CN102902008A - Polymer clad fiber and manufacturing method thereof - Google Patents
Polymer clad fiber and manufacturing method thereof Download PDFInfo
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- CN102902008A CN102902008A CN2012102618137A CN201210261813A CN102902008A CN 102902008 A CN102902008 A CN 102902008A CN 2012102618137 A CN2012102618137 A CN 2012102618137A CN 201210261813 A CN201210261813 A CN 201210261813A CN 102902008 A CN102902008 A CN 102902008A
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Abstract
The invention discloses a polymer clad fiber and a manufacturing method thereof. The polymer clad fiber (11) comprises an optical transmission line (11a) formed by glasses and a cladding (11b) for cladding the optical transmission line (11a). The cladding materials forming the cladding (11b) contain crosslinked and cured perfluoroether polymer due to a hydrosilylation reaction. Therefore, the polymer clad fiber with relatively high numerical aperture and relatively excellent moisture resistance can be obtained.
Description
Technical field
The present invention relates to a kind of polymer-clad fiber and manufacture method thereof.
Background technology
The polymer-clad fiber that the fibre core that has been formed by glass for the useful covering that is formed by polymkeric substance (clad) coating known to everybody as require the to have higher numerical aperture optical fiber that is used for closely data transmission, photoconduction or fiber laser etc. of (below, be called " NA " (numerical aperture)) consists of.
For example Japanese Laid-Open Patent Publication Unexamined Patent 5-112619 communique discloses and has used the covering that is formed by the resin combination that contains following reactive compounds to coat the fibre core that is formed by glass and the polymer-clad fiber that consists of, have at least two silicon atoms with at least two alkoxys bonding in the molecule of this reactive compounds, and have the functional group that at least one can form with UV-cured resin chemical bond.
International open WO96/013739 communique discloses following polymer-clad fiber, and the fibre core that the covering coating that this polymer-clad fiber forms by the solidfied material of using by the resin combination that contains carbamate two (methyl) acrylate (urethane di (metha) acrylate) and thinning agent is formed by glass consists of.
Japanese Laid-Open Patent Publication Unexamined Patent 10-197731 communique discloses following polymer-clad fiber, and this polymer-clad fiber is by using the fibre core that is formed by glass by the covering coating that the end at main chain has carbamate groups and bonding has (methyl) acrylate-based PFPE polymkeric substance to form to consist of.
Japanese Laid-Open Patent Publication JP 2009-198706 communique discloses following polymer-clad fiber, and this polymer-clad fiber is used the covering that is formed by the ultraviolet light curable fluorine resin to coat the fibre core that is formed by glass and consisted of.
In fields such as fiber laser or fiber amplifiers, use doubly clad optical fiber.
Japanese Laid-Open Patent Publication JP 2011-60854 communique discloses the doubly clad optical fiber that the fibre core that is added with rare earth element is coated by the first covering and this first covering is coated by the second covering again and consist of, the fibre core of this doubly clad optical fiber and the first covering are formed by quartz, and the second covering is formed by UV-cured resin.
Japanese Laid-Open Patent Publication JP 2010-250167 communique and Japanese Laid-Open Patent Publication JP 2010-250168 communique disclose the doubly clad optical fiber that fibre core is coated by the first covering and this first covering is consisted of by the coating of the second covering again, the fibre core of this doubly clad optical fiber and the first covering are formed by quartz, the clad that coats this fibre core and this first covering is made of a plurality of layers, and preferably the second clad in this clad is formed by UV-cured resin.
Summary of the invention
-in order to the technical scheme of technical solution problem-
The present invention relates to a kind of polymer-clad fiber, it has the optical transmission line that formed by glass and coats this optical transmission line and the covering established, and the clad material that forms described covering contains because the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation.
The present invention relates to a kind of manufacture method of polymer-clad fiber, the manufacture method of this polymer-clad fiber comprises that optical transmission line forms operation and covering forms operation, it is that the prefabricated component of being made by glass is carried out wire drawing that this optical transmission line forms operation, form the operation of optical transmission line, it is liquid blanket formation material to be attached to by described optical transmission line form on the surface of the established optical transmission line of operation that this covering forms operation, and make this covering form the material heat curing by heating, thereby form the operation of covering, described covering forms material and contains owing to the caused crosslinked perfluor ether polymer that solidifies of silicon hydrogenation.
The present invention relates to a kind of doubly clad optical fiber, it has fibre core, the first covering and the second covering, this fibre core is made by the glass that is added with rare earth element, this first covering is made by glass, coat this fibre core and establish, this fibre core of the refractive index ratio of this first covering is low, and this second covering coats this first covering and establishes, this first covering of the refractive index ratio of this second covering is low, and described doubly clad optical fiber is characterised in that: the second clad material that forms described the second covering is thermoset resin.
The present invention relates to a kind of manufacture method of doubly clad optical fiber, the manufacture method of this doubly clad optical fiber comprises that fibre core and the first covering form operation and the second covering forms operation, it is that the prefabricated component of being made by glass is carried out wire drawing that this fibre core and the first covering form operation, form the fibre core that is added with rare earth element and coat this fibre core and the operation of the first covering that this fibre core of refractive index ratio is low, it is liquid the second clad material to be attached to by described fibre core and the first covering form on the surface of established described the first covering of operation that this second covering forms operation, and make this second clad material heat curing by heating, thereby form the operation of the second low covering of this first covering of refractive index ratio, the manufacture method of described doubly clad optical fiber is characterised in that: described the second clad material contains owing to the caused crosslinked perfluor ether polymer that solidifies of silicon hydrogenation.
The present invention relates to a kind of manufacture method of doubly clad optical fiber heart yearn, the manufacture method of described doubly clad optical fiber heart yearn comprises that surface coating forms operation, this surface coating forms on the surface that operation is the doubly clad optical fiber that produces of the manufacture method that liquid surface coating (overcoat) material is attached to utilize the doubly clad optical fiber among the present invention, and makes the operation of this coating material heat curing by heating.
Description of drawings
Fig. 1 is stereographic map, and the related polymer-clad fiber heart yearn of the first embodiment is shown;
Fig. 2 is the figure that illustrates, the manufacture method of the related polymer-clad fiber heart yearn of the first embodiment is shown;
Fig. 3 (a) and Fig. 3 (b) are the figure of measuring method that the glass transition temperature of clad material is described;
Fig. 4 (a) and Fig. 4 (b) illustrate that the curing of covering formation material begins the figure of the measuring method of temperature;
Fig. 5 is stereographic map, and the related doubly clad optical fiber heart yearn of the second embodiment is shown;
Fig. 6 is stereographic map, and the related doubly clad optical fiber heart yearn of the 3rd embodiment is shown;
Fig. 7 (a)～Fig. 7 (d) is the figure that the glass transition temperature of the second clad material is described and solidifies the measuring method of beginning temperature;
Fig. 8 is the figure that the fiber laser that consists of with the related doubly clad optical fiber heart yearn of the 3rd embodiment is shown;
Fig. 9 is the figure that illustrates, the manufacture method of the related doubly clad optical fiber heart yearn of the 3rd embodiment is shown;
Figure 10 (a) is the figure that illustrates, the manufacture method of using the doubly clad optical fiber heart yearn that adds pressing mold is shown; Figure 10 (b) is the figure that illustrates, the manufacture method of the doubly clad optical fiber heart yearn that uses open die is shown;
Figure 11 is the figure that illustrates, illustrates to form the variation of the second heating furnace of surface coating;
Figure 12 (a) and Figure 12 (b) are curve maps, and the wavelength of Hot water immersion front and back and the relation between the loss are shown;
Figure 13 is curve map, and the relation between the NA of retention time under the hot environment and the first covering is shown;
Figure 14 is curve map, and the relation between the NA of retention time under 85 ℃ and 85% the hot and humid environment and the first covering is shown;
Figure 15 is curve map, and the relation between the NA of fiber lengths and the first covering is shown.
-description of reference numerals-
10-polymer-clad fiber heart yearn; The 11-polymer-clad fiber; 11a, 21a, 51a-fibre core (optical transmission line); 11b, 21b, 51b-(first) covering; 21c, 51c-the second covering; 12,22,52-surface coating; 20,50-doubly clad optical fiber heart yearn (polymer-clad fiber heart yearn); 21,51-doubly clad optical fiber (polymer-clad fiber); 30,80-wire drawing machine; 31,81-spinning stove; 32,82-(second) covering forming portion; 32a, 82a-the first coating mould; 32b, 82b-(first) heating furnace; 33,83-surface coating forming portion; 33a, 83a-the second coating mould; The 33b-ultraviolet lamp; 40A, 40B, 60A, 60B-rigid body pendulum-type physical property test device; 41A, 61A-load sample platform; 41B, 61B-load sample boat; 42A, 62A-tubular edge body; 42B, 62B-cutter shape border body; 43,63-weight; The 70-fiber laser; 71-fiber laser main body; 72-input side FBG; The 72a-diffraction grating; 73-outgoing side FBG; The 73a-diffraction grating; The 74-optical-fiber bundling device; The 74a-optical fiber pigtail; The 75-optical head; The 76-excitation source; 83b-the second heating furnace; 831b-upstream side heating furnace; 832b-downstream heating furnace; The F-film; The M-covering forms material; M1-the second covering forms material; The M2-coating material; The P-prefabricated component.
Embodiment
Polymer-clad fiber in the present embodiment has the optical transmission line that formed by glass and coats this optical transmission line and the covering established.Form as optical transmission line for example has following form: the form that optical transmission line is made of the high fibre core of refractive index ratio covering, and have on the surface of fibre core that the refractive index ratio fibre core is low and refractive index ratio one covering is high and the form of another covering of being formed by glass (in this case, claim that a covering is the second covering, claim that another covering is the first covering).Below,, as the second and the 3rd embodiment, with reference to accompanying drawing above embodiment is described in detail respectively with the latter as the first embodiment with the former.
(the first embodiment)
Fig. 1 illustrates the related polymer-clad fiber heart yearn 10 of the first embodiment.The polymer-clad fiber heart yearn 10 that this first embodiment is related is such as being used for closely data transmission or photoconduction etc.
The related polymer-clad fiber heart yearn 10 of the first embodiment is made of with the surface coating 12 that coats this polymer-clad fiber 11 the rounded polymer-clad fiber 11 of section.Core line diameter is for example 100 μ m～1000 μ m.
Polymer-clad fiber 11 is made of fibre core 11a (optical transmission line) and covering 11b, and this fibre core 11a is positioned at the center of optical fiber, and the section of this fibre core 11a is rounded, and this covering 11b coats this fibre core 11a and establishes.Fibre diameter is for example 50 μ m～700 μ m.
Covering 11b by containing since the clad material of the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation form.The thickness of covering 11b is for example 10 μ m～100 μ m.
The refractive index of the refractive index ratio fibre core 11a of covering 11b is low, for for example below 1.37.When using quartz glass as fibre core 11a, the refractive index of preferred covering 11b is below 1.35.In this polymer-clad fiber 11, because covering 11b has lower refractive index as mentioned above, so when with quartz glass during as fibre core 11a, the NA of fibre core 11a is preferably more than 0.55 for for example more than 0.50.When the light that penetrates from light source is converged, during to fibre core 11a incident, but the higher fibre core of NA can make the scope of incident angle of incident larger, but thereby can increase the light quantity of incident.NA utilizes FFP (far field pattern) method to measure according to Japanese Industrial Standards JIS C6822.
The density that forms the clad material of covering 11b is for example 1.70～1.80.The density of clad material is measured according to Japanese Industrial Standards JIS K0061.
The Young modulus that forms the clad material of covering 11b is for example 0.5MPa～50MPa.From the viewpoint of buffer action to external force, preferably the Young modulus of this clad material is 1MPa～10MPa.The tensile strength that forms the clad material of covering 11b is for example 1MPa～100MPa, and from the viewpoint of anti-external force, preferably the tensile strength of this clad material is more than the 10MPa.The breaking elongation that forms the clad material of covering 11b is for example 5%～100%, collateral security covering 11b follows fibre core 11a when making polymer-clad fiber 11 bending viewpoint, and preferably the breaking elongation of this clad material is 20%～100%.The Young modulus of clad material is obtained by following calculating, that is: according to Japanese Industrial Standards JIS K6251, in situation about the clad material of the strip that forms thickness 200 μ m and width 6mm being stretched with the draw speed of 1mm/min, the tension force when having extended 2.5% is divided by sectional area and length growth rate (0.025).The measurement as described below of tensile strength and breaking elongation, that is: according to Japanese Industrial Standards JIS K6251, setting specimen shape is that No. 2, inferior bell and sample thickness are 200 μ m, with the conditioned measurement of draw speed 50mm/min.
The Shore A level hardness (Shore A hardness) that forms the clad material of covering 11b is for example 10～80.From the viewpoint of the anti-external force of polymer-clad fiber 11, preferably the Shore A level hardness of this clad material is 25～80.The Shore A level hardness of clad material is according to Japanese Industrial Standards JIS K6253 A type hardness tester instrumentation amount.
The glass transition temperature (Tg) of the clad material of formation covering 11b is for for example below 0 ℃.From reducing polymer-clad fiber 11 in the viewpoint of reality with the characteristic variations in the zone, preferably the glass transition temperature of this clad material (Tg) is below-50 ℃.The glass transition temperature of clad material (Tg) is according to rigid body pendulum-type physical property test device 40A (for example, Co., Ltd. A﹠amp of following steps usefulness shown in Fig. 3 (a); D (A﹠amp; D Company, Limited) make model: RPT-3000W) measure.Should illustrate, rigid body pendulum-type physical property test device 40A comprises load sample platform 41A (being made by for example aluminium), is provided with tubular edge body (pipe edge) 42A (for example, the A﹠amp of Co., Ltd. at this load sample platform 41A; D makes, model: RPN160), and weight 43 (for example, the A﹠amp of Co., Ltd.; D makes, model: FRB100) be hung on this tubular edge body 42A, consist of thus pendulum.Under the atmospheric environment of room temperature, to be formed and the film F of the about 100 μ m of thickness is placed on the load sample platform 41A by clad material, the temperature that makes load sample platform 41A with the speed of 10 ℃/min again rises to 150 ℃ from-100 ℃, and pendulum is swung, and measures hunting period.If the viscoelasticity of clad material changes, then represent that with logarithm the value of the attenuation ratio of described hunting period is that logarithmic decrement will change, thereby shown in Fig. 3 (b), will show the maximum rate of change of described logarithmic decrement.With this temperature (that is, the single order differential curve of logarithmic decrement shows peaked temperature) that shows maximum rate of change as Tg.Should illustrate, when Tg is in the scope below-100 ℃, can utilize following methods to obtain Tg, that is: according to measuring with the device that can measure the scope below-100 ℃ with above identical principle, perhaps measure with the dynamic viscoelastic measurement mechanism, with the peak temperature of the tan δ that in the scope below-100 ℃, occurs as Tg.
The gel fraction (gel fraction) that forms the clad material of covering 11b is for example 90%～100%.From the viewpoint that the characteristic that prevents covering 11b changes in the dissolving under the high humidity environment at the volatilization under the hot environment or low molecular weight compositions owing to low molecular weight compositions, preferably the gel fraction of this clad material is 96%～100%.The mass change of the gel fraction of clad material during according to solvent extraction measured.Particularly, take MEK (boiling point is as 79.5 ℃) as solvent, with about 10 rate of circulation of taking turns per hour the Soxhlet that clad material carried out 5 hours is extracted, the dry mass of the clad material after the extraction is divided by proper mass, and the value of gained represents as gel fraction with percentage.
Clad material can become the sign that covering 11b is attached to the close attachment on the fibre core 11a to 90 ° of peel strengths of glass, and preferably this clad material is more than the 10N/m to 90 ° of peel strengths of glass.From the viewpoint that prevents that covering 11b from peeling off from fibre core 11a, further preferred this clad material is more than the 20N/m to 90 ° of peel strengths of glass.Clad material can utilize following methods to obtain to 90 ° of peel strengths of glass, that is: form material according to Japanese Industrial Standards JIS K6854-1 thickness coating covering with 100 μ m～200 μ m on glass substrate, be cured by crosslinked again, make this covering form material and become clad material, then only clad material is cut into strip with the width of 2.5cm, towards an end that up draws this strip clad material perpendicular to the direction of glass substrate with the pulling speed of 100mm/min, measure the tension force of this moment, the tension value that records just can be obtained clad material to 90 ° of peel strengths of glass divided by the width of the strip clad material of this measurement.
The thickness of surface coating 12 is for example 10 μ m～100 μ m.The refractive index of surface coating 12 is for example 1.4～1.57.The viewpoint of scattering and disappearing from suppressing cladding mode light, the refractive index of the refractive index ratio covering 11b of preferred surface coating 12 is high.The Young modulus that forms the resin of surface coating 12 is for example 100MPa～400MPa.From the stress that reduces can produce when the bending and the viewpoint of loss, the Young modulus of resin that preferably should form surface coating 12 is higher than the Young modulus of clad material.The gel fraction that forms the resin of surface coating 12 is for example 80%～100%, and preferably the gel fraction than clad material is low.From allowing the difference of the amount of contraction that the lost low molecular weight compositions that can produce when dry again after suction produces reduce, thereby be limited between surface coating 12 and the covering 11b and form the gap, seek thus the viewpoint of the inhibition of loss, the gel rate variance that is preferably formed the resin of surface coating 12 and clad material is less than 5%.
The related polymer-clad fiber heart yearn 10 of above-described the first embodiment constitutes: utilize the refringence of fibre core 11a and covering 11b, the light that inputs to fibre core 11a is enclosed in the fibre core 11a, and this light is transmitted.
In the polymer-clad fiber that covering is formed by thermosetting silicon resinoid because restriction on the characteristic of heat-curable silicone is arranged, so the refractive index of covering only can drop to about 1.41, thereby NA on be limited to about 0.37.On the other hand, in the polymer-clad fiber that covering is formed by ultraviolet light curable acrylate containing fluorine resin, if will reduce the refractive index of covering, just need to increase fluorinated volume.Yet if increase the fluorinated volume of covering, the intensity of covering will descend, thereby covering easily damages, although and the refractive index of covering drop to about 1.38, numerical aperture is that NA still only can rise to about 0.47.Say again, because acryloyl group has water wettability, so this covering is easy to moisture absorption; when for example being immersed in that water is medium to be directly exposed in the high humidity environment; moisture easily infilters in the covering, if the generation of the interface between fibre core and covering is peeled off thus, the loss of light will increase.Add, because this covering is formed by UV-cured resin, so when adopting the glass of some kind as the glass that forms fibre core, the glass of this formation fibre core can produce defective owing to the irradiation of ultraviolet light.
Yet, the polymer-clad fiber heart yearn 10 related according to the first embodiment, because covering 11b is formed by the perfluor ether polymer because of the caused crosslinked curing of silicon hydrogenation, so the refractive index of covering 11b significantly descends, consequently can make the NA of fibre core 11a higher.Because being the bonding position of carbon atom and silicon atom, the crosslinking points of clad material 11b has hydrophobicity, so can access good moisture resistance.And, by introducing among the clad material 11b with the alkoxy of the silicon atom bonding of covering 11b, then the compatibility between the glass of covering 11b and formation fibre core 11a will increase, thereby the close attachment between this covering 11b and this fibre core 11a will increase, consequently, can access more good moisture resistance.
Say again, can infer, the temperature dependency of the optical characteristics of the covering 11b that is formed by the perfluor ether polymer because of the caused crosslinked curing of silicon hydrogenation is less, thermotolerance is better, therefore can expect and can use under harsh and unforgiving environments and increase the service life.Add because covering 11b is formed by thermoset resin, so when optical fiber be when in fibre core 11a, being doped with the polymer-clad fiber 11 of the adulterants such as rare earth element, can prevent that fibre core 11a is owing to the ultraviolet light that shines worsens when forming covering 11b.
Then, with reference to Fig. 2 the manufacture method of the related polymer-clad fiber heart yearn 10 of the first embodiment is illustrated.Should illustrate, the below describes as an example of the situation that formed surface coating 12 by UV-cured resin example, but the present invention is not limited to this.
At first, be constructed for forming the glass prefabricated component P processed of fibre core 11a.As what the method for making of prefabricated component P can be enumerated known methods such as CVD (chemical vapor deposition) method, VAD (vapor-phase axial deposition) method arranged.Prefabricated component P is the right cylinder of length 100mm～1000mm and external diameter 10mm～50mm for example.
Then, prefabricated component P is placed in the wire drawing machine 30.
At this, wire drawing machine 30 is made of spinning stove 31, covering forming portion 32 and surface coating forming portion 33,31 couples of prefabricated component P of this spinning stove heat, and this covering forming portion 32 is positioned at the latter half of this spinning stove 31, and this surface coating forming portion 33 is positioned at the latter half of this covering forming portion 32.Covering forming portion 32 is made of the first coating mould 32a and heating furnace 32b.Surface coating forming portion 33 is made of the second coating mould 33a and ultraviolet lamp 33b.
Make wire drawing machine 30 work, in spinning stove 31, form fibre core 11a by prefabricated component P, then make fibre core 11a by covering forming portion 32, form covering 11b and make polymer-clad fiber 11, then make polymer-clad fiber 11 by surface coating forming portion 33, form surface coating 12 and produce the related polymer-clad fiber heart yearn 10 of the first embodiment.
At this moment, in spinning stove 31, carry out wire drawing after prefabricated component P heated, form fibre core 11a (optical transmission line formation operation).At this, the design temperature of spinning stove 31 (wire-drawing temperature) is for example 2000 ℃～2300 ℃.Drawing speed is for example 1m/min～100m/min.
In covering forming portion 32, make the fibre core 11a that forms by wire drawing by the first coating mould 32a, making liquid blanket form material is attached on the surface of this fibre core 11a with uniform thickness, then make this be attached with covering and form the fibre core 11a of material by heating furnace 32b, make this covering form the material heat curing by heating, form thus covering 11b (covering formation operation).
At this, covering forms that material contains the two keys of C=C and owing to the caused crosslinked perfluor ether polymer that solidifies of the silicon hydrogenation of SiH.Preferred covering formation material contains the two keys of C=C and SiH with 1: 1 ratio.
Covering forms material and can be formed by single component.The covering that is formed by single component forms material, is formed by the perfluor ether polymer that has the two keys of at least one C=C and at least one SiH in molecule, and after heating, the C=C pair of key and SiH carry out silicon hydrogenation and crosslinked between molecule.
Covering forms material and also can be comprised of Multiple components.The covering that is comprised of Multiple components forms material, become to be grouped into the fluorine-containing organic silicon oxygen alkane that in molecule, has at least two SiH by the perfluor ether polymer composition that for example in molecule, has the two keys of at least two C=C, after heating, the two keys of C=C and SiH carry out silicon hydrogenation and crosslinked between two kinds of compositions.
The two keys of above-mentioned C=C can be contained in the main chain, also can be contained in the side chain, can also be contained in the end of main chain or side chain.The two keys of preferred C=C are introduced in the molecule with the form of thiazolinyl.
At this, if to be added on during covering forms material have in each molecule more than one epoxy radicals and more than one directly and the alkoxy organo-silicon compound of the silicon atom of bonding, described epoxy radicals will be reacted with the two keys of a part of C=C that covering forms in the material, form the material bonding with covering, thiazolinyl can be introduced thus covering and form in the material.At this, directly and silicon atom the alkoxy of bonding can react with the hydroxy on quartz glass surface, bonding so that the close attachment of clad material and glass increases.The addition of alkoxy is for example 0.01%～5%; If the addition of alkoxy is more than 0.01%, the close attachment of clad material and glass will significantly improve; If the addition of alkoxy is below 5%, the refractive index of clad material will be lower, is highly suitable for covering.
As what above-mentioned thiazolinyl can be enumerated for example vinyl, propenyl, styryl, isopropenyl, cyclopropanyl, butenyl group, cyclobutane base, cyclopentenyl, hexenyl, cyclohexenyl group etc. arranged.
Above-mentioned SiH can be contained in the main chain, also can be contained in the side chain, can also be contained in the end of main chain or side chain.Preferred SiH is in the form introducing molecule of Chemical formula 1 with the repetitive structure of siloxane bond.The repeat number of siloxane bond (n) is for example 2～5.
(Chemical formula 1)
R:H or alkyl
Covering forms the perfluor ether polymer that material can only contain single kind, also can contain multiple perfluor ether polymer.
Only otherwise can damage the high NA of polymer-clad fiber 11 and good moisture resistance, covering forms material just can also contain other component of polymer.Covering forms material also can also contain the catalyzer such as platinum class catalyzer.
The viscosity that covering forms material is for example 0.5Pas～50Pas.In order to obtain having filming of the thickness that is applicable to covering 11b, preferably to form the viscosity of material be 1Pas～10Pas to this covering.Covering forms the viscosity of material according to Japanese Industrial Standards JIS Z8803 cone-plate formula rotary viscosity measuring.
The curing of covering formation material begins temperature and is for example 70 ℃～150 ℃.From the viewpoint of up time and process velocity, preferably to begin temperature be 90 ℃～130 ℃ to the curing that forms material of this covering.The curing that covering forms material begins temperature according to rigid body pendulum-type physical property test device 40B (for example, Co., Ltd. A﹠amp of following steps usefulness shown in Fig. 4 (a); D makes, model: RPT-3000W) measure.Should illustrate, rigid body pendulum-type physical property test device 40B comprises load sample boat 41B (being made by for example aluminium), is provided with cutter shape border body (knife edge) 42B (for example, the A﹠amp of Co., Ltd. in this load sample boat 41B; D makes, model: RPN160), and weight 43 (for example, the A﹠amp of Co., Ltd.; D makes, model: FRB100) be hung on this cutter shape border body 42B, consist of thus pendulum.Filling-in clad forms material M in the load sample boat 41B under the atmospheric environment of room temperature, the degree of depth that makes covering form material M becomes 0.5mm, speed with 10 ℃/min makes the temperature of load sample boat 41B rise to 200 ℃ from room temperature again, and pendulum is swung, and measures hunting period.If covering forms material M and solidifies because of crosslinked, then the elasticity of liquid can uprise, and can shorten hunting period.Therefore, obtain the hunting period that begins from the intensification initial stage shown in Fig. 4 (b) of certain constant straight line portion and the intersection point of the straight line portion that descends hunting period, with the temperature of this intersection point as solidifying the beginning temperature.
Should illustrate, forming contained perfluor ether polymer can be enumerated in the material commercially available material as covering has SIFEL series that Shin-Etsu Chemial Co., Ltd (Shin-Etsu Chemical Co., Ltd.) for example makes etc.
The design temperature of heating furnace 32b is for example 100 ℃～500 ℃, and furnace length is for example 30cm～300cm.
In surface coating forming portion 33, allow the polymer-clad fiber 11 that consists of with covering 11b coating fibre core 11a by the second coating mould 33a, making liquid surface coating form material is attached on the surface of this polymer-clad fiber 11 with uniform thickness, then make this be attached with surface coating and form the polymer-clad fiber 11 of material by ultraviolet lamp 33b, making this surface coating form material by UV-irradiation solidifies, forms thus surface coating 12 (surface coating formation operation).
At this, as surface coating having of forming that material can enumerate such as uncrosslinked ultraviolet light curable urethane acrylate resin etc.The viscosity that surface coating forms material is for example 0.5Pas～5Pas.
(the second embodiment)
Fig. 5 illustrates the related doubly clad optical fiber heart yearn 20 of the second embodiment.The doubly clad optical fiber heart yearn 20 that this second embodiment is related is such as being used for fiber laser etc.
The related doubly clad optical fiber heart yearn 20 of the second embodiment is made of the rounded doubly clad optical fiber 21 (polymer-clad fiber) of section and the surface coating 22 that coats this doubly clad optical fiber 21.Core line diameter is for example 100 μ m～1000 μ m.
Doubly clad optical fiber 21 is made of fibre core 21a, the first covering 21b and the second covering 21c, this fibre core 21a is positioned at the center of optical fiber, the section of this fibre core 21a is rounded, and this first covering 21b coats this fibre core 21a and establishes, and this second covering 21c coats this first covering 21b and establishes.Should illustrate, the section peripheral shape of the first covering 21b can be circular, but prevent that this exciting light from becoming not the viewpoint by the skew ray of fibre core 21a when inputing to the first covering 21b when exciting light, preferably this section peripheral shape is polygon or non-geometric configuration.Fibre diameter is for example 50 μ m～700 μ m.
The glass that forms fibre core 21a is that such as the adulterant that is doped with the increase refractive index such as Ge, F etc. reduces the adulterant of refractive index or rare earth element (Er, Yb, Nd) etc. other gives the quartz glass of functional adulterant.Core diameter is for example 5 μ m～100 μ m.The refractive index contrast of fibre core 21a and the first covering 21b (Δ) is for example 0.1%～1.0%.
The glass that forms the first covering 21b can be pure quartz glass (SiO
2), also can be to be doped with the quartz glass that F or Ge etc. change the adulterant of refractive index.The thickness of the first covering 21b is for example 25 μ m～350 μ m.The refractive index of the refractive index ratio fibre core 21a of the first covering 21b is low, and refractive index contrast is for example 0.1%～1.0%.
The second covering 21c by containing since the clad material of the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation form.The thickness of the second covering 21c is for example 10 μ m～100 μ m.
The refractive index of refractive index ratio the first covering 21b of the second covering 21c is low, for for example below 1.37, is preferably below 1.35.In this doubly clad optical fiber 21, because the second covering 21c has lower refractive index as mentioned above, so the NA of the first covering 21b is preferably more than 0.55 for for example more than 0.50.
The structure of covering 11b in other structure of the second covering 21c and the first embodiment is identical.
The related doubly clad optical fiber heart yearn 20 of above-described the second embodiment constitutes: Yi Bian the exciting light of inputting among the first covering 21b is reflected at the interface of first and second covering 21b, 21c, transmit this exciting light on one side, because this exciting light excites the adulterant that is entrained among the fibre core 21a by fibre core 21a the time, produce the population inversion between the energy level, so by its stimulated emission the light of inputting among the fibre core 21a is amplified, and transmits this light.Therefore, in the related doubly clad optical fiber heart yearn 20 of the second embodiment, fibre core 21a and the first covering 21b consist of optical transmission line.
The doubly clad optical fiber heart yearn 20 related according to the second embodiment, because the second covering 21c is formed by the perfluor ether polymer because of the caused crosslinked curing of silicon hydrogenation, so the refractive index of the second covering 21c significantly descends, consequently can make the NA of the first covering 21b higher.Because being the bonding position of carbon atom and silicon atom, the crosslinking points of the second covering 21c has hydrophobicity, so can access good moisture resistance.And, by introducing among the second covering 21c with the alkoxy of the silicon atom bonding of the second covering 21c, then the second covering 21c and the compatibility that forms between the glass of the first covering 21b will increase, thereby the close attachment between this second covering 21c and this first covering 21b will increase, consequently, can access more good moisture resistance.When the light that penetrates from light source is carried out optically focused, and when making it to the first covering 21b incident, if NA is higher as mentioned above, just can make incident angle larger, but thereby can increase the light quantity that excites of incident.Therefore, more exciting light can be enclosed in the first covering 21b, thereby can realize higher oscillation efficiency.
Say again, can infer, the temperature dependency of the optical characteristics of the second covering 21c that is formed by the perfluor ether polymer because of the caused crosslinked curing of silicon hydrogenation is less, thermotolerance is better, therefore can expect and can use under harsh and unforgiving environments and increase the service life.Add, because thereby the second covering 21c is formed by the clad material that makes the crosslinked curing of thermoset resin by heating, so when optical fiber is when being doped with the doubly clad optical fiber 21 of the adulterants such as rare earth element in fibre core 21a, can prevent that fibre core 21a is owing to the ultraviolet light that shines worsens when forming the second covering 21c.
The manufacture method of the doubly clad optical fiber heart yearn 20 that the second embodiment the is related in fact manufacture method with the related polymer-clad fiber heart yearn 10 of the first embodiment is identical, but in the second embodiment, what use is to possess to form the rounded material of core segment and section and coat this rounded material and establish and form the double-deck prefabricated component of the material of the first covering, forms material by covering and forms the second covering 21c.
(the 3rd embodiment)
Fig. 6 illustrates the related doubly clad optical fiber heart yearn 50 of the 3rd embodiment.The doubly clad optical fiber heart yearn 50 that the 3rd embodiment is related is such as being used for fiber laser or fiber amplifier etc.
The related doubly clad optical fiber heart yearn 50 of the 3rd embodiment is made of with the surface coating 52 that coats this doubly clad optical fiber 51 the rounded doubly clad optical fiber 51 of section.Core line diameter is for example 100 μ m～1000 μ m.
Doubly clad optical fiber 51 is made of fibre core 51a, the first covering 51b and the second covering 51c, this fibre core 51a is positioned at the center of optical fiber, be added with rare earth element among this fibre core 51a, the section of this fibre core 51a is rounded, this first covering 51b coats this fibre core 51a and establishes, the refractive index ratio fibre core 51a of this first covering 51b is low, and this second covering 51c coats this first covering 51b and establishes, and refractive index ratio the first covering 51b of this second covering 51c is low.Should illustrate, the section peripheral shape of the first covering 51b can be circular, but prevent that this exciting light from becoming the viewpoint of the skew ray that does not cross fibre core 51a when inputting the first covering 51b when exciting light as described below, preferably this section peripheral shape is polygon or non-geometric configuration.The external diameter of the second covering 51c of doubly clad optical fiber 51 is for example 50 μ m～700 μ m.
Forming the glass of fibre core 51a so long as be added with the glass of rare earth element (Er, Yb, Nd etc.) and get final product, for example also can be quartz glass (SiO
2) in be doped with the increase refractive indexes such as Ge adulterant, F etc. reduce adulterant or other quartz of giving functional adulterant of refractive index.Should illustrate, the concentration that is added on the rare earth element among the fibre core 51a is higher, fibre core 51a produces reaction with regard to more being easy to because of ultraviolet light, therefore the loss that is easy to occur fibre core 51a can increase in the ultraviolet wavelength zone, so that the phenomenon that transport property worsens, the loss that also is easy to occur fibre core 51a can increase near the exciting light of wavelength 1 μ m, the 1.5 μ m etc. in ultraviolet wavelength zone or signal light wavelength zone, so that the phenomenon that transport property worsens.Therefore, as what the example of the concentration of the rare earth element of adding can be enumerated for example 1 quality %～10 quality % are arranged in fibre core 51a.
Core diameter is for example 5 μ m～100 μ m.The refractive index of refractive index ratio the first covering 51b of fibre core 51a is high, and the refractive index contrast (Δ) of fibre core 51a and the first covering 51b is for example 0.1%～1%.
The glass that forms the first covering 51b can be pure quartz glass (SiO
2), also can be to be doped with F etc. to reduce the quartz that the adulterant of refractive index or Ge etc. increase the adulterant of refractive index.The thickness of the first covering 51b is for example 25 μ m～350 μ m.The inscribed circle diameter of the section shape of the first covering 51b is for example 50 μ m～700 μ m.
The second covering 51c is formed by thermoset resin.Wherein, preferred the second covering 51c is formed by the second clad material that contains because of the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation, this is because in this case, the refractive index of the second covering 51c significantly descends, consequently can access outgoing NA (below, also referred to as " NA ".) the higher event of the first covering 51b.The thickness of the second covering 51c is for example 10 μ m～100 μ m.
The refractive index of refractive index ratio the first covering 51b of the second covering 51c is low, is for example 1.32～1.45, if this moment, the first covering 51b was formed by quartz, then the NA of the first covering 51b is when being 0.13～0.60 during measurement at fiber lengths under the condition that is 2m.Particularly in the doubly clad optical fiber 51 that the second clad material with the perfluor ether polymer that contains the caused crosslinked curing because of silicon hydrogenation forms, because the refractive index of the second covering 51c is lower, be 1.32～1.40, so this moment, if the first covering 51b was formed by quartz, then the NA of the first covering 51b is to be 0.40～0.60 during measurement under the condition of 500m at fiber lengths when measuring under the condition that is 2m with at fiber lengths.NA utilizes the FFP method of putting down in writing among the Japanese Industrial Standards JIS C6822 to measure.
Below, to the in addition detailed explanation of the situation of using described the second clad material.
The density of described the second clad material is for example 1.7～1.8.The density of described the second clad material is measured according to Japanese Industrial Standards JIS K0061.
The Young modulus of described the second clad material is for example 0.5MPa～50MPa.From making this second clad material to the viewpoint of buffer action good the external force, preferably the Young modulus of this second clad material is 1MPa～10MPa.The tensile strength of described the second clad material is for example 1MPa～100MPa, from making this second clad material have the viewpoint of good anti-external force, be preferably more than the 10MPa, on the other hand, the crooked followability good viewpoint of collateral security the second clad material when making doubly clad optical fiber 51 bending is preferably below the 70MPa.The breaking elongation of described the second clad material is for example 5%～100%, the crooked followability good viewpoint of collateral security the second clad material when making doubly clad optical fiber 51 bending, be preferably more than 20%, on the other hand, from making this second clad material to the viewpoint of buffer action good the external force, be preferably below 70%.The Young modulus of described the second clad material is obtained by following calculating, that is: according to Japanese Industrial Standards JIS K6251, in the situation that the draw speed with 1mm/min stretches to the second clad material that forms film-form, the tension force when having extended 2.5% is divided by sectional area.The tensile strength of described the second clad material and breaking elongation are measured according to Japanese Industrial Standards JIS K6251.
The Shore A level hardness of described the second clad material is for example 10～80.From making this second clad material have the viewpoint of good anti-external force, preferably the Shore A level hardness of this second clad material is 25～80.The Shore A level hardness of described the second clad material is with the A type hardness tester instrumentation amount of putting down in writing among the Japanese Industrial Standards JIS K6253.
The glass transition temperature of described the second clad material (Tg) for for example-150 ℃～0 ℃.From guaranteeing the viewpoint of the character constancy of this second clad material in actual serviceability temperature zone, preferably the glass transition temperature of this second clad material (Tg) is-150 ℃～-50 ℃.The glass transition temperature of described the second clad material (Tg) is according to rigid body pendulum-type physical property test device 60A (for example, Co., Ltd. A﹠amp of following steps usefulness shown in Fig. 7 (a); D makes, model: RPT-3000W) measure.Should illustrate, rigid body pendulum-type physical property test device 60A comprises load sample platform 61A (being made by for example aluminium), is provided with tubular edge body 62A (for example, the A﹠amp of Co., Ltd. at this load sample platform 61A; D makes, model: RPN160), and weight 63 (for example, the A﹠amp of Co., Ltd.; D makes, model: FRB100) be hung on this tubular edge body 62A, consist of thus pendulum.Under the atmospheric environment of room temperature, to be formed and the film F of the about 100 μ m of thickness is placed on the load sample platform 61A by the second clad material, the temperature that makes load sample platform 61A with the speed of 10 ℃/min again rises to 150 ℃ from-100 ℃, and pendulum is swung, and measures hunting period.If the viscoelasticity of the second clad material changes, then represent that with logarithm the value of the attenuation ratio of described hunting period is that logarithmic decrement will change, thereby shown in Fig. 7 (b), will show the maximum rate of change of described logarithmic decrement.Obtain this temperature that shows maximum rate of change (that is, the single order differential curve of logarithmic decrement shows peaked temperature), with this temperature as glass transition temperature (Tg).Should illustrate, when Tg is in the scope below-100 ℃, can utilize following methods to obtain Tg, that is: according to measuring with the device that can measure the scope below-100 ℃ with above identical principle, perhaps measure with the dynamic viscoelastic measurement mechanism, with the peak temperature of the tan δ that in the scope below-100 ℃, occurs as Tg.
The gel fraction of described the second clad material is for example 90%～100%.Owing to the low molecular weight compositions viewpoint that the dissolving under the high humidity environment for use changes in the volatilization under the applied at elevated temperature environment or low molecular weight compositions, preferably the gel fraction of this second clad material is 96%～100% from the characteristic that prevents the second covering 51c.The mass change of the gel fraction of described the second clad material during according to solvent extraction measured.Particularly, take MEK (boiling point is as 79.5 ℃) as the solvent that described the second clad material is used, extract with the Soxhlet that about 10 rate of circulation of taking turns were per hour carried out 5 hours, the dry mass of described the second clad material after the extraction is divided by proper mass, and the value of gained represents as gel fraction with percentage.
The second clad material can become the sign that the second covering 51c is attached to the close attachment on the first covering 51b to 90 ° of peel strengths of glass, and preferably this second clad material is more than the 10N/m to 90 ° of peel strengths of glass.From guaranteeing the viewpoint of the second covering 51c and the first covering 51b close attachment when making doubly clad optical fiber 51 bending, further preferred this second clad material is more than the 20N/m to 90 ° of peel strengths of glass.The second clad material can utilize following methods to obtain to 90 ° of peel strengths of glass, that is: the thickness with 100 μ m～200 μ m applies the second clad material on glass substrate, and be cured, only the second clad material is cut into strip with the width of 2.5cm again, towards an end that up draws this strip the second clad material perpendicular to the direction of glass substrate with the pulling speed of 100mm/min, measure the tension force of this moment, the tension force that records just can be obtained the second clad material to 90 ° of peel strengths of glass divided by the width of this strip the second clad material.
Surface coating 52 is formed by resin or rubber.As what the resin that forms surface coating 52 or rubber can be enumerated curing property such as thermoset resins such as the light-cured resins such as UV-cured resin, thermoplastic resin, polyimide resin and silicon rubber rubber etc. are arranged.Should illustrate, although in fibre core 51a, be added with rare earth element, fibre core 51a is easy to worsen because of ultraviolet light, but because there is the second covering 51c that forms as mentioned above, even so formed by UV-cured resin at surface coating 52, in the situation of irradiating ultraviolet light, also be difficult to produce the deterioration that causes because of ultraviolet light when forming surface coating 52, the resin that therefore forms surface coating 52 also can be UV-cured resin.But, in order to suppress the generation of the caused deterioration of ultraviolet light, preferred irradiating ultraviolet light not when forming surface coating 52.Therefore, preferred surface coating 52 is formed by curing property such as the thermoset resin such as thermoplastic resin, polyimide resin or silicon rubber rubber etc.Wherein, in order to improve from the exothermicity of optical fiber heat release, further preferably use the good silicon rubber of thermal conductivity.From improving the viewpoint of the wetting state that the second covering 51c is wetting, preferably in the resin that forms surface coating 52, be added with a small amount of fluorine.
The thickness of surface coating 52 is for example 10 μ m～100 μ m.The refractive index of surface coating 52 is for example 1.4～1.57.The viewpoint of scattering and disappearing from suppressing cladding mode light, the refractive index of the refractive index ratio second covering 51c of preferred surface coating 52 is high.The Young modulus that forms the resin of surface coating 52 is for example 100MPa～400MPa.From the stress that reduces can produce when the bending and the viewpoint of loss, the Young modulus of resin that preferably should form surface coating 52 is higher than the Young modulus of the second clad material.The gel fraction that forms the resin of surface coating 52 is for example 80%～100%, and preferably the gel fraction than the second clad material is low.From allowing the difference of the amount of contraction that the lost low molecular weight compositions that can produce when dry again after absorbing moisture produces reduce, thereby be limited between surface coating 52 and the second covering 51c and form the gap, seek thus the viewpoint of the inhibition of loss, the gel rate variance that is preferably formed the resin of surface coating 52 and the second clad material is less than 5%.
At the doubly clad optical fiber that is used for fiber laser or fiber amplifier, because in fibre core, be added with rare earth element, so be easy to occur following phenomenon, this phenomenon is: this rare earth element can produce reaction owing to the ultraviolet light that shines when the wire drawing etc., the loss of fibre core can increase in ultraviolet wavelength exciting light regional or regional wavelength 1 μ m, 1.5 μ m etc. near this or signal light wavelength zone, so that transport property worsens.That is to say, this fibre core is easy to worsen because of ultraviolet light.
Yet, the doubly clad optical fiber heart yearn 50 related according to the 3rd embodiment, because the second covering 51c is formed by thermoset resin, preferably formed by the thermoset resin that contains because of the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation, so the refractive index of the second covering 51c significantly descends, consequently can access the first higher covering 51b of NA.At this, when the second covering 51c when containing thermoset resin because of the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation and form, because the carbon atom in this resin and and the bonding position of silicon atom have hydrophobicity, so can access good moisture resistance.Further preferably, the second covering 51c is formed by the thermoset resin that contains because of the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation, and has the situation with the alkoxy of silicon atom bonding in this resin.In this case, the second covering 51c and the compatibility that forms between the glass of the first covering 51b can increase, and the close attachment of this second covering 51c and this first covering 51b can increase, and consequently, can access more good moisture resistance.When the exciting light that penetrates from light source is carried out optically focused, and when making it to the first covering 51b incident, if NA is higher as mentioned above, just can make incident angle larger, but thereby can increase the light quantity that excites of incident.Therefore, more exciting light can be enclosed in the first covering 51b, thereby can realize higher oscillation efficiency.Should illustrate, up to now, there is the doubly clad optical fiber that possesses the structure that in covering, is formed with airport (air hole) as the doubly clad optical fiber that can access higher NA, yet this doubly clad optical fiber has following shortcoming, that is: its manufacturing technology is difficult, and because will filter out specification product, so yield rate is relatively poor, and because form airport, so enhancement Layer that need to be used for strengthening in the periphery setting of optical fiber, thereby fibre diameter can become greatly, so that allow the bending radius also can be larger.Yet the related doubly clad optical fiber heart yearn 50 of this 3rd embodiment does not have above-mentioned shortcoming.
Say again, can infer, the temperature dependency of the optical characteristics of the second covering 51c that is formed by the perfluor ether polymer because of the caused crosslinked curing of silicon hydrogenation is less, thermotolerance is better, therefore can expect and can use under harsh and unforgiving environments and increase the service life.
In Fig. 8, as one of the device that consists of with the related doubly clad optical fiber heart yearn 50 of the 3rd embodiment example fiber laser 70 is shown.
This fiber laser 70 comprises fiber laser main body 71, is connected with input side FBG (Fiber Bragg Grating: fiber grating) 72, and be connected with outgoing side FBG73 at its output terminal at its input end.Input end at input side FBG72 is connected with optical-fiber bundling device 74, and the output terminal of outgoing side FBG73 is connected with the optical head 75 that consists of laser emitting section.
The fiber lengths of fiber laser main body 71 is for example 3m～100m.
Input side FBG72 is made of the doubly clad optical fiber heart yearn that does not add rare earth element and be formed with diffraction grating 72a in fibre core.Input side FBG72 constitutes: utilize the diffraction grating 72a of fibre core to make light (for example light of wavelength 1085nm) from fiber laser main body 71 sides with 98%～100% reflectivity reflection.The fiber lengths of input side FBG72 is for example 0.3m～10m.
Outgoing side FBG73 also is made of the doubly clad optical fiber heart yearn that does not add rare earth element and be formed with diffraction grating 73a in fibre core.Outgoing side FBG73 constitutes: utilize the diffraction grating 73a of fibre core to make light (for example light of wavelength 1085nm) from fiber laser main body 71 sides with 5%～15% reflectivity reflection.The fiber lengths of outgoing side FBG73 is for example 0.3m～10m.
In optical-fiber bundling device 74, the outgoing of multi-core fiber tail optical fiber 74a is distolateral is restrainted together, and is melted into one.The quantity of optical fiber pigtail 74a is for example two cores～tens of cores, as what typical example can be enumerated for example 7 cores, 19 cores and 37 cores is arranged.Each input end at multi-core fiber tail optical fiber 74a is connected with excitation source 76.Excitation source 76 is by consisting of such as semiconductor laser etc.The output power of each excitation source 76 is for example 5W～500W.
This fiber laser 70 constitutes: through optical fiber pigtail 74a transmission from a plurality of excitation sources 76 in the laser of each excitation source 76, and these laser beam are inputed to input side FBG72 together.The input side FBG72 that is consisted of by the doubly clad optical fiber heart yearn, the fiber laser main body 71 that is consisted of by the related doubly clad optical fiber heart yearn 50 of the 3rd embodiment and constituted by the outgoing side FBG73 that the doubly clad optical fiber heart yearn consists of: with from the laser light of each excitation source 76 in a plurality of excitation sources 76 as the multimode exciting light, and in the first covering 51b the transmission this laser light, because this multimode exciting light excites the rare earth element among the fibre core 51a by fibre core 51a the time, produce the population inversion between the energy level, so in fibre core 51a, the single-mode laser light that produces owing to its stimulated emission is transmitted.Thereby make the single-mode laser light that in fibre core 51a, transmits make its vibration in diffraction grating 72a, the 73a of input side FBG72 and outgoing side FBG73 reflection, the part of laser light that will increase luminous energy and have a specific wavelength by this vibration again through the exit end of outgoing side FBG73 from optical head 75 ejaculations.The output power of fiber laser 70 is for example 10W～200W.
At this, for example when the fibre diameter of optical fiber pigtail 74a be 125 μ m and output NA when being 0.15, if the quantity of optical fiber pigtail 74a is 7 cores, the external diameter of fibre bundle will become 375 μ m; If the quantity of optical fiber pigtail 74a is 19 cores, the external diameter of fibre bundle will become 625 μ m; If the quantity of optical fiber pigtail 74a is 37 cores, the external diameter of fibre bundle will become 875 μ m.Be that the input end of 250 μ m is connected in order to make fibre bundle and the external diameter of input side FBG72, the output end of optical-fiber bundling device 74 need to be formed the thinner shapes in top such as cone-shaped, at this moment, the output NA of 7 cores is 0.225; The output NA of 19 cores is 0.375; The output NA of 37 cores is 0.525.Therefore, the quantity of optical fiber pigtail 74a is more, and output NA is just more.With respect to this, because the NA of doubly clad optical fiber heart yearn 50 is higher, thus can will not input to input side FBG72 from the laser light of multi-core fiber tail optical fiber 74a with not missing, in doubly clad optical fiber heart yearn 50 these laser light of interior transmission.Therefore, described fiber laser 70 can link with more excitation source 76, consequently can export the laser light of high-output power.
Should illustrate, in described fiber laser 70, adopt the structure with optical-fiber bundling device 74 input exciting lights, but be not limited to this.Described fiber laser 70 also can constitute: to inputting exciting light by forming in the side of input side FBG72 in the first covering that V-shaped groove etc. exposes.Described fiber laser 70 can also constitute: welding is used for the multimode optical fiber of input exciting light on the first covering that exposes in the part of the second covering by removing input side FBG72, utilizes this multimode optical fiber input exciting light.
Then, with reference to Fig. 9 the manufacture method of the related doubly clad optical fiber heart yearn 50 of the 3rd embodiment is illustrated.Should illustrate, the below describes as an example of the situation that formed surface coating 52 by thermoset rubber example, but the present invention is not limited to this.
At first, be constructed for forming the glass prefabricated component P processed of fibre core 51a and the first covering 51b.As what the method for making of prefabricated component P can be enumerated known methods such as CVD method, VAD method arranged.Prefabricated component P for example is the right cylinder of length 10mm～1000mm and external diameter 10mm～50mm.
Then, prefabricated component P is placed in the wire drawing machine 80.
At this, wire drawing machine 80 is made of spinning stove 81, the second covering forming portion 82 and surface coating forming portion 83,81 couples of prefabricated component P of this spinning stove heat, this the second covering forming portion 82 is positioned at the latter half of this spinning stove 81, and this surface coating forming portion 83 is positioned at the latter half of this second covering forming portion 82.The second covering forming portion 82 is made of the first coating mould 82a and the first heating furnace 82b.Surface coating forming portion 83 is made of the second coating mould 83a and the second heating furnace 83b.
Make wire drawing machine 80 work, in spinning stove 81, form fibre core 81a and the first covering 81b by prefabricated component P, then make this fibre core 81a and this first covering 81b by the second covering forming portion 82, form the second covering 51c and make doubly clad optical fiber 51, then make this doubly clad optical fiber 51 by surface coating forming portion 83, form surface coating 52 and produce the related doubly clad optical fiber heart yearn 50 of the 3rd embodiment.
At this moment, in spinning stove 81, carry out wire drawing after prefabricated component P heated, form fibre core 51a and the first covering 51b (fibre core and the first covering form operation).At this, the design temperature of spinning stove 81 (wire-drawing temperature) is for example 2000 ℃～2300 ℃.Drawing speed is for example 1m/min～100m/min.
In the second covering forming portion 82, make the fibre core 51a and the first covering 51b that form by wire drawing apply mould 82a by first, make liquid the second clad material be attached on the surface of the first covering 51b with uniform thickness, then make it pass through the first heating furnace 82b, make the second clad material heat curing by heating, form thus the second covering 51c (the second covering forms operation).
At this, mould as the first coating mould 82a, can be to exert pressure to the second clad material M1 on one side to make its lip-deep pressing mold that adds that is attached to the first covering 51b on one side shown in Figure 10 (a), also can be not make it be attached to the lip-deep open die of the first covering 51b to the second clad material M1 shown in Figure 10 (b) with exerting pressure.But, be attached to equably the lip-deep viewpoint of the first covering 51b from making the second clad material M1, preferably use the former namely to add pressing mold.
The second clad material is thermoset resin, contains the two keys of C=C and owing to the caused crosslinked perfluor ether polymer that solidifies of the silicon hydrogenation of SiH.Preferred the second clad material contains the two keys of C=C and SiH with 1: 1 ratio.
The second clad material also can be formed by single component.The second clad material that is formed by single component is formed by the perfluor ether polymer that has the two keys of at least one C=C and at least one SiH in molecule, and after heating, the C=C pair of key and SiH carry out silicon hydrogenation and crosslinked between molecule.
The second clad material also can be comprised of Multiple components.The second clad material that is formed by Multiple components, become to be grouped into the fluorine-containing organic silicon oxygen alkane that in molecule, has at least two SiH by the perfluor ether polymer composition that for example in molecule, has the two keys of at least two C=C, after heating, the two keys of C=C and SiH carry out silicon hydrogenation and crosslinked between two kinds of compositions.
The two keys of above-mentioned C=C can be contained in the main chain, also can be contained in the side chain, can also be contained in the end of main chain or side chain.The two keys of preferred C=C are introduced in the molecule with the form of thiazolinyl.As what described thiazolinyl can be enumerated for example vinyl, propenyl, styryl, isopropenyl, cyclopropanyl, butenyl group, cyclobutane base, cyclopentenyl, hexenyl, cyclohexenyl group etc. arranged.
Above-mentioned SiH can be contained in the main chain, also can be contained in the side chain, can also be contained in the end of main chain or side chain.Preferred SiH is with the repetitive structure ((SiH of siloxane bond
2-O-)
n) form introduce in the molecule.The repeat number of siloxane bond (n) is for example 2～5.
The second clad material can only contain the perfluor ether polymer of single kind, also can contain multiple perfluor ether polymer.
Only otherwise can damage the high NA of doubly clad optical fiber 51 and good moisture resistance, the second clad material just can also contain other component of polymer.The second clad material also can also contain the catalyzer such as platinum class catalyzer.
The viscosity of the second clad material is for example 0.5Pas～50Pas.In order to obtain having as the filming of the applicable thickness of the second covering 51c, preferably the viscosity of this second clad material is 1Pas～10Pas.The viscosity of the second clad material is with the cone-plate formula rotary viscosity measuring of putting down in writing among the Japanese Industrial Standards JIS Z8803.
The curing of the second clad material begins temperature and is for example 70 ℃～150 ℃.From obtaining as applicable up time of the second clad material and the viewpoint of process velocity, preferably to begin temperature be 90 ℃～130 ℃ in the curing of this second clad material.Should illustrate, the curing of the second clad material begins temperature according to rigid body pendulum-type physical property test device 60B (for example, Co., Ltd. A﹠amp of following steps usefulness shown in Fig. 7 (c); D makes, model: RPT-3000W) measure.Rigid body pendulum-type physical property test device 60B comprises load sample boat 61B (being made by for example aluminium), is provided with cutter shape border body 62B (for example, the A﹠amp of Co., Ltd. in this load sample boat 61B; D makes, model: RPN160), and weight 63 (for example, the A﹠amp of Co., Ltd.; D makes, model: FRB 100) be hung on this cutter shape border body 62B, consist of thus pendulum.Under the atmospheric environment of room temperature, in load sample boat 61B, inject the second clad material M1, make the degree of depth of the second clad material M1 become 0.5mm, speed with 10 ℃/min makes the temperature of load sample boat 61B rise to 200 ℃ from room temperature again, and pendulum is swung, and measures hunting period.If the second clad material M1 solidifies because of crosslinked, then the elasticity of liquid can uprise, and can shorten hunting period.Therefore, ask the hunting period that begins from the intensification initial stage shown in Fig. 7 (d) of certain constant straight line portion and the intersection point of the straight line portion that descends hunting period, with the temperature of this intersection point as solidifying the beginning temperature.
Should illustrate, there is the SIFEL series that Shin-Etsu Chemial Co., Ltd (Shin-Etsu Chemical Co., Ltd.) for example makes etc. the commercially available material that can enumerate as perfluor ether polymer contained in the second clad material.
Design temperature is for example 100 ℃～500 ℃ in the stove of the first heating furnace 82b, and the heat treated time in the first heating furnace 82b is for example 0.05 second～0.5 second.
In surface coating forming portion 83, allow with the second covering 51c coat the first covering 51b and the doubly clad optical fiber 51 that consists of by the second coating mould 83a, make liquid coating material be attached on the surface of doubly clad optical fiber 51 with uniform thickness, then make this doubly clad optical fiber that is attached with coating material 51 by the second heating furnace 83b, make this coating material heat curing by heating, form thus surface coating 52 (surface coating formation operation).
At this, mould as the second coating mould 83a, can be to exert pressure to coating material M2 on one side to make its lip-deep pressing mold that adds that is attached to doubly clad optical fiber 51 on one side shown in Figure 10 (a), also can be not make it be attached to the lip-deep open die of doubly clad optical fiber 51 to coating material M2 shown in Figure 10 (b) with exerting pressure.But, be attached to equably the lip-deep viewpoint of doubly clad optical fiber 51 from making coating material M2, preferably use the former namely to add pressing mold.
The second heating furnace 83b can be made of a stove.In this case, design temperature is for example 100 ℃～500 ℃ in the stove of the second heating furnace 83b.The heat treated time in the second heating furnace 83b is for example 0.05 second～0.5 second.
As shown in figure 11, the second heating furnace 83b can be that upstream side heating furnace 831b and downstream heating furnace 832b consist of by a pair of stove also.Heat when reducing to form surface coating 52 is on the viewpoint of the impact of doubly clad optical fiber 51, preferably make the doubly clad optical fiber 51 that is attached with liquid coating material successively by design temperature in the stove relatively high upstream side heating furnace 831b and the interior relatively low downstream heating furnace 832b of design temperature of stove, make the coating material heat curing.In this case, upstream side heating furnace 831b is connected with downstream heating furnace 832b and is set to seamlessly connect each other, also can be set to leave each other for example interval of 0mm～1000mm.The doubly clad optical fiber 51 that is attached with coating material time till when being admitted in the heating furnace 832b of downstream when being sent in upstream side heating furnace 831b is for example 0 second～0.5 second.Design temperature is for example 100 ℃～500 ℃ in the stove of upstream side heating furnace 831b.Design temperature is for example 100 ℃～450 ℃ in the stove of downstream heating furnace 832b.The interior design temperature of stove between preferred upstream side heating furnace 831b and the downstream heating furnace 832b is poor to be 50 ℃～200 ℃, more preferably 50 ℃～100 ℃.
As having such as uncured heat-curable silicone rubber etc. that coating material can be enumerated.The viscosity of coating material is for example 0.5Pas～5Pas.The curing of coating material begins temperature and is for example 70 ℃～150 ℃.
-embodiment-
[test evaluation 1]
(covering formation material)
＜example 1 〉
Adopt owing to the covering formation material of the caused crosslinked perfluor ether polymer that solidifies of silicon hydrogenation as example 1.Its viscosity is 4Pas.The curing that utilizes the method shown in Fig. 4 (a) and Fig. 4 (b) to measure covering formation material begins temperature, and the result is 128 ℃.
Form material at this covering of glass substrate coating, carry out heat cross-linking with 150 ℃ of heating-up temperatures and the condition of 5 hours heat time heating times, solidify thereby make this covering form material, produce the thin slice of thickness 200 μ m.This thin slice is the clad material of example 1.The gel fraction of this clad material is 99%.
＜comparative example 1 〉
The ultraviolet light curable fluorinated acrylate resin that employing is solidified by ultraviolet light cross-linking as a comparative example 1 covering forms material.Its viscosity is 2.4Pas.
Form material at this covering of glass substrate coating, with under the nitrogen environment and accumulative total light quantity 1000mJ/cm
2Condition carry out ultraviolet light cross-linking, solidify thereby make this covering form material, produce the thin slice of thickness 200 μ m.This thin slice is the clad material of comparative example 1.The gel fraction of this clad material is 96%.
(coating material)
The ultraviolet light curable urethane acrylate resin that employing is solidified by ultraviolet light cross-linking forms material as the surface coating of example 1 and comparative example 1.Its viscosity is 2.5Pas.
Under nitrogen environment, accumulative total light quantity 1000mJ/cm
2Condition under make this surface coating form material to carry out ultraviolet light cross-linking, thereby it is solidified, produce the thin slice of thickness 200 μ m.This thin slice is coating material.The gel fraction of this coating material is 96%.
(polymer-clad fiber heart yearn)
＜example 1 〉
Covering with described example 1 forms material and the described surface coating formation material making structure polymer-clad fiber heart yearn identical with above-mentioned the first embodiment, with the polymer-clad fiber heart yearn of this polymer-clad fiber heart yearn as example 1.At this moment, drawing condition is: drawing speed is 20m/min, and the design temperature that is used for making covering form the heating furnace of material curing is 400 ℃.The furnace length of heating furnace is 1m.The illuminate condition that is used for making surface coating form the ultraviolet lamp of material curing is 1000mJ/cm
2
The core line diameter of the polymer-clad fiber heart yearn of example 1 is 350 μ m.The fibre diameter of polymer-clad fiber is 260 μ m.Core diameter is 200 μ m.
Fibre core is formed by pure quartz glass.Covering is by the clad material of foregoing invention example 1, namely by forming because of the caused crosslinked perfluor ether polymer that solidifies of silicon hydrogenation.Surface coating is namely formed by the ultraviolet light curable urethane acrylate resin of solidifying by ultraviolet light cross-linking by described coating material.
＜comparative example 1 〉
Making has except more following all the polymer-clad fiber heart yearn of the structure identical with example 1, and with this polymer-clad fiber heart yearn polymer-clad fiber heart yearn of 1 as a comparative example, this difference is: covering is namely formed by the ultraviolet light curable fluorinated acrylate resin that solidifies by ultraviolet light cross-linking by the clad material of comparative example 1.
(test evaluation method)
The density of＜clad material 〉
Each clad material by example 1 and comparative example 1 is made sample, measures the density of clad material according to Japanese Industrial Standards JISK0061.
The Shore A level hardness of＜clad material 〉
Each clad material of example 1 and comparative example 1 is overlaped, and making thickness is the sample of 6mm, and according to the Shore A level hardness of Japanese Industrial Standards JIS K6253 with A type hardness tester instrumentation amount clad material.
＜clad material is to 90 ° of peel strengths of glass 〉
On glass substrate, be coated in respectively the covering that uses in each example in example 1 and the comparative example 1 with the thickness of 100 μ m～200 μ m and form material, form material curing by crosslinked this covering that makes again, form clad material, then only clad material is cut into the strip of width 2.5cm, produces thus sample.Then, towards an end that up draws this strip clad material perpendicular to the direction of glass substrate with the pulling speed of 100mm/min, measure the tension force of this moment, the tension value that records is obtained clad material to 90 ° of peel strengths of glass thus divided by the width of strip clad material.
Should illustrate, the crosslinked condition of example 1 is: heating-up temperature is that 150 ℃ and heat time heating time are 5 hours; The crosslinked condition of comparative example 1 is: crosslinked under nitrogen environment, and for the accumulative total light quantity of solidifying the ultraviolet light that shines is 1000mJ/cm
2
The refractive index of＜clad material 〉
Each clad material by example 1 and comparative example 1 is made sample, utilizes the film sample measuring method of Abbe refractometer to measure the refractive index of clad material according to Japanese Industrial Standards JISK0062.
The NA of the fibre core of＜polymer-clad fiber heart yearn 〉
Utilize the FFP method polymer-clad fiber heart yearn of example 1 and comparative example 1 to be measured respectively the NA of the fibre core of polymer-clad fiber according to Japanese Industrial Standards JIS C6822.
The loss of＜polymer-clad fiber heart yearn after in impregnated in hot water 〉
Will respectively have the long example 1 of 50m and the polymer-clad fiber heart yearn of comparative example 1 restraint respectively fasciculation, each bundle polymer-clad fiber heart yearn being immersed in temperature in the Water Tank with Temp.-controlled adjusted is in 85 ℃ the hot water, to flood 2 days again.Then, utilize the loss of polymer-clad fiber heart yearn when the flashlight of transmission wavelength 1.31 μ m after cutback technique is measured described dipping.
(test evaluation result)
Table 1 expression test findings.
(table 1)
The density of clad material is: example 1 is 1.77g/cm
3, comparative example 1 is 1.65g/cm
3
The Shore A level hardness of clad material is: example 1 is 29, and comparative example 1 is 41.
Clad material to 90 ° of peel strengths of glass is: example 1 is 21N/m, and comparative example 1 is 11N/m.
The refractive index of covering is: example 1 is 1.34, and comparative example 1 is 1.38.
The NA of the fibre core of polymer-clad fiber heart yearn is: example 1 is 0.59, and comparative example 1 is 0.45.
The loss of polymer-clad fiber heart yearn after in impregnated in hot water is: example 1 is 5dB/km, and comparative example 1 is more than the 100dB/km.
[test evaluation 2]
(doubly clad optical fiber)
＜example 2 〉
Make the structure doubly clad optical fiber heart yearn identical with above-mentioned embodiment, with the doubly clad optical fiber heart yearn of this doubly clad optical fiber heart yearn as example 2.
The core line diameter of the doubly clad optical fiber heart yearn of example 2 is 350 μ m.The external diameter of the second covering of doubly clad optical fiber is 300 μ m.Core diameter is 10 μ m.The external diameter of the first covering is 200 μ m.
Fibre core is formed by the quartz that is added with ytterbium (Yb) and aluminium (Al).The first covering is formed by quartz.The second covering is by forming because of the caused crosslinked perfluor ether polymer that solidifies of silicon hydrogenation (solidifying the beginning temperature is 128 ℃).Surface coating is formed by heat-curable silicone (solidifying the beginning temperature is 86 ℃).
＜comparative example 2 and 3 〉
Make two kinds except the second covering with the identical doubly clad optical fiber heart yearn of external structure and foregoing invention example 2, and with these two kinds of doubly clad optical fiber heart yearns doubly clad optical fiber heart yearn of 2 and 3 as a comparative example.
Should illustrate, comparative example 2 and 3 all is doubly clad optical fiber heart yearns that the second covering is formed by ultraviolet light curable fluorinated acrylate resin, but the ultraviolet light curable fluorinated acrylate resin that uses in comparative example 2 is different with the ultraviolet light curable fluorinated acrylate resin that uses in comparative example 3.
(test evaluation method)
＜loss 〉
Will respectively have the long example 2 of 200m and the doubly clad optical fiber heart yearn bundle fasciculation of comparative example 2, measure according to Japanese Industrial Standards JIS C6823 wavelength modulated and loss when transmitting this modulated flashlight.And, be immersed in temperature in the Water Tank with Temp.-controlled each bundle doubly clad optical fiber heart yearn adjusted and be in 85 ℃ the hot water, flooded 2 days.Then, according to measuring loss with above-mentioned the same step.
<NA>
Utilize the FFP method put down in writing among the Japanese Industrial Standards JIS C6822 that the NA of each the first covering of example 2, comparative example 2 and comparative example 3 is measured.Particularly, light is injected the first covering of doubly clad optical fiber from red-light LED (light emitting diode) through camera lens, is measured again the far field pattern (FFP) of emergent light, with this FFP outer form maximal value namely 5% value as NA.Should illustrate, that use as the measurement mechanism of NA is the FFP measuring system LEPAS11 that shore pine Photonics Co., Ltd. (Hamamatsu Photonics K.K.) makes.As the camera lens use is the NA camera lens slightly larger than the first covering of the doubly clad optical fiber that becomes measuring object.During respectively to fiber lengths 2m and the NA during 500m measure.
＜thermotolerance 〉
Be to keep fiber lengths to be respectively the example 2 of 60m and each doubly clad optical fiber heart yearn of comparative example 2 under the environment of 160 ℃ and 80 ℃ in temperature, ask through fate and the relation between the NA of the first covering.The measuring method of NA is the same with said method.
Should illustrate, the incident angle of light is larger, and the light intensity of the near interface between glass system the first covering and resin the second covering is just higher.If resin the second covering worsens, the higher light of this NA composition is will be owing to the increase of extinction amount and the increase of peeling off caused scattered quantum of the second covering etc. former thereby be subject to larger impact, so that the NA of the first covering also can be less.Therefore, by measuring the NA of this first covering, then can estimate the deterioration of the second covering.
＜moisture-proof heat resisting 〉
Under 85 ℃ and 85% hot and humid environment, keep fiber lengths to be respectively the example 2 of 60m and each doubly clad optical fiber heart yearn of comparative example 2, ask through fate and the relation between the NA of the first covering.The measuring method of the NA of the first covering is the same with said method.
(test evaluation result)
Figure 12 (a) and Figure 12 (b) illustrate before and after the Hot water immersion separately wavelength and the relation between the loss.
As known in the figure, although (for example before Hot water immersion, have the locality peak difference, the absorption peak of the OH of 1400nm wave band), but generally, example 2 and comparative example 2 all show the loss that equates level, on the other hand, and after Hot water immersion, although the variation of the loss of example 2 is minimum, obviously increase with respect to the loss of this comparative example 2.
The NA of table 2 expression the first covering.
(table 2)
In example 2, the NA when fiber lengths is 2m is 0.59, and the NA when fiber lengths is 500m is 0.54.In comparative example 2, the NA when fiber lengths is 2m is 0.46, and the NA when fiber lengths is 500m is 0.45.In comparative example 3, the NA when fiber lengths is 2m is 0.60, and the NA when fiber lengths is 500m is 0.24.
By above result as can be known, in example 2, when fiber lengths shorter (2m) and fiber lengths can both obtain NA first covering higher than comparative example 2 and comparative example 3 when growing (500m), so this example 2 is better.
Maintenance fate under Figure 13 and the table 3 expression hot environment and the relation between the NA.
(table 3)
The NA that remains on the first covering under 160 ℃ the hot environment is as follows: in example 2, the initial stage (fate of process 0 day) is to be to be to be to be to be 0.50 after 0.51,101 day after 0.54,37 day after 0.54,23 day after 0.55,16 day after 0.57,7 day; In comparative example 2, the initial stage (fate of process 0 day) is to be to be to be to be 0.13 after 0.33,92 day after 0.38,28 day after 0.43,14 day after 0.47,7 day.
The NA that remains on the first covering under 80 ℃ the hot environment is as follows: in example 2, the initial stage (fate of process 0 day) is to be to be to be to be 0.57 after 0.57,91 day after 0.57,28 day after 0.57,14 day after 0.57,7 day; In comparative example 2, the initial stage (fate of process 0 day) is to be to be 0.43 after 0.46,71 day after 0.47,8 day.
By above result as can be known, in the example 2 that the second covering is formed by thermoset resin, even the retention time under the hot environment is longer, the NA decrease of the first covering is also less.On the other hand, as can be known in the comparative example 2 that the second covering is formed by UV-cured resin, the NA of the first covering follows the increase of the retention time under the hot environment and significantly reduces again.Can infer, in comparative example 2, the second covering worsens because of heat, so the caused scattered quantum peeled off of extinction amount and the second covering increases, and consequently the NA of the first covering reduces.
Relation between maintenance fate under Figure 14 and the table 4 expression hot and humid environment and the NA of the first covering.
(table 4)
The NA of the first covering when keeping under 85 ℃ and 85% hot and humid environment is as follows: in example 2, the initial stage (fate of process 0 day) is to be 0.57 after 0.57,7 day, be 0.57 after 14 days, be to be to be 0.52 after 0.57,99 day after 0.57,35 day after 28 days; In comparative example 2, the initial stage (fate of process 0 day) is to be to be to be 0.36 after 0.36,70 day after 0.45,15 day after 0.47,8 day.
By above result as can be known, in the example 2 that the second covering is formed by thermoset resin, even the retention time under the hot and humid environment is longer, the NA decrease of the first covering is also less.On the other hand, as can be known in the comparative example 2 that the second covering is formed by UV-cured resin, the NA of the first covering follows the increase of the retention time under the hot and humid environment and significantly reduces again.Can infer, in comparative example 2, the second covering Yin Gaowen and high humidity and peel off, consequently the NA of the first covering reduces.
[test evaluation 3]
(manufacturing of doubly clad optical fiber heart yearn)
Change the heating condition of surface coating, make the identical doubly clad optical fiber heart yearn of example 2 of structure and test evaluation 2.
Particularly, condition 1 is as follows: with adding pressing mold as the first and second coating moulds, and to set design temperature in the stove of the first heating furnace be that design temperature is that 400 ℃ and drawing speed are 20m/min in 300 ℃, the stove of the second heating furnace.
Condition 2 is as follows: the interior design temperature of stove of setting the second heating furnace is 450 ℃.Other is all identical with condition 1.
Condition 3 is as follows: the interior design temperature of stove of setting the second heating furnace is 500 ℃.Other is all identical with condition 1.
Condition 4 is as follows: consist of the second heating furnace by the upstream side heating furnace and the downstream heating furnace that seamlessly connect each other, and set that design temperature is 300 ℃ in the stove that design temperature in the former stove is 400 ℃ and the latter.Other is all identical with condition 1.
(test evaluation method)
To its outward appearance of doubly clad optical fiber heart yearn visualization of producing with condition 1～4, and estimate with Three Estate, this grade is: (A) outward appearance without unusual, (B) have 1 frequency that the abnormal appearance position is arranged with every several meters and (C) most abnormal appearances position arranged.
Also have, the sense of touch when grasping this doubly clad optical fiber heart yearn is estimated its surperficial stickability with two grades, and this grade is: the adhesion sense (A) without the adhesion sense and (B) is arranged.
Have again, utilize the NA of the method identical with test evaluation 2 first covering during for 60m to fiber lengths to measure.
(test evaluation result)
Table 5 expression test evaluation result.
(table 5)
The ocular estimate result is as follows: being B when condition 1, o'clock is A in condition 2～4.
The stickability evaluation result is as follows: being B when condition 1, o'clock is A in condition 2～4.
The NA of the first covering is as follows: being 0.56 when condition 1, is 0.20 when condition 2, is 0.18 when condition 3, is 0.57 when condition 4.
By above result as can be known, condition 2 and 3 o'clock, the NA of the first covering reduced.Can infer, namely when the condition 2 of 450 ℃ and 500 ℃ and condition 3, the character of the second covering changes because of hot the value that design temperature is higher in setting the stove of the second heating furnace.On the other hand, as can be known when condition 1, although the NA of the first covering does not reduce, outward appearance and stickability are relatively poor again.Can infer, namely during 400 ℃ condition 1, surface coating solidifies the value that design temperature is lower in setting the stove of the second heating furnace fully.
With respect to this, consisting of the second heating furnace by upstream side heating furnace and downstream heating furnace, and when to set design temperature in the stove that design temperature in the former stove is 400 ℃ and the latter be 300 ℃ condition 4, can access reducing and outward appearance and the good doubly clad optical fiber heart yearn of stickability of the NA that can not observe the first covering.
[test evaluation 4]
(manufacturing of doubly clad optical fiber heart yearn)
Preparation adds pressing mold as the first coating mould that is used for forming the second covering, make the identical doubly clad optical fiber heart yearn of example 2 of structure and test evaluation 2 with this compression molding, prepare in addition open die as the first coating mould, with the identical doubly clad optical fiber heart yearn of the example 2 of this open die making structure and test evaluation 2.
(test evaluation method)
Prepare when the doubly clad optical fiber heart yearn that produces when adding pressing mold as the first coating mould and the doubly clad optical fiber heart yearn that when applying mould with open die as first, produces, change on one side fiber lengths, utilize with test evaluation 2 identical method to measure the NA of first covering of described two kind doubly clad optical fiber heart yearns on one side.
(test evaluation result)
Figure 15 and table 6 expression is to the relation between the NA that measure when the doubly clad optical fiber heart yearn of producing when adding pressing mold as the first coating mould and the doubly clad optical fiber heart yearn produced when applying mould with open die as first, fiber lengths and the first covering.
(table 6)
The NA of the first covering is as follows: in the situation that use adds pressing mold, when fiber lengths is 1m, be 0.57, when fiber lengths is 8m, be 0.56, when fiber lengths is 13m, be 0.56, when fiber lengths is 23m, be 0.56, being 0.55 when fiber lengths is 33m, is 0.55 when fiber lengths is 43m, is 0.54 when fiber lengths is 53m; In the situation that use open die, when fiber lengths is 1m, be 0.57, when fiber lengths is 2m, be 0.56, when fiber lengths is 7m, be 0.52, being 0.46 when fiber lengths is 17m, is 0.40 when fiber lengths is 27m, is 0.38 when fiber lengths is 37m, being 0.30 when fiber lengths is 47m, is 0.26 when fiber lengths is 57m.
By above result as can be known, when use added pressing mold, the NA of the first covering was less to the dependence of fiber lengths, and when using open die, the NA of the first covering is larger to the dependence of fiber lengths, and the NA of the first covering follows the increase of fiber lengths and reduces.
He-Ne laser is injected in above-mentioned two kinds of doubly clad optical fiber heart yearns, observed.Consequently, in the doubly clad optical fiber heart yearn of producing with open die, many luminous points have been observed.Amplify this Partial Observation with microscope, must cicada light from the external diameter change of the second covering and thinner part appears.On the other hand, in the doubly clad optical fiber heart yearn made from compression molding, do not observe the aforesaid point that sends light.Therefore, can infer, add pressing mold by use, then the external diameter of the second covering can become stable, and printing opacity is suppressed, and consequently the NA of the first covering diminishes to the dependence of fiber lengths, becomes stable at long side direction.
Claims (17)
1. polymer-clad fiber, it has the optical transmission line that is formed by glass and coats this optical transmission line and the covering established, it is characterized in that:
The clad material that forms described covering contains because the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation.
2. polymer-clad fiber according to claim 1 is characterized in that:
The numerical aperture of described optical transmission line is more than 0.50.
3. polymer-clad fiber according to claim 1 is characterized in that:
The Shore A level hardness of described clad material is 10～80.
4. polymer-clad fiber according to claim 1 is characterized in that:
The glass transition temperature of described clad material is below 0 ℃.
5. polymer-clad fiber heart yearn is characterized in that:
Described polymer-clad fiber heart yearn is to coat polymer-clad fiber claimed in claim 1 and the polymer-clad fiber heart yearn that consists of with surface coating.
6. the manufacture method of a polymer-clad fiber, the manufacture method of this polymer-clad fiber comprises that optical transmission line forms operation and covering forms operation, it is that the prefabricated component of being made by glass is carried out wire drawing that this optical transmission line forms operation, form the operation of optical transmission line, it is liquid blanket formation material to be attached to by described optical transmission line form on the surface of the established optical transmission line of operation that this covering forms operation, and make this covering form the material heat curing by heating, thereby form the operation of covering, it is characterized in that:
Described covering forms material and contains owing to the caused crosslinked perfluor ether polymer that solidifies of silicon hydrogenation.
7. doubly clad optical fiber, it has fibre core, the first covering and the second covering, this fibre core is made by the glass that is added with rare earth element, this first covering is made by glass, coat this fibre core and establish, this fibre core of the refractive index ratio of this first covering is low, and this second covering coats this first covering and establishes, this first covering of the refractive index ratio of this second covering is low, it is characterized in that:
The second clad material that forms described the second covering is thermoset resin.
8. doubly clad optical fiber according to claim 7 is characterized in that:
The second clad material that forms described the second covering is to contain because the thermoset resin of the perfluor ether polymer of the caused crosslinked curing of silicon hydrogenation.
9. doubly clad optical fiber according to claim 7 is characterized in that:
The numerical aperture of described the first covering is 0.4～0.6 at fiber lengths when measuring under the condition that is 2m.
10. doubly clad optical fiber according to claim 7 is characterized in that:
The numerical aperture of described the first covering is 0.4～0.6 at fiber lengths when measuring under the condition that is 500m.
11. doubly clad optical fiber according to claim 7 is characterized in that:
The Shore A level hardness of described the second clad material is 10～80.
12. doubly clad optical fiber according to claim 7 is characterized in that:
The glass transition temperature of described the second clad material is-150 ℃～0 ℃.
13. a doubly clad optical fiber heart yearn is characterized in that:
Described doubly clad optical fiber heart yearn coats doubly clad optical fiber claimed in claim 7 with surface coating and consists of.
14. the manufacture method of a doubly clad optical fiber, the manufacture method of this doubly clad optical fiber comprises that fibre core and the first covering form operation and the second covering forms operation, it is that the prefabricated component of being made by glass is carried out wire drawing that this fibre core and the first covering form operation, form the fibre core that is added with rare earth element and coat this fibre core and the operation of the first covering that this fibre core of refractive index ratio is low, it is liquid the second clad material to be attached to by described fibre core and the first covering form on the surface of established described the first covering of operation that this second covering forms operation, and make this second clad material heat curing by heating, thereby form the operation of the second low covering of this first covering of refractive index ratio, it is characterized in that:
Described the second clad material contains owing to the caused crosslinked perfluor ether polymer that solidifies of silicon hydrogenation.
15. the manufacture method of a doubly clad optical fiber heart yearn is characterized in that:
The manufacture method of described doubly clad optical fiber heart yearn comprises that surface coating forms operation, it is liquid coating material to be attached to utilize on the surface of the doubly clad optical fiber that the described method of claim 14 produces that this surface coating forms operation, and makes the operation of this coating material heat curing by heating.
16. the manufacture method of doubly clad optical fiber heart yearn according to claim 15 is characterized in that:
Form in the operation at described surface coating, make the doubly clad optical fiber that is attached with liquid coating material successively by design temperature in the stove relatively high upstream side heating furnace and the interior relatively low downstream heating furnace of design temperature of stove, make the coating material heat curing.
17. the manufacture method of doubly clad optical fiber heart yearn according to claim 15 is characterized in that:
Form in the operation at described surface coating, use the pressing mold that adds of exerting pressure to liquid coating material that liquid coating material is attached on the surface of doubly clad optical fiber.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011164648 | 2011-07-27 | ||
| JP2011-164648 | 2011-07-27 | ||
| JP2011-177134 | 2011-08-12 | ||
| JP2011177134A JP2013041060A (en) | 2011-08-12 | 2011-08-12 | Polymer-clad optical fiber and manufacturing method thereof |
| JP2012-150368 | 2012-07-04 | ||
| JP2012150368A JP6139070B2 (en) | 2011-07-27 | 2012-07-04 | Method for manufacturing double-clad optical fiber, and method for manufacturing double-clad optical fiber |
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| CN102902008A true CN102902008A (en) | 2013-01-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106568581A (en) * | 2016-11-15 | 2017-04-19 | 中电科天之星激光技术（上海）有限公司 | Optical fiber numerical aperture measuring method |
| CN107076945A (en) * | 2014-10-17 | 2017-08-18 | 住友电气工业株式会社 | Optical fiber core wire and optical fiber ribbon core wire |
| CN109633818A (en) * | 2018-12-10 | 2019-04-16 | 河北汉光重工有限责任公司 | A kind of optical fibre gyro optical fiber welding point protection method and device |
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| CN111699566A (en) * | 2018-02-07 | 2020-09-22 | 大日本印刷株式会社 | Battery packaging material, method for producing same, and battery |
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| CN107076945A (en) * | 2014-10-17 | 2017-08-18 | 住友电气工业株式会社 | Optical fiber core wire and optical fiber ribbon core wire |
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| CN109633818A (en) * | 2018-12-10 | 2019-04-16 | 河北汉光重工有限责任公司 | A kind of optical fibre gyro optical fiber welding point protection method and device |
| CN109633818B (en) * | 2018-12-10 | 2020-10-16 | 河北汉光重工有限责任公司 | Optical fiber melting point protection method and device for optical fiber gyroscope |
| CN109813349A (en) * | 2019-02-27 | 2019-05-28 | 华南理工大学 | A composite optical fiber device for detecting optical, electrical and chemical signals and its preparation and application |
| CN113126201A (en) * | 2021-03-26 | 2021-07-16 | 中国科学院西安光学精密机械研究所 | Single crystal optical fiber based on space shaping and processing method and system thereof |
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