Patent Application
20190031571
This invention relates to brazeable zirconia ceramics, methods of brazing zirconia ceramics, and brazed zirconia ceramics.
By “zirconia ceramics” is meant ceramic materials comprising at least 5 wt % ZrO2 and optionally at least 50 wt % ZrO2, or at least 70 wt % ZrO2, or at least 80 wt % ZrO2, or at least 90 wt % ZrO2.
Zirconia is an oxide (ZrO2) that is used in ceramics but which, in its pure form, suffers from a tetragonal/monoclinic phase change that makes manufacture of sintered bodies of pure zirconia ceramics difficult. For this reason zirconia ceramics for use as sintered bodies generally comprise other components that lock the material wholly or partially into a high temperature cubic phase or stabilise the tetragonal phase. Typical components to achieve this effect include, for example, CaO, MgO and Y2O3. Zirconia ceramics may also contain other components (e.g. hafnia, HfO2).
Typical zirconia containing ceramics include (among other types):
It is known that reduction of zirconia results in a darkening of the ceramic from its normal white colour, and this has been attributed, at least in part, to the presence of zirconia sub oxides [ZrO2-x] and (where yttria is present) yttria sub-oxides [Y2O3-x]. [“Origin of Darkening in 8 wt% Yttria-Zirconia Plasma-Sprayed Thermal Barrier Coatings”, Gabriel Maria Ingol, J. Am Ceram. Soc. 74(2), 381-86 (1991)]. Stronger coloration has been attributed to the presence of impurities such as iron [“Reply to “Comment on ‘Black Color in Partially Stabilized Zirconia’”], Javier Soria et al, J. Am Ceram. Soc. 74(7), 1747-48 (1991)]. Whatever the source, such darkening has been seen as a cosmetic disadvantage.
Darkening of a dense Y-TZP monolith and its fracture toughness has been reported in “Mechanical and Magnetic properties of Novel Yttria-Stabilized Tetragonal Zirconia/Ni Nanocomposite prepared by the Modified Internal Reduction Method”, Kondo et al, J. Am Ceram. Soc. 88(6), 1468-1473 (2005)]. No significant change in fracture toughness was shown following heat treating in a pure hydrogen atmosphere at 1300° C. for 2.5 hours.
Brazing and soldering are processes in which a molten filler metal (frequently referred to as a filler) is used to wet facing surfaces of a joint, and is then solidified on cooling to form a joint between the facing surfaces. Reaction or alloying at the junction between the brazing material and the articles to be joined may occur to a limited extent. Conventionally, brazing takes place above 450° C. and soldering at or below that temperature.
Brazing can also be used to provide a metallized surface to an article, or to provide electrically conductive pathways through articles.
According to “Principles of Brazing” by Jacobson and Humpston, (ASM International, ISBN 0-87170-812-4), brazing has been known since about 3200BCE for joining metals, and so for some materials it could be considered a mature technology. However the range of materials that can be successfully brazed has been extended over recent years as methods have been developed to deal with such widely different materials as ceramics, glasses and composite materials. For example “active brazes” incorporate in otherwise conventional brazing alloys a small amount of metals such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, or silicon, to improve wetting and spread on ceramic materials.
For brazing to occur, the brazing material normally has a liquidus temperature below the solidus temperature of the materials to be brazed, and the temperatures used for brazing must not detrimentally affect the materials to be joined.
A significant factor in assessing the quality of a brazed joint to ceramic is the shear strength at the joint. If the joint shears within the ceramic rather than in the braze, or at the braze-ceramic interface, then the braze does not represent a region of weakness.
When brazing zirconia ceramics, it is known to use active brazes, however such active brazes have some drawbacks:—
Brazing zirconia ceramics, with a brazing alloy other than active brazes, does not work as the alloys do not wet to the zirconia ceramics.
The present disclosure provides improved zirconia materials providing improved brazing, and can avoid the use of active braze alloys.
The inventors have found that providing a reduced surface to sintered zirconia ceramic bodies assists wetting of the bodies to metals, such that optionally brazing materials other than active braze alloys may be used.
The inventors have further found that such sintered zirconia ceramic bodies having a reduced surface (in particular, although not exclusively, by the use of reduction in a hydrogen atmosphere at an elevated temperature) have improved shear strength over sintered zirconia ceramic bodies exposed to the same elevated temperature under vacuum.
The scope of the invention is as set out in the claims, and in any new and inventive features described herein with reference to the following non-limitative description.
At this time metallizing does not exist to permit the brazing of yttria stabilised TZP (YTZP) so the only way to braze is to use active brazing (ABA Alloys) in a vacuum furnace.
As part of a study into the brazing of zirconia materials, the inventor observed that exposing Y-TZP to a temperature of 1550° C. in a hydrogen atmosphere resulted in a uniformly darkened material having a shear strength more than 50% higher than a sample of the same material exposed to the same temperature, for the same time, in vacuum.
In looking more closely, the inventor realised that the material exposed to the hydrogen atmosphere had a surface that was more easily wetted by brazing alloys, including brazing materials other than active brazing alloys.
While the particular Y-TZP used in the following examples is uniformly darkened, under other conditions, the zirconia ceramics may only exhibit darkening at the surface.
The following examples illustrate but do not limit the invention and each use an injection moulded and sintered dense (>90% dense) material made from yttria stabilised TZP (YTZP) [made from TZ-3YSE-E grade zirconia powder supplied by Tosoh Corporation which had an analysed composition in weight percent:—Y2O3 5.23%, Al2O3 0.252%, SiO2 at most 0.002%, Fe2O3 at most 0.002%, Na2O 0.007%, ignition loss of 0.45%, balance zirconia].
The material, prior to brazing, had been fired in dry hydrogen (dew point −60° C. or better) at 1500° C. for 30 min and then cooled in dry hydrogen to 150° C.
This heat treatment turned the YTZP dark (material changing from white to black). The YTZP did not become electrically conductive.
Heat treatment temperatures that may be used include (without limitation)>1350° C., >1400° C., >1500° C., >1550° C.
The inventors have brazed articles to titanium, using a 50 μm (2 thousandth of an inch) thick foil of Ticuni® active brazing alloy (15 Cu, 15 Ni, 70 Ti) placed between the YTZP and the titanium. Brazing took place at 980° C. in vacuum.
A good joint resulted that did not pull apart with significant force and that was hermetic.
The heat treated YTZP of example 1 was brazed to titanium using a 50 μm (2 thousandth of an inch) thick pure gold foil as brazing material.
A good joint resulted that did not pull apart with significant force and that was hermetic.
The heat treated YTZP of example 1 was brazed to stainless steel using a 50 μm (2 thousandth of an inch) thick foil of copper-gold brazing alloy.
A good joint resulted showing good wetting of the YTZP.
The heat treated YTZP of example 1 was brazed to another piece of the heat treated YTZP of example 1 using a copper-silver alloy as brazing material.
A good joint resulted showing good wetting of the YTZP.
Although exemplified with respect to TZP, improved wetting properties resulting from reduction of zirconia are predicted to apply to other zirconia containing ceramics such as PSZ and ZTC.
In light of the zirconia content, the improved strength is expected to apply at least to PSZ.
Optionally the zirconia ceramic may comprise other oxides that darken when exposed to reducing conditions (for example, and without limitation, one or more of: iron oxide, titanium oxide, cerium oxide, chromium oxide, nickel oxide, cobalt oxide) to enhance the uniformity and darkness of colour. Such elements need not be present in high quantities to provide such effect [e.g. <1%; <0.5%; <0.1%; <0.05%; <0.01%; or <0.005%] although if appropriate may be at higher levels.
The invention is not limited to any particular brazing materials (other than that they are compatible both with the zirconia ceramic and any other article to which the ceramic is brazed), nor to any particular form of brazing material, and encompasses, for example, foils, pastes, powders, wires.
Brazed zirconia ceramics will have a variety of uses including (without limitation) in: medical implants, electrical feedthroughs, surgical equipment, analytical equipment, aerospace applications, oxygen sensors, fuel cell components.
The above description is illustrative only and the person skilled in the art will recognise that many variants may fall within the scope of the appended claims.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/051692 | 1/26/2017 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62287517 | Jan 2016 | US |
