Air/fuel ratio sensor

An air-fuel ratio sensor including a box member having a wall made of oxygen ion-conductive electrolyte having a pair of porous electrodes on opposite sides and a diffusion-limiting portion providing communication between the inside and outside of the box member, and an oxygen gas sensing element formed within the box member by injection and firing. The oxygen gas sensing element has a resistance which varies in accordance with the oxygen partial pressure of the atmosphere in which the sensor is immersed.

BACKGROUND OF THE INVENTION 
The present invention relates to an A/F (air-fuel) ratio sensor used for 
detecting the A/F ratio of an air/fuel mixture supplied to a combustor 
such as an internal combustion engine. More particularly, the present 
invention relates to an A/F ratio sensor that employs an oxygen pump 
element composed of an oxygen ion-conductive solid electrolyte and an 
oxygen gas sensing element composed of an electron-conductive 
semiconductor metal oxide. 
With a view to improving fuel economy and reducing emissions while 
providing improved operability, it has been proposed that feed-back 
control be performed on combustors, such as internal combustion engines, 
so as to attain a desired A/F ratio according to specific operating 
conditions. Numerous A/F ratio sensors have been proposed for use in such 
feedback control. 
For example, according to the system shown in Unexamined Published Japanese 
Patent Application No. 190652/1984, an oxygen concentration 
electrochemical cell element employing atmospheric air as a reference 
oxygen source and an oxygen pump element using atmospheric air as an 
oxygen supply source are placed in a face-to-face relationship with an 
enclosed compartment formed therebetween. The compartment communicates 
with the ambient atmosphere by way of a diffusion-limiting portion. The 
oxygen pump element is controlled so that the oxygen partial pressure in 
the enclosed compartment is held constant, with the electric current (pump 
current) that flows through the pump element being used to indicate the 
A/F ratio of the sensed atmosphere over the full operating range of the 
combustor, including both the fuel-lean region and fuel-rich region. 
Another A/F ratio sensor system is described in Unexamined Published 
Japanese Patent Application No. 153155/1983. In this system, an oxygen 
concentration electrochemical cell element which contacts the sensed 
atmosphere on one side and an enclosed compartment on the other side and 
an oxygen pump element which also contacts the sensed atmosphere on one 
side and the enclosed compartment on the other side are placed in a 
face-to-face relationship with the enclosed compartment being formed 
therebetween. The compartment communicates with the sensed atmosphere by 
way of a diffusion-limiting portion. The oxygen pump element is controlled 
so that the oxygen partial pressure in the enclosed compartment is held 
constant, with the pump current being used to indicate the A/F ratio of 
the ambient atmosphere over the full operating range including both the 
fuel-lean region and the fuel-rich region. 
The first type of A/F ratio sensor described above requires a channel for 
introducing atmospheric air, hence cannot be sealed completely, and may be 
adversely affected during service by foreign matter such as moisture. The 
second type of A/F ratio sensor mentioned above does not require the 
introduction of atmospheric air, but its output characteristics are 
ambiguous in that one output value is associated with two different values 
of A/F ratio, specifically, values in both the fuel-lean and fuel-rich 
regions. In order to ensure a nonambiguous, one-to-one correspondence 
between the output value and sensed A/F ratio over the full operating 
range including both the fuel-rich and fuel-lean regions, an additional 
sensor is required to indicate whether the combustor is operating in the 
fuel-rich region (.lambda.&lt;1) or fuel-lean region (.lambda.&gt;1). 
This problem may be overcome by an A/F ratio sensor in which an oxygen gas 
sensing element that employs an electron-conductive semiconductor metal 
oxide such as TiO.sub.2 and which does not require a reference source is 
combined with an oxygen pump element composed of an oxygen ion-conductive 
solid electrolyte. However, an oxygen gas sensing element made of an 
electron-conductive semiconductor metal oxide such as TiO.sub.2 and an 
oxygen pump element made of a ZrO.sub.2 -based solid solution compound are 
difficult to produce simultaneously by conventional techniques since they 
require different temperatures and atmospheres for firing. On the other 
hand, if the two elements are fired separately and joined together 
afterward, it is very difficult to attain a perfectly fitting unitary 
assembly. 
SUMMARY OF THE INVENTION 
The latter problem is solved by the A/F ratio sensor of the present 
invention which comprises a box member, at least a portion of whose wall 
is made of an oxygen ion-conductive electrolyte having a pair of porous 
electrodes on opposite sides thereof. The box member also has a 
diffusion-limiting portion that establishes communication between the 
inside and outside thereof. An oxygen gas sensing element formed within 
the box member by means of injection and firing provides a varying 
resistance in accordance with the oxygen partial pressure of the sensed 
atmosphere. 
The oxygen ion-conductive solid electrolye of which the box member is made 
is typically a solid solution compound of zirconia and yttria or calcia. 
Other usable materials include solid solution compounds of cerium dioxide, 
thorium dioxide and hafnium dioxide, a solid solution compound of a 
perovskite type oxide, and a solid solution compound of a trivalent metal 
oxide. Of these solid solution compounds, those based on zirconia are most 
preferred because of their ready availability. The porous electrodes on 
the solid electrolyte may be formed by various methods with platinum, gold 
or other such materials. In one method, a power of a suitable material, 
selected from the above-listed metals and which is used as the principal 
component, is worked into paste and the paste is printed in a 
predetermined pattern on the solid electrolyte by a thick-film deposition 
technique, followed by sintering of the printed coat. In another method, a 
powder of the starting material is applied onto the solid electrolyte by a 
suitable thin-film deposition technique such as flame spraying, chemical 
plating or evaporation. 
The diffusion-limiting portion in the box member may be formed by various 
methods, such as by forming holes or slits that establish communication 
between the inside and outside of the box member, or by replacing part of 
a wall of the box member with a porous material. Holes are particularly 
preferable since they provide for easy injection and firing of the 
material of the oxygen gas sensing element. 
The box member may be in the form of a cylinder with both ends closed, or 
in the form of a closed rectilinear box. In the former case, the box 
member is formed entirely of a solid electrolyte. In the latter case, one 
rectangular plate of a solid electrolyte having a pair of electrodes 
formed thereon is overlaid in sequence with a spacer having a rectangular 
opening (which is later filled with the oxygen gas sensing element) and 
another rectangular plate, and the three members are compressed together 
and fired to form the desired box member. 
The oxygen gas sensing element may be formed of an oxide of a transition 
metal element selected from among those having atomic numbers of 21 (Sc) 
to 30 (Zn), 39 (Y) to 48 (Cd), 57 (La) to 80 (Hg), and 89 (Ac) to 103 
(Lr). Oxides of these transition metal elements have a tendency to form 
nonstoichiometric compounds wherein the ratio of elemental metal to oxygen 
is a nonintegral value. Due to this nonstoichiometricity, the electrical 
conductivity of these oxides strongly varies in accordance with the oxygen 
partial pressure of the sensed atmosphere. Similar effects are attained 
whether these oxides are used independently or in combination. 
Particularly preferable oxides are SnO.sub.2, TiO.sub.2, Nb.sub.2 O.sub.5, 
V.sub.2 O.sub.5, CrO.sub.3, CoO and NiO because their electrical 
conductivities are highly sensitive to variations in oxygen partial 
pressure and because they have high durability. Yet higher durability can 
be achieved by mixing these oxides, for instance, CoO, with a 
non-transition metal oxide such as MgO. 
The A/F ratio sensor of the present invention can be produced by a method 
wherein one or more of the oxides mentioned above is injected into a 
previously made box member and fired in situ. More specifically, a paste 
of the oxides is injected under pressure into the box member through holes 
serving as the diffusion-limiting portion, and subsequently fired. 
Alternatively, the paste may be injected through holes other than those 
serving as the diffusion-limiting portion (which holes are closed at a 
later stage) and subsequently fired. In order to ensure higher stability 
in the face of varying temperatures, a heat generating element is 
preferably provided in the box member or the oxygen gas sensing element. 
Part of the heat generating element may be joined to one of the electrodes 
on the oxygen gas sensing element so that electrical power applied to the 
heating element can also be used for operation of the oxygen gas sensing 
element. This arrangement provides a particular advantage in that the 
measuring circuit for oxygen gas detection can be simplified. 
An A/F ratio sensor of the present invention having the above-described 
construction is operated as follows: 
The solid electrolyte of which the box member is formed and the pair of 
electrodes formed thereon serves as an oxygen pump element. Depending upon 
the polarity of the voltage applied between the electrodes, the oxygen 
pump element will pump oxygen into or out of the box portion. The oxygen 
gas sensing element is designed so that its resistance varies with the 
oxygen partial pressure of the sensed atmosphere. When the sensed 
atmosphere changes from the fuel-lean to fuel-rich region or vice versa, 
the resistance of the oxygen gas sensing element will change by about 
three to four orders of magnitude at the transition from one region to the 
other. 
When the air/fuel mixture is in the fuel lean region, the electrode on the 
outside of the oxygen pump element (i.e., the outside of the box member) 
is supplied with a positive voltage, while a negative voltage is applied 
to the electrode on the inside of the pump element. As a result, oxygen 
ions are caused to migrate through the solid electrolyte in the pump 
element to move from the inner electrode to the outer electrode, whereby 
oxygen gas from inside the box member is pumped to the outside of the 
oxygen pump element. 
When oxygen gas has been pumped out of the box member, a difference is 
produced between the oxygen partial pressure in the box member and that of 
the gas being sensed by the action of the diffusion-limiting portion in 
the box member. The oxygen partial pressure in the box member is measured 
as the electrical resistance of the oxygen gas sensing element. If the 
amount of current (pump current) flowing through the pump element is 
adjusted in such a way that the measured resistance is maintained at a 
predetermined constant level, a substantially linear relationship is 
attained between the pump current (which is proportional to the 
differential partial pressure as described above) and the content of 
oxygen in the gas being analyzed, thereby enabling determination of the 
oxygen level of that gas. 
When the air/fuel mixture is in the fuel-rich region, the oxygen partial 
pressure in the box member will be low, even if the oxygen pump element is 
not actuated in such a way as to reduce the oxygen partial pressure. 
Therefore, in order to maintain the resistance of the oxygen gas sensing 
element at a constant value, the direction of the pump current flowing 
through the oxygen pump element should be reversed. Stated more 
specifically, if the air/fuel mixture is in the fuel-rich region, the 
oxygen in the box member will be partially consumed by unburnt 
hydrocarbons and carbon monoxide in the exhaust gas, and hence the oxygen 
partial pressure in the box member will be sufficiently low that the 
resistance of the oxygen gas sensing element will drop below the 
predetermined level. Therefore, in order to maintain the resistance of the 
oxygen gas sensing element at the predetermined value, oxygen must be 
pumped into the gas diffusion portion by operating the oxygen pump 
element. To this end, the pump current is caused to flow in the direction 
opposite to that when the air/fuel mixture is in the fuel-lean region. The 
value of the required pump current is proportional to the amounts of 
unburnt hydrocarbons and carbon monoxide in the exhaust gas. 
However, since the outer electrode of the oxygen pump element is exposed to 
the sensed atmosphere, the oxygen pump element does not have much oxygen 
available in the fuel-rich region and the linear relationship between pump 
current and A/F ratio applies only for A/F values of up to about 10. If it 
is necessary to effect A/F ratio measurement beyond this point in the 
fuel-rich region, atmospheric air is introduced to make contact with the 
outer electrode of the oxygen pump element to ensure that it has a 
sufficient amount of oxygen available for correct A/F ratio measurement. 
Therefore, whether the air/fuel mixture is in the fuel-lean or fuel-rich 
region, a linear relationship is maintained between the pump current and 
the A/F ratio by controlling the former in such a way that the output of 
the oxygen gas sensing element of the A/F ratio sensor is maintained at a 
predetermined constant level. Alternatively, the A/F ratio may be 
determined from the resistance of the oxygen gas sensing element with the 
pump current held constant. 
As described above, A/F ratio sensor of the present invention is composed 
of a box member and an oxygen gas sensing element formed in the box member 
by means of injecting and firing a suitable oxide material. The oxygen 
pump element provided by the box member and the encased oxygen gas sensing 
element are integrated into a perfectly unitary assembly. This means that 
the atmosphere around the oxygen gas sensing element is always the same as 
the atmosphere around the oxygen pump element and that there will be 
minimum delay in A/F ratio detection, even if fluctuations occur in the 
atmosphere inside of the box member.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
A preferred embodiment of an A/F ratio sensor of the present invention is 
hereunder described with reference to FIGS. 1 and 2, which are a partial 
cutaway view and an exploded view, respectively. 
The A/F ratio sensor of this embodiment includes a box member 2 and an 
oxygen gas sensing element 6 formed by injecting a suitable oxide material 
into the box member through diffusion limiting holes 4 and firing the same 
in situ. 
With reference to FIG. 2, the box portion 2 is formed by stacking a box 
forming member 8, a spacer 12, and a solid electrolyte plate 14. The box 
forming member 8, which has two diffusion limiting holes 4, measures 38.5 
mm long, 5 mm wide and 0.7 mm thick. The spacer 12 measures 38.5 mm long, 
5 mm wide and 80 microns thick, and has an opening 10 (2 mm long and 5 mm 
wide) which is to be filled with the oxide gas sensing element 6. The 
solid electrolyte plate 14 which serves as an oxygen pump element measures 
38.5 mm long, 5 mm wide and 0.7 mm thick. Both the box forming member 8 
and the solid electrolyte plate 14 are made of a ZrO.sub.2 -Y.sub.2 
O.sub.3 solid solution compound, and the spacer 12 is formed of Al.sub.2 
O.sub.3. The box forming member 8 need not be made of a ZrO.sub.2 -Y.sub.2 
O.sub.3 solid solution compound and may be formed of another suitable 
heat-resistant material such as Al.sub.2 O.sub.3. 
The solid electrolyte plate 14 is provided with a pair of electrodes 16 and 
18 and a heat generating element 20. The box forming member 8 is provided 
with one electrode 22 for the oxygen gas sensing element 6. The other 
electrode for the element 6 is in the form of an electrode 18 on the solid 
electrolyte plate 14. Accordingly, the electrode 18 serves not only as the 
other electrode for the oxygen gas sensing element 6, but also as one of 
the two electrodes for the oxygen pump element. 
An insulating Al.sub.2 O.sub.3 layer 24 is provided between electrode 16 
and the solid electrolyte plate 14, another insulating Al.sub.2 O.sub.3 
layer 26 is provided between the solid electrolyte plate 14 and the 
electrode 18, and a third insulating Al.sub.2 O.sub.3 layer 28 is provided 
between the electrode 18 and the heating element 20. An insulating 
Al.sub.2 O.sub.3 layer 30 is also disposed between the electrode 22 and 
the box forming member 8. The electrode 16 is provided with protective 
Al.sub.2 O.sub.3 layers 32 and 34, and the box forming member 8 is also 
provided with a protective Al.sub.2 O.sub.3 layer 36. The underside of the 
solid electrolyte plate 14 is provided with a fastening device 38 with 
which the A/F ratio sensor of the embodiment under discussion can be 
mounted on a metal fixture (not shown). 
The electrodes 16, 18, 22 and heating element 20 are connected to leads 40, 
42, 44 and 46 via through-holes or other suitable arrangement, as 
indicated by broken lines in FIG. 2. The electrode 18 is connected to the 
heating element 20 at about halfway along the length of the element 20 via 
a through-hole so that power applied to the element 20 can be used for 
driving the oxygen gas sensing element 6. If a voltage of 14 volts is 
applied to the heating element 20 which is connected to the electrode 18 
at the point shown in FIG. 2, a voltage of about 1 volt is supplied to the 
oxygen gas sensing element 6. 
The A/F ratio sensor of the embodiment being discussed can be produced by 
the following procedure: 
First, a mixture of 94 mol % ZrO.sub.2 and 6 mol % Y.sub.2 O.sub.3 is 
wet-ground for 45 hours to form a uniform blend. The blend is dried and 
then calcined at 1,380.degree. C. for 2 hours. The calcined product is 
wet-ground for 45 hours to obtain particles at least 80% of which have a 
size of about 2.5 microns or less. 
The resulting ZrO.sub.2 -Y.sub.2 O.sub.3 particles are mixed with solvents 
(e.g., methylethylketone and toluene) and binders (e.g., polyvinyl butyral 
and dibutyl phthalate), and the mixture is defoamed under vacuum to make a 
slurry, which is then worked into green sheets of the box forming member 8 
and the solid electrolyte plate 14. 
In the next step, a 2:1 mixture of platinum black and platinum sponge is 
mixed with a binder (Ethocel.TM.) and solvents (butyl Carbitol.TM. and 
xylene) to make a platinum paste. 
Using this platinum paste, electrodes and a heating element are formed on 
the green sheets in predetermined patterns (see FIG. 2) by a thick-film 
printing technique. At the same time, a spacer 12, insulation layers 24, 
26, 28, 30, and protective layers 32, 34 and 36 are formed by thick-film 
printing of separately prepared alumina pastes in the patterns shown in 
FIG. 2. The spacer 12 is formed of three coatings with a thickness of 30 
microns that are applied by a thick-film printing process. Each of the 
insulating layers 24, 26, 28 and 30 is formed by two coatings with a 
thickness of 15 microns that are applied by thick-film printing. The 
protective layer 36 is formed by three coatings with a thickness of 15 
microns that are applied by thick-film printing. Each of the protective 
layers 32 and 34 is formed of two coatings with a thickness of 15 microns 
and one coating with a thickness of 30 microns, all applied by thick-film 
printing. 
Subsequently, the two green sheets are compressed together, heated at 
300.degree. C. for 10 hours to remove the resinous component, and fired at 
1,520.degree. C. for 4 hours to make a box 2. 
A TiO.sub.2 paste from which the oxygen gas sensing element 6 is formed is 
prepared by the following procedures: 
A TiO.sub.2 powder is mixed with about 7 mol % chloroplatinic acid. After 
drying at 200.degree. C., the mix is calcined at 1,300.degree. C. for 2 
hours in a nitrogen atmosphere. The calcined product is ground in acetone 
for 40 hours to obtain particles at least 80% of which have a size of no 
less than 2.5 microns. To the particles, 2 mol % platinum black, 40 wt % 
methylethylketone, and 20 wt % toluene and added, and the respective 
components are mixed together for 8 hours. To the resulting mixture are 
added binders (2.5% polyvinylbutyral and 1.5% dibutylphthalate) and a 
solvent (40% butyl Carbitol.TM.), and the resulting mix is worked into a 
TiO.sub.2 paste. 
The TiO.sub.2 paste is injected under pressure into one of the two 
diffusion-limiting holes 4 in the box 2 until it reaches the peripheral 
edge of the other hole 4. The injected paste is dried and fired at 
1,200.degree. C. for 1 hour in atmospheric air to obtain the A/F ratio 
sensor of the embodiment being discussed. 
FIG. 3 is a graph showing the operating characteristics of the A/F ratio 
sensor of the present invention. In the graph, the characteristics of the 
sensor produced in accordance with the embodiment described above are 
indicated by the solid line. The characteristics shown in FIG. 3 are 
expressed in terms of the relationship between the A/F ratio of the 
atmosphere being sensed and the pump current I.sub.P (the current flowing 
between the leads 40 and 42) for the case where the oxygen gas sensing 
element 6 is controlled to produce a constant output. 
As is clear from FIG. 3, the A/F ratio sensor of the embodiment under 
discussion is capable of A/F ratio measurement over a broad operating 
range, including both the fuel-rich region and the fuel-lean region and 
extending to atmospheric air. It will be readily appreciated by those 
skilled in the art that the gradient of the I.sub.P vs. A/F ratio profile 
will be changed if the diffusion-limiting effect of the holes 4 is 
modified by changing their number and/or diameter. If the 
diffusion-limiting effect of the holes 4 is increased, the slope of the 
I.sub.P vs. A/F ratio profile becomes less steep (as indicated by a dashed 
line), and it becomes more steep in the opposite case (as indicated by a 
broken line). 
The oxygen gas sensing element 6 of the A/F ratio sensor of the embodiment 
under discussion is formed by injecting a TiO.sub.2 paste into the 
preliminarily constructed box 2 and firing the same in situ. Therefore, 
the element 6 is completely integral with the oxygen pump element, which 
is part of the box 2. The sensor has a very good response to variations in 
A/F ratio and is capable of carrying out A/F ratio detection more rapidly 
than prior art systems. In addition, the inventive A/F ratio sensor can be 
manufactured easily and with a very high yield. 
The A/F ratio sensor of the present invention is composed of a box member 
formed preliminarily and an oxygen gas sensing element formed by injecting 
a suitable oxide material into the box member and firing the same in situ. 
With this arrangement, the oxygen gas sensing element and the oxygen pump 
element forming part of the box member provide a perfectly unitary 
assembly which ensures good response to variations in A/F ratio of the 
sensed atmosphere. As a further advantage, the sensor of the present 
invention can be manufactured easily and with a high yield, thereby 
contributing to the conservation of resources. 
Using the A/F ratio sensor of the present invention, A/F ratio control of 
an internal combustion engine can be accomplished over a broad operating 
range including both the fuel-lean and fuel-rich regions. An additional 
advantages is that the sensor does not require a reference oxygen source 
and can be operated with a simple construction. Due to the absence of a 
reference oxygen source, the sensor provides a more reliable performance 
since there can be no fluctuations due to variations in the oxygen partial 
pressure of the reference oxygen source.