# Patent

## Title
Hot zone igniter

## Abstract

An igniter for igniting combustible gases in a hot zone, such as in a solid oxide fuel cell, comprising a subassembly including an electrical resistance heating tip comprising SiC, metal leadframe clips formed of a nickel-based superalloy and attached to the heating tip, wire leads formed of a nickel-chromium alloy and connected to the leadframe clips for supplying electric current to the heating tip, and a nickel-based braze alloy comprising palladium and cobalt for connecting the leadframe clips to the heating tip and to the wire leads; an alumina ceramic body for receiving the brazed subassembly; and a potting compound comprising zirconia for potting the subassembly into the alumina ceramic body.

## Background
RELATIONSHIP TO GOVERNMENT CONTRACTS
The present invention was supported in part by a U.S. Government Contract, Number DE-FC36-04G014319. The United States Government may have rights in the present invention.


TECHNICAL FIELD
The present invention relates to devices for igniting combustible mixtures of gases; more particularly, to an electrical resistance igniter; and most particularly, to method and materials for forming an improved igniter capable of sustained service at temperatures consistent with a high temperature environment such as, for example, reformer combustion chamber or the anode stack gas of a solid oxide fuel cell system.
BACKGROUND OF THE INVENTION
Solid oxide fuel cell (SOFC) systems require ignition devices to ignite the air/fuel mixture in the fuel reformer during reformer warm-up and also the anode and cathode tail gases exiting the fuel cell stacks. Both the fuel cell reformer and the stacks operate in a very high temperature environment where temperatures can range from about 750° C. to about 1000° C., and typically are about 850° C. In SOFC applications, the ignition devices are completely contained in the high temperature environment, which is an atypical operating environment for prior art ignition devices adapted from other technologies. For example, diesel glow plugs and gasoline spark igniters are intended to withstand very high temperatures (>1000° C.) only at the very tip of the igniter element, while the rest of the device consists of materials, and is manufactured with processes intended to withstand temperatures much lower, typically in the range of about 300° C. to about 600° C. As a result, prior art ignition devices may fail to ignite after relatively short periods of time, such as about 10 hours to about 100 hours, when installed in an SOFC system. Since the working lifetime of an SOFC system at high temperature can be on the order of about 10,000 hours to about 40,000 hours, there is a need for an ignition device which can function reliably under sustained exposure to SOFC operating temperatures and can also reliably ignite a fuel/air mixture when an SOFC system cold re-start is commanded.
Prior art igniters fail in SOFC applications due to loss of electrical connectivity that occurs when the prior art materials used in the igniter undergo catastrophic oxidation due to the high temperature environment. Wire insulation becomes brittle and cracks, leaving the wire exposed to the environment. Prior art wire is formed of pure copper or pure nickel. Such wire cannot be used at temperatures above about 600° C. without suffering severe oxidation. Further, the prior art ceramic potting compound also fails due to a powdering phenomenon which leaves the igniter joint loose and susceptible to vibrations. Further, the prior art igniter braze re-melts, causing electrical disconnection of the metal clip to the igniter tip. Further, the metal clips in a prior art design are made of a metal material which cannot withstand temperatures exceeding about 650° C.
What is needed in the art is a hot zone igniter capable of sustained service at temperatures consistent with the reformer combustion chamber and the anode stack gas of a solid oxide fuel cell system.
It is a principal object of the present invention to increase the working lifetime of a hot zone igniter for a fuel cell system.
SUMMARY OF THE INVENTION
Briefly described, a hot zone igniter in accordance with the present invention employs alloy materials that are resistant to high temperature, such as a silicon carbide and aluminum nitride composite for the heating tip; a nickel-chromium alloy for the igniter wires; a nickel-based superalloy for the metal leadframe clip, such as Inconel 600/Inconel 625; a nickel-based braze alloy; an alumina ceramic body; and a zirconia potting compound.
Prior to brazing the heating tip to the metal leadframe clip, the tip is thoroughly cleaned with alcohol and then air oxidized at high temperature to create a sacrificial SiO2—Al2O3 layer on the igniter tip that prevents reaction of the igniter tip during brazing. A TiH2 layer is added to the igniter tip to insure adequate wetting of the igniter tip by the braze.



BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is an isometric view of an improved hot zone igniter in accordance with the present invention; and
FIG. 2 is a longitudinal cross-sectional view of the igniter shown in FIG. 1.



Corresponding reference characters indicate corresponding parts throughout the several views. The exemplification set out herein illustrates one preferred embodiment of the invention, in one form, and such exemplification is not to be construed as limiting the scope of the invention in any manner.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1 and 2, an improved hot zone igniter 10 is suitable for use at temperatures consistent with the reformer combustion chamber and the anode stack gas of a solid oxide fuel cell system (not shown) wherein combustible gases must be ignited in warming of a hydrocarbon fuel reformer and also at the exit of anode and cathode stacks thereof, as is well known in the fuel cell arts.
Igniter 10 comprises a U-shaped electrical resistance heating tip 12 formed preferably of an alloy of SiC, AlN, and MoSi2. Wire leads 14,16 for supplying electric current to heating tip 12 are preferably formed of an 80Ni-20Cr Nichrome alloy, which resists oxidation up to temperatures of at least 900° C. Metal leadframe clips 18a,18b are provided for connecting tip 12 to wire leads 14,16 and preferably are formed of a nickel-based superalloy such as Inconel 600, Inconel 625, or Haynes 230. Tip 12 and wire leads 14,16 are brazed to metal leadframe clips 18a,18b via an improved brazing compound 20 that is a nickel-based alloy. A currently preferred composition for the braze is 10-15% Pd, 5-7% Co, 15-18% Cr, 2.5-3% B and the balance Ni. Preferably, a TiH2 layer (not visible in FIGS. 1,2) is added to the surface of igniter tip 12 prior to brazing to insure adequate wetting of the igniter tip by the braze. Preferably, an Fmica electrical insulation barrier (not visible in FIGS. 1,2) is added between metal leadframe clips 18a,18b as a braze break to insure that molten braze does not climb and extend between the metal leadframe clips thereby electrically shorting the igniter tip. Insulation on wire leads 14,16 preferably is woven alumina. A tubular body 22 surrounds a portion of the resistance heating tip 12, the metal leadframes 18a,18b, and the wire leads 14,16 (which define a subassembly 19). Body 22 is filled with a curable high-temperature potting compound 24, preferably a compound comprising a zirconia-based adhesive. The material system of the present invention (high temperature oxidation resistant alloys, brazes, wires, and potting compound) enables a high temperature-capable igniter in accordance with the present invention.
One aspect of the process for forming a hot zone igniter in accordance with the present invention comprises at least the following steps:
a) holding the electrical resistance heating tip in air for between about four hours and about eight hours at a temperature of about 975° C. to form a sacrificial oxide layer comprising SiO2 and Al2O3 on the surface of the heating tip to prevent attack of the SiC and MOS2 by the braze during a subsequent brazing step; the sacrificial layer decomposes in the vacuum or hydrogen braze process during which the SiO2 is consumed by the braze alloy slowly over time;
b) applying a layer of TiH2 to the oxide layer on the heating tip surface, preferably by application of a mixture of TiH2 in dehydrated ethanol, then allowing the alcohol to evaporate;
c) applying a paste of braze alloy between the TiH2 layer and the metal leadframe clips 18a,18b, and also between the metal leadframe clips 18a,18b and the wire leads 14,16 to form igniter subassembly 19; and
d) heating and cooling igniter subassembly 19 through a brazing thermal cycle to braze the resistance tip and the wire leads to the leadframe clips. A currently-preferred furnace braze process cycle includes bringing igniter assembly 19 to about 1125° C. and holding the igniter assembly at that temperature for about 30 minutes.
After the brazing, subassembly 19 is inserted into body 22 which then is filled with potting compound 24, as shown in FIGS. 1 and 2, which is then cured to provide improved hot zone igniter 10.
While the invention has been described by reference to various specific embodiments, it should be understood that numerous changes may be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the described embodiments, but will have full scope defined by the language of the following claims.

## Claims

1. An igniter for igniting combustible gases, comprising:
a) an electrical resistance heating tip;
b) at least one wire lead in electrical connection with said electrical resistance heating tip for supplying electric current to said electrical resistance heating tip; and
c) a braze alloy for making said electrical connection with said electrical resistance heating tip and said at least one wire lead,
wherein said electrical resistance heating tip includes silicon carbide and wherein said braze alloy includes palladium and cobalt.

2. An igniter in accordance with claim 1 further comprising a metal leadframe clip in electrical connection between said electrical resistance heating tip and said at least one wire lead.

3. An igniter in accordance with claim 1, further comprising:
a) an alumina ceramic body for containing a portion of said electrical resistance heating tip and said at least one wire lead; and
b) a potting compound for potting said electrical resistance heating tip and said at least one wire lead into said alumina ceramic body.

4. An igniter in accordance with claim 2, further comprising:
a) an alumina ceramic body for containing a portion of said electrical resistance heating tip, said metal leadframe clip, and said at least one wire lead; and
b) a potting compound for potting said electrical resistance heating tip, said metal leadframe clip, and said at least one wire lead into said alumina ceramic body.

5. An igniter in accordance with claim 1 wherein said at least one wire lead is formed of a nickel-chromium alloy.

6. An igniter in accordance with claim 2 wherein said metal leadframe clip is formed of a nickel-based superalloy.

7. An igniter in accordance with claim 6 wherein said nickel-based superalloy is selected from the group consisting of Inconel 600, Inconel 625, and Haynes 214.

8. An igniter in accordance with claim 3 wherein said potting compound includes zirconia.

9. An igniter in accordance with claim 1 wherein said electrical resistance heating tip further comprises MoSi2.

10. An igniter in accordance with claim 2 wherein said wire lead is a first wire lead and wherein said igniter further comprises a second wire lead connected to a second metal leadframe clip.

11. An igniter for igniting combustible gases, comprising:
a) an electrical resistance heating tip including SiC, AlN, and MoSi2;
b) first and second metal leadframe clips formed of a nickel-based superalloy and attached to said electrical resistance heating tip;
c) first and second wire leads formed of a nickel-chromium alloy and connected to said first and second metal leadframe clips, respectively, for supplying electric current to said electrical resistance heating tip; and
d) a braze alloy including palladium and cobalt for connecting said first and second metal leadframe clips to said electrical resistance heating tip and to said first and second wire leads.

12. An igniter in accordance with claim 11 further comprising:
a) an alumina ceramic body for containing a portion of said electrical resistance heating tip, said first and second metal leadframe clips, and said first and second wire leads; and
b) a potting compound containing zirconia for potting said electrical resistance heating tip, said first and second metal leadframe clips, and said first and second wire leads into said alumina ceramic body.

13. An igniter for igniting combustible gases, comprising:
a) a heating tip;
b) at least one wire lead in electrical connection with said heating tip; and
c) a potting compound for potting said electrical resistance heating tip and said at least one wire lead wherein said potting compound includes zirconia.

14. An igniter in accordance with claim 13 further including an alumina ceramic body for containing at least a portion of said heating tip, said at least one wire lead and said potting compound.