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The reproducibility of some thermometric fixed points and the accuracy of temperature

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1999 Metrologia 36 117

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 metrologia

The reproducibility of some thermometric fixed points

and the accuracy of temperature measurements
using platinum resistance thermometers

J. Ancsin and E. Mendez-Lango

Abstract. The reproducibility of some thermometric fixed points and the accuracy of four platinum resistance
thermometers (PRTs) were studied. It was found that the fixed points of aluminium (Al), zinc (Zn), tin (Sn),
indium (In) and gallium (Ga) were realized reproducibly within ± 0.17 mK; ± 0.11 mK; ± 0.10 mK; ± 0.13 mK
and ± 0.12 mK, respectively. Because the actual impurities and their concentration in our samples (of 99.9999 %
or 99.999 99 % purity) are unknown, the systematic uncertainty due to impurities cannot be estimated. However,
any of the samples of Ga, In, Sn, Zn and Al is consistent with the rest within ± 0.2 mK, using a cubic or quadratic
deviation function, in the temperature range 0 C to 660 C. This indicates that the effect of impurities is negligible.
Four PRTs were selected at random. They were calibrated repeatedly, first up to the Zn point and then up to
the Al point. The resistance of each PRT drifted. From time to time, for each PRT, a seemingly well-established
resistance drift suddenly and unpredictably changed to a different rate of drift. Occasionally, the resistance of the
PRTs shifted. Such unpredictable changes obviously limit the accuracy of temperature measurements using PRTs
no matter what the accuracy of their calibrations. In the case of our four PRTs, the uncertainty of temperature
measurements near 660 C ranged from about ± 1 mK to about ± 2.5 mK even though they were all calibrated at
all fixed points well within ± 0.25 mK uncertainty. Possible explanations are offered for the apparently permanent
drifts and the erratic shifts in the resistance of the PRTs. Some comments are made concerning the ambiguity of
“immersion tests” in general. The furnaces of the National Research Council of Canada used in this work are
high-temperature adiabatic calorimeters.

1. Introduction standards of 99.9999 % purity. It was found that the

In 1996 the fixed points of the Centro Nacional de
Metrologı́a (CENAM) used for calibrating platinum
resistance thermometers for domestic clients were
compared with similar working standards used at the
National Research Council of Canada (NRC). The fixed
points involved were those of Hg, Ga, In, Sn and Zn.
A portable calibration laboratory, developed at the
NRC a few years ago, consisting of two sets of small
cells (2.5 cm diameter and 22.5 cm high) and a small
furnace (20 cm 30 cm 35 cm high, accommodating
all cells except Hg), was used to compare the fixed
points [1]. The cells of one set are metal-clad graphite-
encased (for industrial use) and those of the other
set are sealed in quartz (for laboratory use). As all
cells contain 99.9999 % pure samples they all have
similar melting ranges to those of the working primary
above-mentioned fixed points of the NRC and the
CENAM are equivalent to within 0.5 mK.
In a recent exercise, several PRTs were used
with the aim of studying the reproducibility of these
working fixed points at both the NRC and the CENAM.
To combine these reproducibility studies, the water
triple-point cells and the standard resistors used at
the CENAM and the NRC were also compared using
Model F-18 bridges (Automatic Systems Laboratories).
The fixed points involved were those of Ar, Hg,
H2 O, Ga, In, Sn, Zn and Al. However, as the work
progressed, emphasis gradually shifted from study of
the reproducibility of the fixed points to study of the
reproducibility of the PRTs, because it became apparent
that it is the capability of our PRTs, rather than the
fixed points, that limits the accuracy of the temperature
measurements.

2. General behaviour of PRTs

J. Ancsin: Institute for National Measurement Standards, National
Research Council of Canada (NRC), Ottawa, K1A 0R6 Let us assume that a PRT is repeatedly calibrated and
Ontario, Canada.
E. Mendez-Lango: Centro Nacional de Metrologı́a (CENAM),
that all fixed points are realized reproducibly within the
Division Termometrı́a, km 4.5 de la Carretera a los Cués, measuring resolution of an F-18 bridge. If the PRT is
Municipio de El Marqués Querétaro, CP 76900 QRO, Mexico. always placed at the same location within the cell, and

Metrologia, 1999, 36, 117-139 117

J. Ancsin and E. Mendez-Lango
always reaches thermal equilibrium with it, its electrical
resistance should be reproducible within the measuring
resolution unless its physical or chemical state has been
altered by
(a) contamination
(b) rearrangement of impurities within the platinum
lattice of the sensor
(c) quenching or annealing
(d) oxidation, or
(e) (unpredictable) changes in dimensions of the sensor
wire.
We now briefly review the behaviour of a PRT during
calibration.
2.1 Calibrating up to the Zn point
Below the Zn point, temperatures are sufficiently low
that neither sizeable diffusion of impurities within the
sensor wire nor quenching takes place. However, once
oxidation begins the measured resistance at the fixed
points will gradually increase as the sensor wire of
the PRT is oxidized further. (In practice, oxidation
is considered to begin when it can be detected by
resistance measurements.) This increased oxidation
state will be accompanied by a slight decrease in
the fixed-point resistance ratios, . Here
and are the electrical resistance of the PRT
at a given fixed point and at the triple point of water,
respectively. If, on the other hand, the PRT remains in
a given state of quench and oxidation, then at the Zn
point its oxidation will proceed, leading to an increase in
resistance, while soaking at the Zn point will gradually
anneal the PRT, leading to a decrease in resistance.
Data from repeated calibrations suggest that some
reversible and some irreversible changes take place
during sizeable temperature changes between the sensor
wire of a PRT and its supporting structure. Such a
change is clearly noticeable at the Zn point and it is one
of the most serious causes of inaccuracy of our PRTs
because its magnitude and direction are unpredictable.
Due to the difference in thermal expansion between
platinum and quartz, Pyrex or mica, the expansion or
contraction of the (quite soft) platinum wire, especially
at elevated temperatures, may be hindered by the former
or by the capillaries; thus the Pt may be prevented from
achieving its true equilibrium position relative to these
components. In such cases the behaviour of the PRT
can be erratic (irreproducible).
2.2 Calibrating up to the Al point
At the Al point (660 C) the temperature is still
low enough that contamination and rearrangement of
impurities by diffusion within the platinum sensor
remain negligible during several hours of soaking.
118
The temperature is, however, high enough to cause
considerable quenching: if a PRT is removed from the
Al point and cooled naturally at ambient temperatures,
then its will be higher than if it were cooled very
slowly [2]. The difference between the “quenched” and
“annealed” values of is fairly reproducible for a
given cooling rate during annealing and is equivalent to
about 1.5 mK for most PRTs. The temperature is also
high enough for the accumulated platinum oxide to
decompose rapidly. Figure 1 shows an example of the
rate of deoxidation (reduction) of a PRT at the Al point.
This PRT was used extensively in our oxidation studies
(not yet published). By soaking at various temperatures
(between 200 C and 520 C) for several months, it has
gradually built up sufficient oxide to change its from
25.494 to 25.514 , a change equivalent to 0.2 C.
Yet at the Al point it lost most of its oxygen in less
than 1 hour. Thus, repeated calibrations at the Al point
will keep PRTs deoxidized.
Figure 1. Deoxidation of a PRT at the Al point.
3. Experimental procedure and apparatus
3.1 At the NRC
During these experiments our water triple-point cell
was frequently compared with another reference cell
and with the cell used at the CENAM. The working cell
was housed in a separate ice-box. We noted that when
our water triple-point cell was used many times during
a day, its temperature sometimes increased gradually
by up to 0.33 mK by the end of the day. This drift
was detected by a PRT used exclusively to compare
the working water triple-point cell with the reference
cell at the beginning and at the end of the day. Fixed-
point cells of Al, Zn, Sn (both triple and freezing
point), and In were located in their respective furnaces,
and were melted overnight. All cells (except the water
triple-point and Ga cells) and furnaces at the NRC
are home-made. All samples are of 99.9999 % purity
except the Hg, which is of 99.999 99 % purity, and all
are commercially available.
Traditionally, furnaces are used either to melt or
to freeze the ingots of fixed points during melting-
or freezing-point realizations. The disadvantage of this
technique is that samples are forced into transient states.
Thus, during a fixed-point realization the sample is not
in a state of static thermal equilibrium. It seems more
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs
appropriate to use the furnace only as a heat shield
to provide the sample with an isothermal environment.
A separate sample heater can then be used to supply
the sample with a known amount of heat, as required,
either to measure its heat capacity, to determine its
latent heats, or simply to drive it to any given state
of solid/liquid composition and then allow it to reach
thermal equilibrium.
3.1.1 Aluminium
The Al furnace has a Na heat-pipe liner 10 cm i.d.
and 46 cm high, used as an adiabatic heat shield. The
space between the heat pipe and the 5 cm diameter
ingot is insulated using loose Fibrefrax insulation. The
only role of the heat pipe is to provide the sample with
isothermal surroundings. The sample is heated using
a separate sample heater. Complete melting curves
can thus be obtained adiabatically. After supplying a
given fraction of the total heat of fusion by the sample
heater, the sample can approach a state of thermal
equilibrium, unhindered by the heat pipe. Such heating,
followed by temperature observations during the time
it takes for the sample to achieve thermal equilibrium,
can provide an entire equilibrium melting curve [3],
i.e. versus amount of sample melted. The
sample can easily be cooled: by inserting cold metal
rods into the thermometer well, known amounts of heat
can be removed from the sample (after determinining
the enthalpy of the rod, which is a relatively simple
procedure). Realization of the Al point for calibrations
is performed conventionally: the liquid ingot (at about
3 C above its melting point) is lifted out of the furnace
for 20 s, re-inserted, and the furnace temperature
lowered to that of the melting point of Al by turning the
heat-pipe heater off for 1.5 min. After inserting the cold
PRT, Al point readings may be taken after about 20 min.
At this setting of the heat pipe (+ 3 C relative to the
melting point), if the PRT is left within the thermometer
well of the Al ingot then its resistance will gradually
rise by the equivalent of about 0.5 mK until the sample
melts off in about 5 hours. For an adiabatic melting
curve determination the heat-pipe voltage is of course
adjusted to, and kept at, the melting point.
3.1.2 Zinc
The Zn furnace is, similarly, an adiabatic heat-pipe
furnace using a 10 cm i.d. Cs heat pipe from which
the sample is insulated. Again, starting with the molten
sample (prepared overnight by maintaining the heat pipe
about 3 C above the melting point), nucleation of the
external surface is induced by lifting the ingot out of the
furnace for 1 min and lowering the furnace temperature
to near the melting point by switching the heat-pipe
heater voltage off for 3 min (the temperature of the heat
pipe is monitored by Pt-Au thermocouples spot-welded
to it near the top and middle). Nucleation of the inside
Metrologia, 1999, 36, 117-139
surface is then achieved by inserting a cold metal rod
15 cm long and 6 mm diameter for 1 min into each of
the two thermometer wells of the ingot. (This ingot has
two thermometer wells directly in the Zn, i.e. without
a graphite sheath, in order to allow either calibration of
two PRTs simultaneously or observation of the ingot’s
behaviour during PRT insertion, using a monitor PRT
in the second well. Also, one of the thermometer wells
can be used to house an internal sample heater. Thus
the sample can be heated with negligible heat loss to the
surroundings, allowing precise measurements of heats
of fusion and heat capacity. Of course, for accurate
heat-capacity measurements a pressure-controlled heat
pipe is more suitable because its temperature can easily
be made to follow instantaneous temperature variations
of the sample.) The nucleating metal rods are short and
hang on metal wires because, during inside nucleation,
we want to extract heat only from the ingot without
cooling the furnace throat. After realization of the Zn
point a cold PRT is inserted and is ready for reading in
about half an hour. If the PRT is left in the Zn ingot,
then its resistance will gradually rise (by up to about
0.5 mK) until the sample melts completely in about
10 hours. For adiabatic measurements the heat-pipe
heater voltage is, of course, adjusted to keep the heat
shield (i.e. the heat pipe) at the sample temperature.
3.1.3 Tin
The Sn furnace is also an adiabatic furnace. Its shield
is, however, only an Inconel-encased copper cylinder,
10 cm i.d. and 30 cm high. (If the copper were not
protected by its Inconel casing, then it would gradually
disintegrate due to oxidation, especially when the
furnace is used at higher temperatures.) To realize the
Sn point, the liquid sample, kept overnight in another
furnace 3 C to 4 C above the melting point, is removed
from the furnace for 4 min (recalescence following a
reproducible supercool of 14 C ± 1 C normally begins
in about 3 min) and then inserted into the adiabatic
furnace kept permanently at the melting point of Sn.
A cold metal rod (6 mm diameter and 15 cm long) is
then inserted into the thermometer well for 3 min. After
inserting a cold PRT, its reading can be taken in 20 to
30 min. The melting range of the Sn sample is less
than 0.5 mK. As a matter of curiosity, this tin sample
was acquired about thirty years ago, under the name of
“spectro tin”, from the Vulcan Materials Company. We
have recently purchased some 99.9999 % pure Sn but
its melting range is a little broader (about 1 mK).
3.1.4 Indium
The realization of the In point consists of an outside
nucleation of the molten In ingot for 3 min followed
by inside nucleation using a 6 mm diameter metal
rod for 2 min. Readings can be taken 10 min after
insertion of the cold PRT. This fixed point is housed in
119
J. Ancsin and E. Mendez-Lango

a conventional furnace. A block heater is wound around

a sizeable Al cylinder whose bore is slightly larger than
the diameter of the In ingot.

3.1.5 Gallium

The Ga calorimeter and the melting behaviour of the Ga

sample are described in [4]. During the course of this
work, the Ga point was normally realized on Monday
mornings and maintained at its melting point all week.
PRTs were calibrated in the Ga cell whenever required.
The regulator, controlling the temperature of the bath
containing the Ga calorimeter, was turned off on Friday
afternoons. The Ga point is realized as follows: the
temperature controller of the water in a metal Dewar
that contains the home-made calorimeter housing the
commercial Ga cell, is turned on. In about 1 hour
the bath temperature reaches near 30 C. The sample
heater is then turned on for 20 min, supplying 18 W
of power. This energy of 21.6 kJ is sufficient to raise
the temperature of the Ga cell to the melting point and
additionally to supply about one-third of its total heat
of fusion (about 35 kJ).

3.1.6 Mercury

Our quartz Hg cell (see Figure 2) is home-made. It

contains 340 g of 99.999 99 % pure Hg. The cell was
specifically designed for simple, rapid, and accurate
calibration of PRTs and not for the study of the
melting properties of Hg, which involves lengthy
experimentation. To realize the Hg point the cell
with the PRT within its thermometer well (containing
alcohol) is inserted into a small Dewar of alcohol
cooled to about – 60 C using dry ice. (It is important
that the portion of the cell that contains the Hg be
entirely submerged in the cold alcohol bath, otherwise
the sample will be only partially frozen, leaving large
vertical temperature gradients along the sample and
yielding only a poor-quality partial melting curve.) The
Hg freezes in 3 to 5 min, as indicated by the PRT. (Also,
the frozen top of the Hg is clearly visible.) The cell is
then removed from the bath, wiped clean of the dripping
alcohol, kept at ambient temperature for a minute or
so, and inserted into a hole drilled into a rectangular
Styrofoam block, 10 cm 10 cm 30 cm high. The
cell reaches the melting point in 5 to 10 min and melts
for 30 to 40 min. During melting, the temperature rises
gradually by about 0.2 mK then the Hg suddenly melts
off. Because the melting range of high-purity Hg is so
narrow, there is no need to realize the entire melting
curve during each calibration. Thus the entire process of
realization and calibration can be completed accurately
in about 20 min.
3.1.7 Argon
A small Ar triple-point realization cryostat was
developed recently. The apparatus is self-contained and
Figure 2. Mercury cell.
is small enough to be carried as personal luggage.
The only auxiliary items required for a realization of
the Ar point are a rotary pump, liquid nitrogen, and
a Dewar (minimum 8 cm i.d. and 45 cm deep) to
accommodate the vacuum chamber. No temperature
control of any kind is needed. The sample chamber
(1.75 cm diameter and 18 cm high, concentrically
surrounding the lower part of the 7.9 mm diameter
and 40 cm long stainless-steel thermometer well) is
insulated from its surroundings only by a modest
vacuum and the many layers of thin Mylar wrapped
around the sample chamber. The Ar point is realized
as follows: with the PRT within the thermometer well
and the vacuum chamber open to ambient pressure, the
apparatus is lifted and the vacuum chamber is inserted
into a Dewar containing liquid nitrogen. Then, using a
small rubber tube, the cooling coil wound around the
sample chamber is connected to a can of liquid nitrogen.
The flow of liquid nitrogen through the coil rapidly
cools the sample chamber, as indicated by the pressure
gauge of the 5.5 litre reservoir (the absolute pressure
at room temperature is 3 atmospheres, which is similar
to that in a car tyre). The Ar condenses and freezes in
less than 5 min starting from room temperature. After
cooling the sample to near the temperature of liquid
nitrogen, the flow of liquid nitrogen through the cooling
coil is stopped, the vacuum chamber is evacuated and
the sample heater, wound around the sample chamber,

120 Metrologia, 1999, 36, 117-139

 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs
is turned on (supplying about 0.5 W of power). The
sample is heated until the PRT indicates a constant
temperature, and heating continues until slow run-off
begins, in 5 to 10 min. The heater is then switched
off. After a few minutes the sample, overheated by
2 mK to 3 mK, cools back to the melting curve, the
temperature stabilizes, and the resistance of the PRT can
be determined. The PRT can then be removed, replaced
by another, the sample re-frozen using the cooling coil,
and the procedure repeated for this new PRT. With a
little practice, a complete realization and calibration can
be performed in about half an hour. The accuracy of
the calibration depends on the purity of the sample and,
of course, on the reproducibility of the PRT.
3.2 At the CENAM
All furnaces were purchased. Three-zone furnaces are
used for In, Sn, Zn. A potassium heat-pipe furnace
houses the Al point. Cells of Al, Sn, In, and Ga were
purchased; those of H2 O and Hg are home-made. Water
triple-point cells are housed in a commercial liquid bath.
A cryostat used for realizing the Ar point was developed
at the NRC. It can house four PRTs. The fixed-point
realization procedures are as follows:
3.2.1 Aluminium
The liquid sample, 3 C above the melting point of Al,
is removed from the furnace for 1 min, then reinserted.
The furnace temperature is set at 0.1 C above the
melting point. The PRT is inserted cold into the cell
and resistance readings may be taken in 30 min. If a
completely frozen sample is melted continuously with
the furnace setting 0.1 C above the melting point, the
sample has a total melting time of about 3.5 hours and
a melting range of 2.5 mK.
3.2.2 Zinc
Outside nucleation of the liquid sample is performed
for 1.5 min. Inside nucleation is performed by inserting
a 6 mm steel rod for 1.5 min. Resistance readings may
be taken 50 min after inserting the cold PRT. This ingot
has a melting range of about 0.5 mK.
3.2.3 Tin, indium
Both the Sn and the In points were realized by
nucleating freezing of the external surface of the molten
samples for 4 min and nucleating the inside surface,
using a 6 mm steel bar, for 2 min. Following insertion
of the cold PRT, resistance readings can be taken after
40 min in the case of Sn and after 30 min in the case
of In.
Metrologia, 1999, 36, 117-139
3.2.4 Gallium
The Ga point is realized by heating the solid sample
in a furnace at 35 C for 1 hour and then reducing
the furnace temperature to 30 C. A steel bar heated
to 90 C is then inserted into the thermometer well
for 1 min. Following insertion of the PRT at room
temperature, resistance readings may be taken after
about 20 min.
3.2.5 Mercury
The Hg cell is made of quartz. It is similar to that
shown in Figure 2 except that it has no spacers
and contains more Hg. The realization of the triple
point of Hg is achieved as follows: the Hg is frozen
within a liquid-nitrogen-cooled double-walled copper
tube located within a Styrofoam block. The sample
freezes in about 20 min. Then the flow of liquid nitrogen
through the double-walled copper tube is stopped and
heating begins, using the heater wound around the
copper tube. When the sample approaches the triple
point within 1 C the heater is turned off. Melting
begins in a few minutes and lasts for about 40 min.
The melting range is about 0.2 mK.
4. The combined reproducibility
of fixed points and PRTs
The uncertainty of the realization of a fixed point cannot
be determined directly. It is usually described in terms
of the resistance ratio of the PRT, .
The relative uncertainty of this quantity is
(1)
One should bear in mind, however, that ,
i.e. the uncertainty in the measured resistance at a given
fixed point, arises from both the irreproducibility of the
resistance of the PRT and the irreproducibility of the
realized fixed point at the site of the sensor of the PRT;
i.e. . Similarly, at
the water triple point, .
Thus
(2)
The uncertainty of the realization of the fixed point
itself is the second term of (2). There is a disadvantage
in using the above expression: one cannot study the
reproducibility of a fixed point without including the
uncertainty associated with the determination. It
is possible, however, to take a different approach. If
the triple point of water is treated as only one (very
stable) member of a set of fixed points, then, as shown
121
J. Ancsin and E. Mendez-Lango
below, the last two terms can be eliminated from
the above expression. Yet, because one can observe
only the combined reproducibility of the PRT and
the fixed points, if the fixed-point cell has only one
thermometer well (represented by the first two terms on
the right-hand side of (2)) it is not possible to separate,
with certainty, the reproducibility of the PRT from
those of the fixed points. However, as a set of fixed
points is realized repeatedly, a certain pattern in the
measured data becomes apparent, allowing some major
uncertainties arising from the PRT to be separated from
those arising from the fixed points. Because no melting
point can lie outside the melting range, data points
obtained during repeated calibrations that lie outside
a consistently observed melting range are probably
caused by irreproducibility of the PRT and not the
sample. (If the fixed-point cell has two thermometer
wells then, of course, one can observe the first term
of (2) exclusively.) We now consider the experimental
data for the following PRTs.
4.1 Experimental data
4.1.1 YSI 1172
Figure 3 shows the overall resistance change during the
indicated period at the indicated fixed points. It may be
seen that during the course of these measurements the
resistance of the PRT gradually increased at all fixed
points by the equivalent of several millikelvins. It is
improbable that all of our fixed points (including the
water triple point) drifted several millikelvins during
this period. Therefore it must be the PRT that gradually
drifted away from its initial state as a result of
repeated thermal cycling. On careful perusal of the
data accumulated during the period when a set of fixed
points was realized daily (or almost daily), see Figure 4,
one can see that these changes took place in discrete
steps. Consider for example the measured values of
, , , and on 29 and 30 April
and 1 May. These points all lie along straight lines (with
very little scatter). The trend of the values measured on
4, 5, 6, 7 May, on the other hand, is entirely different.
It is more parabolic than linear. It is unlikely that all of
these fixed points would have changed simultaneously
in such a strikingly similar way. It is more likely that
the PRT drifted in such a manner. If one were to
carry out a least-squares fit of the data to a linear
equation during the period 29 April to 1 May, and to a
quadratic equation during the period 4 to 7 May, then
the residuals would represent the maximum combined
irreproducibility of both the fixed points and the PRT
(first two terms in (2)) during its well-behaved stages.
Such an analysis is carried out below.
Before discussing the results for Al it should be
emphasized that the melting range of our Al sample
from the realized state of about 30 % solid fraction
to melt-off was observed to be consistently about
122
0.5 mK (see Figure 13, from 7 to 17 July). Thus
it is extremely unlikely, using consistent realization
procedures, that the realized sample temperatures at the
usual site of location of the PRT within the thermometer
well will lie outside the melting range. It is of course
possible to induce sizeable temperature gradients along
the thermometer well (for example, by inadvertently
subjecting the sample to excessive vertical heat losses),
and hence to entirely upset the desired equilibrium
temperatures. An “immersion test” would reveal such
problems.
In our case all our adiabatic furnaces and sample
containers were specifically designed to minimize
vertical heat losses, either by keeping part of the
insulation above the sample (within the sample tube) at
the sample temperature using a heater and thermocouple
arrangement, or by leaving a few centimetres of the
space above the sample uninsulated (and by removing
the insulation between the heat pipe and the sample
tube in this region), thus exposing it directly to the
temperature of the adiabatic shield. The space above
the sample is thus kept near the sample temperature
and at the same time this section of the PRT stem is
preheated.
We now consider the Al data. We have already
noted that the resistance of this PRT gradually increases
on thermal cycling. This is shown clearly in Figure 5.
We also noted that discrete changes in resistance take
place unpredictably: for example, the Al points of
30 April to 5 May and of 5 to 11 May appear to
lie along different parabolas.
One might imagine such behaviour if the sensor
wire were prevented by its supporting structure from
returning to its equilibrium position after thermal cycles.
As the thermal cycles are repeated, the position of the
sensor might, accumulatively, move further and further
from its equilibrium location until the accumulated
stresses become larger than the restraining influence
of the supporting structure and then, like a compressed
spring, the sensor wire would gradually begin to drift
back towards its equilibrium position, approaching
closer and closer with each thermal cycle (like the points
of 29 April to 1 May and 4 to 7 May of the upper two
graphs of Figure 5). After each drift period the sensor
might retain a small, permanent, residual deformation,
perhaps caused by creep, accumulating it indefinitely.
This may be what is seen in Figure 7 (the Al graph in
particular). If this is more or less the case, then it is
difficult to see how the reproducibility characteristics of
PRTs can be much improved upon in their present form.
Some PRTs may well be remarkably reproducible
on thermal cycling, yet others, apparently made the
same way (and sold for the same price), would not
be. This would make the manufacture of PRTs an art,
not a science. The difference between reproducible
and irreproducible PRTs might be caused by such
small details as the quality of flame-polishing of the
edges of some quartz capillaries, the sensor-supporting
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs
Figure 3. Drift of YSI 1172 during repeated calibrations.
arrangement, the detailed shape of the sensor wire, etc.
Scientific (reproducible) improvements could perhaps
be made either by drastically reducing the differential
thermal expansion between the sensor and the rest
of the PRT structure, or by arranging the supporting
structure in such a way that it does not interfere
with the dimensional changes of the sensor caused by
temperature changes.
In time, the drift of this PRT gradually slowed.
By June, its resistance at the Zn point had more or
less stabilized (see Figure 3) and it became relatively
reproducible apart from the slight periodic drift pattern
Metrologia, 1999, 36, 117-139
(see Figure 5). All points between 30 May and 16 June
lie within the 0.75 mK scatter band, although the PRT
still drifts slowly. The drift pattern of both and
from 6 to 9 June and from 13 to 16 June is similar
(see Figure 5). As a result the values in this
period have a similar scatter band, and the scatter of
points has a similar pattern. Figure 6 shows a summary
of all values obtained during these reproducibility
studies.
To briefly summarize the work with YSI 1172, all
fixed points were realized to within about ± 0.2 mK or
less, as shown below, yet the values of ,
123
J. Ancsin and E. Mendez-Lango
Figure 4. Similarity of drift pattern of YSI 1172 at several fixed points.
and spread across ranges of about 5 mK, 2 mK
and 1 mK, respectively. This clearly shows that the
accuracy of temperature measurements beyond the In
point using this particular PRT is limited by the PRT
and not by the fixed points.
4.1.2 YJ 152 (a Chinese PRT)
This PRT was brought from the CENAM. It was
repeatedly calibrated at the NRC up to the Zn point
until 12 April. During this time its resistance gradually
increased at all fixed points, in an erratic manner,
124
as seen in Figure 7. From 12 April the calibrations
also included the Al point. The first Al point soak for
30 min reduced the of the PRT from 25.4730 to
25.4724 , a drop of 6 mK. An additional 20 hours of
soaking at the Al point reduced its by a further 1 mK.
Clearly, the gradual resistance increase had been caused
mainly by considerable oxidation of the sensor prior to
its insertion into the Al point. Afterwards its resistance
remained more or less constant, within the equivalent
of a few millikelvins, apart from the periodic drift
pattern visible at all fixed points. As seen from these
data, this PRT is not capable of reliable temperature
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs
Figure 5. Drift of YSI 1172 at the Al, Zn and H2 O points.
measurement with sub-millikelvin accuracy if it is
subjected to sizeable temperature changes following
its calibration. None the less, the measurements carried
out at the CENAM between 18 and 30 May blend into
the overall data of the Al, Zn, Sn, In, Ga, H2 O, and
Hg points within about 1 mK (Figure 8, see also
graphs, Figure 9).
4.1.3 YJ 243 (a Chinese PRT)
This PRT was also brought from the CENAM. It was
repeatedly calibrated up to the Zn point until 11 April.
Metrologia, 1999, 36, 117-139
Its resistance also increased gradually, at all fixed
points, after a few days of relative stability. Figure 10
shows its behaviour at the indicated fixed points during
this time interval. However, unlike PRT YJ 152, the
increase in its resistance was more or less unaffected
by the inclusion of the Al point in the calibrations.
This shows that most of the resistance increase was not
caused by oxidation.
Many users do not bother to anneal their PRT
following its use around 650 C. In order to simulate
this situation, from 11 to 19 April the PRT was
calibrated in a quenched state. Figure 10 includes
125
J. Ancsin and E. Mendez-Lango

Figure 6. Fixed-point resistance ratios for YSI 1172. (N.B. The freezing points of all these substances were realized
within ± 0.2 mK or better.)

the results of those measurements. As shown in
the figure, the quenched is, as expected, higher
than the annealed one following determination.
Paradoxically, however, the quenched values of , of its electrical resistance. Similarly, the initial set of Sn
, and are lower than the annealed
ones. The initial drop of values on 11 April could be
attributed to slight deoxidation of the PRT during the Al
point calibration. However, the sudden increase of the
quenched values on 19 April, clearly seen in the
and graphs of Figure 10, is probably caused by
a sudden change in dimensions of the PRT sensor.
Perhaps the sensor, at one point, became restrained
by the quartz components while subjected to repeated
thermal cycles, resulting in such an unpredictable shift
and readings at the CENAM (from 18 to 22 May, see
Figure 11), before the resistance of the PRT at any other
fixed points was determined (an attempt to use it as an
Sn monitor), indicates another shift relative to the value
of 15 May last determined at the NRC. This, however,
may be attributed to a change of dimensions of the
sensor during its transport to Mexico. It is worth noting

126 Metrologia, 1999, 36, 117-139

 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs

Figure 7. Drift of YJ 152 at some of the fixed points. Until 12 April the PRT was calibrated up to the Zn point only.

that during this temporarily stable state of the PRT (18
to 22 May) it gave a highly reproducible value for the
Sn point at the CENAM. The values obtained in the
period 18 to 22 May were 48.617 93 ; 48.161 794 ;
48.161 787 ; 48.161 784 and 48.161 800 , respec-
tively (a total scatter band of 0.16 mK) with the corre-
sponding values of 25.445 005 ; 25.445 017 ;
25.445 017 ; 25.445 018 and 25.445 026 (a
scatter band of 0.21 mK). On the other hand, the values
of and following Al point determinations
(26, 27 May) blend well into the corresponding values
determined at the NRC from 13 to 15 May and 5 to
11 June in spite of the visible drift at all fixed points.
(The agreement of the Zn, Sn, In, Ga and Hg points
between the CENAM and the NRC has already been
shown [1] to be within 0.5 mK.) It should be recalled
that all resistance values in all figures are relative to
the same standard resistor and all values are relative
to the same water triple-point cell. A summary of the
values is given in Figure 12. Again, the overall
scatter indicates the capability of the PRT rather than
the reproducibility of the fixed-point temperatures.

Metrologia, 1999, 36, 117-139 127

J. Ancsin and E. Mendez-Lango
Figure 8. Drift of YJ 152 during repeated calibrations up to the Al point. The Zn, Sn, In and
those of Figure 7 plotted with increased sensitivity.
4.1.4 T-5
This PRT was made at the NRC about one year ago.
Its sensor consists of eight axially parallel Pt wires
0.38 mm diameter and about 2.5 cm long. The wires are
threaded through eight holes drilled near the perimeter
of two quartz baffles, 5 mm in diameter, about 0.5 mm
thick, and about 2.3 cm apart. Every second lead of
the sensor is located within a ceramic tube in order to
prevent the leads from short-circuiting with one another.
128
0 graphs are
The current and potential leads are of the same gauge
as those of the sensor. The PRT is 60 cm long and it
has only six baffles altogether: two within the sensor
and four along the leads. The third baffle is about 1 cm
above the sensor, the fourth is 1 cm higher, the fifth
is about half-way up the stem and the last one is just
below the head. The PRT is open to ambient air.
It may be of interest to describe our attempt to
stabilize this PRT for high-temperature use. After its
assembly, it was soaked overnight at 960 C and in the
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs

Figure 9. Fixed-point resistance ratios for YJ 152. The large scatter of values is caused by the erratic behaviour of the PRT.

morning its quenched value of was determined in units of 10–6 ) 22; 15; 7; 6; 0; – 1. The PRT was
to be 3.375 703. It was then soaked again at 960 C for then soaked from the Al to the Ag point in 50 C
460 hours (from time to time its was determined steps, spending 70 to 120 hours at each temperature.
to check for changes that may have taken place) and The value was determined at each temperature
then it was calibrated in a quenched state. The following and was found to decrease during the soaking from
values were found for , , , 3.375 166 to 3.375 099 (the equivalent of about 20 mK).
, and , respectively: 3.375 144; Unfortunately, after an additional 230 hours of soaking
2.568 360; 1.892 487; 1.609 590; 1.118 100; 0.844 193. at 960 C, the sheath developed unusual, foamy sections
The PRT was then left at the Al point for 4 days near the top of the sensor and around the first baffle
and recalibrated again. This soaking caused the above above the sensor. Eventually, after further soaking at
values to increase by (from Al to Hg respectively, 960 C, the sheath cracked. It may be that the clearance

Metrologia, 1999, 36, 117-139 129

J. Ancsin and E. Mendez-Lango
Figure 10. Drift of YJ 243 during repeated calibrations. Until 10 April the PRT was calibrated up to the Zn point only.
between the baffle and the sheath was too small. Or,
during one of the thermal cycles, the baffle may have
become lodged at an angle, rupturing the sheath during
cooling. We have since obtained some 7 mm quartz
tubing of slightly oversized bore (over 5.2 mm) in
order to avoid similar ruptures in the future. The broken
sheath was changed to that of the oversized bore and
the PRT was put back to use on 22 May, as shown in
Figure 13. The change in sheath resulted in inadvertent
contamination of the sensor (note the decrease in
by the equivalent of 0.4 C at the Al point). It
130
may be that the contamination was caused by our
rather casual cleaning of our newly acquired re-bored
sheath and by the handling of the PRT components
during re-assembly. Certainly, the experience of making
and using PRTs provides an excellent opportunity to
observe at first hand the relation between cleaning
procedures and the resulting drift of values, the
dependence of the immersion characteristics on the
(strategic) location of baffles, and the effect of the
gap between the sensor and the sheath on self heating,
etc.
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs

Figure 11. Drift of YJ 243. Some of the data are those of Figure 10 plotted with increased sensitivity.
Time interval of measurements at the CENAM is indicated.

4.2 Reproducibility of fixed points
As shown in Figure 13, the resistance of PRT T-5
also changed with use. Periods of relative stability are
followed by periods of increase in resistance. In order
to find out if the resistance changes are caused by the
relatively high-temperature soaking or by thermal cy-
cling, the PRT was left permanently in the Al point cell
during the period 7 to 17 July (240 hours). The Al point
was realized daily, in our customary way, except that
the PRT was not removed from the thermometer well.
As shown in the top and bottom graphs of Figure 13,
the PRT remained quite stable. The elimination of large
temperature changes apparently removed much of the
irreproducibility. This would of course be expected if
most of the irreproducibility of the resistance of our
PRTs is caused by the difference in thermal expansion
between the sensor and the rest of the PRT. The rel-
atively stable temperatures (compared with the change
of 660 C when is determined) left stable.
The data plotted in Figure 13 (7 to 17 July) were
least-squares fitted to a linear equation. The residuals,

Metrologia, 1999, 36, 117-139 131

J. Ancsin and E. Mendez-Lango
Figure 12. Fixed-point resistance ratios for YJ 243. Time interval of measurements at the CENAM is indicated.
i.e. the difference between the measured and the
calculated values using the deduced equation, are
plotted in Figure 16 for both the realized and the melt-
off (liquidus point) values, obtained during the above
period. The slope of the linear equation indicates a PRT
drift of 0.02 mK/day at the Al point. The residuals show
that the combined standard Type A uncertainty of our
Al point, as we customarily realize it for calibrating
PRTs, i.e. the first two terms of (2), is within a scatter
band of ± 0.14 mK and that the melt-off temperature is
reproducible within ± 0.12 mK.
132
In order to test the reproducibility of the Zn point,
we inserted the PRT into the Zn cell on 21 July in an
“annealed” state (after the Al point determination the
temperature of the PRT was reduced from 660 C to
450 C in 1 hour in an annealing furnace). The PRT was
left in the Zn cell permanently until 27 July, except to
determine its each time the Zn point was realized. As
shown in Figure 14, there is very little scatter relative to
the smooth lines drawn through these points of
and . The points (from 21 to 27 July) show a
parabolic drift pattern and were therefore least-squares
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs

Figure 13. Drift of T-5 during Al point soak and repeated calibrations (see text for details).

fitted to a quadratic equation. The residuals of
for these six successive realizations of the Zn point lie
within a band of uncertainty of ± 0.07 mK (see Figure
16). This quantity represents the combined standard
Type A uncertainty (the first two terms of (2)) of our
routine Zn point realization.
4.3 Repeated calibrations up to the Zn point
From 28 July to 7 August, the values of ,
and were also repeatedly determined, leaving
the PRT soaking in the Zn cell overnight. Again, the
drift of the fixed-point resistances as a result of thermal
cycling and of oxidation is apparent (see Figures 14
and 15). The residuals of quadratic fits of the data
of 28 July to 7 August lie within scatter bands of
± 0.11 mK, ± 0.1 mK and ± 0.1 mK, respectively, for
the Zn, Sn and In point realizations (see Figure 16),
indicating these values for their combined standard
Type A uncertainties.
4.4 Repeated calibrations up to the Al point
Between 10 and 15 August, the PRT was calibrated
daily up to the Al point. The initial drop in resistance
at all fixed points relative to the values of 7 August

Metrologia, 1999, 36, 117-139 133

J. Ancsin and E. Mendez-Lango
Figure 14. Drift of T-5 during Zn point soak and repeated calibrations (see text for interpretation of data).
(see Figures 14 and 15) was due to deoxidation of the
sensor wire during the first Al point calibration. With
repeated calibrations, the PRT resistance at all fixed
points began to drift (linearly) due to thermal cycling
as seen in Figures 13, 14 and 15. The residuals of a
linear fit of the data from 10 to 15 August are shown in
Figure 16. It is interesting to note that values obtained
on 13 August, at all fixed points, show a remarkably
large deviation from the rest (see Figure 16). It is
unlikely that all fixed points (including the water triple
point) changed simultaneously on that day. It is more
134
likely that the PRT shifted. A perusal of the values of
13 August in Figures 13 and 14 indicate the direction
of the deviation of the values from the established drift
pattern.
If, for example, the sensor wire rapidly expanded
when inserted (on 13 August) into the Al cell up to
some temperature between 420 C and 660 C and
then, perhaps as a result of friction between the
sensor wire and the ceramic spaghetti insulation, was
unable to reach its unrestricted equilibrium position,
being longitudinally compressed at the Al temperature,
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs
Figure 15. Figure 14, continued.
it would then have a slightly larger diameter and
thus a lower resistance than its equilibrium value
(see Figure 13). At lower temperatures, again such
friction might prevent the PRT sensor from reaching its
equilibrium size. Being stretched, the wire would have
a smaller diameter and thus a higher resistance than
its equilibrium value at all fixed points below Al. This
type of behaviour seems to be indicated in Figures 13,
14 and 16. The next heating cycle to the Al point (on
14 August) probably dislodged the sensor wire from its
restrained position, slightly changing its location within
the spaghetti and allowing it to resume its equilibrium
Metrologia, 1999, 36, 117-139
sizes between thermal cycles. Because the anomalous
values of 13 August in Figure 16 are clearly due to
the irreproducibility of the PRT (first term of (2)) they
should not be included when estimating the realization
uncertainties of the fixed points (second term of (2)),
whatever the reason for the irreproducibility of the PRT.
5. “Immersion test”
In order to investigate the temperature distribution along
the ingots, the resistance of the PRT was measured
135
J. Ancsin and E. Mendez-Lango
Figure 16. Least-squares fitting the data of Figures 13, 14 and 15 (see text for details).
along the thermometer well. Starting from the bottom
of the well, the PRT was raised in 1.2 cm steps, and at
each step a reading was taken after its value stabilized
about 5 min later. For Hg the immersion test was
performed in reverse order: the Hg point was realized
with the PRT held 10 cm above the bottom of the well,
which was entirely filled with alcohol. As the PRT
was lowered in 2.5 cm steps the excess alcohol was
expelled, leaving the well filled. Figure 17 shows the
measured values.
136
Although near the bottom of the wells the trend of
the temperature variations along the samples is similar
to that expected due to the hydrostatic pressure effect,
elsewhere the values seem to indicate more closely
either vertical heat exchange between the samples and
their surroundings or heat leaks along the leads of the
PRT to or from the sensor, or possibly a combination
of both effects. The larger the temperature difference
between the sample and room temperature, the larger
the observed temperature variation along the sample, as
Metrologia, 1999, 36, 117-139
 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs
Figure 17. “Immersion test”: observed temperature variations along the ingots using PRT T-5.
seen by the PRT. This apparent temperature variation
could be caused by heat leaks, mostly along the PRT,
and by the hydrostatic pressure effect within the sample.
If the temperature difference is very large between the
sample and room temperature, then the effect of heat
leaks will be very much larger than the hydrostatic
pressure effect. If the sample temperature is relatively
close to ambient temperatures as for Ga and H2 O
(compared with Zn or Al), then the hydrostatic pressure
effect should make a relatively larger contribution to
the detected temperature variation along the sample.
Table 1 indicates some relative magnitudes. The vertical
temperature gradients are the values of [ (fixed point)
– (room temperature)]/distance from the top of the
samples to the top of the furnace. The dependencies
of the hydrostatic pressures are those of Table 2 in the
text of the ITS-90 [5].
Metrologia, 1999, 36, 117-139
As may be seen from the values in Table 1,
the vertical heat leaks are orders of magnitude larger
than the hydrostatic pressure effects near the top of
the samples. By thermally anchoring the leads a few
centimetres above the sensor, one hopes to dramatically
reduce these vertical temperature gradients and thus the
heat flow along the leads to or from the sensor. Still,
it is a matter of opinion if the observed temperature
variation along the sample is considered to be real or
only apparent and whether it is attributed mostly to
heat leaks (primarily along the PRT) or to hydrostatic
pressure effects within the sample.
Our attempt to thermally anchor the PRT leads
is described above. During the “immersion test”, the
further the PRT is from the bottom of the well the
shorter the distance from the top of the sensor to the
tempering region. Because the tempering region is near
to, but not at, the sample temperature, the magnitude
137
J. Ancsin and E. Mendez-Lango

Table 1. Contrasting the magnitude of vertical heat leaks
with hydrostatic pressure effects.
Substance Vertical temperature Temperature variation along
gradients/(K/cm) the sample arising from
hydrostatic pressure/
(mK/cm)
Al 21 0.016
Zn 13 0.027
Sn 7 0.022
In 4 0.033
Ga 0.1 –0.012
H2 O –1.3 –0.0073
Hg –10 0.071
of the heat flow along the leads to or from the sensor
becomes larger and larger as the distance increases from
the bottom of the well to the PRT. Also, there is no
way of knowing the efficiency of the thermal contact
between the leads and the tempering region. For sample
tubes with no tempering region above the sample,
i.e. where the sample tube is packed with insulating
material above the top of the graphite crucible, the
heat flow along the leads of the PRT should have a
more pronounced effect on the detected “immersion”
values. Even if the numerical values coincide with
the expectation of either effect, it still remains to
be proven by unambiguous measurements that the
observed numbers are due to one effect and not to
the other. For capsule-type PRTs the leads are always
very carefully thermally anchored to some components
of the cryostat that are maintained as close as possible
to the sample temperature. For long-stem PRTs no such
lead anchoring is possible. However, one has to attempt
to anchor the leads to near sample temperatures by some
means, even if the method turns out to be inferior to
the cryogenic routine. For example, a baffle cylinder
of substantial surface area, located a few centimetres
above the sensor (within the PRT sheath), could be used
to enhance the heat contact between the leads and their
immediate surroundings. Also, such a baffle cylinder
would probably reduce the minimum “immersion”
necessary for accurate temperature measurements.
6. Consistency of fixed points
High-purity samples obtained from different manufac-
turers will probably have different types of impurities
present in different trace amounts. Based on experience
gained from studying the melting/freezing behaviour of
“pure” substances, one expects samples of 99.9999 %
purity or better, with narrow melting ranges, to have
liquidus points within a temperature range of about one
millikelvin. This is only a crude estimate, however,
which may turn out to be wrong in specific instances.
Because the actual impurities and their concentrations
in our samples used as thermometric fixed points are
unknown, we cannot directly estimate the component
of the uncertainty of a realized fixed point due to these
impurities. What we can do, however, is to estimate
the uncertainty within which a given fixed point is
consistent with the others, spanning a given temperature
range.
Table 2 contains a summary of values obtained
between 10 and 15 August using PRT T-5. The first
two columns are self-explanatory. The third column is
the average of six realizations in the above-mentioned
time interval. (There is a discrepancy between column 3
of Table 2 and the values in Figures 13, 14 and 15. The
data in column 3 are the averages of values in the figures
corrected for hydrostatic pressures.) The fourth column
is the deviation of the resistance ratios in column three
from the reference function values, and the last two
columns are the residuals of least-squares fits of the
values of column four versus column three to quadratic
and cubic equations, respectively. The sensitivity of
values of varies from about 4 10–6 /mK at
the Ga point to about 3.2 10–6 /mK at the Al point.
A set of careful realizations of a fixed point using a
slightly impure sample would yield a of small
realization uncertainty, i.e. a narrow scatter band in
Figure 16 indicates only that a well-behaved PRT was
used and that a given fixed point was carefully realized
using consistent procedures. However, the of
an impure sample would deviate conspicuously from
a low-degree polynomial drawn through a set of
versus points obtained for pure samples. Thus,
if any of the samples of Table 2 contained a significant
amount of impurities, then such a graph would identify
the sample at a glance. These general ideas and some
of their implications are discussed in [6].
The last two columns of Table 2 indicate that any of
the fixed points in the table is consistent with the rest,
within ± 0.2 mK, using either a cubic or a quadratic
deviation function in the temperature range 0 C to
660 C. In other words, the uncertainties arising from
impurities are insignificant for all practical purposes.

Table 2. Fixed-point consistency.

Fixed point 1 (ref) 2 (av.) 1 2 Residuals Residuals

of quadratic fit of cubic fit
Al 3.376 0086 3.373 7399 0.002 2687 0.000 0000 0.000 0000
Zn 2.568 9173 2.567 4398 0.001 4775 –0.000 0002 0.000 0002
Sn 1.892 7977 1.891 9647 0.000 8330 0.000 0008 0.000 0008
In 1.609 8018 1.609 2358 0.000 5660 0.000 0007 –0.000 0007
Ga 1.118 1389 1.118 0340 0.000 1049 0.000 0001 –0.000 0001

138 Metrologia, 1999, 36, 117-139

 The reproducibility of some thermometric fixed points and the accuracy of temperature measurements using PRTs

References 4. Ancsin J., Metrologia, 1993, 30, 105-106.

5. Preston-Thomas H., Metrologia, 1990, 27, 3-10, 107.
1. Ancsin J., Mendez-Lango E., Metrologia, 1996, 33, 6. Ancsin J., Metrologia, 1995/96, 32, 295-300.
415-420.
2. Ancsin J., Zhang Y., Metrologia, 1994, 31, 85-91.
3. Ancsin J., In Temperature: Its Measurement and Control
in Science and Industry, Vol. 6 (Edited by J. F. Schooley), Received on 23 November 1998 and in revised form
New York, American Institute of Physics, 1992, 343-348. on 18 February 1999.

Metrologia, 1999, 36, 117-139 139