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Takashi FURUYA,
Junji KAWAFUKU, AtSUShi AOSHIMA2)
HirOShi SATOH,KazutOShi SHIMOGOR11), and
SeiichirO TAKEDA2)
Research Laboratory, Kobe Steel. Ltd., Wakinohama-cho,Chuo-ku. Kobe, Hyogo-ken, 651 Japan.
Material 1) Kobelco Research
The corrosion resistance of titanium nitric acid vapor is generally inferior to that immersed in nitric acid
exposed in
because of an inhibitor
solution elements dissolved by corrosion of titanium in the solution.
eftect of
Anewtype corrosion testing apparatus, which would not be influenced by such dissolved elements on the corrosion rate,
wasdesigned in order to easily estimate the corrosion rates in a nitric acid condensedzone, a vapor zone and a liquid zone
simultaneously. This apparatus wascomposedof a condenser, an outer vessel, an inner vessel with a siphon pipe, and
an Erlenmeyer flask. The solution condensed in the inner vessel was automatically removed to the flask through the
siphon pipe and renewedat regular intervals. The nitric acid concentration and the temperature of the eibove each zone
in this apparatus
was similar to the data obtained from the previously reported vapor-liquid equilibrium line. As the
concentration of dissolved elements in the solution of the condensedzone of this apparatus wassufficiently negligible, the
corrosion rate in the condensedzone could be accurately estimated without the influence of dissolved elements from the
corroded metal itself.
Using this testing apparatus, the corrosion rate of titanium in the condensedzone was0.37 mm/year(1 .1 7x I 0-11 m/s),
greater value than those in any other zone and general corrosion occurred. Moreover, the corrosion rate in the liquid
zone was less than 0.01 mm/year (3.17x 10-13 m/s) and this rate was regarded as the perfect corrosion resistance.
That is because of concentrated soluble titanium ions in the solution acted as a corrosion inhibitor.
In the case of 304L stainless steel, the corrosion rate was4.5 mm/year(1 .4 x I 0-10 m/s) in the liquid zone at the highest
value, and the intergranular corrosion occurred. Onthe other hand, the rate in the condensedsolution was small to be
0.095 mm/year(3.01 x 10-12 mls).
KEYWORDS: corrosion; corrosion test method; nitric acid; condensed zone; titanium; type 304L stainless steel;
a long time and it is not also very easy to operate elements dissolved from test specimens in the solution
manually. In the latter, circumstances cannot be ob- could not be condensed in the inner vessel. The
served and there is
a possibility for a pipe not to renewing frequency of the condensed nitric acid
189
C 1991 ISI J
ISIJ International, Vol. 31 (1991), No. 2
Condenser
Inner Vessel
( 30c ) ./ Outer Vessel
(
70c )
o
(
CondensedZone
CondensedHN03
gE vapor zone
eo
,N
Solutfon )
SyphonPipe
Erlenmeyer flask
(Volume : I e ) ~\. o
co
(1
x 10 -3m3)
Liquid Zone
(HN03Solution ) Fig. 2. Photograph of testing apparatus,
(
unit
)
: mm
Fig. I .
Schematic diagram of testing apparatus. Vapor PhaseLine in This Test
~
~~
2.2. Concentration of JVlitric Acid Solution Condensedin the *G' 1oo Liquid PhaseLine from
a
E
Inner Vessel Vapor-Liquid Equilibrium Data3)
hO
The concentration of a nitric acid solution con-
densed in the inner vessel ideally must be the sameas 90
the vapor-1iquid equilibrium line. The concentra- 760 mmHg(i.OI x 105Paj
tion of a condensed nitric acid solution in the inner
vessel was analyzed in order to confirm the accuracy
of this testing apparatus, and was comparedwith the O 20 40 60 80 1OO
theoretical line from vapor-liquid equilibrium data.
These results are shownin Fig. 3.
HN03concentration (mass ) '/.
2.4. Renez~)ing Frequency of CondensedJVlitric Acid Solution The renewing frequency and the temperature of the
The renewing frequency acid solution con- of nitric condensed solution were measured by using an inner
densed in the inner vessel can be adjusted by the vessel of a 20 ml (2 x 10-5 m3) volume, a 600 (6>
W
electric
power of heater above mentioned previously. l02J/s) electric power heater and variable resistor to
190
ISIJ International, Vol. 31 (1991), No. 2
control the voltage for heater. The results for 13 used as test materials. Their chemical compositions
mol/1 (1.3 x 104 mol/m3) nitric acid solution are shown are given in Table I .
These materials were cut to
in Fig. 5. specimen coupons 15 wide and 60 long fol-
The renewing frequency of condensed nitric acid mm
lowed by polishing with #400 emerypaper, degreasing
mm
solution
electric
increased as the voltage increased of the
heater. The frequency of renewing, for ex-
in acetone and drying.
tric
A 400 (4.0x 102J/s) elec-
power heater was used at 100 V and the ratio of
W
ample, were 21 times per I at 120 V. h nitric acid solution volume to surface area of all test
The temperature of the solution condensedat 80 V pieces, including condensed zone, vapor zone,
in the
or over was 114'C constantly, while the temperature and liquid zone, was 7ml/cm2 (7 x l0-2 m3/m2). The
at 70 V
or less becamelower than that of the vapor- test results are shownin Table 2.
liquid equilibrium line. Over to times per I of 7 8 h In the case of 304L stainless steel, the concentra-
renewing frequency, the boiling temperature of con- tions of Fe, Cr and Ni ion in the condensed solution
densed solution was considered to be stable. were 2.6, 0.7 and 0.6ppm, respectively, and were
quite lower than those in the liquid zone. As the
2. 5. Concentration of Elements Dissolved in Condensed concentration of soluble titanium ions dissolved in the
JVlitric Acid Solution condensed zone and in the liquid zone were 0.21 and
The corrosion rate of titanium in condensed nitric 20.0 ppm, respectively, the ratio of their concentra-
acid becomeshigher than that in the liquid nitric acid tions in the condensed zone to the liquid zone
was
solution is because of no concentration of dissolved relatively higher than that of 304L stainless steel. It
titanium ions in condensed zone. In other words, is considered that these results would be
cause of the
the corrosion resistance of titanium will be greatly af- low solubility of titanium ions.
fected by the concentration of titanium ions contained
in an exposed environment.
3. Corrosion Test Results and Discussion
The concentration of several ions in a condensed
nitric solution and a nitric acid solution ofliquid zone 3.1. Corrosion Rate in
Each Zone
was analyzed after the corrosion tests were carried Corrosion tests of titanium and 304L stainless steel
out at 13 mol/1 (1.3xl04 mol/m3) for 240 (8.64x h were carried out in ll.5mol/1 (1.15xl04 mollm3)
105 s). The commercially pure Ti (ASTMGrade 2)
and 304L stainless steel with thickness were 2mm
nitric acid solution using this apparatus and 400
(4x 102J/s) (100 V) electric power heater for 240 h
W
(8.64x 105 s). At that time, the nitric acid concen-
tration of condensed solution was 6.2 mol/1 (6.2 x 103
A
2o HN03solution
13mol / L
: 13met
xl04m3)
(1'3
/e l! 130 mol/m3) from the vapor-liquid equilibrium line. The
results are shownin Fig. 6.
HN03condensedSolution :
In the case of titanium, the corrosion rate in the
/ ~ (8'5 x l03movm3)/
8'5mol
Electric power ot Heater : condensed solution was 0.37 mm/year (1.17xl0-11
600w(6 x I 02 Jls) m/s) at the highest value. The general corrosion
:!
o
.:
15 _/~IO~( 120 occurred as shownin Fig. 7. Moreover, the corrosion
c: rate in the liquid zone was less than 0.01 mm/year
> O
o ~0
Oll
=
,D
:, ,D
Table 2 Drssolved ron concentratron from corrosion
:T
,D ~ in HN03 condensed solution and HN03
t 10 110 ~~
*Q, solution.
a,
=
.-~
Al aL
E
CD
'l'
Concentration of ion species
=
1,
H (PPm)
Q: Material Solution
Fe Cr Ni Ti
5 1OO
O HNOSsol,
7OOO 1920 1100
Il 304L stainless
steel
HN03
condensed 2.6 0.7 o.6
sol.
50 60 70 80 90 1OO 120
HN03sol. - 20.0
Voltage of Heater (V) Ti HN03
condensed 0.21
Fig. 5. Relationship between renewing frequency of HN08
condensed solution and heater voltage (A), and
sol. -
temperature of HN03 condensed solution and HN03solution : 13 mol/1 (1.3> 104 mollm3)
heater voltage (O)- Testing time : 240 h (8.64XI05 s)
Material C Si Mn P S Fe Cr Ni o H N Ti
Ti(ASTMGrade 2)
= - - O044. O0955 O0025 0,0029 bal.
304L stainless steel O.012 O.630 1.474 O031 O004 bal. 18.33 10,12
191
ISIJ International, Vol. 31 (1991), No. 2
(1
x l0-13 m/s) and this value was regarded to be the Ti4++H20-> Ti02+4H+ ..... .........(3)
Ti-~Ti8++3e ....
..,......(1)
Consequently, this test apparatus which the con-
Ti8+ _>Ti4++e .........(2)
....... centration of dissolved elements can becomelower in
condensedzone will be effective to estimate accurate-
ly the corrosion resistance of titanium in the con-
-h~ densed nitric acid solution.
~~~ : 304L S,S.
,~]1
C~~: Ti The corrosion rate of 304L stainless steel was 4.5
HN0311.5M b,p, mm/year (1.43x lO-ro m/s) in the liquid zone at the
240h (8.64 XI05s) highest value conversely, and the intergranular corro-
10 (c)
sion occurred. On the other hand, the rate in the
condensed solution was 0.095mmjyear (3.0lxl0-12
,Q
,D
> m/s). For 304L stainless steel, Fe3+, Cr6+ and other
E (D) ions were gradually condensed in the solution by the
E 1 corrosion. And then, the corrosion rate of 304L
Q,
,o
stainless steel was polarized to a trans-passive state
r:
c by Fe3+ and Cr6+ ions as oxidizing agents. This phe-
o
co
o nomenonwas confirmed in Fig. 8 which showedthat
o 0.1
the corrosion rate of 304L stainless steel increased
O remarkably by adding Fe8+ and Cr6+ ions to boiling
3 mol/1 (3 x 103 mol/m3) nitric acid solution.
C~
q, 20
>
E
E
S:;
15
l:
o
o
(a) 304L stainless steel o
O 10
0.5
o
Fe3* o 0.5 1.o 1.5 2.o
+
(b) Titanlum Cre+ o 0,25 0.5 0.75 1.o
Fe+ cr (gll )
100p m Fig. 8. Fe3++Cr6+ions concentration in a boiling
Effect of
Fig. 7. Corrosion morphology of 304L stainless steel and 3MHN03solution on corrosion rate of 304L stain*
titanium in HN08solution. less steel,
192
ISII International, Vol. 31 (1991), No. 2
::
o
O
0.1
/
4. Conclusion
(1) The new type corrosion testing apparatus,
which is
not influenced by dissolved elements on the o,ol
)
corrosion rate, was designed. This apparatus is con- 5 Io 15 20
193