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In this paper, corrosion of steel is reviews. Various sustainable methods were described in detailed.
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Corros Rev 2019; 37(2): 71–
https://doi.org/10.1515/corrrev-2018- Received June 28, 2018; accepted December 13, 2018; previously published online January 11, 2019
*Corresponding author: Lekan Taofeek Popoola, Unit Operation and Material Science Laboratory, Chemical and Petroleum Engineering Department, Afe Babalola University, Ekiti State, Nigeria, e-mail: popoolalekantaofeek@yahoo.com
Angemeldet | chrbfischer@uni-koblenz.de
1.1 Mechanisms of OGCIs
Oils
Extracts
Plants
Drugs
Amino acids
Surfactants
Biopolymers
Ionic liquids (^) Rare earth
Inorganic green corrosion inhibitor
Organic green corrosion inhibitor
Eco-friendly corrosion inhibitor
Figure 2: Sources of eco-friendly OGCIs (Ibrahimi et al., 2017).
Overall chemical reaction
Neutral or basic conditions w/ oxygen contamination
Carbon dioxide “Sweet” corrosion
Hydrogen sulfide “Sour” corrosion
Oxidation half reaction Reduction half reaction
Fe + 2H +^ → Fe2+^ + H 2
O 2 + 2H 2 O + 4e–^ → 4ΟΗ–
Fe → Fe2+^ + 2e–
Fe2+^ + 2OH–^ → Fe(OH)2,(s)
Fe + CO 2 + H 2 O → FeCO3,(s) + H (^2)
Fe + H 2 S → FeS(s) + Η 2
2H+^ + 2e –^ → H 2
Figure 1: Chemical reactions of the corrosion process (Brylee and Advincula, 2015).
Angemeldet | chrbfischer@uni-koblenz.de
1.4 Factors influencing OGCI efficiency
Table 1: Some attaching functional groups in OGCIs (Singh, 1993).
Functional group Name Fuctional group Name
-OH Hydroxy -NH 2 Amino -C-N-C- Amine -SH Thiol -NO 2 Nitro -C≡C- -yne -CONH 2 Amide -S=O Sulfoxide -COOH Carboxy -NH Imino -S- Sulfide -N=N-N- Triazole -C=S- Thio -C-O-C- Epoxy -P=O Phosphonium -P- Phospho -Se- Seleno -As- Arsano
Angemeldet | chrbfischer@uni-koblenz.de
Table 2:
Sources of OGCIs, functional groups, and corrosion inhibitory roles.
OGCI source
Functional groups and compounds
Corrosion inhibitory roles
References
G. biloba
leaf extracts
Flavonoids and terpenoids; phenol groups and aromaticrings
Terpenoids: quercetin adsorption on mild steel surface based on theinteractions of donor-acceptor between
and aromatic ring
p
-electrons and
surface iron vacant
d
-orbitals
Flavonoids: oxygen-adsorption corrosion inhibited via its oxidation tobenzoquinone by O
resolved in the solution 2
Chen et al., 2013
Rothmannia longiflora extract
Monomethyl fumarate, 4-oxonicotinamide-1-(1-
β-D-
ribofuranoside), and D-mannitol
Akalezi et al., 2015
Petersianthusmacrocarpus
plant
Petersaponin,
β
-sitosterol, and ellagic acid
Molecules are adsorbed on the surface of mild steel surface as a result ofhydroxyl group and aromatic ring protonation. Constituent molecules havearomatic rings (
π-electrons) with attached electron releasing groups. Also, the
increase of the ability of
π
-electrons to be bonded to vacant
d
-orbital in Fe
Akalezi et al., 2015
Extract of
Ficus
asperifolia
Saponins, alkaloids, tannins, anthraquinones,flavonoids, reducing sugars,
n
-hexane, ethyl acetate, and
butanol
The electron-donating ability was facilitated as a result of rich bond orheteroatoms present in the chemical structures. Thus, the formation ofcomplexes on the material surface to inhibit corrosion was enhanced
Ebenso et al., 2008
Extracts of
D. kaki
L.f
husk
Vitamins,
p
-coumaric acid, gallic acid, catechin,
flavonoids, carotenoids, and condensed tannin
Zhang et al., 2013
Gum arabic
Arabinogalactan, oligosaccharides, polysaccharides, andglucoproteins
Umoren et al., 2006
Tobacco extract
Polyphenols, terpenes, alkaloids, alcohols, carboxylicacids, and nitrogen-containing compounds
Corrosion inhibition on metals by electrochemical activity due to fusedbenzene ring system with charge dislocation property
Rudresh andMayanna, 1977
Extract of green wildjute tree (
Grewa
venusta
Polysaccharides, polyphenols (catechins and flavonoids)vitamins, tannins, minerals, volatile oils, and alkaloids
Mixed inhibitor corrosion inhibition action
Suleiman et al., 2013
Anthocleista djalonesis
Iridoid glucoside (DJN), dibenzo-
α-pyrone
(djalonensone), ursolic acid, and 3-oxo-∆-4,5-sitosterone
Obame et al., 2008
Guar gum
Polysaccharides, mainly sugars galactose and mannose
1,4-Linked mannose residue linear chain-forming short-side branches, whichlater formed complexes on the metal surface to inhibit corrosion
Abdallah, 2004
Jatropha curcas
leaf
extract
Tannins, flavonoids, terpenes, anthraquinone, apigenin,cardiac glycoside, alkaloids, deoxy sugar, saponins,
α
glucoside, sterols, stigmasterol, and vitexin
Corrosion inhibition via the formation of continuous complex metal ions on themetal surface by polar groups
Ejikeme et al.,2014; Rani andSelvaraj, 2014
Extracts of banana peel
Bananadine (3Z,7Z,10Z)-1-oxa-6-azacyclododeca-3,7,10-triene
Sangeetha et al., 2012
Aloe vera
plant extract
Minerals, polysaccharides, vitamins, glycoproteins, andenzymes
Gupta et al., 2018
Azadirachta indica
Azadirachtin, salannin, meliantriol, and nimbin
Inhibition effects due to electronic, geometry coupled with binding propertybases on the metal surface
Sharma et al., 2015
Locust bean gum
Galactomannan-type polysaccharides
Jano et al., 2012
Oil palm frond
Phenolic constituents (
p -hydroxybenzoic acid, syringic
acid, vanillic acid, vanillin,
p
-hydroxybenzaldehyde,
p -hydroxyacetophenone, and syringaldehyde)
Lignin is cleaved to form aromatic carbonyl compounds (syringaldehyde andvanillin) via alkaline nitrobenzene oxidation to inhibit corrosion
Yokoi et al., 2001
Angemeldet | chrbfischer@uni-koblenz.de
A B A B AB
1 corr corr corr
o o
1
–0.
10 –
10 –
10 –
10 –
10 –
10 –
10 –
–0. E (volts)
I (Amps/cm
2 )
–0.
Blank10 mg/l 50 mg/l100 mg/l 200 mg/l 500 mg/l1000 mg/l
–0.
Figure 3: Polarization curves for Q235A steel corrosion in 1 m HCl in the absence and presence of varying concentrations of persimmon husk extracts as OGCI (Zhang et al., 2013).
Angemeldet | chrbfischer@uni-koblenz.de
CPE
1 1
1
dl max ct
ct( i) ct(o) E ct(i)
0 200 400 Zreal (ohm cm 2 )
–Zimag (ohm cm
2 )
600 800
0.00 m M 0.05 mM 0.10 mM 0.15 mM 0.20 mM 0.25 mM
1000
0
50
100
150
200
250
300
350
Figure 4: Mild steel Nyquist plot in 1 m H 2 SO 4 at 30°C for varying OGCI concentrations (Al-Amiery et al., 2014).
Table 3: Significance of n values on the CPE nature.
n CPE nature (A) Significance References
0 Resistance A metal-solution interface operating as a resistor Bai, 2015 1 Capacitance Plane and homogeneous electrode surface with the metal-solution interface behaving as a capacitor with a regular surface
Lin et al., 2015
−1 Inductance Nonplane and heterogeneous electrode surface with the metal-solution interface behaving as an inductor with an irregular surface
Deyab et al., 2007
1/2 Warburg impedance A metal-solution interface acting as both capacitor and inductor Yurt et al., 2006
Angemeldet | chrbfischer@uni-koblenz.de
2 Previous studies on using OGCIs
2.1 Industrial applications of OGCIs
3 Mathematical modeling of OGCI
influence on metals
3.1 Kinetics of corrosion modeling
a (^) rev,Fe 2 Fe^2
b
φ φ (^) +
−
1 2
1 1 H CO 0,Fe 0,ref H ,ref CO ,ref
a a H
− ∆ (^) −
CO 2
CO ,ref 2
2 2 2
Fe Fe Fe
Observation Significance/implication References
Values of slope and phase angle deviating from the ideal capacitive behavior of the electric double layer (slope = 1 and phase angle = −90°) in the Bode impedance and phase angle plots for inhibited and uninhibited metallic specimens
This resulted from metal surface inhomogeneity Singh et al., 2016
Table 4 (continued)
Angemeldet | chrbfischer@uni-koblenz.de
Table 5:
Summary of literature on sources of previously used OGCIs.
OGCI source
Extraction methodology
Material tested;solution used
OGCI characterization;laboratory analysis
Findings
Future challenges
References
Camelliasinensis (green tea)
Dried and ground leavessubjected to reflux in 70%acetone for 4 h
Mild steel in 1 m HCl SEM, EIS, WLM, FTIR,
79% inhibition efficiency achieved in200 ppm solution
Inhibition effect increases with an increasein solution concentration and temperature
Adsorption kinetics and isothermsstudies were not examined
Nofrizal, 2012
R. longiflora extract
Extraction
Mild steel in 1 m HCland 0.5 m H
4
Increase in corrosion inhibition efficiencyas extract concentration and temperatureincrease
Extraction methodology was notpresented
Extract was not characterized forfunctional groups inhibiting corrosion
Akaleziet al., 2015
A. djalonesis leaf extract
20 g dried leaves underreflux for 3 h in 1 m HCl and0.5 m H
4
Mild steel in 1 m HCland 0.5 m H
4
EIS, PDP, DFT-basedQCC
Corrosion inhibition via mixed-typeinhibition mechanism
Djalonenoside (DJN) and its hydrolysisproduct DJN-hyd were extracts enhancingcorrosion inhibition in the medium
Corrosion of other metals besides mildsteel was not investigated
Ogukweet al., 2012
Theobromacacao
peel
polar extract
Boiling dried pods underreflux for 4 h in 1.0 m HCl
Mild steel in 1 m HCl WLM, EIS, PDP
Increase in corrosion inhibition efficiencyas OGCI concentration increases butdecreased with temperature
Langmuir isotherm was obeyed
More metallic materials should betested
Yetri et al., 2014
o ,
m
, p
Decanoylthioureaderivatives
Mixed substitution andaddition reaction usingdecanoyl chloride,ammonium thiocyanate,and 2-aminopyridine inacetone solution for 10 min
Mild steel in 0.1 mH^2
4
1 H and
(^13)
Compound D3 of the derivatives possessedthe highest efficiency
Compound corrosion inhibition efficienciesaffected by N atom at
o
m
-, and
p -positions affects the pyridine chemicalstructure
Only mild steel was considered
Limited laboratory analysis
Although chemical structures werepresented, the structural morphologyof the synthesized inhibitors need beinvestigated
Kamalet al., 2014
Extracts of
kaki
L.f husk
Husk powder heated underreflux with water or alcoholfor 4 h
Q235A steel in 1 mHCl
Extracts behaved like a mixed-type inhibitor
Extracts exhibited antibacterial activityagainst microbial influenced corrosion(MIC) of oil field microorganism
There is a need to fully explorethe corrosion inhibitory feature ofextracts from this biomass in othercorrosion types besides microbialinfluenced corrosion
SEM analysis was not carried outto ascertain that the corrosion typeinhibited on the metal surface by theextracts was exactly MIC
Zhanget al., 2013
Schiff bases
8 h refluxing of 3-amino-2-methylquinazolin-4(
H )-one with 4-hydroxybenzaldehydeand
-dimethyl-4-
aminobenzaldehyde inacetic acid
Mild steel in 1.0m HCl
p
-position substituent enhanced inhibitionefficiency
Inhibition efficiency relies on OGCI nitrogenamount and their molecular weight andconcentration
m
-position substituent on OGCI molecule affected inhibitionefficiency negatively
Corrosion type prevented was notspecified
Only mild steel was used to test theinhibitor efficiency
Jamil et al., 2018
Angemeldet | chrbfischer@uni-koblenz.de
OGCI source
Extraction methodology
Material tested;solution used
OGCI characterization;laboratory analysis
Findings
Future challenges
References
P.macrocarpus plant
Boiling dried leaves underreflux for 3 h in 1.0 m HCland 0.5 m H
4
Mild steel in 1 m HCland 0.5 m H
4
EIS data revealed organic matter extractinfluence on corrosion inhibitory effect onmild steel
Inhibition efficiency increased with anincrease in concentration and temperatureup to 50
Lower activation energy in the presenceof corrosion inhibitor resulted from theadsorption chemisorptive nature
The influence of the inhibitorin alkaline medium was notinvestigated
Only mild steel was examined
The kinetics of the process was notstudied
The efficiency of the inhibitorused was not compared to thoseof previous inhibitors used by theresearchers
Akaleziet al., 2015
Hibiscus rosa-sinensis
leaf
extract
Mild steel in 1 m HCl WLM, EIS
Inhibition efficiency increased astemperature and solution concentrationincreased
OGCI behaved as mixed type
Spontaneous reaction
Data agreed well with Langmuir, Flory-Huggins, and Freundlich adsorptionisotherms
Limited laboratory analysis to affirmthe inhibitor efficiency
Only mild steel in only acidic mediumwas investigated
Desai, 2015
D-glucosederivatives
Multicomponent reactions
Mild steel in 1 m HCl SEM, EDX, AFM, EIS
The presence of -OH and -OCH
groups 3
exhibited higher inhibition efficiency
E ads
values did not exhibit any regular trend for aqueous and protonatedinhibitor molecules
Vermaet al., 2017
Silica extractfrom rice huskash
Na
Silica extract was preparedby mixing 80 ml of 2.5 mNaOH with rice husk ashproduced by calcination at 600
°C for 6 h. 0.2 m NaOH and distilled water werethen added to form theinhibitor
99.9% Cu, Al alloy(AA6061), carbonsteel (SAE1045) in0.5 m HCl
Each metal alloy influenced the optimalSiO
:Na 2
O ratio determination sodium 2
silicate formulation
Used silicate-based inhibitor has apotential of inhibiting corrosion in testedsamples under examined acidic medium
Limited laboratory analysis for moreconfirmation of inhibitor efficiency
Only acidic medium solution wastested
More metallic samples should beexamined
Mohamadet al., 2013
Gum arabic
Mild steel and Al inH^2
4
Inhibition efficiency increases with anincrease in the concentration of theinhibitor
Inhibitor obeyed Temkin adsorptionisotherm for tested samples
Mild steel corrosion was chemicaladsorption, whereas Al corrosion wasphysical adsorption
Inhibitor acted better on Al than mild steelwith adsorption being spontaneous
The methodology of inhibitorextraction was not adequatelypresented
The kinetics of the adsorption processwas not presented
The reaction mechanism of theinhibitor adsorption process on mildsteel and Al process was not available
Limited laboratory analysis to supportinhibitor efficiency on samples
Umoren, 2008
Table 5
(continued)
Angemeldet | chrbfischer@uni-koblenz.de
OGCI source
Extraction methodology
Material tested;solution used
OGCI characterization;laboratory analysis
Findings
Future challenges
References
Coconut coirdust extract
Hydrogen evolutionextraction method
Al corrosion in 1 mHCl
As temperature and concentrationincreased, inhibition efficiency increased
Langmuir isotherm was obeyed
Only Al was considered. It would bebetter if inhibitor efficiency is testedin other metals
Also, only HCl as acidic mediumwas tested. Both acidic and alkalinesolutions should be checked
Umorenet al., 2006
Jatropha
stem
Jatropha
fine powder
obtained by sun drying andgrinding soaked in ethanolfor 24 h. Evaporation offiltrate to remove excessalcohol
Mild steel inseawater
Coupons without inhibitor corroded more inseawater than those with inhibitor
Presence of active corrosion inhibitors^ Jatropha
extracts revealed by FTIR
Maximum inhibition efficiency of 81.7% at0.90 g/l inhibition concentration
Adsorption isotherm andthermodynamics were not studied
Few laboratory analysis for moreaffirmation of inhibitor efficiency
Inhibitor influence and efficiency inacidic and alkaline media were notinvestigated
Olawaleet al., 2016
Tobaccoextract
Extraction by weighingaqueous solutions, boilingof water, and weighingresidue
1008/1010cold-rolled steeland 3105 H24 AlQ-panels in 1–3%NaCl solution
Tobacco extracts proved to be excellentinhibitors for the corrosion of Al and steel inalkaline solution
Extract also worked in acidic solution andcould prevent corrosion during descalingprocesses
Inhibition effect greater than chromateswithin a solution concentration range aslow as 100 ppm
Thermodynamics, kinetics, andadsorption isotherm equilibrium ofinhibitor effect were not investigated
Inhibition effect in other media wasnot investigated
Davis et al., 2001
Citrusaurantiifolia leaves
Dried and ground leavesunder reflux for 3 h in 1 mH^2
4
Mild steel in 1 m HCl SEM, WLM
Corrosion inhibition increases with anincrease in solution concentration with97% efficiency
Experimental data conformed to Langmuirisotherm
Only mild steel in acidic medium wasinvestigated
Sarathaet al., 2009
Cashew waste
Sun dried and pulverizedfruits soaked in 250 mlethanol for 24 h
Mild steel in 1 m HCland 0.1 m H
4
Inhibitor efficiency increased with anincrease in inhibitor concentration withoptimum 80.5%
Cashew waste was seen as a valuablecorrosion inhibitor
Adsorption kinetics, isotherms, andthermodynamics were not studied forin-depth investigation
Only mild steel in acidic medium wasinvestigated
Olawaleet al., 2015
Locust beangum
Carbon steel 39, 44,and B500 in H
4
Inhibition effect on steel 39 in acidic mediumin the presence of NaCl was revealed
Although different carbon steel sampleswere tested, there was a shallowinvestigation on the extracted corrosioninhibitor on the examined samples
Jano et al., 2012
Extract ofbananapeel
Zn
Carbon steel indistilled water
Zn addition decreased inhibition efficiency.It later increases after increasing Znconcentration
No mathematical model was presentedas a predictive tool for the futurecorrosion of the sample tested
Sangeethaet al., 2012
Table 5
(continued)
Angemeldet | chrbfischer@uni-koblenz.de
OGCI source
Extraction methodology
Material tested;solution used
OGCI characterization;laboratory analysis
Findings
Future challenges
References
Langmuir adsorption isotherms andactivation energies revealed physicaladsorption
SEM images of corroded substrates showedprimary corrosion mechanism to be bypitting
95% Inhibition efficiencies at roomtemperature achievable
Corrosion inhibition increased with anincrease in extract concentration butdecreased with increasing temperature
Guar gum
Pods dried in sunlightand separated manuallyfrom seeds
Seeds heated underreflux with water oralcohol for 6 h
Carbon steel in 1 mH^2
NaCl
Increase in resistance of pitting corrosionwas exhibited
Guar gum acted as a mixed-type inhibitorwhose efficiency increases with an increasein concentration
All data supported Langmuir adsorptionisotherm
Abdallah, 2004
Oil palm frond
Nitrobenzene oxidationmethod for lignindepolymerization
Mild steel in 1 m HCl WLM, PDP, EIS, SEM,
Inhibition efficiency increased withincreased concentration of lignindepolymerized products
Mixed-type inhibitors revealed
Experimental data well fitted with Langmuiradsorption isotherm
Adsorption was dominated byphysisorption
SEM revealed reduction of surfaceroughness in the presence of an inhibitor
Only Langmuir isotherm was used.For comparative purposes, otherexisting isotherms should be used
Oil palm frond extracts have beenshown to have potential of corrosioninhibition in alkaline medium. Thus,various types of metallic materialsshould checked in alkaline medium
Shah et al., 2017
Celeryseeds (
graveolens
Ground and powdered seedboiled in distilled H
O for 2
2 h. Filtrate evaporated todryness and residue usedhigh concentrated stocksolution
Carbon steel in 1 mHCl
Optimum inhibition efficiency obtained at500 ppm inhibitor concentration
Spontaneous adsorption process thatconforms to Temkin isotherm
Percent inhibition efficiency decreased withincreased temperature
Inhibition efficiency increased as celerydoses increased
Only WLM and PDP were used tocheck inhibitor efficiency
Only HCl was used for carbon steelalone to check OGCI efficiency
Active functional groups presentin
A. graveolens
seeds enhancing
corrosion inhibition were not deeplyinvestigated
Megahedet al., 2017
Table 5
(continued)
Angemeldet | chrbfischer@uni-koblenz.de
OGCI source
Extraction methodology
Material tested;solution used
OGCI characterization;laboratory analysis
Findings
Future challenges
References
Eichhorniacrassipes (waterhyacinth)leaves androots
4 g dried and groundleaves and roots soaked in1000 ml of 5 m HCl
Mild steel in HCl
Root and leaf extracts performed excellentlywell as effective OGCIs
Physisorption of extract organicconstituents on corroding mild steel surface
Insufficient laboratory analysis
Equilibrium isotherms and kineticswere not investigated
Ulaetoet al., 2012
G. venusta plant extract
G. venusta
cut into
pieces, dried for 3 days,and ground into powder.Product was refluxed forsome hours using ethanol
Mild steel in 0.5 mH^2
4
Corrosion rate was reduced when OGCIconcentration was increased above 2%(v/v) with time
Increase in temperature massivelyincreased corrosion rate
Plant extract exhibited effective corrosioninhibition potential for mild steel in acidicmedium
At 8% (v/v) optimum concentration of plantextract in acid solution, 86.47% highestefficiency was obtained
Only SEM was used to authenticateinhibitor efficiency
Thermodynamics of adsorptionprocess was not studied
Suleimanet al., 2013
Crude glycerolfrom residueof biodieselproducedfrom a plantseed
Transesterification process
Steel in 0.5 m HClat 25
Corrosion inhibition increased withinhibitor concentration
Maximum inhibition efficiency of 98%) wasachieved after 70 h of residence time with1% inhibitor concentration
Plant source of oil used for biodieselproduction from which glycerol wasobtained was not mentioned
Inhibition efficiency remainedunchanged after residence time
Al-Zubaidiet al., 2018
Table 5 AAS, Atomic absorption spectroscopy; AFM, atomic force microscopy; DFT; density functional theory; ECM, electrochemical measurements; EDX, energy-dispersive X-ray spectroscopy; FTIR,Fourier transform infrared; GM, gravimetric method; GT, gasometric technique; HEM, hydrogen evolution method; LPR, linear polarization resistance; NMR, nuclear magnetic resonance; QCC,quantum chemical computation; SEM, scanning electron microscopy; ST, surface tension; TEM, transmission electron microscopy; TT, thermometric techniques; XRD, X-ray diffraction; XRF, X-rayfluorescence; ZRA, zero-resistance ammeter.
(continued)
Angemeldet | chrbfischer@uni-koblenz.de
φ φ
−^ −
c rev
2 i i 1
n
i
∇ = − (^) ∑ (22)
i i 1
n
i
=
∑ = (23)
a w,Fe Fe
Active functional groups;complexes; ingredients
Inhibitor source fromgreener
How it works; how to solve the problem
Side effects
References
Refrigeratingindustry
Benzotriazole p -Hydroxybenzoic acid andvanillic acid
A. djalonesis Oil palm frond
Galvanic corrosion evolves due to theincrease in dissolved mineral salt contentas evaporation proceeds with the presenceof several dissimilar metals and nonmetals.Inhibitors control corrosion by film formationthat inhibits anodic metal dissolution reactionand cathodic poisoning
Matsuda andUhlig, 1964;Obame et al., 2008
Buildingconstruction
Phosphate ion
When mixed with cement, the durability ofreinforced concrete structures is improved
Yohai et al., 2013
Boiler
Ammonia, alkanol,cyclohexylamine, andmorpholine
Corrosion attack of pipes prevented bysolubilization of limescale
Sanyal, 1981
Table 6
(continued)
Angemeldet | chrbfischer@uni-koblenz.de
Fe (^ corr rev ,Fe)
F E E
α −
Fe Fe
corr rev ,Fe Fe
( )
E E b
−
c ct lim
c
−^ η
lim(H CO ) 2 3
2 3 2 3
H CO 2 3
m r m r
2 / 2 /
δ δ δ δ
− −
2 3 2 3
H CO m m,H CO
H CO 2 3 hyd r hyd
f
3.2 Rate modeling of corrosion-type inhibition using OGCIs
Angemeldet | chrbfischer@uni-koblenz.de