Polarographic oxygen sensor, particularly for combustion exhaust gases

• US 4,842,713 A
• Filed: 11/03/1987
• Issued: 06/27/1989
• Est. Priority Date: 02/14/1984
• Status: Expired due to Fees

• Current Assignee: Robert Bosch GmbH
• Original Assignee: Robert Bosch GmbH
• Inventors: Stahl, Roland
• Primary Examiner(s): TUNG, TA HSUNG
• Application Number:
  US07/119,218
• Time in Patent Office: 602 Days
• Field of Search: 204/15, 204/421-429
• US Class Current: 204/428
• CPC Class Codes: G01N 27/4077 Means for protecting the electrolyte or the electrodes
• CPC Class Codes: G01N 27/48 using polarography, i.e. measuring changes in current under a slowly-varying voltage

Abstract

To accurately control access of measuring gas into the measuring electrode (15) of a polarographic sensor having a tubular body (12) of solid electrolyte material, the tubular body is enclosed within a protective sleeve (38) closed at one end and embodying a diffusion resistance element, or diffusion resistance zone (43/1, 43/2); if the sleeve is of metal, a separate diffusion resistance element, for example, made of aluminum oxide or spinell may be used; if the sleeve is made of ceramic, the end portion may be thickened and the diffusion resistance zone formed therein, for example, by micropores or microchannels or microducts extending therethrough.

Claims

1. A polarographic oxygen sensor, to measure the concentration of oxygen in gases, especially exhaust gases from a combustion process, having

a metal housing (25);

a closed solid electrolyte tubular body (12) sealingly secured to the housing;

a reference electrode (18) located in the inside of the solid electrolyte body (12);

a gas measuring electrode (15) located at the outside of the solid electrolyte body (12);

means (5,25,31) applying a bias voltage, having a value in the range of about 1/2 to 11/2 volts, across said electrodes (15,18), to cause a current to flow, the value of said current depending upon the reaction, with said measuring electrode (15), of the oxygen in the gas reacting said measuring electrode (15);

means (7) providing a signal representative of the value of said current flow;

a protective sleeve (38), essentially solid throughout its length except for an opening (41) formed therein, sealingly secured to the metal housing (25) and surrounding the tubular solid electrolyte body (12);

wherein, to facilitate economical manufacturing,

said protective sleeve (38) includes a diffusion resistance zone (43/1, 43/2), which can be constructed separately from said electrolyte body (12) and said electrodes (15,18), across said opening (41) which is gas-permeable for oxygen molecules and forms a diffusion resistance element, which sufficiently throttles migration of oxygen molecules to the measuring electrode (15) on the solid electrolyte body (12) to control the speed of the consequent reaction and hence, the value of the current which flows, and thereby assure that the sensor operates under diffusion-limited-current conditions,

and wherein, to increase response speed of the sensor, the protective sleeve is tubular and surrounds the solid electrolyte body with a small but finite space (39") therebetween defined by grooves, striations, or a roughened surface, sufficient to allow for vibration and to permit permeation of oxygen molecules, passing to the inside of the protective sleeve, through said diffusion resistance element (43/1, 43/2) and along at least a portion of the measuring electrode (15) on the surface of the solid electrolyte body (12).

2. Sensor according to claim 1, wherein the protective sleeve (38) loosely surrounds and engages the solid electrolyte body (12), leaving sufficient space to permit permeation of oxygen molecules along at least a portion of the measuring electrode without leaving so much space that oxyen passing through said diffusion resistance element mixes with other air in said space rather than reacting promptly with said measuring electrode and that the response speed of the sensor to changes in the oxygen level is slowed.

3. Sensor according to claim 1 wherein at least one of the surfaces of the measuring electrode (15), the solid electrolyte tubular body (12) and the gas tight protective sleeve (38), which are facing each other, is roughened, and the protective sleeve engages the solid electrolyte body and the measuring electrode (15) thereon, the surface roughness on at least one of the engaging surfaces permitting permeation of oxygen molecules along at least a portion of the measuring electrode (15).

4. Sensor according to claim 3 wherein the protective sleeve (38") engages, in part, the measuring electrode (15").

5. Sensor according to claim 3 wherein the protective sleeve is made of metal.

6. Sensor according to claim 3 wherein the protective sleeve is made of ceramic.

7. Sensor according to claim 3 wherein the protective sleeve (38) is formed with a bottom portion (42,42'"'"');

and wherein the diffusion resistance element (43/1,43/2) is located at the bottom portion (42,42'"'"') of the protective sleeve.

8. Sensor according to claim 3 wherein the protective sleeve (38) comprises a sealed tubular element (38) and a carrier (43) closing off the bottom (42) of the sleeve adjacent the closed end portion of the solid electrolyte body;

and wherein the diffusion resistance zone forming the diffusion resistance element (43/1) is located on said carrier element.

9. Sensor according to claim 8 wherein the carrier element (43) is sealed to the protective sleeve;

and wherein said carrier elements includes the diffusion resistance element.

10. Sensor according to claim 9 wherein the carrier element (43) comprises metal.

11. Sensor according to claim 9 wherein the carrier element comprises ceramic.

12. Sensor according to claim 3 wherein the diffusion resistance zone (43/1,43/2) comprises a region of the protective sleeve formed with at least one channel to thereby define said diffusion resistance element.

13. Sensor according to claim 3 wherein the diffusion resistance zone (43/1,43/2) comprises a region of the protective sleeve formed with gas-permeable pores to thereby define said diffusion resistance element.

14. Sensor according to claim 3 wherein said diffusion resistance element has openings therein of such a size that gas-phase diffusion therethrough is possible.

15. Sensor according to claim 3 wherein said diffusion resistance element has openings therein of such a size that Knudsen diffusion is possible.

16. Sensor according to claim 3 wherein a gas tight insulating layer (36a) is provided, secured to a first portion of a solid electrolyte body (12,12'"'"') remote from the closed end of the solid electrolyte tubular body, and interposed between the solid electrolye body and the measuring electrode (15,15'"'"').

17. Sensor according to claim 3 further comprising holding means (44,45,46), selectively separably retaining the protective sleeve (38'"'"') on the metal housing (25).

18. Sensor according to claim 3 further including a heater element (22) extending into the interior of the closed solid electrolyte tubular body (12).

19. A polarographic oxygen sensor according to claim 1, wherein said diffusion resistance element throttles oxygen diffusion to such an extent that migration conditions will occur which are comparable to measuring oxyten concentration in liquid in which the diffusion speed is reduced by a factor of about 10⁵.