Metal surface contacting with solution of electrolyte in some
definite condition transformed to so called passive state. Study of
this phenomena on the border of metal – electrolyte plays an important
role, as they define the process of destruction of metal. And it is
thermodynamically favourable for metal to dissolve as a result of these
process. Such phenomenon was first observed by M. Faraday. This is one
of the main factor of stability of metal in aggressive environment. It
is known that, there is no unified model of passivation. The most
common and in first sight convincing conception of phase oxide is
connecting passivation with mechanical formation of thin film on metal
surface with oxide layer. However, potential of phase oxide formation
differ from critical parameter of polarised curve (pic. 1), specially
from potential of activation ja and passivation jП. In case of iron
this difference is 0,63 v. For this reason the phase film conception of
passivation cannot be taken in that from. In case of metal
passsivation determining role plays water molecule. Some part of water
molecule dissociate in the process of adsorption and ion of oxygen
breaking the bond with proton firmly block the most active centre of
metal surface. This may be considered as start of passivation. In the theory of passivation some physical factor must be taken in account. Most important of those are stated bellow. Strong electric field. It define the transform of metal to metal oxide: . Equilibrium exchange on the border with solution in which take part the ion OH- and Oox. Number of nonequilibrium vacancy in the passivaing oxide lattice. Energetic inhomogeneity of metal surface. Major
factor of the process is inter phase difference of potential, which is
defined by composition of the solution. Depending on its value the
current of dissolution take the form: Breaks
on this curve is connected with the formation of thin protection layer
in sector II. Reaction of this passive layer formation is The
oxygen undertakes from molecules of water, and half metal from the
substrate of metal surface. As a result of formation of this layer the
current falls on 4-7 orders in a very narrow interval of potential
change j. After formation of a continuous monolayer there occur the
state of passivity III. The question, how this passive layer is
formatted was not studied. We shall try to explain the process of
passive layer formation and the kinetic of the process. With
this purpose it would be possible to use the thermodynamic theory of
Gibbs- Folmer, according to which at formation of a new phase the free
energy of system changes in the value . , Where q- the geometrical factor, l- the size of the cluster , M, r- molecular weight and density of a firm phase, -
chemical potentials of supersaturated solution and firm phase with
concentration C1,2 and coefficient of activity f1,2. In the point of
maximum the
cluster is equilibrium, its critical size lkp surpasses few times the
sizes of building particles (molecules) of the layer. The probability
of its formation is defined by the work A of this process , With the condensation of the factor of crystallisation Wc , the probability of crystal cluster formation Wk is . It
is defined by the classical approaches, according to which the
formation of equilibrium crystal take place by consecutive connection
of building particles to the complexes, already available on surface M. At
calculation of probability it is accepted, that on the surface M
spontaneously arise (or on the contrary, break up) twin crystal
particles of various sizes of a and with inter nuclear distance r0. The
sizes change as a result of the consecutive elementary acts
(transitions) of the type such as , i.e. growth or disintegration of crystal particles. Probability of elementary transitions we shall designate Pa® a±r0 , . Their speeds .
These values represent quantity of the acts taking place in 1 cm2 of
the surface M for 1 sec. They are proportional to superficial
concentration na of particles of the given size and probabilities of
the elementary acts . Resulting speed of direct and return transitions . At balance state Proceeding from this it is possible to find out Further we shall define A1 and A2. Proceeding from this it is possible to calculate the speed of cluster formation With the help of this formula it is possible to define the laws of formation of the passive layer on the sector II (in pic.1). Then
taking in to account the energetic inhomogeneity of metal surface it is
possible to find out the integrated current density where y- bond energy. To each pair value of corresponds the certain probability I(j, yi) of formation of twin cluster and the local degree of filling by
them ith platforms of the surface M. With the growth of potential j
formation of cluster becomes more and more intensive. And accordingly
grows the integrated degree of its filling by cluster, Thus
the processing of the first thin superficial layer of metal in oxide is
finished. Take place complete passivation of the surface M, the sector
II on the curve (fig. 1) is replaced by the sector III, for which the
new physical conditions must be taken in account. And further
researched may be done.
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