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Corrosion Corrosion and Corrosion Inhibition of Aluminum and Aluminum Alloys in Acid Mediumand Corrosion Inhibition of Aluminum and Aluminum Alloys in Acid Medium
Corrosion Corrosion and Corrosion Inhibition of Aluminum and Aluminum Alloys in Acid Mediumand Corrosion Inhibition of Aluminum and Aluminum Alloys in Acid Medium
Corrosion Corrosion and Corrosion Inhibition of Aluminum and Aluminum Alloys in Acid Mediumand Corrosion Inhibition of Aluminum and Aluminum Alloys in Acid Medium
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20130288:
2015-2014:
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Contents
1-Introduction about Aluminum: ............................................................................................................................. - 4 1.1-Key Characteristics of Aluminum: .................................................................................................................... - 5 Low Density ........................................................................................................................................................ - 6 Strength. ............................................................................................................................................................... - 7 High Strength-to-Weight Ratio. ........................................................................................................................... - 7 Corrosion Resistance............................................................................................................................................ - 7 The high thermal conductivity of aluminum ........................................................................................................ - 8 High Electrical Conductivity ............................................................................................................................... - 8 Reflectivity. .......................................................................................................................................................... - 8 Non-toxic Characteristic. ..................................................................................................................................... - 8 Finishability. ........................................................................................................................................................ - 9 1.2-Aluminum Alloys: ............................................................................................................................................. - 9 Classifications and Designations: ............................................................................................................................ - 9 Wrought Alloy Families: ....................................................................................................................................... - 10 1.3-Effects of Alloying Additions:......................................................................................................................... - 11 2-Corrosion in Acid Solutions : ............................................................................................................................. - 13 2.1-Corrosion of Aluminium and Aluminium Alloys: ........................................................................................... - 13 2.1-Localized Corrosion: ....................................................................................................................................... - 14 2.1.1-Environmentally Influenced Corrosion: ................................................................................................... - 15 2.1.1.1 Pitting Corrosion ................................................................................................................................ - 15 2.1.1.2 Crevice Corrosion : ............................................................................................................................ - 18 2.1.1.3 Filiform Corrosion : ........................................................................................................................... - 20 2.1.1.4 Biological Corrosion: ......................................................................................................................... - 21 2.1.2 Metallurgically Influenced Corrosion: ...................................................................................................... - 22 2.1.2.1Galvanic Corrosion : ........................................................................................................................... - 22 2.1.2.2 Intergranular Corrosion :.................................................................................................................... - 24 2.1.3 Mechanically Assisted Degradation:......................................................................................................... - 24 2.1.3.1 Erosion ............................................................................................................................................... - 24 2.1.3.2 Fretting Corrosion .............................................................................................................................. - 25 2.1.3.3 Corrosion Fatigue............................................................................................................................... - 25 2.1.4 Environmentally Induced Cracking: ......................................................................................................... - 26 2.1.4.2 Hydrogen Embrittlement :.................................................................................................................. - 27 3- Corrosion Prevention: ........................................................................................................................................ - 27 -
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3.1 Alloy and Temper Selection : ...................................................................................................................... - 28 3.2 Design of Equipment ................................................................................................................................... - 28 3.3- Organic Coating[][]: ................................................................................................................................... - 29 3.3.1 Surface Preparation : ................................................................................................................................. - 30 3.4- Inhibitors : ................................................................................................................................................... - 31 3.4.1 Inhibitors in acid medium: .................................................................................................................... - 33 corrosion inhibition of aluminium by different type of inhibitors ................................................................. - 33 3.4.1.1- 3-alkyloxy aniline sodium sulfonate monomeric surfactants. ......................................................... - 37 3.4.1.2 Different Extracts of Ocimum gratissimum. ................................................................................... - 38 3.4.1.3- Euphorbia hirta extract..................................................................................................................... - 39 3.4.1.4- black mulberry. ............................................................................................................................... - 39 3.4.1.5- Chrysophyllum albidum fruit extract . ............................................................................................. - 40 3.4.1.5- extract of Garlic. ............................................................................................................................... - 40 3.4.1.6- anionic polyeletrolyte pectates (PEC).............................................................................................. - 41 -
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Table2 shows the characteristics of aluminum and their importance for different end uses.
Low Density .
Aluminum has a density of only 2.7g/cm3 , approximately35% that of steel (7.83g/cm3)
and 30% of copper (8.93g/cm3) or brass (8.53g/cm3).
One cubic foot of steel weighs about 222kg ;a cubic foot of aluminum weighs only
about77kg.
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Strength.
Commercially pure aluminum has a tensile strength of about90 MPa .
Thus its usefulness as a structural material in this form is somewhat limited by working
the metal, as by cold rolling, its strength can be approximately doubled. Much larger
increases in strength can be obtained by alloying aluminum with small percentages of one
or more other elements such as manganese ,silicon, copper, magnesium, or zinc. Like pure
aluminum ,the alloys are also made stronger by cold working. Some of the alloys are
further strengthened and hardened by heat treatments.
High Strength-to-Weight Ratio.
The strength to-weight ratio of aluminum is much higher than that of many common
grades of constructional steel soften double or more.
This property permits design and construction of strong, lightweight structures that are
particularly advantageous for anything that moves-space vehicles and aircraft as well as all
types of land- and water-borne vehicles.
Corrosion Resistance.
When aluminum surfaces are exposed to the atmosphere ,a thin
invisible oxide skin
forms immediately, which protects the metal from further oxidation. This self-protecting
characteristic gives aluminum its high resistance to corrosion .Unless exposed to some
substance or condition that destroys this protective oxide coating, the metal remains fully
protected against corrosion. Aluminum is highly resistant to weathering, even in industrial
atmospheres that often corrode other metals .It is also corrosion resistant to many acids.
Alkalis are among the few substances that attack the oxide skin and therefore are
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Corrosive to aluminum Although the metal can safely be used in the presence of certain
mild alkalis with the aid of inhibitors, in general, direct contact with alkaline substances
should be avoided.
The high thermal conductivity of aluminum
(about 50 to 60% that of copper) came prominently into play in the very first large-scale
commercial application of the metal in cooking utensils .This characteristic is important
whenever the transfer of thermal energy from one medium to another is involved, either
Heating or cooling. Thus aluminum heat exchangers are commonly used in the food,
chemical, petroleum, aircraft, and other industries.
High Electrical Conductivity
Aluminum is one of the two common metals having an electrical conductivity high
enough for use as an electric conductor.
The conductivity of electric conductor grade (1350) is about 62%that of the International
Annealed Copper Standard (IACS). Because aluminum has less than one-third the specific
gravity of copper, however, a pound of aluminum will go about twice as far as a pound of
copper when used for this purpose.
Reflectivity.
Smooth aluminum is highly reflective of the electromagnetic spectrum, from radio waves
through visible light and on into the infrared and thermal range. It bounces away about
80%ofthe visible light and 90% of the radiant heat striking its surface.
The high reflectivity gives aluminum a decorative appearance; it also makes aluminum a
very effective barrier against thermal radiation, suitable for such applications as
automotive heat shields.
Non-toxic Characteristic.
The fact that aluminum is nontoxic was discovered in the early days of the industry. It is
this characteristic that permits the metal to be used in cooking utensils without any
harmful effect on the body. Today a great deal of aluminum equipment is used in the food
processing industry.
Non toxicity permits aluminum foil wrapping to be used safely in direct contact with food
products.
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Finishability.
For the majority of applications , aluminum needs no protective coating. Mechanical
finishes such as polishing, sandblasting, or wire brushing meet the majority of needs. In
many instances, the surface finish supplied is entirely adequate without further finishing.
Where the plain aluminum surface does not suffice or where additional protection is
required, any of a wide variety of surface finishes may be applied.
Chemical, electrochemical, and paint finishes are all used. Many colors are available in
both chemical and electrochemical finishes. If paint, lacquer, or enamel is used, any color
possible with these finishes can be applied. Vitreous enamels have been developed for
aluminum, and the metal can also be electroplated.
1.2-Aluminum Alloys2:
The mechanical, physical, and chemical properties of aluminum alloys depend on
composition and microstructure. The addition of selected elements to pure aluminum
greatly enhances its properties and usefulness. Because of this, most applications for
aluminum utilize alloys having one or more elemental additions. The major alloying
additions used with aluminum are copper, manganese, silicon, magnesium,
Aluminum andAluminumAlloys,Metals Handbook Desk Edition,2nd ed.,J.R. Davis,Ed,ASM International, 1998,p 417-505
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of
aluminum,
and
cast
Al-Sn
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(1)
2H++ 2e- H2
(2)
J. Vereecken, Vrije ;Corrosion Control of Aluminium -Forms of Corrosion and Prevention; Universiteit Brussels;p3
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2.1-Localized Corrosion:
Environmentally influenced corrosion :
Pitting corrosion
Crevice corrosion
Filiform corrosion
Biological corrosion
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The potential above which pits will initiate (Ep) decreases with an increase of the Clconcentration. However, only when cathodic reactions can occur (high enough
concentration of O2, low overpotential) pitting corrosion of aluminium starts.
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Of these attractive forces, the largest are the first two interactions, which are ionic, as
shown in Table 3. As stated above, in neutral solutions the oxide film on aluminum will
have a positive surface charge. Thus, adsorption of chloride ions is most favored on a
positively charged oxide surface for which the ionion forces are attractive in nature.
When the oxide surface is negatively charged, ionion forces are not attractive in nature so
that adsorption
of Cl onto the negatively charged oxide surface is much less favored but can proceed
through the operation of van der Waals (dispersion) forces.There is considerable
experimental evidence which shows that chloride ions are adsorbed on the oxide-covered
aluminum surface. Studies involving radiotracer techniques7.
J.H. de Boer, in: H. Mark, E.J.W. Verwey (Eds.), Advances in Colloid Science, vol. III, Interscience
Publishers, New York, 1950, p. 1
7
J.O.M. Bockris, Y. Kang, J. Solid State Electrochem. 1 (1997) 17.
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adsorption from solution onto powders8, X-ray photoelectron spectroscopy (XPS)9, X-ray
absorption spectroscopy (XAS)10, and Auger spectroscopy11 , all show that Cl is adsorbed
onto the oxide film on aluminum prior to the onset of pitting.
There is a growing body of evidence that chloride ions penetrate the passive film on
aluminum. In an XPS study on the uptake of chloride by oxide films on aluminum,
Natishan et al.12
Very high purity aluminium (1099) has excellent resistance to pitting. Among commercial
alloys, the aluminium-magnesium alloys (5xxx) have the lowest pitting probability and
penetration rates. With low (< 0.04 %) copper content aluminium-manganese (3xxx)
alloys show comparable pitting behaviour. In aluminium-magnesium-silicon (6xxx) alloys
pitting is combined with intergranular corrosion. Aluminium-copper (2xxx) and
aluminium-zinc-magnesium-copper (7xxx) alloys are normally clad to protect against
pitting13.
Geometrical factors:
type of crevice (metal-metal, metal-non metal)
crevice tightness
crevice depth
8
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15
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16
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Anodic reaction produces Al+3 which react to form insoluble precipitates with the
hydroxyl (OH-) ions produced in the oxygen reduction reaction occurring in the tail.
Phosphate coatings or chromium containing conversion coatings applied to the metal
surface prior to organic coating are widely used to protect against filiform corrosion but
they are not always completely successful.
2.1.1.4 Biological Corrosion17:
Biological organisms are present in virtually all natural aqueous environments and can
attack and grow on the surface of structural materials, resulting in the formation of a
biological film or biofilm.
The presence of a biological film does not introduce some new type of corrosion, but it
influences the occurrence and/or the rate of known types of corrosion, e.g.:
-increase or decrease of the corrosion rate due to oxygen reduction;
-production of different aeration or chemical concentration cells;
-production of organic and inorganic acids as metabolic by-products;
17
Yang SS, Chen CY, Wei CB, Lin YT. Microbial corrosion of aluminum alloy. Zhonghua Min Guo Wei Sheng Wu Ji Mian Yi Xue
Za Zhi. 1996 Nov;29(4):185-96. PubMed PMID: 10592801.
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Control of this type of attack has usually focused on a combination of reducing the water
content of fuel tanks, coating and using biocides and fuel additives.
2.1.2 Metallurgically Influenced Corrosion19:
2.1.2.1Galvanic Corrosion :
Due to the fact that different metals must be used very often electrically coupled in an
integrated structure a corrosion cell can occur resulting in acceleration of the corrosion
process in less resistant metals.
18
19
J. Vereecken, Vrije ;Corrosion Control of Aluminium -Forms of Corrosion and Prevention; Universiteit Brussels;p11
Edward Ghali; Corrosion Resistance of Aluminum and Magnesium Alloys; John Wiley & Sons;2010;pp215-241
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the galvanic series of aluminium alloys and other metals in a NaCl solution. This galvanic
series, however, is not necessarily valid in non-saline solutions. For example aluminium
is anodic to zinc in an aqueous 1 M sodium chromate (Na2CrO4) solution and cathodic to
iron in an aqueous 1 M sodium sulfate solution (Na2SO4). Under most environmental
conditions, aluminium and its alloys are the anodes in galvanic cells with most other
metals, protecting them by corroding sacrificially.
Contact of aluminium with more cathodic metals results in an increase of the potential of
aluminium; this must be avoided in any environment in which aluminium itself is subject
to pitting corrosion.
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J. Vereecken, Vrije ;Corrosion Control of Aluminium -Forms of Corrosion and Prevention; Universiteit Brussels;pp13-14
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greater for the more corrosion-resistant alloys even though they are lower in strength.
Corrosion inhibitors and cathodic protection have been used to minimize erosioncorrosion,
impingement, and cavitation on aluminum alloys.
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to SCC, however, corrosion fatigue is not appreciably affected by test direction with
respect to the rolling, forging or extrusion direction, because the fracture that results from
this type of attack is predominantly transgranular.
2.1.4 Environmentally Induced Cracking21:
2.1.4.1 Stress Corrosion Cracking (SCC)
SCC is a complex mechanism involving metallurgical, mechanical and environmental
parameters. SCC in aluminium alloys is characteristically intergranular.
According to the electrochemical theory, this requires a condition along the grain
boundaries that makes them anodic to the rest of the microstructure so that corrosion
propagates selectively along them. This theory is confirmed by the fact that cathodic
protection retards or eliminates SCC.
Parameters :
magnitude and duration of tensile strength acting at the surface;
residual stresses during quenching;
grain structure and stress direction (resistance in short transverse direction
controls applications of products);
environment : Cl- and a decrease of the pH-value accelerate the attack.
The SCC of high-strength aluminium alloys such as 2024, 7075 and 7079 is often caused
by sustained residual or assembly tension stresses acting in the short transverse direction.
The stresses developed by service loads are usually intermittent and are designed to
operate in a favorable direction (longitudinal or long transverse) relative to the grain
structure.
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avoid fitup stresses by careful attention to tolerance. Poorly fitted parts and misaligned
parts should not be forced into place.
Where built-in surface tensile stresses cannot be avoided, techniques such as shot
peening and surface rolling, or thermal stress relief from second stage ageing, can be
utilized to reduce the undesired stresses.
postweld heat treat weldments.
2.1.4.2 Hydrogen Embrittlement :
Hydrogen embrittlement is a form of environmentally assisted failure that results most
often from the combined action of hydrogen and residual or applied tensile stress.
Only recently it has been found that hydrogen embrittles aluminium. For many years, all
environmental cracking of aluminium and its alloys was represented as SCC. Hydrogen
damage in aluminium alloys may take the form of intergranular or transgranular cracking
or blistering. Hydrogen diffuses into the aluminium lattice and collects at internal defects
(e.g. during annealing of solution treating in air furnaces prior to age hardening).
Dry hydrogen gas is not detrimental to aluminium alloys; however, with the addition of
water vapor, subcritical crack growth increases dramatically.
The threshold stress intensity of cracking of aluminium also decreases significantly in the
presence of humid hydrogen gas at ambient temperature.
Hydrogen embrittlement of the 7000 series has been more intensively studied.
3- Corrosion Prevention:
They are a number of corrosion preventives measures, special to specific types of
aluminium
corrosion, the main methods of preventing corrosion of aluminium equipment :
alloy and temper selection
design of equipment
organic coating (and sealants)
inhibitors
cathodic protection
surface treatment
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The performance of organic coating systems can be maximized by following the specific
recommendations of suppliers regarding surface preparation, pretreatment, selection of
compatible conversion coat, primer and topcoat, application and curing. If continuing
maximum corrosion protection is required, the organic coating systems must be
maintained periodically.
3.3.1 Surface Preparation 24:
The most important factor in obtaining good paint adhesion is the preparation of the
Surface.
the aluminium alloy surface is relatively complex and is difficult to characterize precisely.
Thus, for example, hydrocarbons present on the surface may shield the substrate giving
rise to non-uniform behaviour; aesthetic reasons may also dictate removal of such
contamination. Consequently, an initial reason for surface treatment is to remove such
contamination and detritus. Degreasing in organic solvents or vapours has been an initial
approach, but a subsequent etching treatment in alkali usually follows. Appropriate rinsing
schedules must also be adopted to remove residual solution or solvent and to limit cross
contamination. It should also be appreciated that electrochemical processes, such as
alkaline etching, leave a residual film on the aluminium surface. A so-called desmut in
nitric acid follows, which removes contaminants, but the alumina film developed in the
alkali, perhaps reinforced through immersion in the acid, largely remains. In addition, such
film formation over the macroscopic surface leaves a more uniform surface, with the nitric
acid immersion serving to remove some residual metal impurity segregates. Such
segregates may result from dissolution of second phase material, with appropriate cations
relocated by deposition on the aluminium surface.
Consequently, a surface with reduced local activity ensues, with a reduced driving force
for corrosion in particular environments.
24
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They are Various pretreatment systems but a chemical conversion coatings are the most
widely used form of pretreatment when painting of aluminium.
Aluminium can be pretreated with
amorphous phosphates
zinc phosphates
chromating
phosphochromating
phosphofluozirconium coating.
Hollingsworth, E.H., Hunsicker, H.Y. and Schweitzer, P.A.: Corrosion and Corrosion
Protection Handbook, Pt. Aluminium Alloys, pp.153-186, Marcel Dekker Inc., New
York and Basel, 1989
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Most of the effective inhibitor have hetero atom such as O, N, S containing multiple bonds
in their molecules through which they can adsorb on the metal surface. The sites of these
elements have higher electron density, making them the reaction centers. An articles on
the
corrosion inhibition of aluminium by different type of inhibitors are summarized in Table
(4)
corrosion inhibition of aluminium by different type of inhibitors
Table (4) :corrosion inhibition of aluminium by different type of inhibitors are27 :
26
27
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dodecyloxy) aniline (MC12) and and their analogues polymeric surfactants poly 3(hexayloxy sulphonic acid) aniline (PC6), poly 3-(decyloxy sulphonic acid) aniline (PC10)
and poly 3-(dodecyloxy sulphonic acid) aniline (PC12).
The inhibition efficiency of the polymeric surfactant was higher than that of the
monomeric surfactant, and the inhibition efficiency increased with increasing inhibitor
concentration but decreased with increasing temperature.
The inhibition efficiency of PC11R is higher than that of PC12. This may be assigned to the
elimination of the terminal -SO3H groups in PC12. The presence of terminal CH3 groups
stabilizes the inhibition efficiency. Also, the presence of terminal CH3 in the alkyl chain
in
PC11R molecules may reduce repulsion between anionic head with similar charge as in
PC12.
This allows a closed layer to form more easily and hence higher inhibition efficiency28.
3.4.1.2 Different Extracts of Ocimum gratissimum.
I. J. Alinnor and P. M. Ejikeme studied Corrosion Inhibition of Aluminium in Acidic
Medium by Different Extracts of Ocimum gratissimum .
Ocimum gratissimum leaf contains alkaloid, saponins, flavonoids and tannins.
This study indicates that extract of Ocimum gratissimum inhibits Al surface in presence of
1M HCl. The corrosion process is inhibited by adsorption of extracts on aluminium
surface.
Inhibition efficiency increase with increase in inhibitor concentrations .
The result of the analysis shows that inhibition efficiency and degree of surface
coverage decreases as temperature increases. Activation energies of different extracts
increase as concentration of inhibitor increases. The negative values of Gads
shows that adsorption of inhibitor on surface of aluminium is spontaneous.
The trend of inhibition efficiency of different extracts was in order:
Distilled H2O > C2H5OH>1M HCl 29.
28
S.M. Sayyah, S.S.Abd El-Rehim, M.M. El-Deeb andS.M. Mohamed; The Corrosion Inhibition of Aluminium by Some of 3alkyloxyaniline Monomeric Surfactants and TheirAnalogues Polymers in 0.5 M HCl Solution;intech;p502
29
I. J. Alinnor, P. M. Ejikeme; Corrosion Inhibition of Aluminium in Acidic Medium by Different Extracts of Ocimum
gratissimum;ACS,2012,2(4)pp122-135
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L. A. Nnanna, I. U. Anozie, A. G. I. Avoaja, C. S. Akoma and E. P. Eti; Comparative study of corrosion inhibition of aluminium
alloy of type AA3003 in acidic and alkaline media by Euphorbia hirta extract; African Journal of Pure and Applied Chemistry
Vol. 5(8), pp. 265-271
31
A. I. Ali* and N. Foaud;J. Mater. Environ. Sci. 3 (5) (2012) 917-924
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32
I. C. Madufor, U. E. Itodoh, M. U. Obidiegwu, M. S. Nwakaudu; Journal of Engineering (IOSRJEN) Volume 2, Issue 9;pp 16-23
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adsorption (H) suggest that the chemical reaction involved in the adsorption of the
inhibitors on the metal surface is an exothermic process, hence increase in the reaction
temperature of the medium will decrease the inhibition efficiency33.
3.4.1.6- anionic polyeletrolyte pectates (PEC).
Refat M. Hassan and Ishaq A. Zaafarany studied Corrosion inhibition of aluminum (Al)
in hydrochloric acid by anionic polyeletrolyte pectates (PEC) as a water-soluble natural
polymer polysaccharide using both gasometric and weight loss techniques. The
results drawn from these two techniques are comparable and exhibit negligible
differences.
The inhibition efficiency was found to increase with increasing inhibitor concentration and
decrease with increasing temperature.
The inhibition action of PEC on Al metal surface was found to obey the
Freundlich isotherm. Factors such as the concentration and geometrical structure of
the inhibitor, concentration of the corrosive medium, and temperature affecting the
corrosion
rates were examined. The kinetic parameters were evaluated and a suitable
corrosion
mechanism consistent with the kinetic results is discussed in the paper.
Anionic polyelectrolyte pectates as a natural polymer may be considered as a safe
and effective inhibitor for decreasing the corrosion of Al in acidic medium. The
geometrical configuration and functional groups within the inhibitor molecule are
the two main important factors to influence the inhibition efficiency34.
33
34
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