polarisation curves are compared to a control
experiment consisting of 0.01M NaCl solution at pH 5.5.
Figure 3. Potentiodynamic polarisation curves for rare earth cinnamates in a 0.01M
NaCl solution at 600 ppm and pH 2.5. Polarisation curves are compared to a control
experiment consisting of 0.01M NaCl solution at pH 2.5.
Figure 4. Potentiodynamic polarisation curves for rare earth cinnamates in a 0.01M
NaCl solution at 600 ppm and pH 5.5. Polarisation curves are compared to a control
experiment consisting of 0.01M NaCl solution at pH 5.5.
| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 8.8 | 7.9 | 8.8 | 8.5 | -603 |
| La(2OHCin) 3 | 11.2 | 11.5 | - | 11.4 | -614 |
| Ce(4OHCin)3 | 9.0 | 9.3 | 9.1 | 9.2 | -601 |
| La (3OHCin) 3 | 5.2 | 5.7 | 4.9 | 5.3 | -601 |
| Pr(4OHCin)3 | 9.2 | 8.8 | 8.9 | 9.0 | -601 |
| La(4OHCin)3 | 4.5 | 4.3 | - | 4.4 | -599 |
DownLoad: CSV| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 2.1 | 2.1 | - | 2.1 | -515 |
| La(2OHCin) 3 | 2.3 | 2.3 | 2.1 | 2.2 | -512 |
| Ce(4OHCin)3 | 1.9 | 1.9 | 1.8 | 1.9 | -415 |
| La (3OHCin) 3 | 0.6 | 0.6 | 0.6 | 0.6 | -371 |
| Pr(4OHCin)3 | 0.4 | 0.4 | 0.4 | 0.4 | -348 |
| La(4OHCin)3 | 0.3 | 0.3 | - | 0.3 | -336 |
DownLoad: CSV| Icorr (μA/cm2) | ||||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr | |
| 0.01M NaCl | 8.8 | 7.9 | 8.8 | 8.5 | -603 | |
| La(2OHCin) 3 | 10.7 | 10.9 | - | 10.8 | -603 | |
| Ce(4OHCin)3 | 9.9 | 10.2 | 9.9 | 10.0 | -601 | |
| La (3OHCin) 3 | 5.5 | 5.9 | 5.2 | 5.6 | -601 | |
| Pr(4OHCin)3 | 4.1 | 4.1 | - | 4.1 | -594 | |
| La(4OHCin)3 | 1.8 | 2.1 | 2.1 | 2.0 | -595 |
DownLoad: CSVIncreasing the pH of the inhibitor solution to pH 5.5 gave a much clearer indication of the trend seen from the potentiodynamic polarisation curves found at pH 2.5, suggesting that the Pr(4OHCin)3 and La (3OHCin) 3 were almost as efficient as the La(4OHCin)3 (Figure 2 and 4). This is supported by the Tafel extrapolation data collected at both concentrations, as presented in Table 2 and 4.
| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 2.1 | 2.1 | - | 2.1 | -515 |
| La(2OHCin) 3 | 1.3 | 1.3 | 1.3 | 1.3 | -481 |
| Ce(4OHCin)3 | 0.5 | 0.4 | - | 0.5 | -419 |
| La (3OHCin) 3 | 0.4 | 0.4 | 0.4 | 0.4 | -372 |
| Pr(4OHCin)3 | 0.3 | 0.3 | 0.3 | 0.2 | -363 |
| La(4OHCin)3 | 0.7 | 0.6 | 0.6 | 0.6 | -278 |
DownLoad: CSVPrevious work has shown that the use of NMR spectroscopy in combination with electrospray mass spectrometry gives valuable information about the species present in solution in a given environment [15].
NMR is a powerful chemical characterisation tool and has been used to evaluate the change in solution speciation of the La(4OHCin)3 under various pH and concentration conditions [15].
However, NMR spectroscopy has limitations in that it can only analyse NMR active nuclei, therefore in this case only the lanthanum species can be evaluated as the cerium and praseodymium nuclei are not active [19]. A spectrum of lanthanum chloride inD2O was used as a reference where the signal resonates at δ 4.89 ppm. From Figure 5 it can be seen that there was a clear shift to higher resonances as the position of the hydroxyl group was changed from 4-hydroxy- to 3-hydroxy- and then the 2-hydroxycinnamate respectively.
Figure 5. 139LaNMR spectra of lanthanum 2-hydroxy cinnamate, La(2OHCin) 3 (blue), lanthanum 3-hydroxy cinnamate, La (3OHCin) 3 (green) and lanthanum4-hydroxy cinnamate, La(4OHCin)3 (red), at 600 ppm and pH 5.5.
Previous work has shown that an increase in concentration of the La(4OHCin)3 at any given pH results in a shift to higher frequencies and increases the broadness of the peak [15]. It was concluded from the speciation study of the La(4OHCin)3 that a shift to higher frequencies and increasing broadness were an indication of the presence of a number of different species in solution, and that the exchange between the species could lead to short relaxation times (T2) and lifetime broadening [20,21].
Table 5 presents the observed shifts found for each solution of lanthanum 2, 3, and 4-hydroxy cinnamate at a concentration of 400 ppm in a solution of pH 5.5 in 0.01 M NaCl. These data clearly indicate that, the resonance shifts to higher frequencies and the peak width at half height increased in going from La(4OHCin)3 to La(2OHCin) 3. The shift in NMR frequency signifies a change in the lanthanum environment possibly brought about by differences in the coordination. The changing width could indicate an increasing number of species and possible exchange between these. Being a quadrupolar nucleus, the width could also indicate an increasingly asymmetric environment. This speciation behaviour was further investigated using ESMS as discussed below.| TestSolution | NMRShift (ppm) | ½Width (Hz) |
| LaCl3Reference in D2O | 4.9 | 179 |
| La(2OHCin) 3 | 16.4 | 630 |
| La (3OHCin) 3 | 12.5 | 500 |
| La(4OHCin)3 | 9.8 | 470 |
DownLoad: CSVESMS measures the mass-to-charge ratio of charged particles. It has been a valuable analytical technique to determine the mass of particles and the elemental composition of a sample in our previous work [15]. The behaviour of the chemical equilibrium will change when there are changes to the reaction conditions, for example a change in the concentration, and therefore a change in the mass-to-charge ratio of the charged species is expected to be observed. Table 6 presents a summary of the rare earth complex species that are expected in the solutions investigated here. Each species containing rare earth metal and/or chloride ions will appear with a particular isotope pattern, these clusters found in the mass spectra, in ESI Figures S1−S5, have been supported by simulated mass spectra and can be found in ESI Figure S6 to S14. Additionally, all reported peaks are the main peak of the associated cluster.
ESI Figures S1 to S5 show, the electrospray mass spectrum obtained for 600 ppm La (xOH-Cin) 3 and RE (4OHCin) 3 (RE = Ce, Pr) at pH 5.5. This data demonstrates the change in the mass-to-charge ratio of the species present according to the expected species in Table 6, and also shows that not all inhibitors have the same species present under the given conditions.
| Mass | Species | Mass | Species | Mass | Species |
| 281 | [LaCl4]- | 282 | [CeCl4]- | 283 | [PrCl4]- |
| 407 | [LaLCl3]- | 408 | [CeLCl3]- | 409 | [PrLCl3]- |
| 535 | [LaL2Cl2]- | 536 | [CeL2Cl2]- | 537 | [PrL2Cl2]- |
| 663 | [LaL3Cl]- | 664 | [CeL3Cl]- | 665 | [PrL3Cl]- |
| 791 | [LaL4]- | 792 | [CeL4]- | 793 | [PrL4]- |
DownLoad: CSVPrevious work published for the speciation work on La(4OHCin)3 suggested the presence of species as listed in Table 6 (given the mass-to-charge ratios) in varying amounts depends on environmental conditions. An equilibrium between these species was postulated as shown in Equation (1). It was found that the concentration and pH condition was linked to the species present in solution (also supported by NMR spectroscopy). The highest inhibition efficiency observed from potentiodynamic polarisation correlated with the speciation tending towards the right of this equilibrium. This suggests that when species such as [LaL3Cl]- and [LaL4]- (L = xOHCin) were present, the observed inhibition was greater than when they were absent.
It was found from the spectrum of La(2OHCin) 3 (ESI Figure S4) that the majority of the species present at this particular concentration and solution pH is of lower molecular weight, and consists mainly of species that lie to the left of the equilibrium reaction (Equation 1). In particular and worth noting is the low concentration of the [LaL4]- species at 791 mass units. Some of the low molecular weight species present in the spectrum have been attributed to species containing lanthanum and hydroxides and may include species such as LaL2 (OH) 3 (H2O) 6Cl]3-, [LaL2 (OH) 3 (H2O) 6Cl2]4- and [LaL2 (OH) 3 (H2O) 6Cl3]4-. These species not being prevalent in the electrospray mass spectrum of La(4OHCin)3.
The electrospray mass spectrum obtained for La (3OHCin) 3 (ESI Figure S3) also shows a number of different species, not unlike the La(2OHCin) 3 spectrum. However, the apparent concentrations of these species were more evenly distributed along with the high mass-to-charge ratios of species such as [LaL3Cl]- and [LaL4]- found in the La(4OHCin)3 spectrum.
As can be seen from the mass spectrum obtained for Pr(4OHCin)3 (Figure 6), it appears similar to that found for La(4OHCin)3 from previous studies. In particular, the peak at 793 mass units is representative of [PrL4]- which appears to be the species contributing to the best inhibition seen for mild steel.
Figure 6. Mass spectrum of praseodymium4-hydroxy cinnamate (Pr(4OHCin)3) at 600 ppm in 0.01 M NaCl solutionat pH 5.5
The spectrum collected for Ce(4OHCin)3 (ESI Figure S1) appears to be very different from the other compounds; there are fewer species present in solution, which may indicate that the solution equilibria for this inhibitor are quite different. Worth noting at this point is that the solubility of the Ce(4OHCin)3 is high in comparison with the other compounds.
We have previously discussed the La(4OHCin)3 inhibition behaviour in the context of the interaction on the metal surface[13,14,15], where a bimetallic film involving the lanthanum complex and the underlying iron from the steel surface forms, and in turn reduces the rate of further metal dissolution at these sites. However, the corrosion is not completely inhibited and some level of corrosion still occurs, leading to changes in the local pH. This change in pH, in particular at the cathodic sites, leads to the hydrolysis of the La(4OHCin)3 species forming a dynamic mixture of lanthanum hydroxide, iron oxide and bimetallic species.
This mechanism was supported in previous work using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) vibrational spectroscopy [16,17]. This technique proved to be a valuable tool in developing an understanding of the nature of the species on the inhibited surface [22], allowing the examination of the inhibiting complexes attached to the surface without the need to remove the film.
In the current study, the reduction in the observed Icorr from La(2OHCin) 3, Ce(4OHCin)3, La (3OHCin) 3, Pr(4OHCin)3 to La(4OHCin)3 may be related to an increase in the availability of hydroxyl groups as donors in bonding to neighbouring molecules on the steel surface, which therefore influences the bimetallic complex formed.
Based on the schematic protective film shown in Figure 7, the orientations of the hydroxyl group are important for further interactions beyond the initial layer of bimetallic complex. As described in previous reports, the terminal hydroxyl group from the 4-hydroxycinnamate ligand (Fig 7a) is capable of intermolecular interactions (through hydrogen bonding) to nearby molecules of the inhibitor. These effectively increase the thickness of the protective film and result in the precipitation of the rare earth metal hydroxide and iron oxides/hydroxides onto the surface due to local changes in the pH. With this ongoing process, it would be reasonable to suggest that the protective film could ultimately lead to a more uniform surface coverage [23].
Figure 7. Aschematic hypothesised mechanism of action for the protection of a steelsubstrate using the inhibitor (a) RE (4OHCin) 3 where RE = La, Ce andPr, (b) La (3OHCin) 3 and (c) La(2OHCin) 3.
For the La (3OHCin) 3, the mechanism of film formation could be very similar in that the hydroxyl group is positioned in a geometry that is accessible to promote further interactions either with the La ion or the underlying substrate, as shown in Figure 7b. Whilst for the La(2OHCin) 3 inhibitor, the ortho-substitution causes the hydroxyl groups to be shielded by the aromatic ring (Fig 7c), sterically hindering further interactions, and therefore eliminating the possibility of forming a multilayer surface film that might be possible for either the La (3OHCin) 3 and the La(4OHCin)3 inhibitors.
In the case of Pr(4OHCin)3 and Ce(4OHCin)3, the hydroxy group is in the para-position, as in the La(4OHCin)3, and therefore capable of further intermolecular interactions. This would explain the excellent inhibition shown by the Pr(4OHCin)3. In contrast, Ce(4OHCin)3 does not show good inhibiting properties consistent with the differences in speciation observed in the electrospray mass spectroscopy. Interestingly, we observed that the solubility of the cerium compounds is generally significantly higher than the praseodymium and lanthanum analogues (for example Ce(4OHCin)3 at 1000 ppm readily dissolves in the sodium chloride solution whereas Pr(4OHCin)3 and La(4OHCin)3 compounds are difficult to dissolve beyond 600 ppm at neutral pH). This is contrary to the solubility data in water for La(4OHCin)3 and Ce(4OHCin) 3 which were found to be 961 ppm and 673 ppm, respectively, where the lanthanum compound was marginally more soluble than the cerium derivative [24]. The difference in solubility is often related to the size of the rare earth metal cation, however given that La3+ > Ce3+ > Pr3+, this cannot explain our observations here. Furthermore, the X-ray powder diffraction patterns show that the compounds are all iso-structural having similar d-spacings and intensities and that the isomorphous RE(4OHCin) 3 have very similar ν(OH) absorptions [18]. Additional information on the solid state compositions and structures of the rare earth n-hydroxycinnamates can be found in the ESI. The other differences amongst these rare earth metal cations is the existence of two redox states for Ce(III/IV) compared with Pr(III) and La(III). It has been previously shown that Ce(III) can readily oxidise from the Ce3+ to Ce4+ in the presence of oxygen and water with some ligands [25]. The presence of this redox couple may result in the formation of different complex species that would not otherwise be seen in the lanthanum and/or praseodymium systems. This possibility is supported by the difference seen in the mass spectrum of the cerium compound, ESI Figure S1, compared to lanthanum 4-hydroxycinnamate (ESI Fig S5). However, further work is required to fully understand the complexation in this system, as we are unable to assign the spectrum obtained in this case. Thus the mechanism of inhibition for the Ce(4OHCin)3 complex differs from that of La(4OHCin)3 and Pr(4OHCin)3 due to both the solubility and the oxidation states (Ce3+ to Ce4+). In our previous work, we have shown that the nature of the metal - ligand complexes in solution are critical for the corrosion inhibition efficiency; in particular the presence of species such as [LnL4]- and [LnL3Cl]-. The absence of these in the case of Ce(4OHCin)3 may contribute to the poorer inhibition. Thus the model proposed in Figure 6 may not apply to Ce(4OHCin)3.
The present work has focussed on understanding the influence of the rare earth metal cations and the hydroxycinnamate structure on the corrosion inhibition properties for the rare earth cinnamate compounds. Consistent with previous work, the La(4OHCin)3 performed best with Pr(4OHCin)3 and La (3OHCin) 3 showing near comparable inhibition efficiencies using potentiodynamic polarisation measurements. On the other hand, the Ce(4OHCin)3 showed poorer inhibition properties correlating with the markedly different species observed in the mass spectrum. We hypothesise that this is related in some way to increased solubility and the two accessible oxidation states for cerium. Furthermore, the availability of the phenol group of the rare earth hydroxycinnamates for intermolecular interactions appears to be imperative for good corrosion inhibition as demonstrated by the poorer performance of La(2OHCin) 3 with the phenol group shielded by the phenyl-ring.
We thank the ARC Centre of Excellence for Electromaterials and the SRC for Green Chemistry for funding resources in this study. We also gratefully acknowledge the invaluable discussions with Dr. Craig Forsyth.
All authors declare no conflicts of interest in this paper.
| [1] |
McCafferty E (1979) Inhibition of the Crevice Corrosion of Iron in Chloride Solutions by Chromate. J Electrochem Soc 126: 385-390. doi: 10.1149/1.2129047
|
| [2] | Maji KD, Singh I (1982) Studies on the effect of sulphide ions on the inhibition efficiency of chromate on mild steel using radio—tracer technique. Anti-Corros Method M 29: 8-14. |
| [3] |
McCafferty E (1989) Thermodynamic aspects of the crevice corrosion of iron in chromate/chloride solutions. Corros Sci 29: 391-401. doi: 10.1016/0010-938X(89)90094-2
|
| [4] | 6. Roberge PR (2000) Handbook of Corrosion Engineering. New Jersey: McGraw Hill. |
| [5] |
7. Sinko J (2001) Challenges of chromate inhibitor pigments replacement in organic coatings. Prog Org Coat 42: 267-282. doi: 10.1016/S0300-9440(01)00202-8
|
| [6] |
8. Monticelli C, Frignani A, Trabanelli G (2002) Corrosion inhibition of steel in chloride-containing alkaline solutions. J Appl Electrochem 32: 527-535. doi: 10.1023/A:1016507713022
|
| [7] |
9. Grundmeier G, Schmidt W, Stratmann M (2000) Corrosion protection by organic coatings: electrochemical mechanism and novel methods of investigation. Electrochim Acta 45:2515-2533. doi: 10.1016/S0013-4686(00)00348-0
|
| [8] |
10. Blin F, Koutsoukos P, Klepetsianis P, et al. (2007) The corrosion inhibition mechanism of new rare earth cinnamate compounds—Electrochemical studies. Electrochim Acta 52: 6212-6220. doi: 10.1016/j.electacta.2007.04.001
|
| [9] |
11. Blin F, Leary SG, Wilson K, et al. (2004) Corrosion Mitigation of Mild Steel by New Rare Earth Cinnamate Compounds. J Appl Electrochem 34: 5-599. doi: 10.1023/B:JACH.0000021932.87043.7b
|
| [10] | 12. Deacon GB, Forsyth M, Junk P, et al. (2008) From chromates to rare earth carboxylates: a greener take on corrosion inhibition. Chemistry Australia 75: 18-21. |
| [11] | 13. Forsyth M, Seter M, Hinton B, et al. (20 New ‘Green’ Corrosion Inhibitors Based on Rare Earth Compounds. Aust J Chem 64:812-819. |
| [12] |
14. Catubig R, Seter M, Neil W, et al. (2011) Effects of Corrosion Inhibiting Pigment Lanthanum 4-Hydroxy Cinnamate on the Filiform Corrosion of Coated Steel. J Electrochem Soc 158: C353-C358. doi: 10.1149/2.012111jes
|
| [13] |
15. Seter M, Hinton B, Forsyth M (2012) Understanding Speciation of Lanthanum 4-Hydroxy Cinnamate and its Impact on the Corrosion Inhibition Mechanism for AS1020 Steel. J Electrochem Soc 159: C181-C189. doi: 10.1149/2.058204jes
|
| [14] |
16. Blin F, Leary SG, Deacon GB, et al. (2006) The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors. Corros Sci 48: 404-419. doi: 10.1016/j.corsci.2005.01.009
|
| [15] |
17. Forsyth M, Forsyth CM, Wilson K, et al. (2002) ATR characterisation of synergistic corrosion inhibition of mild steel surfaces by cerium salicylate. Corros Sci 44: 2651-2656. doi: 10.1016/S0010-938X(02)00024-0
|
| [16] |
18. Deacon GB, Forsyth M, Junk PC, et al. (2009) Synthesis and Characterisation of Rare Earth Complexes Supported by para-Substituted Cinnamate Ligands. Z Anorg Allg Chem 635:833-839. doi: 10.1002/zaac.200801379
|
| [17] | 19. Reuben J, Fiat D (1969) Nuclear Magnetic Resonance Studies of Solutions of the Rare-Earth Ions and Their Complexes. IV. Concentration and Temperature Dependence of the Oxygen-Transverse Relaxation in Aqueous Solutions. J Chem Phys 51: 4918-4927. |
| [18] |
20. Aime S, Fasano M, Terreno E (1998) Lanthanide(III) chelates for NMR biomedical applications. Chem Soc Rev 27: 19-29. doi: 10.1039/a827019z
|
| [19] |
21. Bryant RG (3) The NMR time scale. J Chem Educ 60: 933-935. doi: 10.1021/ed060p933
|
| [20] |
22. Pandey A, Murty NSS, Patel SM (0) Application of infrared spectroscopy in the study of corrosion products. Process Contr Qual 11: 363-368. doi: 10.1163/156856600750250743
|
| [21] | 23. Deacon GB, Forsyth CM, Behrsing T, et al. (2002) Heterometallic CeIII-FeIII-salicylate networks: models for corrosion mitigation of steel surfaces by the Green inhibitor, Ce(salicylate)3. Chem Commun 23: 2820-28 |
| 1. | J. P. Echeverry, I. C. Gerber, Theoretical investigations of the anisotropic optical properties of distorted 1TReS2 and ReSe2 monolayers, bilayers, and in the bulk limit, 2018, 97, 2469-9950, 10.1103/PhysRevB.97.075123 | |
| 2. | Siti Shafiah Shazali, Ahmad Amiri, Mohd. Nashrul Mohd Zubir, Shaifulazuar Rozali, Mohd Zakuan Zabri, Mohd Faizul Mohd Sabri, Facile hydrothermal method for synthesizing nitrogen-doped graphene nanoplatelets using aqueous ammonia: dispersion, stability in solvents and thermophysical performances, 2018, 5, 2053-1591, 035042, 10.1088/2053-1591/aab527 | |
| 3. | Ali Asghar Javidparvar, Reza Naderi, Bahram Ramezanzadeh, Manipulating graphene oxide nanocontainer with benzimidazole and cerium ions: Application in epoxy-based nanocomposite for active corrosion protection, 2020, 165, 0010938X, 108379, 10.1016/j.corsci.2019.108379 | |
| 4. | Weitao Su, Honglei Dou, Jinwei Li, Dexuan Huo, Ning Dai, Li Yang, Tuning photoluminescence of single-layer MoS2using H2O2, 2015, 5, 2046-2069, 82924, 10.1039/C5RA12450F | |
| 5. | Nicholas C. Thomas, Owen A. Beaumont, Glen B. Deacon, Cornelius Gaertner, Craig M. Forsyth, Anthony E. Somers, Peter C. Junk, Preparation and Structures of Rare Earth 3-Benzoylpropanoates and 3-Phenylpropanoates, 2020, 73, 0004-9425, 1250, 10.1071/CH20197 | |
| 6. | Alexander V. Zabula, Soumyajit Dey, Jerome R. Robinson, Thibault Cheisson, Robert F. Higgins, Gaurang Bhargava, Robert C. Nahas, Doug Cinoman, Michael Kerins, Eric C. Houze, Eric J. Schelter, Screening of molecular lanthanide corrosion inhibitors by a high-throughput method, 2020, 165, 0010938X, 108377, 10.1016/j.corsci.2019.108377 | |
| 7. | Ali Asghar Javidparvar, Reza Naderi, Bahram Ramezanzadeh, Designing a potent anti-corrosion system based on graphene oxide nanosheets non-covalently modified with cerium/benzimidazole for selective delivery of corrosion inhibitors on steel in NaCl media, 2019, 284, 01677322, 415, 10.1016/j.molliq.2019.04.028 | |
| 8. | Yu Peng, Anthony E. Hughes, Glen B. Deacon, Peter C. Junk, Bruce R.W. Hinton, Maria Forsyth, James I. Mardel, Anthony E. Somers, A study of rare-earth 3-(4-methylbenzoyl)-propanoate compounds as corrosion inhibitors for AS1020 mild steel in NaCl solutions, 2018, 145, 0010938X, 199, 10.1016/j.corsci.2018.09.022 | |
| 9. | Jhonatan Soto Puelles, Mahdi Ghorbani, Ruhamah Yunis, Laura L. Machuca, Herman Terryn, Maria Forsyth, Anthony E. Somers, Electrochemical and Surface Characterization Study on the Corrosion Inhibition of Mild Steel 1030 by the Cationic Surfactant Cetrimonium Trans-4-hydroxy-cinnamate, 2021, 6, 2470-1343, 1941, 10.1021/acsomega.0c04733 | |
| 10. | Yu Peng, Anthony E. Hughes, James I. Mardel, Glen B. Deacon, Peter C. Junk, Maria Forsyth, Bruce R. W. Hinton, Anthony E. Somers, Leaching Behavior and Corrosion Inhibition of a Rare Earth Carboxylate Incorporated Epoxy Coating System, 2019, 11, 1944-8244, 36154, 10.1021/acsami.9b13722 | |
| 11. | N. T. Hoai, Tran Thi Yen Ngoc, Nguyen Dang Nam, Tran Thu Thuy, Cao Thi Thu Trang, Nguyen Duy Hai, Truong Khoi Nguyen, Effect oF β-Alanine on The Preparation of 4-Ethoxy-Cinnamic Acid, 2018, 12, 1874-088X, 58, 10.2174/1874088X01812010058 | |
| 12. | A. E. Somers, Y. Peng, A. L. Chong, M. Forsyth, D. R. MacFarlane, G. B. Deacon, A. E. Hughes, B. R. W. Hinton, J. I. Mardel, P. C. Junk, Advances in the development of rare earth metal and carboxylate compounds as corrosion inhibitors for steel, 2020, 55, 1478-422X, 311, 10.1080/1478422X.2020.1754600 | |
| 13. | Esther Udabe, Maria Forsyth, Anthony Somers, David Mecerreyes, Metal-free coumarate based ionic liquids and poly(ionic liquid)s as corrosion inhibitors, 2020, 1, 2633-5409, 584, 10.1039/D0MA00243G | |
| 14. | Glen B. Deacon, Peter C. Junk, Winnie W. Lee, Maria Forsyth, Jun Wang, Rare earth 3-(4′-hydroxyphenyl)propionate complexes, 2015, 39, 1144-0546, 7688, 10.1039/C5NJ00787A | |
| 15. | Anthony E. Somers, Bruce R.W. Hinton, Caspar de Bruin-Dickason, Glen B. Deacon, Peter C. Junk, Maria Forsyth, New, environmentally friendly, rare earth carboxylate corrosion inhibitors for mild steel, 2018, 139, 0010938X, 430, 10.1016/j.corsci.2018.05.017 | |
| 16. | Nguyen Dang Nam, Vo Quoc Thang, Nguyen To Hoai, Pham Van Hien, Yttrium 3-(4-nitrophenyl)-2-propenoate used as inhibitor against copper alloy corrosion in 0.1 M NaCl solution, 2016, 112, 0010938X, 451, 10.1016/j.corsci.2016.08.005 | |
| 17. | R. A. Catubig, W. C. Neil, G. McAdam, R. Yunis, M. Forsyth, A. E. Somers, Multifunctional Inhibitor Mixtures for Abating Corrosion on HY80 Steel under Marine Environments, 2020, 167, 1945-7111, 021503, 10.1149/1945-7111/ab681e | |
| 18. | Ana Suárez-Vega, Cecilia Agustín-Sáenz, Luke A. O'Dell, Fabiola Brusciotti, Anthony Somers, Maria Forsyth, Properties of hybrid sol-gel coatings with the incorporation of lanthanum 4-hydroxy cinnamate as corrosion inhibitor on carbon steel with different surface finishes, 2021, 561, 01694332, 149881, 10.1016/j.apsusc.2021.149881 | |
| 19. | Rainier A. Catubig, Agnes Michalczyk, Wayne C. Neil, Grant McAdam, John Forsyth, Mahdi Ghorbani, Ruhamah Yunis, M. Leigh Ackland, Maria Forsyth, Anthony E. Somers, George Koutsantonis, Inhibitor mixture for reducing bacteria growth and corrosion on marine steel, 2022, 75, 0004-9425, 619, 10.1071/CH21266 | |
| 20. | Anđela Simović, Branislav Milovanović, Mihajlo Etinski, Luka Matović, Jelena B. Bajat, Innovative hybrid and bifunctional rare earth complexes as corrosion inhibitors for AA2024 Alloy: Electrochemical and surface analysis enhanced by DFT/MD simulation, 2024, 01694332, 160718, 10.1016/j.apsusc.2024.160718 | |
| 21. | Vidushi P. Vithana, Zhifang Guo, Glen B. Deacon, Peter C. Junk, Syntheses, Structures, and Corrosion Inhibition of Various Alkali Metal Carboxylate Complexes, 2023, 28, 1420-3049, 5515, 10.3390/molecules28145515 |
Figures(7) / Tables(6)
Marianne Seter, Gaetan M. A. Girard, Winnie W. Lee, Glen Deacon, Peter Junk, Bruce Hinton, Maria Forsyth. The influence of organic structure and rare earth metal cation on the corrosion efficiency observed on AS1020 steel compared with La(4OHCin)3[J]. AIMS Materials Science, 2015, 2(1): 1-15. doi: 10.3934/matersci.2015.1.1
| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 8.8 | 7.9 | 8.8 | 8.5 | -603 |
| La(2OHCin) 3 | 11.2 | 11.5 | - | 11.4 | -614 |
| Ce(4OHCin)3 | 9.0 | 9.3 | 9.1 | 9.2 | -601 |
| La (3OHCin) 3 | 5.2 | 5.7 | 4.9 | 5.3 | -601 |
| Pr(4OHCin)3 | 9.2 | 8.8 | 8.9 | 9.0 | -601 |
| La(4OHCin)3 | 4.5 | 4.3 | - | 4.4 | -599 |
DownLoad: CSV| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 2.1 | 2.1 | - | 2.1 | -515 |
| La(2OHCin) 3 | 2.3 | 2.3 | 2.1 | 2.2 | -512 |
| Ce(4OHCin)3 | 1.9 | 1.9 | 1.8 | 1.9 | -415 |
| La (3OHCin) 3 | 0.6 | 0.6 | 0.6 | 0.6 | -371 |
| Pr(4OHCin)3 | 0.4 | 0.4 | 0.4 | 0.4 | -348 |
| La(4OHCin)3 | 0.3 | 0.3 | - | 0.3 | -336 |
DownLoad: CSV| Icorr (μA/cm2) | ||||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr | |
| 0.01M NaCl | 8.8 | 7.9 | 8.8 | 8.5 | -603 | |
| La(2OHCin) 3 | 10.7 | 10.9 | - | 10.8 | -603 | |
| Ce(4OHCin)3 | 9.9 | 10.2 | 9.9 | 10.0 | -601 | |
| La (3OHCin) 3 | 5.5 | 5.9 | 5.2 | 5.6 | -601 | |
| Pr(4OHCin)3 | 4.1 | 4.1 | - | 4.1 | -594 | |
| La(4OHCin)3 | 1.8 | 2.1 | 2.1 | 2.0 | -595 |
DownLoad: CSV| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 2.1 | 2.1 | - | 2.1 | -515 |
| La(2OHCin) 3 | 1.3 | 1.3 | 1.3 | 1.3 | -481 |
| Ce(4OHCin)3 | 0.5 | 0.4 | - | 0.5 | -419 |
| La (3OHCin) 3 | 0.4 | 0.4 | 0.4 | 0.4 | -372 |
| Pr(4OHCin)3 | 0.3 | 0.3 | 0.3 | 0.2 | -363 |
| La(4OHCin)3 | 0.7 | 0.6 | 0.6 | 0.6 | -278 |
DownLoad: CSV| TestSolution | NMRShift (ppm) | ½Width (Hz) |
| LaCl3Reference in D2O | 4.9 | 179 |
| La(2OHCin) 3 | 16.4 | 630 |
| La (3OHCin) 3 | 12.5 | 500 |
| La(4OHCin)3 | 9.8 | 470 |
DownLoad: CSV| Mass | Species | Mass | Species | Mass | Species |
| 281 | [LaCl4]- | 282 | [CeCl4]- | 283 | [PrCl4]- |
| 407 | [LaLCl3]- | 408 | [CeLCl3]- | 409 | [PrLCl3]- |
| 535 | [LaL2Cl2]- | 536 | [CeL2Cl2]- | 537 | [PrL2Cl2]- |
| 663 | [LaL3Cl]- | 664 | [CeL3Cl]- | 665 | [PrL3Cl]- |
| 791 | [LaL4]- | 792 | [CeL4]- | 793 | [PrL4]- |
DownLoad: CSV| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 8.8 | 7.9 | 8.8 | 8.5 | -603 |
| La(2OHCin) 3 | 11.2 | 11.5 | - | 11.4 | -614 |
| Ce(4OHCin)3 | 9.0 | 9.3 | 9.1 | 9.2 | -601 |
| La (3OHCin) 3 | 5.2 | 5.7 | 4.9 | 5.3 | -601 |
| Pr(4OHCin)3 | 9.2 | 8.8 | 8.9 | 9.0 | -601 |
| La(4OHCin)3 | 4.5 | 4.3 | - | 4.4 | -599 |
| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 2.1 | 2.1 | - | 2.1 | -515 |
| La(2OHCin) 3 | 2.3 | 2.3 | 2.1 | 2.2 | -512 |
| Ce(4OHCin)3 | 1.9 | 1.9 | 1.8 | 1.9 | -415 |
| La (3OHCin) 3 | 0.6 | 0.6 | 0.6 | 0.6 | -371 |
| Pr(4OHCin)3 | 0.4 | 0.4 | 0.4 | 0.4 | -348 |
| La(4OHCin)3 | 0.3 | 0.3 | - | 0.3 | -336 |
| Icorr (μA/cm2) | ||||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr | |
| 0.01M NaCl | 8.8 | 7.9 | 8.8 | 8.5 | -603 | |
| La(2OHCin) 3 | 10.7 | 10.9 | - | 10.8 | -603 | |
| Ce(4OHCin)3 | 9.9 | 10.2 | 9.9 | 10.0 | -601 | |
| La (3OHCin) 3 | 5.5 | 5.9 | 5.2 | 5.6 | -601 | |
| Pr(4OHCin)3 | 4.1 | 4.1 | - | 4.1 | -594 | |
| La(4OHCin)3 | 1.8 | 2.1 | 2.1 | 2.0 | -595 |
| Icorr (μA/cm2) | |||||
| Solution | 1 | 2 | 3 | Av. Icorr | Ecorr |
| 0.01M NaCl | 2.1 | 2.1 | - | 2.1 | -515 |
| La(2OHCin) 3 | 1.3 | 1.3 | 1.3 | 1.3 | -481 |
| Ce(4OHCin)3 | 0.5 | 0.4 | - | 0.5 | -419 |
| La (3OHCin) 3 | 0.4 | 0.4 | 0.4 | 0.4 | -372 |
| Pr(4OHCin)3 | 0.3 | 0.3 | 0.3 | 0.2 | -363 |
| La(4OHCin)3 | 0.7 | 0.6 | 0.6 | 0.6 | -278 |
| TestSolution | NMRShift (ppm) | ½Width (Hz) |
| LaCl3Reference in D2O | 4.9 | 179 |
| La(2OHCin) 3 | 16.4 | 630 |
| La (3OHCin) 3 | 12.5 | 500 |
| La(4OHCin)3 | 9.8 | 470 |
| Mass | Species | Mass | Species | Mass | Species |
| 281 | [LaCl4]- | 282 | [CeCl4]- | 283 | [PrCl4]- |
| 407 | [LaLCl3]- | 408 | [CeLCl3]- | 409 | [PrLCl3]- |
| 535 | [LaL2Cl2]- | 536 | [CeL2Cl2]- | 537 | [PrL2Cl2]- |
| 663 | [LaL3Cl]- | 664 | [CeL3Cl]- | 665 | [PrL3Cl]- |
| 791 | [LaL4]- | 792 | [CeL4]- | 793 | [PrL4]- |
