Patent Grant
9931717
The present invention relates to an assembly, which has at least two ceramic bodies joined with one another, especially a pressure measuring cell, as well as to a method for joining ceramic bodies by means of an active hard solder, or braze.
Due to the special relevance of the invention for pressure measurement cells, the invention will be explained based on pressure measurement cells as an example of its application.
Pressure measurement cells according to the state of the art combine a ceramic measuring membrane and a ceramic platform, wherein the measuring membrane is connected pressure-tightly with the platform along a peripheral joint, which contains an active hard solder, or braze, wherein a pressure chamber is formed between the measuring membrane and the platform, wherein the equilibrium position of the measuring membrane results from the difference between a pressure reigning in the pressure chamber and a pressure acting on the outside surface of the measuring membrane, thus its surface facing away from the pressure chamber.
Serving as material for the platform and the measuring membrane are especially aluminum oxide ceramics, which, due to their elastic properties and their media resistance, are suited for the manufacture of pressure measurement cells. The mentioned ceramic components are especially joined with an active hard solder, or braze, which is preferably an active hard solder, or braze, containing Zr, Ni and Ti. The manufacture of such an active hard solder, or braze, is disclosed, for example, in European Offenlegungsschrift (laid open application) EP 0 490 807 A2. According to the method described there, especially rings of the active braze, material can be manufactured, which are positioned between measuring membrane and platform, in order to solder, or braze, these with one another.
For joining the components, for example, the ceramic bodies are heated with an intermediately lying, solder preform in high vacuum to a temperature, which melts the active hard solder, or braze, so that a reaction begins between the active hard solder, or braze, and the ceramic bodies. By cooling, the active hard solder, or braze, solidifies and the reaction between the active hard solder, or braze, and the ceramic body is stopped. During cooling, however, different coefficients of thermal expansion of the material of the ceramic body, on the one hand, and of the active hard solder, or braze, on the other hand, can lead to considerable stresses between the ceramic components and the joint, since after solidification of the solder there is still a cooling of several hundred K.
In selecting an active hard solder, or braze with a coefficient of thermal expansion suitable for the ceramic material, however, attention must be paid that the suitable active hard solder, or braze, does not have too high a melting point and, thus, not be suitable for joining the ceramic components, for example, because electrodes, which are provided on the ceramic bodies cannot withstand such temperatures.
It is, consequently, an object of the invention to provide an assembly and a pressure measuring cell, as well as a manufacturing process therefor, whereby the mentioned disadvantages of the state of the art are overcome.
The object is achieved according to the invention by an assembly, a pressure measuring cell and a method.
The assembly of the invention includes a first ceramic body and a second ceramic body, wherein the first ceramic body and the second ceramic body are connected by means of a joint, wherein the joint contains an active hard solder, or braze, wherein the active hard solder, or braze, averaged over a continuous core volume, which is spaced from the first ceramic body and from the second ceramic body, in each case, by at least 1 μm, especially at least 2 μm, has an average composition CK having a liquidus temperature Tl(CK), wherein the composition CK has a coefficient of thermal expansion α(CK), wherein α(CK)=m·α(K), wherein m≤1.5, especially m≤1.3 and preferably m≤1.2, wherein α(K) is the average coefficient of thermal expansion of the ceramic material, respectively the ceramic materials of the first and second ceramic bodies, wherein the joint has a first boundary layer and a second boundary layer, which border on the first ceramic body, respectively on the second ceramic body, wherein according to the invention at least one of the boundary layers, which lies outside of the core volume, has an average composition CB having a liquidus temperature Tl(CB), which lies not less than 50 K, especially not less than 100 K, and preferably not less than 200 K under the liquidus temperature Tl(CK) of the average composition CK of the core volume.
wherein the composition CK has a coefficient of thermal expansion α(CK), wherein α(CK)=m·α(K), wherein m≤1.5, especially m≤1.3 and preferably m≤1.2, wherein α(K) is the average coefficient of thermal expansion of the ceramic material, respectively the ceramic materials of the first and second ceramic bodies,
wherein the joint has a first bounding layer and a second bounding layer, which border on the first ceramic body, respectively on the second ceramic body,
wherein according to the invention at least one of the bounding layers, which lies outside of the core volume, has an average composition CB having a liquidus temperature Tl(CB), which lies not less than 50 K, especially not less than 100 K, and preferably not less than 200 K under the liquidus temperature Tl(CK) of the average composition CK of the core volume.
In a further development of the invention, the at least one boundary layer has a thickness of no more than 3 μm, especially no more than 2 μm and preferably no more than 1 μm.
In a further development of the invention, at least 40%, preferably at least 60% and especially preferably at least 70%, of the volume of the joint has the composition CK.
In a further development of the invention, the composition CB has a liquidus temperature Tl(CB), which lies no more than 300 K, especially no more than 150 K, and preferably no more than 50 K above the liquidus temperature Tl(Ce) of the eutectic point, respectively the nearest intersection with a eutectic valley, having a composition Ce in the composition space, wherein Ce:=(ce1, . . . , ceN), wherein |Ce|=1, and wherein the cei are the stoichiometric fractions of the components Ki with i=1, . . . , N at the eutectic point, respectively a nearest intersection with a eutectic valley, wherein CB:=(cB1, . . . , cBN), wherein |CB|=1, and wherein the cBi are the stoichiometric fractions of the components Ki=1, . . . , N of the average composition of the active hard solder, or braze in the boundary layer.
In a further development of the invention:
Ce:=(ce1, . . . , CeN), wherein |Ce|=1, wherein the cei are the stoichiometric fractions of the components Ki with i=1, . . . , N at the eutectic point, respectively at the nearest intersection with a eutectic valley;
CK:=(cK1, . . . , cKN), wherein |CK|=1, and wherein the cKi are the stoichiometric fractions of the components Ki, with i=1, . . . , N, of the average composition of the active hard solder, or braze, in the core volume; and
CB:=(cB1, . . . , cBN), wherein |CB|=1, and wherein the cBi are the stoichiometric fractions of the components Ki i=1, . . . , N of the average composition of the active hard solder, or braze, in the bounding layer,
wherein the difference between the composition Ce and the composition CB is describable with a normalized vector difference DeB,
wherein Ce=CB+aeB*DeB, with |DeB|=1,
wherein the difference between the composition CK and the composition CB is describable with a normalized vector difference DKB
wherein CK=CB+aKB*DKB, with |DKB|=1,
wherein aeB and aKB are positive scalars,
wherein for the scalar product seK:=DeB·DKB:
seK<0, especially seK<−0.5, preferably seK<−0.8.
In a further development of the invention, the first ceramic body (1) and/or the second ceramic body (2) comprise/comprises Al2O3.
In a further development of the invention, the active hard solder, or braze, comprises Zr, Ni and Ti.
In a further development of the invention, the composition CK, contains essentially zirconium and titanium, with (50+x) atom-% titanium and (50−x) atom-% zirconium, wherein x<10 especially x<5, wherein the composition CK is present especially in the α-(Zr, Ti) phase.
In a further development of the invention, the composition CK has a coefficient of thermal expansion α(CK), wherein α(CK)≤10·10−6/K, especially α(CK)≤9.5·10−6/K, preferably α(CK)≤9.2·10−6/K.
In a further development of the invention, the boundary layer has a composition CB, which comprises, for instance, 42 to 52 atom-% Zr, 23 to 28 atom-% Ni and 24 to 30 atom-% Ti, wherein, in given cases, Al diffuses in, wherein, in cases where Al is present, especially the titanium fraction is reduced.
The pressure measuring cell of the invention includes an assembly of the invention, wherein the first ceramic body is a membrane body of a measuring membrane of the pressure measuring cell, wherein the second ceramic body is a platform of the pressure measuring cell, and wherein the platform and the membrane body are joined pressure-tightly with one another by means of the joint, which is ring-shaped.
The method of the invention for manufacturing a special assembly of the invention, which assembly comprises a first ceramic body and a second ceramic body, wherein the first ceramic body and the second ceramic body are joined by the method by means of an active hard solder, or braze, includes steps as follows: providing the active hard solder, or braze, between the ceramic bodies, wherein the active hard solder, or braze, has, averaged over a continuous core volume, an average composition CK0 having a liquidus temperature Tl(CK0), wherein the composition CK has a coefficient of thermal expansion α(CK), wherein α(CK)=m·α(K), wherein m≤1.5, especially m≤1.3 and preferably m≤1.2, wherein α(K) is the average coefficient of thermal expansion of the ceramic material, respectively the ceramic materials of the first and second ceramic bodies, wherein the active hard solder, or braze, has, on at least one of its surfaces facing the ceramic bodies, a boundary layer having an average composition CB0, wherein the composition CB0 has a liquidus temperature Tl(CB0), which lies not less than 50 K, preferably not less than 100 K, and especially preferably not less than 200 K, under the liquidus temperature Tl(CK0) of the average composition CK0 of the core volume, and heating the ceramic bodies and the active hard solder, or braze, in a vacuum soldering, brazing process, up to melting of the composition CB0, wherein the melt of the boundary layer mixes in the transition to the core volume with the material of the core volume, whereby the liquidus temperature of the boundary layer is increased, so that the boundary layer at least partially isothermally solidifies or becomes more viscous.
The compositions of the core volume CK0 and the boundary layer CB0 are advantageously describable by vectors, wherein CK0:=(cK01, . . . , cK0N), wherein |CK0|=1, and wherein the cKi are the stoichiometric fractions of the components Ki i=1, . . . , N of the average composition of the active hard solder, or braze, in the core volume, wherein CB0:=(cB01, . . . , cB0N), wherein |CB0|=1, and wherein the cB0i are the stoichiometric fractions of the components Ki i=1, N of the average composition of the active hard solder, or braze, in the boundary layer.
In a further development of the method, the providing of the active hard solder, or braze, includes that a solder preform, which has the composition CK0, is coated by means of gas phase deposition, for example, by sputtering, on at least one surface, preferably on two oppositely lying surfaces, with a boundary layer, which has the composition CB0.
In a further development of the method, the providing of the active hard solder, or braze, includes that at least one surface section of a ceramic body, especially two oppositely lying surface sections of the two ceramic bodies, is, respectively are, coated with a boundary layer, which has the composition CB0, wherein the coating occurs, for example, by gas phase deposition, especially sputtering. In an embodiment of this further development of the method, there is arranged between the ceramic bodies provided with the boundary layer a solder preform, which has a core volume with the composition CK0, and which, in given cases, is coated with a boundary layer of composition CB0.
In a further development of the invention, the composition CK contains essentially zirconium and titanium, with (50+x) atom-% titanium and (50−x) atom-% zirconium, wherein x<10 especially x<5, wherein the composition CK0 is present especially in the α-(Zr, Ti) phase.
In a further development of the method, the composition CB0 comprises, for instance, 42 to 52 atom-% Zr, 23 to 28 atom-% Ni and 24 to 30 atom-% Ti, for example, 45 to 49 atom-% Zr, 24.5 to 27 atom-% Ni and 26 to 29.5 atom-% Ti, and preferably 47 atom-% Zr, 26 atom-% Ni and 27 atom-% Ti.
The invention will now be explained based on the example of an embodiment illustrated in the drawing, the figures of which show as follows:
The diagram shown in
According to the invention, a core volume of an active hard solder, or braze, is provided, which determines the mechanical properties of a joint formed therewith, having a composition CK0, for example, as a solder preform, wherein the surfaces of the core volume are coated with a boundary layer of a composition CB0, wherein the last named composition has a significantly lower melting point than the composition of the core volume.
The composition CK0 of the core volume is preferably so selected that the coefficient of thermal expansion of the composition deviates as little as possible from the coefficient of thermal expansion of the ceramic material of the ceramic bodies to be joined. The coefficient of thermal expansion was ascertained for different compositions. In such case, compositions of zirconium and titanium with (50+x) atom-% titanium and (50−x) atom-% zirconium, wherein x<10, especially x<5, especially in the α-(Zr, Ti) phase proved especially suitable as composition of the core volume CK0 for joining of corundum. For the coefficient of thermal expansion α(CK), α(CK)≤9.5·10−6/K, especially α(CK)≤9.2·10−6/K.
As shown in
The liquidus temperature of a composition of the core volume CK0 with 55 atom-% Zr and 45 atom-% Ni amounts, in contrast, to more than, for instance, 1200° C.
Correspondingly, the boundary layer can be reliably melted at a soldering temperature of 800° C. to 850° C., for example, without melting the core volume of the active hard solder, or braze.
As a result, the fine crystalline, respectively amorphous, structure of the core volume can be retained in the soldering. Solely at the interface between the boundary layer and the core volume is there, in given cases, an exchange of materials between the core volume and the boundary layer, such that the boundary layer experiences, sectionally, an increase of the liquidus temperature, which, depending on the selected soldering temperature, effects that regions of the boundary layer become isothermally viscous or solidify. In any case, however, the structure of the core volume scarcely changes.
As an example of application of this procedure, the components of a pressure measuring cell are joined.
The solder preform has the above described composition CK0 of the core volume, thus Zr and Ti in the stoichiometric ratio of, for instance, 3 to 1. The boundary layer has, in contrast, a composition CB0, which lies near or at the eutectic point E.
By soldering in high vacuum at, for example, 850° C., the boundary layers 4, 5 react with the platform and with the measuring membrane 1, 2, so that a joint is formed, wherein the core volume of the active hard solder, or braze, does not melt and essentially retains its amorphous structure. The measuring membrane and the platform each bear an electrode 7, 6 of a capacitive transducer, wherein the electrodes can be prepared, for example, by depositing Ni.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2012 110 618 | Nov 2012 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2013/072475 | 10/28/2013 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2014/072193 | 5/15/2014 | WO | A |
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|---|---|---|---|
| 5334344 | Hegner | Aug 1994 | A |
| 9136662 | Rossberg | Sep 2015 | B2 |
| 20050161494 | Matsu | Jul 2005 | A1 |
| 20120258322 | Berlinger | Oct 2012 | A1 |
| 20150135844 | Ponath | May 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 102656433 | Sep 2012 | CN |
| 102009054909 | Jun 2011 | DE |
| 102010043119 | May 2012 | DE |
| 102011005665 | Sep 2012 | DE |
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| International Search Report, EPO, The Netherlands, dated Dec. 3, 2013. |
| English Translation of the International Preliminary Report on Patentability, WIPO, Geneva, CH, dated May 21, 2015. |
| Number | Date | Country | |
|---|---|---|---|
| 20150298264 A1 | Oct 2015 | US |
