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Processes, parameters and mechanisms controlling the normal and abnormal growth of porous anodic alumina films

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Abstract

Aluminium was anodised in H2SO4 solutions 0.25–1.53 M, temperatures 0–35 °C, times up to 90 min and voltage 25 V. Anodising was followed chronoamperometrically. The passing charge, consumed Al, formed oxide, transport numbers of oxygen anions in barrier layer and film thicknesses were determined. Films were examined to detect abnormal film growth, called burning. It was found that the current in Al anode is closely solely ionic, and the only processes occurring are those related with ionic charge transport and heat release and its abduction for which suitable equations were formulated relating many parameters. At each concentration, the temperatures, current densities and times up to which normal film growth occurs and above which stain-like mild, island-like intermediate, strong, strong-destructive and mixed burning appears were found. Burning emerges at lower concentrations, temperatures and times for thinner Al. Low concentrations and temperatures among thresholds where mild and next-kind burning first appear define windows of conditions where thick enough dark or black films grow. Peculiar chronoamperometric plot characterises each film growth type. Though other burning kinds can appear at each surface region or in the whole surface, strong and strong-destructive emerge only at the lower Al side around which the efficiency of solution stirring is highest. The mechanisms of normal and abnormal film growth were formulated showing that different processes and interacting variable parameters, some of which are noted for first time, regulate each film growth type. These can predict methods to avoid abnormal film growth.

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Abbreviations

a 2 and a 3 :

Activation (half jump) distances of O2−and Al3+ transport inside the barrier layer (nanometres)

Al3+ aq,hydr :

Hydrated Al3+ in aqueous solution

AM Al :

Atomic mass of Al

A 2 and A 3 :

N 2,m v 2 n 2 FN A −1 and N 3,m v 3 n 3 FN A −1 (milliamperes per square centimetre)

A 2,a and A 3,a :

Average A 2 and A 3 across the barrier layer (milliamperes per square centimetre)

B 2 :

n 2 a 2 and B 3 = n 3 a 3 (manometres)

c a :

Concentration of H2SO4 anodising electrolyte (Molar)

C p,Al :

Molar heat capacity of Al (joules per mole per Kelvin)

d Al :

Density of Al (2.7 g cm−3)

D, D b and D c :

Diameter of the hemispherical section surface across the barrier layer, pore base diameter and cell width in steady state (nanometres)

2−1(D c–D b):

Barrier layer thickness (nanometres)

ΔH :

Enthalpy change between ordinary and transient oxide lattice structures (joules per mole)

ΔH a :

Average ΔH across the barrier layer (joules per mole)

ΔH o 298 K(Al):

Standard formation enthalpy of Al (kilojoules per mole)

ΔH o 298 K(Al2O3):

Standard formation enthalpy of Al2O3 (kilojoules per mole)

ΔH o 298 K(Al3+):

Standard formation enthalpy of Al3+ (kilojoules per mole)

ΔH o 298 K,hydr(Al3+):

Standard hydration enthalpy of Al3+ (kilojoules per mole)

ΔH o 298 K(H+):

Standard formation enthalpy of H+ (kilojoules per mole)

ΔH o 298 K,hydr(H+):

Standard hydration enthalpy of H+ (kilojoules per mole)

ΔH o 298 K(H2Ol):

Standard formation enthalpy of liquid H2O (kilojoules per mole)

ΔH r o 298 K and ΔH r o T :

Standard enthalpy (per mol of Al2O3) of reaction 2Al + tn an3H2O = tn anAl2O3 + tn an6H+ aq,hydr + tn ca2Al3+ aq,hydr + 6e−(kilojoules per mole) and this enthalpy at T ≠ 298 K

Δm :

Difference of Al anode mass after and before anodising (grams)

ΔP bl, ΔP pfs, ΔP attl and ΔP bs :

Potential drops across the barrier layer, in pore-filling solution, in attached layer and in adjacent bath solution layer up to reference electrode (volts)

E :

local field strength in each equipotential surface across the barrier layer (volts per nanometre)

E a = 2ΔP bl(D c–D b)−1 :

Average field strength across the barrier layer (volts per nanometre)

E pfs, E attl and E bs :

Field strength in pore-filling solution, attached layer and adjacent bath solution layer up to reference electrode across each plane parallel to film surface (volts per micrometre)

F :

Faraday’s constant (96,487 C mol−1)

h f, h, h attl and h bs :

Film thickness, length of pores (≈ h f) and thicknesses of attached layer and adjacent layer up to reference electrode (micrometres)

H+ aq,hydr :

Hydrated H+ in aqueous solution

j and j a :

Current density and average current density during potentiostatic anodising (milliamperes per square centimetre)

j pfs, j attl and j bs :

Ionic current density in pore-filling solution, attached layer and adjacent bath solution layer up to reference electrode across each plane parallel to film surface (milliamperes per square centimetre)

k :

Rate constant of film thickness increase 6.9833 × 10−5 cm3 C−1

k ht,ox, k ht,pfs and k ht,attl :

Thermal conductivity of oxide, pore-filling solution and attached layer (watt per centimetre per Kelvin)

k ht,f :

Combined thermal conductivity of oxide and pore-filling solution (watt per centimetre per Kelvin)

k ht,t :

Total coefficient of heat transport from Al anode to bath solution (watt per square centimetre per Kelvin)

l Al,0 :

Initial Al metal thickness (millimetres)

l Al = l Al,0–S Al −1 d Al −1 AM Al Q(3 F)−1 :

Mean thickness of Al metal remaining unconsumed during anodising (millimetres)

me:

Metal

m|o:

Metal|oxide interface

m Al :

Mass of Al remaining unconsumed during anodising (grams)

m Al,sod :

Consumed Al mass found by selective oxide dissolution (grams or milligrams)

m ox,mb :

Mass of oxide found by the mass balance method (grams or milligrams)

m ox,sod :

Mass of oxide found by its selective dissolution (grams or milligrams)

n :

Surface density of oxide cells/pores near Al substrate surface in steady state (per square centimetre)

n 2 and n 3 :

Valences of O2−and Al3+ ions

N A :

Avogadro constant (6.022 × 1023 mol−1)

N 2,m and N 3,m :

Surface concentrations of mobile O2−and Al3+ in each equipotential surface across the barrier layer (per square centimetre)

v 2 and v 3 :

Vibration frequencies of O2−and Al3+ ions or the number of chances per s the ions may jump the energy barrier (activation energy) if they have sufficient energy (per second)

o|e:

Oxide|electrolyte interface

ox:

Oxide

p and p a :

Local porosity at each position across the film and average porosity of the entire film (dimensionless)

P an :

Anodic potential versus SHE (volts)

P an–P cath :

Potential difference between anode and cathode or anodising voltage (volts)

P an–P ref :

Potential difference between anode and reference electrode (volts)

Q :

Passing electric charge (coulomb)

Q ac,Al, Q ac,ox, Q ac,pfs and Q ac,attl :

Heat accumulated in Al metal substrate, oxide, pore-filling solution and attached layer (joules)

R :

Universal gas constant (8.314 J K−1 mol−1)

R pfs, R attl and R bs :

Ohmic resistances in pore-filling solution, attached layer and adjacent bath solution layer up to reference electrode (ohm)

S:

Equipotential hemispherical surface across the barrier layer

SS:

Plane across the film parallel to film and Al substrate surfaces

S’S’:

Outer boundary plane of attached layer on Al anode

S Al :

One face entire geometric surface area of Al specimen (square centimetres)

S g :

Geometric surface area of Al specimens that is oxidised during anodising (square centimetre)

S = 2−1 S g πnD 2 :

Area of hemispherical surface with diameter D across the barrier layer per unit of S g (square centimetres)

S a :

Average S across the barrier layer ≈ 2−1 S g(2.093 + 2−1 πnD b 2) (square centimetres)

t :

Anodising time (minutes or seconds)

tn an and tn ca :

Transport numbers of O2−and Al3+ across the barrier layer (dimensionless)

tn an,a :

Average tn an when j and/or T an vary during anodising (dimensionless)

T :

Temperature of bath bulk solution (degrees Centigrade or Kelvin)

T an :

Real anodising temperature in the barrier layer region (degrees Centigrade or Kelvin)

T fs :

Temperature at film surface during anodising (degrees Centigrade or Kelvin)

u i,pfs, u i,attl and u i,bs,:

Specific ionic conductance (conductivity) of i species in pore-filling solution, attached layer and adjacent bath solution layer up to reference electrode at each plane parallel to film surface (per ohm per micrometre)

û i,pfs, û i,attl and û i,bs :

Average u i,pfs, u i,attl and u i,bs along pores and in attached and adjacent layer (per ohm per micrometre)

W 2 and W 3 :

Real activation energies of O2−and Al3+ transport across the barrier layer (joules per mole)

W 2,a and W 3,a :

Average W 2 and W 3 across the barrier layer (joules per mole)

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Authors and Affiliations

  1. Department of Physics, Chemistry and Materials Technology, School of Technological Applications, Technological Education Institute of Piraeus, P. Ralli & Thivon 250, 11244, Egaleo, Attiki, Greece

    G. Patermarakis & G. Kapiris

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  1. G. Patermarakis
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  2. G. Kapiris
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Correspondence to G. Patermarakis.

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Patermarakis, G., Kapiris, G. Processes, parameters and mechanisms controlling the normal and abnormal growth of porous anodic alumina films. J Solid State Electrochem 17, 1133–1158 (2013). https://doi.org/10.1007/s10008-012-1976-0

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  • DOI: https://doi.org/10.1007/s10008-012-1976-0

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