WO2008037291A1 - Buffered optical fibre and method for improving the lifetime thereof - Google Patents
Buffered optical fibre and method for improving the lifetime thereof Download PDFInfo
- Publication number
- WO2008037291A1 WO2008037291A1 PCT/EP2006/066693 EP2006066693W WO2008037291A1 WO 2008037291 A1 WO2008037291 A1 WO 2008037291A1 EP 2006066693 W EP2006066693 W EP 2006066693W WO 2008037291 A1 WO2008037291 A1 WO 2008037291A1
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- WIPO (PCT)
- Prior art keywords
- optical fibre
- coating
- buffered optical
- fibre according
- buffered
- Prior art date
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Classifications
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- 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
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/106—Single coatings
-
- 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
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/465—Coatings containing composite materials
- C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4401—Optical cables
- G02B6/4402—Optical cables with one single optical waveguide
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
Definitions
- the present invention relates to a buffered optical fibre and a method for improving the lifetime thereof.
- the present invention relates to a buffered optical fibre comprising a tight-buffer coating and a method for improving the lifetime thereof under high power and small diameter bend improving the energy removal therefrom.
- An optical fibre generally comprises a core surrounded by a cladding (hereinafter both collectively referred to as "optical waveguide”), said core and cladding being preferably made of glass, and at least one exterior coating.
- the exterior coatings are two.
- the exterior coating directly contacting the optical waveguide is called “first coating” or “primary coating” and the exterior coating overlying the first one is called “second coating” or “secondary coating”.
- first coating or “primary coating”
- second coating or “secondary coating”.
- said first and second coatings are made of polymer material.
- optical fibre to be further coated by a buffer coating provided over the at least one exterior coating.
- a buffered optical fibre can be used as semi-finished component to form a cable in association with other components as required by the use.
- the buffered optical fibre can be used as such to act as a cable.
- these applications are indoor and premises applications, cable termination, pigtails, patchcords and, more generally, those applications implying the optical fibre to be subjected to additional mechanical and friction stress often repeated in time.
- said buffer coating is provided in contact with the at least one exterior coating it is said “tight buffer”, when said buffer coating is in form of a tube having an internal diameter larger than the overall external coating diameter it is said "loose buffer”.
- thermo runaway The phenomenon caused, e.g., by the accidental bending of a fibre in loops with small radius, or by an excess of power transmitted can be also referred to as "thermal runaway". Part of the guided light beam escapes from the fibre core and crosses the protective layers, where it is at least partially absorbed, and the absorption process heats the coating materials.
- US 2004/0175086 teaches that a portion of the input light energy can be incident on the core/cladding interface at an angle less than the critical angle of incidence. Upon such an occurrence, this light energy passes from the core and continues through the interface between the cladding and the coating, because the conventional coating has a higher index of refraction than that of the cladding. This light energy may be absorbed by the coating or any surrounding materials and converted into heat energy. The heat energy can cause localized damage to the optical fibre and surrounding materials, which significantly reduces the operational life of the fibre. This is particularly consequential in high-power applications, such as but not limited to those where the transmission signal has a power above 0.5 W.
- a severe bend such as one having a radius or kink smaller than about 10 mm, may cause signal energy propagating along the core to be injected into the cladding. Again, the escaping light energy is converted to heat upon leaving the cladding, which can overheat a localized portion of the optical transmission fibre, resulting in premature failure.
- US 2004/0175086 suggests to solve this problem with an optical transmission fibre, comprising:
- cladding material located around said core and having a second index of refraction less than said first index of refraction; - a first coating material located around a first portion of said cladding material and having a third index of refraction greater than the second index of refraction;
- this fibre has also the drawback that it cannot be "upjacketed" with a tight- buffer coating which would hinder dissipation of the light energy escaping the second coating material.
- WO 2004/066007 teaches an optical fibre that can stabilize and propagate high-power light without causing damage and the like to the optical fibre even if the optical fibre is temporarily bent with small curvature diameters, through the use of coating material with little absorption of the escaped light in the optical fibre, in particular through the use of transparent UV-cured resin as the coating material.
- the coating layer of the optical fibre is formed by a primary coating layer made of ultraviolet-cured resin, secondary coating layer, and coloured layer where the coloured layer intermittently does not coat - A -
- the secondary coating layer at a portion in the direction of the circumference.
- this fibre has the drawback that it cannot be "upjacketed” with a tight-buffer coating which would hinder dissipation of the light energy escaping the second coating material.
- US 2003/0133679 relates to an optical fibre including a glass or plastic core (or waveguide), a cladding on the waveguide, a primary coating on the cladding and a secondary coating on the primary coating.
- the optical fibre is coated with a flame retardant tight-buffer coating composition.
- the tight-buffer coating can be halogen-free or substantially halogen-free.
- Halogen-free flame retardants that have been found to be useful are flame retardant plasticizers and flame retardant acrylate oligomers.
- US 6,215,931 relates to flexible thermoplastic polyolefin elastomers for buffering a telecommunication cable element.
- Said thermoplastic polyolefin material may also contain organic or inorganic fillers. A reduction in the density of the material is advantageous because it allows for a reduction in cable weight.
- the buffer material is halogen free and can be made flame retardant.
- the Applicant faced the problem of protecting the optical fibres from damages arising from heat originated inside the fibre by light transported therethrough.
- the Applicant faced the problem of providing this kind of protection by means of a solution applicable to an optical fibre without of changing the chemical or physical features of the at least one exterior coating or coatings and/or of the cladding layer of the fibre.
- the Applicant perceived that the function of protecting the fibre from the said internally generated heat could be performed by a buffer coating made of a material endowed with specific physical properties.
- the present invention relates to a buffered optical fibre comprising a tight-buffer coating and a method for improving the lifetime thereof , even under high power and/or in the presence of small diameter bend.
- a buffer applied over the fibre not only does not hinder the heat dissipation, but rather it helps transferring the heat to the exterior of the without causing undesired overheating in the fibre, provided that such buffer is made of a material capable of withstanding the temperature and of effectively transmitting the heat.
- the lifetime of an optical fibre can be improved by providing a tight- buffer coating with a density greater than a predetermined value, in combination with a thermal conductivity higher than a predetermined value.
- Another physical property useful for characterizing a tight buffer coating material capable of removing energy from an optical fibre is the thermal diffusivity.
- - "high power” is intended a transmission signal having a power of at least 0.15 W, e.g. of 1 or 2 W;
- - "small diameter bend” is intended a U-bend having a radius equal to or lower than 15 mm; typically, said radius can be of from 12 to 4 mm;
- - "density” is intended the ratio of mass to volume; the unit of measurement is Kg/dm 3 ; - "thermal diffusivity” is intended the ratio of thermal conductivity to volumetric heat capacity; the unit of measurement is m 2 /(sec-10 ⁇ 6 ); the thermal diffusivity is the measure of the way heat flows through a material to the other side; the thermal diffusivity also provides indication of the capability of a material to adjust its own temperature to that of the surroundings;
- thermo conductivity is intended the physical property of a material that denotes its ability to transfer heat through its thickness; the unit of measurement is W/m-K;
- single-mode fibre is intended an optical fibre through which only one mode will propagate as defined in ITU-T G.652.
- the present invention provides a buffered optical fibre comprising an optical waveguide, at least one exterior coating surrounding said optical waveguide and a buffer coating surrounding said at least one exterior coating, wherein the said buffer coating is a tight buffer made of a material having a density of at least 1.2 Kg/dm 3 and a thermal conductivity of at least 0.4 W/m-K.
- the density of the coating material is of from 1.2 to 1.7 Kg/dm 3 . More preferably, the density of the coating material is of from 1.4 to 1.6 Kg/dm 3 .
- the thermal conductivity of the coating material is of from 0.4 to 0.8 VWmK, more preferably of from 0.6 to 0.75 VWmK.
- the coating material of the tight buffer coating according to the invention has a thermal diffusivity of at least 0.2 m 2 /(sec-10 "6 ).
- the thermal diffusivity of the coating material is of from 0.2 to 0.3 m 2 /(sec-10 "6 ).
- the optical waveguide according to the invention is a single-mode fibre
- the optical waveguide of the present invention is a glass fibre including a glass core surrounded by a glass cladding .
- the tight buffer coating of the present invention can have a thickness such to provide a buffered optical fibre with a diameter of from 650 to 1000 ⁇ m, more preferably of from 800 to 900 ⁇ m.
- the tight buffer coating material of the invention comprises a polymeric matrix and an inorganic filler.
- the polymeric matrix is selected from the group comprising polyethylene, polypropylene, ethylene-propylene copolymer, polymers and copolymers of C2 to Cs olefins ( ⁇ -olefin) such as polybutene, poly(4-methylpentene-1) or the like, copolymers of these olefins and diene, ethylene-acrylate copolymer, polystyrene, ABS resin,
- ⁇ -olefin such as polybutene, poly(4-methylpentene-1) or the like
- AAS resin AS resin, MBS resin, vinyl acetate resin, phenoxy resin, polyacetal, polyamide, polyimide, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, methacrylic resin, and mixture thereof.
- said polymeric matrix is selected from the group consisting of polymers and copolymers of C2 to Cs olefins ( ⁇ - olefin), ethylene-vinyl acetate copolymer resin, ethylene-butyl acrylate copolymer resin, and mixture thereof.
- polypropylene-based resins such as polypropylene homopolymers and ethylene-propylene copolymers
- polyethylene-based resins such as high-density polyethylene, low- density polyethylene, straight-chain low-density polyethylene, ultra low- density polyethylene
- EVA ethylene-vinyl acetate resin
- EEA ethylene-ethyl acrylate resin
- EBA ethylene-butyl acrylate resin
- EMA ethylene-methyl acrylate copolymer resin
- EAA ethylene-acrylic acid copolymer resin
- ultra high molecular weight polyethylene and polymers and copolymers of C2 to C ⁇ olefins ( ⁇ -olefin) such as polybutene and poly(4-methylpentene-1 ).
- thermosetting resins such as epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, alkyd resin and urea resin and synthetic rubbers such as EPDM, butyl rubber, isoprene rubber,
- SBR SBR
- NIR urethane rubber
- polybutadiene rubber acrylic rubber
- silicone rubber and NBR are included.
- the inorganic filler is selected from inorganic oxides and hydroxides, for example aluminium hydroxide and magnesium hydroxide, and mixtures thereof.
- the magnesium hydroxide is a synthetic magnesium hydroxide.
- the expression "synthetic magnesium hydroxide” is intended to mean a magnesium hydroxide in form of flattened hexagonal crystallites substantially uniform both in size and morphology. Such a product may be obtained by various synthetic routes involving the addition of alkalis to an aqueous solution of a magnesium salt and subsequent precipitation of the hydroxide by heating at high pressure (see for example US-4,098,762 or EP-780,425 or US-4,145,404).
- the amount of inorganic filler is of at least 30% by weight, preferably of from 50% to 80% by weight, relative to the total weight of the coating material composition.
- a coupling agent is preferably added.
- a coupling agent capable of increasing the interaction between the hydroxyl groups of and the polyolefin chains may be added to the mixture.
- This coupling agent can be selected from: saturated silane compounds or silane compounds containing at least one ethylenic unsaturation; epoxides containing an ethylenic unsaturation; monocarboxylic acids or, preferably, dicarboxylic acids having at least one ethylenic unsaturation, or derivatives thereof, in particular anhydrides or esters.
- Preferred silane compounds suitable for this purpose are: ⁇ -meth- acryloxypropyl-trimethoxysilane, methyltriethoxysilane, methyltris (2- methoxyethoxy)silane, dimethyldiethoxysilane, vinyltris (2-methoxyeth- oxy)-silane, vinylthmethoxysilane, vinyl-triethoxysilane, octyltriethoxysi- lane, isobutyl-triethoxysilane, isobutyltrimethoxysilane and mixtures thereof.
- Preferred epoxides containing an ethylenic unsaturation are: glycidyl acrylate, glycidyl methacrylate, monoglycidyl ester of itaconic acid, glycidyl ester of maleic acid, vinyl glycidyl ether, allyl glycidyl ether, or mixtures thereof.
- Preferred monocarboxylic or dicarboxylic acids, having at least one ethylenic unsaturation, or derivatives thereof, as coupling agents are, for example: maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, acrylic acid, methacrylic acid and the like, and anhydrides or esters derived therefrom, or mixtures thereof.
- Maleic anhydride is particularly preferred.
- Th e coupling agents can be used as such or pre-grafted onto a polyolefin, for example polyethylene or copolymers of ethylene with an alpha-olefin, by means of a radicalic reaction (see for example patent EP-530,940).
- the amount of grafted coupling agent is generally of from 0.05 to 5 parts by weight, preferably of from 0.1 to 2 parts by weight, with respect to 100 parts by weight of polyolefin.
- Polyolefins grafted with maleic anhydride are available as commercial products known, for example, under the trademarks Fusabond® (Du Pont), Orevac® (EIf Atochem), Exxelor® (Exxon Chemical), Yparex® (DSM).
- the coupling agents of carboxylic or epoxide type mentioned above for example maleic anhydride
- the silanes with ethylenic unsaturation for example vinylthmethoxysilane
- a radical initiator so as to graft the compatibilizing agent directly onto the polymer matrix.
- An organic peroxide such as tert-butyl perbenzoate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide and the like can, for example, be used as initiator.
- the amount of coupling agent that can be added to the mixture can vary mainly depending on the type of coupling agent used and on the amount of inorganic filler added, and is generally of from 0.01 % to 5%, preferably of from 0.05% to 2%, by weight relative to the total weight of the base polymer mixture.
- antioxidants which are suitable for this purpose are, for example: polymerized thmethyldihydroquinoline, 4,4'-thio-bis(3-methyl- 6-tert-butyl)phenol; pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxy- phenyl)propionate], 2,2'-thio-diethylene-bis-[3-(3,5-di-tert-butyl-4- hydroxy-phenyl)propionate] and the like, or mixtures thereof.
- fillers which may be used in the present invention include, for example, glass particles, glass fibres, calcined kaolin, talc and the like, or mixtures thereof.
- Processing co-adjuvants usually added to the polymer base are, for example, calcium stearate, zinc stearate, stearic acid, paraffin wax, silicone rubbers and the like, or mixtures thereof.
- the buffered optical fibre of the invention can comprise at least one exterior coatings.
- the buffered optical fibre of the invention comprises two exterior coatings which in the following of the description could also be referred to as first and second coating, the second coating being radially external to the first one.
- a first exterior coating suitable for the present invention can be made from a radiation curable coating composition comprising a radiation curable oligomer, said oligomer comprising a backbone derived from polypropylene glycol and a dimer acid based polyester polyol.
- the oligomer is a urethane acrylate oligomer comprising said backbone, more preferably a wholly aliphatic urethane acrylate oligomer.
- the polymeric material of said second exterior coating is also based on a radiation curable composition, preferably compatible with the first coating formulation. For example, if the first exterior primary coating has an acrylic base, the second exterior coating shall preferably have an acrylic base, too.
- the diameter of the optical waveguide can be of from 120 ⁇ m to 130 ⁇ m.
- the thickness of the first exterior coating can be of from 25 ⁇ m to 35 ⁇ m, while the thickness of the second exterior coating typically can be of from 10 ⁇ m to 30 ⁇ m.
- the diameter of the optical waveguide can be of from 120 ⁇ m to 130 ⁇ m.
- the thickness of the first coating 2 can be of from 18 ⁇ m to 28 ⁇ m, preferably of 22-23 ⁇ m, while the thickness of the second coating 3 can be of from 10 ⁇ m to 20 ⁇ m, preferably of 15 ⁇ m.
- the present invention provides a method for controlling the heat dispersion from an optical fibre, comprising an optical waveguide, by providing the optical fibre with a buffer coating in direct contact with said optical fibre, said buffer coating being made of a coating material having a density of at least 1.2 Kg/dm 3 and a thermal conductivity of at least 0.4 W/m-K.
- the present invention relates to the use of a material having a density of at least 1.2 Kg/dm 3 and a thermal conductivity of at least 0.4 W/m-K as energy removing tight buffer coating for a buffered optical fibre.
- the density of the coating material is of from 1.2 to 1.7 Kg/dm 3 .
- the density of the coating material is of from 1.4 to 1.6 Kg/dm 3 .
- the thermal conductivity of the coating material is of from 0.4 to 0.8 VWmK, more preferably of from 0.6 to 0.75 VWmK.
- the coating material of the tight buffer coating according to the invention has a thermal diffusivity of at least 0.2 m 2 /(sec-10 "6 ).
- the thermal diffusivity of the coating material is of from 0.2 to 0.3 m 2 /(sec-10 ⁇ 6 ).
- the above described material is used as tight buffer coating with a thickness such to provide a buffered optical fibre with a diameter of from 650 to 1000 ⁇ m, more preferably of from 800 to 900 ⁇ m.
- the tight buffer coating material of the invention comprises a polymeric matrix and an inorganic filler.
- Figure 2 shows the experimental set-up used to investigate the behaviour of a buffered optical fibre.
- a buffered optical fibre comprises a glass optical waveguide 1 (core+cladding), a first exterior coating 2, also known as primary coating, disposed to surround said waveguide 1 , and a second exterior coating 3, also known as secondary coating, disposed to surround said first coating 2.
- a tight buffer coating 4 is disposed to surrounding direct contact said second exterior coating 3. .
- the diameter of the optical fibre is of 250 ⁇ m with a first exterior coating thickness of 32.5 ⁇ m, while the thickness of the second exterior coating typically can be of from 27.5 ⁇ m.
- the thickness of the exterior first and second coating can be reduced to an overall diameter of 200 ⁇ m.
- the thickness of the first coating 2 can be of 22-23 ⁇ m, while the thickness of the second coating 3 can be of 15 ⁇ m.
- the thickness of the tight buffer coating 4 is such to bring the buffered optical fibre diameter to a value of 0.8 or 0.9 mm.
- the first coating 2 is made from a radiation curable composition comprising a radiation curable oligomer as disclosed by WO 01/05724.
- Th e buffered optical fibre of the invention can be manufactured according to known techniques. For example, the manufacturing process can be carried out in two steps, the first one comprising the sub-steps of drawing the optical waveguide and coating it with at least one exterior coating. At the end of this first step the resulting unbuffered optical fibre is collected on a reel and prepared for the second step. Said second step comprises the deposition of the tight buffer coating, for example, by extrusion.
- Zone 1 150 0 C / Zone 2:160 0 C / Zone 3:170°C / Collar: 180 0 C / Head: 180°C / Die: 180 °C
- Example 1 Composition 1-4
- Tight buffer coating materials according to the invention were made as set forth in Table 1.
- EscoreneTM UL Ethylene vinyl-acetate with 19 % vinylacetate (by
- KisumaTM 5-A synthetic magnesium hydroxide ( by KYOWA Chemical
- VestamideTM 1670 polyamide 12
- GrilamidTM L 20 LF graphite filled polyamide 12.
- the amount of the material is provided in phr
- Composition 3 and 4 are provided as comparison.
- the same kind of commercial optical fibre as above was provided with a tight buffer coating (final diameter: 900 ⁇ m) made with the composition 3 of Example 1 (F3), and tested according to the set-up discussed above.
- the buffer coating of F3 melted shortly and burnt afte 1.5 hour.
- SM Light (1) with DeSolite® 3471-1-129 as first exterior coating and DeSolite® 3471-2-136 as second exterior coating (by Prysmian Cavi e Navii Telecom); SF-SMF: by Samsung;
- Anywave® low water peak single mode fibre by Optomagic
- SMF28TM single mode optical fibre by Corning
- SM Light (2) with DeSolite® 6D1-78 as first exterior coating and DeSolite® 3471-2-136 as second exterior coating (by
- optical fibres buffered with a tight buffer according to the invention are capable to withstand high power while in small bend configuration without substantial damages such as melting of the buffer layer or burnt.
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Abstract
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2006/066693 WO2008037291A1 (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
BRPI0622013A BRPI0622013B1 (en) | 2006-09-25 | 2006-09-25 | buffered optical fiber, method for controlling heat dispersion of an optical fiber, and use of a material |
CN2006800559245A CN101588999B (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
US12/311,210 US8189979B2 (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
CA2664261A CA2664261C (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
PL06793800T PL2069253T3 (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
ES06793800T ES2745077T3 (en) | 2006-09-25 | 2006-09-25 | Protected fiber optic and method to improve its useful life |
EP06793800.1A EP2069253B1 (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
AU2006348909A AU2006348909B2 (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
ARP070104198A AR062951A1 (en) | 2006-09-25 | 2007-09-24 | OPTICAL FIBER WITH PROTECTIVE COATING AND METHOD TO IMPROVE THE USEFUL LIFE OF THE SAME |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2006/066693 WO2008037291A1 (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
Publications (1)
Publication Number | Publication Date |
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WO2008037291A1 true WO2008037291A1 (en) | 2008-04-03 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2006/066693 WO2008037291A1 (en) | 2006-09-25 | 2006-09-25 | Buffered optical fibre and method for improving the lifetime thereof |
Country Status (10)
Country | Link |
---|---|
US (1) | US8189979B2 (en) |
EP (1) | EP2069253B1 (en) |
CN (1) | CN101588999B (en) |
AR (1) | AR062951A1 (en) |
AU (1) | AU2006348909B2 (en) |
BR (1) | BRPI0622013B1 (en) |
CA (1) | CA2664261C (en) |
ES (1) | ES2745077T3 (en) |
PL (1) | PL2069253T3 (en) |
WO (1) | WO2008037291A1 (en) |
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Also Published As
Publication number | Publication date |
---|---|
AU2006348909B2 (en) | 2013-05-02 |
US8189979B2 (en) | 2012-05-29 |
CA2664261A1 (en) | 2008-04-03 |
CN101588999A (en) | 2009-11-25 |
AR062951A1 (en) | 2008-12-17 |
BRPI0622013A2 (en) | 2011-12-20 |
CA2664261C (en) | 2014-07-08 |
AU2006348909A1 (en) | 2008-04-03 |
ES2745077T3 (en) | 2020-02-27 |
PL2069253T3 (en) | 2020-02-28 |
EP2069253A1 (en) | 2009-06-17 |
EP2069253B1 (en) | 2019-06-19 |
BRPI0622013B1 (en) | 2017-03-21 |
CN101588999B (en) | 2013-01-09 |
US20090274424A1 (en) | 2009-11-05 |
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