### Operating principle and construction of zirconium

```Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
1. PHYSICAL BACKGROUND
1.1 Partial pressure
Definition:
The partial pressure is defined as the pressure of a
single gas component in a mixture of gases. It
corresponds to the total pressure which the single
gas component would exert if it alone occupied the
whole volume.
In biology and medicine above all the partial
pressures of oxygen and carbon dioxide are of
importance. Here, the term partial pressure is also
used for the concentration of gases dissolved in
liquids, e.g. in blood or water. Thereby the partial
pressure of a gas dissolved in a liquid is the partial
pressure of that gas which would be generated in a
gas phase in equilibrium with the liquid at the same
temperature.
Dalton's law:
The total pressure (ptotal) of a mixture of ideal gases is
equal to the sum of the partial pressures (pi) of the
individual gases in that mixture.
k
p total = ∑ pi
i =1
(1)
From equation (1) it can be derived that the ratio of
the number of particles (ni) of an individual gas
component to the total number of particles of the gas
mixture equals the ratio of the partial pressure (pi) of
the individual gas component to the total pressure
(ptotal) of the gas mixture.
ni
pi
=
n total p total
ni
ntotal
pi
ptotal
:
:
:
:
Example 1:
The atmospheric pressure at sea level under standard
conditions is 1013.25 hPa. Here the main components
of dry air are nitrogen (78.09 %Vol.), oxygen
(20.95 %Vol.), argon (0.927 %Vol.) and carbon
dioxide (0.033 %Vol.). The volumetric content (%) can
be equated to the number of particles (n) since the
above gases can be approximated as ideal gases.
Equation (2) can be solved for the partial pressure of
an individual gas to get:
pi =
ni
n total
⋅ p total
(3)
The oxygen partial pressure then equates to:
pi =
20.95 %
⋅ 1013 .25 hPa = 212.28 hPa
100 %
However, this value is only relevant when the
atmosphere is dry (0 % humidity). If moisture is
present a proportion of the total pressure is taken up
by water vapour pressure. Therefore the partial
oxygen pressure (ppO2) can be calculated more
accurately when relative humidity and ambient
temperature are measured along the total barometric
pressure.
Firstly water vapour pressure is calculated:
WVP = HRe l ⋅ WVPMax
(4)
WVP : Water vapour pressure [mbar]
HRel
: Relative humidity [%]
WVPMax : Max. water vapour pressure [mbar]
(2)
Number of particles in gas i
Total number of particles
Partial pressure of gas i
Total pressure
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
For a known ambient temperature, maximum water
vapour pressure (WVPMax) can be determined from
Table 1. The maximum water vapour pressure is also
referred to as the dew point.
Partial oxygen pressure then equates to:
 20.95 
ppO 2 = (BP − WVP ) ⋅ 

 100 
ppO2
BP
WVP
(5)
: Partial pressure O2 [mbar]
: Barometric pressure [mbar]
: Water vapour pressure [mbar]
Example 2:
The effect of humidity reducing the partial oxygen
pressure and therefore the volumetric content
of oxygen is shown using the following meteorological
data:
Temperature
: 22 °C
Humidity
: 32 %
Barometric pressure : 986 mbar
Using Table 1, WVPMax for 22 °C can be found to be
26.43 mbar. Equation (4) than gives
 32 
WVP = 
 ⋅ 26.43 = 8.458 mbar
 100 
Partial oxygen pressure then equates to:
T (°C)
WVPMax (mbar)
T (°C)
WVPMax (mbar)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
6.10
6.57
7.06
7.58
8.13
8.72
9.35
10.01
10.72
11.47
12.27
13.12
14.02
14.97
15.98
17.04
18.17
19.37
20.63
21.96
23.37
24.86
26.43
28.11
29.82
31.66
33.60
35.64
37.78
40.04
42.42
31
32
33
34
35
36
37
38
39
40
42.5
45
47.5
50
52.5
55
57.5
60
62.5
65
67.5
70
75
80
85
90
95
100
110
120
130
44.92
47.54
50.30
53.19
56.23
59.42
62.76
66.27
69.93
73.77
84.19
95.85
108.86
123.38
139.50
157.42
177.25
199.17
223.36
250.01
279.31
311.48
385.21
473.30
577.69
700.73
844.98
1013.17
1433.61
1988.84
2709.58
Table 1: Maximum water vapour pressure (WVPMax)
 20.95 
ppO 2 = (986 − 8.458 ) ⋅ 
 = 204 .795 mbar
 100 
As we now know the oxygen partial pressure and the
total barometric pressure we can work out the
volumetric content of oxygen as:
O 2 % Vol. =
E / 11154 / C
204 .8
⋅ 100 = 20.77 %
986
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
2. SENSOR FUNCTION
1.2 Nernst voltage
2.1 Sensor construction
Two different ion concentrations on either side of an
electrolyte generate an electrical potential known as
the Nernst voltage. This voltage is proportional to the
natural logarithm of the ratio of the two different ion
concentrations.
First Sensors XYA oxygen sensors consist of two
zirconium dioxide (ZrO2) discs coated with thin porous
layers of platinum which serve as electrodes (see Fig.1).
The two discs are attached to a platinum ring, forming
a hermetically sealed chamber. At the outer surfaces
of the ZrO2 discs there are two further platinum rings
to provide for the sensors electrical contacts. The first
disc is connected to a reversible current source, at
the second disc a voltage (Nernst voltage) can be
measured.
∆U = −
kB
T
e0
ci
:
:
:
:
k B T  c1
⋅ ln
e0
 c2



(6)
-23
Boltzmann constant (kB=1.38•10 J/K)
Temperature in K
-19
Elementary charge (e0=1.602•10 C)
Ion concentration in mol/kg
1.3 Zirconium dioxide (ZrO2)
At high temperatures >650 °C zirconium dioxide
(ZrO2) exhibits two mechanisms:
1. ZrO2 partly dissociates to produce oxygen ions
which can be transported through the material
when a voltage is applied.
2. ZrO2 behaves like an solid electrolyte for oxygen. If
two different oxygen pressures exist on either side
of an ZrO2 element a voltage (Nernst voltage) can
be measured across that element (see 1.2 Nernst
voltage).
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Two outer alumina (Al2O3) elements prevent any
ambient particulate matter from entering the sensor
and also remove any unburnt gases. This prevents
contamination of the cell which may lead to unstable
measurement readings. The complete assembly is
surrounded by a heating coil which provides for the
necessary operating temperature of the sensor (not
shown in Fig. 1). Additionally, First Sensors XYA
series is housed in stainless steel caps to protect the
sensors against dirty environments and mechanical
destruction.
chemicals which have an influence on the measuring
results and life of the sensor please see chapter 4
Cross Sensitivity.
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
2.3 Sensing disc
Platinum
electrode
Sealed chamber,
p2
Platinum ring
Alumina filter
ZrO2
pumping
disc
ZrO2
sensing
disc
This voltage is sensed and compared with two
reference voltages V1 and V5 (see Fig. 2). Each time
either of these two references is reached the constant
current source is reversed and the Nernst voltage
approaches its other reference value. Thereby V1 is
the sensing voltage for the highest and V5 the sensing
voltage for the lowest oxygen pressure achieved in the
chamber.
+i
SENSE
i
COMMON
p1
PUMP
p1
A difference in oxygen pressure across the second
ZrO2 disc (sensing disc) generates a Nernst voltage
which is logarithmically proportional to the ratio of the
oxygen ion concentrations (see 1.2 Nernst voltage).
Vs
Pump
Current
Pump Sensing
voltage
Fig. 1:
-i
Sensor construction
2.2 Pumping disc
p2 high
Oxygen
pressure
in chamber
on
ati
s
i
r
su
es
r
P
Ev
ac
ua
tio
n
p2 low
The first ZrO2 disc (pumping disc) works as an
electrochemical oxygen pump, evacuating or
pressurising the sealed chamber. Depending on the
direction of the connected reversible constant current
source the oxygen ions move through the disc from
one electrode to the other thus changing the oxygen
concentration and therefore the pressure (p2) inside
the chamber (see Fig. 1).
V5
V4
Nernst
Voltage
(Vs)
V3
V2
V1
t1
t2
t4
t5
tp
time
period tp is proportional to the
partial pressure of the ambient
oxygen (p1)
Fig 2:
E / 11154 / C
Nernst voltage as a function of the oxygen
pressure in the chamber
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
3. MEASUREMENT
The duration of a complete pump cycle, i.e. the time
taken to once evacuate and refill the chamber,
depends on the partial pressure of the ambient
oxygen (see Fig. 3). This time is equivalent to the
cycle duration of the Nernst voltage (tp). The higher
the ambient oxygen pressure is, the longer it takes
for the oxygen pump at constant pump current to
reach the same reference voltages. This is because a
greater number of oxygen ions are required to be
pumped in order to create the same ratiometric
pressure difference across the sensing disc. Thus,
the pumping cycle and therefore the cycle time of the
Nernst voltage is a measure of the ambient oxygen
partial pressure.
pumping cycle period tp
at p1 = 200 mbar
time
pumping cycle period tp
at p1 = 50 mbar
Pumping cycle period depending on the
ambient oxygen partial pressure p2
3.1 Practical considerations
In theory any two values can be chosen for V1 and V5 ,
in practice they are chosen to:
1. Eliminate the effect of an electric double layer in
the ZrO2 square formed by space charges.
2. Create the best response time for the application.
3. Eliminate temperature dependence.
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To overcome the influence of the double layer near the
pump reversal points, Nernst voltages are chosen well
away from V1 and V5. (see V2, V3 and V4 in Fig. 2)
Response time
Because the pump cycle time increases as the
oxygen pressure increases, at higher oxygen
pressures V1 and V5 should be made close to each
other in order to ensure a fast response.
Oxygen
pressure p2
in chamber
Fig. 3:
Compensating for the electric double layer
Not all of the charge supplied by the constant current
source contributes to a pressure change in the
chamber, some is absorbed by an electric double
layer formed at the platinum/ ZrO2 interface as the
current source is reversed. This effect is particularly
noticeable at the extremes of pressure and near the
pump reversal voltages. As pressure increases the
amount of charge required to change the chamber
pressure also increases. To reduce this effect the
working chamber pressure should only vary 1-10 %
from the ambient pressure.
Compensating for temperature dependence
It can be seen that the Nernst voltage (equation (6)) is
temperature dependant. However the temperature
dependence is such that under certain operating
conditions, the combined temperature dependence of
Nernst law and the gas laws that govern oxygen can
be vastly reduced. Again much of this temperature
dependence occurs around the pump reversal points
so by choosing to measure Nernst voltages at V2, V3
and V4 we can make the temperature co-efficient (TC)
virtually equal zero.
When operating in this TC = 0 mode the time taken to
reach V2, V3 and V4 are measured. These are
highlighted as t1, t2, t4 and t5 in Fig 2. The revised
cycle time (td) is then calculated as follows:
t d = (t1 − t 2 ) + (t 5 − t 4 )
(7)
Not only does td give a linear output proportional to
the ambient oxygen pressure but unlike tp, it also
goes through the origin.One of the major benefits of
having a linear response that goes through the origin
is that sensor calibration (gain) can occur at one point
anywhere on the slope. By measuring tp, two point
calibration is required not only to set the gain but
also to remove the zero offset.
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
Sensitivity
Sensitivity is defined as the cycle time (td or tp) in
milliseconds divided by the ppO2 in mbar of the known
calibration atmosphere.
When calculating td (one calibration point), sensitivity
is defined as:
Sensitivit y =
td
ppO 2
(8)
When calculating tp (two calibration points), sensitivity
is defined as:
Sensitivit y =
t p − offset
ppO 2
(9)
Sensitivity for a nominal sensor, when calculating td,
is typ. 1.05 ms/mbar. Though due to many factors
that may influence the sensitivity (chamber volume,
ZrO2 thickness etc), there is a production tolerance of
±15 %. This makes calibration a necessity to ensure
good sensor to sensor repeatability.
3.3 Calibration
First Sensors XYA zirconium dioxide oxygen sensors
do not directly measure the concentration (volumetric
content) of the ambient oxygen but instead measure
the partial oxygen pressure. However, the volumetric
content can easily be calculated from Dalton's law
(see equation 2) if the total pressure of the gas
mixture is known.
If a relative content (percent by volume) is to be
determined, the oxygen sensor has to be calibrated in
the actual measurement environment with a known
oxygen concentration. Typically this would involve
calibration in normal air to 20.7 % (not 20.95 %) to
take into account average humidity levels. In order to
maintain accuracy, calibration should occur regularly
to remove variance caused by fluctuations in
barometric/application pressure. As barometric
pressure changes relatively slowly daily calibrations
are recommended. Regular calibration also removes
any sensor drift which is typical in the first few
hundred hours of operation.
3.2 Recommended values
When using the sensor to measure ppO2 of approx
1...1000 mbar (0.1...100 % of typical barometric
pressure), the following values are recommended:
td (TC = 0 mode)
Constant current source:
i=40 µA
Pump reversal voltages:
V1=40 mV, V5=90 mV
Sense Voltages:
V2=45 mV, V3=64 mV, V4=85 mV
tp (basic period calculation)
Constant current source:
Pump reversal voltages:
i=40 µA
V1=25 mV, V5=115 mV
When using the sensor in higher O2 pressures
alternate values can be recommended on request.
Due to the many benefits of operating the sensor in
TC = 0 mode (calculating td), this is the recommended
mode of operation.
Calculating tp, as it is relatively simple, is only
recommended for basic applications where high
accuracy is not necessarily required.
E / 11154 / C
First Sensors control circuit boards (ZBXYA, ZBXYAF)
offer oxygen measuring ranges of 0...25 % Vol.,
0...100 % Vol. and custom ranges. For further details
please refer to the ZBXYA and ZBXYAF data sheets.
Typical calibration procedure
1. Sensor placed in calibration gas, typically normal
air (20.7 % O2), though can be any gas of known
concentration.
2. Oxygen sensor heats up until the correct operating
temperature is reached, ~100 s from cold.
3. Pumping cycles commence.
4. Sensor is left at the operating temperature for
5-10 min. to fully stabilise.
5. Output (td or tp) is calculated. Usually over at least
ten cycles to average out any noise. The greater
the averaging the better.
6. Output value is normalised to equal the known % of
the calibration gas. When calculating td the
calibration process is now complete.
7. When calculating tp if better accuracy is required it
is recommended that a second calibration at a
lower % is completed. This two point calibration
will remove any zero offset. If accuracy is not
critical single point calibration is sufficient.
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
3.4 Initial sensor drift and active burn-in
In the first 200 h the sensor output can drift by up to
±3 %. This is due to a number of factors including:
1. Impurities in the zirconium dioxide migrating to the
surface of the platinum electrode bond which alters
the catalytic properties.
2. Heater coil ageing.
3. The internal stainless steel surface of the cap
becoming less reflective due to thermal oxidation.
Regular calibration removes the effect of initial sensor
drift as the sensor output is constantly re-referenced
against the known calibration gas. However if regular
calibration is not possible and the output is required
to have stabilised prior to use in the application then it
may be necessary to actively burn-in the sensor .
Active burn-in involves operating the sensor normally
in a controlled atmosphere where the exact partial
oxygen pressure (ppO2) is known. If this is normal air
then all weather data must be recorded and the ppO2
calculated as previously described in chapter 1.1,
Example 2. With the ppO2 known the sensor output
(td or tp) can be normalised as described in Equation 8.
By calculating slope any variance in the sensor
output can be considered to be drift and not due to
environmental fluctuations. The level of stability
required will be dependant on the application
specifications. However, in general the output can be
considered stable when the slope value has varied by
less than ±0.2 % of reading in the last 48 h.
When performing active burn-in at First Sensor,
measurements are taken at 12 h intervals and the
environmental temperature is also kept constant to
negate any temperature dependence the sensor
output may exhibit.
3.5 Using a barometric pressure sensor to scale
the XYA output.
If regular calibrations in normal air are not possible it
may be necessary to use a barometric pressure
sensor in conjunction with the XYA sensor to
automatically compensate the output. This is a
relatively simple process as variations in the barometric
pressure change the output of the oxygen sensor by
the same proportion. So if the barometric pressure
changes by 1 % the sensor output will also change by 1 %.
Ideally the initial system calibration should be
performed after the sensor has burned in for 200 h.
This will ensure any sensor drift, which may effect
future accuracy, has occurred beforehand.
Typical calibration procedure when using a barometric
pressure sensor:
1. Sensor is placed in the calibration gas, typically
normal air (20.7 % O2), though can be any gas of
known concentration.
2. Oxygen sensor heats up until the correct operating
temperature is reached, ~100 s from cold.
3. Pumping cycles commence.
4. Sensor is left at the operating temperature for
5-10 min. to fully stabilise.
5. Output (td or tp) is calculated. Usually over at least
ten cycles to average out any noise. The greater
the averaging the better.
6. Output value is normalised to equal the known % of
the calibration gas.
7. The barometric pressure at the time of the
calibration is stored.
Subsequent O2 and barometric pressure readings are
then entered into following equation:
p
O 2 comp = O 2 cur ⋅  cal
 p cur




(10)
Example:
The sensor output is calibrated to 20.7 % and the
barometric pressure is measured at 1000 mbar. The
following day the pressure has changed by 1 % to
990 mbar. Without compensation the O2 output would
also reduce by 1 % to 20.493 %.
Using equation (10) the compensated O2 value is:
 1000 mbar 
 = 20.7 %
O 2 comp = 20.493 % ⋅ 
 990 mbar 
E / 11154 / C
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
4. CROSS SENSITIVITY
5. APPLICATION HINTS
The XYA oxygen sensors measure partial oxygen
pressure as explained above and show some cross
sensitivity with other gases. Described below are
gases or chemicals that will have an influence on the
life of the sensor or on the measuring results.
5.1 Fail safe operation
The sensors have been primarily developed for boiler
combustion control applications. Therefore, life tests
have been performed in a laboratory atmosphere, in
exhaust gases of natural gas fired boilers as well as
in exhaust gases of light oil.
One of the main benefits of the dynamic and active
cell employed within the XYA oxygen sensor is that it
is inherently fail safe. The continual cycling and
measurement of the generated Nernst voltage is
effectively the heart beat of the sensor, if this stops
something fatal has occurred with the cell. This can
very quickly be detected by a microprocessor which
can generate the relevant error code.
5.2 Sensor asymmetry
4.1 Combustible gases
Small amounts of combustible gases will be burned
at the hot platinum electrode surfaces or alumina
filters of the sensor. In general combustion will be
stoichiometric as long as enough oxygen is available.
The sensor will measure the residual oxygen pressure
which leads to a measurement error. The sensor is
not recommended for use in applications where there
are large amounts of combustible gases present and
an accurate O2 measurement is required.
Investigated gases (stoichiometric combustion) are:
• H2 (hydrogen) up to 2 %;
• CO (carbon monoxide) up to 2 %;
• CH4 (methane) up to 2.5 %;
• NH3 (ammonia) up to 1500 ppm;
4.2 Heavy metals
The generated Nernst voltage shown in Fig. 2 is
symmetrical, which is a strong indication of sensor
health. If an asymmetric output waveform is detected
it could be one of the following causes:
1. The heater voltage is too low
2. The sensor has been contaminated meaning the
cell is not pumping correctly.
3. The hermetic seal which surrounds the sensing
chamber has a leak. This means it is far more
difficult to evacuate the chamber than it is to repressurise it.
4. The cell has been excessively loaded with
capacitive impedance.
To measure asymmetry we can simply calculate the
following at the same time as measuring td or tp.
Asymmetry =
(t1 + t 2 )
(t 5 + t 4 )
(11)
Vapours of metals like Zn (zinc), Cd (cadmium), Pb
(lead), Bi (bismuth) will have an effect on the catalytic
properties of the platinum electrodes. Exposures to
these metal vapours has to be avoided.
The result of this calculation should ideally be 1 to
indicate perfect sensor health. In production the sensor
asymmetry has a tolerance of ±2.5 % (0.975 to 1.025).
4.3 Halogen and sulphur compounds
5.3 Operation in humid environments
Small amounts (< 100 ppm) of halogens and/or
sulphur compounds have no effect on the performance
of the oxygen sensor. Higher amounts of these gases
will in time cause readout problems or, especially in
condensing environments, corrosion of sensor parts.
When operating the sensor in warm, humid
environments it is important the sensor remains at a
higher temperature than its surroundings, especially if
there are corrosive components in the measurement
gas. During operation this in not a problem due to the
700 °C generated by the heater, but this means when
the sensor or application is being powered down the
sensor heater must be the last thing to be turned off
after the temperature of the surroundings have
suitably cooled. Ideally the sensor should be left
powered or at a lower standby voltage (2 V typically)
at all times in very humid environments.
Investigated gases are:
• Halogens, F2 (flourine), Cl2 (chlorine)
• HCL (hydrogen chloride), HF (hydrogen fluoride)
• SO2 (sulphur dioxide)
• H2S (hydrogen sulphide)
• CFC's, HCFC's (Freons)
• CS2 (carbon disulfide)
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Operating principle and construction of zirconium dioxide
oxygen sensors of the XYA series
Failure to adhere to these rules will result in
condensation forming on the heater and sensing cell
as these will be the first components to cool due to
their connections to the outside world. When the
sensor is re-powered the condensation will evaporate,
leaving behind corrosive salts which very quickly
destroy the heater and cell .
5.4 Protecting from water droplets
In environments where falling water droplets are likely
the sensor should be protected since water falling
directly onto the very hot sensor cap can cause massive
temperature shocks to the cell and heater. Popular
methods include a hood over the sensor cap or for the
sensor to be mounted in a larger diameter cylinder.
At a very minimum the sensor cap should be angled
downwards as this will deflect any falling moisture
and prevent the sensor cap from filling with water.
5.5 Using the sensor with silicones (rubbers, plastics)
The XYA oxygen sensors, like all other zirconium
dioxide sensors, are damaged by the presence of
silicone in the measurement gas. Vapours (organic
silicone compounds) of RTV rubbers and sealants are
the main culprits and are widely used in many
applications. These materials are often made of
cheaper silicones, that when heated still outgas
silicone vapours into the surrounding atmosphere.
When this reaches the sensor the organic part of the
compound will be burned at hot sensor parts, leaving
behind a very fine divided SiO2 (silicon dioxide, also
known as silica). This SiO2 completely blocks the
pores and active parts of the electrodes. If RTV rubbers
are used we advise to use high quality, well cured
materials.
5.6 Reducing atmospheres
The sensor by definition requires at least some
ambient oxygen to operate. Otherwise the sensor,
due to applied constant current source, will try to
pump the O2 within the ZrO2. This will in time damage
the ZrO2 and degrade sensor performance. It is
therefore imperative that the sensor is not used for
prolonged periods in very low oxygen environments
(less than 1 mbar ppO2), especially in reducing
atmospheres (an atmosphere in which there is little
free oxygen and oxygen is consumed).
E / 11154 / C
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