№ 10 (91)
октябрь, 2021 г.
69
Figure 2 is taken from an article of Lin, Frankel and
Abbot [12], where it can be seen that all silver salts are
present at the same time during street corrosion. The re-
gion is distinguishable on the polarographic curve if the po-
tentials of the substances differ by more than 0.1–0.2 V.
If the potential difference is less than 0.1–0.2 V, the two
substances merge into one. Various signal processing
methods are used to increase the resolution of the polar-
ographic method.
Auger spectroscopy (AES) is a method for studying
the elemental composition of surfaces. The composition
of several molecular layers is calculated using Auger
spectra and then the surface is etched with ions to a cer-
tain depth. The composition calculation and etching is
repeated over and over again until the specified analysis
depth is reached.
The elemental composition of the layers and their
condition when exposed to light were investigated using
XPS and AES. First, the dependence of the effect on the
wavelength of light is the opposite: the longer the length,
the weaker the effect. As a result, the experimental
wavelengths, according to the effect produced, are ar-
ranged in the following order: 1537 Å> 3650 Å> sun-
light. Moreover, the longer the exposure time, the
stronger the tarnish. The proportion of Ag2O was 42.9%
of silver after exposure for 18 hours to ultraviolet light
1537 Å, but 17.6% if within 24 hours. The proportion of
oxide is reduced by exposure to light. The XPS meas-
urement showed that the surface, when exposed to light
in the atmosphere, first oxidized and chlorinated, and
then silver chloride could be converted to Ag2O, which
eventually reduced to black superfine silver particles
and again. (In the work [13] Fang Jingli and Yu Yaohua
(1985) only the abstract was read)
Saleh, Xu, and Sanvito [14] used the ReaxFF [15]
program to tarnish silver. Sulfur compounds, especially
hydrogen sulfide (H2S), are believed to tarnish silver
even at 1 ppb. Correct simulation can answer any ques-
tion, but the power of the computer must be greater than
the processes it counts. Or you have to use some tricks.
The team used a method called ReaxFF (Reactive Force
Fields). ReaxFF can "train" a computer to reproduce
quantum chemical results and reveal the mechanisms
underlying the silver-oxygen and silver-sulfur reactions.
Simulation showed that the rate of sulfide formation is
much lower than the rate of oxide formation. When the
S8 molecules approach the silver, they quickly dissoci-
ate into individual atoms and react with the silver. Con-
versely, O2 dissociates slowly and has less "sticking"
capacity. Moreover, it is generally expected that the
growth of the oxide or sulfide will slow down after the
formation of the first tarnishing layer due to the oxygen
or sulfur atoms having to diffuse through it in order to
react with the silver atoms. The researchers found that
silver atoms appear to diffuse upward towards the sulfur,
allowing the silver sulfide to grow much faster. “Ag
ion… highly mobile in Ag2S” as opposed to oxygen.
Do'stlaringiz bilan baham: