GB2125442A - A procedure for the hardening of materials - Google Patents
A procedure for the hardening of materials Download PDFInfo
- Publication number
- GB2125442A GB2125442A GB08314104A GB8314104A GB2125442A GB 2125442 A GB2125442 A GB 2125442A GB 08314104 A GB08314104 A GB 08314104A GB 8314104 A GB8314104 A GB 8314104A GB 2125442 A GB2125442 A GB 2125442A
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- GB
- United Kingdom
- Prior art keywords
- matrix material
- additive
- crystal lattice
- atoms
- additive element
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
Abstract
A method of hardening metals or ceramics which have fcc, bcc or hcp structures in which two species of differing atomic radii are introduced into the material to be hardened. One species is of a size such that it can diffuse through the lattice normally. The other is of a size such that it can diffuse readily only along dislocations. Ion bombardment is the preferred method of introducing the species with different atomic radii. The material to be hardened is subjected to heat and plastic deformation so as to cause a large number of dislocations with jogs. The species meet at the jogs where they interact and are trapped and set up strain fields which prevent further deformation of the material.
Description
SPECIFICATION
A procedure for the hardening of materials
The present invention relates to the hardening of materials having face centred cubic (fcc), body centred cubic (bcc) or hexagonal close packed (hcp) structures, and in particular metals and alloys.
The durability of metallic surfaces is of great industrial importance for the life and reliability of many systems. Repair and replacement consume both energy and materials among other problems.
Thus a general method for treating metals and alloys, either throughout their bulk or within a surface zone, can be of considerable value.
A great many techniques for the hardening of metals for the incorporation of substitutional or interstitial impurities have already been developed. For instance, the introduction of nitrogen into steel by diffusion creates small precipitates of nitride, and dissolved nitrogen which form obstacles to the easy propagation of dislocations during subsequent plastic deformation during wear or mechanical stress.
It is known that in a few instances, for example
Hadfield steel (Fe12% Mn-i %C) there occurs a remarkable work hardening phenomenon which takes place during the first application of cold work on plastic deformation. After this, the alloy becomes extremely hard and tough, a feature which finds application in tank tracks, military helmets and earth-moving equipment. For the same reason, however, the alloy cannot be readily worked or machined but must be cast, ground or explosively deformed. The mechanism by which these properties are induced have been poorly understood since the alloy was discovered about 100 years ago. Martensitic tranformations were first proposed, but this suggestion has since been disproved.It has been suggested also that magnetic spin flip properties of manganese are involved, but this does not account for the occurrence of similar behaviour in titanium containing tin and nitrogen. Another suggestion is that manganese-carbon couples reorient in the elastic strain field of a nearby dislocation, presumably thereby converting local mechanical strain energy into heat by the dissipative Snoek relaxation.
An alternative explanation can be offered as follows. At an appropriate temperature, substitutional over-sized impurities such as Mn in
Fe or Sn in Ti can migrate along dislocations, this transport being known as pipe diffusion. The behaviour is complicated by the existence of discontinuities on dislocations known as jogs which, again at the appropriate temperature, may create traps that arrest the migrating atoms. The elastic strain field surrounding such a misfit atom at a jog may then trap mobile, small interstitial atoms such as carbon or nitrogen, to form a substitutional-interstitial pair or couple. Suppose now that a stress is applied to the metal in excess of Peierls-Nabarro stress at which a dislocation would normally be induced to move.The pinning effect of the trapped misfit atom will impede dislocation movement, effectively hardening the alloy, while the local anisotropy of the applied stress will cause a relocation of the associated interstitial by a Snoek relaxation to an energetically-favoured neighbouring interstitial site, thus dissipating mechanical energy into heat, which will be conducted away. As in the inelastic interaction between interstitials decorating dislocations (the so-called Cottrell atmosphere) this inelastic interaction between otherwise mobile dislocations and substitutional-interstitial pairs decorating jogs will be a beneficial process that relieves local mechanical strain energy.
According to the present invention there is provided a process for hardening materials having face centred cubic, body centred cubic or hexagonal close packed crystal structures, other than steel having a composition of approximately 97% iron, 12% manganese and 1% carbon, comprising the operations of incorporating into a body of matrix material of one of the above specified types, atoms of a first element such that they will be oversize in relation to the crystal lattice of the matrix material together with atoms of a second element such that they will be capable of occupying interstitial sites within the crystal lattice of the matrix material, heating the matrix material to a temperature such that the atoms of the first element can migrate through the crystal lattice of the matrix material and form substitutionalinterstitial pairs with the atoms of the second element which accuniulate at dislocations within the crystal lattice of the matrix material, and subjecting the body of matrix material to a forming process so as to form discontinuities in the dislocations in the crystal lattice of the matrix material.
According to another aspect of the present invention there is provided a process for hardening materials having face centred cubic, body centred cubic or hexagonal close packed crystal structures, comprising the operations of depositing upon a surface of a body of a matrix material to be hardened a layer of a first additive element having atoms which will be over-size in relation to the atoms of the matrix material in the crystal lattice of the matrix material, subjecting the body of matrix material to bombardment with ions of a second additive element such that they will be capable of occupying interstitial sites within the crystal lattice of the matrix material, heating the body of matrix material to a temperature such that the atoms of the additive materials are mobile within the crystal lattice of the matrix material, and subjecting the body of matrix material to physical stress so as to cause the formation of dislocations having discontinuities therein at which entities formed by the association of pairs of the additive elements, or one of the additive elements and a vacancy in the crystal lattice of the matrix material, can be trapped.
If one or more of the additives is added by the non-equilibrium process of ion implantation, another beneficial effect can occur. If there is a strong binding energy between an implanted atom in the matrix material and a vacancy in the crystal lattice of the matrix material which has been produced by the ion bombardment, and either species is mobile, then a pair, or complex, may be formed. This entity may then migrate to a dislocation and become trapped there. A second mobile implanted atom subsequently may be trapped by the strain field of the first additive atom vacancy complex, thereby providing an additional hardening action.
The invention will now be described with reference to the following examples: Example 1
Bodies of titanium had a layer of thin tin some 600A thick deposited on a region of one surface.
The tin was then bombarded with energetic ions of nitrogen having an energy of 100 keV at temperatures in the range of 450-5500C until concentrations of about 10 atomic per cent were introduced into the said regions of the surfaces of the bodies by the process of ion beam mixing. In subsequent tests using standard pin-on-disc wear measuring machines, which will not be described further as they do not form part of the present invention, reductions in the wear rate by factors of between 300 and 1000 were measured. Similar results were obtained when the ion beam mixing was carried out using neon or oxygen ions. The temperature was found not to be critical providing that it was greater than that at which the implanted species and vacancies become mobile in titanium.The ion beam mixing process also provided at least some of the mechanical stressing to produce the required jogs in dislocations in the titanium lattice, which is of the hexagonal close packed form. The preparation of the titanium surface prior to the implantation process provided the remainder of the required physical stress.
Example 2
A layer of tin some 600A thick was deposited on the surface of samples of iron and other ferrous alloys as before, and then subjected to bombardment with nitrogen ions, having an energy of 100 keV again until about the same concentrations of the added elements were present in the surface regions of the iron and ferrous alloy samples. The ion bombardment was carried out at temperatures in the range 2503500C. Similar reductions in wear rate to those for Example 1 were measured.
Example 3
Yttrium and nitrogen were introduced into stainless steel specimens by simultaneous ion bombardment in approximately stoichiometric proportions. The ion beam energies were in the range 100--200 keV, and the temperatures were in the range 200--3 500C. Reductions in the wear rate by a factor of at least 900 were measured.
In all three examples, the performance greatly exceeds that which can be achieved by the incorporation of the substitutional species (the tin or the yttrium) or the interstitial species (the nitrogen, neon or oxygen) alone.
Example 4
An example of the invention applied to a nonmetallic material is the incorporation of titanium or zirconium together with boron into the corrosion scale that grows on the nickelcontaining steels which are used for the tips of the burners which are used in oil-fired power stations. Again the implantation was done at temperatures in the region of 5000 C, and with ion energies in the range 100--200 keV.
Boron was chosen as the light interstitial species because it reacts strongly with titanium which is over-sized in the iron or nickel-based constituents of the scale. Boron was selected also in order to minimise out-diffusion from the implanted steel at the initial stage of heating.
Over 8,000 hours of use at an operating temperature of 5500C, the rate of erosion of the treated tips by sand particles entrained in fuel oil was reduced by a factor of ten, at least, compared with untreated burner tips.
The examples quoted above all use ion implantation to introduce the alloying species, but the invention is not restricted to such a method of introduction of the alloying species.
In general terms what is required is that there should be a combination of an alloying procedure of any convenient kind together with a thermomechanical process designed to induce the maximum density of substitutional-interstitial, or impurity-vacancy pairs trapped at dislocation jogs, preferably in fcc or hcp crystal structures.
This series of treatments can be applied either throughout the bulk of the material, as in the manufacture of Hadfield steel, or locally, as in the examples quoted above.
The principles of the process are that:
(i) There must be chosen a first additive material which is over-size in the crystal lattice of the matrix material. Examples, some of which are used above, are Mn in Fe, Sn in Ti, Y in stainless steel.
(ii) There must be chosen a light second additive which can be interstitial in the crystal lattice of the matrix material. Examples are B, C,
N, O, Ne.
(iii) The phase diagram of the alloy must allow the achievement of an fcc, hcp or bcc crystal structure. Thus Hadfield steel is a single phase y fcc alloy.
(iv) There must be at an early stage in the process a thermal process designed to cause the oversized additive atoms to segregate to dislocations and to form pairs with the interstitial atoms, rather than allowing second phase precipitates such as nitrides or carbides to develop. What is required is a solid solution of paired additive atoms. In regard to the behaviour of Hadfield steel, for example, it is known that manganese has the property in iron of greatly suppressing nitride formation, while in hcp titanium and zirconium, tin has a similar influence on the precipitation of nitride or oxide precipitates, a feature used in the alloy Zircalloy 2.
The temperature should also be such that the migration of either substitutional-interstitial or impurity-vacancy complexes to dislocations and their trapping there will occur rapidly, and dissociation of the pairs will be unlikely.
(v) Finally, if the process is carried out in bulk, there must be a rapid and massive application of plastic deformation. (For example, by explosive forming, shot peening, etc.) carried out at that temperature so as to create a maximum density of dislocations and entanglements containing many jogs.
There will be an optimum concentration of substitutional and interstitial atoms, ideally stoichiometric for any given matrix material, which can be found empirically, and is related to the maximum density of dislocation jogs which is obtainable.
Claims (8)
1. A process for hardening materials having face centred cubic, body centred cubic or hexagonal close packed crystal structures, other than steel having a composition of approximately 97% iron, 12% manganese and 1% carbon, comprising the operations of incorporating into a body of matrix material of one of the above specified types, atoms of a first element such that they will be oversize in relation to the crystal lattice of the matrix material together with atoms of a second element such that they will be capable of occupying interstitial sites within the crystal lattice of the matrix material, heating the matrix material to a temperature such that the atoms of the first element can migrate through the crystal lattice of the matrix material and form substitutional-interstitial pairs with the atoms of the second element which accumulate at dislocations within the crystal lattice of the matrix material, and subjecting the body of matrix material to a forming process so as to form discontinuities in the dislocations in the crystal lattice of the matrix material.
2. A process for hardening materials having face centred cubic, body centred cubic or hexagonal close packed crystal structures, comprising the operations of depositing upon a surface of a body of a matrix material to be hardened a layer of a first additive element having atoms which will be over-size in relation to the atoms of the matrix material in the crystal lattice of the matrix material, subjecting the body of matrix material to bombardment with ions of a second additive element such that they will be capable of occupying interstitial sites within the crystal lattice of the matrix material, heating the body of matrix material to a temperature such that the atoms of the additive materials are mobile within the crystal lattice of the matrix material, and subjecting the body of matrix material to physical stress so as to cause the formation of dislocations having discontinuities therein at which entities formed by the association of pairs of the additive elements, or one of the additive elements and a vacancy in the crystal lattice of the matrix material, can be trapped.
3. A process according to Claim 2, wherein the ion bombardment is utilised both to heat the body of matrix material and to cause at least partially the physical stress to the body of matrix material.
4. A process according to Claim 1, Claim 2 or
Claim 3, wherein the matrix material contains at least a predominance of titanium, the first additive element is tin, the second additive element is selected from the group comprising boron, carbon, nitrogen, oxygen and neon, the body of matrix material is heated to a temperature in the range 450550 C, and the additive elements are present at a concentration of approximately ten atomic per cent.
5. A process according to Claim 1, Claim 2 or
Claim 3, wherein the matrix material is predominantly iron, the first additive element is tin, the second additive element is nitrogen which is implanted into the body of matrix material with energies of approximately 100 keV and the body of matrix material is heated to a temperature in the range 250-35O0C.
6. A process according to Claim 2 or Claim 3, wherein the body of matrix material is made of stainless steel, the first additive element is yttrium, the second additive element is nitrogen, the body of matrix material is heated to a temperature in the range 200-3500C and the additive elements are both implanted into the body of stainless steel by means of ion bombardment, the ions having energies in the range of 100200 keV.
7. A process according to Claim 2 or Claim 3, wherein the matrix material is a nickel-containing predominantly non-metallic substance, the first additive element is titanium or zirconium, the second additive element is boron, and both the additive elements are implanted by means of ion bombardment at ion energies in the range 100200 keV and at temperatures of approximately 500"C.
8. A process for hardening materials having face centred cubic, body centred cubic or hexagonal close packed crystal lattices substantially as hereinbefore described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08314104A GB2125442B (en) | 1982-05-24 | 1983-05-24 | A procedure for the hardening of materials |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8215107 | 1982-05-24 | ||
| GB08314104A GB2125442B (en) | 1982-05-24 | 1983-05-24 | A procedure for the hardening of materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2125442A true GB2125442A (en) | 1984-03-07 |
| GB2125442B GB2125442B (en) | 1986-02-19 |
Family
ID=26282925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08314104A Expired GB2125442B (en) | 1982-05-24 | 1983-05-24 | A procedure for the hardening of materials |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2125442B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181073A1 (en) * | 1984-10-05 | 1986-05-14 | Osaka University | Method for controlling the injection and concentration of a supersaturation of exotic atoms deeply into a solid material |
| EP0192874A1 (en) * | 1985-02-27 | 1986-09-03 | Osaka University | Method for injecting exotic atoms into a solid material with electron beams |
| EP0193674A1 (en) * | 1985-03-06 | 1986-09-10 | Osaka University | Method of amorphizing a solid material by injection of exotic atoms with electron beams |
| GB2175316A (en) * | 1985-05-17 | 1986-11-26 | Atomic Energy Authority Uk | Improved cutting edges |
| US4724016A (en) * | 1985-09-19 | 1988-02-09 | Combustion Engineering, Inc. | Ion-implantation of zirconium and its alloys |
| EP0374557A2 (en) * | 1988-12-19 | 1990-06-27 | Mca Micro Crystal Ag | Ion diffusion-induced anti-wear layer |
| US6335062B1 (en) * | 1994-09-13 | 2002-01-01 | The United States Of America As Represented By The Secretary Of The Navy | Reactive oxygen-assisted ion implantation into metals and products made therefrom |
| EP1507023A1 (en) * | 2003-08-14 | 2005-02-16 | Voith Paper Patent GmbH | Alloy for making wear-resistant tools. |
| WO2005084584A1 (en) * | 2004-03-02 | 2005-09-15 | Boston Scientific Scimed, Inc. | Medical devices including metallic films and methods for making same |
| US7901447B2 (en) | 2004-12-29 | 2011-03-08 | Boston Scientific Scimed, Inc. | Medical devices including a metallic film and at least one filament |
| US8591568B2 (en) | 2004-03-02 | 2013-11-26 | Boston Scientific Scimed, Inc. | Medical devices including metallic films and methods for making same |
| US8632580B2 (en) | 2004-12-29 | 2014-01-21 | Boston Scientific Scimed, Inc. | Flexible medical devices including metallic films |
| US8992592B2 (en) | 2004-12-29 | 2015-03-31 | Boston Scientific Scimed, Inc. | Medical devices including metallic films |
| US8998973B2 (en) | 2004-03-02 | 2015-04-07 | Boston Scientific Scimed, Inc. | Medical devices including metallic films |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7854760B2 (en) | 2005-05-16 | 2010-12-21 | Boston Scientific Scimed, Inc. | Medical devices including metallic films |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB207254A (en) * | 1922-08-22 | 1923-11-22 | Harry Ewart Weight | Improvements in and relating to the inner tubes of pneumatic tyres |
| GB1380583A (en) * | 1971-01-21 | 1975-01-15 | Gillette Co | Cutting edges |
| GB1423412A (en) * | 1972-08-09 | 1976-02-04 | Engel N N | Ion plating method and product therefrom |
-
1983
- 1983-05-24 GB GB08314104A patent/GB2125442B/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB207254A (en) * | 1922-08-22 | 1923-11-22 | Harry Ewart Weight | Improvements in and relating to the inner tubes of pneumatic tyres |
| GB1380583A (en) * | 1971-01-21 | 1975-01-15 | Gillette Co | Cutting edges |
| GB1423412A (en) * | 1972-08-09 | 1976-02-04 | Engel N N | Ion plating method and product therefrom |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181073A1 (en) * | 1984-10-05 | 1986-05-14 | Osaka University | Method for controlling the injection and concentration of a supersaturation of exotic atoms deeply into a solid material |
| EP0192874A1 (en) * | 1985-02-27 | 1986-09-03 | Osaka University | Method for injecting exotic atoms into a solid material with electron beams |
| EP0193674A1 (en) * | 1985-03-06 | 1986-09-10 | Osaka University | Method of amorphizing a solid material by injection of exotic atoms with electron beams |
| GB2175316A (en) * | 1985-05-17 | 1986-11-26 | Atomic Energy Authority Uk | Improved cutting edges |
| GB2175316B (en) * | 1985-05-17 | 1989-04-26 | Atomic Energy Authority Uk | Improved cutting edges |
| US4724016A (en) * | 1985-09-19 | 1988-02-09 | Combustion Engineering, Inc. | Ion-implantation of zirconium and its alloys |
| EP0374557A2 (en) * | 1988-12-19 | 1990-06-27 | Mca Micro Crystal Ag | Ion diffusion-induced anti-wear layer |
| EP0374557A3 (en) * | 1988-12-19 | 1991-08-07 | Mca Micro Crystal Ag | Ion diffusion-induced anti-wear layer |
| US6335062B1 (en) * | 1994-09-13 | 2002-01-01 | The United States Of America As Represented By The Secretary Of The Navy | Reactive oxygen-assisted ion implantation into metals and products made therefrom |
| EP1507023A1 (en) * | 2003-08-14 | 2005-02-16 | Voith Paper Patent GmbH | Alloy for making wear-resistant tools. |
| WO2005084584A1 (en) * | 2004-03-02 | 2005-09-15 | Boston Scientific Scimed, Inc. | Medical devices including metallic films and methods for making same |
| US8591568B2 (en) | 2004-03-02 | 2013-11-26 | Boston Scientific Scimed, Inc. | Medical devices including metallic films and methods for making same |
| US8998973B2 (en) | 2004-03-02 | 2015-04-07 | Boston Scientific Scimed, Inc. | Medical devices including metallic films |
| US7901447B2 (en) | 2004-12-29 | 2011-03-08 | Boston Scientific Scimed, Inc. | Medical devices including a metallic film and at least one filament |
| US8632580B2 (en) | 2004-12-29 | 2014-01-21 | Boston Scientific Scimed, Inc. | Flexible medical devices including metallic films |
| US8864815B2 (en) | 2004-12-29 | 2014-10-21 | Boston Scientific Scimed, Inc. | Medical devices including metallic film and at least one filament |
| US8992592B2 (en) | 2004-12-29 | 2015-03-31 | Boston Scientific Scimed, Inc. | Medical devices including metallic films |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2125442B (en) | 1986-02-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20010524 |