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Materials and Corrosion 54, 609–611 (2003) Kurztitel 609

Corrosion Concepts
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Carbon and stainless steel in solutions of lithium


nitrate in ammonia at moderate temperatures
Kohlenstoffstahl und nichtrostender Stahl in Lithiumnitratlösungen in Ammoniak
bei mittleren Temperaturen
C. L. Heard* and R. Ayala

The lithium nitrate in ammonia solution has been proposed and Lithiumnitrat in Ammoniaklösung wird als thermodynamisch at-
demonstrated as a thermodynamically attractive working mixture traktive Arbeitsmischung für Absorptions-Wärmepumpen nach-
for absorption heat pumps. A literature search failed to find corro- weislich empfohlen. Eine duchgeführte Literaturrecherche konnte
sion studies of said solution. The corrosion of carbon and stainless keine Korrosionsstudien zu besagter Lösung finden. Das Korrosi-
steel in solutions of lithium nitrate in ammonia was studied for a onsverhalten von Kohlenstoffstahl und nichtrostendem Stahl in Li-
series of concentrations and temperatures from 50 to 150 8C. The thiumnitratlösungen in Ammoniak wurde mit verschiedenen Kon-
materials studied were found to be suitable for construction of ab- zentrationen und in Temperaturbereichen zwischen 50 und 150 8C
sorption heat pump process equipment for this working mixture. untersucht. Die studierten Materialien erwiesen sich als geeignet
für die Herstellung von Absorptions-Wärmepumpenprozessanla-
gen.

1 Introduction pital equipment that is expected to have a very high plant fac-
tor and trouble free operation for decades. Copper and its al-
There are a substantial number of studies indicating the loys are not suitable as construction materials when using am-
thermodynamic advantages of the lithium nitrate/ammonia monia as a working fluid. Standard texts [9] indicate that am-
working pair for absorption refrigeration systems, especially monia is compatible with carbon and stainless steel. Although
those driven with low grade heat such as solar or geothermal lithium nitrate has been widely studied as an anticorrosion ad-
heat [1 – 8]. In order to produce reliable designs of absorption ditive for aqueous solutions of lithium bromide and other
heat pumps and refrigeration systems a knowledge of corro- lithium salts, a literature search didn’t reveal any studies
sion rates is needed. Absorption heat pumps systems are ca- on the corrosion of steel in solutions of lithium nitrate in am-
monia. Jones, Kim and Wilde [10] described a mechanism of
stress corrosion cracking where the presence of oxygen in am-
*
Christopher L. Heard monia helps to refilm bare metal. They also reported that the
Exergy Group, Instituto Mexicano del Petróleo, Eje Central La- presence of oxygen in ammonia caused the corrosion potential
zaro Cardenas No. 152, to increase to a more positive i.e. noble potential value.
Col. San Bartolo Atepehuacan, 07730 México D.F. (Mexico) Lithium nitrate is a strong oxidant. It was thus thought that
Ramón Ayala steel should be compatible with the lithium nitrate in ammonia
Wabashtech, Mexicali (Mexico) solution. It was then necessary to confirm this.

F 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0947-5117/03/0808-0609$17.50þ.50/0


610 Heard and Ayala Materials and Corrosion 54, 609–611 (2003)

The concentrations found in different potential applications Table 1. Solution concentrations and test parameters
from refrigeration to heat transformers range from 30% to Tabelle 1. Konzentration der Lösungen und Versuchsparameter
70% by weight of lithium nitrate, with temperatures from
40 to 160 8C. The solutions are in contact with heat transfer Test No. Temperature Time Pressure Concentration
surfaces as ammonia is absorbed into or evaporated from the ( 8C) (Hours) (Bar) LiNO3 (%wt)
solution in an ammonia atmosphere. These solutions circulate 1 50 24 7 47.4
between the two processes (evaporation and absorption) via 2 100 24 8.3 64.8
liquid/liquid heat exchangers. 3 150 24 8.7 77
4 50 72 8.6 45.6
5 100 72 9.8 66.6
2 Experimental method 6 150 72 9.3 78
7 50 120 9.4 47.7
The test regime consisted of three temperatures (50, 100 8 100 120 8.8 67.5
and 150 8C) and three resulting concentrations of salt (ap- 9 150 120 13 73.7
proximately 47, 65 and 77 weight % of LiNO3) with three
time periods (24, 72 and 120 h) being used. The materials
tested were two stainless steels (SS 304 and SS 316) and Table 2. Corrosion rate results (mm per year)
one carbon steel (CS A37). The 1.1 cm by 6.9 cm test coupons Tabelle 2. Ergebnisse für die Korrosionsgeschwindigkeit (mm pro
were prepared in accordance with ASTM G1 81 [11]. The cou- Jahr)
pons were prepared from equal leg angles of 304 and 316
stainless steel and A37 carbon steel in triplicate. They were Test No. SS 304 SS 316 CS A37
cut and manually polished with sandpaper until a smooth sur-
1 0.0281 0.0135 0.0384
face was achieved. They were then cleaned and degreased in 2 0.0129 0.0309 0.056
hexane vapour. Each coupon was weighed and its dimensions 3 0.0263 0.0421 0.0487
measured. The coupons were mounted on ceramic bars with 4 0.0065 0.0055 0.0137
Teflon separators. The set of coupons was put into a Hastalloy 5 0.0102 0.0091 0.0134
C laboratory autoclave. The lithium nitrate salt was placed in 6 0.0237 0.025 0.0349
the autoclave and this was closed. The amount of salt neces- 7 0.0013 0.0019 0.0036
sary had been previously determined by initial immersion 8 0.0053 0.0042 0.0186
tests. The air in the autoclave was displaced by venting 9 0.0048 0.0018 0.0123
with ammonia from a cylinder of anhydrous ammonia. The
discharge was dissolved in water. Once the air had been dis-
placed the vent valve was closed and anhydrous ammonia was
admitted to form a solution with the salt. The solution concen-
tration was calculated by use of the temperature/pressure/con-
centration relationships of Infante-Ferreira [12]. The auto-
clave heater and agitator unit were started up. During the
test the temperature, concentration and agitation remained
constant. Once the test period had been completed the ammo-
nia was purged from the autoclave and the coupons were re-
moved. These were then cleaned by immersing them in a 4N
sodium hydroxide solution at 75 8C with a current density of
20 A  dm2 for approximately three minutes. The corrosion
products were removed with a non-abrasive rubber tool. They
were then weighed.

3 Results
Fig. 1. Average corrosion rates for each test (24, 72 and 120 h)
The corrosion rate was determined by use of equation (1) Abb. 1. Durchschnittliche Korrosionsgeschwindigkeit für jeden
from ASTM standard G1-81. Where R is Versuch (24, 72 und 120 h)

Kw
R¼ ð1Þ general the highest corrosion rates were for the carbon steel
ATd
coupons and least for the SS 316 coupons. The general trend in
the corrosion rate in millimetres per year, K is a constant almost all the cases is to lower average rates for longer time
(8.76  104), w is the mass loss in grams, A is the surface periods and higher rates for higher temperatures.
area of the coupon in square metres, T is the time of exposure
in hours and d is the density in grams per cubic centimetre.
Table 1 shows the test conditions for nine test runs. The ex- 4 Discussion and conclusions
act concentrations of salt were a function of temperature and
pressure of each test as the solution was in equilibrium with The overall corrosion rates correspond to less than 0.05 mm
vapour phase ammonia. Table 2 shows the test parameters and per year which for process equipment is the lowest corrosion
the average corrosion rates for each of the nine tests. Fig. 1 category [13]. In general the average rates decrease rapidly as
shows the average corrosion rate against the test period. In the test periods increase from 24 to 120 h. Jones, Kim and
Materials and Corrosion 54, 609–611 (2003) Kurztitel 611

Wilde [10] considered that it was not appropriate to speak of [3] R. Best, W. Rivera, I. Pilatowsky, F. A. Holland, J. Heat Re-
active and passive states in ammonia as is the case in aqueous covery Systems and CHP 1991, 11, 103.
solutions. None-the-less it is possible that the presence of a [4] R. Best, W. Rivera, I. Pilatowsky, F. A. Holland, J. Heat Re-
strong oxidant such as lithium nitrate has an effect similar covery Systems and CHP 1991, 11, 199.
[5] K. P. Tyagi, presented at the 26th intesociety energy conver-
to the one that they found with the presence of dissolved oxy- sion engineering conference, Boston MA, 1991, 13 – 16.
gen in anhydrous ammonia in which the potential state is no- [6] R. Ayala, J. L. Frı́as, L. Lam, C. L. Heard, F. A. Holland, Heat
ble. In future work galvanic studies of steels in lithium nitrate Recovery Systems & CHP 1994, 14, 437.
in ammonia solutions would shed more light on the corrosion [7] C. L. Heard, R. Ayala, R. Best, presented at the International
process. The results of the present study indicate that 304 and Ab-sorption heat pump Conference ’96, Montreal, Québec,
316 stainless steel and A37 carbon steel can be used in the Canada, 1996, 245 – 252.
construction of absorption refrigeration and heat pump sys- [8] C. A. Infante Ferreira, presented in 19th International Con-
tems which contain the ammonia/lithium nitrate working pair. gress of Refrigeration, IIR-IIF, The Hague, The Netherlands,
1995.
[9] ASHRAE Refrigeration Handbook, American Society of
Heating, Refrigerating and Air-Conditioning Engineers Inc.
5 Acknowledgements Atlanta, 2002.
[10] D. A. Jones, C. D. Kim, B. E. Wilde, Corrosion-NACE, 1977,
The work herein reported was carried out as part of the In- 33, 50.
stituto de Investigaciones Electricas (Mexico)/University of [11] American Society of Testing Materials (ASTM), Standard
Salford (UK) collaborative postgraduate programme. The G1-81, Preparing, cleaning, and evaluating corrosion test
authors would like to thank N. Rosas for his valuable advice specimen, Laboratory corrosion tests and standards, ASTM
in the execution of the experimental work and P. Birkle for the Special technical publication 1981, 505 – 510.
German language version of the abstract. [12] C.A. Infante Ferreira, Solar Energy 1984, 32, 231
[13] W. F. Bogaerts, K. S. Agema, Active Library on Corrosion,
Elsevier and NACE, Amsterdam, The Netherlands 1992.
6 References (Received: November 21, 2002) W 3675
[1] Da-Wen Sun, Energy Conversion Management 1998, 39, 357.
[2] R. Best, L. Porras, F. A. Holland, J. Heat Recovery Systems
and CHP 1991, 11, 49.

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