AU686320B2 - Soldering of high-temperature joints in solid-electroltye high-temperature fuel cells - Google Patents
Soldering of high-temperature joints in solid-electroltye high-temperature fuel cells Download PDFInfo
- Publication number
- AU686320B2 AU686320B2 AU16306/95A AU1630695A AU686320B2 AU 686320 B2 AU686320 B2 AU 686320B2 AU 16306/95 A AU16306/95 A AU 16306/95A AU 1630695 A AU1630695 A AU 1630695A AU 686320 B2 AU686320 B2 AU 686320B2
- Authority
- AU
- Australia
- Prior art keywords
- chromium
- temperature
- high temperature
- weight
- hard solder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000000446 fuel Substances 0.000 title claims description 18
- 238000005476 soldering Methods 0.000 title claims description 18
- 229910000679 solder Inorganic materials 0.000 claims description 45
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052804 chromium Inorganic materials 0.000 claims description 25
- 239000011651 chromium Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 8
- 238000005304 joining Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000005097 cold rolling Methods 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005098 hot rolling Methods 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910000599 Cr alloy Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Fuel Cell (AREA)
Description
OF HIGHEPE2wFruRE IOImTrs (0 5OLIO ELECTRLLYTE HIGH- TEMPErr-mee~. FuEL CELLS The invention relates to a hard solder for high-temperature soldering operations for joining high temperature-resistant materials, especially chromium and alloys based on chromium.
Known solders for the hard soldering of such materials are hard solders such as zirconium, titanium, vanadium, or hard solders based on nickel, with up to about 20% by weight chromium content, and up to about 4% by weight boron and/or silicon content, which are used especially for soldering chromium or alloys based on chromium. In addition to boron and/or silicon, the last-mentioned solders may contain low contents of molybdenum and/or iron as well.
Said solders based on nickel are manufactured from powders, using a special melt-metallurgical process (melt spinning) for producing such solders in the form of amorphous foils, such solders being referred to as "rapidly solidified filler metals". The boron and/or silicon components in the solders .serve the purpose of lowering the melting point, on the one hand, and of enhancing the wettability of the solder on the other hand.
-1- It is a drawback in connection with the above process that in the soldering process, the boron and/or silicon components cause the formation of intermetallic phases with undesirable hardness values or insufficient strength to some extent. Furthermore, because of their low chromium content, the known solders have a melting point of about 1200°C at the most, which is often inadequate in many application cases.
SChemical Abstract 103-11394c describes the use of an Ni-Cr-alloy with up to 44% by weight chromium component for melting down porcelain in dental prosthetics. Chemical Abstract 108-60867w describes the use of an Ni-Cr-alloy with up to 50% by weight chromium component for objects Sthat are exposed to corrosive stress. The use of such alloys as solder material for high-temperature soldered joints is not disclosed in said two earlier publications.
Chemical Abstracts 119-165908, 114-231119j, 112-1,22117v and 120-251017b describe solder alloys based on Ni-Cr, with a maxium chromium content of 30% by weight. Such solder alloys, however, are only insufficiently suitable for high-temperature soldered joints of objects consisting of chromium, or of alloys based on chromium.
-2- 3 Therefore, the problem of the present invention is to make available a process for soldering high-temperature soldered joints, in solid-electrolyte hightemperature fuel cells with a hard solder which, during the soldering process, does not cause any formation of embrittling intermetallic phases, and which permits the soldered materials to be exposed to operational temperatures of at least up to 13000C.
Accordingly to the invention, this is accomplished in that the hard solder consists of 40% to 70% by weight chromium, up to 2% by weight of one or several metals selected from the group of vanadium, niobium, tantalum, titanium, zirconium and hafnium, up to 2% by weight of one or several metals and/or their oxides selected from the group of rare earths and yttrium, as well as nickel as the balance.
It comes as a complete surprise that the solder employed according to the invention excellently wets the materials to be joined even without any boron and/or silicon components, and exhibits a well-controllable flow of the solder, which prevents the solder from exiting from the soldered gap, and consequently avoids reworking of the parts joined by soldering. The solder is particularly suitable for joining chromium or chromium-containing materials. However, other o: high-temperature-resistant °o «o materials, and particularly high-melting metals such as tungsten or molybdenum, graphite, and also ceramic materials such as SiC, TiC, TiB 2 and the like are highly suitable as well for being joined by soldering with application.of the solder according to the invention.
In addition to said properties, the solder according to the invention exhibits high ductility, good thermal and good electrical conductivity, as well as excellent resistance to corrosion.
By using one or several of the metals selected from the group of vanadium, niobium, tantalum, titanium, zirconium and hafnium in amounts of up to 2% by weight, the ductility of the solder can be enhanced further without any notable negative influence on the other good properties.
An improvement of the solder with respect to its resistance to corrosion caused by hot gases is achieved by adding rare earths, yttrium and/or their oxides in amounts of up to 2% by weight.
A solder with 50% by weight chromium, the balance nickel has been found to be particularly advantageous.
-4- ILi cp~ Preferably, the solder is used in the form of thin foils with a sheet thickness between 50 and 200 pm..
Advantageously, the foils are manufactured by powdermetallurgical processes. In a particularly preferred process, a compact is produced by mixing, pressing and sintering of the powdery starting materials. Subsequently, the compact is encased airtight and the encased compact is hot-rolled to a sheet thickness of approximately 2 mm. Following removal of the encasing material, the sheet is cold-rolled to the Sdesired sheet thickness. In addition to the sheet form, the solder according to the invention can be manufactured in the S form of wire as well. The solder according to the invention has been successfully used especially for soldering parts in solid electrolyte, high-temperature fuel cells (SOFC fuel cells).
SWith such fuel cells, a ceramic solid electrolyte based on Zr02 is used, which is connected to metallic electrodes on both sides, whereby oxygen is supplied on one electrode and the fuel on the other. In addition to hydrogen, hydrocarbons are suitable fuels for SOFC fuel cells as well.
In the manufacture of SOFC fuel cell'modules, several seriesconnected fuel cells which are arranged one flat on top of the other can be interconnected by way of so-called bipolar plates, whereby the bipolar plate electrically conductively connects the cathode of the one cell to the anode of the adjacent cell.
Alloys based on chromium are used as the preferred materials for the bipolar plates, but also for other components of the high-temperature fuel cells. The individual parts of such fuel cells are advantageously joined with each other by soldering, whereby the solder is expected to meet a great number of different requirements. For example, the solder has to exhibit good thermal conductivity and good electrical conductivity; the coefficient of thermal expansion has to be as close as possible to the one of the ceramic electrolyte and of the metallic parts; and most of all, it has to be resistant to corrosion vis-a-vis the hot gases such as air and hydrogen, as well as hydrocarbons.
The solder according to the invention satisfies each one of said properties in an excellent way, so that it is especially suitable for said special case of application.
The invention is explained in greater detail in the following on the basis of examples.
-6- EXAMPLE 1: For the manufacture of a bipolar plate for a high-temperature fuel cell, several sheets with the dimensions of 200 x 200 mm and a sheet thickness of 2 mm and consisting of a chromium alloy with 5% by weight iron and 1% by weight yttrium oxide were joined flat with each other, using the solder according to the invention. For this purpose, the sheets were cleaned in the ultrasound bath. Thereafter, the soldering structure was arranged, using three sheets arranged one on top of the other and with solder foils consisting of 50% by weight nickel and 50% by weight chromium and with a layer thickness of 0.075 mm arranged between each two sheets. The soldering structure was loaded with weights, about 20 to 40 g/cm 2 and charged in a soldering furnace. Soldering was carried out in a hydrogen atmosphere. The soldering furnace was heated within 2 hours and 30 minutes from room temperature to 1350 0 C, and maintained at the latter temperature for 5 minutes. Subsequently, cooling to room temperature took place within 3 hours. A nondestructive testing of the soldered composite showed a flawless condition of the soldered joint between the individual sheets. No solder material had exited from the soldering gaps, so that no reworking of the bipolar plate was required. A bipolar plate so produced was installed in an SOFC-fuel cell and tested. After the fuel cell had operated about 1000 hours, no cracks of any -7type or negative effects of corroding influences were found on the bipolar plate.
EXAMPLE 2: For the manufacture of a solder foil with the composition by weight chromium, the balance nickel, 5 kg chromium powder with an average grain size of 30 pm, and 5' kg nickel powder with an average grain size of 3 pm was mixed together.
Subsequently, the powder mixture was compressed with a 2 pressing pressure of 3 t/cm to obtain a compact with the dimensions 25 x 170 x 400 mm. The compact was sintered for 6 hours at a temperature of 1200°C and subsequently encased airtight by welding in a steel jacket with a wall thickness of 2 mm, following evacuation of said jacket. The encased sintered compact was hot-rolled to a thickness of 2 mm at a temperature of 1200 0 C. Following chemical removal of the steel jacket, the sheet was ground and cold-rolled to a foil thickness of 50 pm.
Claims (5)
1. A process for joining high temperature-resistant parts in solid-electrolyte high-temperature fuel cells, which construction parts are made of chromium and alloys based on chromium, comprising the steps of: applying a hard solder between the high temperature-resistant parts, the hard solder consisting essentially of: 40% to 70% by weight chromium; up to 2% by weight of at least one of the metals selected from the group consisting of vanadium, niobium, tantalum, titanium, zirconium and hafnium; up to 2% by weight of at least one of the metals or their oxides selected from the group consisting of rare earths and yttrium; and the balance being nickel; heating the hard solder and high temperature-resistant parts; and cooling the hard solder and high temperature-resistant parts to create a high-temperature soldered joint connecting the high temperature- resistant parts.
2. Process for joining high temperature-resistant parts according to claim 1, characterised in that the hard solder consists of 50% by weight chromium, the balance nickel.
3. Process for joining high temperature-resistant parts according to claim 1 and 2, characterized in that the hard solder is present as a ductile foil.
4. Process for joining high temperature-resistant parts according to claim 3, characterised in that the hard solder used is manufactured by the following process steps: manufacture of a compact by mixing, pressing and sintering of the powdery starting materials; L s airtight encasing of the compact; hot-rolling of the encased compact to a sheet thickness of about 1 to 3mm; removal of the encasing material; and cold rolling of the sheet to the desired foil thickness. DATED this 7th day of October, 1997 PLANSEE AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 4TH FLOOR, "DURACK CENTRE" 263 ADELAIDE TERRACE PERTH W.A. 6000 AUSTRALIA f** 1 '=111 ABSTRACT The invention relates to a hard solder for high-temperature soldered joints for joining high temperature-resistant materials, especially chromium and alloys based on chromium. The hard solder consists of 40% to 70% by weight chromium, up to 2% by weight of one or several of the metals selected from the group of vanadium, niobium, tantalum, titanium, zirconium and hafnium, up to 2% by weight of one or several of the metals or their oxides selected from the group of rare earths and ego**** yttrium, as well as nickel as the balance. The solder according to the invention is particularly suitable for joining by soldering parts in solid-electrolyte, high-temperature fuel cells.
5 -11- L
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT75994 | 1994-04-13 | ||
| AT759/94 | 1994-04-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1630695A AU1630695A (en) | 1995-10-26 |
| AU686320B2 true AU686320B2 (en) | 1998-02-05 |
Family
ID=3499042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU16306/95A Ceased AU686320B2 (en) | 1994-04-13 | 1995-04-03 | Soldering of high-temperature joints in solid-electroltye high-temperature fuel cells |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU686320B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017093700A1 (en) * | 2015-12-04 | 2017-06-08 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Method for assembling a first metal part and a second metal or ceramic part by brazing, brazing composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB487263A (en) * | 1937-02-12 | 1938-06-17 | Patent Treuhand Ges Fure Elek | Improvements in solders for uniting the metallic parts of vacuum devices |
| US3787202A (en) * | 1970-11-18 | 1974-01-22 | Cyclops Corp | High temperature chromium-nickel alloy |
| JPH03199337A (en) * | 1989-12-27 | 1991-08-30 | Tosoh Corp | High-temperature corrosion resistant material and production thereof |
-
1995
- 1995-04-03 AU AU16306/95A patent/AU686320B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB487263A (en) * | 1937-02-12 | 1938-06-17 | Patent Treuhand Ges Fure Elek | Improvements in solders for uniting the metallic parts of vacuum devices |
| US3787202A (en) * | 1970-11-18 | 1974-01-22 | Cyclops Corp | High temperature chromium-nickel alloy |
| JPH03199337A (en) * | 1989-12-27 | 1991-08-30 | Tosoh Corp | High-temperature corrosion resistant material and production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017093700A1 (en) * | 2015-12-04 | 2017-06-08 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Method for assembling a first metal part and a second metal or ceramic part by brazing, brazing composition |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1630695A (en) | 1995-10-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |