CN102183565A - Sensor element with improved air inlet - Google Patents
Sensor element with improved air inlet Download PDFInfo
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- CN102183565A CN102183565A CN201010621971XA CN201010621971A CN102183565A CN 102183565 A CN102183565 A CN 102183565A CN 201010621971X A CN201010621971X A CN 201010621971XA CN 201010621971 A CN201010621971 A CN 201010621971A CN 102183565 A CN102183565 A CN 102183565A
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Abstract
The invention provides a sensor element with improved air inlet. The element (110) has an electrode (124) separated from a measurement gas chamber (114) by a layer of a laminated structure (112) and connected to the measurement gas chamber by a gas access path (128). The gas access path is provided with a gas passage opening (130) comprising two cylindrical or conical zones (148, 152) having different diameters. Maximum diameter of the gas passage opening is at a level of an upper surface (116) of the laminated structure. The electrode is placed in an electrode cavity (126). An independent claim is also included for a method for manufacturing a sensor element.
Description
Technical field
The present invention relates to the sensor element that air inlet is improved.
Background technology
Known from prior art to be used for the sensor element that the characteristic to the gas of measurement gas chamber detects that described sensor element is based upon on the basis of use of one or more solid electrolyte.Solid electrolyte is the especially solid of pottery of solid, and described solid can conduct specific ionic species such as oxonium ion.This specific character occurs on ultimate temperature or temperature range limit usually.The typical solid electrolytic condenser is the stable zirconia of yttrium or the metal oxide of other kind in this way, is the metal oxide that mixes under typical situation.Such sensor element detects such as characteristic physics and/or chemistry that is used for the gas of measurement gas chamber.Typical example be in the gas of measurement gas chamber at least a gas componant qualitatively and/or quantitative proof.Especially this gas componant can be an oxygen.But also can prove other gas componant in principle.The share of gas componant is such as the number percent share that can be used as the gas in the measurement gas chamber or also detect as the partial pressure of gas.The example of such sensor element is such as the illustrated so-called lambda sensor in " sensor in the automobile (the Sensoren im Kraftfahrzeug) " that published in 2007 the 154th to 159 page in Robert Bosch company limited.Such lambda sensor is used for proving oxygen and such as the gas exhaust piping that is used in internal combustion engine or be used in the combustion apparatus.Lambda sensor is such as so-called transition sensor or also known as so-called broadband sensor.Such as can from the energy nernst voltage, inferring air coefficient λ directly or indirectly.Scheme or additional project as an alternative are such as inferring the oxygen share from the pump electric current that flows through solid electrolyte.
For many sensor elements by prior art, such as being provided with two or also can be provided with under the situation of more a plurality of electrodes, at least one arrangement of electrodes in the described electrode that is to say by at least one layer of described layer structure to cover in the inside of the layer structure of pottery.In many cases, among the so-called air admission hole (GZL) of this inner electrode by passing described floor structure at least in part and measurement gas chamber are in and are connected.Described connection typically comprises diffusion impervious layer, and described diffusion impervious layer is arranged in the outside of described air admission hole and restriction oxygen is followed the electrode place that flow to described inside.Described air admission hole typically has the shape of cylindricality, and the shape of this cylindricality has unified diameter.Although this is simpler structure and design proposal typically, air admission hole must satisfy a large amount of aspect its characteristic and the requirement aspect its manufacturability.Therefore need the very high diameter of air admission hole in many cases, be used to regulate unlimited air inlet, thereby air admission hole itself is not as the elements act that hinders diffusion.Such as for the modern more broadband sensor with temperature jump protective seam (TSP), the air admission hole that has greater than 0.45 millimeter diameter is essential, is used to make air inlet to keep opening wide.The damage of sensor element can appear when making air admission hole in addition.Therefore for common manufacture method, before standing final sintering process, structure typically gets out air admission hole in the layer structure at described pottery at layer.But in this boring method physical damage or pollution can appear.Therefore, the diffusion impervious layer such as the inside of layer structure can be damaged.Described TSP applies by means of the plasma spraying of atmosphere later on usually.In typical case, this point should guarantee the coating of sensor end face thus to carry out with respect to the angle of 60 ° of sensor surfaces.Because jet angle, TSP may enter into air admission hole, and described TSP can make dirty or even stop up diffusion impervious layer and may obviously improve diffusional resistance thus.
Summary of the invention
Therefore, task of the present invention is, proposes a kind of sensor element and a kind of method that is used to make sensor element, and described sensor element and method have been avoided the known sensor element and the shortcoming of manufacture method at least to a great extent.The sensor element that is proposed especially can be made by method of the present invention according to a kind of, and the method that is proposed especially can be used for making by sensor element of the present invention.Therefore, in principle can be with reference to the explanation of the possible design proposal of described sensor element about the possible design proposal of described method, vice versa.But also can use in principle other manufacture method and/or make the sensor element of other kind.
The sensor element that is proposed is used for detecting at least a characteristic of the gas of measurement gas chamber.As described above the same, described at least a characteristic especially can be characteristic physics and/or chemistry, especially the share of the gas componant in the gas, such as the oxygen share, this share can be tried to achieve and such as trying to achieve with number percent or as partial pressure in qualitative and/or quantitative mode.About the possible design proposal of these sensor elements, in principle can be with reference to the above explanation of prior art.Also can consider other design proposal in principle.Described sensor element especially can be used in the gas exhaust piping of internal combustion engine, in the gas exhaust piping that is used in the internal combustion engine in the automotive field.Also can consider other use field, such as being used in the combustion apparatus or being used in the process control.
The sensor element that is proposed comprises at least one layer structure, and this layer structure then has the solid electrolyte that at least one first electrode, at least one second electrode and at least one couple together described first electrode and second electrode.Layer structure typically refers to a kind of element at this, and this element has at least two stacked up and down layer and/or layer planes.Described layer is in this mode that can distinguish that can cause by the manufacturing of layer structure and/or made by different materials and/or starting material.Especially described layer structure can completely or partially be configured to the layer structure of pottery.Solid electrolyte as described abovely equally is meant a kind of solid at this, and this solid has the characteristic of conducting ion at least concerning specific ion ratio such as oxonium ion from ultimate temperature given in advance.Especially described solid electrolyte can comprise the metal oxide that metal oxide especially mixes, such as the stable zirconia of yttrium.Also can use other solid electrolyte material.Electrode typically refers to a kind of element, and this element can so contact solid electrolyte, thereby can keep electric current by described solid electrolyte and described electrode.Correspondingly, described electrode can comprise a kind of element, ion can be installed on this element in the solid electrolyte and/or ion can be drawn off from solid electrolyte.In typical case, described electrode comprises noble metal electrode, this noble metal electrode such as can be used as that metal-ceramic-electrode is applied on the solid electrolyte or can be in other mode and solid electrolyte be connected among.Typical electrode material is platinum-metallic ceramics-electrode.But the noble metal that also can use other in principle is also known from prior art such as gold and/or palladium and other noble metal.
Described layer texture ratio is as can so constituting, make described first electrode and described second arrangement of electrodes in the side opposite each other of described solid electrolyte, such as being arranged in the opposite each other side of solid electrolyte layer such as solid electrolyte film or solid electrolyte cream.But scheme or additional project as an alternative, described at least two electrodes also can be arranged in an identical side of solid electrolyte.Preferred common at least one battery that forms of electrode and solid electrolyte.Described sensor element can be configured to the sensor element of monocell, has only single battery, and this battery is such as can or also being used as the pump battery as this special battery (Nernstzelle) of energy.But, scheme as an alternative, described sensor element also can be configured to the sensor element of many batteries, and this sensor element has a plurality of such batteries, and these batteries also can be realized different functions.Such as can be provided with at least one pump battery and as following at least one can be set also will exemplarily illustrating extraly can this special battery.
At least one electrode in described at least two electrodes is also referred to as second electrode (these electrodes are not weighted or sort) below and is arranged in the inside of described layer structure by the present invention at this.In other words, described second electrode separates with the measurement gas chamber by at least one floor of described floor structure.Especially described at least one layer can be at least one solid electrolyte layer.Described at least one second electrode so is arranged in the darker layer plane of described layer structure, just away from described solid electrolyte in the layer plane on the surface of measurement gas chamber.Described at least one other electrode, just can be arranged in the darker layer plane equally according to described at least one first electrode of employed term here, but above also can being arranged in, that is to say such as be arranged in described floor structure on the surface of measurement gas chamber.Can be configured to external electrode such as described first electrode, and such as can be only protective seam by ventilative porous separate with described measurement gas chamber and in addition such as being among the direct gas exchange with the measurement gas chamber.Can consider different design proposals.
Described at least one second electrode is connected with the measurement gas chamber by at least one air inlet path at this.The air inlet path generally is meant a kind of element at this, can carry out exchange gas between the measurement gas chamber and second electrode by this element, wherein can guarantee gas exchange completely or also can only guarantee the exchange of each gas componant.Can comprise one or more boring, passage, opening or similar structures such as described air inlet path.Described air inlet path can be configured to especially to guarantee that gas is followed from the measurement gas chamber flows and/or be diffused into second electrode again or following in opposite direction flowed and/or diffusion again, flows and/or diffusion again such as following of oxygen.Described air inlet path has at least one air admission hole in layer structure.Air admission hole is meant a kind of opening at this, and this opening extends through at least one layer plane of described layer structure, especially passes described at least one layer, and this floor separates described at least one second electrode with the measurement gas chamber.Air admission hole can have xsect arbitrarily in principle, such as the xsect or the polygonal xsect of circle.Air admission hole especially can extend perpendicular to the layer plane of described layer structure and such as the profile that can have cylindricality, such as columniform profile.
Propose at this by the present invention, so construct described air admission hole, make it have at least two zones that diameter is different.Diameter generally is meant the quantification of transverse extension of the xsect of described air admission hole at this.If air admission hole is such as having circular xsect, so described diameter also is meant this diameter of a circle.If there is other cross-sectional geometry, so described diameter just has the diameter of a circle with in esse xsect area identical such as being meant equivalent diameter.Described at least two zones are such as being adjacent to each other directly or indirectly along the axis of air admission hole or occupying different sections on this root axis.Can be provided with two or also more a plurality of zones can be set.
Described air admission hole can import in the surface of described layer structure, such as importing in the surface of measurement gas chamber.Air admission hole especially can have its maximum diameter on this surface.The diameter of air admission hole can be from this surface towards layer structure such as continuously and/or the sublevel terrace land reduce.Such as reducing of branch ladder can so be set, thereby at first following first area with first diameter from the beginning of described surface, that is to say directly or indirectly in the inside of described layer structure connecting at least one second area on this first area after transitional region, described second area has second diameter littler than described first diameter.In this case, that is to say that air admission hole is such as the profile that can have the branch ladder.That is to say that described at least two zones are taper, cylindricality such as being configured to, rounding or otherwise constitute.
Said at least two zones can relative to each other be arranged with one heart or coaxially, that is to say such as having the same axis of symmetry or drilling axis.But not necessarily be exactly this situation.Such as preferably, described at least two zones relative to each other are not or not to arrange coaxially with one heart in other words.Therefore described at least two zones such as can relative to each other arranging with setovering.Being arranged in this and being meant a kind of arrangement of biasing, one or more the regional central axis in zone described in this arrangement or the axis of symmetry are not to arrange with one or more the regional central axis or the axis of symmetry in other zone of described air admission hole.Can carry out along direction such as this biasing perpendicular to the elongation of described air admission hole.
Described sensor element such as can have parallel with its longitudinal tensile strain and with the parallel plane longitudinal tensile strain axis of layer structure.Extend in the measurement gas chamber under the situation of encapsulation or not encapsulation such as the direction of described sensor element along this longitudinal tensile strain axis.The direction towards the measurement gas chamber of described floor structure is arranged in the end of farthest such as being called end face.Especially the layout that can so setover makes describedly have bigger diameter and arrange to such an extent that the first area on more close surface is compared from described end face skew with described at least one second area with less diameter.In other words, such as the central axis of described first area or the axis of symmetry longitudinally prolonging direction be arranged in the axis of the second area of depths more or the axis of symmetry than in the layer structure of described sensor element more away from described end face.
The arrangement of this biasing applies at least one temperature jump protective seam obliquely such as helping, and the material of described temperature jump protective seam can not enter into the inside of described air admission hole.Especially a kind of spraying process that is used to apply described at least one temperature jump protective seam be can use, plasma spraying or plasma spraying method used such as that is to say from a direction that has departed from the normal of layer structure with the angle that tilts with respect to layer plane.Such as can so using spraying process, thereby also described temperature jump protective seam is applied on the described end face.The arrangement of the biasing in described at least two zones can prevent the intrusion of the material of temperature jump protective seam effectively, for this arrangement such as described first area than described at least one be in more that the second area with less diameter of depths departs from described end face more.
Such as the axis of described first area or the axis of symmetry (such as drilling axis and/or milling axis) with respect to the axis of described second area or the axis of symmetry such as be offset 50 to 700 microns from described end face, preferably be offset the 80-500 micron and especially preferably be offset 115 to 420 microns.
Described air admission hole is thus such as can have first diameter on described surface, wherein air admission hole has at least one first area with described first diameter and at least one and has the second area of at least a second diameter, and wherein said second area can be arranged in more the depths in described layer structure and wherein said second diameter can be less than described first diameter.That described first area and/or described second area and/or other the zone that may exist can be configured to cylindricality or taper.
Described air admission hole especially can be configured to the structure of branch ladder, is provided with between described first area and second area especially that at least one is stair-stepping or be configured to the transitional region of convex shoulder.Stair-stepping transitional region is extended at the axis that this is meant that the transitional region with at least one smooth surface from first diameter to second diameter, described surface are substantially perpendicular to described air admission hole.Convex shoulder is meant the transitional region with crooked or smooth surface, and wherein described surface can preferably not be vertically such as extending with the angle that is between 80 ° and 10 ° with respect to the axis of described air admission hole under latter event.Because equally described as explained above at least one first area and described at least one second area also can be are relative to each other arranged with setovering, so that described convex shoulder also can correspondingly be configured to is asymmetrical.
If such as there being at least two zones, such as at least two zones with profile cylindricality and/or taper, wherein said at least two zones have at least a first diameter or at least a second diameter, so described first diameter such as can than described second diameter big factor k.This factor k especially can be preferably greater than 1.8 greater than 1.2, and especially preferably is at least 2.0.Described factor k especially can be in 1.2 to 5 the scope, preferably is in 1.8 to 4.0 the scope and especially preferably is in 2.0 to 3.0 the scope.
If be provided with at least two zones with just at least a first diameter of at least two kinds of diameters and at least a second diameter, wherein said first diameter is greater than described second diameter, so described first diameter be such as being in 0.15 millimeter to 1.0 millimeters the scope, especially is in 0.4 millimeter to 0.8 millimeter the scope and especially preferably is in 0.5 millimeter to 0.75 millimeter the scope.Described second diameter especially can be in 0.1 millimeter to 0.5 millimeter the scope, especially is in 0.2 millimeter to 0.4 millimeter the scope and is preferably 0.25 millimeter especially.Can be 0.6 millimeter or 0.8 millimeter or 1.0 millimeters such as described first diameter.Described second diameter is such as being 0.25 millimeter.Can be 0.25 millimeter for 0.8 millimeter and second diameter such as described first diameter.
Described at least one second electrode especially can be arranged in the electrode cavity.This electrode cavity can be arranged in the inside of described layer structure and such as the cavity that can be configured to open wide.Scheme as an alternative, this electrode cavity also can be completely or partially with ventilative porous materials such as filling with ventilative aluminium oxide.Described electrode cavity especially can be connected with described air admission hole by at least one diffusion impervious layer.In this case, the air inlet path that leads to described at least one second electrode just air admission hole comprises described diffusion impervious layer or passage and described electrode cavity, has wherein arranged diffusion impervious layer in described passage.Diffusion impervious layer generally is meant a kind of element at this, and this element stops or slows down gas at least and directly follow from air admission hole and flow to the electrode cavity.Diffusion impervious layer thereby be a kind of element, this element provides high resistance to flow, and phase inverse gas or gas componant can spread by described diffusion impervious layer with comparalive ease.Described diffusion impervious layer is such as the element of the pottery that can comprise porous, especially multiporous aluminium oxide.If be provided with such diffusion impervious layer, preferred so especially this diffusion impervious layer is configured to respect to contracting behind the described air admission hole.After the diffusion impervious layer that contracts be meant a kind of diffusion impervious layer at this, this diffusion impervious layer not directly with not described air admission hole in abutting connection with but with respect to this air admission hole by post-tensioning.Can be arranged in passage or other the opening such as described diffusion impervious layer, described opening is the ingredient in air inlet path, but wherein said diffusion impervious layer does not have directly to be stretched over this passage in other words on the transitional region between this opening and the described air admission hole always, but stops separatedly with this transitional region.Such as described diffusion impervious layer with leave at least 0.05 millimeter of this transitional region, preferred at least 0.1 millimeter or even at least 0.2 millimeter spacing stop.The advantage of the diffusion impervious layer of that contract after this or post-tensioning is also will explaining in detail as following, this diffusion impervious layer can not be damaged when making air admission hole, otherwise may occur the pollution of diffusion impervious layer thus or unevenness may occur thus when regulating the limiting current of determining by the width of diffusion impervious layer.In addition, the design proposal of being mentioned is especially being improved operating continuous service stability aspect the erosion (Versottung) that causes by the particle from dirt ash (such as putty) and/or metal oxide.
In another aspect of the present invention, sensor element that a kind of at least a characteristic that is used for making to the gas of measurement gas chamber detects is proposed especially by the method for the sensor element of one or more design proposals in the top illustrated design proposal.For described method, make a kind of layer of structure, this layer structure has the solid electrolyte that at least one first electrode, at least one second electrode and at least one couple together described first electrode and second electrode.Can make by the layer technology of using thin film technique and/or thick film technology and/or other pottery such as this layer structure.Described second electrode especially separates with the measurement gas chamber by at least one floor of solid electrolyte at this at least one floor by described floor structure.Described second electrode is connected with the measurement gas chamber by at least one air inlet path, and wherein the air inlet path has at least one air admission hole in described layer structure.So construct described air admission hole at this according to the present invention, make it have at least two zones that diameter is different.For other design proposal, can be with reference to top explanation.
Being manufactured on this and can carrying out in a different manner of air admission hole.Especially preferredly be under the situation of the method for milling of boring method that uses at least a machinery and/or at least a machinery, to produce described air admission hole.
If as top the explanation, be provided with at least two zones, so especially can use boring method with at least one step bit.Step bit is meant a kind of drill bit at this, and this drill bit has at least two diameter boring sections different, that relative to each other arrange to biasing in the axial direction.Between these boring sections, can construct transitional region such as convex shoulder.But be to use the boring method of step bit can only be used in the zone of relative to each other coaxial or concentric orientation usually.For the zone of relative to each other biasing, be used to make described second area such as using multiple boring to be used to make described first area and at least one second boring such as at least one first boring, wherein drilling axis can be relative to each other layout with setovering.As the replacement scheme or the additional project of the boring method of machinery, also can use the method for milling of machinery.Such method for milling also can be used to make the relative to each other zone of biasing, wherein can use a unique milling step, perhaps also can use a plurality of milling steps, such as the independent milling step that is used for described at least one first area and is used for described at least one second area.
But also can use boring method and/or the punching method of at least a other method such as laser drill method or other type.Can consider different design proposals.
Described at least a boring method especially can use in the moment of making, in the also not sclerosis or also not sclerosis fully of this constantly described layer structure.Can use constantly at one such as described boring method, be in the green state and/or be in brown base (Braunling) state in this moment described layer structure, that is to say also not sclerosis fully, wherein real being hardened at least one rearmounted Temperature Treatment step made in the just so-called sintering step.
Sensor element that is proposed and the manufacture method that is proposed have a large amount of advantages with respect to known sensor element and known method.Such as, described air admission hole with the different zone of diameter especially divides the air admission hole of ladder to improve the manufacturability and the function of sensor element in principle such as the air admission hole of minute ladder with setovering.This especially advantageously becomes obvious for the broadband sensor element.Especially can make and have big diameter such as the air admission hole that has greater than 0.45 millimeter diameter.Especially the air inlet that can regulate or guarantee to open wide in this way.But at the air admission hole that does not divide ladder or do not realize existing such danger in principle at this under the situation by design proposal of the present invention of air admission hole, promptly described at least one diffusion impervious layer is damaged such as being holed when making air admission hole.Can cause the extra diffusion (Streuung) of limiting current thus.In addition for this traditional method, by post-tensioning be not directly and the diffusion impervious layer of air admission hole adjacency may be guaranteed no longer fully.But directly exist such danger sensor element in service in principle with the diffusion impervious layer of described air admission hole adjacency for such, promptly diffusion impervious layer is because of contaminated from the foul of measurement gas chamber, and this is typically called erosion.Be subjected to material limiting current by diffusion impervious layer thus and can change again, described limiting current may depend on the diffusion property of described diffusion impervious layer fatefully.But, can so construct described air admission hole by the present invention at this, make it especially in the zone of diffusion impervious layer, have littler diameter, thereby can realize the diffusion impervious layer of post-tensioning as beforely.Not only can avoid damage dangerous of diffusion impervious layer thus but also can avoid the danger that is etched of diffusion impervious layer.
In addition, described sensor element can have at least one temperature jump protective seam (TSP).Described at least one temperature jump protective seam such as can be arranged in described floor structure at least one towards on the surface of measurement gas chamber and/or be arranged on the end face of described floor structure.Such temperature jump protective seam is such as obtain explanation in DE 10 2,004 054 014 A1.Described temperature jump protective seam typically has two or more a plurality of layer, and described layer improves the temperature jump performance of described layer structure and forms such as the crackle that prevents or reduce at least in the ceramic body.The design proposal of the air admission hole by having different-diameter especially divides the design proposal of ladder can prevent this point such as the design proposal of the branch ladder of air admission hole with setovering, and promptly the material of temperature jump protective seam especially enters into the inside of described layer structure towards diffusion impervious layer.As top the explanation, such as can after the sintering process of layer structure, applying described temperature jump protective seam.Such as using spraying process, the optional painting method with other of described spraying process is used in combination as painting method.The design proposal of the branch ladder in the zone that especially has biasing by described air admission hole can prevent the pollution of darker layer plane, and this pollution can cause the reduction of limiting current and extra diffusion.The material that especially can prevent the temperature jump protective seam arrives diffusion impervious layer.
Utilize step bit and/or milling cutter especially can make a kind of air admission hole, the diameter of its underpart is such as being 0.25 millimeter, and this is corresponding to the diameter of common air admission hole.That is to say that in the zone on top at least one can be set has the second area of bigger diameter such as the diameter of 0.6 millimeter, 0.8 millimeter or 1.0 millimeters in the zone on surface.In this way such as the air inlet that also can after applying, guarantee in the zone on described surface to open wide with the temperature jump protective seam.Because air admission hole design former thereby suppressed the temperature jump protective layer material enter into preferred narrower part below the air admission hole when applying and/or make the temperature jump protective seam, this coating and/or manufacturing are such as carrying out after having bored air admission hole.In a word, the air admission hole design that is proposed especially biasing ground divides the design of ladder to reduce the diffusion of limiting current, has improved the resistance to fouling of diffusion impervious layer and has improved continuous service stability.
Description of drawings
Embodiments of the invention are shown in the drawings and explain in detail in the following description.Wherein:
Fig. 1 is by sensor element of the present invention with by first embodiment of manufacture method of the present invention; And
Fig. 2 to 4 is by the different view of second embodiment of the sensor element of the air admission hole of branch ladder of the present invention with having biasing.
Embodiment
Figure 1 illustrates first embodiment by sensor element 110 of the present invention.Also should the embodiment by manufacture method of the present invention of such sensor element 110 be made an explanation by means of this synoptic diagram.Described sensor element 110 has layer structure 112, and this layer structure 112 can be made with the film process and/or the thick-film methods of pottery.This floor structure 112 comprises towards the surface 116 of measurement gas chamber 114, has arranged first electrode 118 on this surface 116.In embodiment illustrated in fig. 1, described first electrode 118 is such as being configured to ring-type, because the sensor element among Fig. 1 110 can major part have rotational symmetric structure.But also can consider other design proposal.Described first electrode 118 is such as separating with measurement gas chamber 114 by ventilative protective seam 120.In addition, described layer structure 112 has one or more solid electrolyte 122 in shown embodiment.Can be used as solid electrolyte film and/or make such as these solid electrolytes 122 by means of thick film technology.Can comprise the stable zirconia of yttrium (YSZ) such as described solid electrolyte 122.
In addition, described layer structure 112 comprises at least one second electrode 124 at described solid electrolyte 122 with described first electrode, 118 opposed sides in by the embodiment of Fig. 1.This second electrode 124 is such as arranging and be configured to multimember structure in shown embodiment in rotational symmetric mode equally again.Described second electrode 124 is arranged in the electrode cavity 126.This electrode cavity 126 is the parts in air inlet path 128, described second electrode 124 by described air inlet path 128 and measurement gas chamber 114 be in be connected among.As one other component, described air inlet path 128 comprises air admission hole 130, this air admission hole 130 perpendicular to the layer plane of described layer structure 112 from described surperficial 116 inside that extend to layer structure 112.Described electrode cavity 126 is such as can annularly air admission hole 130 being surrounded.Also can consider other design proposal.Arranged passage 132 between described air admission hole 130 and electrode cavity 126, this passage 132 is the ingredient in air inlet path 128 equally.Arranged diffusion impervious layer 134 in this passage 132, this diffusion impervious layer 134 reduces or even stops gas to be followed from measurement gas chamber 114 to flow into the electrode cavity 126 and only can allow diffusion.Can regulate the limiting current of the pump battery 136 that comprises described first electrode 118, second electrode 124 and solid electrolyte 122 by this diffusion impervious layer 134.
In addition, described sensor element 110 comprises air reference channel 138 in shown embodiment, and this air reference channel 138 is such as being connected with the environmental facies with known oxygen content.In this air reference channel 138 such as arranging reference electrode 140.By this reference electrode 140 and described second electrode 124 or the other potential electrode that is arranged in the electrode cavity 126, such as the pump electric current that can so regulate by described pump battery 136, make in described electrode cavity 126, to exist condition λ=1 or other known composition.In addition, described sensor element 110 can comprise at least one heating element 142, can be with the adjustment of described solid electrolyte 122 and/or whole layer structure 112 or its parts to working temperature by means of this heating element 142.Described heating element 142 also can comprise one or more insulation course 144.
Described sensor element 110 is configured to the sensor element of double cell thus in embodiment illustrated in fig. 1, this sensor element also comprises except pump battery 136 and comprising reference electrode 140, solid electrolyte 122 and second electrode 124 and/or the other measurement battery 146 that is arranged in the potential electrode in the electrode cavity 126.Described sensor element 110 such as can be configured to broadband sensor and in this regard such as can corresponding to known be the sensor element of LSU4.9 such as model at commercial obtainable sensor element 110.This can apply temperature jump protective seam (TSP) on external surperficial 116, is used to avoid layer structure 112 because the damage that the temperature jump load causes.As can be seen, described air admission hole 130 has a plurality of zones by the present invention among this external Fig. 1.Therefore in shown embodiment, 116 beginnings at first are provided with and have first diameter d from the surface
1 First area 148, after the transitional region 150 at the convex shoulder shape on this first area 148, connecting and have diameter d
2Second area 152.Described first area 148 and second area 152 exemplarily are configured to the zone of cylindricality respectively in shown embodiment.Also can consider other design proposal.Described transitional region 150 is such as being configured to taper.This second area 152 is such as also finishing up with taper on its end or being provided with the tip.Scheme also it is contemplated that the flat design proposal of this end of described second area 152 as an alternative.Scheme as an alternative, the extra zone of optional again consideration.Described first diameter d
1Construct greater than described second diameter d at this
2Such as diameter d
1Can be 0.55 millimeter, 0.65 millimeter or 0.75 millimeter.Described second area 152 is such as the diameter d that can have 0.25,0.3 or 0.35
2
In addition, as can be as seen from Figure 1, described diffusion impervious layer 132 with respect to air admission hole 130 by post-tensioning, contract after that is to say and not directly in passage 132 with air admission hole 130 adjacency.Avoided diffusion impervious layer 134 to weather thus actually.The less diameter d of the second area 152 by being used for air admission hole 130
2Selection, such as preventing this point, promptly diffusion impervious layer 134 is holed when making air admission hole 130.Keep described thus by the diffusion impervious layer 134 of post-tensioning.Can avoid the damage of diffusion impervious layer 134 thus, this damage can cause the diffusion of limiting current here.In addition, described transitional region 150 also forms and captures the highland, and this capture highland can prevent that the material of temperature jump protective seam from entering into diffusion impervious layer 134 places.This also reduces to produce active influence to limiting current diffusion.For making air admission hole 130, such as using step bit 154.Described step bit 154 has diameter d such as having
1The first boring section 156 and have diameter d
2The second boring section 158 and corresponding transitional region 160, this transitional region 160 can be corresponding to transitional region 150.Can prevent effectively that at this heater insulation layer 144 from being holed.
Second embodiment by sensor element 110 of the present invention has been shown in Fig. 2 to 4.Show the view that is similar to Fig. 1 at this Fig. 2, opposite Fig. 3 shows the detailed view of air admission hole 130 and the microscopical micro-synoptic diagram that passes through that Fig. 4 shows intercepting part shown in Figure 3.This sensor element 110 is basically corresponding to the design proposal of pressing Fig. 1, thereby the top explanation about this Fig. 1 of reference to a great extent for the 26S Proteasome Structure and Function of each element.But, with by the design proposal of Fig. 1 different be that described air admission hole 130 is configured to divide the structure of ladder with setovering in the embodiment of Fig. 2 to 4.Described air admission hole 130 has two zones 148,152 again in shown embodiment, wherein said first area 148 has first diameter of phi
1And described second area 152 has second diameter of phi
2Can be 600 to 1000 microns such as described first diameter.Described second diameter is such as being 150 to 300 microns.Described regional 148 and 152 arrange from the nearest seamed edge of the end face 166 of sensor element 110 such as the numerical value δ that can relative to each other setover, this numerical value δ is such as can be greater than 5 microns and less than 70 microns.The layer thickness d of described solid electrolyte 122 preferably is at least 320 microns such as film thickness.Described two zones 148 and 152 have respectively first axle 162 in other words second axis 164 such as drilling axis or milling axis.These axis 162 and 164 are such as the offset value delta of can relative to each other having setovered, and this offset value delta is such as being 115 microns to 420 microns.This offset value delta be such as can so finishing, make distance that the axis 162 of described first area 148 leaves end face 166 than described second axis 164 far away the numerical value Δ.
Described regional 148 and 152 manufacturing can be carried out in a different manner.Such as using boring separately, described boring has the relative to each other drilling axis of biasing.But, scheme or additional project as an alternative, described regional 148 and 152 also can be by other method such as making by one or more method for milling.
Unshowned temperature jump protective seam 168 applies described sensor element 110 among Fig. 1 to 3 such as being used in, and this is such as carrying out after sintering process.At this such as using spraying process such as plasma spraying.This spraying preferably is not perpendicular to surface 116 and carries out.In Fig. 3, schematically show the spraying direction and represent with Reference numeral 170.Such as can so selecting this spraying direction 170, thereby also come to apply with temperature jump protective seam 168 at least in part to end face 166.Figure 4 illustrates the micrograph of the intercepting part shown in Figure 3 of sensor element 110.In addition, exemplarily indicated size at this.From this Fig. 4 as can be seen; for spraying direction 170 shown in Figure 3, do not have the material of temperature jump protective seam 168 or only this material of minute quantity can arrive in the described second area 152 and especially arrive lead to the opening part of diffusion impervious layer 134 there.
Claims (13)
1. be used for the sensor element (110) that at least a characteristic to the gas of measurement gas chamber (114) detects, comprise a layer structure (112), this layer structure (112) has at least one first electrode (118), the solid electrolyte (122) that at least one second electrode (124) and at least one couple together described first electrode (118) and described second electrode (124), wherein, described second electrode (124) separates with described measurement gas chamber (114) by at least one floor of described floor structure (112), wherein, described second electrode (124) is connected with described measurement gas chamber (114) by at least one air inlet path (128), wherein, described air inlet path (128) has at least one air admission hole (130) in described layer structure (112), wherein, described air admission hole (130) has at least two zones (148 that diameter is different, 152).
2. by last the described sensor element of claim (110), wherein, described air admission hole (130) imports in the surface (116) of described layer structure (112).
3. by last the described sensor element of claim (110), wherein, described air admission hole (130) has maximum diameter on described surface (116).
4. by each described sensor element (110) in preceding two claims, wherein, described air admission hole (130) has first diameter on described surface (116), wherein, described air admission hole (130) has at least one first area with described first diameter (148) and at least one has the second area (152) of at least a second diameter, wherein, described second area (152) is arranged deeply than described first area (148) in described layer structure (112), and wherein, described second diameter is less than described first diameter.
5. by last the described sensor element of claim (110), wherein, that described first area (148) and/or described second area (152) are configured to cylindricality or taper.
6. by each described sensor element (110) in preceding two claims, wherein, described air admission hole (130) is configured to the branch ladder, has between described first area (148) and described second area (152) especially that at least one is stair-stepping or be configured to the transitional region (150) of convex shoulder.
7. by each described sensor element (110) in the first three items claim, wherein, described first area (148) and/or described second area (152) are arranged with relative to each other setovering.
8. by each described sensor element (110) in the aforementioned claim, wherein, described air admission hole (130) has at least one first area with at least a first diameter (148) and at least one has the second area (152) of at least a second diameter, wherein, described first diameter than described second diameter big factor k, wherein, this factor k is greater than 1.2, be preferably greater than 1.8, and especially preferably be at least 2.0.
9. by last the described sensor element of claim (110), wherein, described factor k is in 1.2 to 5 the scope, especially is in 1.8 to 4.0 the scope, and especially preferably is in 2.0 to 3.0 the scope.
10. by each described sensor element (110) in the aforementioned claim, wherein, described air admission hole (130) has at least one first area with at least a first diameter (148) and at least one has the second area (152) of at least a second diameter, wherein, described first diameter is greater than described second diameter, wherein, described first diameter is in 0.15 millimeter to 1.0 millimeters the scope, especially be in 0.4 millimeter to 0.8 millimeter the scope, and especially preferably be in 0.55 millimeter to 0.75 millimeter the scope, and wherein, described second diameter is in 0.1 millimeter to 0.5 millimeter the scope, especially be in 0.2 millimeter to 0.4 millimeter the scope, and be preferably 0.25 millimeter especially.
11. by each described sensor element (110) in the aforementioned claim, wherein, described second electrode (124) is arranged in the electrode cavity (126), wherein, described electrode cavity (126) is connected with described air admission hole (130) by at least one diffusion impervious layer (134), wherein, described diffusion impervious layer (134) contracts after with respect to described air admission hole (130).
Be used for sensor element (110) that at least a characteristic to the gas of measurement gas chamber (114) detects in particular for making method 12. be used for making by each described sensor element (110) of aforementioned claim, wherein, make layer structure (112), this layer structure (112) has at least one first electrode (118), the solid electrolyte (122) that at least one second electrode (124) and at least one couple together described first electrode (118) and described second electrode (124), wherein, described second electrode (124) separates with described measurement gas chamber (114) by at least one floor of described floor structure (112), wherein, described second electrode (124) is connected with described measurement gas chamber (114) by at least one air inlet path (128), wherein, described air inlet path (128) has at least one air admission hole (130) in described layer structure (112), wherein, construct described air admission hole (130), make this air admission hole have at least two zones (148 that diameter is different, 152).
13., wherein, use at least a boring method and/or at least a method for milling for making described air admission hole (130) by last the described method of claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009055421.1 | 2009-12-30 | ||
| DE200910055421 DE102009055421A1 (en) | 2009-12-30 | 2009-12-30 | Sensor element with improved gas access |
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| CN102183565A true CN102183565A (en) | 2011-09-14 |
| CN102183565B CN102183565B (en) | 2015-11-25 |
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| CN (1) | CN102183565B (en) |
| DE (1) | DE102009055421A1 (en) |
| FR (1) | FR2954827B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104422724A (en) * | 2013-08-27 | 2015-03-18 | 浙江福爱电子有限公司 | Oxygen sensor probe and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102013226947A1 (en) | 2013-12-20 | 2015-06-25 | Robert Bosch Gmbh | Sensor element for detecting at least one property of a sample gas in a sample gas space |
| DE102014118153A1 (en) * | 2014-12-08 | 2016-06-09 | Werner Reiter | Gas sensor element |
| DE102020206662A1 (en) * | 2020-05-28 | 2021-12-02 | Robert Bosch Gesellschaft mit beschränkter Haftung | Ceramic sensor element for an exhaust gas sensor and method for its manufacture |
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| WO2003102570A1 (en) * | 2002-05-31 | 2003-12-11 | Robert Bosch Gmbh | Method for calibrating a sensor element for a limiting current probe |
| DE10260849A1 (en) * | 2002-12-23 | 2004-07-15 | Robert Bosch Gmbh | probe |
| US20060137979A1 (en) * | 2004-11-30 | 2006-06-29 | Walter Strassner | Sensor element for determining gas components in gas mixtures and method for manufacturing the same |
| US20070108049A1 (en) * | 2003-09-29 | 2007-05-17 | Thomas Wahl | Sensor element |
| EP2075576A2 (en) * | 2007-12-27 | 2009-07-01 | Robert Bosch Gmbh | Sensor element with improved poison resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102004054014A1 (en) | 2004-11-09 | 2006-05-11 | Robert Bosch Gmbh | ceramic component |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003102570A1 (en) * | 2002-05-31 | 2003-12-11 | Robert Bosch Gmbh | Method for calibrating a sensor element for a limiting current probe |
| DE10260849A1 (en) * | 2002-12-23 | 2004-07-15 | Robert Bosch Gmbh | probe |
| US20070108049A1 (en) * | 2003-09-29 | 2007-05-17 | Thomas Wahl | Sensor element |
| US20060137979A1 (en) * | 2004-11-30 | 2006-06-29 | Walter Strassner | Sensor element for determining gas components in gas mixtures and method for manufacturing the same |
| EP2075576A2 (en) * | 2007-12-27 | 2009-07-01 | Robert Bosch Gmbh | Sensor element with improved poison resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104422724A (en) * | 2013-08-27 | 2015-03-18 | 浙江福爱电子有限公司 | Oxygen sensor probe and preparation method thereof |
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| DE102009055421A1 (en) | 2011-07-07 |
| FR2954827A1 (en) | 2011-07-01 |
| CN102183565B (en) | 2015-11-25 |
| FR2954827B1 (en) | 2017-01-06 |
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