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ISIJ International, Vol. 31 (1991), No.

2, pp, 189 193

ACorrosion Testing Method for Titanium in Nitric Acid Environme=n.,ts

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

Inc,, Wakinohama-cho.Chuo-ku, Kobe, Hyogo-ken, 651 Japan.


Institute, 2) Tokai Works, Power Reactor and Nuclear Fuel Develop-
ment Corporation, Muramatsu, Tokai-mura, Naka-gun, Ibaraki-ken, 319-1 1Japan,
(Received on June 29, 1990; accepted in the final form on September14, 1990)

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;

corrosion inhibitor; general corrosion; intergranular corrosion.

corrode uniformly because of the existence of partial


1. Introduction
streams of the condensed nitric acid solution.
The corrosion resistance of titaniurn exposed in a In this paper, the performance of a new corrosion
nitric acid vapor is generally inferior to that immersed testing apparatus for estimation of the corrosion re-
in nitric acid solution because of an inhibitor effect of sistance of titanium in condensed nitric acid solution
elements dissolved by the corrosion of titanium in the is introduced, and the results of a corrosion test of
solution.1) In other words, that in the condensed titanium using this apparatus are also described, com-
solution of a nitric acid vapor is very poor because of paring it with Type 304L stainless steel.
continuous renewing of solution and no concentration
of the above elements. Therefore, when an actual 2. Performance of Testing Apparatus
plant was designed without taking into the considera-
tion of the poor corrosion resistance of titanium ex-
2. 1. Constitutian of Apparatus
posed in the condensed nitric acid solution with re- As shownin Fig. l, this apparatus is composedof
newing, somecorrosion troubles have often occurred. a condenser, an outer vessel, an inner vessel with a
Sometesting methods to renew the nitric acid solu- siphon pipe, and an Erlenmeyer flask. Condensed
tion at an interval, for example, hl) (1.44x 104 s) or4 nitric acid solution from the condenser enters the
to expose the inner surface of a pipe in a nitric acid inner vessel. inner vessel is automatically
Whenthis
vapor2) have been adoped in order to estimate the filled with condensed nitric acid solution (about 20
corrosion rate in a vapor condensedzone. However, ml x(2 l0-5 m3)), all of the solution drop to the flask
both of these methods have some disadvantages. through the siphon pipe. The nitric acid solution in
Specially, in the former it is not suitable to testing for the inner vessel is renewed at regular intervals, so

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

solution can be adjusted by the electric power of the HN03Concentration (mol 12 )


heater. 2 4 6 8 10 12 14
120
Moreover, the corrosion rate in the vapor and
liquid zone of nitric acid solution can be estimated by
hanging test pieces between the inner and outer vessel ;~ /
and setting test pieces in the flask at that sametime. 110 Vapor PhaseLine from
/
l Vapor-Liquid Equil~brium Data3)
A photograph of the testing apparatus is shownin O
Fig. 2. 1,

~
~~

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 ) '/.

Fig. 3. Concentration of HN03Condensedsolution.


This line given from analyzed concentrations was
nearly equal to the reported line3) as is clear from this
flgure. Therefore, the liquid in this inner vessel was
theoretically considered to be able to condense in this
apparatus .
111RC
HN03Concentration :
2.3. Temperature 7.2 mol / E 107~)
The temperature of each zone in this testing ap-
paratus was measured with a thermo-couple at 12
mol/1 (1.2x 104 mol/m3) nitric acid solution using a
400 W(4x
sults are
102J/s)
shownin Fig.
electric
4.
power heater. The re-
113PC
The temperatures in the inner vessel
liquid and the
v
zone of the flask were 107 and 15'C, respectively. 1 115RC
According to the reported data,3) these values should HN03Solution :
be 109.4 and 117.2'C. So, the temperatures in this /
12 mol E

apparatus were considered to be almost equal to that


(1 .2
x 104mollm3)
of the vapor-1iquid equilibrium line. Fig, 4, Temperature of each zone in testing apparatus.

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)

Table l. Chemical compositions of tested materials. (masso/o)

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)

perfect corrosion resistance.


In this test, Ti02 passive film would be formed on the
The high corrosion resistance of titanium in the titanium in the nitric acid solution also.
liquid zone is attributable to concentration of titanium
ions dissolved in the liquid acted as a corrosion in- Onthe other hand, the oxidation ability of a nitric
acid in the condensed zone would be mild as com-
hibitor.2) Namely, it was considered that whentita-
pared with the case of coexistence of dissolved tita-
nium was immersedin a nitric acid solution without
renewing of solution for a long time, the corrosion nium ions. Therefore, passive fllm on the titanium
in the mild oxidizing environment would consist of
rate would be decreased with immersion time be-
Ti203, not to oxidize to Ti02 as Eq. (4), which has
cause the most stable passive film of Ti02 was formed protection ability against corro-
not so sufficient
on titanium by accumulating of Ti3+ and Ti4+ ions, sion.5'6)
as shownin following equations.4)
2Ti3++3H20-~ Ti203+6H+ ............(4)

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.

3.2. Effect of the Renez~)ing Frequency on the Corroslon Rate


0.01
The effect of renewing frequency of the solution
A B C D
3.0
Condensed Vapor Zone Liquid Zone
Zone 304L S.S.
Fig. 6. Results of corrosion test,
2.5

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

condensedin the inner vessel on the corrosion rates of


titanium was investigated. The frequency was ad-
justed by controlling a electric power (600
J/s)) of heater. If the concentration of nitric
W
(6 x 102
acid
HN03Solution :
13mol / 2 (1.3 x 104mol!m3)
HN03condensedSolution :
8.5mol / a (8.5 x 103mollm3)
was 13 mol/1 (1.3x 104 mol/m3), then the concentra- 10 Electric Powerof Heater : 600W(600J/s,
tion of condensed solution would be 8.5 mol/1 (8.5x
103 mol/m3) as shown in Fig, 3. These results are
shownin Fig. 9. Q,
:~
The corrosion rate of titanium was about maximum E 1
0.95 mm/year(3.01 x 10-11 m/s) constant at more than E
o-0-0 o-
7 times per I h of renewal frequency, so, more than
'!'

::

7times of the renewing frequency would hardly affect


the corrosion rate of titanium.
o,o

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

stituted of a condenser, an outer vessel,


an inner vessel (
RenewingFrequency n / hour )
with a siphon pipe, and an Erlenmeyer flask. The Fig. 9. Relationship between renewing frequency of HN03
solution condensed in the inner vessel was automati- condensed solution and corrosion rate of titanium.
cally renewed at regular intervals.
The nitric acid concentration and temperature of the highest value, and the corrosion modewas inter-
each zone in this apparatus was considered to be granular. On the other hand, the rate in the con-
almost equal to data of the reported vapor-liquid densed solution was 0.095 mm/year(3.01 x l0-12 m/s).
equilibrium line. As the concentration of dissolved It
was considered that condensated oxidizing ions in
elements in the condensed zone of this apparatus was the liquid solution would accelerate the corrosion
sufficiently lower than that in liquid zone, the corro- rate.
sion rate of metal in the condensed zone
was accu-
rately estimated without the influence of dissolved REFERENCES
ions from a corroded metal itself. l) H. Satoh: Chem.Eng,, 2 (1984), 31.
(2) In the case of titanium, its corrosion rate in 2) A. Takamura, K. Arakawa and Y. Moriguchi : The Sci-
the condensedsolution was 0.37 mm/year (1 17
x 10-11
. ence Technology and Application of Titanium. Pergamon
m/s) at the highest value, and the surface morphology Press, Oxford, (1970), 209.
showed general corrosion. In particular, its 3) J.Hirata : Vapor-Liquid Equilibrium Data Book, Kodan-
corro-
sion rate in the liquid zone was less than 0.01 mm/ sha, Tokyo, (1974), 200.
4) H. Satoh. F. Kamikubo. K. Shimogori and T. Fukuzuka:
year (1x 10-13 m/s) and this rate was considered as Corros. Eng. (Jpn.), 31 (1982), 769.
the perfect corrosion resistance. That is because of 5) M. Pourbaix : Atlas of Electrochemical Equlibria in Aque-
concentrated dissolved titanium ions such as Ti3+ and
ous Solutions, PergamonPress, Oxford, (1966), 213.
Ti4+ ions in the solution acted as a corrosion inhibitor. 6) T. Fukuzuka, K. Shimogori, H. Satoh, F. Kamikuboand
(3) The corrosion rate of 304L stainless steel was H. Hirose: ASTM Special Tech. Publ. No. 728, (1981),
4.5 mm/year (1.42x lO-ro m/s) in the liquid zone at 71.

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