GB2114040A - Sealing ceramic to ceramic or to metal - Google Patents
Sealing ceramic to ceramic or to metal Download PDFInfo
- Publication number
- GB2114040A GB2114040A GB08203497A GB8203497A GB2114040A GB 2114040 A GB2114040 A GB 2114040A GB 08203497 A GB08203497 A GB 08203497A GB 8203497 A GB8203497 A GB 8203497A GB 2114040 A GB2114040 A GB 2114040A
- Authority
- GB
- United Kingdom
- Prior art keywords
- seal
- tin
- ceramic
- articles
- article
- 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.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 238000007789 sealing Methods 0.000 title 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005350 fused silica glass Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- 238000005275 alloying Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 7
- -1 titanium hydride Chemical compound 0.000 description 3
- 229910000048 titanium hydride Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
- C04B37/026—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of metals or metal salts
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/04—Joining glass to metal by means of an interlayer
- C03C27/042—Joining glass to metal by means of an interlayer consisting of a combination of materials selected from glass, glass-ceramic or ceramic material with metals, metal oxides or metal salts
- C03C27/046—Joining glass to metal by means of an interlayer consisting of a combination of materials selected from glass, glass-ceramic or ceramic material with metals, metal oxides or metal salts of metals, metal oxides or metal salts only
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/08—Joining glass to glass by processes other than fusing with the aid of intervening metal
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
- C04B37/006—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of metals or metal salts
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
- C04B2237/126—Metallic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
- C04B2237/127—The active component for bonding being a refractory metal
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/40—Metallic
- C04B2237/405—Iron metal group, e.g. Co or Ni
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Structural Engineering (AREA)
- Joining Of Glass To Other Materials (AREA)
- Gasket Seals (AREA)
Abstract
A satisfactory seal between two ceramic articles, or between a ceramic article and a metal article, the articles being of materials each having a low coefficient of linear expansion less than 2 x 10<-6> per degree Kelvin, at 20 DEG C, the seal being provided by forming layers of an alloy of tin with titanium or zirconium adjacent to the article surfaces, and with unalloyed tin between the alloy layers. A ceramic article may be of a glass ceramic, or of fused silica; and a metal article may be of a suitable nickel-iron alloy.
Description
SPECIFICATION
Seals between ceramic articles or between ceramic articles and metal articles
This invention relates to seals between two ceramic articles, or between a ceramic article and a metal article, and in particular to such seals associated with articles of materials having low coefficients of linear expansion, each less than 2 x 10-6 per degree Kelvin at 200C.
The articles may be of a glass ceramic, or of fused silica, or of a nickel-iron alloy.
Titanium or zirconium reacts with the surfaces of such articles, but titanium or zirconium alone is unsuitable to comprise such a seal, being too reactive for this purpose, being capable of damaging the articles. However, an alloy containing titanium or zirconium can be provided, and is suitable for this purpose.
It is known to provide seals between such articles by providing an assembly including titanium or zirconium to form a liquid alloy with a larger quantity of an alloying material, when the alloying material is melted. The liquid alloy including the titanium or zirconium reacts with the article surfaces, and wets these surfaces, the alloy layers adhering to the article surfaces when solidified, and substantially only sufficient titanium or zirconium is provided for this purpose. Known alloying materials include the copper-silver eutectic, and pure silver. The liquid alloy including the titanium or zirconium is formed, at least, at the melting point of the alloying material.
For convenience, in this specification and the accompanying claims, the term alloy is employed to include a reference to a solution of the material referred to above as the alloying material and either the titanium or zirconium.
Also for convenience, in this specification and the accompanying claims, such a seal containing an alloy of titanium or zirconium is referred to as a seal of the type referred to.
Usually, pure titanium or zirconium is not provided initially on the article surfaces, but instead a compound, such as the hydride thereof, is provided, and when the compound decomposes the element thereby provided is capable of forming the required liquid alloy. The liquid alloy may be formed immediately, or at a higher temperature. Thus, it is required that the alloying material is stable, at least, at the temperature at which the compound decomposes. Usually, the whole of the seal providing operation is performed in a substantial vacuum.
Further, it is required that the temperature at which the compound decomposes, and the time the materials are held at this, or at a higher temperature, are sufficient to cause any surface oxide to be absorbed.
It is essential that the articles are not damaged by being held at the temperature referred to in the preceding paragraph. Thus, this temperature may be required to be lower than that associated with the use of the copper-silver eutectic, or of pure silver, in forming a seal of the type referred to.
In addition, the higher the solidification temperature of the composite seal the greater the effect of any differences between the coefficients of expansion of the different materials of the composite body comprising the articles, and the constituent parts of the formed composite seal of the type referred to between the articles.
In contrast, the solidification temperature may not be required to be so low that the composite body, comprising the articles with the formed composite seal of the type referred to therebetween, cannot be effectively outgassed, if such outgassing is desirable.
Other desirable properties of the alloying material are that it is soft when solidified, to enable it to accommodate any differential thermal expansion within the composite body; and it is required to have a low vapour pressure at the temperature at which the assembly is held.
It is an object of the present invention to provide a novel and advantageous alloying material, for forming an alloy with titanium or zirconium, in order to provide a seal of the type referred to between two ceramic articles, or between a ceramic article and a metal article, such that an advantageous combination of the desirable criteria referred to above for such an alloying material is obtained.
According to the present invention a seal of the type referred to, between two ceramic articles, or between a ceramic article and a metal article, the articles being of materials having low coefficients of linear expansion, each less than 2 x 10-6 per degree Kelvin at 200 C, includes an alloying material comprising tin, there being alloy layers of tin with titanium or zirconium adjacent to the article surfaces, with soft tin, containing little or no titanium or zirconium, between the alloy layers.
Such a seal is satisfactory, and the composite body so provided readily can be baked in vacuo at 2000C for several hours, in order to outgas the composite body.
According to another aspect, the present invention comprises a method of providing a seal of the type referred to, the method comprising coating the articles with layers containing titanium or zirconium, providing tin between the titanium or zirconium containing layers, and heating the assembly to cause the tin to alloy with the titanium, or zirconium, the alloy to wet the article surfaces, and there is provided the required seal between the articles when the composite body, thereby obtained, is cooled.
Usually the titanium or zirconium layers are provided by coating the articles with a suspension of a titanium or zirconium compound, such as the hydride thereof, in a suitable binder, and allowing the suspension to dry. Subsequently, the binder and the hydrogen are removed by the heating, the titanium or zirconium, and the tin, forming the liquid alloy.
An oxide layer readily forms on tin, and such an oxide layer is deleterious for the required seal.
Consequently, the tin is coated with a thin layer of silver, or is washed in an acid to remove the oxide layer, before the tin is incorporated into the seal.
The present invention will now be described by way of example with reference to the following
Examples.
EXAMPLE 1
An article of a glass ceramic, having a low coefficient of linear expansion of 0.03 x 10-6 per degree Kelvin at 200 C, is coated in any convenient way with a suspension of titanium hydride in a nitrocellulose binder, and is allowed to dry.
Another article of the glass ceramic is similarly coated. A layer of tin foil, or tin wire, coated with a thin layer of silver, and approximately, 10 times the volume of the provided titanium, is p!aced between the titanium hydride layers. The whole is then placed in a vacuum furnace, with an atmosphere of less than 1 x 1 0-6 newtons per square metre, and a small load is applied to the assembly. The furnace is heated at a temperature of 6000C for 1 5 minutes, and is allowed to cool to 2000 C, before being gas cooled to 1 000C, and fast cooled from 1000C to room temperature.
During the heating process step, the binder and the hydrogen are removed from the titanium hydride layers, and the titanium alioys with the tin, adjacent to the article surfaces, the element immediately forming the liquid alloy. Any surface impurity on the silver is absorbed in the melt; and the titanium-tin alloy wets the surfaces of the articles. Soft tin, containing little or no titanium, remains between the alloy layers. Upon cooling, a satisfactory seal is provided between the two articles. The composite body is then outgassed by being heated at a temperature of 2000C for 3 hours in vacuo.
EXAMPLE 2
Example 1 is repeated, except that one of the glass ceramic articles is replaced by an article of a nickel-iron alloy, having a composition of 36% by weight of nickel, 64% by weight of iron, together with incidental impurities. This alloy has a low coefficient of linear expansion of less than 1 x 10-6 per degree Kelvin at 200C. The titaniumtin alloy wets the surface of the nickel-iron alloy article. A satisfactory seal is provided between the two articles.
The required titanium containing layers on the articles may be provided on the articles in any convenient way.
One, or both, of the articles may be of fused silica, having a coefficient of linear expansion of 0.4 x 10-6 per degree Kelvin at 200C.
Zirconium may replace the titanium.
The tin is coated with silver to prevent a deleterious oxide layer being formed on the tin.
Alternatively, such an oxide layer is removed by washing the tin in an acid immediately before the tin is incorporated into the seal.
Claims (14)
1. A seal of the type referred to, between two ceramic articles, or between a ceramic article and a metal article, the articles being of materials having low coefficients of linear expansion, each less than 2 x 10-6 per degree Kelvin at 200C. the seal including an alloying material comprising tin, there being alloy layers of tin with titanium or zirconium adjacent to the article surfaces, with soft tin, containing little or no titanium or zirconium, between the alloy layers.
2. A seal as claimed in claim 1 in which a ceramic article is of a glass ceramic, or of fused silica.
3. A seal as claimed in claim 1 or claim 2 in which a metal article is of a nickel-iron alloy.
4. A method of providing a seal of the type referred to, and of a form claimed in any one of the preceding claims, the method comprising coating the articles with layers containing titanium or zirconium, providing tin between the titanium or zirconium containing layers, and heating the assembly to cause the tin to alloy with the titanium or zirconium, the alloy to wet the article surfaces, and there is provided the required seal between the articles when the composite body, thereby obtained, is cooled.
5. A method as claimed in claim 4 in which initially the articles are coated with a suspension of a titanium or zirconium compound in a suitable binder, and allowing the suspension to dry, and the compound is caused to decompose, the element forming the alloy with tin.
6. A method as claimed in claim 5 in which the compound is the hydride thereof.
7. A method as claimed in any one of claims 4 to 6 in which the seal is formed in a substantial vacuum.
8. A method as claimed in any one of the claims 4 to 7 in which the assembly is heated at a temperature of 6000C for 1 5 minutes.
9. A method as claimed in any one of claims 4 to 8 in which the tin is coated with a layer of silver before being incorporated in the seal.
10. A method as claimed in any one of claims 4 to 8 in which the tin is washed in an acid to remove any oxide layer on the tin, before the tin is incorporated in the seal.
11. A seal between two ceramic articles substantially as described herein with reference to
Example 1.
12. A seal between a ceramic article and a metal article substantially as described herein with reference to Example 2.
13. A method of providing a seal between two ceramic articles substantially as described herein with reference to Example 1.
14. A method of providing a seal between a ceramic article and a metal article substantially as described herein with reference to Example 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08203497A GB2114040B (en) | 1982-02-06 | 1982-02-06 | Sealing ceramic to ceramic or to metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08203497A GB2114040B (en) | 1982-02-06 | 1982-02-06 | Sealing ceramic to ceramic or to metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2114040A true GB2114040A (en) | 1983-08-17 |
| GB2114040B GB2114040B (en) | 1985-08-07 |
Family
ID=10528165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08203497A Expired GB2114040B (en) | 1982-02-06 | 1982-02-06 | Sealing ceramic to ceramic or to metal |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2114040B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192295A (en) * | 1986-02-19 | 1987-08-22 | デグツサ・アクチエンゲゼルシヤフト | Soft solder alloy for mutual bonding of ceramic part or bonding with part consisting of metal |
| FR2619562A1 (en) * | 1987-08-18 | 1989-02-24 | Ferranti Int Signal | METHOD FOR SEALING TWO CERAMIC OR CERAMIC AND METALLIC ARTICLES |
| EP1065180A3 (en) * | 1999-06-30 | 2002-08-07 | Bormioli Rocco & Figlio S.p.A. | A method for treating a glass container for the adhesion of a thermoplastic polymer |
-
1982
- 1982-02-06 GB GB08203497A patent/GB2114040B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192295A (en) * | 1986-02-19 | 1987-08-22 | デグツサ・アクチエンゲゼルシヤフト | Soft solder alloy for mutual bonding of ceramic part or bonding with part consisting of metal |
| EP0235546A3 (en) * | 1986-02-19 | 1988-09-14 | Degussa Aktiengesellschaft | Use of a solder alloy for bounding ceramic parts |
| FR2619562A1 (en) * | 1987-08-18 | 1989-02-24 | Ferranti Int Signal | METHOD FOR SEALING TWO CERAMIC OR CERAMIC AND METALLIC ARTICLES |
| EP1065180A3 (en) * | 1999-06-30 | 2002-08-07 | Bormioli Rocco & Figlio S.p.A. | A method for treating a glass container for the adhesion of a thermoplastic polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2114040B (en) | 1985-08-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940206 |