INORGANIC SYNTHESIS AND INDUSTRIAL
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 8, pp. 1049−1053. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © O.V. Popova, E.A. Mar’eva, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 8, pp. 1064−1068.
Synthesis of Titanium Nitride by Anodic Polarization
of Titanium in Electrolytes Based on Ethylene Glycol
O. V. Popova and E. A. Mar’eva
Engineering-Technological Academy, Southern Federal University, Nekrasovskii per. 44, Taganrog, 347928 Russia
Received May 13, 2014
Abstract—Possibility of forming titanium nitride ﬁ lms by anodic polarization in water-containing ethylene
glycol in the presence of various electrically conducting additives was demonstrated and substantiated. The
electrochemical processes were studied by chronoamperometry and cyclic voltammetry. Titanium nitride ﬁ lms
were subjected to microstructural, X-ray diffraction, and elemental analyses.
The synthesis of titanium nitrides is in high demand
by techniques for fabrication of protective-decorative
coatings possessing high chemical stability, hardness,
and wear resistance and decorative properties. At pres-
ent, titanium nitride ﬁ lms also ﬁ nd use in micro- and
nanoelectronics. However their application is limited
because the photolithography on this material is dif-
ﬁ cult. One of possible ways to solve this problem is to
form titanium nitride layers by anodic polarization of
It has been found that light yellow to bronze titanium
nitride layers are formed on the titanium surface in
water-containing organic electrolytes based on ethylene
glycol and glycerol at low NH4F concentrations or in
the presence of KF, LiClO
, or other background addi-
tives [1, 2].
Our communication presents the results of a study
concerned with processes in which ﬁ lms of titanium ni-
trides are formed in electrolytes containing no ammonium
ﬂ uoride on titanium plates or glass-ceramic plates coated
with metallic titanium.
We performed electrochemical syntheses in the
potentiostatic mode with an P-30I potentiostat at the
ambient temperature (~20°C) in electrolytes based on
ethylene glycol (EG) with addition of 10% water. The
role of anodes in synthesis processes was played by
plates with a vacuum-deposited titanium area of 1 cm
For this purpose, Ti layers (99.99%) with a thickness
of about 10 μm were deposited by thermal evaporation
in a vacuum onto plates of glass-ceramics, polikor, and
oxidized or unoxidized silicon. In addition, metallic Ti
(99.99%) plates were subjected to anodic polarization.
AS electrically conducting additives served compounds
, KOH, NH
SCN, etc. A titanium plate with
an area of 2 cm
was used as the auxiliary electrode.
Prior to each synthesis, the electrode was cleaned
by the cathodic-anodic polarization method. The
completion of a synthesis was determined from the
I–τ dependence, when the current became zero. The
oxidation processes were studied by the method of
potentiodynamic curves on a point titanium anode with
a working area of 0.01 cm2. The electrical conductivity
of the electrolyte solutions was measured with an OK-
102/1 conductometer (Radelkis).
We examined the composition of the products we
obtained and made an X-ray diffraction analysis with
a D2 Phaser X-ray diffractometer (Bruker). Electron
micrographs were obtained with a Quanta 200 scanning
electron microscope (SEM). The elemental composition
was analyzed with a Q4 Tasma optical-emission spec-
trometer (Bruker Elemental).