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Apparatus and techniques
References
Aramu F and Maxia V 1970 Nucl. Instrum. Meth. 80 35
Brook R J and Kingery W D 1967 J . Appl. Phys. 38 3589
Cranshaw T E 1974 J. Phys. E: Sci. Instrum. 7 497
Guarnieri C R and Walker J C 1971 Proc. 4th Int. Con$ on
Mossbauer Effect, Dresden (Berlin : Deutsche Akademie der
Wissenschaften) p 321
Hershkowitz N and Walker J C 1967 hrucl. Znstrum. Meth. 53
273
Keune W, Lauer J and Williamson D L 1974 Proc. Int.
ConJ on iklossbauer Effect, Bendor, France: J. Phys., Paris 35
C6-473
Keune W, Williamson D L and Lauer J 1975 Proc. Int. Conf.
on Mossbauer Effect, Cracow, eds A Z Hrynkewicz and
J A Sawicki (Cracow : Academia Gorniczo-Utnicza) p 39
Lauer J, Keune W and Shinjo T 1975 Proc. Int. ConJ on
Mossbauer EfSect, Cracow, eds A Z Hrynkewicz and J A
Sawicki (Cracow : Academia Gorniczo-Utnicza) p 41
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13 800
Rabinovitch K and Schechter H 1968 J. Appl. Phj's. 39 2464
Semper R J 1973 Dissertation The Johns Hopkins University,
Baltimore, Maryland
Semper R J, Chien C L and Walker J C 1975 Proc. Int.
Cor$ on Mossbauer Effect, Cracow, eds A Z Hrynkewicz and
J A Sawicki (Cracow: Academia Gorniczo-Utnicza) p 37
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Trousdale W L and Lindgren R A 1965 J. Appl. Phys. 36968
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(New York: Plenum) p 171
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118
Journal of Physics E : Scientific Instruments 1976 Volume 9
hinted in Great Britain 0 1976
A pressure vessel for corrosion
testing at high temperatures
P E Francis and C W Carter
Division of Materials Applications, National Physical
Laboratory, Teddington, Middlesex TWl 1 OLW, UK
Receiued 14 March 1976, in final form 5 August 1976
Abstract A description is given of the design and operation
of an apparatus for testing the resistance of materials to
corrosion in a variety of aqueous environments at
temperatures up to 250°C. Particular features include the
ability to allow tests in static solutions of very corrosive
substances and to refresh or change less corrosive solutions
during the test to keep contamination to a minimum.
1 Introduction
Conventional autoclaves which are only partly filled with
solution have a number of disadvantages. The volume of
solution must be sufficiently large to minimize contamination
of the solution by corrosion products and to enable corrosion
specimens of a reasonable size to be used. Even so constituents
such as oxygen can be rapidly depleted by the corrosion reac-
tion and have to be replaced regularly. This makes it difficult
to work with low controlled concentrations of oxygen. A
positive closure is also absolutely essential to prevent changes
in composition of the solution which could occur, for example,
by loss of oxygen and water vapour or, in the case of sodium
bicarbonate solution, loss of carbon dioxide. Even in a
perfectly sealed autoclave, changes occur on heating as a
result of expansion of the solution and evaporation into the
steam space above the liquid, and although these changes have
been computed for a partly filled vessel with a steam phase
(McKie 1973) the existence of cold connections to pressure
gauges, valves, etc can make the exact determination of the
composition of the solution difficult in a practical system.
The above problems have now been overcome by using a
pressure vessel which is fully filled with the test solution and
operated at a pressure above the saturated vapour pressure of
the solution to avoid the formation of a steam phase. Changes
in composition resulting from expansion of the solution can be
easily calculated using existing data (Voukalovitch 1958).
Contamination of solutions and depletion in oxygen have been
overcome by arranging for the test solution to be refreshed
during the experiment. To reduce the possibility of corrosion
of the pressure vessel itself, which would contaminate the test
solution with extraneous ions, the vessel is lined with a noble-
metal alloy. Further advantages of this pressure vessel are its
ease and speed of assembly and, since the thermal mass of the
vessel has been kept low, rapid heat-up to the test temperature
(30 min to 250'C) and rapid cooling (the test specimen can be
recovered within 20 min) which allow short-term experiments
to be performed.
2 The pressure vessel
The pressure vessel, shown in figure 1, consists of a vertical
stainless steel tube of 25.4 mm bore fitted with a noble-metal
liner (75 % palladium/25 % gold) 0.38 mm thick and sealed at
each end with Bridgman-type seals. The end thrust is support-
ed by retaining caps which are threaded on to the body of the
pressure vessel. The pressure seal is made by expanding the
Viton O-ring directly on to the liner, thus positively preventing
leakage of the test solution between the liner and the vessel wall.
The vessel is heated in the centre section by electrical band
heaters and water-cooled at each end to protect the O-ring
seals and other vulnerable parts of the apparatus from damage
by overheating.
3 Pressurizing circuit
The test solution is pressurized to keep it in the liquid phase
and to produce a flow of solution when required. The pres-
surizing arrangement, shown in figure 2, includes a pressure
transducer (protected from contact with the test solution by
a PTFE separator) which operates set-point detectors. The
latter actuate the hydraulic pump when the pressure falls
below the desired level and the pressure release valve V1 when
the pressure rises, for instance when the temperature of the
pressure vessel is increased. The flow of solution through the
vessel is controlled by the metering valve V3.
4 Internal components of the pressure vessel
To prevent loss of heat from the hot central zone to the cooled
ends of the pressure vessel by convection of the solution, the
1067
Apparatus and techniques
Band heaters
Pal Stainless steel
Figure 1 Pressure vessel with palladium/gold liner to
operate up to 250°C
hot zone is enclosed by two PTFE cylinders. Two types of
cylinder assembly have been used. Type 1 (figure 3(a)) is
normally used. The cylinders are a loose fit inside the pressure
vessel to allow for their thermal expansion and a flow of test
solution. The lower cylinder is slotted to hold the specimen.
During refreshment the test solution flows in a thin layer
between the wall of the pressure vessel and the lower cylinder
so that efficient heat transfer can occur. The solution reaches
final thermal equilibrium in the reservoir near the end of the
lower piston before entering the working zone. To leave the
hot zone the solution flows between the upper cylinder and the
wall of the pressure vessel, through the O-ring bypass, which
prevents convective flow, and is cooled by the upper water
jacket before finally leaving the vessel.
Type 2 cylinder assembly (figure 3(b)), which allows experi-
ments with static solutions only, is used when the test solution
Presswe gauge
Flow control
Pressure valve V3
Test solution
Figure 2 Ancillary pressurizing circuit
1068
Flow control Outlet valve
valve closed
t
Reservoir
PTFE blov+out
4
f
Pressurized Hydraulic pressure
t e s t solution ( v i a distilled w a t e r )
(01 I61
Figure 3 (a) Arrangement to allow a flow of test solution.
(b) Arrangement to isolate the test solution
would attack 316 stainless steel used in the pressurizing circuit.
The test solution is trapped between the O-ring seals on the
cylinders. The remainder of the system is filled with pressurized
distilled water. When the temperature is raised the lower
piston moves downwards to accommodate the expansion of
the test solution. The lower cylinder incorporates a PTFE blow-
out disc which will operate and bypass the O-ring seal to
prevent excessive pressure from developing between the
cylinders if the piston reaches the end of its travel. This safety
device would be required in the event of excessive hydrogen
evolution from the specimen.
5 Operating experience
The apparatus has been used to determine the corrosion
behaviour of various alloys (Incoloy 825, Hastelloy C and
MP35N (35Ni, 35Co,20Cr, 10Mo)) in a range of salt and acid
solutions at 2 5 0 T (Beynon et a1 1974). The experiments were
from 3 to 100 h duration, depending on the aggressivity of the
solution towards the alloy under test. Using the refreshed
mode of operation experiments have been carried out with the
following solutions: 0.01 M NaOH, 0.2 M MgS04, 0.5 M
H3P04, 0.2 M Has04 and 0.1 M HCI. Hydrolysis of MgS04
occurred in the hot zone of the apparatus and when a 2 M
solution was used the white hydrolysis product blocked the
flow of solution. Using the static mode of operation a wider
range of solutions was used as follows: 2 M CaC12, 2 M
MgS04, 2 M NaCl, 2 M Na2S04, 2 M MgC12, 1 M NaOH,
1 M H3P04,0.5 M HN03,l M HnS04 and 1 M HCl. Although
the salt solutions caused only slight corrosion of the alloys
(metal losses were typically 10mg dm-* in a 24 h period)
many of the solutions were exceedingly corrosive at 250°C; for
example Hastelloy C lost 1100 mg dm-2 during a 3 h test in
0.5 M H&04 solution.
Apparatus and techniques
The apparatus has been used for corrosion tests at 250°C
but the apparatus has been designed to operate at 350°C. The
PTFE cylinders, however, must be made from a more tempera-
ture-resistant material; alumina, or PTFE loaded with 50%
zirconia, could be used.

6 Conclusions
Conventional autoclaves which are only partly filled with
solution have certain disadvantages. An apparatus which
overcomes these disadvantages has been constructed and used
to measure corrosion rates in solutions at 250°C. The com-
position of the solutions was maintained by refreshing the test
solution and contamination by extraneous ions was prevented
by a noble-metal liner. Tests with extremely corrosive liquids
were successfully carried out. These tests were necessarily of
short duration because of rapid attack on the alloys being
tested and were only possible because of the quick rates of
heating and cooling of the apparatus. The apparatus could be
easily modified for use up to 350°C.

References
Beynon J G, Butler G and Francis P E 1974 NationalPhysical
Laboratory Internal Report DMA 166
McKie A S 1973 Proc. ConJ on High-temperature High-
pressure Electrochemistry in Aqueous Solutions, University of
Surrey
Voukalovitch M P 1958 Thermodynamic Properties of Water
and Steam, 6th edn (Berlin: Veb. Verlag. Technik)

Journal of Physics E: Scientific Instruments 1976 Volume 9

Printed in Great Britain 0 1976

1069